CA1075696A - 3-phenyl-5-substituted-4(1h)-pyridones-(thiones) - Google Patents

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

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Publication number
CA1075696A
CA1075696A CA233,945A CA233945A CA1075696A CA 1075696 A CA1075696 A CA 1075696A CA 233945 A CA233945 A CA 233945A CA 1075696 A CA1075696 A CA 1075696A
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Prior art keywords
pyridone
phenyl
methyl
halo
alkyl
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French (fr)
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Harold M. Taylor
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Eli Lilly and Co
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Eli Lilly and Co
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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
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • 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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    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
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    • C07C49/227—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing halogen
    • 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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    • C07D213/00—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
    • C07D213/61—Halogen atoms or nitro radicals
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    • 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
    • C07D213/63—One oxygen atom
    • C07D213/68—One oxygen atom attached in position 4
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/84—Nitriles
    • C07D213/85—Nitriles 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
    • C07D213/89—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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

Abstract of the Disclosure A class of novel 3-phenyl-4(IH)-pyridones and pyridinethiones which are broad-spectrum herbicides are described herein. The new compounds are characterized by a small substituent on the nitrogen, and usually bear a 5-substituent chosen from a class described herein. The phenyl ring may be substituted. The compounds are effective herbicides when applied both before and after the emergence of weeds, and are particularly useful for the control of weeds in cotton cropland.

Description

~75~ig~;

3-PHENYL-5-SUBSTITUTED-4(lH)-PYRIDONES(THIONES) This invention belongs to the field of agricul-tural 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 of 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 been performed in the field of agricultural chemistry, active compounds closely related to the compounds o formula I herein have not been previously discovered. The poly-halopyridones, 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 of Eormula I.
The organic chemical art has explored the pyri-dones rather extensively. For example, Ishibe et al., J.
Am. Chem. Soc. 9S, 3396-3397 (1973), disclosed a rear-rangement of 3,5-diphenyl-1,2,6-trimethyl-4(lH)-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-1-methyl-4(1H)-pyridones, which compounds also have no herbicidal activity. The same principal author also disclosed 3,5-di(substituted-ben-zylidene)tetrahydro-4-pyridones, J. Am~ Chem. Soc. 79, 156-160 (1957~. These compounds also have no herbicidal activity. --;.

~ .

.. . . . . .

75~96 .
Light et al., J. Org. Chem. 25, 538-546 (1960), taught a number of 4-pyridone compounds including 2,6-diphenyl-l-methyl-4(1H)-pyridone, and related compounds bearing phenyl-ring substituents, none of which are her- , bicidally active.
An interesting recent article was published by El-Kholy _ al. in J. Hetero. Chem. 10, 665-667 (published_ _ _ September 7, 1973). El-Kholy described a synthesis of 3,5-diphenyl-l-methyl-4(lH)-pyridone and related compounds by the reaction with methylamine of the sodium salt of 1,5-dihydroxy-2,4-diphenyl-1,4-pentadien-3-one.
A series of novel 3-phenyl-4(lH)-pyridones-(thiones) are herbicides which are active against an un-usually wide range of weeds. New methods and compGsitions 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~

\~/ , , R

wherein: X is oxygen or sulfur;
R is Cl-C3 alkyl; Cl-C3 alkyl substituted with halo, cyano~ carboxy or methoxycarbonyl; C2-C3 alkenyl; C2-C3 alkynyl; Cl-C3 alkoxy; acetoxy; or dimethylamino; provided that R co~prises no more ~ ;
then 3 carbon atoms;

-~C~7S6~

the Rl groups independently are halo; Cl-C8 alkyl; Cl-C8 alkyl substituted with halo; Cl-C8 alkyl monosubstituted with phenyl, cyano or Cl-C3 alkoxy; C2-C8 alkenyl; C2-C8 alkenyl substituted with halo; C2-C~ alkynyl; C2-C8 alkynyl substituted with halo; C3-C6 cycloalkyl; C4-C6 cycloalkenyl; C4-C8 cycloalkylalkyl; Cl-C3 alkanoyl-oxy; Cl-C3 alkylsulfonyloxy; phenyl; phenyl mono-substituted with halo, Cl-C3 alkyl, Cl-C3 a:Lkoxy, or nitro; nitro; cyano; carboxy; hyd~oxy; Cl-C3 alkoxycarbonyl; -O-R ; -S-R3; -So-R3; or -SO2-R ; : ~
R is Cl-C12 alkyl; Cl-C12 alkyl substituted ::
with halo; Cl-C12 alkyl monosubstituted with phenyl, cyano or Cl-C3 alkoxy; phenyl;
phenyl monosubstituted with halo, Cl-C3 ~: :
alkyl, Cl-C3 alkoxy or nitro; C3-C6 cycloalkyl; -C4-C8 cycloalkylalkyl; C2-C12 alkenyl; C2-C12 :
alkenyl substituted with halo; C2-C12 alkynyl; ~.
or C2-C12 alkynyl substituted with halo; :
provided that R comprises no more than 12 carbon atoms; ~ .
R2 is halo; hydrogen; cyano; Cl-C3 al}coxycarbonyl;
Cl-C6 alkyl; Cl-C6 alkyl substituted with halo .
or Cl-C3 alkoxy; C2-C6 alkenyl; C2-C6 alkenyl substituted with halo or Cl-C3 alkoxy; C2-C6 alkynyl; C3-C6 cycloalky1; C3-C6 cycloalkyl sub-stituted with halo, Cl-C3 alkyl or Cl-C3 alkoxy;
C4-C6 cycloalkenyl; C4-C8 cycloalkylalkyl;
phenyl-Cl-C3 alkyl; furyl; naphthyl; thienyl;
-o-R4; -S-R ; -So-R4; -So2-R4~ or .
..

... : , -~:

~75~'36 \~ = aX R5 R4 is Cl-C3 alkyl; Cl-C3 alkyl substituted with halo; C2-C3 alkenyl; C2-C3 alkenyl substituted with halo; benzyl; phenyl; or phenyl substituted with halo, Cl-C3 al]cyl : :
or Cl-C3 alkoxy;
the RS groups independently are halo;
Cl-C8 alkyl; C1-C8 alkyl substituted with ~:~
halo; Cl-C8 alkyl monosubstituted with phenyl, .
cyano or Cl-C3 alkoxy; C2-C8 alkenyl, C2-C8 alkenyl substituted with halo; C2-C8 ~ :;
alkynyl; C2-C8 alkynyl substituted with halo, C3-C6 cycloalkyl; C4-C6 cycloalkenyl; C4-C
: cycloalkylalkyl; Cl-C3 alkanoyloxy; C1-C3 alkylsulfonyloxy; phenyl; phenyl mono- :~
substituted with halo, Cl-C3 alkyl, Cl~C
alkoxy or nitro; nitro; cyano; carboxy;
hydroxy; Cl-C3 alkoxycarbonyl; -o-R6;
-S-R6; -SO-R6; or -SO2-R6; : .
. 1 12 lkyl; Cl C12 alkyl sub stituted with halo; Cl-C12 alkyl mono-substituted wi~h phenyl, cyano or Cl-C3 alkoxy; phenyl; phenyl monosubstituted with halo, Cl-C3 alkyl, Cl-C3 alkoxy or nitro; C3-C6 cycloalkyl; C4-C8 cyclo-alkylalkyl; C2-C~2 alkenyl; C2-C12 ' ~C~7~6~6 alkenyl substituted with halo; C2-C12 alkynyl; or C2~C12 alkynyl substituted with halo; provided that R6 comprises no more than 12 carbon atoms;
m and n independently are 0, 1 or 2; provided that when X is oxygen, R is methyl, and R2 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

7 ~_~0 ¢ ~Rp R
- `. .
wherein: X is oxygen or sulfur; ;
R is Cl-C3 alkyl; C2-C3 alkenyl; acetoxy;
20or methoxy;
q and p independently are 0, 1 or 2;
the R7 groups independently are halo; Cl-C3 alkyl; trifluoromethyl; or Cl-C3 alkoxy;
the R8 groups independently are halo; Cl-C
alkyl; trifluoromethyl; or Cl-C3 alkoxy; or two R8 groups occupying adjacent o and _ positions combine with the phenyl ring to which they are attached to form a l-naphthyl group.
~ Another preferred group of compounds are of the 30 formula , ;

~7569~

-D/ \~__R2 III

N
R

wherein the various symbols are defined as before. The most highly preferred compounds are those of formula III
wherein R is trifluoromethyl.
In the above formulae, the general chemical terms are used in their normal meanings. For example, the terms Cl-C3 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, Cl-C3 alkoxy, Cl-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, Cl-C6 alkyl, C2-C6 alkenyl and C2-C6 alkynyl refer to such groups as methyl, ethyl, isopropyl, vinyl, allyl, methoxy, isopropoxy, propargyl, isobutyl, hexyl, octyl, l,l-dimethylpentyl, 2-octenyl, pentyl, 3-hexynyl, 1-ethyl-2-hexenyl, 3-octynyl, ;
5-heptenyl, 1-propyl-3-butynyl and crotyl.
The terms C3-C6 cycloalkyl and C4-C6 cycloalkenyl refer to such groups as cyclopropyl, cyclobutyl, cyclohexyl, cyclobutenyl, cyclopentenyl and cyclohexadienyl.
The term C4-C8 cycloalkylalkyl refers to such groups as cyclopropylmethyl, cyclobutylmethyl, cyclohexyl~
methyl and cyclohexylethyl.
The term Cl-C3 alkanoyloxy refers to groups such as formyloxy, acetoxy and propionyloxy.
The term Cl-C3 alkoxycarbonyl refers to groups such as methoxycarbonyl, ethoxycarbonyl and isopropoxy-carbonyl.

' X~4097A ~ -7_ , ', ~ .

.. .. . ... . .

1~756~

The term Cl-C3 alkylsulfonyloxy refers to such groups 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 hydroiodides, hydrobromides, hydrochlorides and hydrofl~orides. Salts of the sulfonic acids are also particularly desirable. Such salts include sulfonates, methylsulfonates and toluenesulfonates.
Although the above general description of the compounds is believed to describe them unambiguousIy, a group of exemplary compounds of formula I will be named below to assure that the invention is understood by those skilled in the art. Additional novel and useful compounds generally falling within the scope of formula I are described and claimed in copending Canadian application Serial No. 305,980, filed June 22, 1978.
l~methyl-3,5-bis(3-methoxyphenyl)-4tlH~-pyridinethione l-ethyl-3-~4-ethoxyphenyl)-5--phenyl 4(1~)-pyridinethione 3-(3,5-diiodophenyl) 5-(3-propylphenyl)-1-propyl-4(lH)-pyridinethione 3-(2,6-dimethylphenyl)~l isopropyl-5-(1-naphthyl) -4(lH)-pyridone 3-(4-methylphenyl)-5-phenyl-1-vinyl-4(1H)-pyridone, hydroiodide 1-allyl-3-(3-chlorophenyl)-5 (2,3-diethoxyphenyl) -4(lH)-pyridinethione 3,5-diphenyl-1-ethyl-4(lH)-pyridinethione 3-(3/5-difluorophenyl3-1-methoxy-5-phenyl-,f ... ,. , .. ~ . .

~L~7S6~ ;

4(lH)-pyridone l-acetoxy-3-(3,5-diethylphenyl)--5-(2,4-diethyl-phenyl)-4(lH)-pyridinethione l-allyl-3-(1-naphthyl)-5-(4-propoxyphenyl)~4(lH)-pyridinethione l-propyl-3-(4-trifluoromethylphenyl)-5-(3-trifluoromethylphenyl)-4(1H)-pyridone 3-(2,6-difluorophenyl)-5-(3-iodophenyl)~
vinyl-4(lH)-pyridone 3-(3,5-dibromophenyl)-5-(3-isopropoxyphenyl)-1- :
propyl-4(lH)-pyridone ::
l-methyl-3-phenyl-S-(2-propylphenyl)-4(lH)-pyridinethione, hydrochloride 3-(3-bromophenyl)-1-methyl-5-phenyl-4(1~
pyridone .
3-(4-chlorophenyl)-5-(2,4-dimethoxyphenyl)--1-propyl-4(lH)-pyridone .
l-allyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridinethione 1-acetoxy-3,5-diphenyl-4(lH)-pyridinethione -3-(2-iodophenyl)-5-(3-isopropylphenyl)-1-methoxy-4(1H)-pyridinethione 3-(2-iodo~4-methylphenyl)-5-phenyl-1-vinyl-4(lH)-pyridinethione l-acetoxy-3-(4-chlorophenyl)-5-(1-naphthyl)-4tlH)-pyridone 3,5-diphenyl-1-isopropyl-4(lH)-pyridinethione 3-(3-bromo-5-ethylph~nyl)-5-(3-methylphenyl~-l-propyl-4(1H)-pyridinethione ..
', ' ~

: . ...
. :.

.. ..

~7~ 96 3-(4-ethoxy-2-fluorophenyl)-1-methoxy-5-phenyl-4(1H)-pyrldone l-allyl-3,5-bis(3-ethyl-4-methoxyphenyl)-4(1H)-pyridone 3-(2-iodo-4-propylphenyl)-1-methyl-5-~4-trifluoro-methylphenyl)-4(lH)-pyridinethion~
l-methyl-3-(3-methyl-5-propylphenyl)-5-phenyl-4(lH)-pyridinethione 3-(2-chloro-4-iodophenyl)-5-(3-fluorophenyl)-1-propyl-4(lH)-pyridinethione 3-(3-chlorophenyl)-5-[2,4-bis(trifluoromethyl)-phenyl]-l-methoxy-4(lH)-pyridone 3-benzyloxy-1-chloromethyl-5-(3-ethynylphenyl)-4(lH)-pyridone 3-benzylthio-1-(2-bromoethyl)-5-(2,4-dimethyl-phenyl)-4(lH)-pyridone 3-benzylsulfinyl-1-ethyl-5-(3-fluoro-5-propyl-phenyl)-4(lH)-pyridone 3-benzylsulfonyl-5-~3-octyIphenyl)-l-propyl~
4(lH)-pyridone 3-(2-butylphenyl)-1-trifluoromethyl-4(lH)-pyridone, hydrobromide 1-(2-chloroethyl)-3-cyano-5-phenyl-4~1H)-pyridine~
thione 3-(3-hexylphenyl~ methyl-5-(2-methylphenyl)-4(1H)-pyridone ' 1-~3,3-dibromopropyl)-3-~2,4-dichlorophenyl)-5-methyl-4(lH)-pyridone 3-(2,4-dimethylphenyl)-5-methoxycarbonyl-1- -~
: 30 methyl-4(lH)-pyridone - ,, .~ ' ~ . ~ , : , . , ., : . . : : . .

~7~696 l-m~thyl-3-13-(1-propylpentyl)phenyl]-5-propyl-4(111)-pyridon~
1-(2-cyanoethyl) 3-(3-octyl-4-methylphenyl)-5-propoxycarbonyl-4(lH)-pyridone 3-[3-(2-ethylpentyl)phenyl]-1-carboxymethyl-5-(3-trifluoromethylphenyl)-4(lE~j-pyridone 3-(2-chloromethylphenyl)-1-methoxycarbonylmethyl-4(lH)-pyridone 3,5-diphenyl-1-ethynyl-4(lH)-pyridinethione 3-(4-heptafluoropropylphenyl)-5-hexyl-1-methyl-4(lH)-pyridinethione :
3-(3,5-diethylphenyl)-1-propargyl-5-[3-(5,5-dibromopentyl)phenyl]-4(lH)-pyridone 3-(2,4-dipropylphenyl)-1-methyl-5-triEluoro-methyl-4(lH)-pyridone ~:
3-(4-benzylphenyl)-1-ethoxy-5-(2-fluoroethyl)-4(lH)-pyridone 3-(2-chloroethy~)-5-[4-(2,2-diiodooctyl)phenyl]- -l-methoxy-4(lH)-pyridinethione 3-(3-chloro-2-methoxyphenyl)-5-(1,1-dibromo-pentyl)-l-methyl-4(lH)-pyridone 3-(6-iodohexyl)-1-isopropoxy-5-phenyl-4(1H)-pyridinethione 3-(3-hexylphenylj-5-methoxymethyl-1-methyl-4(lH)-pyridone l-dimethylamino-3,5-bis(3-tri~luoromethylphenyl)- -:
4(lHj-pyridinethione ~ -l-methyl-3-[4-(4-phenylhexyl)phenyl]-5-(3-propylphenyl)-4(lH)-pyri.done , , . ~. . .

1~756g6 1-(2-chloroethyl)-3-[4-(2-cyanoethyl)phenyl]-4(1H)-pyridinethione l-methyl-3-(2-propoxyethyl)-5-phenyl-4(lH)-pyridinethione, hydrofluoride 3-(6-ethoxyhexyl)-5-(3-ethyl-5-iodophenyl)-1-(3-iodopropyl) 4(lH)-pyridone l-methyl-3-phenyl-5-vinyl-4(lH)-pyridinethione 3-allyl-5-[4-t3-cyanohexyl)phenyl]-1-propoxy-4(lH)-pyridinethione 103-[4-(8-cyanooctyl~phenyl] 1-methyl-5-~2-pen-tenyl)-4(lH)-pyridone 3-(3-hexenyl)-5-[2-(2-methoxyethyl)phenyl]-1-methyl-4(lH)-pyridinethione 3-(2,2-dichlorovinyl)-1-methyl-5-[3-(3-propoxy-heptyl)phenyl]-4(lH)-pyridone 3-(2-bromo-1-butenyl)-5-13-(6-ethoxyheptyl)-phenyl]-l-ethoxy-4(lH)-pyridone .
3-(2-iodo-1-hexenyl)-1-methyl-5-(3-vinylphenyl)-4(lH)-pyridinethione 203-(4-allylphenyl)-1-dimethylamino-5-phenyl 4(lH)-pyridinethione 3-(2-methoxyallyl)-1-methyl-5-(4-trifluoromethyl-phenyl)-4(lH)-pyridinethione : ~:
3-(4-etlloxy-2-pentenyl)-5-[2-(2,4-hexadienyl)- . .
phenyl]-l-methoxy-4(lH)-pyridone . : :
: l-methoxycarbonylmethyl-3-[3-(3-octenyl)phenyl]-5-phenyl-4(lH)-pyridone, methanesulfonate 3-[3-(2-hexenyl)phenyll-1-methyl-5-(3-propyl-phenyl)-4(1H)-pyridinethione ' 3-(2-ethyl-3-~luorophenyl)-5-ethynyl-1-methyl-4(llI)-pyridinethione 3-(2-butynyl)-5-(2,4-diiodophenyl)-1-ethoxy-4(lH)-pyridone 3-[~-(2,6-dibromo-2-heptenyl)phenyl]-1,5-di-methyl-4(lH)-pyridone 3-(2-hexenyl)-1-methyl-5-[3-(1,1,2,2-tetrachloro-4-octenyl)phenyl]-4(lH)-pyridone 3-cyclopropyl-5-[2-(2-fluoro-1-pentenyl)phenyl~-1-methoxy-4(lH)-pyridinethione 3-cyclobutyl-5-[4-(2-iodovinyl)phenyl]-1-propoxy-4(lH)-pyridone 3-cyclohexyl-5-(3-ethynylphenyl)-1-iodomethyl-4tlH)-pyridinethione .
l-(l-carboxyethyl)-3-(2-chlorocyclopropyl~-~5- .
[3-(3-chloropropargyl)phenyl]-4(lH)-pyridone 3-(2,2-dibromocyclohexyl)-1-methyl-5-12-(3-pentynyl)phenyl-4~lH)-pyridinethione :
3-[4-(1,1-dibromo-4-pentynyl)phenyl]-1-isopro- .~
20 poxy-5-(2-methylcyclobutyl)-4(lH)-pyridone : -3-(2,4-diiodocyclopentyl)-1-ethyl-5-[4-(2-octynyl)phenyl]-4(lH)-pyridone l-acetoxy-3-(4-propylcyclohexyl~-5-[3-(6,6,6-trifluoro-2-hexynyl)phenyl]-4(lH)-pyr.idinethione ~ 3-[3-(4-octynyl)phenyl]-5-(2-methoxycyclopropyl)~
l-methyl-4(lH)-pyridinethione -~:
3-[Z-(l,l-dichloro-4-heptynyl)phenyl]-5-(4- ::
methoxycyclohexyl)-l-methoxy-4(lH)-pyridone 3-(4-cyclopropylphenyl)-1-(2-methoxycarbonyl-methyl)-5-(2-propoxycyclobutyl)-4(lH)-pyridinethione ' .

.

569~ii 3-(2-cyclobutenyl)-5-(3-cyclopentylphenyl)-1-ethoxy-4(lH)-pyridinethione 3-(3-cyclohexenyl) 5-(3-cyclohexylphenyl)~l-dimethyl~mino-4(lH)-pyridone 3-14-(1-cyclobutenyl)phenyl]~5--methoxy-1-vinyl-4(lH)-pyridone, toluenesulfonate 3-chloromethoxy-1-cyanomethyl-5-(2-formyloxy-phenyl)-4(lH)-pyridinethione 1-(2-carboxyethyl)-3-(3-propionyloxyphenyl)-5-trifluoromethoxy-4(1H)-pyridinethione 3-l4-(2-cyclohexenyl)phenyl~-5-isopropoxy-1-trifluoromethyl-4(lH)-pyridone 3-(1,2-dibromopropoxy)-1-ethoxy-5-(2-methyl-sulfonyloxyphenyl)-4(lH)-pyridinethione l-dichloromethyl-3-(2-iodoethoxy)-5-(4-isopropyl~
sulfonyloxyphenyl)-4(1H)-pyridone 3-(3-biphenylyl)-1-methyl-5-vinyloxy-4(lH)-- :
pyridinethione ::
3-allyloxy-5-[4-(2-chlorophenyl)phenyl]-1-20 isopropyl-4(1H)-pyridone, hydrochloride -;
3-(2,2-dichlorovinyloxy)-5-[2-(3-iodophenyl)~
phenyl]-l-methyl-4(lH)-pyridone i~
3-(2-bromoallyloxy)-5-[3-(3-bromophenyl)phenyl]-l-vinyl-4(lH)-pyridone l-allyl-3-[4-(2-methylphenyl)phenyl]-5-(3,3,3-trifluoro-l-propenyloxy)-4(lH)-pyridone : l-methoxy-3~phenoxy-5-[3-(4-propylphenyl)phenyl]- ..
4(lH)-pyridone 3-~2-chlorophenoxy)-5-~4-methoxyphenyl)phenyl]~

3~ l~propargyI-4(1H)-pyridone : X-4097A -14-' ..
' :
, ~ . ~ .: . . . ::

` ~75696 3-(4-bromophenoxy)-5-[4-(2-ethoxyphenyl)phenyl]-l-ethyl-4(lH)-pyridone 3-(2-iodophenoxy)-5-[3-(4-isopropoxyphenyl)-phenyl]-l-methoxycarbonylmethyl-4(lH)-pyridone 1-cyanomethyl-3-(2-methylphenoxy)-5-[3-(4-nitro-phenyl)phenyl]-4(lH)-pyridinethione l-methyl-3-(4-nitrophenyl)-5-(3-propylphenoxy~-4(lH)-pyridone 3-(4-cyanophenyl)-1-ethoxy-5-(2-methoxyphenoxy)-4(lH)-pyridone 3-(3-carboxyphenyl)-5-(2-ethoxyphenoxy)-1-isopropyl-4(lH)-pyridone, hydrofluoride :
1-(2-carboxyethyl)-3-(4-hydroxyphenyl)-5-(3~ .
propoxyphenoxy) 4(lH)-pyridone 3-benzyl-5-(2-methoxycarbonylphenyl)~
methyl-4(lH)-pyridone l-dimethylamino-3-(3-phenylpropyl)-5-(4-propoxy-carbonylphenyl)-4tlH)-pyridone 3-(3-butoxyphenyl)-5-(2-furyl)-1-trifluoromethyl-20 4(lH)-pyridone :~; :
3-(1-ethylpentyl)-5-(3-furyl)-1-methyl-4(lH)~
pyridone 3-[4-(2-propylhexyloxy)phenyl]-1-methoxycarbonyl- ;:
methyl-5-(2-thienyl)-4(lH)-pyridone ::
l-methyl-3-(4-nonyloxyphenyl)-5-(3-thienyl)- ~:
4(lH) pyridinethione l-methyl-3-[4-(2-propylnonyloxy)phenyl]-5-(4-trifluoromethylphenyl)-4(1~)-pyridinethione 3-(3,5-diethylphenyl~-1-ethyl-5-(4-trifluoro-30 methoxyphenyl)-4(1H)-pyridinethione ~;

s~

3-(2,4-divinylphenyl)-5-[4-(2-~luoroetho~y)-phenyl]-1-isopropoxy-4(1~1)-pyridinethione 3-[3-(5,5-dibromopentoxy)phenyl]-5-(3,5-dicyclo-propylphenyl)-l-ethyl~4(lH)-pyridone 3-(2,4-dimethoxyphenyl)-1-(2-methoxycarbonyl-methyl)-5-[2-(12-iodododecyloxy)phenyl]-4(lH)-pyridinethione 3 (4-benzyloxyphenyl)-1-cyanomethyl-5-[3,5-di-(isopropenyl)phenyl]-4(lH)-pyridinethione 3-(2,6-dinitrophenyl)-1-methoxy-5-[5-phenyl- : :
10 pentoxy)phenyl]-4(lH)-pyridone -:
3-(2,4-diformyloxyphenyl)-1-ethoxy-5-[4-(3-phenylhe~yloxy~phenyl]-4(1H) pyridinethione 3-[4-(3-cyanopropoxy)phenyl]-5-(3-ethoxy-5-iodophenyl)-l-methyl-4(lH)-pyridinethione 3-[4-(7-cyanoheptyloxy)phenyl]-1-ethyl-5-phenyl-4(1H)-pyridinethione 3-[3-(4-cyanoundecyloxy)phenyl]-5-[2,4-di(2-ethoxyethyl)phenyl]-l-methoxy-4(lH)-pyridinethione 3-[2-(2-ethoxyethoxy)phenyl]-1-(2-iodoe~hyl)-5-(3,4-diacetoxyphenyl~-4(lH)-pyridinethione 3-(4-butoxy-2-difluoromethylphenyl)-1-cyano-methyl-5-[3-(6-methoxyhexyloxy)phenyl]-4(lH)-pyridone 3-(2-cyclohexyl-4-ethylphenyl)-1-methoxycarbonyl-methyl-5-[2-16-propoxynonyloxy)phenyl]-4(lH)-pyridone : :
3-~2,4-di~2-pentynyl3phenyl]-1-isopropoxy-5-(2-vinyloxyphenyl)-4(lH)-pyridinethione 3-(2,4-diallyloxyphenyl)-1-(2,2-dichloropropyl)-5-(2-methyl-6-nitrophenyl?-4(lH)-pyridone 3-13-(2,4-hexadienyloxy)phenyl]-1-isopropyl-5-phenyl-4(lH)-pyridinethione, hydroiodide X-409~A -16-~75~9~

l-(2-carboxyethyl)-3-(2,6-d`ipropylphenyl)-5-[4-(5-dodecenyloxy)phenyl~-~(lH)-pyridinethione 3-[2-(2-chloroallyloxy)phenyl]-l-(2,2-dichloro-ethyl)-5-(2,~-diethoxyphenyl)-4(l~)-pyridinethione l-allyl-3-(4-cyano-3-e~hoxycarbonylphenyl)-5-[4-(4,4,4-tri~luoro-2-butenyloxy)phenyl]-4~l~)-pyridone l-chloromethyl-3-(3-methylsulfonyloxy-5-vinyl-phenyl)-5-[3-(2,2-dibromo-3-hep~enyloxy)phenyl]-~(lH)- :
. : .
pyridinethione ,~'.
l-ethoxy-3-[3-~9-iodo-l-nonenyloxy)phenyl]-5-phenyl-4(lH)-pyridone ,~
l-chlorodifluoromethyl-3-[2,4-di(,chloromethyl)-phenyl]-5-[2-(l,2,3-trichloro-6-dodecenyloxy)phenyl]-4(lH)-pyridinethione ' 3-[3-(4-chloro-2-butynyloxy)phenyl]-l-ethoxy-5-(3-fluoro-4-isobutoxyphenyl)-4(,lH)-pyridone 3-[3-~6,6-dibromo-3-(hexynyloxy)phenyl]-l-methyl-5-(3-nitro-4-propylphenyl)-4(,lH)-pyridinethione :
l-acetoxy-3-(2,4-dibromophenyl)-5-[3-(l,l,2,2- ,:
tetrafluoro-3-decynyloxy)phenyl]-4(lH)-pyridone 3-(3-ethynyloxyphenyl)-l-methyl-5-phenyl-4(lH)- ' pyridinethione, hydrobromide 3-[2-(10-dodecynyloxy~phenyl]-l-methyI-5-(2-propyl-4-propylsulfonyloxyphenyl)-4(lH)-pyridone 3-~2,4-di(3-pentenyl)phenyl]-5-(3-phenoxyphenyl)-l-~l,l,2,2-tetrafluoroethyl~-4(l~)-pyridone 3-~4-(4-fluorophenoxy)phenyl]-l-isopropyl-5-phenyl~4(lH)-pyridinethione :

X-4097A -17- :
.

.

~L~75696 1-(3~chloropropyl)-3-(3-cyanomethyl-5-ethyl-phenyl)-5-13-(3-iodophenoxy)phenyl]-4(lH)-pyridone 3-~3-octyl-5-fluorophenyl~-5-[2-(3-ethylphenoxy)- :
phenyl]-l-trifluoromethyl-4(1H)-pyridone 3-(2-ethyl-4-propylsulfonyloxyphenyl)-1 ethynyl-5-[2-(4-isopropylphenoxy)phenyl~-4(1H)-pyridone l-carboxymethyl-3-(2,4-dinonyloxyphenyl)-5-[3-(4-methoxyphenoxy)phenyl~-4(lH)-pyridone l-chloromethyl-3-(2,4-difluorophenyl)-5-[2-(3-propoxyphenoxy)phenyl]-4(lH)-pyridinethione l-methyl-3-[4-(2-nitrophenoxy)phenyl]-5-phenyl- :
4(lH)-pyridinethione 3-(3-isobutylthiophenyl)-1-isopropyl-5-phenyl-4(lH)-pyridinethione 3-(3-chloro-4-heptylthiophenyl)-5-[3-(4-cyano-pentyl)phenyl]-l-methyl-4(1H)-pyridone l-methyl-3-phenyl-5-[2-(3-ethylhexylthio)phenyl]-4(lH)-pyridone, hydrofluoride ~ :
3-(2-chloro-4-ethylphenyl)-1-ethyl-5-(3-nonyl-thio-4-vinylphenyl)-4(lH)-pyridone l-ethynyl-3-phenyl-5-E3-(2-ethylpentylthio~-phenyl~-4(lH)-pyridone ~;
1-(2-methoxycarbonylmethyl)-3-[4-(3-iodophenyl)-phenyll-5-(3-trifluoromethylthiophenyl)-4(lH)-pyridinethione ~ ~
. l-acPtoxy-3-(3-cyclopentylphenyl~-5-E3-(2- -1uoroethylthio)phenyl]-4(1H)-pyridinethione 3-(2-cyano-4-hydroxyphenyl)-1-dimethylamino-5 ~3-~5,5-dlbromopentylthio)-4-nitrophenyl]-4(1H)-pyridone :

.
.: :

.

~756g~

3-~4-(4,4-diiodododecylthio)phenyl)-1-methyl-5-phenyl-4(lH)-pyridone ' 3-(3-benzylthio-5-ethynylphenyl)-1-cyanomethyl-5-(2-hexylphenyl)-4(lH)-pyridinethione 3-[3,5-bis(4-phenylbutylthio)phenyl]-5-(2-methylphenyl)-l-(1,1,2,2-tetrafluoroethy:L~-4(lH)-pyridone 3-[2-bromo-4-(6-phenylhexylthio)phenyl]-5-[4-(2-cyanopropylthio)-2-ethylphenyl]-1-methyl-4(1H)-pyridine-thione 3-[4-(6-cyanoheptylthio)phenyl]-1-fluoromethyl-4(lH)-pyridone 3-(3-acetoxy-5-ethylphenyl)-5 [2-(8-cyanoundecyl- :
thio)phenyl]-l-chlorodifluoromethyl-4(lH)-pyridone 3-(~-benzyl-2-ethoxyethoxyphenyl)-1-(2-carboxy-ethyl)-5-[3-(2-ethoxyethoxy)-5-propargylphenyl]-4(1H)-pyridone, toluenesulfonate 1-ethyl-3-14-(6-methoxyhexylthio)phenyl]-5-phenyl-4(lH)-pyridinethione l~isopropenyl-3-[3-(3-phenylpentyl)phenyl]-5-[4-(6-isopropoxynonylthio)phenyl]-4(lH)-pyridone 3-(2-cyanomethyl-4-vinylthiophenyl)-1-ethyl-5-[2-(7-phenylheptyl~phenyl]-4(lH)-pyridone 3-(3-a~lylthio-4-methoxymethylphenyl)-5-[2-(6-cyanohexyl)-4 vinylphenyl]-1-methyl-4(1H)-pyridone l~methoxycarbonylmethyl-3-[3-(2-pentenylthio)-phenyl]-5-phenyl-4(lH)-pyridinethione 3-~3-(2-decenylthio)-5-~2,4-hexadienyl)phenyl]-1-ethoxy-5-phenyl-4(lH)-py~idone ', ,~

X-4097A ~ -19-.:
- , . . , :

756~6 3-[4~ ~dichloroallylthio)phenyll 5-l3-(4-octenyl)-2-propylphenyl]-1-trifluoromethyl-4~1~l) pyridone 3-(4-carboxy-2-hydroxyphenyl)-5-[3-(2-chloro-3-butenylthio)-5-nitrophenyl]-1-vinyl-4(1H)-pyridone 3-[4-(5,5-dibromo-3-heptenylthio)phenyl]-1-methyl-5-phenyl-4(lH)-pyridone 3,5-bis[4-(9-iodo-8-nonenylthio)phenyl~-1-isopropyl-4(lH)-pyridinethione l-ethyl-3-(3-fluorophenyl)-5-[4-(12,12,12-tri-. 10 chloro-2,6-dodecadienylthio)phenyl]-4(lH)-pyridinethione 3-[2-(1-chloropropargylthio)phenyl]-1-dimethyl- : ~ :
amino-5- E3- (4-pentenyl)-5-methoxycarbonylphenyl]-4(1H)-pyridone 3-14-(3,3-dibromo-5-hexynylthio)phenyl]-1-methoxy-5-phenyl-4(lH)-pyridone 1-(2-chloropropyl)-3-[2-cyclopropyl-4-(1,1,2,2-tetrafluoro-5-decynylthio)phenyl]-5-phenyl-4(lH)-pyridine-thione :
l-acetoxy-3-(3-ethynylthiophenyl)-5-(3-ethynyl- .
5-fluorophenyl)-4(lH)-pyridone 3-14-(4-decynylthio)-2-methylphenyl]-1-ethoxy- :
5-(5-fluoro-3-trifluoromethylphenyl)-4(lH)-pyridinethione ~
l-cyanomethyl-3-(4-phenylthiophenyl)-5-phenyl- : .
4(1H)-pyridinethione, hydrochloride :.
3-(3-chlorophenyl)-5-12~(3-fluorophenylthio)-phenyl]-l-methyl-4(lH)-pyridone : : .
carboxymethyl-3-[3-(2-iodophenylthio)phenyl]-` 5-(3-methyl-5-methoxycarbo~ylphenyl)-4~lH)-pyridone ~ :

: 1-(2-chloroethyl~-3-(2,4-diethylphenyl)-5- -:
[4-(4-ethylphenylthio~-2-methoxyphenyl]-4(1H)-pyridone :~
: X-4097A ; ` . -20-: ' , . ~: .
: .
: ~

... . . , . - , ,,, .. ,. ,." . .... .. . . .. . . . . . . ....

9~ii 3-~3-(3-isopropylphenylthio)phenyl]-5-phenyl-1-trifluoromethyl-4(lH)-pyridone l-acetoxy-3-(4-butylphenyl)-5~[4-(3-methoxy-phenylthio)phenyl]- 4(lH)-pyridinethione 3-(2-methyl-6-propoxyphenyl)-3-[4-(3-propoxy-phenylthio)phenyl]-l-propargyl-4(1H)-pyr:idone 3-[3-chloro-5-(4-nitrophenylthio)phenyl]-1-methyl-5-(2,4-divinylphenyl)-4(lH)-pyridone 3-(4-butylsulfinylphenyl)-5-phenyl-1-propargyl-4(lH)-pyridone l-ethyl-3-(3-heptylsulfinylphenyl)-5-(4-propoxy-carbonylphenyl)-4(lH)-pyridone 3-(2-carboxyphenyl)-1-dimethylamino-5-[2-hydroxy-4-(2-propylpentylsulfinyl)phenyl]-4(lH)-pyridinethione l-acetoxy-3-(2-cyano-5-nonylsulfinylphenyl) 5-(3,5-dinitrophenyl)-4(lH)-pyridinethione l-ethoxy-3-[3-(4-propylnonylsulfinyl)phenyll-5-phenyl-4(lH)-pyridone l-methoxy-3-(2-nitrophenyl?-5-(4-trifluoromethyl-sulfinylphenyl)-4(lH)-pyridinethione 3-(2-ethoxyphenyl)-1-isopropyl-5-14-(2-fluoro-ethylsulfinyl)-2-isopropylphenyl~-4(lH)-pyridone 3-13,5-di(4-chlorophenyl)phenyl]-3-14~(5,5- :
dibromopentylsulfinyl-2-ethoxyphenyl]-1-ethynyl-4(lH)~
pyridone `~
3-[3-(12-iodododecylsulfinyl)phenyll-5-phenyl-l-propargyl-4~lH)-pyridone, hydroiodide ~:
3-(4-benæylsulfinylphenyl~-5-(3-biphenylyl)-1-isopropenyl-4(1H?-pyridone . ` , -- 1~7Si~9~i 3-[3,5-di(methylsulfonyloxy)phenyl]-5-[3-(5-phenylpentylsulfinyl)phenyl]-l-vinyl-4(1H)-pyridone 3-[2-(3-cyanopropylsulfinyl)phenyl]-1-methoxy-carbonylmethyl-5-phenyl-4(lH)-pyridineth:ione 3-(3-acetoxyphenyl)-5-[2-(7-cyanoheptylsulfinyl)-phenyl]-l-methoxycarbonylmethyl 4(1H)-pyridone 1-(2-carboxyethyl)-3-[3-(3-cyc:Lohexenyl)-5-(3-cyanoundecenylsulfinyl)phenyl]-4(lH)-pyridone 3-(2-chloro-4-cyclohexylphenylj-5-[3-chloro-5-(2-ethoxyethylsulfinyl)phenyl]-1-(2-cyanoethyl)-4(1H)-pyridinethione 1-(2-chloroethyl)-3-[4-(6-methoxyhexylsulfinyl)-phenyl]-4(1H)-pyridone 3-(4 cyclopropylphenyl)-1-iodomethyl-5-[3-(6-propoxynonylsulfinyl)phenyl~-4(lH)-pyridone 3-E3-(2-chloro-~-undecynylsulfinyl)phenyl~
(2,2-dibromoethyl)-5-t2-ethyl-5-vinylsulfinylphenyl)-4(lH)-pyridinethione - :
3-[3,5-di(allylsulfinyl)phenyl]-5-phenyl-1- : :
propyl-4(lH)-pyridone, hydrofluQride 3-[3-(2,4-hexadienylsulfinyl)phenyl]-1-methyl-5-phenyl-4(lH)-pyridinethione ~
l-dimethylamino-3-[2-(5-dodecenylsulfinyllphenyl]- -5-(3-isobutylphenyl~-4(lH)-pyridone l-acetoxy-3-[4-(2-bromoallylsulfinyl?phenyl]-5-(2,4 dimethylphenyl)-4(lH)-pyridinethione l-ethoxy-3-(3-iodo-4-pentylphenyl~-5-~3-~3,3,4,4- ~:
tetrafluoro-1-butenylsulfinyl)-5-hexylphenyl]-4(1H)-pyridone ': ~ ' - . . . . . . . . . . .. ..
' ' . ' : . ' ,: , . . .

11 ~)756~6 l-isopropoxy-3-phenyl-5-[4-(1,1,2-trichloro-3-heptenylsulfinyl)phenyl]-4(lH)~pyridinethione 3-~4-t9-bromo-4-nonenylsulfinyl)phenyll-5-[2-(3-ethylhexyl)phenyl]-1-ethynyl-4(1H)-pyridinethione 3-[2,4-di(chlorodifluoromethyl)phenyl]-1-propargyl-5-[3-(1,2,3-triiodo-6-dodecenylsulfinyl)phenyl]-4(lH)-pyridone 3-[3-(4-bromo-2-butynylsulfinyl)-5-methylphenyl]-5-[2-iodo-3-(1,2,3-trichloropentyl)phenyl]-1-vinyl-4(lH)-pyridone l-allyl-3-~2-(2,2-dibromo-4-hexynylsulfinyl)-phenyl]-5-phenyl-4(lH)-pyridone l-methoxycarbonylmethyl-3-[3-ethyl-5-(9,9,10,10-tetrafluoro-2-decynylsulfinyl)phenyl]-5-phenyl-4(lH)-pyridinethione 3-(4-benzyl-2-bromophenyl)-1-(2-carboxyethyl)-5-[3 (1-chlorobutyl)-~5-(6-dodecynylsulfinyl)phenyl]-4(lH)- .
pyridone 1-~2-cyanoethyl)-3-(4-phenylsulfinylphenyl)-5-phenyl-4(lH)-pyridinethione l-cyanomethyl-3-[4-(3-fluorophenylsulfinyl)phenyl]-5-[3-~4-octenyl)phenyl]-4(lH)-pyridone l-chloromethyl-3-[3-(1,1-dichloro-4-octenyl)-4-nitrophenyl~-5-[3-(2-iodophenylsulfinyl)phenyl]-4(lH)-pyridone 3-[3-(2-chlorovinyl)-5-(4-methylphenylsulfinyl~-phenyl]-l-ethoxy-5-~3-(8-iodo-4-octenyl)phenyl~-4(lH)-pyridone :

3-[4-(3-isopropylphenylsuIfinyl)phenyl]-5-phenyl-1-propyl-4(1H)-pyridone X-4097~ -23-' ~L~756~6 3-[3-(2-ethoxyphenylsulfinyl)phenyl]-l--methyl-5-[4-(2-propoxyphenoxy)phenyl]-4(lH)-pyr:idone 3-[4-(2,4-cyclohexadienyl)-3-f:Luorophenyl]-l-ethyl-5-[3-hydroxy-5-(3-nitrophenylsulfinyl)phenyl]-4(lH)-pyridinethione l-methyl-3-(4-methylsulfonylphenyl)-5-phenyl-4(lH)-pyridinethione l-ethyl-3-(3-hexylsulfonylphenyl)-5-(4-hydroxy~
phenyl)-4(lH)-pyridone 3-(2-carboxy-4-ethylphenyl)-l-dimethylamino-5-[4-(3-ethylheptylsulfonyl)phenyl]-4(lH)-pyridone ~-l-acetoxy-3-(2-hexyl-5-~luorophenyl)-5-(3-nitro-5-nonylsulfonylphenyl)-4(lH)-pyridone ~ :
3-phenyl-l-propoxy-5-[2-(3-propylnonylsulfonyl)-phenyl]-4(lH)-pyridone l-ethoxy-3-phenyl-5-(3-trifluoromethyl-5-tri- ~:
fluoromethylsulfonylphenyl)-4(lH)-pyridone 3-[4-(2-chloroethylsulfonyl)phenyl]-5-(3-fluoro 4-octylphenyl)-1-methoxy-4(lH)-pyridinethione 3-(3-bromo-5-nitrophenyl)-l-ethynyl-5-[4-cyano-2-(6,6-dibromohexylsulfonyl)phenyl]-4(lH)-pyridone 3-[3-(4,4-diiodododecylsulfonyl)phenyl~-5-(2- ~:~
naphthyl)-l-(l-propynyl)-4(lH)-pyridone 3-(4-benzylsulfonylphenyl)-5-~3-(2-ethoxy-phenyl)phenyl]-l-isopropenyl-4(lH~-pyridinethione 3-[5-chloromethyl-4-(2-propylphenyl)phenyl]-l- :
vinyl-5-~4-(3-phenylbutylsul~onyl)phenyl]-4(lH~-pyridone 3-~3-(3-cyanopropylsulfonyl)phenyl]-l-methoxy-carbonylmethyI-5-phenyl-4(lH)-pyridone '., .' .

.: . - : :

~L~7~i6~6 1-(2-carboxyethyl)-3-[4-(7-cyanoheptylsulfonyl)-phenyl]-5-[3-(4-chlorophenyl)phenyl]-4(1H)-pyridone l-cyanomethyl-3-[3-(11-cyanoundecylsulfonyl)-5-fluorophenyl]-5-(4-propylsulfonyloxyphenyl)-4(lH)-pyridone 3-(2-acetoxy-4-ethoxyethylsulfonylphenyl)-1-chloromethyl-5-(5-cyclopropyl-2-trifluoromethylphenyl~-4(lH)-pyridone 3-(3-ethoxyhexylsulfonylphenyl)-5-phenyl-1-trifluoromethyl-4(1H)-pyridinethione 3-[4-(3~cyclohexenyl)phenyl~-1-propyl-5-[3-(9-propoxynonylsulfonyl)phenyl]-4(lH)-pyridone 3-[3-cyanomethyl-4-(1-cyclobutenyl~phenyl]~l-methyl-5-(4-vinylsulfonylphenyl)-4(1H)-pyridinethione ~:.
3-(2-allylsulfonyl 4-chlorophenyl)-5-(2-allyl-3-cyclohexylphenyl)-1-dimethylamino-4(lH)-pyridinethione l-acetoxy-3-~4-(2,3-hexadienylsulfonyl)phenyl]-5-phenyl-4(lH)-pyridone 3,5-bis[3-(4-decenylsulfonyl)phenyl]-1-methoxy-4(lH)-pyridone :~
3-[4-(2-bromoallylsulfonyl)-2-methylphanyl]-1-methyl-5-[3-(7,7,8,8-tetrafluoro-2-octynyl)phenyl]-4(1H) pyridone 3-[4-(6-heptynyl)-3-methylphenyl]-1-ethyl-5-~3-(1,1,2-triiodo-3-butenylsulfonyl)-5-chlorophenyl~-4(1H~-pyridone 3-[2-(5,5-dibromo-2-pentynyl)phenyl]-1-di~lethyl-amino-5-~3-~5-fluoro-2-nonenylsulfonyl)phenyl]-4(1H~--pyridone ~7~6~6 l-acetoxy-3-[2-ethyl-4-(5-methoxypentyl)phenyl]-5-[3-(12,12,12-trichloro-6-dodecenylsulfonyl)phenyl]-4(1H)-pyridone 3-[2-(3-chloro-5-hexynylsulfonyl)-4-nitrophenyl]-5-[3-bromo-5-(6-cyanohexyl)phenyl]-1-methoxy-4(lH)-pyridone 3-[4-(6,6-dibromo-3-hexynylsul:Eonyl)phenyl]-5-phenyl-l-propoxy-4( lH ) -pyridone 3-[3-(2-cyanoethyl)phenyl]-1-ethynyl-5-[1,1,2,2-tetrafluoro-6-decynylsulfonyl)phenyl]-4(1H)-pyridone 3-(3-benzyl-5-ethynylsulfonylphenyl)-5-[2-~7-phenylheptyl)phenyl]-l-vinyl-4(lH)-pyridinethione ~ l-cyanomethyl-3-[3-(6-dodecynylsulfonyl)-5-methylphenyl]-5-[2-methyl-4-(1,1,2,2-tetrafluoroethyl)-phenyl]-4tlH)-pyridone 1-(2-carboxyethyl)-3-phenyl-5-(3-phenylsulfonyl-phenyl)-4(lH)-pyridone ~:
3-[3-(4,4-diiodobutyl)phenyl]-5-[4-(4-fluoro- :
phenylsulfonyl)phenyl]-l-trifluoromethyl-4~lH)-pyridone .
3-[2-chloromethyl-3-(6,6-dibromohexyljphenyl]-5- ~ :
[3-(3-iodophenylsulfonyl)phenyl]-1-methyl-4(1H)-pyridone ~:
l-ethyl-3-[3-ethyl-5-(4-methylphenylsulfonyl)-phenyl]-5-[4-iodo-3-(2-propylbutyl)phenyl]-4(1H)-pyridine-thione l-(l-cyanoethyl)-3-[3-(2-propylphenylsulfonyl)-phenyl]-5-phenyl-4(1H)-pyridinethione 3-[5-butyl-2-(3-methoxyphenylsulfonyl)phenyl]-~ carboxyethyl)-5-phenyl-4(1H~-pyridinethione ~6~t75~;~6 3-(3-isopropyl-4-trifluoromethylphenyl)~
methyl-5-[3-(2-propoxyphenylsulfonyl)phenyl]-4(11l)-pyridone 3-[2-chloro-4-(4-nitrophenylsulfonyl)phenyl]-1-ethyl-5-~3-fluoro-5-(4-heptyl)phenyl]-4(1H)-pyridone 3-(3-cyclopropylmethylphenyl)-1-methyl-5-(2-trifluoromethylphenyl)-4(lH)-pyridone 3,5-bis[3-(2-cyclopentylethyl)phenyl~-1-methoxy~
4(lH)-pyridone 3-(2-cyclopropoxyphenyl)-1-ethyl-5-(2-fluoro- :
phenyl)-4(lH)-pyridinethione 3-(4-cyclohexyloxyphenyl)-1-methyl-5-phenyl-4(lH)-pyridone, methanesulfonate 3-(4-chlorophenyl)-5-(3-cyclobutylthiophenyl)- :
l-ethoxy-4(lH)-pyridone 3-(2-cyclopentylsulfinylphenyl)-5-(3-hexylphenyl)-1-propoxy-4(lH)-pyridone, hydrochloride 3-(4-cyclopropylsulfonylphenyl)-5-(2,4-diethyl- :
phenyl)-l-propyl-4(lH)-pyridinethione 3-(3-cyclohexylsulfonylphenyl)-5-(3,5-difluoro-phenyl)-1-trifluoromethyl-4(1H)-pyridone l-cyanomethyl-3-(2-cyclopropylmethoxyphenyl)-5-(3-trlfluoromethylphenyl)-4(lH)-pyridone l-acetoxy-3 [3-(2-cyclohexylethoxy)phenyl]-5-phenyl-4(lH)-pyridone, hydrobromide 3-~4-(2-cyclobutylethylthio)phenyl]-1-dimethyl-amino-5-(3,5-dimethylphenyl)-4(lH)-pyridone 3-(3-cyclopentylmethylsulfinylphenyl) 1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone 3-[4-(2-cyclohexylethylsulfonyl~phenyl~ ethyl-5-(3-propylphenyl)-4(lH)-pyridone X-4097~ -2~-~ ~75;69~

3-cyclopropylmethyl-5-(3-fluorophenyl)~
methoxy-4(lH)-pyridone, methanesulfonate 3-(4-chlorophenyl)-3-(2-cyclohexylethyl)-1-ethoxy-4(lH)-pyridone 3-(3-fluorophenyl)-1-methyl-5-phenylthio-4(lH)-pyridone 3-(3-chloro-5-methylphenyl)-1-ethoxy-5-phenyl-sulfinyl-4(lH)-pyridone l-acetoxy-3-phenylsulfonyl-5-(4-trifluoromethyl-10 phenyl)-4(lH)-pyridinethione :~
. 3-(2-butylphenyl)-5-~3,5-dichlorophenylthio)-1-(l-propenyl)-4(lH)-pyridone 3-(2,4-dibromophenyl)-1-dimethylamino-5-(4-ethylphenylsulfinyl)-4(lH)-pyridone l-cyanomethyl-3-phenyl-5-(3-propoxyphenyl-sulfinyl)-4(lH)-pyridinethione 3-methylthio-5-phenyl-1-ll-propynyl)-4(1H)-pyridone ::
3-(2-chlorophenyl)-1-methyl-5-propylsulfinyl- .
4(lH)-pyridinethione, hydrofluoride 3-ethylsulfonyl-1-isopropyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone .~ . .
l-ethoxy-3-(4-fluorophenyl)-5-trifluoromethyl-thio-4(1H)-pyridinethione, toluenesulfonate 3-(2-chloroethylsulfinyl)-1-chloromethyl-5-(3-methylphenyl~-4(lH)-pyridone 3-(2-bromopropylsulfonyl)-1-chlorodifluoro-methyl-5-phenyl-4~1H)-pyridinethione 1 (1-carboxyethyl~-3-(2,4-dimethylphenyl)-5- :
vinylthio-4(lH)-pyridone 7S6~

3-allylsulfinyl-3-(3,5-diiodophenyl)-1-methyl-4(lH)-pyridinethione l-methyl-3-(2-trifluoromethylphenyl)-5-vinyl-sulfonyl-4(lH)-pyridinethione 3-(3-allylphenyl)-S-(2-chlorovinylthio)-1-ethoxy-4(1H)-pyridinethione 1-(2-bromoethyl)-3-(2-chloro-3-fluorophenyl)-5-(1,2-difluoroallylsulfinyl)-4(lH)-pyridone 3-(2-bromo-1-propenylsulfonyl)-1-methyl~5-(3-methylphenyl)-4(lH)-pyridinethione l-dimethylamino-3-(4-methoxy-2-butenyl)-5-phenyl-4(lH)-pyridone l-ethynyl-3-(2-propoxyvinyl)-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone.
3-(6-ethoxy-2~hexenyl)-1-methyl-5-phenyl-4(lH)-pyridinethione, hydrochl.oride The following are the preferred compounds of ormula I.
l-methyl-3-phenyl-5-~3-trifluoromethylphenyl)-4(lH) pyridone 3-(3-fluorophenyl)-1-methyl-5-phenyl-4(lH)--pyridone 3-(3-chlorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone 3,5-bis(3-chlorophenyl)-1-methyl-4(1H)-pyridone 3-(3-chlorophenyl)-5-(3-~luorophenyl)-1-methyl-4(lH)-pyridone l-methyl-3-(3~methylphenyl)-5-phenyl-4(1H)-pyridone ' X 4097A -29- :
' ':

... . - , . .

756~6 3,5-diphenyl-1-methyl-4(lH)-pyridone ;.~ :
l-methyl-3,5-bis~3-trifluoromethylphenyl)-4(lH)-pyridone 3 (3-bromophenyl)-1-methyl-5-p:henyl-4(lH)--pyridone 3-(3-methoxyphenyl~-1-methyl-5-phenyl-4(lH)-pyridone 3-(3-ethoxyphenyl)-1-methyl-5-phenyl-4(lH)-pyridone :
1-methyl-3-phenyl-5-(3-propoxyphenyl)-4(lH)-pyridone 3-(3-isopropoxyphenyl)-1-methyl-5-phenyl-4(lH)~
pyridone l-methyl-3-phenyl-5-13-(1,1,2,2-tetrafluoro-ethoxy)phenyl]-4(1H)-pyridone 3,5-bis(3-fluorophenyl)-1-methyl-4(lH)-pyridone ..
3-(2-chlorophenyl)-1-methyl-5-(3-trifluoro methylphenyl)-4(lH)-pyridone 3-(3-chlorophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone 3-(4-chlorophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(1H)-pyridone 3-(2-fluorophenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone 3-(3-fluorophenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4t1H)-pyridone 3-(4-fluorophenyl)-1-methyl-5-(3-trifluoro-; methylphenyl-4(1H)-pyridone 3-(3-chlorophenyl)-5-(4-chlorophenyl)-1-methyl- :~

4(1H)-pyridone ''':~ ' ' "
," ~ ' l-ethyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridone l-allyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridone l-methyl-3-(3-trifluoromethylphenyl)-4(lH)-pyridone 3-chloro-1-methyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridone 3-bromo-1-methyl-5-~3-trifluoromethylphenyl)-4(lH)-pyridone 1,3-dimethyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridone 3-ethyl-1-methyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridone 3-isopropyl-1-methyl-5-(3-trifluoromethylphenyl)-4~lH)-pyridone l-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridinethione The process for preparing the compounds of formula I is an analogous process. Benary and Bitter, Ber.
61, 1058 (1928) taught the synthesis of an intermediate di-sodium salt of l,5-dih~droxy-2,4-diphenyl-1,4-pentadien-3-one 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.(1H)-pyridone.

:: : .: . .

7~6~

Analogously, 3,5-diphenyl-4(lH)-pyridones can be prepared by the reaction of an appropriately ring-sub-stituted 1,3-diphenyl-2-propanone with formamide and for-mamidine acetate. Reaction at reflux temperature produces the corresponding 3,5-diphenyl-4(lH3-pyridone, which is reacted with a halide of the desired l-substitiuent 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 ~ C-C-C-R~ IV

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 when one of Ql and Q2 is 2 hydrogen atoms and the other is =CHNHY wherein Y is hydrogen; hydroxy; C1-C3 alkyl; Cl-C
alkyl substituted with halo, cyano, carboxy or methoxy- ~:
carbonyl; C2-C3 alkenyl; C2-C3 alkynyl; Cl-C3 alkoxy; or .. -~:
dimethylamino; provided that Y comprises no more than 3 carbon atoms; and with a compound of the formula wherein Y is defined as before or the acid addition salt thereof, when both Ql and Q2 are independently selected from the group consisting of :~ :
; . ' ~ ' :

756~6 =CHOH
=CHN(R )2 in which the R9 groups independently are Cl-C3 alkyl, or the R groups combine with the nitrogen atom to which they are attached to form pyrrolidino, piperidino, mor-pholino or N-methylpiperazino;
to provide a compound of the formula R~ V
y 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 P2S5.
Therefore, the compounds of formula I can be prepared by cycli~ing a compound of the formula ::

O
~C~ C---R2 R1 X~ = ~/ Q1 Q2 VI

wherein Rl, R2 and m are defined as before~ ~

with a compound of the formula -N 2 ~ :
wherein Y is defined as before or the acid addition salt thereof, 7569~

when both Ql and Q2 are independently selected from the group consisting of =CHOH
=CHN(R )2 in which R9 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 . 10 when the compounds of formula I are desired wherein X is sulfur, treating the compounds of formula I wherein X is oxygen with P2S5.
Thus, it is possible to prepare the compounds of formula I by cyclizing a compound of the formula R1 X ~ c__c~ R2 VII

wherein Rl, R2 and m are defined as before, with an agent selected from the group consisting of a formylating agent, and an aminoformylating agent ::
when one of Ql and Q2 is 2 hydrogen atoms and the other is =CHNHY wherein Y is defined as before, to provide a compound of formula V;
followed by alky~ating 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 . ~

~75~;96 X is sulfur, treating the compounds of formula I wherein X
is oxygen with P2S5.
An embodiment o~ the cyclizing process described above comprises reacting a compound of ~ormula IV wherein both of Ql and Q2 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 o~ 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. ~n appro-priately 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 l-(R-amino)-2-phenyl-l-buten-3-one of formula VII. Some pyridone is also ~ormed 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 1-unsubstituted pyridones by using NH3 in place of YN~2 in the process, or by using the process of Benary and Bitter.
The pyridone is then alkylated at the l-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 l-unsubstituted pyridone to the ~-halo or X-~Og7A -35-, 7~i69~

4-alkoxy derivative by reaction with a halogenating ayent, or an alkylating agent. Suitable halogenating agents include such agents as POC13 t POBr3, PC15 and the like.
O-alkylating agents include such reagents as methyl tri fluoromethanesulfonate, methyl fluorosulfonate and the like, 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-sub-stituted 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, RNH2, may be used in the form of salts, preferably hydrohalide salts, including hydrochlorides, hydrobromides and the like. Such salts are often more convenient than the free amines.
The formylating agents-used in the proc~ss are chosen from the common agents used for such reactions. The preferred agents are esters of formic acid of the formulae H--C~O-~(Cl-C6 alkyl) or O ~ :

o_~ .

Similar formylations are discussed in Organic Syntheses 300-02 ~Collective Vol. III 1955).
The esters are used in the presence of strong bases, of which alkali metal alkoxides are preferred, such as sodium methoxide, potassium ethoxide and lithium pro-- ~9756~6 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 dia~abicyclononane and diazabicyclo-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 tetra-hydrofuran, aromatic solvents such as benzene and xylene, and al~anes such as hexane and octane can be used as for-mylation solvents.
Bec~use of the strong bases used in the formylation reactions, low temperatures produce the best yields. Reaction at temperatures in the range of from about -25C. to about 10C~ 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 synthe-ses may be any compounds capable of reacting with an active methylene group to introduce a =CHN(R912 group, or its acid addition salt. Such agents are chosen from among the orthoformamides, HC[N(R )2]3 the formate ester aminals, ~-4097A

, ... .. -.. . . . . . . ........... - - .
: - . :, - .... . . .. . .

1~7S696 Hl[N(R9) ]
the formamide acetals, Q3 _ R10 f ( , 2 the tris(formylamino)methanes, ~-HC(NHCH)3 and the formiminium halides, 9 '.' HC=N(R )2Halo ~
Halo ;
Q3 in the structures above represents oxygen or sulfur, and R10 represents Cl-C6 alkyl or phenyl.
Useful references on the aminoformylating agents include DeWolfe, Carboxylic Acid Derivatives 420-506 (Academic Press 1970), and Ulrich, Chemistry of Imidoyl Hali~es 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.
104y 2709-26 (1971); Ber. 106, 3732-4Z (1973)i 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~ 10Ç, 3725-31 (1973); and Angew. Chem.~ Int'l Ed. 5, 132 (1966).
Other notable papers on the sub~ect include Kreutæberger et -al., Arch. der Pharm. 301, 881-96 (1968), and 302, 362-75 (1969), and Weingarten et al., J. ~. Chem. 32, 3293-94 (1967).

::

:: ,, ~ . ~ , - . , lLlD'7S6,96 ~ minoformylations are usually carried out without solvent, at elevated temperatures from ~bout 50C. to about 200C. Solvents such as dimethylformamide are sometimes used, however, particularly when it is clesirable 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 0C. to about 50C., preferably at room temperature. Halogenated solvents such as chloroform and methylene chloride can also be used in such amino-formylations if desired.
The exchange reactions with YNH2 are best per-formed in protic solvents of which alkanols are preferred and ethanol is most appropriate. Temperatures from about -20C. to about 100C. can be used for the exchange re-actions. Room temperature is satisfactory and is preferred.
The starting materials of formula IV are pre-pared by reacting a compound of the formula CH --C--CH ---RZ

m wherein:
Rl, R2 and m are defined as before, with an agent selected from the group consisting of a formylating agent, and an aminoformylating agent.

:
X-~097A _39-; ::

~75696 :
If a formylating agent is used, a ketone inter-mediate of the formula Rm,~ _. O
o--C-~C--CH --R2 IX
HOCH

is produced. Reaction with an aminoformylating agent produces an enaminoketone such as X below.

1 0 , , ~--~9 î ~ x (R )2N ~1 Organic chemists will understand that, although formulae IX and X show the first formylation or amino-formylation 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 Rl 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 com-pounds and the disubstituted compound.
The monosubstituted product is formylated or ;~
aminoformylated again, and exchanged with an amine of the formula YNH2. The steps may be performed in either order.
If ~he exchange is performed first, the intermediate product `
is an enaminoketone of the formula , :.

.: :

9~ :

Rm ~ i~ ~ XI
C---'C--Ctl - R2 YHNCH

Either formylation or aminoformylation o:E the above enamino-ketone, 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 :
methylel1e group.
Either of compounds IX or X may be either for-mylated or aminoformylated to provide intermediates of any of the formulae below.

R1 0_~ 0 ~---C--C~C R2 XII

HOCH HI~OH - ~ .

~o~C--C C~R2 XIII
HOCH HeN (R~
2 . -~~C^--C~C - R2 o/ 11 11 ~ ~ ~
(R ) 2N~H H~N (R ) 2 :. . .

: :: . ' 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 , ,~", . ~ . .. . . . . .

~7569~

the intermediate with an amine of the formula YNH2.
- The 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 o~ Hemi-fluorinated 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:

(A) ~ -CH2 C -Halo + (R9)2NCH=CH -R2 O
C--C R2 ~, ~ HCN(R )2 It will be understood that reaction (A) can also be per-formed in the opposite manner, as shown below:

'~

~1~--====~ ¦¦ 2 It is also possible to form the starting materials of formula VI wherein both Ql and Q2 are identical by using phos-~ ,'.

, ;i6~6 gene as the carbonyl halide when the 3- and 5-substituents of the pyridone product of formula I are identical.

(C) .
R1 ,~
m ~ ~ COCI
\ /o CH=CI~N (R~ 2 __ ., Rm ~ O " ~ Rm \
(R9) NCH HCN (R9) t In general, intermediate compounds in the syn-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, magnesium oxide and the like, 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 Rl and R5 substituents by first making the corresponding hydroxy-substituted compound, and then substituting on the oxygen atom.
The pyridinethiones of formula I are readily prepared by the treat~ent of the corresponding pyridones with P2S5 in pyridLne at reflux temperature, according to known methods.

..~
X-4097A -43- ~

:. : ` . . . : :

;~7~6~6 The l-acetoxy compounds of formula I are made by first making the corresponding l-hydroxypyridone, using NH2OH as the amine, and esterifying it with acetic an-hydride~ The other l-substituents are provided by appro-priate Y substituents on the amines, YNE12, 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 pre~ious 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 prep-aration of a compound by the preferred synthetic process using a compoun~ of formula VII.

~ -7S6~

Example 1 To a solution of 4 1. of tetrahydrofuran and 284 g. of sodium methoxide was added 556 g. of 1-(3-trifluoro-methylphenyl)-3-phenyl-2-propanone at 10-15C. over a 20-minute period. The reaction mixture waic~ 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 10-15C. To the mixture was added an additional ~96 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 methyl-amine hydrochloride in 1 1. of water was added. The two-phase mixture was stirred at 30C. 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 con-taining l-methylamino-2-phenyl-4-(3-trifluoromethylphenyl)-l-buten-3-one and 1-methylamino-4-phenyl-2-(3-trifluoro-methylphenyl)-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 puri~ied product was identified as l-methyl-3-phenyl-5-(3-trifluoromethyl phenyl)-4(1H)-pyridone, m.p. 153-155C., by infrared, nuclear magnetic resonance, and thin-layer chromatography analyses.

The elemental analysis was as follows.
-.:- . ' - .

5~6 Theoretical Found C6~.30% 69.48 El4.29 4.42 N 4.25 4.27 The process of Example 1 was a]Lso used to produce all of the following exemplary compounds.
Example 2 l-methyl-3,5-bis(3-trifluoromethylphenyl)-4(lH)-pyridone, m.p. 152-154C., yield 39 Example 3
3-phenyl-1-(2,2,2-trifluoroethyl)-5-(3-trifluoro-methylphenyl)-4(lH)-pyridone, NMR, quartet centered at 256 CPS; aromatic protons at 420-468 CPS; yield 46 Example 4 3-(3-bromophenyl)-5-(3-chlorophenyl~-1-methyl-
4(lH)-pyridone, m.p. 192C., yield 23 Example 5 _ _ :
3-(3-chlorophenyl)-5-(4-chlorophenyl) l-methyl-4(lH)-pyridone, m.p. 170-172C., yield 26%
Example 6 3-(2-fluorophenyl)-1-methyl-5-(3-trifluoromethyl-phenyll-4(1H)-pyridone, m.p. 152-154C., yield 20%
Example 7 .
3-(2-chlorophenyl)-5-(3-chlorophenyl)-1-methyl-4(lH~-pyridone, m.p. 160-161C~, yield 15%

Example 8 3-(3-methoxyphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4~1H~-pyridone, m.p. 113-115C., yield 7 X-4097A ~46-.

11g75~ 6 Example 9 3-(4-chlorophenyl)-1-methyl-S-(3 trifluoro-methylphenyl)-4(1H~-pyridone, m.p. 153-155C., yield 26%
Example _ l-allyl-3-phenyl-5-(3-trifluoxomethylphenyl)-4(lH)-pyridone, m.p. 107-109C.~ yield :38%
Example 11 3-(4-isopropylphenyl)-1-methyl-5-phenyl-4(lH)~
pyridone, m.p. 159~C., yield 60%
10 Example 12 3-(2-chlorophenyl)--1-methyl-5-(3-trifluoro- ~i methylphenyl)-4(lH)-pyridone, m.p. 191-193C., yield 14 Example 13 3-(3-fluorophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 94-96C., yield 13%
Example 14 3-(4-fluorophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 133-134C., yield 29%
Example 15 3-(4-methoxyphenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 162-165C,, 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.

~(117~69~
Example 16 An enaminoketone, ~-pheny~ diethylaMino-4-(3-methylthiophenyl)-1-buten-3-one, was made according to the procedure of the first step of Example 73, starting with 17.5 g. of N,N-diethylstyrylamine and 15 g. of (3-methyl-thiopheny])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 l-methylamino-4-(3-methylthiophenyl)-2-phenyl-1-buten-3-one.
The residue was mixed with 50 ml. of dimethyl-formamide 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 me-thylene chloride. Both extracts were washed with water, dried and evaporated to dryness. The product was 9 g. of 1-methyl-3-(3-methylthiophenyl)-5-phenyl-4(lH)-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 _-chloro-perbenzoic acid.
Examele 17 ._ l-methyl-3-(3-methylsulfinylphenyl1-5-phenyl-4(lH)-pyridone, m.p. 161-164C., yield 57%

~175696 Example 18 l-methyl-3-(3-methylsulfonylphenyl)-5-phenyl-4(lH)-pyridone, m.p. 176-181C., yield 31 Example 19 l-methyl-3-phenyl-5-~4-trifluoromethylphenyl)-4(1H)-pyridone, m.p. 164-166C., yield 16%
The following example illustra~es 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 oE the intermediate.
Example 20 An enaminoketone was prepared, namely, 4-(3-benzyloxyphenyl)-l-diethylamino-2~-phenyl-1-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 N,N-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 sepa-rated! dxied, filtered and evaporatedl to dryness. The resulting intermediate, 4-(3-benzyloxyphenyl)-1-methyl-amino-2-phenyl-1-buten-3-one, was dissolved in 125 ml. of -ethyl ether.
.

X-40g7A -49-.. .

.. .... .... ..... . .. ..
: . . . :.

~7S6~

The solution was cooled to 5C., and 12 g. of sodium methoxide was added. While the xeaction mixture was held at about 5C., 50 ml. of ethyl formate was added slowly. The mixture was then stirred as it was allowed tv 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 e~apor$ted to dryness. The product was recrystallized from ethyl acetate to produce 1.5 g. of 3-(3-benzyloxyphenyl)-l-methyl-5-phenyl-4(lH)-pyridone, m.p. 158-160C.
The following exemplary compounds were also pro-duced according to the process of Example 20 above, Example 21 l-methyl-3-phenyl-5-(2-thienyl~--4(lH)-pyridone, m.p. 147-148~C., yield 6%
Example 22 3-(3-isobutylphenyl) :L-methyl-5-phenyl-4(lH)-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-nitrophenylj-5-phenyl-4(1H)-pyridone, m.p. 135-136.5C., yield 33~
The following example demonstrates the preparation of a pyridone by the formamidine acetate process, followed by alkylation at the l-position.
Example 24 Ten g. of 1-(2,4-dichlorophenyl)-3-phenyl-2-X-4097A -sa-7~ 9~

propanone was heated a-t reflux with 10 g. of formamldine acetate in 75 ml. of formamide for 3 hours. The mixture was then poured on-to ice and water was addedO After the ice had melted, the mixture was filtered and the separated solids were washed with ethyl ether. The solids were then dis-solved in ethanol, decolorized with charcoal and recrystal-lized to produce 1.3 g. of 3-(2,4-dichlorophenyl)-5-phenyl-4(lH)-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)-1-methyl-5-phenyl-4tlH)-pyridone, m~p, 202-204C., 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 3.33 4.05 N ~.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 o~ Benary and Bitter, cited aboveO
' X-4097A -51- ~
:

. .

: L~375696 Example 25 3,5-diphenyl-1-ethyl-4(1H)-pyridone, m.p. 171C., yield 75~
~xample 26 l-allyl-3,5-diphenyl-4(lH)-pyridone, m.p. 174C., yield 79~
Example 27 3,5-diphenyl-1-isopropyl-4~1H)-pyridone, m.p.
152C., yield 15 Example 28 l-cyanomethyl-3,5-diphenyl-4(lH)-pyridone, m.p.
221-224C., 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 1,3-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 0-5C. 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 1,5-dihydroxy-2,4-diphenyl-1,4-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 con-centrated hydrochloric acid in 75 ml. of watsr. The mixture was stirred for one-half hour at room temperature. The '' 756g6 reaction mixture was tllen e~tracted witll ethyl ether, an~
the aqueous layer was evaporated to dryness. The residue was extracted with chloroform, the co~bined organic extracts were evaporated to dryness, and the residue was recrystal-lized from benzene-hexane to produce 3.05 g. of 3,5-di-phenyl-l-propyl-4(lH)-pyridone, m.p. 172-174C.
The following typical compounds were also made by the general process of Example 29.
Example _ 3,5-diphenyl-1-methoxy-4(lH)-pyridone, m.p.
165C., yield 95%
Example 31 3-(3-fluorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 133.5C., yield 69 Example 32 ~ . _ 3-(4-bromophenyl)-1-me-thyl-5-phenyl-4(lH)-pyridone, m.p. 172C., yield 63%
Example 33 3-(4-methoxyphenyl)-1-methyl-5-phenyl-4(lH)-pyridone, m.p. 165C., yield 32%
Example 34 3-(3-chlorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 17205C., yield 27 Example 35 _ 3-~4-chlorophenyl)-1-methyl-5-phenyl-4(lH)-pyridone, m.p. 141.5C., yield 76%
Exam~ 36 l-methyl-3-(1-naphthyl)-5-phenyl-4(lH)-pyxidone, NMR peaks at 204 and 483 CPS; aromatic protons at 430 470 CPS; yield 12~

X~4~9~ -53-~ ~7S6~6 Example _ 3,5-bis(3-chlorophenyl)-1-methyl-4(lH)-pyridone, m.p. 164-167C., yield 59%
Example 38 l-methyl-3-(3-methylphenyl)-5-phenyl-4(1H)-pyridone (complex containing 1/2 mole of benzene), m.p. 79.5C., yield 25%
Example 39 l-methyl-3-(4-methylphenyl)-5-phenyl-4(1H)-pyridone, m.p.
144.5C., yield 28%
Example _ l-methyl-3-(2-methylphenyl)-5-phenyl-4(lH)-pyridone, NMR
peaks at 133 and 201 CPS; aromatic protons at 420-440 and 442-460 CPS; yield 16%
Example 41 3-(4-fluorophenyl)-1-methyl-5-phenyl-4(lH)-pyridone, m.p.
166C., yield 60%
Example 42 . _ . _ .
l-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone, mOp. 152-156C., yield 52%
Example 43 _ _ _ _ 3-(3-methoxyphenyl)-1-methyl-5-phenyl-4(1H)-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)-1-methyl-5-phenyl-4(lH)-pyridone, m.p. 166.5C., yield 54 Example 45 3-(2,5-dichlorophenyl)-1-methyl-5-phenyl-4(1H~-pyridoné, m.p. 155.5C., yield 22%

X-4097A -54_ ~C~75~

~xample 46 _ 3-(2-chlorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p.
145C., yield 29%
Example 47 3,5-bis(3-fluorophenyl)-1-methyl-4(lH)-pyridone, m.p.
149-151C., yield 60%
Example 48 3-(3-chlorophenyl)-5-(3-fluorophenyl)-1-methyl-4(lH)-pyridone, m.p. 145-146C., yield 64%
_xample 49 3-(3,5-dichlorophenyl)-1-methyl-5-phenyl-4(lH)-pyridone, m.p. 131-135C., yield 28%
Example 50 3,5-bis(3-bromophenyl)-1-methyl-4(1H)-pyridone, m.p.
216.5C., yield 43%
Example 51 3-(3-bromophenyl)-1-methyl-5-phenyl-4(lH)-pyridone, m.p.
172C., yield 38%
Example 52 3-(2-fluorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p.
165C., yield 19 Example 53 3-(3-bromophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 151-153C., yield 37%
Example 54 . .
l-(l-carboxyethyl)-3-phenyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 236-237C., yield 13 Example 55 . . ._ _ l-dimethylamino-3,5-diphenyl-4(lH)-pyridone, m.p.
143C., yield 94~

~ 13756~6 Example 56 l-methyl-3-(2-naphthyl)-5-phenyl-4(1H)-pyridone, m.p. 101-105C., yield 45%
Example 57 l-ethyl-3-phenyl 5-(3-trifluoromethylphenyl)-4(lH)-pyridone, m.p. 98-100C., yield 66 Example 58 3-phenyl-1-propyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridone, NMR, triplet peaks at 60 and 230 CPS, and a sextuplet at 114 CPS; yield 42 Exam~le 59 l-methoxy-3-phenyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridone, NMR peak at 248 CPS
Example 60 3-(3-chlorophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl)-4~lH)-pyridone, m.p. 133-135C., yield 28 Example 61 ~ 3-(4-biphenylyl)-1-methyl-5-phenyl-4(lH~-pyridone, m.p. 186-190C., yield 1%
Example 62 .. . ~
3-(3-biphenylyl)-1-methyl-5-phenyl-4(lH)-pyridone, m.p. 186-190C., yield 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.

.

.

~75696 Analysis of the remaining dark red oil showed that itconsisted of about 75% of the desired 1,5-bis(dimethylamino)-2-phenyl-1,4-pentadien-3-one, and about 25~ of the cor-responding 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 hydro-chloride 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 solutionO 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 pre-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 1-methyl 3-phenyl-4(lH)-pyridone, m.p. 123-125C.
Example 64 A 3 g. portion of the product of Example 63 was dissolved in 10~ 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 recrystalli7ed from ethanol to yield 3 g. oE 3-bromo-1-methyl 5-phenyl-4(1H~-pyridone, m.p. 195~ 197Co The procedure of Example 63, and of Example 64 where appropriate, was used to prepare the following com--pounds.

X-4097A - _57_ .: , ~L~75696 Example 65 3-bromo-1-methyl-5-(3-trifluor~methylphenyl)-4(lH)-pyridone, m.p. 167-169C., yield 76 Example _ l-methyl-3-(3-trifluoromethylphenyl)~4(lH)-pyridone, m.p. 122-123C., yield 16~

~ _ 3-chloro-1-methyl-5-(3-trifluoromethylphenyl)-4(lH~-pyridone, m.p. 170-172C., yield 67%
Exam~le 68 3-(3-carboxyphenyl)-1-methyl-5-phenyl-4(lH3-pyridone, hydrochloride, m.p. 266-268C,, yield 10 EXample 69 3-(3-cyanophenyl)-1-methyl-5-phenyl-4(lH)-pyridone, m.p. 164-166C~, yield 33%
Example 70 .. ..
3-(3-ethoxycarbonylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone! m.p. 167-168C., yield 11%
Example 71 3,5-bis(3-cyanophenyl)-1-methyl-4~lH)-pyridone, m.p, 322-327C., yield 22 Example 72 l-methyl-3-phenyl-$-(3-thienyl)~4(1H)-pyridone, NMR peaks at 204 and 495 CPS; aromatic protons at 430-460 CPS: yield 34%
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.

.

- - . .
~, . - .

.. : .: .: . : :

~97S6~6 Example 73 A mixture of 1.92 g. of dime-thylaminoacrylonitrile and 1.6 g. of pyridine was dissolved in ~5 ml. of ethyl ether at 0C. 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 O~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-1-dimethylamino-4-phenyl-1-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 th~n 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 Eor 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 ~rom isopropyl ether acetone to yield 260 mg. of 3-cyano-1-methyl-5-phenyl-4(lH)-pyridone, m.p. 209-210.
The following exemplary compounds were prepared according to the general process of Example 73 above.

~a~7s696 Example 74 1,3-dimethyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridone, m.p. 130-131C., yield 12%
Example 75 1,3-dimethyl-5-phenyl-4(lH)-pyridone, m.p. 111-113C., yield 8%
Example 76 3-(3-chlorophenyl)-1,5-dimethyl-4(1H)-pyridone, m.p. 143-143.5C., yield 6%
Example 77 3-ethyl-1-methyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridone, m.p. 95.5-96.5C.I yield 7%
Example 78 3-cyclohexyl-1-methyl-5-(3-trifluorome~hylphenyl)-4(lH)-pyridone, m.p. 174-175C., yield 40%
Example _ 3-isopropyl-1-methyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridone, m.p. 98.5-99.5C., yield 10%
Example _ 3-hexyl-1-methyl-S (3-trifluoromethylphenyl)-4(lH)-pyridone, m.p. 89.5-90.5C., yield 7%
Example 81 3-benzyl-1-methyl-5-(3-trifluoromethylphenyl)--4(lH)~pyridone, m.p. 98-100C., yield 18%
Example 82 .
3-butyl-1-methyl-5-~3-trifluoromethylphenyl) 4~lH)-pyridone, m.p. 82.5-84C., yield 9%

Example 83 ;

3-(3-cyclohexenyl)-l~methyl-5-(3-trifluoromethyl phenyl)-4(lH)-pyridone, m.p. 194-195C., yield 43 .. . . . . .. . .

~ 75g;;96 Example 84 l-methyl-3-propyl-5-(3-trifluoromethylphenyl)-4(1H~-pyridone, m.p. 45-47C~, yield 3%
Example 85 l-methyl-3-(4-nitrophenyl)-5-phenyl-4(lH)-pyridone, m.p. 212-214C., yield 48 Example 86 3,5-bis(3,4-dimethoxyphenyl)-1-methyl-4(1H)-pyridone, m.p. 182-184C., yield 1 Exam~le 87 3-ethoxycarbonyl-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 107-108C., yield 68%
Exam~e 88 3-(2-furyl)-1-methyl-5-phenyl-4(lH)-pyridone, m.p. 191-192C., yield 69 Example _ 3-cyano-1-methyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridone, m.p. 228-229C., yield 40%
Example 90 3-(3,4-dimethoxyphenyl~-1-methyl-5-phenyl~4(1~)-pyridone, m.p. 154- 157C., yield 4%
Exam~le 91 ::
3-~3,4-dibromocyclohexyl)-1-methyl-5-(3-tri-fluoromethylphenyl)-4(lH~-pyridone, hydrobromide, m.p.
196-198C., yield 26%, made by bromination of the cor-responding 3-(3-cyclohexenyl) compound Example 92 ____ _ :
3-(3-isopropenylphenyl~ methyl-5-phenyl-4(1H)-pyridone, NMR peaks at 125, 214, 302 and 327 CPS; aromatic protons at 420-470 CPS; yield 4%

6g6 Example 93 3-(3-ethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 135-137C., yield 5 Exam~
3-(3-hexylphenyl)-l~methyl-5-phenyl-4(lH)-pyridone, m.p. 93-95C., yield 6 Example 95 3-(4-ethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 143-145C., yield 6%
Example _ 3-(3-cyclohexylmethylphenyl)-1-methyl-5-phenyl-4(lH)-pyridone, m.p. 147-148C., yield 9%
Example 97 l-methyl-3-phenyl-5-benzylthio-4(lH)-pyridone, m.p. 155-157C., yield 36 Example 98 l-methyl-3-phenyl-5-phenylthio-4(lH)-pyridone, ;
m.p. 164-165C., yield 18 Example 99 1-methyl-3-phenoxy-5-phenyl-4(lH)-pyridone, m.p.
176-177C., yield 19%
~xam~le 100 l-methyl-3-phenyl-5-phenylsulfonyl-4(lH)-pyridone, m.p. 218-220C., yield 50%, made by oxidation of the cor-responding phenylthio 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.

X~4097A -62~

1~7~i6~6 Example 101 An enaminoketone was formed from 3.5 g. of N,N-diethylstyrylamine 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, l-diethylamino-4-methoxy-2-phenyl-1-buten-3-one.
The above enaminoketone was mixed with 3.2 g. of sodium methoxide in 50 ml. of dry tetrahydrofuran at 0C., 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 xoom 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-methyl-5-phenyl-4(lH)-pyridone, m.p. 153-155C.
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 25~ ml. of acetic acid, and 1 g. of 5~ pal-ladium on carbon was addedO The mixture was hydrogenated for about 45 minutes, fil~ered, and the filtrate was evapo-rated to dryness. The product was recrystallized from ethyl X-~097~ -63-,. ~ .

~L~756~;

acetate-hexane to produce 0.45 g. of 3-(3-hydroxyphenyl)-l-methyl-5-phenyl-4(1H)-pyridone, m.p. 223-225C.
The same compound was also made by a cleavage with pyridine hydrochloride as follows.
A 2 g. portion of 3-(3-methoxyphenyl)-1-methyl-
5-phenyl-4(lH)-pyridone was mixed with 15 g. of pyridine hydrochloride and the mixture was heated at reflux temp-erature 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 recrystal-lized from ethanol-ethyl ether to yield 1.1 g. of 3-(3-hydroxyphenyl)-l-methyl-5-phenyl-4(lH)-pyridone. An ad-ditional 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)-1-methyl-4(lH)-pyridone, m.p. 155-165C., 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 u~der vacuum. The .. . .

75~96 product was 2.2 g. of 3-(3-ethoxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone, m.p. 133-135C.
The exemplary compounds below were prepared according to methods similar to that of Example 104.
Example 105 3-(3-allyloxyphenyl)-1-methyl-5-phenyl-4(lH)-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-methyl-5-phenyl-4(lH)-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(lH)-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-phenyl-4(1H) pyridone, NMR peaks at 207 and 275 CPS; aromatic protons at 396-456 CPS; yield 6%
Example 109 3-(3-dodecyloxyphenyl)-1-methyl-5-phenyl-4~1H)-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 l l-methyl-3-[3-(4-nitrophenoxy)phenyl~-5-phenyl-4(1H)-pyridone, NMR peaks at 222 and 488.5 CPS; aromatic protons at 414-463 CPS; yield 14%

i~756~a6 Example 111 .
l-methyl-3-(3-methylsulfonyloxyphenyl)-5-phenyl-4(lH)-pyridone, NMR peaks at 185 and 213 CPS aroma~ic protons at 422-472 CPS; yield 20%
Example 112 l-methyl-3-phenyl-5-[3-(1,1,2,2-tetrafluoro-ethoxy)phenyl]-4(1H)-pyridone, m.p. 119-121C., yield 84%, made by using tetrafluoroethylene, in the presence of potassium hydroxide Example 113 3-(3-acetoxyphenyl)-1-methyl-5-phenyl-4(lH)~
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(lH)-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(lH)-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(lH)- :
pyridone, NMR peaks at 54, 101.5, 208 and 232 CPS; aromatic protons at 400-463 CPS; yield 31 Example 117 l-methyl-3-phenyl-5-(3-propargyloxyphenyl)-4(lH)-pyridone, NMR peaks at 150 and 215 CPS; a broad peak at 280-285 CPS; aromatic pr~tons at 430-470 CPS; yield 6 . ,. . ,. : . . .

1~7Si696 Exam~le 118 3-(3-cyclohexylmethoxyphenyl)-1-methyl-5-phenyl-4(lH)-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(1H)-pyridone, NMR peaks at 52, 218 and 239 CPS; a broad peak at 58-122 CPS; aromatic protons at 403-467 CPS; yield 19 Example 120 -1-methyl-3-(3-phenoxyphenyl)-5-phenyl-4(lH)-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 20 in 150 ml. of ethyl ether~ The suspension was chilled in an ~ -ice bath, and 28g. of 1-phenyl--3-(3-trifluoromethylphenyl)~-2-propanone 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 Pxtracted with water, and the water layer was made acid with dilute hydrochloric acid and was ex-tracted 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 ... - . . . . . . . . , . . ., .
. : , . . , , . : ..

~L~7S6~6 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-hydroxy-2-phenyl-4-(3-trifluoromethylphenyl)-1-buterl-3-one An 11 g~ portion of the above intermediate product was heated on the steam bath with 20 ml. of dimethylform-amide 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% aquaous 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 chloro-forml and the solution was washed with water and dried over sodium sulfate. The solvent was then removed under vacu~m, and the residue was triturated with ethyl ether. The ether was filtered to produce l-methyl-3-phenyl-5-(3-trifluoro-methylphenyl)-4~lH)-pyridone, m.p. 153-155C.
The next examples below shows the synthesis of a pyridone, starting from a ketone, by successive amino-formylation 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 dimethylfor-mamide 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 .. . . . . .

~L~756~;

evaporated to produce an oil which was primarily a mixture of l-dimethylamino-4-phenyl-2-(3-trifluoromethylphenyl) l~buten-3-one and 1-dimethylamino-2-phenyl-4 (3-trifluoro-methylphenyl)-l-~uten-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(lH)-pyridone, m.p. 153-155C.
The following example illustrates the synthesis of a l-unsubstituted pyridone by reaction of a ketone with a tris(formylamino)methane. To obtain a compound of formula I, this product is alkylated.
Example 123 A 1.4 g. portion of 1,3-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 ":~

X-4097A -69- ~

. . . :

~75696~

with water, and then with chloroform. The yield was about 100 mg. of 3,5-diphenyl-4(lH)-pyridone, m.p. greater than 335C.
The example next below shows the synthesis of a 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 phenyl-3-(3-trifluoro-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 evapo-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 soiution was filtered, and the solids were recrystallized from acetone-ethyl ether to produce l-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridone, m.p. 153-155C.
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.

Exam~le 125 3~ A 39 g. portion of 3-phenyl-5-~3-trifluoro--:' ' ' . ' ' , ' .' ' ~ ' ' ' " ' ~L~7S696 methylphenyl)-4(1H)-pyridone, made by the method of Benary and Bitter, was refluxed with 100 ml. of POC13 and 5 ml. of dimethyl~ormamide for three hours. The excess POC13 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 temp-erature. The aqueous mixture was then e~tracted with chloro~orm, 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-phenyl-5-(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 ~rom chloroform-hexane to produce pure 4-chloro-3-phenyl-5-(3-trifluoromethylphenyl)-1-methyl-pyridinium 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 reElux for one hour, coo]ed, and the solids ~-were separated by filtration. The product was l-methyl-3-pllenyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridone, m.p.
153-155C.
The following example illustrates the l-alkylation of a l-unsubstituted pyridone by reaction with a methylating agent.

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Example 126 .
A 8 g. portion of 3-phenyl-1-(3-trifluoromethyl-phenyl-4(lH)-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 fil-tered, and the precipitate was washed with additional chloroform. The organic layer of the filtrate was sepa-rated, dried over magnesium sulfate and evaporated to dry-ness. The residue was an oily gum which was identified by NMR analysis as essentially pure 3-phenyl-5 t3-trifluoro-methylphenyl)-l-methyl-4-methoxypyridinium trifluoromethane 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 tri-turated 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.

1L~75~96 The product was l-methyl-3-phenyl-5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone, m.p. 152-156C.
The following example illustrates the use of a formate ester aminal as an aminoformylating agent in the process.
~xample 127 A 15 g. portion of 1-phenyl-3-(3-trifluoromethyl-phenyl)-2-propanone was added to ~n ethyl ether solution, at ice bath temperature, of 70 g. of (t-butoxy)-di(dimethyl-amino)methane. The mixture was warmed to evaporate theether, 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 organlc layer was washed with water, dried, and chroma-tographed on a silica gel column with ethyl acetate:benzene.
Collection and evaporation of the product-containing fractions gave about 0.9 g. of 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(lH)-pyridone, m.p. 152-156C.
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 g. of dimethylformamide dropwise to 20 g. of phosgene in 150 mlO of chloroform at 0C. A 10 g~ portion of 1,3-bis-(A~-chlorophenyl)-2-propanone in 50 ml. of chloroform was ' ' ': , ~7S6g6 then added. The mixture was stirred for 3 hours, after which 50 ml. of 40~ aqueous methylamine was added. Chloro-form 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)-1-methyl-4(lH)-pyridone, 0.85 g., m.p.
164-167C.
Continued elution of the column with methanol re-moved a compound identified by NMR as 4-chloro-3,5-bis(3-chlorophenyl)-l-methylpyridinium chloride. Hydrolysis of the compound with a~ueous ethanolic sodium hydroxide solu- -tion at reflux temperature yielded additional pyridone upon dilution with water, filtration, and recrystalliza-tion from acetone-ethyl ether.
The next example illustrates how l-acetoxy com-pounds of formula I are prepared.
Example 129 A 2.4 g. portion oE 3,5-diphenyl-1-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. o~ 1-acetoxy-3,5-diphenyl-4~lEI)-pyridone, m.p. 197 199C.

X-4097A ~74-, ~756g6 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 l-methyl-3,5-diphenyl-4(lH)-pyridone, hydroiodide, m.p. 110C., yield 100 Example 131 l-methy]-3,5-diphenyl 4(1H)-pyridone, hydro-chloride, m.p. 187-194C., yield 100~
The example below is typical of the formation of pyridinethiones of formula I.
Example 132 A 10 g. portion of 3,5-diphenyl-1-methyl-4(lH)~-pyridone, prepared by the process of Example 1, was mixed with a 10 g. portion of P2S5 in 100 ml. of 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-di-phenyl-l-methyl-4(lH)-pyridinethione, m.p. 168-171C.
The following typical pyridinethiones were pre-pared by following the general procedure of Example 132.
Example 133 3,5-bis(3-chlorophenyl)-1-methyl-4(lH)-pyridine-thione, m.p. 210-212C., yield 86%
Example 134 .
3-l3-chloroPhenyl)-l-methyl-5-phenyl-4(1H)-pyridinethione, m.p. 190-193C., yield 71~

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Example l l-methyl-3-phenyl-5-(3-trifluoromethylphenyl) 4(lH)-pyridinethione, m.p. 210C., 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 o~ 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 re-presentative tests reported below are exemplary of the outstanding activity of the compounds.
Compound application rates are expressed in kilo-grams of the compound per hectare of land (kg./ha.) through-out 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 ~756~6 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 1~8-150, 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 ~road spectrum greenhouse test . .
S~uare plastic pots were filled with a sterilized sandy loam soil and were planted to seeds of tomato, large crabgrass and pigweed. ~ach pot was individually fer-tilized.
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 appli-cations were sprayed on the soil the day after the seeds were planted.
Each test compound was dissolved in 1:1 ace-tone:ethanol at the rate of 2 g. per 100 ml. The solutionalso contained about 2 g. per 100 ml. of an aniGnic-non-ionic surfactant blend. One ml. of the solution was diluted to 4 ml. with deionized water, and 1-1/2 ml~ of the re-sulting 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 com-pounds. Untreated control plants were used as standards in every test.

~-4097A _77_ --' ~ll.C3756~

The table below reports results of testing typical compounds of formula I. The compounds a:re identified by their example numbers above.

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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
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.

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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./100 ml. of the test compound, and one part of the organic solution was diluted with 9 parts of water before applica-tion. 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.

~L~75~96 Table 5 Compound of Example Preemergence Postemergence No. 9 kg./ha. 9 kg./ha.

.

32`

34 4 ;~ :

36 3 ~ :
129 1 ~-38 5 4 ::
, 41 5 4 ~.

43 5 4 ~. :
: . 44 3 2 3 2 .

.

~ ;X-4097A~ 106-, .

.. . . .. :.. : .

Table S Continued _ of Example Preemergence Postemergence No. 9 kg./ha. 9 kg./ha.

.
~ 3 3
6 5 5
7 5 5
8 S 5 . :
9 5 4 . 14 5 S

: 59 3 3 . ~ :

: 61 X-4097A -107- :
~ ~ ' :: ' ~. :

~4~7S~6 Table 5 Continued Compound of Example Preemergence Postemergence No. 9 k~./ha.~ kg./ha.

69 ~ 4 . ~1 3 2 87 5 . 2 89 5 4 :~

:18 2 ' ...'.' '-:., ~ : ,', ,: . ~ . ., . , : , , .: : .
., . - . . . . . .
,. . . -, ~ . . .. .

:1~7S696 Table 5 Continued Compound of Example Preemergence Postemergence No. 9 kg./ha. 9 kg./ha. _ 116 . 4 4 ~: X-4097A -109-,,:

~ , ~75696 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, exceE~t that only pre-emergence applications of the compounds were made~ All compounds were tested at 9.0 kg./ha.
Table 6 Compound of Garden Black Example Huckle- Sickle- Common Prickly Night No. berrypod Ragweed Sida shade 26 ~ 2 3 :

.
,, - . . .

~6~7569~

Table 6 Continued Compound of Garden Black Example Huckle- Sickle- Colmmon Prickly Night No. berrypod _gweed Sida shade 7 5 5 5 . :
8 5 5 5 .. :
9 5 5 5 :~ :
~ ::

14 5 5 5 ~--; ;~ X-4097A -111- ~

' ;. . :

:
Table 6 Continued Compound of Garden Black Example Huckle- Sickle- Common Prickly Night No. be.r~y_ pod a~weed Sida shade 53 5 4 4 . :

130 5 s 5 13~ 5 2 4 135 5 5 5 ..

: ~:
~: 20 66 5 5 5 ~
68 2 1 2 . .
69 5 5 5 ;

74 5 5 5 ~ :
4 3 4 .
78 4 2 ~ 4 ~ 2 2 3 :
: 81 ~ 4 4 4: .:

X-4097A : -112-., :
' ~L~75696 Table 6 Continued Compound of Garden Black Example Huckle- Sickle- Common Prickly Night No. berr~pod Ragweed Sid~ shade . _ la6 5 3 5 ;;

~ 110 3 2 2 : 116 5 5 5 . . :
: .

' :

~ : ' ." ' .
~ X~4097A -113-.

,. : :.. : :, , - :

~75~6 Example 143 soil-incorporated fourteen-species test This test was performed to evaluate typical com-pounds of formula I against a number of crop and weed 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 com-pounds were dissolved in acetone-ethanol at 1 g./100 ml.
concentration before dilution with water for application.

.

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56~
Example 144 14-species_greenhouse test In this test, the test compounds of formula I
were applied to the surface of -the soil preemergence to the test plants. Again, the test method was in general the method of Example 141. Various applicat:ion rates were used as indicated below, and typical results were as follows~
Different plant species were used in testing different compounds.

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, ' ~CIi7569~ii Example 145 soil incor~orated test In this test, the compounds of formula I were incor-porated 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.

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ExamE~ 146 surface-applied multiple-crop test Representative compounds of formula I were tested against a number of representative crop plants in a field 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 afte:r the seeds were planted. The bands were about 1 meter wide, so that each test plot included a l-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 ater 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.

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Exam~le 1 107S696 soil-incorporated multiple-cro~ test The procedure of Example 146 was followed, except that the compounds of formula I were incorporated with a rotary tiller immediately after application. Crop and weed seeds were planted immediately after application and in-corporation of the compounds.

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~7~6 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 green-house soil which had been planted with bindweed, bermuda-grass, 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 Bind- Bermuda- Johnson- Quack-kg./ha. weed grass grass grass 0.28 10 5 1 8 0.S6 10 7 3 10 1.1 10 7 5 9 2.2 10 8 5 g -~
The same compound was also tested against the ~ame weeds in a postemergence test, wherein the weeds were al-lowed 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-B inches, and ' ' ' ~75696 , 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.
Rate Bind- Bermuda- Johnson- Quack-kg./ha. weed grass gras grass 0.56 8 8 8 10 1.1 ~ 8 8 10 2.2 8 7 8 10 Example 149 perennial weed tests .. .. _ .
In this typical experiment, the weeds and con-ditions were similar to those of Example 148. A number of exemplary compounds of formula I were used. The weeds w~re observed about four weeks after application of the com-pounds. The preemergence results were as follows.

X-4097~ -135-.

1~75696 Compound of Appln.
Example Rate Bind- Bermuda- Johnson- Quack-No. ka./ha. weed grass ~rass 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 ~
0.14 ~0 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 1.1 10 9.5 10 10 0.56 10 9 10 10 0.28 10 9 7 9 0.14 10 7 7 7 20 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 follow~

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Compound of Appln.
Example Rate Bind- Bermuda- Johnson- Quack-No. k~./ha. weed grass arass grass .l 9.5 9O5 0.56 9 9.5 8 9 0.28 8 g.s 0.14 3 9 ,, , 51 1.1 9 9 0.56 9 8 7 9 0.28 7 5 o 0.14 5 4 2 1.1 9 9 0.56 9.5 9 8 7 0.28 ~ 5 0.14 7 4 4 1.1 9 9 0.56 9.8 9 8 9 0.28 8 8 b.14 7 57 l.l 9 9 0.56 9.5 9 7 8 0.28 5 6 0.14 4 3 EXample 150 -mesquite test Typ1cal compounds of formula I were tested against mesquite trees growing in the greenhouse~ The trees were transplanted,~when 5-12 inches tall, into l-gallon metal ::~ pots. After~the trees had begun to grow vigorously in the : ~ ~pots, the compounds were applied as a soil drench. T~e ~compounds were formulated for application by dissolving them X-4097A : -137-:

: . . ` ..

in acetone:ethanol as described in Example 138, and dis-persing 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 scale.
Compound of Appln.
Example Rate No. kg./ha.Ratings 34 1.1 6 2.2 6 4,5 7.5 37 1.1 7 2.2 4 4.5 8.5 1 1.1 9.8 2.2 9.9 4.5 9-9 47 1.1 9 2.2 9.5 4.5 9.9 48 1.1 10 2.2 9.9 4.5 10 51 1.1 0 2.2 4 4.5 7 6 1.1 10 2.2 9,5 ~;
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Example Rate No._kg./ha. ~atings 7 1.1 2 2.2 7.5 4.5 4 8 1.1 6 2.2 7 4.5 9.9 12 1.1 3 2.2 9 4.5 6 13 1.1 10 2.2 10 4.5 lQ
14 1.1 10 2.2 10 4.5 10 57 1.1 o 2.2 0 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 oompound was applied.
The compound was formulated according to the method of ~xample 138, and was applied as a surface spray . ~
to a 1 meter square plot around the base o~ each tree.

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.; ' :' 11~756~6 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 Or21 0~28 0~42 0~56 1~1 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.

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, , ~L~7~ ;96 Exam le 152 purple nutsQdge control in cotton tests The compound of Example l was tested in field-growing cotton infested with purple nutsedge. The cotton was grown in a clay soil in flat cul1ure, with no irriga-tion, in a sub-tropical climate. The compound was applied as a water-dispersed 80~ we~table powder, and was incor-porated into the soil immediately before the cotton was planted. Crop injury and weed con~rol observations were made, in percent injury or control, approximately eight weeks after the compound was applied. The results were as ~ollows.

Appln. Bristly Purple Red Rate Crop Starbur Nutsedge Tassellower kg.~ha. Injury Control Control Control .
0.56 0 27 20 33 0.84 0 60 67 80 l.l 0 68 73 90 1.7 0 90 90 lO0 2.2 0 99 99 lO0 3.4 o 99 99 ~o Example 153 weed control in coffee tests . . . _ _ , The compound of Example l was also applied to j -e~tablished 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 : '":

~:- ,, ~7~69~ii control of annual grasses, annual broadleavesl Paraguay starbur, bristly starbur, hairy beygarticks, 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 easily-controlled broadleaves such as pigweed, and the more dif-ficult to kill broadleaves such as the nightshades, ragweed and sicklepod. Further, the compounds control such peren-nial weeds as johnsongrass, quackgrass, bindweed, bermuda-grass and nutsedge, which are very difficult to control.
The compounds also control algae and aquatic weeds, such as coontail, hydrilla and the like. Still further, the com-pounds 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 exempli-~ied activity of the compounds shows that the compounds areeffective against all types of weeds.
A 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 ger-minating and emerging, and can also be used to kill emerged weeds by dlrect contact with the exposed portions of the 1~75~i96 weed. 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 water 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 com-pounds, a method of using the compounds for killing weedsis an important embodiment of the present invention. This embodiment is a method of selectively killing weeds which comprises contacting the weeds with an herbicidally-effective amount of one of the compounds of formula I de-scribed above. In the context of this invention, weed seeds! which are contacted with the compounds through preemergence 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 compcunds 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. Because of the safety with which this crop may be treated with the : . "' "
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~L0756~6 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 xigh~s 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 re-strictive 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 un-derstood 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 populatlon 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 kllled and another part of the population is injuredO The X-4097~ -l~S-~:

... . .
- ., , : , , , , -~L~75696 mere injury of a weed is beneficial, because the surrounding crop, growing normally, shades out and kills the slow-growing injured weed.
The best application rate of a given compound of formula I for the control of a given weed varies, of course, depending upon the method of compound application, climate, 50il type, water and organic matter contents of the soil and other factors known to those skilled in plant science. It wil~ 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 com- - -pounds 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 ger-minating. They may also be applied to the soil during a dormant season to kill weeds germinating during the fol-lowing 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 in-corporated, it will usually be applied and incorporated immedlately before planting. If it is to be surface applied, it is usually simplest to apply the compound immediately af~er planting.

., . ~ ~ , . . . .. .

~L~7~696 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-dis~ersed 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 chemicals over soil or standing vegetation. ~hen a compound is to be soil-incorporated, any of the usual soil incorporation equip-ment, such as the disc harrow, the power-dxiven rotary hoe and the like, are effective.
The compounds are normally applied in the form of the herbicidal compositions which are an important embodi- ;
ment of the invention. An herbicidal composition of this invention comprises a compound of formula I and an inert carrier. Tn general r 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 con-centrated 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 S
percent of the compound. Water-dispersible or emulsifîable compositions are either solids usually known as wettable powders, or liquids usually known as emulsifiable concen-trates. These concentrated compositions are used in the range;

~ .
' : . . , - . : . .. ~ .. . . .. ., . . , . ,:
. . . . . . . ..

~S6~6 %_by wei ht compound of formula I 10-80 surfactant 3-10 inert carrier 87-10 Wettable powders comprise an intimate, finely-divided mixture of the compound, an inert carrier and sur-factants. 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 con-densed naphthalenesulfonates, the naphthalenesulfonates, the alkylbenzenesulfonates, the alkyl sulfates and nonionic sur-factants such as ethylene oxide adducts of phenol.
Typical emulsifiable concentrates of the com-pounds of formula I comprise a convenient concentration of the compound, such as from about 100 to about 500 g. per liter of liquidr dissolved in an inert carrier which is a mixture of water-immiscible solvent and emulsiiers. 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-ethoxy-ethanol. Suitable emulsifiers for emulsifiable concentrates are chosen from the same types of surfactants used fox wet~able powders, When a co~pound is to be applied to the soil, as X~4097A 148-..

.. ' .' ~7~696 for a preemergence application of the compound, it is con-venient 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 - si~e 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 fol-lowing range:
% by weight compound of formula I 1-10 surfactant 0-2 inert carrier 99-88 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 (133)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A compound of the general formula I

wherein: X is oxygen or sulfur;
R is C1-C3 alkyl; C1-C3 alkyl substituted with halo, cyano, carboxy or methoxycarbonyl; C2-C3 alkenyl; C2-C3 alkynyl; C1-C3 alkoxy; acetoxy; or dimethylamino; provided that R comprises no more then 3 carbon atoms;
the R1 groups independently are halo; C1-C8 alkyl; C1-C8 alkyl substituted with halo; C1-C8 alkyl monosubstituted with phenyl, cyano or C1-C3 alkoxy; C2-C8 alkenyl; C2-C8 alkenyl sub-stituted with halo; C2-C8 alkynyl; C2-C8 alkynyl substituted with halo; C3-C6 cycloalkyl; C4-C6 cycloalkenyl; C4-C8 cycloalkylalkyl; C1-C3 alkanoyloxy; C1-C3 alkylsulfonyloxy; phenyl;
phenyl monosubstituted with halo, C1-C3 alkyl, C1-C3 alkoxy, or nitro; nitro; cyano; carboxy;
hydroxy; C1-C3 alkoxycarbonyl; -O-R3; -S-R3;
-SO-R ; or SO2-R3;

R3 is C1-C12 alkyl; C1-C12 alkyl substituted with halo; C1-C12 alkyl monosubstituted with phenyl, cyano or C1-C3 alkoxy; phenyl;
phenyl monosubstituted with halo, C1-C3 alkyl, C1-C3 alkoxy or nitro; C3-C6 cycloalkyl;
C4-C8 cycloalkylalkyl; C2-C12 alkenyl; C2-C12 alkenyl substituted with halo; C2-C12 alkynyl;
or C2-C12 alkynyl substituted with halo;
provided that R3 comprises no more than 12 carbon atoms;
R2 is halo; hydrogen; cyano; C1-C3 alkoxycarbonyl;
C1-C6 alkyl; C1-C6 alkyl substituted with halo or C1-C3 alkoxy; C2-C6 alkenyl; C2-C6 alkenyl substituted with halo or C1-C3 alkoxy; C2-C6 alkynyl; C3-C6 cycloalkyl; C3-C6 cycloalkyl sub-stituted with halo, C1-C3 alkyl or C1-C3 alkoxy;
C4-C6 cycloalkenyl; C4-C8 cycloalkylalkyl;
phenyl-C1-C3 alkyl; furyl; naphthyl; thienyl;
-O-R4; -S-R4; -SO-R ; -SO2-R , or ;

R4 is C1-C3 alkyl; C1-C3 alkyl substituted with halo; C2-C3 alkenyl; C2-C3 alkenyl substituted with halo; benzyl; phenyl; or phenyl substituted with halo, C1-C3 alkyl or C1-C3 alkoxy;
the R5 groups independently are halo;
C1-C8 alkyl; C1-C8 alkyl substituted with halo; C1-C8 alkyl monosubstituted with phenyl, cyano or C1-C3 alkoxy; C2-C8 alkenyl, C2-C8 alkenyl substituted with halo; C2-C8 alkynyl; C2-C8 alkynyl substituted with halo;
C3-C6 cycloalkyl; C4-C6 cycloalkenyl; C4-C8 cycloalkylalkyl; C1-C3 alkanoyloxy; C1-C3 alkylsulfonyloxy; phenyl; phenyl mono-substituted with halo, C1-C3 alkyl, C1-C3 alkoxy or nitro; nitro; cyano; carboxy;
hydroxy; C1-C3 alkoxycarhonyl; -O-R6;
-S-R6; -SO-R ; or -SO2-R ;
R6 is C1-C12 alkyl; C1-C12 alkyl sub-stituted with halo; C1-C12 alkyl mono-substituted with phenyl, cyano or C1-C3 alkoxy; phenyl; phenyl monosubstituted with halo, C1-C3 alkyl, C1-C3 alkoxy or nitro; C3-C6 cycloalkyl; C4-C8 cyclo-alkylalkyl; C2-C12 alkenyl; C2-C12 alkenyl substituted with halo; C2-C12 alkynyl; or C2-C12 alkynyl substituted with halo; provided that R6 comprises no more than 12 carbon atoms;
m and n independently are 0, 1 or 2; provided that when X is oxygen, R is methyl, and R2 is unsubstituted phenyl, then m is 1 or 2;
and the acid addition salts thereof.
2. A compound of Claim 1 of the general formula II

wherein: X is oxygen or sulfur;
R° is C1-C3 alkyl; C2-C3 alkenyl; acetoxy;
or methoxy;
q and p independently are 0, 1 or 2;
the R7 groups independently are halo; C1-C3 alkyl; trifluoromethyl; or C1-C3 alkoxy;
the R8 groups independently are halo; C1-C3 alkyl; trifluoromethyl; or C1-C3 alkoxy; or two R8 groups occupying adjacent o and m positions combine with the phenyl ring to which they are attached to form a 1-naphthyl group.
3. A compound of Claim 1 of the general formula III

wherein R, R1 and R2 are defined as in Claim 1.
4. 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone
5. 1-methyl-3,5-bis(3-trifluoromethylphenyl)-4(1H)-pyridone
6. 3-phenyl-1-(2,2,2-trifluoroethyl)-5-(3-trifluoro-methylphenyl) 4(1H)-pyridone
7. 3-(3-bromophenyl)-5-(3-chlorophenyl)-1-methyl-4(1H)-pyridone
8. 3-(3-chlorophenyl)-5-(4-chlorophenyl)-1-methyl-4(1H)-pyridone
9. 3-(2-fluorophenyl)-1-methyl 5-(3-trifluoromethyl-phenyl)-4(lH)-pyridone
10. 3-(2-chlorophenyl)-5-(3-chlorophenyl)-1-methyl-4(1H)-pyridone
11. 3-(3-methoxyphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone
12. 3-(4-chlorophenyl)-l-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone
13. 1-allyl-3-phenyl-5-(3-trifluoromethylphenyl-4(1H)-pyridone
14. 3-(4-isopropylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone
15. 3-(2-chlorophenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone
16. 3-(3-fluorophenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone
17. 3-(4-fluorophenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone
18. 3-(4-methoxyphenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone
19. 1-methyl-3-(3-methylthiophenyl)-5-phenyl-4(1H)-pyridone
20. 1-methyl-3-(3-methylsulfinylphenyl)-5-phenyl-4(1H)-pyridone
21. 1-methyl-3-(3-methylsulfonylphenyl)-5-phenyl-4(1H)-pyridone
22. 1-methyl-3-phenyl-5-(4-trifluoromethylphenyl)-4(1H)-pyridone
23. 3-(3-benzyloxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone
24. 1-methyl-3-phenyl-5-(2-thienyl)-4(1H)-pyridone
25. 3-(3-isobutylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone
26. 1-methyl-3-(3-nitrophenyl)-5-phenyl-4(1H)-pyridone
27. 3-(2,4-dichlorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone
28. 3,5-diphenyl-1-ethyl-4(1H)-pyridone
29. 1-allyl-3,5-diphenyl-4(1H)-pyridone
30. 3,5-diphenyl-1-isopropyl-4(1H)-pyridone
31. 1-cyanomethyl-3,5-diphenyl-4(1H)-pyridone
32. 3,5-diphenyl-1-propyl-4(1H)-pyridone
33. 3,5-diphenyl-1-methoxy-4(1H)-pyridone
34. 3-(3-fluorophenyl)-1-methyl-5-phenyl-4(1H) pyridone
35. 3-(4-bromophenyl)-1-methyl-5-phenyl-4(1H)-pyridone
36. 3-(4-methoxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone
37. 3-(3-chlorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone
38. 3-(4-chlorophenyl)-1-methyl-5-phenyl-4(1H) pyridone
39. 1-methyl-3-(1-naphthyl)-5-phenyl-4(1H)-pyridone
40. 3,5-bis(3-chlorophenyl)-1-methyl-4(1H)-pyridone,
41. 1-methyl-3-(3-methylphenyl)-5-phenyl-4(1H)-pyridone
42. 1-methyl-3-(4-methylphenyl)-5-phenyl-4(1H)-pyridone
43. 1-methyl-3-(2-methylphenyl)-5-phenyl-4(1H)-pyridone
44. 3-(4-fluorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone
45. 3-(3-methoxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone
46. 3-(3,4-dichlorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone
47. 3-(2,5-dichlorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone
48. 3-(2-chlorophenyl)-1-methyl-5-phenyl-4(1M)-pyridone
49. 3,5-bis(3-fluorophenyl)-1-methyl-4(1H) pyridone
50. 3-(3-chlorophenyl)-5-(3-Eluorophenyl)-1-methyl-4(1H)-pyridone
51. 3-(3,5-dichlorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone
52. 3,5-bis(3-bromophenyl)-1-methyl-4(1H)-pyridone
53. 3-(3-bromophenyl)-1-methyl-5-phenyl-4(1H)-pyridone
54. 3-(2-fluorophenyl)-1-methyl-5-phenyl-4(1H)-pyridone
55. 3-(3-bromophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl-4(1H)-pyridone
56. 1-(1-carboxyethyl)-3-phenyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone
57. 1-dimethylamino-3,5-diphenyl-4(1H)-pyridone
58. 1-methyl-3-(2-naphthyl)-5-phenyl-4(1H)-pyridone
59. 1-ethyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone
60. 3-phenyl-1-propyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone
61. 1-methoxy-3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone
62. 3-(3-chlorophenyl)-1-methyl-5-(3-trifluoromethyl-phenyl-4(1H)-pyridone
63. 3-(4-biphenylyl)-1-methyl-5-phenyl-4(1H)-pyridone
64. 3-(3-biphenylyl)-1-methyl-5-phenyl-4(1H)-pyridone
65. 1-methyl-3-phenyl-4(1H)-pyridone
66. 3-bromo-1-methyl-5-phenyl-4(1H)-pyridone
67. 3-bromo-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone
68. 1-methyl-3-(3-trifluoromethylpllenyl)-4(1H)-pyridone
69. 3-chloro-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone
70. 3-(3-carboxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone
71. 3-(3-cyanophenyl)-1-methyl-5-phenyl-4(1H)-pyridone
72. 3-(3-ethoxycarbonylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone
73. 3,5-bis(3-cyanophenyl)-1-methyl-4(1H)-pyridone
74. 1-methyl-3-phenyl-5-(3-thienyl)-4(1H)-pyridone
75. 3-cyano-1-methyl-5-phenyl-4(1H)-pyridone
76. 1,3-dimethyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone
77. 1,3-dimethyl-5-phenyl-4(1H)-pyridone
78. 3-(3-chlorophenyl)-1,5-dimethyl-4(1H)-pyridone
79. 3-ethyl-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone
80. 3-cyclohexyl-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone
81. 3-isopropyl-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone
82. 3-hexyl-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone
83. 3-benzyl-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone
84. 3-butyl-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone
85. 3-(3-cyclohexenyl)-1-methyl-5-(3-trifluoro-methylphenyl)-4(1H)-pyridone
86. 1-methyl-3-propyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone
87. 1-methyl-3-(4-nitrophenyl)-5-phenyl-4(1H)-pyridone
88. 3,5-bis(3,4-dimethoxyphenyl)-1-methyl-4(1H)-pyridone
89. 3-ethoxycarbonyl-1-methyl-5-phenyl-4(1H) pyridone
90. 3-(2-furyl)-1-methyl 5-phenyl-4(1H)-pyridone
91. 3-cyano-1-methyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridone
92. 3-(3,4-dimethoxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone
93. 3-(3,4-dibromocyclohexyl)-1-methyl-5-(3-tri-fluoromethylphenyl)-4(1H)-pyridone, hydrobromide
94. 3-(3-isopropenylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone
95. 3-(3-ethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone
96. 3-(3-hexylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone
97. 3-(4-ethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone
98. 3-(3-cyclohexylmethylphenyl)-1-methyl-5-phenyl-4(1H)-pyridone
99. 1-methyl-3-phenyl-5-benzylthio-4(1H)-pyridone
100. 1-methyl-3-phenyl-5-phenylthio-4(1H)-pyridone
101. 1-methyl-3-phenoxy-5-phenyl-4(1H)-pyridone
102. 1-methyl-3-phenyl-5-phenylsulfonyl-4(1H)-pyridone
103. 3-methoxy-1-methyl-5-phenyl-4(1H)-pyridone
104. 3-(3-hydroxyphenyl)-1-methyl-5-phenyl-4(1H) pyridone
105. 3-cyclohexyl-5-(3-hydroxyphenyl)-1-methyl-4(1H)-pyridone
106. 3-(3-ethoxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone
107. 3-(3-allyloxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone
108. 3-[3-(1-fluoro-2-iodovinyloxy)phenyl]-1-methyl-5-phenyl-4(1H)-pyridone
109. 3-(3-isopropoxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone
110. 3-(3-cyanomethoxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone
111. 3-(3-dodecyloxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone
112. 1-methyl-3-[3-(4-nitrophenoxy)phenyl]-5-phenyl-4(1H)-pyridone
113. 1-methyl-3-(3-methylsulfonyloxyphenyl)-5-phenyl-4(1H)-pyridone
114. 1-methyl-3-phenyl-5-[3-(1,1,2,2-tetrafluoro-ethoxy)phenyl]-4(1H)-pyridone
115. 3-(3-acetoxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone
116. 3-(3-hexyloxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone
117. 3-(3-decyloxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone
118. 1-methyl-3-phenyl-5-(3-propoxyphenyl)-4(1H)-pyridone
119. 1-methyl-3-phenyl-5-(3-propargyloxyphenyl)-4(1H)-pyridone
120. 3-(3-cyclohexylmethoxyphenyl)-1-methyl-5-phenyl-4(1H)-pyridone
121. 1-methyl-3-(3-octyloxyphenyl)-5-phenyl-4(1H)-pyridone
122. 1-methyl-3-(3-phenoxyphenyl)-5-phenyl-4(1H)-pyridone
123. 1-acetoxy-3,5-diphenyl-4(1H)-pyridone
124. 1-methyl-3,5-diphenyl-4(1H)-pyridone, hydro-iodide
125. 1-methyl-3,5-diphenyl-4(1H)-pyridone, hydro-chloride
126. 3,5-diphenyl-1-methyl-4(1H)-pyridinethione
127. 3,5-bis(3-chlorophenyl)-1-methyl-4(1H)-pyridine-thione
128. 3-(3-chlorophenyl)-1-methyl-5-phenyl-4(1H)-pyridinethione
129. 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4(1H)-pyridinethione
130. A process for the preparation of a compound of the general formula I
wherein X, R, R1, R2 and m are defined as in claim 1, which comprises cyclizing a compound of the formula IV
wherein R1, R2 and m are defined as in claim 1, with an agent selected from the group consisting of a formylating agent, and an aminoformylating agent when one of Q1 and Q2 is 2 hydrogen atoms and the other is =CHNHY wherein Y is hydrogen; hydroxy; C1-C3 alkyl; C1-C3 alkyl substituted with halo, cyano, carboxy or methoxy-carbonyl; C2-C3 alkenyl; C2-C3 alkynyl; C1-C3 alkoxy; or dimethylamino; provided that Y comprises no more than 3 carbon atoms; and with a compound of the formula wherein Y is defined as before or the acid addition salt thereof, when both Q1 and Q2 are independently selected from the group consisting of =CHOH
=CHN(R9)2 in which the R9 groups independently are C1-C3 alkyl, or the R9 groups combine with the nitrogen atom to which they are attached to form pyrrolidino, piperidino, mor-pholino or N-methylpiperazino;
to provide a compound of the 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 P2S5.
131. The process of claim 130 for preparing a com-pound of formula I which comprises cyclizing a compound of the formula VI
wherein R1, R2 and m are defined as in claim 1, with a compound of the formula wherein Y is defined as in claim 5 or the acid addition salt thereof, when both Q1 and Q2 are independently selected from the group consisting of =CHOH
=CHN(R9)2 in which R9 is defined as in claim 5, 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 P2S5.
132. The process of claim 130 for preparing a com-pound of formula I which comprises cyclizing a compound of the formula VII
wherein R1, R2 and m are defined as in claim 1, with an agent selected from the group consisting of a formylating agent, and an aminoformylating agent when one of Q1 and Q2 is 2 hydrogen atoms and the other is =CHNHY wherein Y is defined as in claim 5, 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 P2S5.
133. A method of controlling noxious vegetation which comprises applying a compound of the general formula I

wherein R, R1, R2 and m, are defined as in claim 1, to an area containing said noxious vegetation.
CA233,945A 1974-08-28 1975-08-22 3-phenyl-5-substituted-4(1h)-pyridones-(thiones) Expired CA1075696A (en)

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US6048823A (en) 1996-02-02 2000-04-11 Kumiai Chemical Industry Co., Ltd. Pyridone derivatives and herbicides
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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

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160286802A1 (en) * 2013-04-17 2016-10-06 Sepro Corporation Herbicidal compositions and methods
US11026423B2 (en) * 2013-04-17 2021-06-08 Sepro Corporation Herbicidal compositions and methods
US20220125048A1 (en) * 2013-04-17 2022-04-28 Sepro Corporation Herbicidal compositions and methods

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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
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
IE42444B1 (en) 1980-08-13

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