IE42444B1 - 3-phenyl-5-substituted-4(1h)-pyridones-(thiones) - Google Patents

3-phenyl-5-substituted-4(1h)-pyridones-(thiones)

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Publication number
IE42444B1
IE42444B1 IE1833/75A IE183375A IE42444B1 IE 42444 B1 IE42444 B1 IE 42444B1 IE 1833/75 A IE1833/75 A IE 1833/75A IE 183375 A IE183375 A IE 183375A IE 42444 B1 IE42444 B1 IE 42444B1
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Ireland
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pyridone
phenyl
methyl
compound
halo
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IE1833/75A
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IE42444L (en
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Lilly Co Eli
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/69—Two or more oxygen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
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    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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    • C07C49/233—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing halogen containing six-membered aromatic rings
    • C07C49/235—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing halogen containing six-membered aromatic rings having unsaturation outside the aromatic rings
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/80—Acids; Esters in position 3
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/89—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom
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    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Pyridine Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Furan Compounds (AREA)

Abstract

3-Phenyl-5-(substituted)-4(1H)-pyridones of the formula I are prepared by cyclising a compound of the formula IV in which one of the two substituents Q<1> or Q<2> represents two hydrogen atoms, while the other of the two substituents represents a group of the formula =CHNHR, using a formylating agent. In the compounds of the formulae I and IV, the radicals R, R<1> and R<2>, and m, have the meaning given in Patent Claim 1. The pyridones can be reacted with phosphorus pentasulphide to prepare the corresponding pyridothiones. Both the pyridones and the corresponding pyridothiones, and also the salts of these compounds, are employed as the active component in herbicides. They display their activity against an unusually broad range of weeds.

Description

This invention belongs to the field of agricultural chemistry, and provides to the art new preemergence and postemergence herbicides, and compositions and methods of applying the compounds for the control of weeds. Since the control of weeds is known to be a vital step in the maximization ol crop yields, herbicides are now established as vital tools of the farmer and new and improved herbicidal compounds are in constant demand.
Despite the great amount of research which has IO been performed in the field of agricultural chemistry, active compounds closely related to the compounds of formula I herein have not been previously discovered. The polyhalopyridones, which have two or more chlorine atoms as well as other alkyl and halo substituents on the pyridine ring, are known herbicides, but are obviously quite distinct from the compounds pf formula I.
The organic chemical art has explored the pyridones rather extensively. For example, Ishibe et al., J.
Am. Chem. Soc· 95, 3396-3397 (1973) , disclosed a rear20 rangement of 3,5-diphenyl-l,2,6-trimethyl-4(IH)-pyridone. Such compounds, however, are not herbicides. Leonard et al., J. Am. Chem. Soc. 77, 1852-1855 (1955), taught the synthesis of 3,5-dibenzyl-l-methyl-4(lH)-pyridones, which compounds also have no herbicidal activity. The same principal author also disclosed 3,5-di(substituted-benzylidene)tetrahydro-4-pyridones, J. Am. Chem. Soc. 79, 156-160 (1957). These compounds also have no herbicidal activity. -242444 Light et al., J. Org. Chem. 25, 538-546 (1960), described a number of 4-pyridone compounds including 2,6diphenyl-l-methyl-4(IH)-pyridone, and related compounds bearing phenyl-ring substituents, none of which are her5 bicidally active.
An interesting recent article was published by El-Kholy et al. in J. Hetero. Chem. 10, 665-667 (published September 7, 1973). El-Kholy described a synthesis of 3,5diphenyl-l-methyl-4(IH)-pyridone and related compounds by the reaction with methylamine of the sodium salt of 1,5dihydroxy-2,4-diphenyl-l,4-pentadien-3-one.
The invention provides a series of novel 3-phenyl-4(lH)pyridones-(thiones) whioh are herbicides and which are active against an unusually wide range of weeds. New methods and comIb positions for applying the compounds for the control of weeds, which methods are particularly useful in cotton cropland, are also disclosed. The novel compounds are of the general formula X R wherein: X is oxygen or sulfur; R is C^-C^ alkyl; C^-C^ alkyl substituted with halo, cyano, carboxy or methoxycarbonyl; C2~C3 alkenyl; C2~C3 alkynyl; C^-C^ alkoxy; acetoxy; or dimethylamino; provided that R comprises no more than 3 carbon atoms; -343444 the R1 groups independently are halo; c^-cg alkyl; C^-Cg alkyl substituted with halo; C^-Cg alkyl monosubstituted with phenyl, cyano or Cj-C3 alkoxy; C2-Cg alkenyl; C2-Cg alkenyl substituted with halo; C2-Cg alkynyl; C2~Cg alkynyl substituted with halo; Cg-Cg cycloalkyl; C^-Cg cycloalkenyl; C^-Cg cycloalkylalkyl; C^-Cg alkanoyloxy; C^-Cg alkylsulfonyloxy; phenyl; phenyl monosubstituted with halo, C^-Cg alkyl, C^-Cg alkoxy, or nitro; nitro; cyano; carboxy; hydroxy; C^-Cg 3 3 3 alkoxycarbonyl; -O-R ; -S-R ; -SO-R ; or -SO2~R ; R3 is ci-cj_2 alkyl; c^-c12 alkyl substituted with halo; cg“c32 alkyl monosubstituted with phenyl, cyano or C^-Cg alkoxy: phenyl; phenyl monosubstituted with halo, C^-Cg alkyl, C^-Cg alkoxy or nitro; Cg-Cg cycloalkyl; C^-Cg cycloalkylalkyl; C2-C12 alkenyl; c2~c12 alkenyl substituted with halo; C2-C^2 alkynyl; or C2~C12 alkynyl substituted with halo; provided that R comprises no more than 12 carbon atoms; R2 is halo; hydrogen; cyano; C^-Cg alkoxycarbonyl; Cj.-Cg alkyl; C^-Cg alkyl substituted with halo or C^-Cg alkoxy; Cg-Cg alkenyl; Cg-Cg alkenyl substituted with halo or Q^-Cg alkoxy; Cg-Cg alkynyl; C3~Cg cycloalkyl; Cg-Cg cycloalkyl substituted with halo, C^-Cg alkyl or C^-Cg alkoxy; C^-Cg cycloalkenyl; C^-Cg cycloalkylalkyl; phenyl-Cg-Cg alkyl; furyl; naphthyl; thienyl; 4 4 4 —O—R ; —S—R ; -SO-R ; -SOg-R , or -443444 R is Cj-Cj alkyl; C^-Cg alkyl substituted with halo; C2~C3 alkenyl; C2-C3 alkeny1 substituted with halo; benzyl; phenyl; or phenyl substituted with halo, C^-Cj alkyl or C1”C3 alkoxy; the R3 groups independently are halo; Cl-C8 Cl-C8 alkyl substituted with halo; C^-Cg alkyl monosubstituted with phenyl, cyano or C^-C^ alkoxy; C2~Cg alkenyl, C2”Cg alkenyl substituted with halo; C2~Cg alkynyl; C2~Cg alkynyl substituted with halo; Cg-Cg cycloalkyl; C^-Cg cycloalkenyl; C4-Cg eycloalkylalkyl; C^-C3 alkanoyloxy; C^-Cj alkylsulfonyloxy; phenyl; phenyl monosubstituted with halo, C^-C3 alkyl, C^-Cj alkoxy or nitro; nitro; cyano; carboxy; hydroxy; C^-Cg alkoxycarbonyl; -0-R6; -S-R6; -SO-R6; or -SC>2-R6; R6 is C^-C^2 alkyl; C^-C^2 a3-kyl substituted with halo; C^-C.^ alkyl monosubstituted with phenyl, cyano or C^-Cj alkoxy; phenyl; phenyl monosubstituted with halo, C^-C3 alkyl, C^-C3 alkoxy or nitro; Cg-Cg cycloalkyl; c4~Cg cycloalky lalkyl; C2-Ci2 alkenyl; c2-ci2 -54 3 4 4 4 alkenyl substituted with halo; C2_C12 alkynyl; or a33iyny1- substituted with halo; provided that R3 comprises no more than 12 carbon atoms; m and n independently are 0, 1 or 2; provided that 2 when X is oxygen, R is methyl, and R is unsubstituted phenyl, then m is 1 or 2; and the acid addition salts thereof.
A preferred group of compounds are of the formula X II II wherein; X is oxygen or sulfur; R° is Cj-C3 alkyl; C2~C3 alkenyl; acetoxy; or methoxy; q and p independently are 0, 1 or 2; provided that both are not zero when X is oxygen and R° is methyl; the r7 groups independently are halo; C.-C, 3 alkyl; trifluoromethyl; or alkoxy; the R groups independently are halo; C^-C3 alkyl; trifluoromethyl; or C^-C3 alkoxy; or two g R groups occupying adjacent o and m positions combine with the phenyl ring to which they are attached to form a 1-naphthyl group.
Another preferred group of compounds are of the formula -642444 ϋ ιι I R wherein the various symbols are defined as before. The most highly preferred compounds are those of formula III wherein R1 is trifluoromethyl.
In the above formulae, the general chemical terms are used in their normal meanings. For example, the terms C^-Cj alkyl, C2-C3 hlkenyl, C2~C3 alkynyl, Cj-C^ alkoxy, alkyl, C2-Cg alkenyl, ^2~cs alkYnY1' Ci-C6 alkY1/ C2~Cg alkenyl and c2-c6 alkynyl refer to such groups as IO methyl, ethyl, isopropyl, vinyl, allyl, methoxy, isopropoxy, propargyl, isobutyl, hexyl, octyl, 1,1-dimethylpentyl, 2octenyl, pentyl, 3-hexynyl, l-ethyl-2-hexenyl, 3-octynyl, 5-heptenyl, l-propyl-3-butynyl and crotyl.
The terms C3-Cg cycloalkyl and C^-Cg cycloalkenyl refer to such groups as cyclopropyl, cyclobutyl, cyclohexyl, cyclobutenyl, cyclopentenyl and cyclohexadienyl.
The term C4~Cg cycloalkylalkyl refers to such groups as cyclopropylmethyl, cyclobutylmethyl, cyclohexylmethyl and cyclohexylethyl.
The term C^-C^ alkanoyloxy refers to groups such as formyloxy, acetoxy and propionyloxy.
The term C3--C3 alkoxycarbonyl refers to groups such as mcthoxycarbonyl, ethoxyearbonyl and isopropoxycarbonyl. -74 3 114 The term Cj-Cj alkylsulfonyloxy refers to such qroups as methylsulfonyloxy and propylsulfonyloxy.
The term halo refers to fluoro, chloro, bromo, and iodo.
The compounds described above can form acid addition salts, and such salts are useful embodiments of the invention. The preferred salts are the hydrohalides such as hydriodides, hydrobromides, hydrochlorides and hydrofluorides. Salts of the sulfonic acids are also particu10 larly desirable. Such salts include sulfonates, methylsulfonates and toluenesulfonates.
Although the above general description of the compounds is believed to describe them unambiguously, a group of exemplary compounds of formula I will be named IS below to assure that the invention is understood by those skilled in the art. 1-methy1-3,5-bis(3-methoxyphenyl)-4(IH)-pyridinethione l-ethyl-3-(4-ethoxyplienyl)-5-phenyl-4(IH)— pyridinethione 3-(3,5-diiodophenyl)-5-(3-propylphenyl)-1propyl-4(IH)-pyridinethione 3-(2,6-dimethylphenyl)-l-isopropyl-5-(1-naphthyl) 4(IH)-pyridone 3-(4-methylphenyl)-5-phenyl-l-vinyl-4(IH)pyridone, hydriodide l-allyl-3-(3-chlorophenyl)-5-(2,3-diethoxyphenyl)4(IH)-pyridinethione 3,5-dipheriyl-l-et.h'/l-4 (1H)-pyridinethione 30 3-(3,5-difluorophenyl)-l-methoxy-5-phenyl-842444 (111)-pyridone l-acetoxy-3-(3,5-diethylphenyl)-5-(2,4-diethylphenyl)-4(IH)-pyridinethione l-allyl-3-(1-naphthyl)-5-(4-propoxyphenyl)-4(1H)5 pyridinethione l-propyl-3-(4-trifluoromethylphenyl)-5-(3trifluoromethylphenyl)-4(IH)-pyridone 3-(2,6-difluorophenyl)-5-(3-iodophenyl)-lvinyl-4(IH)-pyridone 3-(3,5-dibromophenyl)-5-(3-isopropoxyphenyl)-1propyl-4(IH)-pyridone 1-methyl-3-pheny1-5-(2-propylphenyl)-4(1H)~ pyridinethione, hydrochloride } 3-(3-bromophenyl)-lrmethyl-5-phenyl-4(IH)15 pyridone 3-(4-chlorophenyl)-5-(2,4-dimethoxyphenyl)-lpropyl-4(IH)-pyridone l-allyl-3-phenyl-5-(3-trifluoromethylphenyl)4(IH)-pyridinethione l-acetoxy-3,5-diphenyl-4(IH)-pyridinethione 3-(2-iodophenyl)-5-(3-isopropylphenyl)-1-methoxy4(IH)-pyridinethione 3-(2-iodo-4-methylphenyl)-5-pheny1-1-vinyl4(IH,-pyridinethione l-acetoxy-3-(4-chlorophenyl)-5-(1-naphthyl,4 (111) -pyridone 3,5-diphenyl-l-isopropyl-4(IH)-pyridinethione 3-(3-bromo-5-ethylphenyl)-5-(3-methylphenyl)l-propyl-4(IH)-pyridinethione -94 3 4 1 4 3-(4-ethoxy-2-fluorophenyl)-l-methoxy-5-phenyl4(IH)-pyridone 1-ally1-3,5-bis(3-ethy1-4-methoxyphenyl)-4(IH)— pyridone 3-(2-iodo-4-propylphenyl)-l-methyl-5-(4-trifluoro methylphenyl)-4(IH)-pyridinethione 1-methy1-3-(3-methy1-5-propylphenyl)-5-pheny14(IH)-pyridinethione 3-(2-chloro-4-iodophenyl)-5-(3-fluorophenyl)-ΙΙΟ propyl-4 (IH)-pyridinethione 3-(3-chlorophenyl)-5-[2,4-bis(trifluoromethyl)phenyl1-l-methoxy-4(IH)-pyridone 3-benzyloxy-l-chloromethyl-5-(3-ethynylphenyl)4(IH)-pyridone 3-benzylthio-l-(2-bromoethyl)-5-(2,4-dimethylpheny1) -4(IH)-pyridone 3-benzylsulfinyl-l-ethyl-5-(3-fluoro-5-propylphenyl)-4(IH)-pyridone 3-benzylsulfonyl-5-(3-octylphenyl)-l-propyl20 4(1Π)-pyridone 3-(2-butylphenyl)-l-trifluoromethyl-4(111)pyridone, hydrobromide 1-(2-chloroethyl)-3-cyano-5-phenyl-4 (IH)-pyridinethione 3-(3-hexylphenyl)-l-methyl-5-(2-methylphenyl)4(IH)-pyridone 1-(3,J3-dibromopropyl)-3-(2,4-dichlorophenyl)5-methy1-4(IH)-pyridone 3-(2,4-dimethylphenyl)-5-methoxycarbonyl-l30 methyl-4(1H)-pyridone tIO48444 1-ine thy 1-3-(3-(] -propylpenty 1) pheny 11 -5-propy 1 4(IH)-pyridono 1-(2-cyanoethyl)-3-(3-octyl-4-methylphenyl)-5propoxycarbonyi-4(1W)-pyridone 3- [3-(2-ethylpentyl)phenyl]-l-carboxymethyl-5(3-trifluoromethylphenyl)-4(IH)-pyridone 3-(2-chloromethylpheny1)-1-methoxycarbonylmethy14(IH)-pyridone 3,5-diphenyl-l-ethynyl-4(IH)-pyridinethione 10 3-(4-heptafluoropropylpheny1)-5-hexyl-l-methyl4(IH)-pyridinethione 3-(3,5-diethylphenyl)-l-propargyl-5-[3-(5,5dibromopentyl)phenyl]-4(IH)-pyridone 3-(2,4-dipropylpheny1)-l-methyl-5-trifluoro15 methyl-4(IH)-pyridone 3-(4-benzylphenyl)-l-ethoxy-5-(2-fluoroethyl)4 (HI)-pyridone 3-(2-chloroethyl)-5-14-(2,2-diiodooctyl)phenyl]l-methoxy-4 (III) -pyridinethione 3-(3-chloro-2-methoxyphenyl)-5-(1,1-dibromopentyl)-i-methyl-4(IH)-pyridone 3-(6-iodohexyl)-l-isopropoxy-5-phenyl-4(1H)pyridinethione 3-(3-hexylpheny1)-5-methoxymethyl-l-methyl25 4(IH)-pyridone l-dimethylamino-3,5-bis(3-trifluoromethylphenyl)4 (IH)-pyridinethione l-methyl-3-[4-(4-phenylhexyl)phenyl]-5-(3propylphenyl) -4 (111) -pyridone 114 3 4 4-1 1-(2-chloroethy1)-3-(4-(2-cyanoethyl)phenyl]4 (111) -pyridinethione l-methyl-3-(2-propoxyethyl)-5-phenyl-4(III)pyridinethione, hydrofluoride 3-(6-ethoxyhexyl)-5-(3-ethy1-5-iodophenyl)-1(3-iodopropy1)-4(IH)-pyridone 1-methyl-3-phenyl-5-vinyl-4(IH)-pyridinethione 3-allyl-5-[4-(3-cyanohexyl)phenyl]-1-propoxy4 (lH)-pyridinetlxione 3-[4-(8-cyanooctyl)phenyl]-l-methyl-5-(2-pentenyl)-4(IH)-pyridone 3-(3-hcxenyl)-5-[2-(2-methoxyethyl)phenyl]-1methyl-4(IH)-pyridinethione 3-(2,2-dichlorovinyl)-l-methyl-5-[3-(3-propoxy15 heptyl)phenylj-4(IH)-pyridone 3-(2-bromo-l-butenyl)-5-[3-(6-ethoxyheptyl)phenyl]-l-ethoxy-4(IH)-pyridone 3-(2-iodo-l-hexeny1)-l-methyl-5-(3-vinylpheny1); 4 (III)-pyridinethione 3-(4-allylphenyl)-l-dimethylamino-5-phenyl4(IH)-pyridinethione 3-(2-methoxyallyl)-l-methyl-5-(4-trifluoromethyl phenyl )-4(111)-pyridinethione 3-(4-e thoxy-2-pen tony 1)-5-(2-(2,4-hexadieny1) 25 phenyl ] -]-methoxy-4 (111) -pyridone l-methoxycarbonylmothyl-3-[3-(3-octeny1) phenyl]5-phenyl-4 (111)-pyridone, methanesulfonate 3-[3-(2-hexenyl)phenyl]-l-methyl-5-(3-propylpheny1) -4(IH)-pyridineth ione -1243444 3-(2-ethyl-3-fluorophenyl)-5-ethynyl-l-methy14(1H)-pyridinethione 3-(2-butynyl)-5-(2,4-diiodophenyl)-1-ethoxy4(IH)-pyridone 3-[4-(2,6-dibromo-2-heptenyl)phenyl]-1,5-dimethy 1-4(IH)-pyridone 3-(2-hexenyl)-l-methyl-5-[3-(1,1,2,2-tetrachloro4-octenyl)phenylj-4(IH)-pyridone 3-cyclopropyl-5-[2-(2-fluoro-l-pentenyl)phenyl]10 l-methoxy-4(HI)-pyridinethione 3-cyclobutyl-5-[4-(2-iodovinyl)phenyl]-l-propoxy4(IH)-pyridone 3-cyclohexyl-5-(3-ethynylphenyl)-1-iodomethyl4(IH)-pyridinethione 1-(1-carboxyethyl)-.3-(2-chlorocyclopropyl)-5[3-(3-chloropropargyl)phenyl]-4(IH)-pyridone 3-(2,2-dibromocyclohexyl)-l-methyl-5-[2-(3pentynyl)phenyl-4(IH)-pyridinethione 3-(4-(1,l-dibromo-4-pentynyl)phenyl]-1-isopro20 poxy-5-(2-methylcyclobutyl)-4(IH)-pyridone 3-(2,4-diiodocyclopentyl)-l-ethyl-5- [4- (2octynyl)phenyl]-4(IH)-pyridone l-acetoxy-3-(4-propylcyclohexyl)- 5-(3-(6,6,6t.ri fluoro-2-hexynyl)pheny1J-4(IH)-pyridinethione 3-(3-(4-octynyl)phenyl]-5-(2-methoxycyclopropyl)l-methyl-4(IH)-pyridinethione 3-(2-(1,l-dichloro-4-heptynyl) phenyl]-5-(4methoxycyclohexyl)-l-methoxy-4(IH)-pyridone 3-(4-cyclopropylphenyl)-1-(2-methoxycarbonyl30 methyl)-5-(2-prqpoxycyclobutyl)-4(IH)-pyridinethione -134 3444 3-(2-cyclobutenyl)-5-(3-cyclopentylphenyl)-1ethoxy-4 (TH)-pyridinethione 3-(3-cyclohexenyl)-5-(3-cyclohexylphenyl) --1dimethyldmino-4(IH)-pyridone 3-(4-(1-cyclobutenyl) phenyl]-5-methoxy-l-vinyl4(IH)-pyridone, toluenesulfonate 3-chloromethoxy-l-cyanomethyl-5-(2-formyloxyphenyl)-4(IH)-pyridinethione 1-(2-carboxyethyl)-3-(3-propionyloxyphenyl)-5trifluoromethoxy-4(IH)-pyridinethione 3-(4-(2-cyclohexenyl)phenyl]-5-isopropoxy-ltrifluoromethyl-4(IH)-pyridone 3-(1,2-dibromopropoxy)-l-ethoxy-5-(2-methylsulfonyloxyphenyl)-4(IH)-pyridinethione l-dichloromethyl-3-(2-iodoethoxy)-5-(4-isopropylsulfonyloxyphenyl)-4(IH)-pyridone 3-(3-biphenylyl)-l-methyl-5-vinyloxy-4(IH)pyridinethione 3-allyloxy-5-[4-(2-chlorophenyl)phenyl]-1isopropyl-4 (III) -pyridone, hydrochloride 3-(2,2-dichlorovinyloxy)-5-[2-(3-iodophenyl)phenyl]-l-methyl-4(IH)-pyridone 3-(2-bromoallyloxy)-5-[3-(3-bromophenyl)phenyl]l-vinyl-4(IH)-pyridone l-allyl-3-[4-(2-methylphenyl)phenyl]-5-(3,3,3trifluoro-l-propenyloxy,-4(IH)-pyridone l-methoxy-3-phenoxy-5-[3-(4-propylphenyl)phenyl]4(IH)-pyridone 3-(2-chlorophenoxy)-5-(4-methoxyphenyl)phenyl)l-propargyl-4(IH)-pyridone -1442444 3-(4-bromophenoxy)-5-[4-(2-ethoxyphenyl)phenyl]l-ethyl-4(IH)-pyridone 3-(2-iodophenoxy)-5-[3-(4-isopropoxyphenyl) phenyl]-1-methoxycarbonylmethy1-4(IH)-pyridone l-cyanomethyl-3-(2-methylphenoxy)-5-[3-(4-nitrophenyl)phenyl]-4(IH)-pyridinethione 1-methyl-3-(4~nitrophenyl)-5-(3-propylphenoxy)4 (IH)-pyridone 3-(4-cyanophenyl,-l-ethoxy-5-(2-methoxyphenoxy)4(IH)-pyridone 3-(3-carboxyphenyl)-5-(2-ethoxyphenoxy)-lisopropyl-4(IH)-pyridone, hydrofluoride 1-(2-carboxyethyl)-3-(4-hydroxyphenyl)-5-(3propoxyphenoxy)-4(IH)-pyridone 3-benzyl-5-(2-methoxycarbonylphenyl)-1methyl-4(IH)-pyridone l-dimethylamino-3-(3-phenylpropyl)-5-(4-propoxycarbonylphenyl)-4(IH)-pyridone 3-(3-butoxypheny1)-5-(2-furyl)-l-trifluoromethyl4(IH)-pyridone 3-(1-ethylpentyl)-5-(3-furyl)-l-methyl-4(1H)— pyridone 3-[4-(2-propylhexyloxy) phenyl]-1-methoxycarbonylmethyl-5-(2-thienyl)-4(lH)-pyridone 1-methyl-3-(4-nonyloxypheny1)-5-(3-thienyl)4(IH)-pyridinethione 1-methy1-3-[4-(2-propylnonyloxy)phenyl]-5(4-trifluoromethylphenyl)-4(IH,-pyridinethione 3-(3,5-diethylphenyl)-l-ethyl-5-(4-trifluoromethoxyphenyl)-4(IH)-pyridinethione -153-(2,4-divinylphenyl)-5-[4-(2-fluoroethoxy)phenyl]-l-isopropoxy-4(IH)-pyridinethione 3-)3-(5,5-dibromopentoxy) phenyl)-5-(3,5-dicyclopropylphenyl)-l-ethyl-4(IH)-pyridone 3-(2,4-dimethoxyphenyl)-1-(2-methoxycarbony1methyl)-5-[2-(12-iodododecyloxy)phenyll-4(IH)-pyridinethione V 3-(4-benzyloxyphenyl)-l-eyanomethyl-5-[3,5-di(isopropenyl)phenyl]-4(IH)-pyridinethione 3-(2,6-dinitrophenyl)-l-methoxy-5-[5-phenyl10 pentoxy)phenyl]-4(1H)-pyridone 3-(2,4-diformyloxyphenyl)-l-ethoxy-5-(4-(3phenylhexyloxy)phenyl]-4(IH)-pyridinethione 3-)4-(3-cyanopropoxy)phenyl]-5-(3-ethoxy-5iodophenyl)-l-methyl-4(IH)-pyridinethione 3-[4-(7-cyanoheptyloxy)phenyl]-l-ethyl-5-phenyl4(IH)-pyridinethione 3-)3-(4-cyanoundecyloxy)phenyl]-5-[2,4-di(2ethoxyethyl)phenyl]-1-methoxy-4(IH)-pyridinethione 3-[2-(2-ethoxyethoxy)phenyl]-1-(2-iodoethyl)20 5-(3,4-diacetoxyphenyl)-4(IH)-pyridinethione 3-(4-butoxy-2-difluoromethylphenyl)-1-cyanomethyl-5-)3-(6-methoxyhexyloxy)phenyl]-4(IH)-pyridone 3-(2-cyclohexyl-4-ethylphenyl)-l-methoxycarbortylmethy1-5-)2-(6-propoxynonyloxy)phenyl]-4(IH)-pyridone 3-[2,4-di(2-pentynyl)phenyl]-l-isopropoxy-5(2-vinyloxyphenyl)-4(IH)-pyridinethione 3-(2,4-diallyloxyphenyl)-1-(2,2-dichloropropyl)5-(2-methyl-6-nitropheriyl)-4(IH)-pyridone 3-)3-(2,4-hexadienyloxy)phenyl]-1-isopropy1-530 phenyl-4(IH)-pyridinethione, hydriodide -1642444 1-(2-carboxyethyl)-3-(2,6-dipropylphenyl)· 5(4-(5-dodecenyloxy)phenyl]-4(IH)-pyridinethione 3-[2-(2-chloroallyloxy)phenyl]-l-(2,2-dichloroethyl)-5-(2,4-diethoxyphenyl)-4(1H)-pyridinethione 1-ally1-3-(4-cyano-3-ethoxycarbonylphenyl)-5(4-(4,4,4-trifluoro-2-butenyloxy)phenyl]-4(IH)-pyridone l-chloromethyl-3-(3-methylsuXfonyloxy-5-vinylphenyl)-5-(3-(2,2-dibromo-3-heptenyloxy)phenyl]-4(IH)pyridinethione l-ethoxy-3-[3-(9-iodo-l-nonenyloxy)phenyl]-5phenyl-4(IH)-pyridone l-chlorodifluoromethyl-3-[2,4-di(chloromethyl)phenyl]-5-[2-(1,2,3-trichloro-6-dodecenyloxy)phenyl]4(IH)-pyridinethione 3-[3-(4-chloro,-2-butynyloxy)phenyl]-l-ethoxy-5(3-fluoro-4-isobutoxyphenyl)-4(IH)-pyridone 3-(3-(6,6-rdibromo-3-(hexynyloxy)phenyl]-1methyl-5-(3-nitro-4-propylphenyl)-4(IH)-pyridinethione 1-acetoxy-3-(2,4-dibromopheny1)-5-(3-(1,1,2,220 tetrafluoro-3-decynyloxy)phenyl]-4(IH)-pyridone 3-(3-ethynyloxyphenyl)-1-methyl-5-pheny1-4(IH)pyridinethione, hydrobromide 3-(2-(10-dodecynyloxy)phenyl]-l-methyl-5-(2propyl-4-propylsulfonyloxyphenyl)-4(IH)-pyridone 3-[2,4-di(3-pentenyl)phenyl]-5-(3-phenoxyphenyl) 1-(1,1,2,2-tetrafluoroethyl)-4(HI)-pyridone 3-(4-(4-fluorophenoxy)phenyl]-l-isopropyl-5phenyl-4(IH)-pyridinethione -1742-114 1-(3-chloropropyl)-3-(3-cyanomethy1-5-ethylphenyl)-5-13-(3-iodophenoxy)phenyl]-4(IH)-pyridone 3-(3-octylr5-fluorophenyl)-5-(2-(3-ethylphenoxy)phenyl]-l-trifluoromethy1-4(IH)-pyridone 3-(2-ethyl-4-propylsulfonyloxyphenyl)-1-ethynyl5-(2-(4-isopropylphenoxy)phenyl]-4(IH)-pyridone l-carboxymethyl-3-(2,4-dinonyloxyphenyl)-5-[3(4-methoxyphenoxy)phenyl]-4(IH)-pyridone l-chloromethyl-3-(2,4-difluorophenyl)-5-(2-(310 propoxyphenoxy) phenyl]-4(IH)-pyridinethione l-methyl-3-[4-(2-nitrophenoxy)phenyl]-5-phenyl4(IH)-pyridinethione 3-(3-isobutylthiophenyl)-l-isopropyl-5-phenyl4(IH)-pyridinethione 3-(3-chloro-4-heptylthiophenyl)-5-(3-(4-cyanopentyl) phenylJ-1-mpthy1-4(IH)-pyridone l-methyl-3-phenyl-5-[2-(3-ethylhexylthio)phenyl]4(IH)-pyridone, hydrofluoride 3-(2-chloro-4-ethylpheny1)-l-ethyl-5-(3-nonyl20 thio-4-vinylphenyl)-4(IH)-pyridone l-ethynyl-3-phenyl-5-[3-(2-ethylpentylthio)phenyl]-4(IH)-pyridone 1-(2-methoxycarbonylmethyl)-3-(4-(3-iodophenyl)phenyl]-5-(3-trifluoromethylthiophenyl)-4(IH)-pyridinethione l-acetoxy-3-(3-cyclopentylpheny1)-5-[3- (2fluoroethylthio) phenyl]-4(IH)-pyridinethione 3-(2-cyano-4-hydroxyphenyl) -l-dimethylamino-5[3-(5,5-dibromopentylthio)-4-nitrophenyl]-4(IH)-pyridone -1842444 3-14-(4,4-diiodododecy1thio)phenyI1-1-methy1-5phenyl-4(IH)-pyridone • 3-(3-benzylthio-5-ethynylphenyl)-l-cyanomethyl5-(2-hexylphenyl)-4(IH)-pyridinethione 3-(3,5-bis(4-phenylbutylthio)phenyl]-5-(2methylphenyl)-l-(1,1,2,2-tetrafluoroethyl)-4(1H)-pyridone 3-[2-bromo-4-(6-phenylhexylthio)phenyl]-5-[4(2-cyanopropylthio)-2-ethylphenyl]-l-methyl-4(IH)-pyridinethione 3-(4-(6-cyanoheptylthio)phenyl]-l-fluoromethyl4(IH)-pyridone 3-(3-acetoxy-5-ethylphenyl)-5-[2-(8-cyanoundecylthio)phenyl]-1-chlorodifluoromethy1-4(IH)-pyridone 3-(4-benzyl-2-ethoxyethoxyphenyl)-1-(2-carboxy15 ethyl)-5-(3-(2-ethoxyethoxy)-5-propargylphenyl]-4 (IH) — pyridone, toluenesulfonate l-ethyl-3-[4-(6-methoxyhexylthio)phenyl]-5phenyl-4(IH)-pyridinethione 1-isopropenyl-3-13-(3-phenylpentyl)phenyl]-520 (4-(6-isopropoxynonylthio)phenyl]-4(IH)-pyridone 3-(2-cyanomethyl-4-vinylthiophenyl)-l-ethyl-5[2-(7-phenylheptyl)phenyl]-4(lH)-pyridone 3-(3-allylthib-4-methoxymethylphenyl)-5-[2(6-cyanohexyl)-4-vinylphenyl]-l-methyl-4(IH)-pyridone 1-methoxycarbonyImethy1-3-[3-(2-pentenylthio)phenyl]-5-phenyl-4(IH)-pyridinethione 3-(3-(2-decenylthio)-5-(2,4-hexadienyl)phenyl]l-ethoxy-5-phenyl-4(lH)-pyridone -193-[4-(1,1-dichloroallylthio)phenyl]-5-(3-(4octenyl)-2-propylphenyl]-l-tri£luoromethyl-4(IH) - pyridono 3-(4-carboxy-2-hydroxyphenyl)-5-[3-(2-chloro3-butenylthio)-5-nitrophenyl]-l-vinyl-4(IH)-pyridone 3-(4-(5,5-dibromo-3-heptenylthio)phenyl]-1methyl-5-phenyl-4(IH)-pyridone 3,5-bis[4-(9-iodo~8-noneny1 thio)phenyl]-1isopropyl-4 (1 il) -pyridinethione l-ethyl-3-(3-fluorophenyl)-5-[4-(12,12,12-trichloro-2,6-dodecadienylthio)phenyl]-4(IH)-pyridinethione 3-[2-(1-chlorOpropargylthio)phenyl]-1-dimethylamino-5-[3-(4-pentenyl)-5-methoxycarboiiylphenyl]-4(Hi) ι pyridone 3-(4-(3,3-dibromo-5-hexynylthio) phenylJ-1methoxy-5-phenyl-4(IH)-pyridone 1-(2-chloropropyl)-3-[2-cyclopropyl-4-(1,1,2,2tetrafluoro-5-decynylthio)phenyl]-5-phenyl-4(IH)-pyridinethione 1-acotoxy-3-(3-ethynylthiophenyl)-5-(3-ethynyl5-fluorophenyl)-4(IH)-pyridone 3-[4-(4-decynylthio)-2-methylphenyl]-l-ethoxy5-(5-fluoro-3-trifluoromethylphenyl)-4(IH)-pyridinethione l-cyanomethyl-3-(4-phenylthiophenyl)-5-phenyl4(IH)-pyridinethione, hydrochloride 3-(3-chlorophenyl)-5-(2-(3-fluorophenylthio)phenyl]-l-methyl-4(IH)-pyridone l-carboxymethyl-3-[3-(2-iodophenylthio)pheny1J5-(3-methyl-5-methoxycarbonylphenyl)-4(IH)-pyridone 1-(2-chloroethyl)-3-(2,4-diethylpheny1)-5[4-(4-ethylphenylthio)-2-methoxyphenyl]-4(IH)-pyridone -2042444 3-13-(3-isopropylphenylthio)phenyl]-5-phenyli-trifluoroniethyl-4 (III) -pyridone 1-acetoxy-3-(4-butylphenyl)-5-[4-(3-methoxyphonylthio)phenyl]-4(IH)-pyridinethione 3-(2-methyl-6-propoxyphenyl)-3-[4-(3-propoxyphenylthio)phenyl]-l-propargyl-4(IH)-pyridone 3-[3-chloro-5-(4-nitrophenylthio)phenyl]-1methyl-5-(2,4-divinylphenyl)-4(IH)-pyridone 3-(4-butylsulfinylphenyl)-5-pheny1-1-propargyl4(IH)-pyridone l-ethyl-3-(3-heptylsulfinylphenyl)-5-(4-propoxycarbonyIpheny1)-4(IH)-pyridone 3-(2-carboxyphenyl)-l-dimethylamino-5-[2-hydroxy4-(2-propylpentylsulfinyl)phenyl]-4(HI)-pyridinethione 1-acetoxy-3-(2-cyano-5-nonylsulfinylphenyl) 5(3,5-dinitrophenyl)-4(IH)-pyridinethione l-ethoxy-3-[3-(4-propylnonylsulfinyl)phenyl]-5phenyl-4(IH)-pyridone l-methoxy-3-(2-nitrophenyl)-5-(4-trifluoromethylsulfinylphenyl)-4(IH)-pyridinethione 3-(2-ethoxyphenyl)-l-isopropyl-5-[4-(2-fluoroethylsulfinyl)-2-isopropylphenyl]-4(IH)-pyridone 3-[3,5-di(4-chlorophenyl) phenyl]-3-[4-(5,5dibromopentylsulfinyl-2-ethoxyphenyl]-l-ethynyl-4(IH)pyridone 3-[3-(12-iodododecylsulfinyl)phenyl]-5-pheny 1l-propargyl-4 (IH)-pyridone, hydriodide 3-(4-benzylsulfinylphenyl)-5-(3-biphenylyl)-1isopropenyl-4(IH)-pyridone -2143444 3-[3, 5-di(methylsulfonyloxy) phenyl]-5-[3-(5phenylpentylsulfinyl)phenyl]-l-vinyl-4(IH)-pyridone 3-[2-(3-cyanopropylsulfinyl)phenyl]-1-methoxycarbonylmethyl-5-phenyl-4(IH)-pyridinethione 3-(3-acetoxyphenyl)-5-[2-(7-cyanoheptylsulfinyl)phenyl]-l-methoxycarbonylmethyl-4(IH)-pyridone 1-(2-carboxyethyl)-3-[3-(3-cyclohexenyl)-5(3-cyanoundecenylsulfinyl)phenyl]-4(IH)-pyridone 3-(2-chloro-4-cyclohexylphenyl)-5-[3-chloro-510 (2-ethoxyethylsulfinyl)phenyl]—1-(2-cyanoethyl)-4(III)— pyridinethione 1-(2-chloroethyl)-3-[4-(6-methoxyhexylsulfinyl)phenyl]-4 (III)-pyridone 3-(4-cyclopropylphenyl)-l-iodomethyl-5-[3-(615 propoxynonylsulfinyl)phenyl]-4(IH)-pyridone 3-]3-(2-chloro-6-undecynylsulfinyl)phenyl]-1(2,2-dibromoethyl)-5r(2-ethyl-5-vinylsulfinylphenyl)-4(IH)pyridinethione 3-[3,5-di(allylsulfinyl)phenyl]-5-phenyl-l20 propyl-4(IH)-pyridone, hydrofluqride 3-(3-(2,4-hexadienylsulfinyl) phenyl]-1-methy1-5phenyl-4(IH)-pyridinethione l-dimethylamino-3-[2-(5-dodecenylsuXfinyl)phenyl]5-(3-isobutylphenyl)—4(IH)-pyridone l-acetoxy-3-[4-(2-bromoallylsuJ finyl)phenyl]5-(2,4-dimethylphenyl)-4(IH)-pyridinethione l-ethoxy-3-(3-iodo-4-pentylphenyl)-5-[3-(3,3,4,4tetrafluoro-l-butenylsulfinyl)-5-hexylphenyl]-4(IH)-pyridone -2242444 l-isopropoxy-3-phenyl-5-[4-(1,l,2-trichloro-3heptenylsulfinyl)phenyl]-4(IH)-pyridinethione 3-14-(9-bromo-4-nonenylsulfinyl)phenyl]-5-[2(3-ethylhexyl)phenyl]-1-ethyny1-4(IH)-pyridinethione 3-(2,4-di(chlorodifluoromethyl)phenyl]-1-propargyl5-[3-(1,2,3-triiodo-6-dodecenylsulfinyl)phenyl]-4(IH)pyridone 3-(3-(4-bromo-2-butynylsulfinyl)-5-methylphenyl]5-(2-iodo-3-(1,2,3-trichloropentyl) phenyl]-l-vinyl-4(IH)10 pyridone 1-ally1-3-(2-(2,2-dibromo-4-hexynylsulfinyl)~ phenylJ-5-phenyl-4(IH)-pyridone 1-methoxycarbonyImethy1-3-[3-ethy1-5-(9,9,10,10tetrafluoro-2-decynylsulfinyl)phenyl]-5-phenyl-4(IH)15 pyridinethione 3-(4-benzyl-2-bromophenyl)-1-(2-carboxyethyl)5-(3-(1-chlorobuty1)-5-(6-dodecynylsulfinyl)phenyl]-4(III)— pyridone 1- (2-cyanoethyl)-3-(4-phenylsulfinylphenyl)-520 phenyl-4 (III) -pyridinethione l-cyanomethyl-3-[4-(3-fluorophenylsulfinyl)phenyl]5- (3- (4-octenyl)phenyl]-4(IH)-pyridone l-chloromethyl-3-[3-(1,l-dichloro-4-octenyl)4-nitrophenyl]-5-[3-(2-iodophenylsulfinyl)phenyl]-4(1H)25 pyridone 3-[3-(2-chlorovinyl)-5-(4-methylphenylsulfinyl)phenyl]-1-ethoxy-5-[3-(8-iodo-4~octenyl)phenyl]-4(IH)pyridone 3-[4-(3-isopropylphenylsulfinyl)phenyl]-5-phenyl30 l-propyl-4(IH)-pyridone -23434 :·ί 3- 13- (2-ethoxyphenylsulfinyl)phenyl]-1-methyl5-[4-(2-propoxyphenoxy)phenyl]-4(IH)-pyridone 3-(4-(2,4-cyclohexadienyl)-3-fluorophenylJ-1othyl-5-I3-hydroxy-5-(3-ni Lrophenylsulfiny1)pheny1]-4(III)j pyridinethione l-methyl-3-(4-methylsulfonylphenyl)-5-phenyl-4(IH) pyridinethione l-ethyl-3-(3-hexylsulfonylphenyl)-5-(4-hydroxyphenyl) -4(IH)-pyridone 3-(2-carboxy-4-ethylphenyl)-l-dimethylamino-5(4-(3-ethylheptylsulfonyl)phenyl]-4(lH)-pyridone 1-acetoxy-3- (2-hexy1-5-fluoropheny1)-5-{3-ni tro5-nonylsulfonylphenyl)-4(IH)-pyridone 3-pheny1-1-propoxy-5-[2-(3-propylnony1suifony1)15 phenyl]-4 (111)-pyridone l-cthoxy-3-phenyl-5-(3-trifluoromethyl-5-trifluoromethylsulfonylphenyl)-4(IH)-pyridone 3-[4-(2-chloroethylsulfonyl)phenyl]-5-(3fluoro-4-octylphenyl)-l-methoxy-4(IH)-pyridinethione 3-(3-bromo-5-nitrophenyl)-l-ethynyl-5-[4cyano-2-(6,6-dibromohexylsulfonyl)phenyl]-4(IH)-pyridone 3-(3-(4,4-diiodododecylsulfonyl)phenyl]-5-(2naphthyl)-1-(1-propynyl)-4(IH)-pyridone 3-(4-benzylsulfonylphenyl)-5-(3-(2-ethoxy25 phenyl)phenylj-1-isopropeny1-4(IH)-pyridinethione 3-[5-chloromethyl-4-(2-propylphenyl)phenyl]-1vinyl-5-[4-(3-phenylbutylsulfonyl)phenyl]-4(IH)-pyridone 3-[3-(3-cyanopropylsulfonyl)phenyl]-l-methoxycarbonylmethyl-5-phenyl-4(IH)-pyridone -2442444 1-(2-carboxyethyl)-3-14-(7-cyanoheptylsulfonyl)phenylJ-5-[3-(4-chlorophenyllphenylJ-4(IH)-pyridone l-cyanomethyl-3-[3-(11-cyanoundecylsulfonyl) --5fluorophenyl]-5-(4-propylsulfonyloxyphenyl)-4(IH)-pyridone 3-(2-acetoxy-4-ethoxyethylsulfonylphenyl)-1chloromethyl-5-(5-cyclopropyl-2-trifluoromethylphenyl)4(IH)-pyridone 3-(3-ethoxyhexylsulfonylphenyl)-5-pheny1-1trifluoromethy1-4(IH)-pyridinethione 3-[4-(3-cyclohexenyl)phenyl]-l-propyl-5-[3-(9propoxynonylsulConyl)phenyl]-4(IH)-pyridone 3-[3-cyanomethy1-4-(1-cyclobutenyl)phenyl]-1methyl-5-(4-vinylsulfonylphenyl)-4(IH)-pyridinethione 3-(2-allylsulfonyl-4-chlorophenyl)-5-(2-allyl15 3-cyclohexylphenyl)-l-dimethylamino-4(1H)-pyridinethione l-acetoxy-3-[4-(2,3-hexadienylsulfonyl)phenyl]5-pheny1-4(IH)-pyridone 3,5-bis[3-(4-decenylsulfonyl)phenyl]-l-methoxy4(IH)-pyridone 3-[4-(2-bromoallylsulfonyl)-2-methylphenyl]-1methyl-5-[3-(7,7,8,8-tetrafluoro-2-octynyl)phenyl]-4(IH) pyridone 3-[4-(6-heptynyl)-3-methylphenyl]-l-ethyl-5[3-(1,1,2-triiodo-3-butenylsulfonyl)-5-chlorophenyl]-4(1H)25 pyridone 3-[2-(5,5-dibromo-2-pentynyl)phenyl]-l-dimethylamino-5-[3-(5-fluoro-2-nonenylsulfonyl) phenyl]-4(IH) — pyridone -2543444 l-acetoxy-3-[2-cthyl-4-(5-methoxypentyl)phenyl]5-(3-(12,12,12-trichloro-6-dodecenylsulfonyl)phenyl]-4(IH)pyridone 3-[2-(3-chloro-5-hexynylsulfonyl)-4-nitrophenyl]5 5-[3-bromo-5-(6-cyanohexyl)phenyl]-l-methoxy-4(IH)-pyridone 3-(4-(6,6-dibromo-3-hexynylsulfonyl)phenyl]-5phenyl-l-propoxy-4(IH)-pyridone 3-(3-(2-cyanoethyl)phenyl]-l-ethynyl-5-[l,l,2,2tetrafluoro-6-decynylsulfonyl)phenyl]-4(IH)- pyridone 3- (3-benzyl-5-ethynylsulfonylphenyl) · 5- [2-(7phenylheptyl)phenyl]-1-viny1-4(IH)-pyridinethione l-cyanomethyl-3-[3-(6-dodecynylsulfonyl)-5me thylpheny1)-5-(2-methyl-4-(1,1,2,2-tetrafluoroethy1) phenyl]-4(HI)-pyridone 1-(2-carboxyethyl)-3-phenyl-5-(3-phenylsulfonylphenyl)-4(IH)-pyridone 3-(3-(4,4-diiodobutyl)phenyl]-5-(4-(4-fluorophenylsulfonyl)phenyl]-l-trifluoromethyl-4(IH)-pyridone 3-[2-chloromethyl-3-(6,6-dibromohexyl)phenyl]-520 (3-(3-iodophenylsulfonyl)phenyl]-1-methy1-4(IH)-pyridone 1-ethy1-3-[3-ethy1-5-(4-methylphenylsulfonyl)phenyl]-5-[4-iodo-3-(2-propylbutyl)phenyl]-4(IH)-pyridinethione 1-(1-cyanoethyl)-3-(3-(2-propylphenylsulfonyl) 25 phenyl]-5-pheny1-4(IH)-pyridinethione 3-[5-buty1-2-(3-methoxyphenylsulfonyl) phenyl]1-(1-carboxyethyl)-5-pheny1-4(IH)-pyridinethione -264 2 4 4 4 3-(3-isopropy1-4-trifluoromethylphenyl)-1methyl-'j-[3-(2-propoxyphenylsulfonyl)phenyl]-4(IH)-pyridone 3-[2-chloro-4-(4-nitrophenylsulfonyl)phenyl)-1ethyl-5-[3-fluoro-5-(4-heptyl)phenyl]-4(IH)-pyridone 3-(3-cyclopropylmethylphenyl)-l-methyl-5-(2trifluoromethylphenyl)-4(IH)-pyridone 3,5-bis[3-(2-cyclopentyIethyl)phenyl]-1-methoxy4 (IH)-pyridone 3-(2-cyclopropoxyphenyl)-l-ethyl-5-(2-fluoro10 phenyl)-4(IH)-pyridinethione 3-(4-cyclohexyloxyphenyl)-l-methyl-5-phenyl4(IH)-pyridone, methanesulfonate 3- (4-chlorophenyl)-5-(3-cyclobutylthiophenyl)l-ethoxy-4(lH)-pyridone 3-(2-cyclopentylsullinylphenyl)-5-(3-hexylphenyl) l-propoxy-4(Hi)-pyridone, hydrochloride 3-(4-cyclopropylsulfonylphenyl)-5-(2,4-diethylphenyl)-l-propyl-4(IH)-pyridinethione 3-(3-cyclohexylsulfonylphenyl)-5-(3,5-difluoro20 phenyl)-1-trifluoromethy1-4(HI)-pyridone 1-cyanomethyl-3-(2-cyclopropylmethoxyphenyl)-5(3-trifluoromethylphenyl)-4(IH)-pyridone 1-acetoxy-3-(3-(2-cyclohexylethoxy)phenyl]-5pheny1-4(IH)-pyridone, hydrobromide 3-(4-(2-cyclobutylethylthio)phenyl]-1-dimethylamino-5-(3,5-dimethylphenyl)-4(IH)-pyridone 3-(3-cyclopentylmethylsulfinylphenyl)-l-methyl-5(3-trifluoromethylphenyl)-4(IH)-pyridone 3-(4-(2-cyclohexylethylsulfonyl)phenyl]-1-ethyl30 5-(3-propylphenyl)-4(IH)-pyridone 274 2 4 14 3-cyclopropylmethy1-5-(3-fluorophenyl)-1metlioxy-4 (HI)-pyridone, methanesulfonate 3-(4-chlorOphenyI)-3-(2-cyclohexylethyl)-1cthoxy-4 (III)-pyridone 3-(3-fluorophenyl)-l-methyl-5-phenylthio-4(HI)pyridone 3-(3-chloro-5-methylphenyl)-l-ethoxy-5-phenylsulfinyl-4(IH)-pyridone l-acetoxy-3-phenylsulfonyl-5-(4-trifluoromethylphenyl)-4(IH)-pyridinethione 3-(2-butylphenyl)-5-(3,5-dichlorophenylthio)-1(l-propenyl)-4(HI)-pyridone 3-(2,4-dibromophenyl)-l-dimethylamino-5-(4ethylphenylsulfinyl)-4(IH)-pyridone 1-cyanomethyl-3-pheny1-5-(3-propoxyphenylsulfinyl)-4(HI)-pyridinethione 3-methylthio-5-phenyl-l-(1-propynyl) -4(IH)pyridone 3-(2-chlorophenyl)-l-methyl-5-propylsulfinyl4(HI)-pyridinethione, hydrofluoride 3-ethylsulfonyl-l-isopropyl~5-(3-trifluoromethylphenyl)-4(IH)-pyridone l-ethoxy-3-(4-fluorophenyl)-5-trifluoromethy1thio-4(IH)-pyridinethione, toluenesulfonate 3-(2-chloroethylsulfinyl)-l-chloromethyl-5(3-methylphenyl)-4(IH)-pyridone 3-(2~bromopropylsulfonyl)-1-chlorodifluoromethyl-5-phenyl-4(IH)-pyridinethione 1-(1-carboxyethyl)-3-(2,4-dimethylphenyl)-5vinylthio-4(IH)-pyridone -2842444 3-allylsulfinyl-3-(3,5-diiodophenyl)-l-methyl4(IH)-pyridinethione l-methyl-3-(2-trifluoromethylphenyl)-5-vinylsulfonyl-4(IH)-pyridinethione 3-(3-allylphenyl)-5-(2-chlorovinylthio)-1ethoxy-4(IH)-pyridinethione 1-(2-bromoethyl)-3-(2-chloro-3-fluorophenyl)-5(1,2-difluoroallylsulfiny1)-4(IH)-pyridone 3-(2-bromo-l-propenylsulfonyl)-l-methyl-5-(3methylphenyl)-4(IH)-pyridinethione 1-dimethylamino-3-(4-methoxy-2-butenyl)-5phenyl-4(IH)-pyridone 1-ethyny1-3-(2-propoxyvinyl)-5-(3-trifluoromethylphenyl)-4(IH)-pyridone. 3-(6-ethoxy-2-hexenyl)-l-methyl-5-phenyl-4(IH)pyridinethione, hydrochloride The following are the preferred compounds of formula I. l-methyl-3-phenyl-5-(3-trifluoromethylphenyl)4(IH)-pyridone 3-(3-fluorophenyl)~l-methyl-5-phenyl-4(IH)pyridone 3-(3-chlorophenyl)-1-methyl-5-phenyl-4(IH)pyridone 3,5-bis(3-chlorophenyl)-l-methyl-4(IH)-pyridone 3-(3-chlorophenyl)-5-(3-fluorophenyl)-1-methyl4(IH)-pyridone l-methyl-3-(3-methylphenyl)-5-pheny1-4(IH)pyridone -2943444 l-methyl-3,5-bis(3-fcrifluoromethylphenyl)4 (III)-pyridone 3-(3-bromophenyl)-1-methy1-5-pheny1-4(IH)pyridone 3-(3-methoxypheny1)-l-methyl-5-phenyl-4(IH)pyridone 3-(3-ethoxyphenyl)-l-methyl-5-pheny1-4(IH)pyridone 1-methy1-3-pheny1-5-(3-propoxyphenyl)-4(IH)10 pyridone 3-(3-isopropoxyphenyl)-l-methyl-5-pheny1-4(IH)pyridone 1-methy1-3-pheny1-5-[3-(1,1,2,2-tetrafluoroethoxy) phenyl) -4(IH)-pyridone 3,5-bis(3-fluorophenyl)-l-methyl-4(IH)-pyridone 3-(2-chlorophenyl)-1-methy1-5-(3-trifluoromethylphenyl) -4 (IH)-pyridone 3-(3-chlorophenyl)-1-methyl-5-(3-trifluoromethyl phenyl)-4(IH)-pyridone 2o 3-(4-chlorophenyl)-l-methyl-5-(3-trifluoromethyl phenyl) -4 (III) -pyridone 3-(2-fluorophenyl)-l-methyl-5-(3-trifluoromethylphenyl )-4 (IH) -pyridone 3-(3-fluorophenyl)-l-methyl-5-(3-trifluoro25 methylphenyl)-4(IH)-pyridone 3-(4-fluorophenyl)-l-methyl-5-(3-trifluoromethylphenyl-4(IH)-pyridone 3-(3-chlorophenyl)-5-(4-chlorophenyl)-1-methy14 (111) -pyridone -3042444 1-ethy1-3-pheny1-5-(3-trifluoromethylphenyl)4(IH)-pyridone l-allyl-3-pheny1-5-(3-trifluoromethylphenyl)4(IH)-pyridone 1-methyl-3-(3-trifluoromethylphenyl)-4(1H)pyridone 3-chloro-l-methyl-5-(3-trifluoromethylphenyl)4(IH)-pyridone 3-bromo-1-methy1-5-(3-trifluoromethylphenyl)10 4(IH)-pyridone 1,3-dimethyl-5-(3-trifluoromethylphenyl)4(IH)-pyridone 3-ethy1-1-methy1-5-(3-trifluoromethylphenyl)4 (III) -pyridone 3-isopropyl-l-methyl-5-(3-trifluoromethylphenyl)4(1H)-pyridone 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)4(IH)-pyridinethione Benary and Bitter, Ber. 61, 1058 (1928) described the synthesis of an intermediate disodium salt of 1,5-dihydroxy-2,4-diphenyl-l,4-pentadien-3one by the condensation of 1,3-diphenyl-2-propanone with ethyl formate in the presence of sodium methoxide. The intermediate pentadienone is neutralized by strong acid and forms 3,5-diphenyl-4-'pyrone. Reaction of the pyrone with ammonium acetate at an elevated temperature produces 3,5-diphenyl-4(IH)-pyridone. -314 2 4 14 Analogously, 3,5-dipheny1-4(1H)-pyridones can be prepared by the reaction of an appropriately ring-substituted 1,3-dipheny1-2-propanone with formamide and formamidine acetate. Reaction at reflux temperature produces the corresponding 3,5-dipheny1-4(IH)-pyridone, which is reacted with a halide of the desired 1—substituent in the presence of a suitable strong base to form the desired compound.
The compounds of formula I are prepared by cyclizing a compound of the formula R1 Hi IV 2 wherein R , R and m are defined as before, with an agent selected from the group consisting of a formylating agent, and an aminoformylating agent I 2 when one of Q and Q is 2 hydrogen atoms and the other is =CHN11Y wherein Y is hydrogen; hydroxy; C^-Cg alkyl; C^-Cg alkyl substituted with halo, cyano, carboxy or methoxycarbonyl; Cg-Cg alkenyl; Cg-Cg alkynyl; C^-Cg alkoxy; or 2b dimethylamino; provided that Y comprises no more than 3 carbon atoms; and with a compound of the formula YNHg wherein Y is defined as before or the acid addition salt 1 2 thereof, when both Q and Q are independently selected from 30 the group consisting of -3243444 =CHOH =chn(r9)2 g in which the R groups independently are C|_C3 alkyl, 1 or the R groups combine with the nitrogen atom to which 5 they are attached to form pyrrolidine, piperidine, morpholine or N-methylpipe^azine; to provide a compound. of the formula X \ /\X z-V I Y followed by alkylating or esterifying the compound so 10 obtained wherein Y is hydrogen or hydroxy respectively to provide the corresponding compound wherein Y is R; and when the compounds of formula I are desired wherein X is sulfur, treating the compounds of formula I wherein X is oxygen with Therefore, the compounds of formula I can be prepared by cyclizing a compound of the formula A. -o—·c—c-~κι, II VI 2 wherein R , R and m are defined as before, with a compound of the formula YNH2 wherein Y is defined as before or the acid addition salt thereof, -334 2 4 4 4 2 when both Q and Q are independently selected from the group consisting of =CHOH =CHN(R9)2 g in which R is defined as before, to provide a compound of formula V; followed by alkylating or esterifying the compound so obtained wherein Y is hydrogen or hydroxy respectively to provide the corresponding compound wherein Y is R; and when the compounds of formula I are desired wherein X is sulfur, treating the compounds of formula I wherein X is oxygen with P2Sg.
Thus, it is possible to prepare the compounds of formula I by cyclizing a compound of the formula ii C—C—C-Ry II II Q1 VII 2 wherein R , R and m are defined as before, with an agent selected from the group consisting of a formylating agent, and an aminoformylating agent 1 2 when one of Q and Q is 2 hydrogen atoms and the other is =CHNHY wherein Y is defined as before, to provide a compound of formula V; followed by alkylating or esterifying the compound so obtained wherein Y is hydrogen or hydroxy respectively to provide the corresponding compound wherein Y is R; and when the compounds of formula I are desired wherein -3442444 X is sulfur, treating the compounds of formula X wherein X is oxygen with P2S,..
An embodiment of’ the cyclizing process described above comprises reacting a compound of formula XV wherein 1 2 both of Q and Q are 2 hydrogen atoms with formamide or 1,3,5-triazine to provide an intermediate compound of formula V wherein Y is hydrogen, followed by alkylation to provide the corresponding compound of formula I. This above embodiment also comprises the use of formamide with formamidine acetate.
The preferred embodiment of the synthesis of the compounds of formula I is adapted from the methods of Benary and Bitter and of El-Kholy et al., cited above. An appropriately substituted l-phenyl-2-propanone is formylated at low temperature with sodium methoxide and ethyl formate in ether, and the product is treated with an amine salt of the desired R substituent in aqueous medium. The resulting intermediate is predominantly a 1-(R-amino)-2-phenyll-buten-3-one of formula VII. Some pyridone is also formed at this step, as reported by El-Kholy et al. The butenone is reformylated as before, and spontaneously cyclizes to form the l-substituted-3-phenyl-4(lH)-pyridone of formula I.
It is possible to prepare the intermediate 1unsubstituted pyridones by using NH3 in place of YNH2 in 2b the process, or by using the process of Benary and Bitter. The pyridone is then alkylated at the 1-position with a halide of R, or with a dialkyl sulfate, according to common procedures to yield the compounds of formula I.
Another embodiment of alkylation proceeds by converting the 1-unsubstituted pyridone to the 4-halo or -354 3 444 4-alkoxy derivative by reaction with a,halogenating agent, or an alkylating agent. Suitable halogenating agents include such agents as P0C1,, POBr,, and PCI,, i j 5 O-alkylating agents include such reagents as methyl tri5 fluoromethanesulfonate, and methyl fluorosulfonate, as well as alkyl halides used in the presence of base. In the next step, the 4-halo or 4-alkoxy compound is reacted with a halide of R to form the 1-R-substituted, 4-substituted pyridinium salt. The salt is then hydrolyzed with either a mineral acid or an alkali metal hydroxide to produce the desired product. See, for example, Takahashi et al., Pharm. Bull. (Japan) 1, 70-74 (1953).
As a chemist would expect, the amines, RNH^, may be used in the form of salts, preferably hydrohalide salts, including hydrochlorides, and hydrobromides. Such salts are often more convenient than the free amines.
The formylating agents used in the process are chosen from the common agents used for such reactions. The preferred agents are esters of formic acid of the formulae ll H—C— 0— (C -C. alkyl) or . .
H—C—0— Syntheses bases, of as sodium Similar formylations are discussed in Organic 300-02 (Collective Vol. Ill 1955).
The esters are used in the presence of strong which alkali metal alkoxides are preferred, such methoxide, potassium ethoxide and lithium pro-3642444 poxide. Other bases may also be used, including alkali metal hydrides, alkali metal amides, and inorganic bases including alkali metal carbonates and hydroxides. Such strong organic bases as diazabicyclononane and diazabicyclo5 undecane are also useful.
Reactions with formylating agents are performed in aprotic solvents such as are regularly used in chemical synthesis. Ethyl ether is usually the preferred solvent. Ethers in general, including solvents such as ethyl propyl ether, ethyl butyl ether, 1,2-dimethoxyethane and tetrahydrofuran, aromatic solvents such as benzene and xylene, and alkanes such as hexane and octane can be used as formylation solvents.
Because of the strong bases used in the formylation reactions, low temperatures produce the best yields. Reaction at temperatures in the range of from about -25°C. to about 10°C. is preferred. The reaction mixture may be allowed to warm to room temperature, however, after the reaction has proceeded part way to completion. Reaction times from about 1 to about 24 hours are adequate for economic yields in the formylation reactions.
The aminoformylating agents used in these syntheses may be any compounds capable of reacting with an active methylene group to introduce a =CHN(R )g group, or its acid 2b addition salt. Such agents are chosen from among the orthoformamides, HC[N(R9)2]3 the formate ester aminals, -374 2444 Ί 9 HC[Ν(κ)2)2 the formamide acetals, Q3—R10 I 9 HCN (R ), i3—lJ° the tris (formylamino)methanes, Q3 II HC(NHCH)3 and the formiminium halides, +9 HC=N(R ),Halo I 2 Halo Q in the structures above represents oxygen or sulfur, and R10 represents C^-C alkyl or phenyl.
Useful references on the aminoformylating agents include DeWolfe, Carboxylic Acid Derivatives 420-506 (Academic Press 1970), and Ulrich, Chemistry of Imidoyl Halides 87-96 (Plenum Press 1968). Bredereck et al. have written many papers on such agents and reactions, of which the following are typical. Ber. 101, 4048-56 (1968); Ber. 104, 2709-26 (1971); Ber. 106, 3732-42 (1973); Ber. 97, 3397-406 (1964); Ann. 762, 62-72 (1972); Ber. 97, 3407-17 (1964); Ber. 103, 210-21 (1970); Angew. Chem. 78, 147 (1966); Ber. 98, 2887-96 (1965); Ber. 96, 1505-14 (1963); Ber. 104, 3475-85 (1971); Ber. 101, 41-50 (1968); Ber. 106, 3725-31 (1973); and Angew. Chem. Int'l. Ed. 5, 132 (1966). Other notable papers on the subject include Kreutzberger et al., Arch, der Pharm. 301, 881-96 (1968), and 302, 362-75 (1969), and Weingarten et al., J. Org. Chem. 32, 3293-94 (1967). -3842444 Aminoformylations are usually carried out without solvent, at elevated temperatures from about 50°C. to about 200°C. Solvents such as dimethylformamide are sometimes used, however, particularly when it is desirable to raise the boiling point of the reaction mixture.
When aminoformylating with formiminium halides, however, aprotic solvents, such as described above in the description of solvents for formylation, are used at temperatures from about 0°C. to about 50°C., preferably at room temperature. Halogenated solvents such as chloroform and methylene chloride can also be used in such aminoformylations if desired.
Tlie exchange reactions with YNH2 are best performed in protic solvents of which alkanols are preferred and ethanol is most appropriate. Temperatures from about -20°C. to about 100°C. can be used for the exchange reactions. Room temperature is satisfactory and is preferred.
The starting materials of formula XV are prepared by reacting a compound of the formula > II CH —C—CH--Re a a VIII wherein: 2 R , R and m are defined as before, with an agent selected from the group consisting of a formylating agent, and an aminoformylating agent. -39424 44 If a formylating agent is used, a ketone intermediate of the formula If λ------» 'V \ II >—c—c—cn —Ra ii a HOCH IX is produced. Reaction with an aminoformylating agent 5 produces an enaminoketone such as X below.
R1 - -C— C— CH —Rs z (r9) ijCh Organic chemists will understand that, although formulae IX and X show the first formylation or aminoformylation as occurring on a certain side of the ketone, it may in fact occur on either side of the ketone, depending on the activating characteristics of R1 and R2. The course of the reaction is the same in either case. It will also be understood that, in many instances, the product of the formylation or aminoformylation step will actually be a mixture containing the two possible monosubstituted compounds and the disubstituted compound.
The monosubstituted product is formylated or aminoformylated again, and exchanged with an amine of the formula YNH^. The steps may be performed in either order.
If the exchange is performed first, the intermediate product is an enaminoketone of the formula -4010 43444 r’ m . . 0 < >—C—C—CH —R \=Z YHNCH XI Either formylation or aminoformylation of the above enaminoketone, which also can be represented by formula VII, affords the pyridone product, as the intermediate cyclizes as soon as the second group is introduced on the other methylene group.
Either of compounds IX or X may be either formylated or aminoformylated to provide intermediates of any of the formulae below.
•—C—C—C—R XII hoI!h HCOH R1 ,·Χ . 0 C-C~C-Ra * HC)I!h hI!n(R9) XIII XIV C—R'' (rh) nch hcn(r9) z : It will be understood that the compound similar to XIII, wherein the formyl and aminoformyl groups are reversed, is equivalent in all respects to compound XIII. Pyridones are formed from any of the above three intermediates, which can all be represented by formula VI, by simple contact of -414244^ the intermediate with an amine of the formula YNH2The starting 2-propanones of formula VIII may be prepared by syntheses in the literature. For example, see Coan et al., J. Am. Chem. Soc. 76, 501 (1954); Sullivan et al., Disodium Tetracarbonylferrate, American Laboratory 49-56 (June 1974); Collman et al., Synthesis of Hemifluorinated Ketones using Disodium Tetracarbonylferrate, J. Am. Chem. Soc. 95, 2689-91 (1973); Collman et al., Acyl and Alkyl Tetracarbonylferrate Complexes as Intermediates in the Synthesis of Aldehydes and Ketones, J. Am. Chem. Soc. 94, 2516-18 (1972).
The compounds of formula X also are prepared as follows: Μ- (R3) NCH=CH—R2 Ξ II -r hcn(r ) it will be understood that reaction (A) can also be performed in the opposite manner, as shown below: (B). R’ 0 \ II •ζ >—CH=CHN(RS) t- Hal-C-CH -R2 \ / 2 y \_u_o, _« l (Ra) NCH It is also possible to form the starting materials of 1 2 formula VI wheretn both 0 and Q' arc identical by using phos4242444 gene as the carbonyl halide when the 3- and 5-substituents of the pyridone product of formula I are identical.
(C).
R1 m V CII=CH—n(r°) COCI II ~c—c-cR1 m HCN(R ) In general, intermediate compounds in the syn5 thesis are not purified, but are simply used in successive steps after separation by extraction, neutralization or removal of excess solvent or reactant as appropriate.
The enamine acylation reactions, A-C, are performed in the presence of bases such as tertiary amines, alkali metal carbonates, and magnesium oxide, and in aprotic solvents as described above.
In some instances, as organic chemists will understand, it is necessary to apply additional synthetic steps after the pyridone compound has been formed. For example, it is convenient to form compounds having alkoxy, alkanoyloxy and like R and R substituents by first making the corresponding hydroxy-substituted compound, and then substituting on the oxygen atom.
The pyridinethiones of formula I are readily 20 prepared by the treatment of the corresponding pyridones with P2S5 ·*·η pyridine at reflux temperature, according to known methods. -434 2 4 14 The 1-acetoxy compounds of formula X are made by first making the correspondiny ]-hydroxypyridone, using ΝΙΙ,,ΟΗ as the amine, and esterifying it with acetic anhydride. The other l-substituents are provided by appro5 priate Y substituents on the amines, YNII^, used to prepare the pyridones.
The following preparative examples are presented to assure that those skilled in organic chemistry can obtain any desired compound of formula I.
The examples below show the various processes by which compounds of formula I have been made. It will be understood, however, that all of the various processes can be used, with appropriate variations, to make any compound of formula I.
Many exemplary compounds are indicated as made by the general process of a previous exemplary compound. In such instances, an ordinarily skilled organic chemist will readily see the minor changes to the exemplary process which will be needed to prepare the other exemplary compounds.
Temperatures are given in degrees Centigrade (°C.) Nuclear magnetic resonance spectra (NMR) were determined on a 60-megaHertz instrument using tetramethylsilane as an internal reference and are indicated in cycles per second (CPS). Melting points (m.p.) were determined by using a thermal block.
The first example below illustrates the preparation of a compound by the preferred synthetic process using a compound of formula VII. -4442444 Example To a solution of 4 1. of tetrahydrofuran and 284 g. of sodium methoxide was added 556 g. of 1-(3-trifluoromethylphenyl)-3-phenyl-2-propanone at 10-15°C. over a 20minute period. The reaction mixture was stirred for 15 minutes. Then 370 g. of ethyl formate was added over a period of 30 minutes and the mixture stirred for 1 hour at -15°C. To the mixture was added an additional 296 g. of ethyl formate over a period of 30 minutes. The reaction mixture was allowed to warm to room temperature and was stirred overnight. Then, a solution of 336 g. of methylamine hydrochloride in 1 1. of water was added. The two-phase mixture was stirred at 30°C. for 30 minutes. The mixture was then extracted with methylene chloride, and the extracts were combined and concentrated under vacuum, leaving an oily residue which consisted of a mixture containing l-methylamino-2-phenyl-4-(3-trifluoromethylphenyl) l-buten-3-one and l-methylamino-4-phenyl-2-(3-tri£luoromethylphenyl)-l-buten-3-one.
The residue was reacted by the same procedure of the previous paragraph. After being dissolved in methylene chloride, the mixture was washed with water and dried.
After drying and removal of the solvent, the solid product was found to weight 430 g., yield 65%. The product was recrystallized from ethyl ether, and the purified product was identified as l-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m.p. 153-155°C., by infrared, nuclear magnetic resonance, and thin-layer chromatography analyses. The elemental analysis was as follows. -454 3 4 4 4 Theoretical Pound c 69.30% 69.48% H 4.29 4.42 N 4.25 4.27 The process of Example 1 was also used to produce all of the following exemplary compounds.
Example 2^ l-methyl-3,5-his(3-trifluoromethylphenyl)4(IH)-pyridone, m.p. 152-154°C., yield 39% Example 3_ 3-pheny1-1-(2,2,2-trifluoroethyl)- 5-(3-trifluoromethylphenyl) -4(IH)-pyridone, NMR, quartet centered at 256 CPS; aromatic protons at 420-468 CPS; yield 46% Example 4 3-(3-bromophenyl)-5-(3-chlorophenyl)-1-methyl4(IH)-pyridone, m.p. 192°C., yield 23% Example 5 3- (3-chlorophenyl)-5-(4-chlorophenyl)-1-methyl4(IH)-pyridone, m.p. 170-172°C., yield 26% Example £ 3-(2-fluorophenyl)-l-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m.p. 152-154°C., yield 20% Example Ί_ 3-(2-chlorophenyl)-5-(3-chlorophenyl)-1-methyl4(IH)-pyridone, m.p. 160-16l°C., yield 15% Example 8^ 3-(3-methoxyphenyl)-l-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m.p. 113-115°C., yield 7% -464^444 Example 9 3-(4-chlorophenyl)-l-methyl-5-(3-trifluoromethylphenyl) -4 (IH) -pyridone, m.p. 153-155’C., yield 26% Example 10 1-allyl-3-pheny1-5-(3-trifluoromethylphenyl)4(IH)-pyridone, m.p. 107-109°C., yield 38% Example 11 3-(4-isopropylphenyl)-1-methy1-5-pheny1-4(IH)pyridone, m.p. 159°C., yield 60% Example 12 3-(2-chlorophenyl)-l-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m.p. 191-193°C., yield 14% Example 13 3-(3-fluorophenyl)-l-methyl-5-(3-trifluoromethy115 phenyl)-4(IH)-pyridone, m.p. 94-96°C., yield 13% Example 14 3-(4-fluorophenyl)-l-methyl-5-(3-trifluoromethylphenyl) -4 (HI) -pyridone, m.p. 133-134°C., yield 29% Example 15 3-(4-methoxyphenyl)-l-methyl-5-(3-trifluoromethylphenyl ) -4 (IH) -pyridone, m.p. 162-165eC., yield 33% The next example illustrates a synthesis where the enaminoketone of formula X is reacted first with an amine to form a compound of formula VII, and then with an aminoformylating agent to form the desired pyridone of formula I. -4742444 Example 16 Λη enaminoketone, 2-phenyl-I-diothylamino-4(3-methylthiophenyl)-l-buten-3-one, was made according to the procedure of the first step of Example 73, starting with 17.5 g. of Ν,Ν-diethylstyrylamine and 15 g. of (3-methylthiophenyl) acetyl chloride. The enaminoketone was dissolved in 300 ml. of ethanol, mixed with 20 g. of methylamine hydrochloride and stirred for about 24 hours. The solvent was then evaporated, the residue was extracted with ethyl ether, and the solution was washed with water. The organic layer was dried over anhydrous sodium sulfate, and the dried solution was evaporated to dryness to yield 1-methylamino4-(3-methylthiophenyl)-2-phenyl-l-buten-3-one.
The residue was mixed with 50 ml. of dimethylformamide dimethyl acetal and heated at reflux temperature for 20 hours. The reaction mixture was then poured into water, and the mixture was extracted first with ether and then with methylene chloride. Both extracts were washed with water, dried and evaporated to dryness. The product was 9 g. of l-methyl-3-(3-methylthiophenyl)-5-phenyl4(IH)-pyridone, which was identified by NMR, which showed peaks at 144 and 227 CPS, with aromatic protons at 420-440 and 442-458 CPS.
By a similar process, the following compounds were also produced. Examples 17 and 18 were produced by oxidation of the compound of Example 16 with m-chloroperbenzoic acid.
Example 17 l-methyl-3-(3-methylsulfinylphenyl)-5-pheny14(III)-pyridone, m.p. 161-164°C., yield 57% -4842444 Example 18 l-methyl-3-(3-methylsulfonylphenyl)-5-phenyl4(IH)-pyridone, m.p. 176-181°C., yield 31% Example 19 1-methyl-3-phenyl-5-(4-trifluoromethylphenyl)4(IH)-pyridone, m.p. 164-166°C., yield 16% The following example illustrates a variation of the process beginning with a carbonyl halide, wherein the enaminoketone of formula X is first exchanged with an amine to form a compound of formula VII, and the pyridone of formula I is then formed by formylation of the intermediate. Example 20 An enaminoketone was prepared, namely, 4-(3benzyloxyphenyl)-l-diethylamino-2-phenyl-l-buten-3-one, following the first step of the procedure of Example 73, from 14.4 g. of (3-benzyloxyphenyl)acetyl chloride and 9.6 g. of Ν,Ν-diethylstyrylamine. A 13 g. portion of the enaminoketone was dissolved in 100 ml. of methanol and 26 g. of methylamine hydrochloride was added. The reaction mixture was heated at reflux temperature overnight. The solvent was removed under vacuum, 100 ml. of water was added, and the mixture was then extracted with methylene chloride. The extract was washed with dilute hydrochloric acid and then with water, and the organic layer was separated, dried, filtered and evaporated to dryness. The resulting intermediate, 4-(3-benzyloxyphenyl)-1-methylamino-2-phenyl-l-buten-3-one, was dissolved in 125 ml. of ethyl ether. -4942444 The solution was cooled to 5°C., and 12 g. of sodium methoxide was added. While the reaction mixture was held at about 5°C., 50 ml. of ethyl formate was added slowly. The mixture was then stirred as it was allowed to warm slowly to room temperature. The reaction mixture was then evaporated to dryness, the residue was extracted with chloroform, and the extract was washed with water and dried. The product was purified by chromatography over silica gel with a 50:50 mixture of ethyl acetate:hexane.
The product-containing fractions were collected, combined, and evaporated to dryness. The product was recrystallized from ethyl acetate to produce 1.5 g. of 3-(3-benzyloxyphenyl)1-methyl-5-phenyl-4(lH)-pyridone, m.p. 158-160°C.
The following exemplary compounds were also produced according to the process of Example 20 above.
Example 21 l-methyl-3-phenyl-5-(2-thienyl) --4(IH)-pyridone, m.p. 147-148°C., yield 6% Example 22 3-(3-isobutylphenyl)-l-methyl-5-phenyl-4(IH)pyridone, NMR doublets at 54 and 147 CPS; a septet at 113 CPS; aromatic protons at 420-460 CPS.
Example 23 l-methyl-3- (3-nit'rophenyl)-5-pheny 1-4 (IH) pyridone, m.p. 135-136.5°C., yield 33% The following example demonstrates the preparation of a pyridone by the formamidine acetate process, followed by alkylation at the 1-position.
Example 24 Ten g. of 1-(2,4-dichlorophenyl)-3-phenyl-25042444 propanone was heated at reflux with 10 g. of formamidine acetate in 75 ml. of formamide for 3 hours. The mixture was then poured onto ice and water was added. After the ice had melted, the mixture was filtered and the separated solids were washed with ethyl ether. The solids were then dissolved in ethanol, decolorized with charcoal and recrystallized to produce 1.3 g. of 3-(2,4-dichlorophenyl)-5pheny1-4(IH)-pyridone, which was identified by infrared and nuclear magnetic resonance analyses.
The above pyridone was added to a solution of 0.5 g. of 50 percent sodium hydride in 60 ml. of DMSO and warmed until the pyridone dissolved. Excess methyl iodide was then added and the mixture was stirred for one-half hour. The mixture was then poured into water and filtered. The solids were extracted with methylene chloride, which was then dried with magnesium sulfate and evaporated to dryness. The residue was recrystallized from benzene-hexane to give 1.1 g. of 3-(2,4-dichlorophenyl)-l-methyl-5-pheny1-4(1H)pyridone, m.p. 202-204°C., which was identified by nuclear magnetic resonance and infrared analyses. The results of elemental microanalysis were as follows.
Theory Found C 66.68% 66.84% H 3.83 4.05 25 N 4.09 4.01 The following exemplary compounds were made by the general process of Example 24. In some instances, the 1-unsubstituted pyridone intermediate was made by the prior art procedure of Benary and Bitter, cited above. -51424 44 Example 25 3.5- diphenyl-l-ethyl-4(1H)-pyridone, m.p. 171eC., yield 75% Example 26 1-ally1-3,5-dipheny1-4(IB)-pyridone, m.p. 174°C., yield 79% Example 27 3.5- diphenyl-l-isopropyl-4(IH)-pyridone, m.p. 152°C., yield 15% Example 28 l-cyanomethyl-3,5-dipheny1-4(IH)-pyridone, m.p. 221-224°C., yield 55% The next example illustrates the variation of the formylation process wherein the starting ketone of formula VIII is diformylated to form a compound of formula VI, and the pyridone is formed by exchange with an amine.
Example 29 A 100 g. portion of l,3-diphenyl-2-propanone was dissolved in 35 g. of ethyl formate and added to 25 g. of sodium methoxide in 500 ml. of ethyl ether at 0-5°C. over a 30-minute period. The reaction mixture was then allowed to warm to room temperature and was stirred overnight. The mixture was then filtered to yield 460 g. of the disodium salt of l,5-dihydroxy-2,4-diphenyl-l,4-pentadien-3-one, which was used in the next step without purification.
A 20 g. portion of the crude salt above was added to a solution of 20 g. of propylamine and 5 ml. of concentrated hydrochloric acid in 75 ml. of water. The mixture was stirred for one-half hour at room temperature. The -5242444 reaction mixture was then extracted with ethyl ether, and the aqueous layer was evaporated to dryness. The residue was extracted with chloroform, the combined organic extracts were evaporated to dryness, and the residue was recrystallized from benzene-hexane to produce 3,05 g. of 3,5-dipheny1-1-propy1-4(IH)-pyridone, m.p. 172-174°C.
The following typical compounds were also made by the general process of Example 29.
Example 30 3,5-diphenyl-l-methoxy-4(IH)-pyridone, m.p. 165°C., yield 95% Example 31 3-(3-fluorophenyl)-l-methyl-5-phenyl-4(IH)pyridone, m.p. 133.5°C., yield 69% Example 32 3-(4-bromophenyl)-l-methyl-5-phenyl-4(IH) — pyridone, m.p. 172°C., yield 63% Example 33 3-(4-methoxyphenyl)-l-methyl-5-phenyl-4(IH)pyridone, m.p. 165°C., yield 32% Example 34. 3- (3-chlorophenyl)-l-methyl-5-pheny1-4(IH)pyridone, m.p. 172.5°C., yield 27% Example 35 3-(4-chlorophenyl)-l-methyl-5-phenyl-4(IH)pyridone, m.p. 141.5°C., yield 76% Example 36 l-methyl-3-(1-naphthyl)-5-phenyl-4(IH)-pyridone, NMR peaks at 204 and 483 CPS; aromatic protons at 430-470 CPS; yield 12% -5342444 Example 37 3,5-bis(3-chlorophenyl)-l-methyl-4(IH)-pyridone, m.p. 164167°C., yield 59% Example 38 l-methyl-3-(3-methylphenyl)-5-phenyl~4(IH)-pyridone (complex containing 1/2 mole of benzene), m.p. 79.5°C., yield 25% Example 39 l-methyl-3-(4-methylphenyl)-5-phenyl-4 (IH)-pyridone, m.p. 144.5°C., yield 28% Example 40 l-methyl-3-(2-methylphenyl)-5-phenyl-4(IH)-pyridone, NMR peaks at 133 and 201 CPS; aromatic protons at 420-440 and 442-460 CPS; yield 16% Example 41 3-(4-fluorophenyl)-l-methyl-5-pheny1-4(IH)-pyridone, m.p. 166°C., yield 60% Example 42 l-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(IH)pyridone, m.p. 152-156“C., yield 52% Example 43 3-(3-methoxyphenyl)-l-methyl-5-phenyl-4(IH)-pyridone, NMR peaks at 200 and 220 CPS; aromatic protons at 420-440 and 442-460 CPS; yield 33% Example 44 3-(3,4-dichlorophenyl)-l-methyl-5-phenyl-4(IH)-pyridone, m.p. 166.5°C., yield-54% Example 45 3-(2,5-dichlorophenyl)-l-methyl-5-phenyl-4(IH)-pyridone, m.p. 155.5aC., yield 22% -5442444 Example 46 3-(2-chlorophenyl)-l-methyl-5-phenyl-4(1H)-pyridone, m.p. 145°C., yield 29% Example 47 3,5-bis(3-fluorophenyl)-l-methyl-4(IH)-pyridone, m.p. 149-151°C., yield 60% Example 48 3-(3-chlorophenyl)-5-(3-fluorophenyl)-l-methyl-4(IH) pyridone, m.p. 145-146°C., yield 64% Example 49 3-(3,5-dichlorophenyl)-1-methyl-5-phenyl-4(IH)-pyridone, m.p. 131-135°C., yield 28% Example 50 3,5-bis(3-bromophenyl)-l-methyl-4(IH)-pyridone, m.p. 216.5°C., yield 43% Example 51 1-(3-bromophenyl)-l-methyl“5-phenyl-4(IH)-pyridone, m.p. 172°C., yield 38% Example 52 3-(2-fluorophenyl)-l-methyl-5-phenyl-4(IH)-pyridone, m.p. 165°C., yield 19% Example 53 3-(3-bromophenyl)-l-methyl-5-(3-trifluoromethylphenyl) -4 (IH) -pyridone, m.p. 151-153°C., yield 37% Example 54 1-(1-carboxyethyl)-3-phenyl-5-(3-trifluoromethylphenyl) -4 (IH) -pyridone, m.p. 236-237°C., yield 13% Example 55 l-dimethylamino-3,5-dipheny1-4(IH)-pyridone, m.p. 30 143°C., yield 94% -554 2 114 Example 56 l-methyl-3-(2-naphthyl)-5-pheny1-4(IH)-pyridone, m.p. 101-105°C., yield 45% Example 57 l-ethyl-3-phenyl-5-(3-trifluoromethylphenyl)4(IH)-pyridone, m.p. 98-100°C., yield 66% Example 58 3-phenyl-l-propyl-5-(3-trifluoromethylphenyl)4(IH)-pyridone, NMR, triplet peaks at 60 and 230 CPS, and a sextuplet at 114 CPS; yield 42% Example 59 1-methoxy-3-phenyl-5-(3-trifluoromethylphenyl)4(IH)-pyridone, NMR peak at 248 CPS Example 60 3-(3-chlorophenyl)-l-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m.p. 133-135°C., yield 28% Example 61 3-(4-biphenylyl)-l-methyl-5-phenyl-4(IH)-pyridone, m.p. 186-190°C., yield 1% Example 62 3-(3-biphenylyl)-l-methyl-5-phenyl-4(IH)-pyridone, m.p. 186-190°C., yie|d 2% The following example illustrates the synthesis of pyridones by the di(aminoformylation) of ketones, followed by exchange with amines.
Example 63 A mixture of 26.8 g. of phenylacetone and 71.4 g, of dimethylformamide dimethyl acetal in 100 ml. of anhydrous dimethylformamide was refluxed for 5 days. The reaction mixture was then evaporated to dryness under vacuum. -5642444 Analysis of the remaining dark red oil showed that it consisted of about 75% of the desired l,5-bis(dimethylamino)2-phenyl-l,4-pentadien-3-one, and about 25% of the corresponding monoaminoformylated compound. The yield was 30 g., and the intermediate was used without purification.
The mixture prepared above was dissolved in 100 ml. of denatured ethanol, and 30 g. of methylamine hydrochloride was added. The mixture was refluxed overnight, and the solvent was removed under vacuum. The residue was taken up in methylene chloride, and the solution was washed with water and saturated aqueous sodium chloride solution. The washed organic layer was dried over magnesium sulfate, and the solvent was removed under vacuum. The remaining oil was shaken with ethyl ether. The solid product which pre15 cipitated from the ether was washed with further ether and air dried. The product was recrystallized from isopropyl ether-methylene chloride to produce 10 g. of purified 1methyl-3-phenyl-4(IH)-pyridone, m.p. 123-125°C.
Example 64 A 3 g. portion of the product of Example 63 was dissolved in 100 ml. of water, and aqueous bromine was added dropwise until no more precipitate formed on further addition. The precipitate was removed by filtration, washed with water and air dried. The product was recrystallized from ethanol to yield 3 g. of 3-bromo-l-methyl-5-phenyl4(IH)-pyridone, m.p. 195-197°C.
The procedure of Example 63, and of Example 64 where appropriate, was used to prepare the following compounds . -57424 44 Example 65 3-bromo-l-methyl-5-(3-trifluoromethylphenyl)4(IH)-pyridone, m.p. 167-169°C., yield 76% Example 66 1-methy1-3-(3-trifluoromethylphenyl)-4(IH)pyridone, m.p. 122-123°C., yield 16% Example 67 3-chloro-l-methyl-5-(3-trifluoromethylphenyl)4(IH)-pyridone, m.p. 170-172°C., yield 67% Example 68 3-(3-carboxyphenyl)-1-methyl-5-phenyl-4(IH)pyridone, hydrochloride, m.p. 266-268“C., yield 10% Example 69 3-(3-cyanophenyl)-l-methyl-5-phenyl-4(IH)15 pyridone, m.p. 164-166°C., yield 33% Example 70 3-(3-ethoxycarbonylphenyl)-l-methyl-5-phenyl4(IH)-pyridone, m.p.'167-168°C., yield 11% Example 71 3,5-bis(3-qyanophenyl)-l-methyl-4(IH)-pyridone, m.p. 322-327°C., yield 22% Example 72 l-methyl-3-phenyl-5-(3-thienyl)-4(IH)-pyridone, NMR peaks at 204 and 495 CPS; aromatic protons at 430-460 CPS; yield 34% t The following example demonstrates the synthesis where the corresponding enaminoketone of formula X is aminoformylated to form a compound of formula VI, and the pyridone is formed by exchange with an amine. -5842444 A mixture oi' l.l)2 g. of dimethylaminouccylonitrLie and 1.6 g. of pyridine was dissolved in 25 ml. of ethyl ether at 0°C. A 3.08 g. portion of phenylacetyl chloride in 25 ml. of ethyl ether was added dropwise, and the mixture was stirred for 2 hours at 0°C. after completion of the addition. The mixture was then evaporated to dryness under vacuum. The residue was taken up in methylene chloride, washed with water, dried and evaporated to dryness again. Upon standing, the mixture began to crystallize, and the solids were separated by filtration and recrystallized from isopropanol to yield 400 mg. of 2-cyano-l-dimethylamino4-phenyl-l-buten-3-one.
A 300 mg. portion of the above enaminoketone and 10 ml. of dimethylformamide dimethyl acetal was heated at reflux temperature for 12 hours. The mixture was then evaporated under vacuum. To the residue was added 25 ml. of denatured ethanol and 1 g. of methylamine hydrochloride.
The ethanol solution was heated at reflux for 12 hours more and evaporated to dryness, and the residue was taken up in methylene chloride. After washing with water and drying, the organic solution was evaporated to dryness, and the residue was triturated in ethyl ether and filtered. The solids were recrystallized from isopropyl ether-acetone to yield 260 mg. of 3-cyano~l-methyl-5-phenyl-4(1H)-pyridone, m.p. 209-210.
The following exemplary compounds were prepared according to the general process of Example 73 above. -594 2 4 14 Example 74 1,3-dimethyl-5-(3-trifluoromethylphenyl)-4(IH)pyridone, m.p. 130-131°C., yield 12% Example 75 1,3-dimethyl-5-phenyl-4(IH)-pyridone, m.p. 111113°C., yield 8% Example 76 3-(3-chlorophenyl)-1,5-dimethyl-4(IH)-pyridone, m.p. 143-143.5°C., yield 6% Example 77 3-ethy1-l-methyl-5-(3-trifluoromethylphenyl)4(IH)-pyridone, m.p. 95.5-96.5”C,, yield 7% Example 7_0_ 3-cyclohexyl-l-methyl-5-(3-trifluoromethylphenyl)15 4(IH)-pyridone, m.p. 174-175°C., yield 40% Example 79 3-isopropyl-l-methyl-5-(3-trifluoromethylphenyl)4(IH)-pyridone, m.p. 98.5-99.5°C., yield 10% Example 80 3-hexyl-i-methyl-5-(3-trifluoromethylphenyl)4(IH)-pyridone, m.p.· 89.5-90.5°C., yield 7% Example 81 3-benzyl-l-methyl-5-(3-trifluoromethylphenyl)4(IH)-pyridone, m.p. 98-100°C., yield 18% Example 82 3-butyl-l-methyl-5-(3-trifluoromethylphenyl)4(HI)-pyridone, m.p. 82.5-84°C., yield 9% Example 83 3-(3-cyclohexenyl)-l-methyl-5-(3-trifluoromethyΙΒΟ phenyl)-4(IH)-pyridone, m.p. 194-195°C., yield 43% -6042444 Example 84 l-methyl-3-propyl-5-(3-trifluoromethylphenyl) 4(IH)-pyridone, m.p. 45-47°C., yield 3% Example 85 l-methyl-3-(4-nitrophenyl)-5-phenyl-4(IH) pyridone, m.p. 212-214°C., yield 48% Example 86 3,5-bis(3,4-dimethoxyphenyl)-l-methyl-4(1H)pyridone, m.p. 182-184°C., yield 1% Example 87 3-ethoxycarbonyl-l-methyl-5-phenyl-4(IH) pyridone, m.p. 107-108°C., yield 68% Example 88 3-(2-furyl)-l-methyl-5-phenyl-4(IH)-pyridone, m.p. 191-192°C., yield 69% Example 89 3-cyano-l-methyl-5-(3-trifluoromethylphenyl)4(IH)-pyridone, m.p. 228-229°C., yield 40% Example 90 3-(3,4-dimethoxyphenyl)-l-methyl-5-pheny1-4 (1H)pyridone, m.p. 154-157°C., yield 4% Example 91 3-(3,4-dibromocyclohexyl)-l-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, hydrobromide, m.p. 196-198°C., yield 26%, made by bromination of the corresponding 3-(3-cyclohexenyl) compound Example 92 3-(3-isopropenylphenyl)-l-methyl-5-pheny1-4(IH) · pyridone, NMR peaks at 125, 214, 302 and 327 CPS; aromatic protons at 420-470 CPS; yield 4% -6142414 Example 93 3-(3-ethylphenyl)-l-methyl-5-phenyl-4(IH) pyridone, m.p. 135-137°C., yield 5% Example 94 3-(3-hexylphenyl)-l-methyl-5-phenyl-4(IH) pyridone, m.p. 93-95°C., yield 6% Example 95 3-(4-ethylphenyI)-l-methyl-5-phenyl-4(lH)pyridone, m.p. 143-145°C., yield 6% Example 96 3-(3-cyclohexylmethylphenyl)-l-methyl-5-phenyl4(lH)-pyridone, m.p. 147-148°C., yield 9% Example 97 l-methyl-3-phenyl-5-benzylthio-4(IH)-pyridone, m.p. 155-157°C., yield 36% Example 98 l-methyl-3-phenyl-5-phenylthio-4(lH)-pyridone, m.p. 164-165°C., yield 18% Example 99 l-methyl-3-phenoxy-5-phenyl-4(111)-pyridone, m.p. 176-177°C., yield 19% Example 100 l-methyl-3-phenyl-5-phenylsulfonyl-4(IH)-pyridone, m.p. 218-220°C., yield 50%, made by oxidation of the cor25 responding phenyIthio compound with m-chloroperbenzoic acid The next example illustrates a process wherein the enaminoketone of formula X is first formylated to form a compound of formula VI and then exchanged with the amine to form the pyridone. -6242444 Example 10] An enaminoketone was formed from 3.5 g. of N,Ndiethylstyrylamine and 2.16 g. of methoxyacetyl chloride in the presence of 2 g. of triethylamine. The yield was about 5 g. of the desired enaminoketone, 1-diethylamino4-methoxy-2~phenyl-l-buten-3-one.
The above enaminoketone was mixed with 3.2 g. of sodium methoxide in 50 ml. of dry tetrahydrofuran at 0°C., and 4.4 g. of ethyl formate was added dropwise. After the mixture had stirred for three hours, 25 ml. of 40% aqueous methylamine was added, followed by 5 g. of methylamine hydrochloride. The mixture was stirred overnight at room temperature, and the solvents were removed under vacuum.
The residue was taken up in methylene chloride, washed with water and saturated sodium chloride solution and dried. The solvent was then removed under vacuum, and the residue was triturated with ethyl ether. The solids were recrystallized from isopropyl ether-methylene chloride to produce 1 g. of 3-methoxy-1-methy1-5-pheny1-4(IH)-pyridone, m.p. 153-155°C.
The following examples illustrate the preparation of 3-hydroxyphenyl-substituted compounds, from which other substituted compounds are prepared in the next examples following.
Example 102 A 1 g. portion of the product of Example 20 was dissolved in 250 ml. of acetic acid, and 1 g. of 5% palladium on carbon was added. The mixture was hydrogenated for about 45 minutes, filtered, and the filtrate was evaporated to dryness. The product was recrystallized from ethyl -634 3 411 acetate-hexane to produce 0.45 g. of 3-(3-hydroxyphenyl)~ 1-methy1-5-pheny1-4(IH)-pyridone, m.p. 223-225°C.
The same compound was also made by a cleavage with pyridine hydrochloride as follows.
A 2 g. portion of 3-(3-methoxyphenyl)-1-methyl5-pheny 1-4 (III)-pyridone Was mixed with 15 g. of pyridine hydrochloride and the mixture was heated at reflux temperature for about 1 hour. The mixture was then poured into a large amount of water, and the precipitated solids were separated by filtration. The solids were then recrystallized from ethanol-ethyl .ether to yield 1.1 g. of 3-(3hydroxyphenyl)-1-methy1-5-pheny1-4(IH)-pyridone. An additional 0.65 g. was recovered by concentration of the filtrate above. The product was identical to that of the above paragraph.
The following compound was made by a process similar to Example 102.
Example 103 > 3-cyclohexyl-5-(3-hydroxyphenyl)-l-methyl-4(IH)20 pyridone, m.p. 155-165°C., yield 13% Example 104 A 3.2 g. portion of the product of Example 102 was added to a suspension of 0.86 g. of sodium hydride in 50 ml. of dimethylsulfoxide. The mixture was stirred at room temperature, and 3.5 g. of ethyl iodide was added. The mixture was stirred for two and one-half hours more, poured into water, and the aqueous mixture was extracted with ethyl acetate. The extract was washed with dilute hydrochloric acid and then with water, and dried. The dried extract was then filtered and concentrated to dryness under vacuum. The -6442444 product was 2.2 g. of 3-(3-ethoxyphenyl)-1-methy1-5pheny 1-4 (1H) -pyridone, m.p. 133-135°C.
The exemplary compounds below were prepared according to methods similar to that of Example 104.
Example 105 3-(3-allyloxyphenyl)-1-methy1-5-pheny1-4(IH)pyridone, NMR peaks at 211 and 270 CPS; broad peaks at 296-328, 341-378 and 399-458 CPS; yield 10% Example 106 3-[3-(1-fluoro-2-iodovinyloxy)phenyl]-1-methyl5-pheny1-4(IH)-pyridone, NMR peaks at 218 CPS; a broad peak at 270-316 CPS; aromatic protons at 416-464 CPS; yield 67% Example 107 3-(3-isopropoxyphenyl)-1-methyl-5-phenyl-4(IH)pyridone, NMR peaks at 81, 209 and 276 CPS; aromatic protons at 401-468 CPS; yield 18% Example 108 3-(3-cyanomethoxyphenyl)-1-methyl-5-pheny1-4(IH)pyridone, NMR peaks at 207 and 275 CPS; aromatic protons at 396-456 CPS; yield 6% Example 109 3-(3-dodecyloxyphenyl)-l-methyl-5-phenyl-4(IH)pyridone, NMR peaks at 52, 207 and 234 CPS; a broad peak at 60-122 CPS; aromatic protons at 396-461 CPS; yield 26% Example 110 l-methyl-3-[3-(4-nitrophenoxy)phenyl]-5-phenyl4(IH)-pyridone, NMR peaks at 222 and 488.5 CPS; aromatic protons at 414-463 CPS; yield 14% -6542444 Example 111 l-methyl-3-(3-methylsulfonyloxyphenyl)-5-phenyl4(IH)-pyridone, NMR peaks at 185 and 213 CPS; aromatic protons at 422-472 CPS; yield 20% Example 112 1-methyl-3-phenyl-5-[3-(1,1,2,2- tetrafluoroethoxy) phenyl]-4 (1H)-pyridone, m.p. 119-121°C., yield 84%, made by using tetrafluoroethylene, in the presence of potassium hydroxide Example 113 3-(3-acetoxyphenyl)-1-methy1-5-pheny1-4(IH)— pyridone, NMR peaks at 134 and 210 CPS; aromatic protons at 415-466 CPS; yield 28%, made by using acetic anhydride Example 114 3-(3-hexyloxyphenyl)-1-methyl-5-phenyl-4(IH) -pyridone, NMR peaks at 53, 214 and 239 CPS; a broad peak at 60-120 CPS; aromatic protons at 402-465 CPS; yield 55% Example 115 3-(3-decyloxyphenyl)-1-methyl-5-phenyl-4(IH)20 pyridone, NMR peaks at 53, 211 and 239 CPS; a broad peak at 62-123 CPS; aromatic protons at 404-467 CPS; yield 24% Example 116 1-methyl-3-phenyl-5-(3-propoxyphenyl)-4(IH)pyridone, NMR peaks at 54, 101.5, 208 and 232 CPS; aromatic 25 protons at 400-463 CPS; yield 31% Example 117 l-methyl-3-phenyl-5-(3-propargyloxyphenyl)4(IH)-pyridone, NMR peaks at 150 and 215 CPS; a broad peak at 280-285 CPS; aromatic protons at 430-470 CPS; yield 6% -6642444 Example 118 3-(3-cyclohexylmethoxyphenyl)-l-methyl-5-phenyl4(IH)-pyridone, NMR peaks at 214 and 226 CPS; a broad peak at 35-124 CPS; aromatic protons at 402-466 CPS; yield 16% Example 119 l-methyl-3-(3-octyloxyphenyl)-5-phenyl-4(IH)pyridone, NMR peaks at 52, 218 and 239 CPS? a broad peak at 58-122 CPS; aromatic protons at 403-467 CPS; yield 19% l-methyl-3-(3-phenoxyphenyl)-5-phenyl-4(IH)pyridone, NMR peak at 214 CPS; aromatic protons at 410-470 CPS; yield 34% The following example demonstrates a synthesis starting with a ketone, wherein the starting compound is first formylated to form a compound of formula IX, then aminoformylated to form a compound of formula VI, and finally exchanged with an amine to form the pyridone.
Example 121 A 12 g. portion of sodium methoxide was suspended in 150 ml. of ethyl ether. The suspension was chilled in an ice bath, and 28g. of l-phenyl-3-(3-trifluoromethylphenyl)-2propanone was added. A 14 g. portion of ethyl formate was then added dropwise to the stirred mixture. While the reaction mixture was stirred constantly, it was allowed to warm slowly to room temperature overnight. In the morning, the mixture was extracted with water, and the water layer was made acid with dilute hydrochloric acid and was extracted with methylene chloride. The organic layer was then extracted with dilute aqueous sodium hydroxide, and the water layer was made acid with dilute hydrochloric acid and -6742 144 was then extracted with methylene chloride. The organic extract was dried, and was evaporated to dryness under vacuum to produce an oil which was predominantly 1-hydroxy2- pheny1-4-(3-trifluoromethylphenyl)-l-buten-3-one.
An 11 g. portion of the above intermediate product was heated on the steam bath with 20 ml. of dimethylformamide dimethyl acetal for 16 hours. The reaction mixture was then evaporated to dryness under vacuum, and the residue was taken up in 150 ml. of ethanol. Ten g. of methylamine hydrochloride and 20 ml. of 40% aqueous methylamine was added, and the mixture was stirred at reflux temperature overnight. The reaction mixture was then evaporated under vacuum to produce an oil. The oil was taken up in chloroform, and the solution was washed with water and dried over sodium sulfate. The solvent was then removed under vacuum, and the residue was triturated with ethyl ether. The ether was filtered to produce l-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m.p. 153-155°C, The next example below shows the synthesis of a pyridone, starting from a ketone, by successive aminoformylation to form a compound of formula X, formylation to form a compound of formula VI, and exchange with an amine.
Example 122 A 28 g. portion of 1-(3-trifluoromethylphenyl)3- phenyl-2-propanone was mixed with 12 g. of dimethylformamide dimethyl acetal, and heated on the steam bath under a trap which removed ethanol as it was formed. Heating was continued overnight, after which the reaction mixture was -6842444 evaporated to produce an oil which was primarily a mixture o£ l-dimethylumino-4-phenyl-2-(3-trifluoromethylphenyl) l-buten-3-one and l-dimethylamino-2-phenyl-4-(3-trifluoromethylphenyl ) -l-buten-3-one.
A 5 g. portion of the above intermediate was formylated with ethyl formate in the presence of sodium methoxide according to the process of Example 121. The product of the formylation was dissolved in ethanol, and treated with 5 g. of methylamine hydrochloride and 20 ml. of 40% aqueous methylamine. The mixture was stirred overnight at reflux temperature, after which the solvent was removed under vacuum, 100 ml. of water was added to the residue and the mixture was extracted with ethyl ether. The ether solution was dried over sodium sulfate and evaporated to dryness to give l-methyl-3-phenyl-5-(3-trifluoromethylphenyl)4(IH)-pyridone, m.p. 153-155°C.
The following example illustrates the synthesis of a 1-unsubstituted pyridone by reaction of a ketone with a tris(formylamino)methane. To obtain a compound of formula X, this product is alkylated.
Example 123 A 1.4 g. portion of l,3-diphenyl-2-propanone was mixed with 1.0 g. of tris(formylamino)methane in 20 ml. of dimethylformamide. The reaction mixture was stirred at reflux temperature for 3 hours. The mixture was then cooled to approximately room temperature, and poured into water.
The precipitated solids were separated by filtration, and the solids were suspended in chloroform. The chloroform was then filtered, and the solids remaining were washed first -6942414 with water, and then with chloroform. The yield was about 100 mg. of 3,5-dipheny1-4(1H)-pyridone, m.p. greater than 335°C.
The example next below shows the synthesis of a 5 pyridone of formula I by the formylation of a ketone to form a compound of formula IX, followed by exchange with an amine to form a compound of formula VII and aminoformylation. Example 124 The formylation of 1-pheny1-3-(3-trifluoro10 methylphenyl)-2-propanone was carried out according to the method of Example 121. A 5 g. portion of the product was dissolved in 50 ml. of ethanol, and. 20 ml. of 40% aqueous methylamine was added. The mixture was allowed to stand overnight at room temperature. The mixture was then evapo15 rated to dryness under vacuum, leaving a heavy viscous oil. The oil was mixed with 10 ml. of dimethylformamide dimethyl acetal, and was heated on the steam bath overnight under a trap which removed ethanol as it was formed. The next day, ' the reaction mixture was evaporated to dryness under vacuum, and the residue was triturated with ether. The ether solution was filtered, and the solids were recrystallized from acetone-ethyl ether to produce l-methyl-3-phenyl5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m.p. 153155°C.
The following example illustrates the synthesis of compounds of formula I by the 4-chlorination of a 1-unsubstituted pyridone, followed by 1-alkylation and hydrolysis.
Example 125 A 39 g. portion of&-phenyl-5-(3-trifluoro-7042444 methylphenyl)-4(IH)-pyridone, made by the method of Benary and Bitter, was refluxed with 100 ml. of POCl^ and 5 ml. of dimethylformamide for three hours. The excess POCl^ was then removed under vacuum, and the residue was taken up in chloroform. The solution was poured into ice-water and the mixture was stirred until the mixture reached room temperature. The aqueous mixture was then extracted with chloroform, and the organic solution was washed with dilute sodium hydroxide solution, and dried. The organic solution was then evaporated to dryness under vacuum, and the residue was recrystallized from hexane to produce 4-chloro-3-phenyl5-(3-trifluoromethylphenyl)pyridine.
A 2 g. portion of the above compound was dissolved in 20 ml. of chloroform, and 10 ml. of methyl iodide was added. The mixture was allowed to stand for four days. The mixture was then evaporated to dryness, and the residue was recrystallized from chloroform-hexane to produce pure 4chloro-3-phenyl-5-(3-trifluoromethylphenyl)-1-methylpyridinium iodide A portion of the above intermediate product was dissolved in methanol, and the solution was made basic with aqueous sodium hydroxide solution. The basic mixture was then heated at reflux for one hour, cooled, and the solids were separated by filtration. The product was l-methyl-3phenyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m.p. 153-155°C.
The following example illustrates the 1-alkylation of a 1-unsubstituted pyridone by reaction with a methylating agent. -7143 1 ii Example 126 Λ 8 g. portion of 3-phenyl_]-(3-trifluoromethylphenyl-4(III)-pyridone was suspended in 30 ml. of chloroform, and 6 g. of methyl trifluoromethanesulfonate was added. The reaction mixture was stirred for 3 hours, 10 g. more of the sulfonate was added, and the mixture was stirred overnight. In the morning, the reaction mixture was poured into aqueous sodium carbonate solution. The aqueous mixture was filtered, and the precipitate was washed with additional chloroform. The organic layer of the filtrate was separated, dried over magnesium sulfate and evaporated to dryness. The residue was an oily gum which was identified by NMR analysis as essentially pure 3-phenyl-5-(3-trifluoromethylphenyl) -l-methyl-4-methoxypyridinium trifluoromethane15 sulfonate.
The residue was mixed with 30 ml. of ethanol and 3 ml. of concentrated hydrochloric acid, and the mixture was stirred at reflux for 2 hours. The reaction mixture was then concentrated under vacuum to an oil, which was taken up in methylene chloride. The mixture was washed with aqueous sodium carbonate solution, and the organic layer was again evaporated to dryness under vacuum. The residue was triturated with ethyl acetate, leaving a precipitate, which was held and combined with the later-separated product. The ethyl acetate solution was concentrated under vacuum, the residue was mixed with 30 ml. of ethanol and 10 ml. of 10% sodium hydroxide solution, and the mixture was stirred at reflux temperature for 2 hours. The reaction mixture was then poured into water, the insoluble product was removed by filtration, and the solids were recrystallized from acetone. -72424 44 The product was l-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone, m.p. 152-156°C.
The following example illustrates the use of a formate ester aminal as an aminoformylating agent in the process.
Example 127 A 15 g. portion of 1-pheny1-3-(3-trifluoromethy1phenyl)-2-propanone was added to an ethyl ether solution, at ice bath temperature, of 70 g. of (t-butoxy)-di(dimethyl10 amino)methane. The mixture was wanned to evaporate the ether, and was then heated on the steam bath for 2 hours.
The volatiles were then evaporated under vacuum, and the residue combined with 15 g. of methylamine hydrochloride, 40 ml. of 40% aqueous methylamine and 200 ml. of ethanol. The reaction mixture was then heated on the steam bath for 6 hours, and evaporated to dryness. The residue was taken up in water, and extracted with methylene chloride. The organic layer was washed with water, dried, and chromatographed on a silica gel column with ethyl acetate:benzene.
Collection and evaporation of the product-containing fractions gave about 0.9 g. of l-methyl-3-phenyl-5~(3trifluoromethylphenyl)-4(IH)-pyridone, m.p. 152-156°C.
The next example shows the use of a formiminium halide for aminoformylating the starting propanone.
Example 128 The aminoformylating reagent was made by adding 30 y. of dimethylformamide dropwise to 20 g. of phosgene in 150 ml. of chloroform at 0°C. A 10 g. portion of 1,3-bis(3-ehlorophenyl)-2-propanone in 50 ml. of chloroform was -7342444 then added. The mixture was stirred for 3 hours, after which 50 ml. of 40% aqueous methylamine was added. Chloroform was then evaporated from the mixture, and 200 ml. of ethanol and 50 ml. of additional 40% aqueous methylamine were added. The mixture was then stirred under reflux overnight. In the morning, the product was extracted as described in the example above, and chromatographed on a silica gel column with ethyl acetate containing successively larger quantities of methanol. The product formed is 3,5-bis(3-chlorophenyl)-l-methyl-4(lH)-pyridone, 0.85 g., m.p. 164-167’C.
Continued elution of the column with methanol removed a compound identified by NMR as 4-chloro-3,5-bis(3chlorophenyl)-l-methylpyridinium chloride. Hydrolysis of the compound with aqueous ethanolic sodium hydroxide solution at reflux temperature yielded additional pyridone upon dilution with water, filtration, and recrystallization from acetone-ethyl ether.
The next example illustrates how 1-acetoxy compounds of formula I are prepared.
Example 129 A 2.4 g. portion of 3,5-diphenyl-l-hydroxy-4(1H)pyridone was made by the process of Example 29, using hydroxylamine as the aminating agent. The pyridone was added to 25 ml. of acetic anhydride and the mixture was heated on the steam bath for about 1 hour. The volatiles were then evaporated under vacuum, and the residue was washed with benzene and then recrystallized, first from benzene and then from chloroform-hexane. The yield was 2.1 g. of l-acetoxy-3,5-diphenyl-4(IH)-pyridone, m.p. 197-199°C. -7442444 The following typical salt compounds were prepared by making the free base compounds according to the general procedure of Example 29, and forming the salts by contact with the appropriate acids in aqueous solvents.
Example 130 1-methy1-3,5-diphenyl-4 (1H)-pyridone, hydriodide, m.p. 110°C., yield 100% Example 131 l-methyl-3,5-dipheny1-4(IH)-pyridone, hydro10 chloride, m.p. 187-194°C., yield 100% The example below is typical of the formation of pyridinethiones of formula I.
Example 132 Λ 10 g. portion of 3,5-diphenyl-l-methyl-4(IH)·· pyridone, prepared by the process of Example 1, was mixed with a 10 g. portion of P2S5 ml. pyridine, and the mixture was heated under reflux for 2 hours, after which it was poured into a large amount of water and stirred for one hour. The mixture was then filtered, and the solids were recrystallized from ethanol to yield 9.8 g. of 3,5-diphenyl-l-methyi-4(IH)-pyridinethione, m.p. 168-171°C.
The following typical pyridinethiones were prepared by following the general procedure of Example 132. Example 133 3,5-bis(3-chlorophenyl)-l-methyl-4(IH)-pyridinethione, m.p. 210-212°C., yield 86% Example 134 3-(3-chlorophenyl)-l-methyl-5-phenyl-4(III)pyridinethione, m.p. 190-193°C,, yield 71% -7542444 Example 135 1-methy1-3-pheny1-5-(3-trifluoromethylphenyl) · 4(IH)-pyridinethione, m.p. 210°C., yield 70% Example 136 The compounds of formula I prepared in Examples 1-23 can also be prepared by the process of Example 29. Example 137 The compounds of formula I prepared in Examples 24-122 can also be prepared by the process of Example 1.
The compounds of formula I described above have been tested in a number of herbicidal test systems to determine the range of their herbicidal efficacy. The outstanding results produced by the compounds in the representative tests reported below are exemplary of the lb outstanding activity of the compounds.
Compound application rates are expressed in kilograms of the compound per hectare of land (kg./ha.) throughout this specification and claims.
Blank spaces in the tables below indicate that the compound was not tested against the named species. In some instances, the results of testing a compound repeatedly against a plant species have been averaged.
Untreated control plants or plots were included in all tests. Ratings of the control produced by the compounds were made by comparison of the treated plants or plots with the controls.
In the tests of Examples 138-142, plants were rated on a 1-5 scale, on which 1 indicates normal plants and 5 indicates dead plants or no emergence. A 0-10 rating -7642444 scale, on which 0 indicates normal plants and 10 indicates dead plants or no emergence, was used in the tests of Examples 143-145 and 148-150, and the tests of Examples 146-147 and 152 were rated as percent control of the plants. Rating scales used in the tests of Example 151 are indicated in the description of the example.
Example 138 broad spectrum greenhouse test Square plastic pots were filled with a sterilized sandy loam soil and seeds of tomato, large crabgrass and pigweed were planted. Each pot was individually fertilized.
Test compounds were applied postemergence to some pots and preemergence to others. Postemergence applications of the compounds were sprayed over the emerged.plants about 12 days after the seeds were planted. Preemergence applications were sprayed on the soil the day after the seeds were planted.
Each test compound was dissolved in 1:1 acetone: ethanol at the rate of 2 g. per 100 ml. The solution also contained about 2 g. per 100 ml. of an anionic-nonionic surfactant blend. One ml. of the solution was diluted to 4 ml. with deionized water, and 1-1/2 ml. of the resulting solution was applied to each pot, resulting in an application rate of 16.8 kg./ha. of test compound.
After the compounds were applied, the pots were moved to the greenhouse, watered as necessary, and observed and rated about 10-13 days after application of the compounds. Untreated control plants were used as standards in every test. -774 24 4 4 The table below reports results of testing typical compounds of formula I. The compounds are identified by their example numbers above. -7842444 Ό a) Φ & CP •H d. fl Compound of _Pre erne r gene e___ Posfcemercrence Example Large ~-Larae— ω U) ) (0 h M ι tr I Λ I IQ M U *0 a) G) •rl A CO (0 fl > M Λ fl υ in fl fl m in fl 04 OJ OJ in in in in in Γ0 w Μ Φ β O' fi fi Cn ββ β β fi Φ ϋ α φ Οι fi Φ ε φ φ ρ fa ra ra φ β Cn fi fi tr β β β β fi ri Ο Φ Ό Η G ft · fi ε ο Ο β ζ ft * ε w ο ο inminminminin ΓΟ ri in tn in ιη -8042444 Compound of _Preemergence_ _Postemergence Example Large Large a w (ϋ CP X) nJ M U Φ ο & »W A m io <ΰ tt M <*) ΓΩ rH m in in rn ι—j cj* •H rf m m cn m «Η xf xj» CN Xf xf CN m CN rf rH rf xf rf rf rf in rH in xf *f rH *f rf rH CN rf PH in rH in ID m oo rH CN cn in in io r- co σ» in in in in tn rH IO 81424 14 *o φ φ s tP Φ υι ο ω £ Φ ΐϋ Φ ο* to tn to οι Μ ra A Φ A ra £ to Φ U fi G φ O φ U I-1 Ή 04 Φ fi A U) ra Φ W Eh 0 φ ra G Cn to Φ to Cn On ra a to a ra Φ to £ υ Φ Φ to A 0 fi ra £ O U-7 ο φ Ό Η G CU · G £ Ο ο ra 53 £ Μ Ο U ι—Ι fO η to Φ a c ω tr u a) ε φ +> (A & (A (A Φ Φ tr k M Cn fi XI XI fi M U Table 1 Continued φ ss Pigweed ϋ Φ fi c Cn M Φ m tr tr fi rQ M XI fi a) u i O φ H Λ 0 +> fi e 0 Φ Ό H « a · 3 Ε O 0 fi 23 ChM ε ra o a *a* m ro CM CM CM CM TT in in in m cm rf H co iH cn r~i CM co CM CM 1*1 o o r-4 τ—I -834 2 14 4 Example 139 seven-species greenhouse test The test was conducted in general like the test described in Example 138. In this test, the seeds were 5 planted in flat metal trays, rather than in pots. The com pounds were formulated according to the procedure above, except that about 6 g./ΙΟΟ ml. of the compound was dissolved in the surfactant-containing solvent, and about 1 part of the organic solution was diluted with 12 parts of water before application to the trays. 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ro -8742444 Preemergen.ce Postemergence eruurz Αχοχβ -Butujoh Xjeqxoj peowbrg sseufiqBJO efijeq uroo OJ Ol cn oj oi m oj cn cn cn cn cn oi oi oi cn oi cn cn fl cn fl oi cn Ol ’T OJ r-l cn rd cn cn cn oi cn oi fl oi cn cn m cn cn cn fl fl m oi fl fl fl fl eTUUTZ Λιοχβ -burujow ΧΒΘΉΘΛΧΟΛ Xregxoa peaMfija ssejfiqeao oBxeg uroo IM o 0 S Ό C Φ 3 H ο a Pi β ο κ u w in sf in in in m in in in in in m m cn in in m in in m in in in in in in in in in fl m m m m in in in in in m A m cn «-4 fl κ in oi in oi m oi in oi fl H in in in in m m in in in in in tn in tn cn ο H i-4 r—I oi cn <—I i-4 Preernergence Postemergence BTUUTZ CM CM fi CM CM fi CM CM CM CM Λ joi 5 -Butujow CM CM fi CM CM fi CM CM CM CM 3Βθχ}θΛΐθΛ fi CM fi CM CM fi co CM CM CM lyegxod CM CM fi CM CM fi co CM CM CM pSOMfiTJ CM CM fi CM CM fi CM CM CM CM ssBjfiqeJo CM CM fi CM CM fi -cf CM CO CM afijeg ujoo m CM ι—1 CM CM fi CO CM CO CO BTUUTZ in in CM in CO fi XT fi co in Λ joi 5 -Butujow tn in fi sr xr fi XC fi xf in jBsigsAiSA tn m CM in in r—1 in CM xp in IfBqxoj in in CM in in fi in CM xp in psaMfiTd m in ΓΟ tn in fi in CM XT in ssEJbqEJO in tn fi in in fi in •«a* in in ebjeg UJO3 xT ro CM fi fi fi in CM co in M4 . 0 0 τ,3 G QJ G fi in CO fi tO r-« CO cn o 0 0 fi fi CM in in in in in in to £ 3 0 X o w Preemergence Postemergence eruujz rH CN CN CN CN CN CN CN cn Αιοχβ CN cn m CN CN CN CN CN CN cn -fiururow χΒθχχθΛχοΛ rH en m CN CN CN CN cn en ITE4XOJ CN cn m CN CN cn CN CN cn cn ρθθΜβτ<3 rH en cn CN CN CN CN CN cn ssejfiqBJO sfiaeg rH en cn CN CN Sf CN CN cn cn UJOQ rH en sf CN CN cn CN CN cn cn BTUUTZ Αιοχβ iH CN CN sr sr CN CN in in in -fiUTUIOK rH CN cn sr sr cn CN sr sr Sf ΧΒΘΤΧΟΛ-[8Λ rH cn Sf tn cn CN in in m XTB4XOJ rH sr sr in m in CN sr in in ρθθΜβχΗ rH en sf in in cn CN tn in in ssBifiqBJO rH in sr in in in CN in in in θβπεχ UJOO rH rH cn sf sr cn rH CN in in UH o 'ϋ c 0) α κ o a 0*8 O X Q W rH O rH id m m rH rH m m rH sr in cn cn m \n rH rH sf ΙΛ VD ID VD kO Preemergence Postemergence btuutz Π rd cn CM CM CM CM cn cn Ααοτβ -Butujow cn CM m CM CM m CM cn m jeoigeATSA cn CM m CM CM CM CM cn CM Xfegxoa m rd cn CM CM cn CM n m ρθθΜβτ^ cn CM sp CM CM CM sp *4* cn ssBjfiqcjo efiUBq sp rd sr CM CM cn cn sr cn UJO3 sp CM sp CM CM cn CM cn sp CM CM rd CM CM CM CM ETUUTZ Ζαοχβ -Butujow jeaWATSA ρθθΛβτ^ sstubqvao θβ-χυτ: UJtOQ m 0 O z v c φ rd Ο Λ α ε ε fi ο x υ ω in h in h in h in rd in rd m h in h m m in cm in in in sp in sp m in in cn cm in m in cn in cm m cn in cn in cm in cn in sp in cn in cn in in in sp in h in m sp in sp in in m in in in m in in cn co ιθ ιο Γ'' -9142 4 44 φ o c φ cr M Φ ε φ -P ω Ο Λ Table 2 Continued Φ ϋ « φ bi Μ φ ε φ φ Μ CU BTUUTZ ro CJ CI cn cn rH rH Cl rH CI Αιοχβ -fiUTUJOW ro CJ Cl cn cn r—I rH Cl rH ΓΟ jeanaftTSA ro CI Cl cn tn rH rH CI rH CJ χ-EBqxoj tp CJ ro cn <·# ι—1 rH CJ rH Cl paaMfija ro Cl co cn en rH rH Cl rH Cl ssBJbqEao a&aei Tp CJ tp τρ tp rH rH CI rH CI UUO3 tp CJ Cl Tp ro rH r-1 CI rH Cl btuutz in r—1 in in m rH H Cl Cl in Λαοχβ -fiuxuxow in co τρ in in rH rH rH Cl in 5ΒΘΧ4ΘΛΧΘΛ in Tp to in in CI rH Cl Cl in XXB4XOJ in CO in m m CJ rH Cl Cl in paaMbXd in tn m in in cl rH ro ro m SSEjbqBJX) abauq in in in tn m co H Tp cn in ujoo in ci ro in in rH rH Cl rH Tp <Η · Ο ο ζ Ό ΰ φ rH ο & %% ο κ υ w σ» Ο Η P- CO 00 cj' τρ in M3 00 co 00 ΓΟΟ οο σι co co -9242444 Preemergen.ee Postemergence BTUUJZ ri CM CM ri OJ ri CM CM ri ro CM Ααοχβ -fiuyurow ri CM CM ri CM ri Ol CM ri ro CO χΒοχχθΛχθΛ ri OJ Ol ri OJ ri CM Ol ri ro OJ XXBqxoj ri co ro ri CM ri CM CM ri ro CM peertfira ri ro Ol ri CM ri CM CM ri ro CM ssejBqeaa efireq ri ro 04 ri CM ri 04 OJ ri ro OJ uroo ri ro CM ri CM ri OJ CM ri ro CO BTUUTZ Λ-ίοχβ ri in in ri OJ ri CM ri ri ri in -fiUTUJOH ri in in ri ri ri CM CM ri ri in geexqeAXSA ri m ri Ol in ri CO ri ri in in χτηχχο,χ ri m in CM ri CM CM co ri in in pesMfixd ri in m ri in CM CM m ri ri in ssBrfiqera afizeq ri tn in CM in ri ri in ri in in ujoa >H · 0 0 J3 r) C 0) ri ro ri CM ro CM ro CM ri ri in 3 r-l O ID r- cn o ri ro CM ro ri m 0 ft ft ε 0 X σι ri ri ri OJ CJ CM o ri o ri O ri o ri -9343444 Preemergence Postemergence eyuuyz ro co CM CM CM CM CM rri CM CM CM ΛαοχΒ -Buyujow co ri CM CM CM CM CM iri CM CM CO jeaygaAyan co co CM rri CM CM ro rri CM CM CM Xyeqxoj co co CM CM CM CM to rri CM CM CO paaMBya CM co ro CO Γ0 CM ro CM CO CO CM sserBqero aBaeq CM ri CO CM CM CM ri CM rO CM CM ujcoa to ri CO CM CM CM ri CM CM CM CO eyuuyz CO in ri rri CM CM in ri rri CM ri AroyB -Buyurow ri m ro rri CM co in CM rri CM to jeeygeAyeA ri m m rri ri ri in CM CM rri in Xtegxoj ri in ri rri co ri in CM CO rri ri paaw&ya in tn ri ri ri in in CM in CO in ssErBqeao afijeq in in in iri ri ri in CO UO CM in uroo CO m ri iri CM in uo rri rri iri ri M-I 0 '0 ffl *ϋ c w fi tri o 04 £§ 0 X υ w VO I*» 05 OOO tri i—| rri VO iri »—I ri rri rri -9442444 Example 140 multiple-species greenhouse test In general, the test method was the same as the method of the test above. Various compounds of formula I 5 were tested preemergence and postemergence at different application rates which are indicated in the tables below. A number of additional weed and crop species were used in the preemergence tests as is shown in the table. Typical results were as follows. -9543414 Preemergence BTUUTZ AaoxbfiuTUJOW paaMuosurrp ΧΒΘΧ^ΘΔΧΘΛ XBO PXXM XXB4XOJ pee/iBra pjBgsnw ssBjfiqBXO aBqsq aeqjBnbsqureq SSBJ9 PjbAujbs OqBUIOJ, aaqumono soya qaaa JBfins BJXBjxv qeaqM UBaqAog uoqqoj ujoo m · · OCO Γ-4 JO oi a\ +J Qj nJ < O’ κ JC MH · O O & . C (!) □ rH 0 iX ε «ί O X u w CN CN rH CN «Η CN xf rH CN rH CN CN CN CN rH cn in CN CN rH CN cn CN cn rH co Xf CN CO CN cn xf CO cn CN CN co CN co rH xf Xf cn Xf cn xf xf CN in CN CN CN CN CO rH CN cn CN Xf rH CN rH CN rH CN rH rH CN rH xf cn CN xf rH Xf xf CN co rH CN CN rH CO CN CN CO rH xf «Η rH rH rH H rH CN CN rH xf •H KO •H in CN CM rH O CN CN xf rH cn m CN cn CN CN CN cn rH CN rH CN in CO CN CN CN Xf CN CN CN CN in CN CN rH CN xf CO Xf cn tn xf cn CN in in CN CN CN cn m xf xf CN Xf in Xf xf cn xf in cn Xf rH cn xf co cn CN co Xf CN CN CN CN xf CN CN rH r-H CN cn Xf cn CN in CN co CN CN CN CN cn CN CN cn rH cn CN CN xf rH rH rH H rH CN cn •H CN xf CN rH «—{ rH CN rH CN rH rH rH CN H xf io r- co co cn cn cn O rH rH Xf Xf 964244 Table 3 Continued ω ο fi φ tr Μ φ β φ Φ Μ Αι DTUUTZ Ol fl in Ol co co Ol 01 fl Aaoxbbufujow co in in Ol OJ fl co Ol fl pasMUosurrp Ol in fl OJ Ol fl Ol co fl ΙΒΘΧ^ΘΛΧΘΛ fl in m co rd Ol fl Ol fl geo ΡΧΤΜ Ol α in Ol Ol CO Ol OJ fl XTBqxoj CO co in fl co in fl fl fl paertBya co in in co fl in fl in pjB^snw Ol fl in co OJ co co in in sseafiqBJO m in in m fl in fl fl in ab^Bq jaqjBnbsqureq fl in in fl fl in in fl fl fl tn in co co in co fl fl pjBAujtBg oq.puioj; OJ in in Ol Ol fl Ol co fl aaqumono co in in Ol i-4 ι—1 Ol r-l fl aoTH OJ CO co i—l r—4 OJ H H Ol qaag JBfins fl in in co Ol in in CO fl ejXBjxv Ol in in OJ CO fl co CO fl qeaqM CO CO fl co Ol co co co fl UBaqZog CO fl fl H r-4 Ol co r-l co uoqqoo p-4 OJ 01 r-l r-4 1—1 r-l r—1 r-l ujoo fl fl fl Ol Ol co CO Ol fl IW . . 0 fi Φ κ x: Φ Ch\ +j p, . Ol r4 r4 .56 .14 fl I—1 Ol fl H ι—1 Ol H ι—1 o o o Ol O « ΛίΙ in · 0 0 V* fi Φ □ H co r- CO σι o ι—1 Ol Ol Ol 0 CL fl fl fl fl in in in £§ 0 X Preemergence βτιηχτζ fi XP CM CM in χρ CM CM CM in Aroibburujow fi in fi CM xP xp fi CM Xp in psoAtiosurrr fi fi CM CM XP co fi co CM in ΙΒ9τ^θΛΐ«Λ fi tn CM CM m tn CM fi CM in 4B0 puM fi CM CM CM xp in CM fi CM m Xxeqxoj fi xp fi XP in xP xp fi fi in ρθθΜβτ^ fi xp in XP tn xP xp xp fi in pjpisnw fi tn co in in fi fi fi CM in ssejbqEij fi in in in in in xp in fi tn ebjBg jeqjBti&squiB'i fi xp xp *5* XP in XP xp fi in ss-eao fi XP fi fi in in xp Xp fi in PjbAujbh ogBUioi fi fi CM fi in in fi fi CM m asquinono fi CM fi CM xp in CM CM CM in eopa fi CM fi fi CM CM CM CM fi CO qeeg jBbns r—1 XP CM fi in in xp CM xp in Bgxegiv fi CO CM CM in in fi CM fi in heeqM fi fi fi fi XP co CM fi ro in treeqXog fi CM fi CM xp Xp CM CM co xp uoggoo fi fi fi fi CM fi fi fi fi fi ujoo fi fi fi CM xp xp fi fi CM in tw . . o g ra fi A 00 XP in co io CO © xp fi CM fi © fi in CM in fi +j a . ra < oi tss λ; m · 0 0 2 *Ό fi © © © fi o O o © fi G G r-l 0 a fi xp in © c* co at © CM fi CM fi &ε e ra 0 X -98424 4 1 Table 3 Continued U1 cu btuitcz ro in Ci rd CJ rd Cl rd CJ Cl Cl ZaoxBbUTUXOW ro sp CJ rd CJ Ci Cl rd sp Cl CJ ροοΑίιοΞίπτρ co sp SP CJ CJ Cl co rd CO rd Cl geoxqoATOA CJ sp CJ CJ ro sp co CO sr co CJ 4B0 ΡΠΜ CJ sp CJ rd Cl rd Cl CJ Cl CJ CJ TtBqxog sf in sp CO sp SP sp co sp cn Sp paeMBfa sp sp sP CJ sp sp in CO SP cn sp pjegsriK sj· in sp CO in CO co Cl sp Cl co sseuBqeuo sp in in co in in in sp in co Sp ebxeq usqjenbsqurcq CO in sp co sp SP in SP sp sp co SSBX3 ro uo CO ro Sp CJ in CJ sp rd co pjeZuuEg ro in CO ro Cl CJ sp rd «Ρ rd CJ ogBuioj, joqumono CJ in Cl rd CJ rd Cl rd d CJ Cl ΘΟΤΗ rd in rd rd rd rd rd rd Cl rd rd qasg JEbng SP SP SP ro SP sp sp rd sp CO *P BJTBJIV m in CJ CJ CO sp CJ rd CO m cn qBOtjM ΓΟ in ci CJ Cl CJ CO CJ CJ Cl co UBsqZog CM in Cl rd Cl rd Cl rd cn Cl Cl uoqqoo rd sp rd rd rd rd rd rd CJ rd rd uuoo CJ CJ CJ rd Cl rd CO CJ cn rd Cl Ψ) · . o fi <« Κ Λ uo co 00 rd CO Γ· sp co VO © o a\ o O CJ o CJ rd CJ Cl in in +j a · • • • • • • • • • • ro ri fr o sp © O o CJ O Cl © © © « «1 O 0 z Ό fi ro fi H co ro SP m co sp c* Ch o © rd o a a ε H rd rd rd in in in in 10 cn rd CO rd Com Exa -9942444 Table 3 Continued 0) o fi φ tr fi1 ω e d> Φ fi fa BTUUTZ ΖαοχββιιτιιιΟΗ pesrtuosuirp 4*0 PTTM Xyeqxoa ρθθΜβτ<ι pzeqsnw ssexBqMO efirreq aaqjpnbsqureq ssejx) ρπυΑΐίαυπ oqeuioj, jraqumono ΘΟΤΗ qsag jrefins *?T*JTV qeeqM ucsqAos uoqqoa ujoo im · · O fi β ri β 1 m · o 0 Z Ό fi Φ fi ri 0 ft ft f= ε β ο χ u w CM ‘ CM CM CM CM ri CM in CM ri t—l CM CM CM Γ0 CM ri co ri CM ri r4 CM CM CM CM CM ri ro ri CM ro CM ro CM CM CM CM CM ro in ri ri rM CM CM CM CM CM ri co co ri ri CM ro in ri CM ri in ri in ro ri ι—1 in CM in ro ri CM CM in ri ri CM m CO ro ro ro ri ri in CM ri CM ri in ri ri tn in tn in CM in r-l ro ri ri ro ro ri co in CM ri ri ro CM ri CM co in ri in ri ri r-1 CM CM CM CM CM ri rO ri ri ri r-l ri ri CM ro CM in co ri ri ri CM r—1 ri ri ri ri CM CM CM CM CM r—I ro ri ri ro ro in ri in ro CM CM ro ro CM ro ro m in in ri ro CM CM CM CM ro ro ri ri in CM ri CM ri CM CM ro ro ri co ri CM ri CM ri ri ri ri ι—1 ri ri r—f ri «—1 ri ri CM ri CM ro CM in CM to H ri \o ri in o o CM CM O CM r* ri o ri o o O' O ri O ri ri in ri ri o ro ri in ro ro ro ri ri ri ri kD in kO ko r- σι o kD kD kD Γ-* ri Γ* in r-1004244 Table 3 Continued BTUUfZ Γ0 CN in rH CN CN in ro CN CN rH AjoiBBuTuaow fN CN in rH CN CN in co Xf CN CN paaMuosurrp ro CN in CN CN Xf in co CN CN CN 5βθΧ^θλχθλ CN CN m CN ro ro in ro CN CN CN 4E0 PXTM CN CN in rH rH *f m CN rH CN CN XtBqxoj CO xf en CO Xf Xf in Xf CO xf ro pasMBya CN CO in CO in Xf in Xf CO Xf in pjeqsnw CN in in ro in in in co CN ro co ssejfiqejQ ΟβίΒΊ in in in xf in in in in xf Xf co jaqjBnbsquiB'i xf co in xf Xf xf in Xf xf Xf xf ssbj£) pjEAttiBg H xf in CN xf CO in Xf co xf co oqpuioj, rH CN in rH CN Xf in co CN CN CN jequmono CN CN xf rH rH co in Xf CN CN CN BOTH rH CN co rH rH CN in rH rH CN r-H qeea oibBus CN rH in CN Xf in xf Xf CO Xf xf ejtejTV CN CN m CN Xf co in xf CN CN Xf qBaqji CN CO in rH Xf ro m CO CN rH H UBaqAog CN rH Xf rH CN CN xf ro CN CN CN uoqqoo rH rH rH H rH CN CN i-l rH rH rH UJO0 rH CN xf rH CN Xf in CO rH rH rH UH · · β d Η X3 φ «Ρ Ol · d < Cn X AT oo rH O O rH rH rH rH Xf rH © rH «—} (N in © H rH in o UH -d! β Pr rH CN xf rrH © CN -10142444 Table 3 Continued φ u fi φ tr fi Φ ε φ φ μ ffl BtUUyZ co CM co CM in CM CM in CM CM AjoyBBuyuaow CM CM ri ri in CM CM ri CM •—I pseMuosuiyp CM CM ri ri m CM CO ri rH CO jeayganyaA CM CM ri ri in CM CM ri CM CM geo pyyM iri iri CM CM in CM CM ri ι—1 CM yyegxoa CO ri in ri in CM CO in CO in paaMBya in CO in in in ri ri in in ri pjeysuK co CO in ri in ri ri in in ri ssegfiqejo aBjEq ri CO in in in ri ri in m ri gagxEnbsquiEq ri CO in in in ri ri in ri co SSEJD pjeAujeg CM ri in O' in CM CM ri CO co ognuioj; CM CM in CM in CM co in H CM jaqumonQ iri iri CO CM in l—l CM in CM CM aoya rri rri rri CM ro ι—1 ifi co ι—1 r-4 geaa JBfing CO ri in ri m CM ri in CO in ejyesxv CM ri in ri in CM ri in ri ri geaqM iri ri m CM ri CM CM ri CM ri uaaqAog iri - CO co CM ri rH CM ri r—1 CM uoggoo iri «ri iri rri CM »—1 l-1 r—1 «—1 r-1 ujod iri rri (O CM ri r-1 CM ri r-1 CM M · * σ c ra H ft Φ ffl\ ft ffl nJ < tr ffl ffl1 ri «ri VO m ri «ri V* -fi Φ fi «ri O ffl ffl ε1 b! u w m vo r* ooo rri «—I «—I rri CM rri iri «ri «ri 116 -10242444 Μ Ο rH tt σ β •Η δ. § rodrororoddrororo co ci co CJ ro d ci ro rodrororoddrororo (A to rt rt Cn P M tr rt Λ >4 rt μ υ d ro d to d d τρ d ci d G M O ol ddrodddfororod Mh · · Ο β rt rH fi Φ CU\ Ρ Λ · rt rfj Cn ex fi m · O 0 z •rt β rt β rH a §·§ O X o w rH d ro co tp to oo ο rH ro co to τρ τρ ro τρ m vo r*· tP *4» τρ tP -10342444 tr cn G -H G M a.
•H rt -P Ό rt X Q> o 0 β G ft G ω •H IT 4J Jh G rt O ε rt O rt rt TP -μ to s o Ή rt ft ft rH fi rt e< to co cj cj cj ro co d cn ro cn ro dddddrororoco to rt rt Cn k M tn . rt Λ hl rt M O G M O ol MH · · O G rt ·—I Λ Φ ft\ P ft rt < tn ft fi rH rH rH rH rH rH m · o o z τι G rt G rH Ο ft ft £ O X o w σι > d Γ* O rH rH rH 10442444 Example 141 yellow nutsedge test Typical compounds of formula I were evaluated in the greenhouse against yellow nutsedge in a test method which followed in general the method of Example 138, except that the acetone-ethanol solution contained about 1.5 g./lOO ml. of the test compound, and one part of the organic solution was diluted with 9 parts of water before application. Both preemergence and postemergence tests of the compounds were made, at the rate of 9.0 kg./ha. The results of testing these typical compounds are presented in the table below. -105Table 5 Compound of Example Preemergence No. 9 kg./ha. 2 2 1 1 1 ’ 3 4 1 1 4 3 3 129 1 1 ' 5 3 3 4 Postemergence 9 kg./ha. -10643444 Table !> Continued Compound of Example No. 132 Preemergence Postemergence 9 kg./ha. 9 kg./ha. -10742444 Table Continued Compound of Example No. 130 131 133 134 135 Preemergence Postemergence 9 kg./ha. 9 kg./ha. -10843444 Table 5 Continued Compound of Example No. 102 103 105 106 107 109 110 111 112 113 114 116 Preemergence 9 kg./ha.
Postemergence 9 kg./ha. 10942444 Example 142 broadleaf weed test A number of typical compounds of formula I were tested in the greenhouse against broadleaf weeds which are representative of families of weeds which exhibit resistance to many known herbicides. The test method was generally the same as the method of Example 141, except that only preemergence applications of the compounds were made. All compounds were tested at 9.0 kg./ha.
Table 6 Compound of Example No. Garden Huckle- berry Sickle- pod Common Ragweed Prickly Sida Black Night shade 24 3 2 4 25 4 3 5 26 2 2 3 27 2 1 2 29 2 2 2 . 30 3 3 4 31 5 5 5 32 2 5 4 33 2 3 2 34 5 5 5 35 5 3 4 36 5 2 4 129 1 1 1 .37 5 4 5 38 5 5 5 -11048444 Table 6 Continued Compound of Example NO. Garden Huckle- berry Sickle- pod Common Ragweed Prickly Sida Black Night shade 39 3 2 3 41 5 5 5 1 5 5 5 43 5 5 5 10 44 3 3 4 45 5 4 5 46 5 4 5 47 5 5 5 48 5 5 5 15 49 4 3 4 50 4 3 3 51 5 5 5 52 3 4 5 132 3 3 3 20 2 5 4 4 4 5 2 4 5 5 5 4 6 5 5 5 7 5 5 5 25 8 5 5 5 9 5 5 5 10 5 5 5 11 4 3 4 14 5 5 5 30 15 5 3 3 28 3 1 2 -11142444 Table £ Continued Compound of Example No. Garden Huckle- berry Sickle- E°d Common Ragweed Prickly Sida Black Night shade 53 5 4 4 54 5 2 3 55 1 1 1 56 1 1 1 10 57 5 5 •5 58 3 2 5 60 5 5 5 61 1 1 1 130 5 5 5 15 131 5 5 5 133 4 2 3 134 5 2 4 135 5 5 5 63 3 3 3 20 64 5 4 3 65 5 5 5 66 5 5 5 68 2 1 2 69 5 5 5 25 70 3 1 1 74 5 5 5 75 4 3 4 78 4 2 4 SO 2 2 3 30 81 4 4 4 -11243444 Table £ Continued Compound of Example No. Garden Huckle- berry Sickle- pod Common Ragweed Prickly Sida 85 2 1 2 87 2 2 5 89 5 5 5 90 2 2 2 17 5 5 5 18 2 2 2 19 1 1 1 20 5 3 3 21 2 2 2 23 5 2 5 102 3 1 2 103 1 1 1 105 5 5 5 106 5 3 5 107 5 5 5 109 2 1 2 110 3 2 2 111 5 5 5 112 i 5 5 5 113 1 4 114 1 3 116 5 5 5.
Black Night shade -113' Example 143 soil-incorporated fourteen-species test This test -was performed to evaluate typical compounds of formula I against a number of crop and weed 5 species. The compounds were tested in the greenhouse at various rates as indicated in the table below. In all cases, the compounds were applied preemergence to the test plants and were incorporated in the soil before the seeds were planted. ; In general, the formulation of the compounds and planting and observation of the test plants proceeded according to the method of Example 141, except that the compounds were dissolved in acetone-ethanol at 1 g./ΙΟΟ ml. concentration before dilution with water for application. -114γΊ Table paaMtiosurtp aaqumona paaMfiya uoqqoo epyg Zyjjayja tteaqAog Ajroyfi -bujUJtow qeaqM SSBJD pjBAujEg aoya 4B0 PITM uinqfijos UTBJ9 ιθτπκ χ-TBqxoa UJO3 £ rH Ρ Ή PJ B)O& pi «Γ M-) · 0 o •o* G a) 3 «η O ft ft & ε *3 o « υ ω in r· tp o rH in CO o rH o TP o rH Γ0 σι d © © ro 00 o o o σι Γ0 in H rH σι © 00 © © o © o © © Tp © rH rH rH «Η rH o o O o o O o © Ο o © m rH O kD kD O o rH kD Tp Tp rH rH σι σι d © in o © rH d Γ- in d rH • r—1 rH • 00 σι 00 d σι in o in rH Γ0 © d • • rH • σ» 00 σι Ο 00 O o © o di in © σι Ol rH rH rH rH rH » rH σι Ο Γ O O © O © in O σι © rH ι—1 rH rH rH Ch rH 00 M3 in kD 00 o TP in in rH © « • » rH » • cn co σι σι © ο 00 o O o © Ch m o Γ σι rH rH rH rH rH « rH σι Ο kD in σι in © Γ- r· in Γ» © rH • • rH • Ch ch σι in in σι σ* tn © in m m m m • • rH • • σ\ σι σι σι ο co © σι © O »' in o ω r- rH rH rH rH • rH • © σι CO Tp TP 00 Tp 00 ID kD © Tp d rH rH d H d m in d rH rd O o O ο © o © o © rH O Tp Γ rH ro Γ- co σι © H d d CO co Tp Tp Tp Tp in in in 24 44 115 Table 7 Continued peeMUOsuixp asqumono UO44O3 EpTS ueaqAos ΛαοχΒ -buruaow 4*9ψ4 ssb^d pjeAujeg θοέη 4*0 PXTtt umqB^os utpjo 4θτττκ χττ24χο*3 UJOJ fi φ H ffl < P- O CM CO in O © © © in «—I rd rd rd CM o o σ σι vo O in O o in rd • rd rd ch CO r- CO cn © vo P~ 00 in O in • rd ch σ o O σ o © o o © © CM o O 00 o rd o o o O o rd rd rd rd in o © VO in CM © in in in o rd • ♦ • Ch 00 cn in o CO ri m CM © in o O o • • rd rd ch 00 σι m © σ» r- in O © p- rd « rd rd Ch vo O 00 Ch CO in in © © r* rd • rd rd co r·' o o ri co P- CM m m O CM • • rd σ\ σι σ» in © in o in vo o © o r- rd rd « rd rd rd σι σι co in P« VO co in in m © ri • • • rd σι σι ch co co © ρ- VO vo CO tn m © in rd • • rd Ch 00 © in O tn σ» ch VO © o O vo rd • rd rd rd Ch co co ri ri ri 00 00 ri ri CO vo CM CM rd rd rd CM CM rd rd CM tn o O O O o © o O © O o M-I · O 0 z fi -11642444 Table 7 Continued peewuosuncp aequmono pBBMfipa uoqqoo epys ApiOTJa ueeqXog Λαοχβ -Butuqoti qeeqM ssbud pjEAuqeg both 4eo PTTM umqfiqos utBjg τθτττΜ XTBqxoa uqoo β (1) rH PUH a d 0 ft « < M-l · O 0 £ Ό β Φ ft H O a £§ O X o w r-oocorNrHcororoco© H H XfOrH COfOfOOOOOO rH rH I-l cnofNinmcNtOCsmoo rH · · ch ov OOOO iHOOOOO rOOOKOOCM©CNO© Η · · · Ch © Oi chocNinoxrr*ooKomo rH · * rH OOinrHOrHrHinfOCNlDCh Ch Ch O © σιοκοοοχτιηιηιηοιη rH rH · rH · ch CO 00 ID CO CN CN in CN KO CO KO Xf *f xf LT) CN m *H rH rH' OOOOrHOOOOOO m r» cn o o rH ro Xf m in KO in in in KO ro ro ro ro ro KO KO rH rH rH rH rH -117· Table 7 Continued paaMuosuitp o o rd I—l asqumona O o H H paaM&td O CM uopqoo O o upts Axjptja σ» co ueeqAog o o -butujOH qeaijM SSBJ3 pjeZuiEa aoty TUO PTTM umqfiaos UTBJ9 73T1TW TTB4XO3 ujoo G Φ H 4J Ή P <0 0 ft ei 5? Ό C Φ fi H 0 Ql ar S β 0 X o w οσιιηιηονΟ'ΤιΗΗΗ ooooooooooo ososmosocnoinkotn o intMooooom i—! · r—1 r-1 oomofooomcor·'© β ι—I i—l i—l σΐοοοσιοοο οσοοΜΟ OOOOCMOOCMOOO ooroomoocnrifo r—I r—I r-l r—J OOrOOI/JOOlDCMr-lO I—I I—I r4 ι—I riricorivorioori r-VrHCMHinHCMrq OOOOOOOOH r*riio r*oocj%ochkDr· koc-r-r'r-r-cocoHH -11842444 Table Ί Continued paewiosurtp uaqumono peewBxd uoqgoo BPTS Axxoxud ueaqAog AjtoiB -Buxtiuow qEsqM SSBJ9 pjpAtticg aoxg 4B0 PUM uinqBuog UTEJt9 ΊθΉΤΗ XTEqxod uuo3 ro H +i »4 a « 0 % Cl 00 © © © © © rd rd o 00 © © o O © rd rd rd © r* Sp 00 © O O rd rd © o © © Cl O © O r- r- r« in © in • rd © O o © sp © 00 r* rd © 00 © sp o © Cl rd t r* o © © © © © rd rd rd rd rd c- © © © © ro in rd rd • • © © sp Ch C' ro © in ro © © O 00 © o o ro rd rd r4 Cl in 00 in in in ro • • « • © 00 © © co © © © © in ro © iD in m © © © © • • rd rd © ro © 00 00 00 00 ro 00 in Cl Cl Cl Cl Cl CI o © o o o o o m · o o z Ό C CJ Ο Ο Ο Ο H rd rd rd r-d rd rd rd -11942444 Example 144 14-species greenhouse test Xn this test, the test compounds of formula I were applied to the surface of the soil preemergence to the 5 test plants. Again, the test method was in general the method of Example 141. Various application rates were used as indicated below, and typical results were as follows. Different plant species were used in testing different compounds. -12042444 co ι Table jequinono k sfipssqnN mottsa 4ΘΘ9 jefins qreqM ssej6 -PJeAujeh □oth PXTM umqbjos utejo Bpxs XixoxJd jBeiqeAieA ssBjbqBJO jeqjBnbsquiB1! UJO3 paart&ia qB'tTTW TTPqxoa peertuosuiTf Αιοχ& -buTiiJOW motyew 3θτ«θΛ uesqAos paawbBH uojjod AjjeqetXonH uepjBS podeTXOjs •Bq/-bq •ujddv JO 3JBH •ON sxduiBxa jo punoduioo fi in oo in © in co in © co O CM © o oj cn in fi · © © σ» © in cm cn o in fi in xp cn in © oo in »n cn in σ» σ» © fi © fi o fi © o fi © o fi o fi fi fi o © xp fi fi cn O o o o fi fi fi fi in CO © © o fi fi fi O © in Γ in in © in • • fi • © © © tn o o xp fi r> o fi fi xp fi r—1 χί* r- © in © o o © © o fi • fi fi fi fi fi fi © xp in © co in co © © © fi fi fi fi xp o o o r*. o XP © © fi fi fi fi fi co © © fi fi fi Xp xp in xp co fi ro xp fi © fi o o © o © © © o o o fi fi 00 m fi fi in © in in © co ro © ro co fi in fi CM fi fi CM in CM CM fi © fi o fi fi © © © © in fi XP r- co fi fi fi p* CO CM fi fi fi fi xP XP XP xp -1214 2 4 14 Table 8 Continued aaqumono afipasgnN Μοχχθχ gaag jBfing qeoqM sseaB -pjBAuaeg aoxg geo pxxm umq&aos uxexa BPTS Ax^o-rag ίΒοχ^θΛχθΛ ssBiBqeao aaqjBnbsqniBq uaoo paaMfiya gsXXTW XfBqxoa paaMuosuiyp Αιοχβ -fiUXUJOK moxxbw aoxuaA unaqAog paawBca uoqqoo AjaaqsXXong uapjBo podaxxoxg •Bq/'βχ •uqddv go aqaa οοιηΜΓ-οι οϊοοοιηιη oor*mi>inflOo in flfl cninocnmcnmoooo rd * « rd rd rd rd σι cn OO COOtn Ao ooocorofl cor'.ovr» cNCh©flor~tnooocn rd rd rd rd rd CM CM co CM cn m fl o o VO r* rd rd in in o fl o cn co © O o o rd rd rd rd H rd o in O Γ' O cn r· © O © rd rd rd rd rd rd CM in σι <*> m VO m O in in r~> rd • σι fl CM Γ> fl fl fl CM 00 co VO cn ooflenflAOcor-fom ooooooooooo vo co 00 co VO HHincMfMcMCMcMrdin rdrdOCMOO CMOrdO •ON sjduiGX3 I σι ο H cm cm a in vo r* co σι jo punoduioo I m tn tn 122 Table 8 Continued jaquinonj afipasqnN Μοχχοχ gaag asbng qeaqM SSBjfi -pjBAujBq θοχΗ 4B0 PXTM umqbjos utbjo Bpxg Αχχοτα^ χΒ9χχθΛχθΛ ssBJbqBJa jequBnbsquiBq ujtoo pssMbfa qeXXXW XTBq.xoj peeMuosiuTp Αιοχβ -Butujoh «οχχΒΗ aoxusA UBeqAog psaMbBH uoqqoa Ajjaqaxjfonn uapjEy podaxqoxg a1 r~ ο ο γί P4 in ko © oo γ·- cm H ο ο ο ο σ' oi Γ-1 H r-1 ι—J oom H r* in m cm cm ο σι o ko in mkooioocMinr^cMincMO r* r- oo σι m r* in c* σι in cm m m σι in o H m m γοο tnoooomo'coriinmoi oooioiotri cMoimr-tnm ο O' o o o o Η Η Η Η H O' Ο Ο Ο Ο Ο H I—I t—| r-| J—I in σ' ο o co ri r-l r-l ri in ο o m m Η r—I r- © o r-l ι—I o r* o H r-l in o • p-i O' o cm in ri m co ri σ» cm ri mkot»cocMCMkoor*mm OOOOCMOOOOOO -Bq/-5q •upddv jo eq.BM co 00 00 CM CM CM CM CM ID CM CM in HOOOCMOOCMOHH •ON ojduiexa o cm m ri in m jo punoduioo | η η η h w in -123Table 8 Continued jequmono BfipssqnN «οχχθχ qeeg JBfing 1ΕΘΜΜ SSBjfi -pjeAujeg soya jeo PXTM umqfiqos utbjo epys Αχχοτα^ 5Εθχ4θΛχθΛ sssaSqBJO JBqjBnbsqureq uqoo peeMfiya gexxyw Xysqxoa pBBMUOSUltp Aqoyfi -fiUTUJOW «οχI^K eoyusA treeqAog ρθθΜβΒΗ uoqqoo AiqsqsxjpnH irapjBo podsyipyg ·ΒΙΓ/-β}[ •uyddv qo equa oorjoooininr· rH rH rH r- r-cNxrxfcoincNin cn σ\οοσ»οσοοσ>© rd rH r-J r—i rH O O rH rH xfcocNcoinooKOOf^oxf xrinmcoKp'oxxi'mooM'ro xftn coaixfchxrcNoooin xrvomocnochooo H rH rH inchCNomoxrxrotnr·' rH * rH rH Ch ocichfomror-nr-'foin σ\οοοοοο\θοο rH r-H rH ι-H rH rH O O rH rH tnxrmr-coo^incoxfr* xfKD foor-oootnKo rH rH ΟΟΟΟΟΟΟΟΟΟ© KO KO 00 KO 00 KO 00 00 CN CN in tn CN in CN in CN CN CN CN CN o o o o o o O CN O CO XT m in KO r- Xp KO n- 00 ch CO CO CO KO KO KO r* r- r· r- rH rH rH -124Table 8 Continued jequmona efipesgnN «oyysA geeg jEbns qeeqM ssbjcB -pjeAujpg eoTH 3B0 ΡΤΪΜ umqBuog utbjd spys Λχχοταα jBeygsAysA sSBJbqBJD jegjBnbsqtuBq ujoo peaM&ya qamw TfBgxoj peeMUosuiff Ajoyfi -buyujow «oyyBw eoyueA UBeqAos peewfiBH uoggoo Ajjeqey χοηΗ uepjBD podexjpxs OlOCOChCOCMOCMP'OOCh 0 CO CM CM 0 CM CO CM Ρ» σι ch VO P· Ch O 00 in Ρ» 0' m 00 o © © rd rd • • rd rd rd σι σι 0 ri O 0 0 CM in co ri VO in VO CM in CM CM CM CM in 0 VO ri co in 0 ri CO CM 0 CM in co r* ri P- p- CM © in in in © vo 00 0 0 0 co rd rd rd rd OOOriCMfMritnfMr^O OOP* ©mcMCMrocMomoi riooeotninco osco rd rd O Ol rd O rd O © rd rd © O Ch o p. oooooooooooo •Bq/-63[ •uyddv eyea >£> 00 CdinCdCMriCMrdCM Pl O PM PM ri Pl ON Olduivxg jochiDp'Cooriinvo JO punoduioo |C003rdrdrdCMOOO -125 P* rd VO in Example 145 soil-incorporated test In this test, the compounds of formula I were incorporated in the soil before the seeds were planted. Again, the method of Example 141 was followed in general. Various compounds in this test were applied at a number of different application rates, and, the various compounds were tested against various plant species. 12642444 oil Table jnqayjpoa BJXO ΛΟχχΒΜ ΘΟΤΠΘΛ χοομλχχοΗ ssv-ΐβ -paeAuaea ^Β3χ4θΛχ9Λ 43TTTW xyBqxoj abpasqnN Λοχχθχ ssBjbqBJO Ααοχβ -Buxujom aaqaBnbsqureq Bpys Ayjpyaa uoqqoo paa«Bya AjjaqaxxanH uap.ie3 pasMuosuiyf • rt c rt x: rH+»X ft rt ' ftft © < 441 © O rH O rH © Ol © O rH O © d © © o rH rH © © O rH rH rH o © O © © , © © © rH rH rH rH rH rH rH rH © © © O © © O O © rH rH rH H H H rH rH © © © O © o © © rH rH rH rH rH rH rH rH in 00 O O © O © O rH rH rH rH © © O O © © O © rH rH rH rH rH rH rH rH O o O o © O O © © rH rH rH rH rH rH rH rH O © O © O © O © rH rH rH rH rH rH rH rH © © © O Ol O O O © H rH H rH rH H H rH © © TP © © O © o O TP Γ* o O o © o O rH rH rH rH rH rH © © © o O © o O rH rH rH rH rH rH rH rH © O © O © © O © rH rH rH rH rH rH rH © k£> rH © © © kO CM in r—J CN d d m d in © O rH d O O O O o MH ♦ O O to Ό β rt β rH O ft O X u w ι-l rm c> m 127 ©I Table jnqex^ooo exjjo Μοχχυνι odtuoa ^ooqZxion SSBjfi -pieAuxeg jeexgaAxaA gaiTTW TTEgxog eBpasg-ng woiyax sseuBqeao Λ,ιοχβ -Buxujow jaqjBnbsquiBl Bpys Aiqa-fjta uoqgoo paawfira AjjcaqaiXong uapsiBi) paaMuosuixp (0 O © © rd rd rd 0 r-| i-d 0 O O © O rd rd rd rd O O O O O O O Γ- o O rd rd id rd rd rd rd rd rd ro in 00 0 0 © © © O © 00 © © rd rd rd rd rd rd rd rd rd 00 O ό © O O O VO Γ- Γ- rd rd rd rd rd rd © © O rd rd 0 O O O © Γ- 00 Γ- ΟΟ ΟΟ rd rd rd rd rd O O ro © O Ο © Ο O © cMsft-oo©©cooo rd rd rd rd r—oocoovr— coinr- £— U Q> Λ H-P\ CU fi · α,Κ Cn ri fi Ψ1 · 0 0 ni β Φ 3 rd 0 a cue ε a 0 X u w rd VO rd VO rd CJ ci in cm in cm sr .56 0 rd © ο ο ο ο ο ό -12843444 Example 146 surface-applied multiple-crop test Representative compounds of formula I were tested against a number of representative crop plants in a field 5 screen test wherein the test plots were artificially seeded with weeds. Seeds of the crops shown in the table below were planted in rows in a medium-heavy midwestern soil. The compounds identified below were applied in bands across the rows of crop seeds, and were applied immediately after the seeds were planted. The bands were about 1 meter wide, so that each test plot included a 1-meter length of a row of each crop shown below. The compounds were sprayed on the surface of the soil in the form of an aqueous dispersion similar to those described above in Example 139.
All of the test plots were overseeded with pigweed and foxtail immediately before the plots were planted and treated with the compounds. Untreated control plots were provided for comparison with the treated plots.
A skilled plant scientist observed the plots 39 days after they were planted and treated, and estimated the percent control of the weeds and the percent injury to the crops. The results are shown in the table below. -129c rQ Φ Λ Ο ω φ Φ & •Μ Λ CO ΡΦ r-4 Λ CM Ο tn ο «—1 α σι σι σι ο Γγο VO ο ο σι α © σι tn co © co CM co co p- vo νο σι σι οο Ρσι σι σι σι σι σι co co to oo r* co σι σι •r| ra 4J * Cm 4-> (Q Φ Λ cm σι σι σι σι σι σι σι σι σι ο σι σι ο σι σι σι γσι οο ιη © Ρσι ο σι r4 co ρCM cm CM ΓΟ Ο ro r- ro co fl Γ— γΗ r4 ro m r- r- co vo Φ o © •ril CM Ail ro rfl m o rcm tn P- O' P- r-4 r- o ι-i tn r— co CM r4 ρ- σ CM r4 rfi CP M tn co H o tn o p* σι icm o CO Ο Ρ- Pσι N fl vo p~ co σ Γοο oo ro tn -P fi C rti G) A< r- r-o tr-4 co m r- co o fl fl r4 oom m r- co cm co c -P -P o r- o Ο γγο O r4 o m κ ro r4Q)\r4CMin»-4 CMinHCMtnr4fMin CU-P......... · CU rtJ tP r-l CM fl H CM fl r4 CM fl H CM fl 0$ Λί VO in © P- 00 rd CO CO 13042444 Example 147 soil-incorporated multiple-crop test The procedure of Example 146 was followed, except that the compounds of formula I were incorporated with a 5 rotary tiller immediately after application. Crop and weed seeds were planted immediately after application and incorporation of the compounds. -13142444 G ra A cn Ό Φ QJ o fi o CM rfi oo > xp © Xp © r* © CM rin © © © ηοο o fi fi fi © fi © r© fi oo fi © Γ» r- fi A IT 0 fi © fi to A A ra G ' G ra φ 04 g 0 A A 0 O Γ** © fi © fi © Γ*» fi • ra G A fi Φ\ CUA * p< ra tr a CM © CM © CM CM fi fi CM CM G Φ G fi ο a £§ ο X a w fi -13242444 c d Φ XJ o w Ό Q) 0) & •H ft [*· O m rr- oo r•H d P X ft o o xr io cn oo cn oo cn m r* η o rH χί* ό cn cn cn Table 11 Continued 0) □ o *h| n Oil cn rxf in in co cn co XJ tt M w © CN cn cn n in o cn ο o rH CN • d β Λ rH Q)X ftp ft d tt < oi Ai co CN KO in KO cn m CM O m · 0 S3 TJ β Φ ft Η 0 ft ft£ £ d 0 X υ w CO rH rO -133 3444 Example 148 perennial weed test The compound of Example 1 was tested against typical perennial weeds. The compound was formulated according to the procedure of Example 138. Applications of the formulated compound were made to plastic pots of greenhouse soil which had been planted with bindweed, bermudagrass, johnsongrass and quackgrass. Bindweed root stocks and johnsongrass and quackgrass rhizomes were obtained from field-growing plants, and bermudagrass stolons were rooted from greenhouse-grown bermudagrass flats.
The compound, in its formulated form, was sprayed evenly over the pots immediately after the weeds were planted, and was lightly watered into the soil. The pots were individually fertilized a few days after treatment.
The pots were stored in the greenhouse, and the plants were observed five weeks after application of the compound. Weed control was rated on the 0-10 scale.
Appln.
Rate kg./ha. Bind- weed Bermuda- grass Johnson- Quack- grass grass 0.28 10 5 1 8 0.56 ID 7 3 10 1.1 10 7 5 9 2.2 10 8 5 9 The same compound was also tested against I weeds in a postemergcnce test, wherein the weeds were allowed to grow for 30-60 days after planting before the compound was applied. Before application of the compound, the plants were trimmed back to a height of 4-8 inches, and -13442444 the bindweed runners were trimmed back to the edge of the pot. The plants were observed four weeks after treatment.
The results were as follows.
Appln. 5 Rate Bind- Bermuda- Johnson- Quack- kg./ha. weed grass grass grass 0.28 8 8 8 5 0.56 8 8 8 10 1.1 8 8 8 10 10 2.2 8 7 8 10 Example 149 perennial weed tests In this typical experiment, the weeds and conditions were similar to those of Example 148. A number of exemplary compounds of formula I were used. The weeds were observed about four weeks after application of the compounds. The preemergence results were as follows. -13542444 Compound of Example No. Appln. Rate kg./ha. Bind- weed Bermuda- qrass Johnson- grass Quack- grass 1 1.1 10 9.8 10 10 ' 0.56 10 9.8 10 10 0.28 10 8 10 10 0.14 10 8 9.5 10 51 1.1 10 9.5 10 10 0.56 10 9 10 10 0.28 10 5 7 6 0.14 10 4 7 12 ‘ 1.1. 10 9.5 9.5 10 0.56 10 8 9 10 0.28 10 8 8 8 0.14 10 6 8 14 i.i 10 9.5 10 10 0.56 10 9 10 10 0.28 10 9 7 9 0.14 10 7 7 7 57 1.1 10 9.5 10 10 0.56 10 9 9.5 10 0.28 10 7 10 9 0.14 10 5 7 7 The results of the postemergence experiments were as follows. -13642444 Compound of Appln.
Example No. Rate kg./ha. Bind- weed Bermuda- grass Johnson- grass Quack- grass 1 1.1 9.5 9.5 0.56 9 9.5 8 9 0.28 8 9.5 0.14 3 9 51 1.1 9 9 0.56 9 8 7 9 0.28 7 5 0.14 5 4 12 1.1 9 9 0.56 9.5 9 8 7 0.28 8 5 0.14 7 4 14 1.1 9 9 0.56 9.8 9 8 9 0.28 8 8 0.14 7 6 57 1.1 9 9 0.56 9.5 9 7 8 0.28 5 6 0.14 4 3 Example 150 mesquite test Typical compounds of formula I were tested against mesquite trees growing in the greenhouse. The trees were transplanted, when 5-12 inches tall, into 1-gallon metal pots. After the trees had begun to grow vigorously in the pots, the compounds were applied as a soil drench. The compounds were formulated for application by dissolving them -13742444 in acetone:ethanol as described in Example 138, and dispersing the proper amount of the solution in 25 ml. of water for application to each pot. The mesquite trees were observed approximately 90 days after application of the compounds, and control was rated on the 0-10 Compound of Example No. Appln. Rate kg./ha. Rating 10 34 1.1 6 2.2 6 4.5 7.5 37 1.1 7 2.2 4 15 4.5 8.5 1 1.1 9.8 2.2 9.9 4.5 9.9 47 1.1 9 20 2.2 9.5 4.5 9.9 48 1.1 10 2.2 9.9 4.5 10 25 51 1.1 0 2.2 4 4.5 7 6 1.1 10 2.2 9.5 30 4.5 9.9 -13842444 Compound of Example No.
Appln. Rate kg./ha. 1.1 2.2 4.5 1.1 2.2 4.5 1.1 2.2 4.5 1.1 2.2 4.5 1.1 2.2 4.5 1.1 2.2 4.5 Ratings 7.5 9.9 Example 151 grapefruit test The compound of Example 1 was tested in a grapefruit grove in a tropical climate. The soil was sandy and the trees were grown with sprinkler irrigation in bedded culture. The trees were approximately two years old when the compound was applied.
The compound was formulated according to the method of Example 138, and was applied as a surface spray to a 1 meter square plot around the base of each tree. -13942444 Crop injury to the trees was rated on the 0-10 scale about 14 weeks after application of the compounds, with the following results.
Rate kg./ ha. 0.14 0.21 0.28 0.42 0.561.1 2.2 4.5 0.0 0.0 0.0 0.0 0.0 0.7 0.0 0.0 Weed control was also observed about 14 weeks after application of the compound. The following results were observed, expressed as percent control based on the weed population of untreated control plots. -14043444 Appln. Cutleaf Rate Purple Evening- Florida Black kg,/ha. Bahiaarass Bermudagrass Cudweed primrose Pusley Nightshade r* rcn cn ID 10 o o o o r-l H CM o lO o H ooo ooo I—I rH I—I moo CD Ο O r-l H o o ri ri r-l ι-l CM o o o o i—l «—I o in o cn o σ» o «—I rn o H 00 CM CM ri co m co Γ* o co cn kD in η o o o o Η ΓΗ o o O' o o o o o r—I ι—I O 00 CD <Λ o CO ο σι r-f CM in CM ri 141· Example 152 purple nutsedge control in cotton tests The compound of Example 1 was tested in fieldgrowing cotton infested with purple nutsedge. The cotton 5 was grown in a clay soil in flat culture, with no irrigation, in a sub-tropical climate. The compound was applied as a water-dispersed 80% wettable powder, and was incorporated into the soil immediately before the cotton was planted. Crop injury and weed control observations were made, in percent injury or control, approximately eight weeks after the compound was applied. The results were as follows.
Appln. . Rate kg./ha. Crop Inj ury Bristly Starbur Control Purple Nutsedge Control Red Tasselflower Control 0.56 0 27 20 33 0.84 0 60 67 80 1.1 0 68 73 90 1.7 0 90 90 100 2,2 7 0 99 99 100 3.4 0 99 99 100 Example 153 weed control in coffee tests The compound of Example 1 was also applied to 25 established coffee in experiments much like those of the example immediately above, except that the compound was surface applied. Application of the compound at rates up to 2 kg./ha. showed no injury to the coffee when the crop was observed approximately six weeks and approximately four months after application of the compound. Excellent -14242444 control of annual grasses, annual broadleaves, Paraguay starbur, bristly starbur, hairy beggarticks, southern sandbur, and purple nutsedge was observed in the experiment.
The outstanding broad-spectrum activity of the compounds of formula I is clearly illustrated by the above examples. The examples point up the efficacy of the compounds against annual grasses, the relatively easilycontrolled broadleaves such as pigweed, and the more difficult to kill broadleaves such as the nightshades, ragweed and sicklepod. Further, the compounds control such perennial weeds as johnsongrass, quackgrass, bindweed, bermudagrass and nutsedge, which are very difficult to control.
The compounds also control algae and aquatic weeds, such as coontail, and hydrilla. Still further, the compounds kill such woody plants as mesquite, which is an economically harmful weed in arid climates. Thus, plant scientists will recognize that the compounds can be used to control undesirable woody plants where such plants are not wanted. Plant scientists will recognize that the exemplified activity of the compounds shows that the compounds are effective against all types of weeds. Λ preferred embodiment of the herbicidal method, however, is the use of the method to selectively kill herbaceous weeds.
Most unusually, the compounds of formula I are herbicidally effective when applied both preemergence and postemergence. Thus, they can be applied to the soil to kill weeds by soil contact when the weed seeds are germinating and emerging, and can also be used to kill emerged weeds by direct contact with the exposed portions of the -143weed. When the compounds are applied preemergence, the weeds are killed either during germination or shortly after emergence.
The compounds are effectively brought into contact with aquatic weeds by either suspending or dissolving the compound in the wafer in which the weeds grow, or by applying the compound to the sub-aqueous soil in which the weeds are rooted.
Because of the outstanding efficacy of the compounds, a method of using the compounds for killing weeds is an important embodiment of the present invention. This embodiment is a method of selectively killing weeds which comprises contacting the weeds with an herbicidallyeffective amount of one of the compounds of formula I described above. Xn the context of this invention, weed seeds, which are contacted with the compounds through preernergence applications of the compounds, are regarded as weeds.
Preemergence applications of the compounds are effective, as the examples show, whether the compounds are applied to the surface of the soil or are incorporated in the soil.
As the examples above illustrate, many of the compounds are acceptably safe to a number of crops, such as peanuts, soybean, sorghum, wheat, rice and tree crops when applied at proper rates and at appropriate times. It will be noted that the compounds are particularly and notably harmless to cotton in the exemplified experiments. Becauscof the safety with which this crop may be treated with the -14442444 compounds, the use of the method to kill weeds in cotton cropland is a preferred embodiment of the invention.
The compounds can also be used, at appropriate application rates, for the total control of vegetation. Such control is often desired, as for keeping cropland fallow for a time, or on industrial property and rights-of-way.
The compounds' ability to control perennial weeds and woody plants makes them particularly valuable total vegetation control agents.
The method is notable for its ability selectively to kill weeds. The term weeds is not used here in a restrictive sense, but is used to refer broadly to undesired and undesirable plants; hence, noxious vegetation. For example, the method may be used in cotton cropland to kill not only plants which are undesirable per se, such as johnsongrass and ragweed, but also volunteer crop plants which are undesirable in a cotton field. It will be understood that the proper application rates must be used to achieve selective control of weeds, as plant scientists are well aware.
The proportion of the weed population which is killed by an application of one of the compounds of formula I depends upon the species of the weed and the identity and amount of the compound applied. In many instances, of course, the whole population is killed. In other instances, part of the weeds are killed and part are injured, as some of the examples above illustrate. It will be understood that an application of one of the compounds is effective and beneficial, even though only part of the weed population is killed and another part of the population is injured. The -14542444 mere injury of a weed is beneficial, because the surrounding crop, growing normally, shades out and kills the slowgrowing. injured weed.
The best application rate of a given compound of 5 formula I for the control of a given weed varies, of course, depending upon the method of compound application, climate, soil type, water and organic matter contents of the soil and other factors known to those skilled in plant science. It will be'found, however, that the optimum application rate is in the range of from about 0.1 to about 20 kg./ha. in virtually every case. The optimum rates will usually be found to be within the preferred range of from about 0.1 to about 5 kg./ha.
The time when the compounds should be applied to the soil or the Weeds is widely variable, since the compounds are effective both preemergence and postemergence.
At least some control of weeds will result from application of the compounds at any time when weeds are growing or germinating. They may also be applied to the soil during a dormant season to kill weeds germinating during the following warm season.
When the compounds are used for weed control in an annual crop, it is usually best to apply a preemergence application of the compound to the soil at the time the crop is being planted. If the compound is to be soil incorporated, it will usually be applied and incorporated immediately before planting. If it is to be surface applied, it is usually simplest to apply the compound immediately after planting. -14642444 The compounds are applied to the soil or to emerged weeds in the manners usual in agriculture. They may be applied to the soil in the form of either water-dispersed or granular formulations, the preparation of-which will be discussed below. Usually, water-dispersed.formulations will be used for the application of the compounds to emerged weeds. The formulations are applied with any of the many types of sprayers and granular applicators which are in wide use for the distribution of agricultural cheihicals over soil or standing vegetation. When a compound is to be soil-incorporated, any of the usual soil incorporation equipment, such as the disc harrow, and the power-driven rotary hoe are effective.
The compounds are normally applied in the form of the herbicidal compositions which are an important embodiment of the invention. An herbicidal composition of this invention comprises a compound of formula I and an inert carrier. In general, the compositions are formulated in the manners usual in agricultural chemistry, and are novel only because of the vital presence of the novel herbicidal compound.
Very often, the compounds are formulated as concentrated compositions which are applied either to the soil or the foliage in the form of water dispersions or emulsions containing in the range of from about 0.1 percent to about 5 percent of the compound. Water-dispersible or emulsifiable compositions are either solids usually known as wettable powders, or liquids usually known as emulsifiable concentrates. These concentrated compositions are used in the range; -147% by weight compound of formula I 10-80 surfactant 3-10 inert carrier 87-10 Wettable powders comprise an intimate, finelydivided mixture of the compound, an inert carrier and surfactants. The concentration of the compound is usually from about 10 percent to about 90 percent. The inert carrier is usually chosen from among the attapulgite clays, the kaolin clays, the montmorillonite clays, the diatomaceous earths or the purified silicates. Effective surfactants, comprising from about 0.5 percent to about 10 percent of the wettable powder, are found among the sulfonated lignins, the condensed naphthalenesulfonates, the naphthalenesulfonates, the alkylbehzenesulfonates, the alkyl sulfates and nonionic surfactants such as ethylene oxide adducts of phenol.
Typical emulsifiable concentrates of the compounds of formula I comprise a convenient concentration of the compound, such as from about 100 to about 500 g. per liter of liquid, dissolved in an inert carrier which is a mixture of water-immiscible solvent and emulsifiers. Useful organic solvents include the aromatics, especially the xylenes, and the petroleum fractions, especially the high-boiling naphthalenic and olefinic portions of petroleum.
Many other organic solvents may also be used such as the terpenic solvents, and the complex alcohols such as 2-ethoxyethanol. Suitable emulsifiers for emulsifiable concentrates are chosen from the same types of surfactants used for wettable powders.
When a compound is to be applied to the soil, as -14830 4244 for a preemergence application of the compound, it is convenient to use a granular formulation. Such a formulation typically comprises the compound dispersed on a granular inert carrier such as coarsely ground clay. The particle size of granules usually ranges from about 0.1 to about 3 mm. The usual formulation process for granules comprises dissolving the compound in an inexpensive solvent and applying the solution to the carrier in an appropriate solids mixer. Granular compositions are usually in folio lowing range: % by weight compound of formula I 1-10 surfactant 0-2 inert carrier 99-88 lb Somewhat less economically, the compound may be dispersed in a dough composed of damp clay or other inert carrier, which is then dried and coarsely ground to produce the desired granular product.

Claims (15)

CLAIMS:
1. A compound ol the general formula V II I R wherein: X is oxygen or sulfur; R is C^-Cg .alkyl; Cg-Cg alkyl substituted with halo, cyano, icarboxy or methoxycarbonyl; Cg-Cg alkenyl; Cg-Cg alkynyl; Cg-Cg alkoxy; acetoxy; or dimethylamino; provided that R comprises no more than 3 carbon atoms; the R 3 groups independently are halo; Cg-C fi alkyl; CpCg alkyl substituted with halo; Cg-Cg alkyl monosubstituted with phenyl, cyano or Cg-Cg alkoxy; Cg-Cg alkenyl; <' 2 ~0θ alkenyl substituted with halo; Cg-Cg alkynyl; Cg-Cg alkynyl substituted with halo; Cg-Cg cyeloalkyl; C^-Cg cycloalkenyl; C^-Cg cycloalkylalkyl; Cg-Cg alkanoyloxy; Cg-Cg alkylsulfonyloxy; phenyl; phenyl inonosubstituted with halo, Cg-Cg alkyl, Cg-Cg alkoxy, or nitro; nitro; cyano; carboxy; hydroxy; Cg-Cg alkoxycarbonyl; -0-R 3 ; -SO-R 3 ; or -SOg-R 5 ; R 3 is Cg-C| 2 alkyl; C|-C^ 2 alkyl substituted with halo; Cg-Cg 2 alkyl nionosubstituted -15042444 with phenyl, cyano or Cj-C 3 alkoxy; phenyl; phenyl monosubstituted with halo, Cj-Oj alkyl, alkoxy or nitro; C^-Cg cycloalkyl; C' 4 “C g cycloalkylalkyl; C 2 ~C^ 2 alkenyl; C 2~ C ~L2 alkenyl substituted with halo; C2 -C i2 alkynyl; or ^2 -ε ΐ2 alkynyl substituted with halo; provided that R comprises no more than 12 carbon atoms; R is halo; hydrogen; cyano; O^-C-j alkoxycarbonyl ; Cj-C (j alkyl; alkyl substituted with halo or C^-C g alkoxy; alkenyl; C’2~ c g alkenyl substituted with halo or Cj-C g alkoxy; C 2 ~Cg alkynyl; C^-Cg cycloalkyl; C^-Cg cycloalkyl substituted with halo, C-^-C^ alkyl or C^-C^ alkoxy; C 4 ~Cg cycloalkenyl; C 4 -C g cycloalkylalkyl; phenyl-C^-Cg alkyl; furyl; naphthyl; thienyl; -0-R 4 ; -S-R 4 ; -SO-R 4 ; -SO 2 ~R 4 , or n R is Cj-Cj alkyl; C^-C^ alkyl substituted with halo; Cj-C^ alkenyl; C^-C^ alkenyl substituted with halo; benzyl; phenyl; or phenyl substituted with halo, C^-C^ alkyl or C^-Cg alkoxy; the R 5 groups independently are halo; C l -C 8 al kyl; C^-c g alkyl substituted with -1514 3444 halo; Cg-ζθ alkyl monosubstituted with phenyl, cyano or Cg-Cg alkoxy; C 2 ~Cg a lkenyl, C^-Cg alkenyl substituted with halo; C 2 ~Cg alkynyl; C 2 ~Cg alkynyl substituted with halo; '5 C 3~ C C c y clOi, lkyl; C^-Cg cycloalkcnyl; C^-Cg cycloalkylalkyl; C-g-Cg alkanoyloxy; Cg-Cg alkylsulfonyloxy; phenyl; phenyl monosubstituted with halo, Cg-Cg alkyl, Cj'C^ alkoxy or nitro; nitro; cyano; carboxy; 10 hydroxy; Cg-Cg alkoxycarbonyl; -O-R 3 ; -S-R 3 ; -SO-R 3 ; or -SO 2 -R 6 ; R 3 is alkyl; Cg-Cg 2 alkyl substituted with halo; Cg-Cg 2 alkyl monosubstituted with phenyl, cyano or Cg-Cg 15 alkoxy; phenyl; phenyl monosubstituted with halo, Cg-Cg alkyl, Cg-Cg alkoxy or nitro; Cg-Cg eycloalkyl; C^-Cg cycloalkylalkyl; C 2 -C 12 alkenyl; Cg-Cg 2 alkenyl substituted with halo; C 2 —C 12 20 alkynyl; or ^-^12 alkynyl substituted with halo; provided that R 3 comprises no more than 12 carbon atoms; m and n independently are 0, 1 or 2; provided that 2 when X is oxygen, R is methyl, and R is unsubstituted 25 phenyl, then m is 1 or 2; or an acid addition salt thereof. -15210 48444
2. A compound of Claim 1 of the general formula ,,X_Z II wherein: X is oxygen or sulfur; R° is C^-Cg alkyl; Cg-Cg alkenyl; acetoxy; or methoxy; q and p independently are 0, 1 or 2; the R groups independently are halo; Cg-Cg alkyl; trif].uoromethy1; or Cg-Cg alkoxy; th ,!i o R groups independently arc halo; Cg-Cg alkyl; trifluoromethyi; or Cg-Cg alkoxy; or two R 3 groups occupying adjacent o and m positions combine with the phenyl ring to which they are attached to form a 1-naphthyl group; or an acid-addition salt thereof.
3. A compound of Claim 1 of the general formula III I R 1 2 wherein R, R and R are defined as in Claim 1; or an acidaddition salt thereof. -1534. Any one of the following compounds· 1-methyl-3-pheny1-5-(3-trif1uoromethylphenyl)
4. (111)-pyridone 1-methy1-3,5-bis(3-trifluoromethylpheny1) 5 4 (III) -pyridone 3-pheny1-1-(2,2,2-trifluoroethyl)-5-(3-trifluoro methylphenyl)-4(IH)-pyridone 3-(3-bromophenyl)-5-(3-chlorophenyl)-1-methyΙΑ (HI) -pyridone 10 3-(3-chlorophenyl)-5-(4-chlorophenyl)-1-methyl4(IH)-pyr idone 3-(2-fluorophenyl)-1-methy1-5-(3-trifluoromethy1 phenyl)-4(IH)-pyridone 3-(2-chlorophenyl)-5-(3-chlorophenyl)-1-methy115 4 (111)-pyridone 3-(3-methoxyphenyl)-1-methy1-5-(3-trifluoromethylphenyl) -4 (III) -pyridone 3-(4-chlorophenyl)-l-methyl-5-(3-trifluoromethylphenyl)-4(IH)-pyridone 20 l-allyl-3-phenyl-5-(3-trifluoromethylphenyl4 (HI)-pyridone 3-(4-isopropy1 phenyl)-1-methyl-5-phonyl-4(111)pyridone 3-(2-chlorophenyl)-l-methyl-5-(3-trifluoro25 methylphenyl)-4(HI)-pyridone 3-(3-fluorophenyl)-l-methyl-5-(3-trifluoromethylphenyl)-4(HI)-pyridone -15442444 3-(4-fluorophenyl)-l-methyl-5-(3-trifluoromethylphenyl) -4 (IH)-pyridone 3-(4-methoxyphenyl)-l-methyl-5-(3-trifluoromethylphenyl) -4 (IH)-pyridone 5. L-methyl-3-(3-methylthiophenyl)-5-pheny14(IH)-pyridone l-methyl-3-(3-methylsulfinylphenyl)-5-phenyl4(IH)-pyridone 1-methy1-3-(3-methytsulfonylphenyl)-5-phenyΙΙΟ 4 (111)-pyridom.» I~mothyl~ 3-pheny 1 - 5- (4-t.r.i I I in iromet hyl phenyl) 4(IH)-pyridone 3- (3-benzyloxyplienyl) -l-methyl-5-phenyl-4 (111) pyridone 15 l-methyl-3-phenyl-5-(2-thienyl)-4(IH)-pyridone 3-(3-isobutylphenyl)-l-methyl-5-phenyl-4(IH)pyridone l-methyl-3-(3-nitrophenyl)-5-phenyl-4(lH)pyridone 20 3-(2,4-dichlorophenyl)-1-methy1-5-pheny1-4(IH) pyridone 3.5- diphenyl-l-ethyl-4(IH)-pyridone l-allyl-3,5-diphenyl-4(IH)-pyridone 3.5- diphenyl-l-isopropyl-4(111)-pyridone 23 l-cyanomethyl-3,5-diphenyl-4(lH)-pyridone 3.5- diphenyl-l-propyl-4(lH)-pyridone 3.5- diphenyl.-l-methoxy-4 (IH) -.pyridone 3-(3-fluorophenyl)-l-methyl-5-phenyl-4(IH) · pyridone -15542444 ~ 3-(4-bromophenyl)-l-methyl-5-phenyl-4(IH)pyridone 3-(4-methoxyphenyl)-l-methyl-5-phenyl-4(IH)pyridone 5 3-(3-chlorophenyl)-l-methyl-5-phenyl-4(IH)pyridone 3-(4-chlorophenyl)-l-methyl-5-pheny1-4(IH)pyridone l-methyl-3-(1-naphthyl)-5-phenyl-4(IH) 10 pyridone 3,5-bis(3-chlorophenyl)-l-methyl-4(IH)-pyridone, l-methyl-3-(3-methylphenyl)-5-phenyl-4(IH)pyridone l-methyl-3-(4-methylphenyl)-5-pheny1-4(lH)pyridone l-methyl-3-(2-methyIphenyl)-5-pheny1-4(IH)pyridone 3-(4-fluorophenyl)-l-methyl-5-phenyl-4(IH)20 pyridone l-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(III)-pyridone 3-(3-methoxyphenyl)-l-methyl-5-phenyl-4(IH)-pyridone 3-(3,4-dichlorophenyl)-l-methyl-5-phenyl-4(IH)-pyridone 3-(2,5-dichlorophenyl)-1-methyl-5-phenyl-4(IH)pyridone 25 3-(2-chlorophenyl)-l-methyl-5-phenyl-4(IH)pyridone 156 3.5- bis(3-fluorophenyl)-l-methyl-4(Hi)pyridone 3- (3-chlorophenyl) -5- (3-f luorophenyl.) -1-methyl4 (111) -pyridone 5 3-(3,5-dichlorophenyl) -1-nnrthy 1 - 5-pheny 1.--4 (111)pyridone 3.5- bis(3-bromophenyl)-1-methyl-4 (IH)-pyridone? 3-(3-bromophenyl)-l-methyI-5-pheny1-4(HI)pyridone 10 3-(2-fluorophenyl)-l-methyl-5-phenyl-4(IH)pyridone 3- (3-bromophenyl)-l-methyl-5-(3-trifluoromethylphenyl-4 (III) -pyridone 1- (1-carboxyet.hyl) -3-pheny 1.-5- (3-trifluoro15 methylphenyl)-4(IH)-pyridone l-dimethylamino-3,5-diphenyl-4(IH)-pyridone l-methyl-3-(2-naphthyl)-5-phenyl-4(IH)-pyridone l-ethyl-3-phenyl-5-(3-trifluoromethylphenyl)4 (111) -pyridone 20 3-pheny1-1-propy1-5-(3-trifluoromethylphenyl)4 (111) -pyridone 1-methoxy-.3-phenyI-5-(3-tri F1uoromothylphenyl) 4 (111) -pyridone 3- (3-chlorophenyl) -l-methyl-5- ( 1-trif luorome l.hyl25 phenyl-4 (111)-pyridone 3-(4-biphenylyl)-l-methyl-5-phenyl-4(IH)pyridone 3- (3-biphenylyl) -l-meth'yl-5-pheny 1-4 (In) pyridone -15743444 1-methyl-3-phenyl-4(IH)-pyridone 3-bromo-l-methy1-5-pheny1-4(IH)-pyridone 3-bromo-l-methyl-5-(3-trifluoromethylphenyl)-4(IH)pyridone l-methyl-3-(3-trifluoromethylphenyl)-4(IH)pyridone 3-chloro-l-methyl-5-(3-trifluoromethylphenyl)4 (111) -pyridone 3-(3-carboxyphenyl)-l-methyl-5-phenyl-4(IH)pyridone 3-(3-cyanophenyl)-l-methyl-5-phenyl-4(IH)pyridone 3-(3-ethoxycarbonylphenyl)-l-methyl-5-phenyl4 (IH)-pyridone 3,5-bis(3-cyanophenyl)-l-methyl-4(IH)-pyridone 1-methyl-3-phenyl-5-(3-thienyl)-4(IH)-pyridone 3-cyano-l-methyl-5-phenyl-4(IH)-pyridone 1.3- dimethyl-5-(3-trifluoromethylphenyl)-4(III)pyridone 1.3- dimethyl-5-phenyl-4(IH)-pyridone 3-(3-chlorophenyl)-l,5-dimethyl-4(IH)-pyridone 3-ethy1-l-methyl-5-(3-trifluoromethylphenyl)4 (IH)-pyridone 3-cyclohexyl-l-methyl-5-(3-trifluoromethylphenyl)4(IH)-pyridone 3-isopropy1-1-methyl-5-(3-trifluoromethylphenyl)4(IH)-pyridone 3-hexyl-l-methyl-5-(3-trifluoromethylphenyl)4(IH)-pyridone -15842444 J-benzyl-l-methyl -5- (3-trifluoromethylphenyl) 4 ( HI) -pyridone 3-butyl-l-methyl-5-(3-trifluoromethylphenyl) 4(IH)-pyridone 5 3-(3-cyclohexenyl)-l-methyl-5-(3-trifluoromethylphenyl) -4(IH)-pyridone l-methyl-3-propyl-5-(3-trifluoromethylphenyl) 4(IH)-pyridone l-methyl-3-(4-nitrophenyl)-5-phenyl-4(IH)10 pyridone I, 'j-bi.s (3,4-d iinethaxyphonyI) - 1 -mt:thy 1-4 (III) pyridone 3-ethoxycarbonyl-l-methyl-5-phenyl-4(IH) pyridone 15 3-(2-furyl)-i-methyl-5~phenyl-4(IH)-pyridone 3-cyano-l-njethyl-5-(3-trifluoromethylphenyl)4 (IH)-pyridone 3-(3,4-dimethoxyphenyl)-1-methy1-5-pheny14(IH)-pyridone 20 3-(3,4-dibromocyclohexyl)-l-methyl-5-(3-t.rifluoromethylphenyl)-4(HI)-pyridone, hydrobromide 3- (3-isopropenylphenyl) -l.~methyl-5-phenyl4 (111) -pyridone 3-(3-ethylphenyl)-1-methy1-5-pheny1-4(IH)25 pyridone 3-(3-hexylphenyl)-1-methyl-5-phenyl-4(IH)pyridone 3-(4-ethylphenyl)-1-methyl-5-phenvl-4(IH)pyridone -15942444 3-(3-cyclohexylme thylphonyl) -1-methyl-5-phenyl4(IH)-pyridone l-methyl-3-phenyl-5-benzylthio-4(IH)-pyridone l-methyl-3-phenyl-5-phenylthio-4(IH)-pyridone 5 l-methyl-3-phenoxy-5-phenyl-4(IH)-pyridone l-methyl-3-phenyl-5-phenylsulfonyl-4(IH)pyridone 3-methoxy-1-methyl-5-phenyl-4(IH)-pyridone 3-(3-hydroxyphenyl)-l-methyl-5-pheny1-4(IH) 10 pyridone 3-cyclohexy 1-5- (3-hydroxyphenyl) - l-methyl-4 ( ill) pyri done 3-(3-ethoxyphenyl)-l-methyl-5-phenyl-4(III)pyridone 15 3- (3-ailyloxyphenyl)-l-methyl-5-phenyl-4(IH)pyridone 3-(3-(1-fluoro-2-iodovinyloxy)phenyl]-1-methyl5-phenyl-4(IH)-pyridone 3-(3-isopropoxyphenyl)-l-methyl-5-phenyl-4(IH)20 pyridone 3-(3-oyanomethoxyphenyl)-1-methyl-5-phenyl-4(IH) pyri done 3-(3-dodecyloxyphenyl)-l-methyl-5-phenyl-4(IH)pyridone 25 l-methyl-3-[3-(4-ni trophenoxy)phenyl|-5- plumyI4 (HI)-pyridone l-methyl-3-(3-methylsulfonyloxyphenyl)-5-phenyl4 (Hl) -pyridone -16042444 1-methyl-3-plieny1-5-[3-(1,1,2,2-tetrafluoroethoxy) phenyl] -4 (IH)-pyridone 3-(3-acetoxyphenyl)-l-methyl-5-phenyl-4(IH)pyridone 5 3-(3-hexyloxyphenyl)-1-methyl-5-phenyl-4(IH)pyridone 3-(3-decyloxyphenyl)-l-methyl-5-phenyl-4(IH)pyridone l-methyl-3-phenyl-5-(3-propoxyphenyl)-4(IH)10 pyridone l-methyl-3-phenyl-5-(3-propargyloxyphenyl)4 (IH)-pyridone 3-(3-cyclohexylmethoxyphenyl)-1-methy1-5-pheny14(IH)-pyridone J.5 l-methyl-3-(3-octyloxyphenyl)-5-phenyl-4(IH)pyridone l-methyl-3-(3-phenoxyphenyl)-5-phenyl-4(IH)pyridone l-acetoxy-3,5-diphenyl-4(IH)-pyridone 20 3,5-diphenyl-l-methyl-4(IH)-pyridinethione 3,5-bis(3-chlorophenyl)-l-methyl-4(IH)-pyridinethione 3-(3-chlorophenyl)-1-methy1-5-pheny1-4(IH)pyridinethione 25 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)4(IH)-pyridinethione -16148444
5. A process for the preparation of a compound as claimed in any one of claims 1 to 4, which comprises cyclizing a compound of the formula 1 2 5 wherein R , R and m are as defined as in claim 1, with a formylating agent, or an aminoformylating agent 1 2 when one of Q and Q is 2 hydrogen atoms· and the other is =CHNHY wherein Y is hydrogen; hydroxy; C^-C^ alkyl; C^-C 3 alkyl substituted with halo, cyano, carboxy or 10 methoxycarbonyl; C 2 ~C 3 alkenyl; C 2 -C 3 alkynyl; alkoxy; or dimethylamino; provided that Y comprises no more than 3 carbon atoms; and with a compound of the formula YNH 2 15 wherein Y is defined as before or the acid addition salt 1 2 thereof, when both Q and Q are independently selected from - 162 48444 =CHOH , or =CHN(R 9 ) 2 9 in which the R groups independently are C^-C^ alkyl, or the R groups combine with the nitrogen atom to which they are attached to form pyrrolidine, piperidine, mor5 pholine or N-methylpiperazine; to provide a compound of the formula ,-Λ Ax A /1 j ” V i Y followed by alkylating or esterifying the compound so obtained wherein Y is hydrogen or hydroxy respectively to 10 provide the corresponding compound wherein Y is R; and when the compounds of formula I are desired wherein X is sulfur, treating the compounds of formula I wherein X is oxygen with P 2 S 56. The process of claim 5 for preparing a com15 pound of formula I which comprises cyclizing a compound of the formula 0 II c—(>—If VJ O' 1 2 wherein R , R and m are defined as in claim 1, with a compound of the formula YNH_ -16342444 wherein Y is defined as in claim 5 or the acid addition salt thereof, 1 2 when both Q and Q are independently selected from =CHOH, or =chn(r 9 ) 2 9 . in which R is defined «is in claim 5, to provide a compound of formula V as defined in claim 5; followed by alkylating or esterifying the compound so obtained wherein Y is hydrogen or hydroxy respectively to provide the corresponding compound wherein Y is R; and when the compounds of formula I are desired whereih X is sulfur, treating the compounds of formula I wherein X is oxygen with P 2 S[..
6. 7. The process of claim 5 for preparing a compound of formula I which comprises cyclizing a compound of Ihe formula ,,x V / II -C-II -R' vrx 1 2 wherein R , R and m are defined as in claim with a formylating agent, or an aminoformylating agent 12 20 when one of Q and Q is 2 hydrogen atoms and the other is ‘CIINHY wherein Y is defined as in claim 5, to provide a compound of formula V as defined in claim 5; -1644244 followed by alkylating or esterifying the compound go obtained wherein Y is hydrogen or hydroxy respectively to provide the corresponding compound wherein Y is R; and when the compounds of formula I are desired wherein X is 5 sulfur, treating the compounds of formula I wherein X Is oxygen with
7. 8. A compound of formula I whenever prepared by a meIhod according to any one of claims 5 to 7.
8. 9. A herbicidal composition which comprises an inert carrier
9. 10 and as an active ingredient a compound of the general formula I, II, or III as claimed in any one of claims 1,2,3,4 or 8, or an acid-addition salt thereof. 10. The herbicidal composition of claim 9 wherein the active ingredients is any of the compounds of claim 4. 15
10. 11. A method of controlling or eradicating undesired vegetation Which comprises applying a compound as claimed in any one of claims 1 to 4, or 8, or a herbicidal composition according to claim 9 or 10, to an area in which said undesired vegetation is growing oar is likely to grow. 20
11. 12. A method according to claim 11 wherein the compound which is applied is as claimed in claim 4.
12. 13. A process as claimed in claim 5 substantially as hereinbefore described with particular reference to any one of the Examples 1 to 122 or 124 to 137. 25
13. 14. A composition as claimed in claim 9 substantially as hereinbefore described with particular reference to any one of the Examples 138 to 153.
14.
15. A method as claimed in claim 11 substantially as hereinbefore described with particular reference to any one of the 30 Examples 138 to 153.
IE1833/75A 1974-08-28 1975-08-20 3-phenyl-5-substituted-4(1h)-pyridones-(thiones) IE42444B1 (en)

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AT362613B (en) * 1975-08-27 1981-06-10 Lilly Co Eli HERBICIDAL AGENT
US4051142A (en) * 1976-05-24 1977-09-27 Rohm And Haas Company 1-Aryl-4-pyridones
US4174209A (en) * 1978-06-19 1979-11-13 Eli Lilly And Company Herbicidal 1-alkyl-3-phenylpyridinium salts
EP0073999B1 (en) * 1981-09-05 1986-01-15 Bayer Ag Pyridin-4-one derivatives substituted by a heterocyclic ring, process for their preparation and their use as herbicides
AU570466B2 (en) * 1983-06-17 1988-03-17 Rhone-Poulenc Agro 3-oxo-2,3-dihydrofuran derivatives
US4537623A (en) * 1984-03-29 1985-08-27 Chevron Research Company Herbicidal 2-(oxa or thia heterocycle)5-amino-3-oxo-4-(substituted-phenyl)-2,3-dihydrofurans
US4568376A (en) * 1984-05-09 1986-02-04 Chevron Research Company Herbicidal 5-amino-3-oxo-4-(substituted-phenyl)-2,3-dihydrofuran and derivatives thereof
US4596595A (en) * 1984-06-22 1986-06-24 Chevron Research Company Herbicidal 5-amino-3-oxo-4-(substituted-phenyl)-2,3-dihydrothiophene and derivatives thereof
DE3430232A1 (en) * 1984-08-17 1986-02-27 Bayer Ag, 5090 Leverkusen N-METHYL-4-PYRIDONE
US4606756A (en) * 1984-10-26 1986-08-19 Chevron Research Company Herbicidal 2-(nitrogen heterocycle)5-amino-3-oxo-4-(substituted-phenyl)-2,3-dihydrofurans
US4568375A (en) * 1984-10-26 1986-02-04 Chevron Research Company 2-Substituted 5-amino-3-oxo-4-(substituted-phenyl)-2,3-dihydrofuran herbicides
US4568378A (en) * 1984-12-21 1986-02-04 Chevron Research Company Herbicidal 5-cycloalkylamino-3-oxo-4-(substituted-phenyl)-2,3-dihydrofuran and derivatives thereof
US4568377A (en) * 1985-04-26 1986-02-04 Chevron Research Company Herbicidal 5-amino-3-oxo-4-(substituted-phenyl)-2,3-dihydrofuran
US4978386A (en) * 1985-06-11 1990-12-18 Chevron Research Company Herbicidal 2-(substituted-phenyl)-3-amino-2-cyclopentenone derivatives
DE3531773A1 (en) * 1985-09-06 1987-03-19 Bayer Ag 3.5 DISUBSTITUTED 4-PYRIDONE
JPH07121911B2 (en) 1986-03-26 1995-12-25 クミアイ化学工業株式会社 4 (1H) -pyridinone derivatives and agricultural and horticultural fungicides
DE19518739A1 (en) * 1995-05-22 1996-11-28 Basf Ag N-aminopyridone derivatives
US6048823A (en) 1996-02-02 2000-04-11 Kumiai Chemical Industry Co., Ltd. Pyridone derivatives and herbicides
EP2052612A1 (en) 2007-10-24 2009-04-29 Bayer CropScience AG Herbicide combination
DE102008037629A1 (en) 2008-08-14 2010-02-18 Bayer Cropscience Ag Herbicide combination with dimethoxytriazinyl-substituted difluoromethanesulfonylanilides
US11026423B2 (en) * 2013-04-17 2021-06-08 Sepro Corporation Herbicidal compositions and methods
JP2017206440A (en) * 2014-09-10 2017-11-24 日本曹達株式会社 Pyridine compound and use therefor
KR102338966B1 (en) * 2017-06-23 2021-12-13 니토 코키 가부시키가이샤 air tool

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TR19047A (en) 1978-03-20
NL181272C (en) 1987-07-16
AR218211A1 (en) 1980-05-30
DE2537753C2 (en) 1984-05-30
YU216375A (en) 1982-02-28
SU716522A3 (en) 1980-02-15
CH632248A5 (en) 1982-09-30
CA1075696A (en) 1980-04-15
IT1042113B (en) 1980-01-30
NL7509935A (en) 1976-03-02
ATA660375A (en) 1981-06-15
BE832702A (en) 1975-12-16
FR2283130A1 (en) 1976-03-26
JPS5151520A (en) 1976-05-07
FR2283130B1 (en) 1983-04-08
NO145617B (en) 1982-01-18
PL109320B1 (en) 1980-05-31
IE42444L (en) 1976-02-28
IL47938A0 (en) 1975-11-25
NO145617C (en) 1982-04-28
OA05093A (en) 1981-01-31
PL111873B1 (en) 1980-09-30
NZ178426A (en) 1978-06-20
AT365577B (en) 1982-01-25
IL47938A (en) 1979-07-25
CH630356A5 (en) 1982-06-15
JPS60350B2 (en) 1985-01-07
JPS611401B2 (en) 1986-01-17
GB1521092A (en) 1978-08-09
NL181272B (en) 1987-02-16
DD127452A5 (en) 1977-09-21
HU169687B (en) 1977-02-28
LU73264A1 (en) 1976-04-13
AU8427875A (en) 1977-03-03
NO752942L (en) 1976-03-02
JPS5148671A (en) 1976-04-26
DD123461A5 (en) 1976-12-20
DK385075A (en) 1976-02-29
DE2537753A1 (en) 1976-03-11
EG12953A (en) 1980-03-31
BR7505487A (en) 1976-08-31
SU1074403A3 (en) 1984-02-15
YU39076B (en) 1984-04-30
MX5136E (en) 1983-03-28

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