DE2219702A1 - Pyrazole derivatives and plant growth regulating agents containing them - Google Patents

Description

Various types of compounds have been found useful in modifying or directing the growth of plants. In position 2 Pyrazoloisoindolone (USA Patents 3,407,206 and 3,409,425) substituted exhibit this property.

When used in the appropriate dosages, the compounds according to the invention result in a modification of the growth, development and reproduction of plants or can be used to kill undesired plants. The effects of using in low doses include reduced vegetative development, increased fruit set and yield in relation to the size of the plant, increased carbon

- Ί -

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29 ^ 9-1 / 2-σ

hydrate content, inhibition of terminal growth, elimination of fruiting in the late stage of the growing season, stimulation of separation, prevention of seed formation in certain weeds and stimulation of root growth, axillary development and parthenocarpic fruiting. Treatment at higher doses results in a kill, burn, defoliation or severe inhibition of certain plants. .

The compounds according to the invention have the formula

or

where I. '

-C = C

C-C

.N

or N

H
-C - CH

w / ι

Hydrogen, fluorine, chlorine or bromine, Hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy

with 1 to 4 carbon atoms or trifluoromethyl,

an integer from 1 to 5,

Hydrogen, alkyl having 1 to 4 carbon atoms or

a group from the class -CHg-, -CHgCJLj "and

-CHaCH-, where the group is the 4-position of the pyrazole rings with the 2-position of the substituent E. ver

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2949-1 / 2-G

binds,

. tert-alkyl with 4 to 12 carbon atoms, naphthyl, Phenanthryl,

or

X hydrogen, halogen, alkyl with 1 to 4 carbon atoms, hydroxy, alkoxy with 1 to 4 carbon atoms, Alkylthio with 1 to 4 carbon atoms, nitro, Methylsulfonyl, trifluoromethyl, cyano carboxy or Carbalkoxy with 1 to 4 carbon atoms,

Ϊ hydrogen, halogen, alkoxy with 1 to 4 carbon atoms or alkyl with 1 to 4 carbon atoms,

Z is hydrogen, halogen, alkoxy having 1 to 4 carbon atoms or alkyl with Ί to 4 carbon atoms,

Q is hydrogen, alkyl of 1 to 4 carbon atoms or

If

-CR ₄

R. alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or

B -OM, -SM or -N:

M is hydrogen, benzyl, alkyl having 1 to 6 carbon atoms, if desired, substituted by hydroxy or halogen, Sodium, lithium, potassium, calcium, mag-

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nesium, barium or

Eg

where in the case of M is hydrogen, benzyl or Alkyl of 1 to 6 carbon atoms which, if desired, is substituted by hydroxy or halogen, the compounds can also be in the form of their salts with strong acids, in which the acid part of the Belongs to group phosphoric, sulfuric, hydrochloric and nitric acid,

Ep and E, each hydrogen or alkyl of 1 to 6 carbon atoms ,

Er hydrogen or alkyl with 1 to 4 carbon atoms, E ^ hydrogen or alkyl with 1 to 4 carbon atoms, Er ₇ hydrogen or alkyl with 1 to 4 carbon atoms and

Eg hydrogen, alkyl having 1 to 12 carbon atoms or Benzyl.

The invention further comprises compositions which contain these compounds and the use of the compounds and Agents as plant growth regulators.

Of the above-described class of compounds, on the basis of their plant growth regulating activity, the Compounds particularly preferred in which the substituent R. phenyl, p-methoxyphenyl, p-methylphenyl or p-Chlorophenyl is the compounds in which the substituent R is hydrogen, and the compounds in which the substituent B is hydroxy.

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The preparation of the compounds according to the invention can by opening the appropriately substituted, ring-condensed ones Compounds, pyrazolo, / 3,1-a7isoindol. ~ 8-one, an the carbon in the 8-position take place. Of the Use of methanol for this one-opening reaction, the to form the corresponding 3- (2-Carboiaethoxyphenyl) pyrazoles is explained below:

CH _x OH. P.

Venn between those in the 3- and Ja-position of the pyrazole ring If there is no double bond in the carbon atoms present, a methanolic chemical is used instead of methanol Solution of sodium methoxide. . .

The preparation of the 3 »3 ^a ~ dihydropyrazolo / 5» 1-i * 7isoin & Ql- »8-ones is described in US Pat. No. 3,407,206. These compounds can, as described in US Patent Application Serial Ko. 9'AO ^ ^{+ on} December 10, 1970, with dehydrating agents such as oxygen, iodine or 2,3 ~ dichloro-5,6-dicyanobenzoquinone (DDQ), to form the pyrazolo

- 5 - +) DT-OS 2 161 18O

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2949-1 / 2-G

/ 5 »1-.fi/isoindol-8-one are implemented:

DDQ,

^ ₁

Using the appropriate alkyl, acyl, dimethyl carbamoyl or alkoxycarbonyl halides in the presence of sodium hydride, substituents such as alkyl, acyl, Alkylcarbamoyl and alkoxycarbonyl are introduced:

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W N

.0 + CH _x -C-Ol

Close

O = C

CH.

0 OCH,

Il / 5

The existence of isomers, such as those shown above, in which the substituent is each on one of the nitrogen atoms is located is recognized; it is the result of the rapid interconversion of the isomeric forms present in the Case of Q equals hydrogen.

The compounds according to the invention can also be obtained by reacting methyl sodium phthalate and acetophenone. The product of this reaction, the disodium salt of 2-Benzoylacety! Benzoic acid, is used to form a compound implemented according to the invention with hydrazine hydrate:

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2949-1 / 2-G

C-ONa

C-OCH ₂ .

C-ONa

Il KTo Il

0 ^ ^a

HCl

The use of alky! Substituted hydrazines instead of the hydrazine hydrate in the above method gives a general synthesis of the N-alkyl pyrazoles:

C-O-Na

C-CH-C

ti It

0 Na 0

Il

C-OH

CH ₃ NH-NH,

■ HCl

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As in the above-mentioned method, the substituents in the 2-position of the phenyl group can be modified by reactions of a type known per se. Similarly, one can introduce other substituents on the nitrogen of the pyrazole ring as above. The use of substituted phthalic anhydride or ketones which are not acetophenone provides the end product with the desired substituents. . '. .

Many acids form with the pyrazoles of the invention Addition compounds. Preferred acids are halogenated, aliphatic acids with 2 to 5 carbon atoms, halogenated Benzoic acids, halogenated phenylacetic acids, halo- ' genated phenoxyacetic acid ^ organic sulfonic acids, orr ganic phosphoric acids and inorganic phosphoric acids. These acids are preferred because the pyrazole addition compounds formed with them are highly phytotoxic and result in good oil solubility. The following are used to explain these acids:

2,3,5-trichlorobenzoic acid 2,3,6-trichlorobenzoic acid 2,3,5ι6-tetrachlorobenzoic acid 2,3,5-triiodobenzoic acid 2-methoxy-3,6-dichlorobenzoic acid 2-methoxy-3j5i6-trichlorobenzoic acid 2-methyl-3, 6-dichlorobenzoic acid 2,5-dichloro-3-aminobenzoic acid 2,5-dichloro-3-nitrobenzoic acid 2,3,6 _{-trichlorophenylacetic acid 2,4,5 5} 6-tetrachlorophenylacetic acid 2-methoxy-3> 6-dichlorophenylacetic acid 2,4 -Dichlorophenoxyacetic acid 2,4,5-trichlorophenoxyacetic acid phosphoric acid

Methane phosphoric acid Pheny! Phosphoric acid.

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Particularly preferred for its ability to kill grasses and ease of making them Addition compounds become acids of iOrmel

D.
YC-COOH

where D is halogen, Y is hydrogen, halogen, alkyl having 1 to 3 carbon atoms or haloalkyl and Z is hydrogen, Halogen or alkyl of 1 to 3 carbon atoms. The following are used to explain these acids:

Chloroacetic acid

Dichloroacetic acid

Trichloroacetic acid

Bromoacetic acid

Dibromoacetic acid

Tribromoacetic acid

Trifluoroacetic acid

α, α-dichloropropionic acid

α, α-dibromopropionic acid,

cc, α, ß-trichloropropionic acid

α, α, ß-trifluoropropionic acid

α, α-dichlorobutyric acid

α, ß-dichloroisobutyric acid

α, ß, ß-trichloroisobutyric acid

α, α-Di chi ο rval eri anä ur e.

Also preferred due to the high activity of their pyrazole addition compounds when spraying foliage are acids of the formula E ₁ -SOJS, where B ₁ - is an aliphatic hydrocarbon radical, an aromatic hydrocarbon radical or a halogen- or alkyl-substituted aromatic hydrocarbon radical. The following are used to explain these acids:

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Methanesulfonic acid

Ethanesulfonic acid

Do de cylsulfonic acid

Benzenesulfonic acid

p-toluenesulfonic acid

Dodecylbenzenesulfonic acid 2,4,6-trichlorobenzenesulfonic acid Naphthalene-ß-sulfonic acid. . .

The agents according to the invention contain a compound according to the invention together with one or more surface-active substances Means.

The surfactant for the purposes of the invention can be a wetting, dispersing or emulsifying agent, the supports the dispersion of the compound. To the surface-active Agents include anionic, cationic or nonionic agents as they have been generally used up to now have been used in plant regulating agents of a similar nature. Surfactants for the purposes of the invention are z. B. in U.S. Patents 2,426,417, 2,655,447, 2 412 510 and 2 139 276. A detailed list such agents are also found in the "Detergents and Emulsifiers Annual", 1969, John W. McCutcheon, Inc.

The surface-active agents for use in agents according to the invention include polyethylene glycol fatty acid esters and Eettalkylolamidkondensate, Alkylarylsulfonate, Fatty alcohol sulfates, dialkyl esters of iatrium sulfosuccinate, Fatty acid esters of sodium isethionate, polyoxyethylene ether and thioethers and long chain quaternary ammonium chloride compounds.

Surface-active dispersants, such as salts of lignosulfonic acids, low viscosity methylcellulose and polymerized sodium salts of alkylnaphthalenesulfonic acids,

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are also suitable for use in the weed control compositions according to the invention.

The more preferred surfactants include the anionic and nonionic types. Preferred anionic "Surfactants" are alkali or amine salts of alkylbenzenesulfonic acids, such as dodecylbenzenesulfonic acid, Sodium lauryl sulfate, alkylnaphthalene sulfonate, sodium N-methyl-N-oleoyl taurate, oleic acid ester of sodium isethionate, Dioctyl sodium sulfosuccinate and sodium dodecyl diphenyl oxide disulfonate. Preferred nonionic compounds are alkylphenoxypoly (ethyleneoxy) ethanols, such as nonylphenol adducts with ethylene oxide, polyethylene oxide adducts with long-chain, aliphatic alcohols, such as trimethylnonyl polyethylene glycol ether, Polyethylene oxide adducts of fatty and eolophonic acids, long-chain alkyl-mercaptan adducts with ethylene oxide and polyethylene oxide adducts with sorbitan fatty acid esters.

In general, the surfactants in the Agents according to the invention used in amounts of less than 10% by weight; usually the amount of surface active Mean ranges from 1 to 5%, but it can even be less than 1% by weight.

IU, e c "bige formulation can contain additional surfactants Agents are added to keep the ratio of surface-active agent to active ingredient up to such a high level Increase weight ratios like 5: 1. The addition larger amounts of surface-active agents normally have the purpose of reducing the growth-regulating effect of the To increase active compounds. When used in Höhren Dosages of the surfactant are preferably in the range from 1/5 to 5 parts per part of active ingredient.

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Plant growth-regulating agents according to the invention can, in addition to surface-active agents, also _{contain finely divided r} -inert diluents, such as talc, natural clays, including. Attapulgite and kaolinite clay, pyrophyllite, kieselguhr, artificial, fine silicon dioxide, calcium silicate, carbonates, calcium phosphates, sulfur, lime and flours such as walnut shell, wheat, redwood, soybean and cottonseed flour.

Preferred diluents are. Clays hydrated Aluminum silicate, hydrated aluminum magnesium silicate and hydrated aluminum magnesium iron silicate.

The amount of the finely divided, inert, solid diluent can be selected very differently, but will generally be in the range from 10 to 98% of the weight of the growth-inhibiting agent. The particle size can also be chosen very differently, but will usually be slightly below 50 microns in the finished formulation. To produce such agents, the ingredients are mixed and ground on a hammer mill or jet mill or similar device until uniform powders with a particle size of less than 50 microns are present. Agents containing surfactant and solid, inert diluent are preferably in the form of wettable powders containing from 25 to 90 % pyrazole.

ι "

The pyrazoles according to the invention can also be formulated in the form of highly concentrated agents in which the active ingredient can be present in amounts in the range from 90 to 99% , while the remainder of the agent consists of surface-active agents, preferably in amounts of 0.2 to 2 % and diluents as above. To produce such agents, the ingredients are mixed and ground

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a homogeneous powder of small particle size.

Agents made from these plant growth regulators and inert, solid diluents can also be formulated in grain and pellet form. In the case of such agents, the amount of diluent is generally in the range from 65 to 99 % and that of the active ingredient in the range from 1 to 35 %. Naturally, it is not a requirement to include a surface-active agent in the granular and pelletized agents. To produce granular form agents, the pyrazole can be dissolved in a solvent and this solution applied by spraying onto preformed clay granules, expanded or exfoliated vermiculite or the like, while the mixture is moved to distribute the active ingredient over and in the granular mass. Such granules can have a particle size in the range from 0.25 to 4.8 mm (corresponding to +60 to +4 mesh); the active ingredient content is preferably 1 to 6 %. Peinkorngut ("minikorn") of even smaller sizes can also be produced in a similar way and applied with appropriately designed devices. Such grains can also be produced by mixing the finely divided diluent and finely divided pyrazoles, e.g. B. grinds together, and then forms the grain by adding water, circulating and drying the resulting spheroids. Finally, a finely divided pyrazole can also be mixed with granular carriers, such as attapulgite or vermiculite, and then the active substance can be bound to the carrier by spraying a non-volatile liquid onto the whole.

For pellet production you can use a pyrazole, pelletizing clay Extrude the mixture containing diluent and water, cut the strands and that Dry product. The pellet size can range from 2 mm (10 mesh) to coarser shapes, such as cubes of 9 »5

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(3/8 in.), Range. Pellets preferably contain 5 ms 35% pyrazole. In addition to the diluents, pelletized and granular agents can also contain additives Binders, surfactants and the like.

In addition to the formulation described above, suspension concentrates can also be produced. To produce these formulations, the constituents are wet-milled, such as ball milling or sand milling according to the method of US Pat. No. 2,581,414 or 3,060,084. Using the methods described in these patents, uniform digestion of the fine particles of the active compounds according to the invention in the diluent is obtained. Such agents normally contain 15 to 50 % active ingredient and are characterized by the presence of particles with a diameter of essentially less than 5 to 20 microns »

Water-extendable oils can also be used in conjunction with a or more pyrazoles according to the invention use Find. In these plant growth regulators, surface active agents and an oil form a liquid, which is easy to pour and measure »Such liquid concentrates can then be used at the place of application Formation of a dilute spray containing the herbicide and surfactant with Water to be mixed. Such means have the advantage that the oil often acts as a foam inhibitor and in this way the tendency to large amounts of surface-active substances Means to form disruptive foam, reduced. These oil formulations are dispersions of the pyrazoles in finely divided form in non-solvent carriers. A non-dissolver carrier is an oil in which the pyrazole is sparingly soluble, e.g. B. less than about 0.1% at 25 ° G. Examples of such® Might dissolver carriers are many aliphatic hydrocarbons

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fabrics. To produce the dispersions, the components are wet-ground, e.g. on a ball or sand mill. The ingredients are mixed to form the solutions and moves, possibly with the application of heat.

The pyrazoles are in these emulsifiable oil concentrates in amounts ranging from 5 to 35 wt.%. The respective Exact active ingredient concentrations naturally depend on the intended use of the product away. When mixed with water at the application site, the oil concentrate becomes diluted so that in the final formulation the active ingredient is present in amounts in the range from 0.5 to 2% by weight. Emulsifiable agents are suitable for regulating foliage on country roads and railways as well as in other places.

Naturally, such oil formulations of the pyrazoles can be used for use also with other oils, z. B. with diesel oil, herbicidal oil and the like for application s purposes as with railroad lines.

Solution formulations can be in organic solvents be set. All solution formulations can be used for low-volume direct use; in such a use is only a practicable solubility and stability of the active ingredient in the chosen one Solvent required. An important subclass of solution formulations are those that can be emulsified Concentrates that have a water immiscible solvent as well as a surfactant system is needed to ensure the formation and stabilization of the aqueous emulsion that the end user is applying for will produce, support.

Another liquid formulation that is particularly easy to use on a small scale is the Aerocol

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Formulation packaged under pressure in a suitable container. The liquid phase can be a Be suspension, emulsion or solution. Solutions are preferred in the interests of ease of manufacture and use. The pressure can be achieved by means of low-boiling liquids such as propane or chlorofluorocarbons, or by means of relatively insoluble gases such as carbon dioxide or nitrous oxide are generated. It is preferable to rely on the combination good dissolving power and lack of flammability the chlorofluorocarbons. '

The active ingredient in all solution formulations preferably remains at 0 ° C or, at the lowest storage temperatures, which can reasonably be expected over longer periods of time, completely resolved. To ensure this permanent insolation you can add co-solvents to the formulations, which can be miscible with water even in emulsifiable concentrates.

To organic liquids for the preparation of solutions, suspensions and emulsifiable concentrates of the compounds according to the invention include alcohols, glycols, ethylene glycol ethers (Cellosolve), diethylene glycol ethers (Carbitol), ketones, esters, sulfoxides, sulfones, sulfamides, Amides, paraffinic hydrocarbons, aromatic hydrocarbons and halogenated hydrocarbons. The choice of Liquid depends on the solubility of the active compound to be used and on whether a suspension. " or solution is desired. Many compounds of the formula I do not have good solubility properties, but for different purposes are relatively ' low concentrations of active ingredients are desirable.

The quantity ranges of the active ingredient mentioned in the formulations described above are based on the normal, commercial ones Practice. But of course there is no reason

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which would prohibit preparation in much lower concentrations. At the very low doses of the active ingredient required for various plant growth effects, the additional cost (based on active ingredient) of dilute formulations is more than outweighed by an increased convenience of precise application. For example, at an application dosage of about 0.004 kg / ha (about 0.004 pounds / acre) with the ultra-small volume of 2.3 l / ha (1 quart / acre), only 0.2 % drug solubility is necessary. In the case of wettable powders, an application of. 1 kg substance / ha should be regarded as low, but a 0.4% wettable powder would result in the same dosage of 0.004 kg active substance / ha. These dilute formulations must be mixed more carefully than the more concentrated formulations, but otherwise do not present any particular difficulties.

Di & compounds according to the invention are made at the site applied, on which the plants to be influenced grow. Below the place of growth is the immediate one Area to understand in dsm the plant develops and in which it grows. This applies both before and after emergence.

Low application doses of the active ingredient from 0.001 to 4 1/2 kg / ha (0.001 to 4 pounds / acre) constitutes an average to regulate the growth of plants, e.g. B. to inhibit growth, to delay flowering, to the parthenocarp Fruit set, for increased fruit set, for carbohydrate enrichment and to control the leaf axil el constant growth. At higher dosages, e.g. B. from 1/2 to 11 kg / ha (0.5 to 10 pounds / acre) and more the compounds according to the invention have herbicidal activity against various plant species in certain Growing conditions. The application of the compound is carried out with conventional agricultural

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Devices and usually in one of the above means. The actual dose of active ingredient used must be different of course, according to the respective situation, d. H. the respective plant species, their vigor, the Season and the condition of the soil. Those skilled in the art are familiar with these slight adjustments.

The following examples serve to further illustrate the invention. All pro ζ ent data relate if not otherwise specified, based on weight.

example 1

The following formulation was produced:

.JL

3- (2-carbomethoxyphenyl) -5- (4-methoxyphenyl) pyrazole 40

Dioetyl Sodium Sulphosuccinate 1j5

Sodium lignosulfonate 3

Low viscosity methyl cellulose 1 »5

Attapulgite 54

The ingredients were mixed thoroughly to form an average particle size of less than 15 microns Passed through a jet mill, remixed, and passed through a 0.1 mm aperture sieve before packaging (U.S. Sieve Series 50-mesh sieve).

All compounds according to the invention can be used in the same Wise to be formulated.

2.2 to 3 * 4 kg of the above formulation were used in 561 1 Water entered, and this combination was in the form of a targeted spray at ground level on 1 ha of sugar cane culture applied from a height of at least 46 cm, at the

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Weeds such as Stellaria media, Ch.en.opodium album, Amarantlius retroflexus, Echinochloa crusgalli and Brachiarai sp. just came out. The formulation gave on application in the above way combating the weeds and not damaging the sugar cane.

Example2

3- (2-carbomethoxyphenyl) -5-

phenylpyrazole 25 »0

Sodium lauryl sulfate. 0.5

Ca, Mg lignosulfonate 1.0

Kaolin clay 73.5

These components were mixed and ground in the same way as in the formulation according to Example 1.

It was a suspension of 2.2 to 4.5 kg of active ingredient this formulation in 561 1 of water and this Suspension by spraying evenly on 1 ha of Poa lawn (Bluegrass) upset.

The treatment inhibited the growth of the grass for a long period of time, which resulted in a reduction in the growth of the grass Care of the area necessary mowing revealed. It promoted the development of axillary buds on the treated Plants, which made the lawn more dense. At the same time there was good control of broad-leaved weeds ascertain.

The AU. Delivery of 45 g of active ingredient in the form of the above Formulation in 227 1 V / water per "Sieve" resulted in a strong inhibition or destruction of young Amaranthus retroflexus and from Chenopodium album. With other compounds formulated and applied in the same way according to FIG In the invention, similar effects are obtained.

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Example 5

JL

.3- (2-Carbomethoxyphenyl) -5-

phenylpyrazole 25 »O

Alkylnaphthalene sulphonic acid, Na salt 1.0

Anhydrous sodium sulfate 15 »0

Non-swelling Ca, Mg bentonite 30.0

Kaolin clay. 29.0

These components were mixed and finely ground (Micropul veriz er), mixed on a heavy kneader with 15 to 20 % water and extruded in the form of cylindrical 3 »2 mm strands, which in conjunction with the. Extrusion cut into lengths of 3 »2 mm to form pellets, which were then dried.

These pellets were in the form of a soil treatment in a Dosage of 1 tablespoon "per 2 1/2 cm trunk base diameter used to encourage the growth of shrubbery plants inhibit.

Example 4-

Λ ·.

3- (2-carbomethoxyphenyl) -5- (4-methoxyphenyl) pyrazole 35 “Q

Ca, Mg lignin sulfonate 15.0

Hydrated attapulgite 1.5

Sodium pentachlorophenate 0.7

Sodium hydroxide. 0.6

Water 4-7.2

First the active ingredient was finely ground and then combined with the other components and then the slurry ground on a sand mill until essentially all of the particles were finer than 5 microns.

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This formulation was mixed with water in the ratio of 2.27 kg of active ingredient to 379 l of water and with 1.81 kg of polyoxyethylene sorbitan monolaurate are added. The suspension thus obtained was by spraying until Run off on roadside vegetation that is a mixture of grasses and herbaceous annuals and perennial plants included.

The treatment inhibited the growth of vegetation along the roadside and reduced the number of mows, necessary to keep the road looking good. The treatment also prevented flowering and seed set on many of the present plants and thereby diminished those present for reproduction Seeds of unwanted annual weed grasses and broad-leaved ones Weeds.

Example 5

Jk

3- (2-carbomethoxyphenyl) -5- (4-chlorophenyl) pyrazole 5

Fine silica. 1.25

Granular vermiculite 88.75

Trimethylnonyl polyethylene glycol ether 5 »

First, the active ingredient and silicon dioxide were mixed and finely ground and then gently mixed with the granular vermiculite mixed. The surfactant was mixed with the same amount by weight of water and added to the previously formed mixture sprayed on. Evaporation of the water provided the end product.

Using conventional grain application, this formulation was applied at a dosage of 22 kg / ha Spread over a freshly ordered, weed-free peanut crop. The grain material showed an effective in-

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penetration into the peanut foliage. The growth of annuals broadleaf weeds were prevented, while the crops remained undamaged and the yields were good. was.

Example 6

0.45 to 1.36 kg of the formulation of Example 4 and 0.91 to 1.81 kg of maleic hydrazide were dispersed in 379 l of water. This mixture was made by spraying Trees pruned to run down on the foliage applied along a power line, in which there was a regrowth of about 10 cm.

This slowed down the growth of the pruned trees. The trees needed pruning less often to keep them under the power lines.

Example 7

3 «(2-Carbomethoxyphenyl) -5- (4Hnethoxy-

phenyl) pyrazole 80.0

Alkylnaphthalenesulfonic acids, Na salt 1.5

Partially desulphonated sodium

lignosulfonate '. 2.0

Synthetic fine silica 16.5

These components were blended on a ribbon blender, finely ground until essentially all of the particles were finer than 50 microns were, and remixed to make a slightly

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2 0 9 8 A 7/1 2 3 1

to obtain dispersible, wettable powder for application as an aqueous spray.

2.2 kg of this formulation were suspended in 935 l of water and 2.2 kg of nicMphytotoxic wetting agents, such as polyoxyethylene sorbitan monolaurate, are added. The received Suspension was sprayed over 1 ha of sugar cane * - culture applied about 40 days before harvest.

The treated plants showed no bloom before harvest, while sugar cane developed blooms in an adjacent field. The treated plants provided increased amounts of sugar.

Example 8

85 g of the formulation of Example 7 were in 294 l of water suspended, including 0.45 kg non-phytotoxic wetting agent, such as polyoxyethylene sorbitan monolaurate were added. The resulting suspension was sprayed onto 0.4 ha about 8 weeks old culture sorghum of the syrup type applied. The plants at that time were 9I to 107 cm high, while a seed head development had not yet appeared.

The treatment prevented flowering and subsequent grain development. After the millet had been harvested and a comparison with 0.4 ha of untreated millet, it was found that the treated millet produced a significantly higher yield of syrup.

Example 9

A cotton field became after about 2/3 of the normal growing season with 3 ~ (2-carbomethoxyphenyl) ~ 5 ~ (4-metho: xyphenyl) -

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pyrazole In a dosage of 1 kg active ingredient / ha in the form. of the formulation of Example 1. The sprayed ■ cotton plants did not grow any further and did not plant any new capsules. The capsules already available, however, performed particularly well and produced an early yield of high quality lint. Furthermore, due to the reduced foliage and the lack of it, wrapping capsules to control insects better and to increase the number of survivors in the winter and for the next year. the number of insects still present was lower.

Example 10

The following formulation was produced:

3 "(2" carboxyphenyl) - * 5-phenylpyrazole 8o

Bentonite (Wyoming) 15

Sodium lignosulfonate 3

Sodium alkyl naphthalene sulfonate 2

The ingredients were thoroughly blended and passed through a hammer mill to form a wettable powder that had a particle size greater than 50 microns below 10 % .

With this formulation, at a dosage of 1 kg active ingredient / ha, a peanut field in the break-up * stage ("cracking" ' Stage), which is used to combat a strong mixed "population of annual weeds without damaging the oak tree" plants led.

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Example 11

3- (2-carbomethoxyphenyl) -5- (4-chlorophenyl) -pyrazole formulated as in Example 1 was applied at a dosage of 2.2 kg / ha on a field in which cabbage plants are currently being planted had been set. The treatment prevented "annual weeds from growing, while the cabbage growth.

Example 12

Perennial climbing plants in a citrus plantation were thoroughly splashed with water made up to 379 1 3.6 kg 3 ~ (2-Carbomethoxyphenyl) ~ 5 - (^ "methoxyphenyl) '·' pyrazole active ingredient, as formulated in Example 1, ent « held. The climbing plants included Morrenia odorat.a, Nomordica charantis and Passiflora incarnata. All injected Climbing plants were killed or damaged, while the citrus trees did not suffer any permanent damage suffered.

Example 13

Before emergence, a peanut field was made with as in example 1 formulated 3 «(2-carbomethoxyphenyl) -5 ~ (4Hnetho:> cy · phenyl) pyrazole in a dosage of 1 kg active ingredient / ha treated. As a result, a strong mixed population of annual weeds was controlled, while the peanut was not damaged became,

Example 14

A soybean field that difficult broad-leaved one

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Weeds such as Xanthium pensylvanicum, Iponea sp., Convolulus arvensis, Cassia obtusifolia and Sicla having spinosa, was formulated as in Example X 3 ~ (2-Carbomethoxyphenyi) -5- (4-chlorophenyl) pyrazole in a dose of 3/4 kg of active ingredient / ha sprayed, with the application taking place before the weed bloom and the spraying agent being directed in such a way that the weed foliage was wetted, but the soybean plants were largely spared. The weeds were killed or severely inhibited. The persistent weeds did not develop a viable seed. The soybeans, on the other hand, grew well and had a high yield.

Example 15

A dense stand of soybeans in the last tenth of the stage of whole blood was obtained by applying to the Foliage with 2- (2-Carbo.xyphenyl) -5-phenylpyrazole in a dosage of 0.004 kg active ingredient / ha (formulated as in Example 10). The top dominance has been eliminated, the stalk enlarged, and the suppression of the lateral growth ceased, which led to the development a larger number of new flowers and the setting of a larger number of pods per plant. The directed vegetative growth made the plant extraordinary stable, and the plants remained upright even in harsh weather conditions, while untreated Plants fell over. The total yield was compared to corresponding, untreated areas (control areas) and the upright plants made harvest easier in comparison with those that were turned down Control plants.

- 27 -

209847/1231

Dosage, yield kg / ha

Control goods

3- (2 ~ carboxy-0.004 phenyl) -5-pheny1-pyrazole

l / ha yield,% of (bu / acre) control plants

3762 (42.7)

5 (51.2)

100 120

Example 16 Oil suspension

3 ~ (2 ~ carboxyphenyl) «5- (4 ~ fluorophenyl) ~ pyrazole

Polyoxyethylene sorbitol hexaoleate

strong aliphatic hydrocarbon oil

JL

25th

5 70

The ingredients were ground together on a sand mill until the fineness of the pesticide particles fell below was about 5 microns. The resulting, rather thick suspension can be applied directly, or stretched with oils be emulsified in water.

With this formulation, peanut culture was sprayed at the stage of fruit stalk development ("pegging" stage) at a dosage of 1 / K kg active ingredient / ha. The firmness of the pod and vine set increased and the yields were higher than without treatment.

Example I7

- 28 -

2098A7 / 1231

2949-1 / 2-G

¹ EmUIgI erable concentrate %

3- (2-Carboxyphenyl) -5- (p ~ tolyl) -pyrazole 1 Isophorone 94

Mixture of oil-soluble .sulfonates and Polyoxyethylene ethers. · 5 \

The ingredients were combined and stirred to make one Form solution; There was a fine sieve filter in the discharge line provided to ensure the final product is free of any undissolved material.

This material was used to plant gynoezischer hybrid gherkins at a dosage of 56I 1 water / ha at a content of 50 ppm of active ingredient immediately before the flower, which led to the strengthening of the parthenocarpic fruit development and an increase in yield.

Example l8

Aqueous suspension . j>

^ - (2-Carboxyphenyl) -5 "(3 ^ pyridyl) -pyrazole 50.0" Polyacrylic acid thickener '. 0.3 Dodecylphenol polyethylene glycol ether 0.5

Polyvinyl alcohol. 1.0

Pentachlorophenol 0.4

Water 47.8

The ingredients were ground together on a sand mill, until essentially all of the particles were less than 5 microns in fineness. ·

A strongly of Galium sp. infested oilseed rape plantation sprayed with the formulation in a dosage of 1kg / ha from the aircraft using 94 liters of water / ha, '

29 «

2098Α7 / Ί231

2949-1 / 2-G

before the Galium produced flowers> which resulted in weed control and improved rapeseed yields.

Example IQ

Solution ■ · $>

3 «(2 ~ carboxyphenyl) -5- (2 ~ furyl.) - pyrazole 2.5 Dimethylformamide 97.5

These ingredients were combined and stirred with heating to form a solution. This solution is suitable for low-volume application.

The formulation was made from the plug stuff at a dosage of 4.7 l / ha 'in the initial stage of fruit set sprayed onto soybean culture, whereby vegetative growth stopped, but pod development stopped continued. Turning was reduced and the crop yield increased.

209847/12 3 "1

Examples of chemical manufacturing ^: " _% Example 20 7> - (2-Qarboxyphenyl) -5-phenylpyrazole

24 g of a suspension of 50% sodium hydride in mineral oil are stirred into a solution of 60 g of acetophenone in 100 ml of dimethylformamide. This mixture is stirred without heating for 3 hours or until the evolution of hydrogen has ceased.

A solution of 74 g of phthalic anhydride is added 300 ml of dimethylformamide with 27 g of sodium methoxide, the mixture thus obtained leads after half an hour into the sodium acetophenone solution and stir the resulting mixture for 3 hours at 120 ° C, whereupon the crystals filtered off, washed with acetone and dried. 118 g of the disodium salt of 2-benzoylacetylbenzoic acid fall in the process at.

A slurry of 100 g of the disodium salt is added of 2-benzoylacetylbenzoic acid in 400 ml of methanol first with 12.5 g of concentrated hydrochloric acid and on top 11 g hydrazine hydrate, this reaction mixture heats a half an hour at reflux conditions, cool to 5 to 10 ° C., acidify to pH 3 with concentrated hydrochloric acid and diluted with 300 ml of water, whereupon the crystals are filtered off and recrystallized from ethanol-water. Here fall 59 g of 3- (2-carboxyphenyl) -5-phenylpyrazole, P. 204 to 205.5 ° C.

Following the procedure of Example 20 using of the following anhydrides and ketones produced the following pyrazoles:

- 31 -

209847/1231

example

21
22nd

• 23

24

25th
26th

27
j

28

29 30th

anhydride

Ketone

product

77

Phthalic anhydride

Phthalic anhydride

Phthalic anhydride

Phthalic anhydride

Phthalic anhydride

Phthalic anhydride

4-Ethyl phthalic anhydride

Phthalic anhydride

Phthalic anhydride

Phthalic anhydride

Phthalic anhyaride

Phthalic anhydride

4-iErifiu.onn.ethylphthalic acid-

3-methoxyacetophenone

Methyl tert-butyl ketone

4 -]? Luoroacetophenone 4-methyl ac et ophenon 3-Acetylpyridine 2-Acetylfuran Acetophenon Butyrophenon ^ -Bromac etophenon

2,4,6-trimethyl acetophenone

4-ChIοracetophenon 2-Methoxyacetophenon

Pentyl 2-naphthyl ketone

hydride 3- (2-carboxyphenyl) -5- (3-methoxyphenyl) pyrazole

3- (2-Car'boxyphenyl) -5-bert.-butylpyrazole

3- (2-carboxyphenyl) -5- (4-

fluorophenylj-py'razole

3- (2-carboxyphenyl) -5- (4-methylphenyl) pyra2ol

3- (2-cartoxyphenyl) -5- (3-pyridyl) pyrazole

3- (2-Carboxyphenyl) -5 ~ (2-furyl) -pyrazole

3- (2-carboxy-4-methylphenyl) -5-phenylpyraz oil

3- (2-Carboxyphenyl) -4r-ethyl-5-phenylpyrazcl

3- (2-Carbo ^^ Tphenyl) - 3- (3-bromophenyl) -pyrazöl

3- (2-carboxyphenyl) -5- (2,4,6-

trimethylphenyl) pyrazole

3- (2-carboxyphenyl) -5- (4-chlorophenylj-pyrazole

3- ( 2- Carboxypheny1) -5- (2-mefchoxyphenyl) pyrazole

4-butyl-3- (4-trifluonaethyl-2-carboxyphenyl) -5- (2-naphthyl) pyrazole

170 164.5-166.5

.252 -

-

182 - 185 199 - 202 232 - 236 190 - 194 258 , 5 - 260

251 - 251.5, sj

Example anhydride

Ketone product

Ν »
O
CO
GO

. 34 35 36

37 38

39 .40

42

43 44

4-S ¹ I aorplitfaalsä ure anhydri d

4-chlorophthal-

, acid anhydride

3,4,6-triflaorphthalic acid

aiihydride

3,4,5-triehlophthalic anhydride

4-Garbomethoxyacetο piLenon

AcetoplieiiorL '

Acetopiieiioii

.AcetopiienoxL Acetoplienoii

phthalic anhydride

4-butylphthalacetophenone

acid anhydride

4-methoxyphthal- ■ 4-acetylpyridine ■ acid ahydride

4-butoxyphthalic anhydride

Phthalic anhydride

Phthalic anhydride

Phthalic anhydride

Propiophenone

3,3-DimetiLyloctaii-2-one

3,

1-acetyl-4-butyl naphthalene 3- (2-carboxy-5-i'luoroplienyl.) - 5- (4-car "bomethoxyp3ienyl) -pyrazole

3- (2-Carboxy-5-chloroplienyl) -5-phenylpyrazole

3 ~ (2-carboxy-3 ί 5,6-trifluorophenyl) -5-

3- (2-carboxy-4,5,6-trichloro- ' phenyl) -5-phenylpyrazole

3- (2-Carboxy-3 »5, '6-tribromophenyl) -5-phenylpyrazole

3-C2-carboxy-5-butylphenyl) -5 phenylpy r az ο 1

3- (2-carboxy-5-m ethoxypheny 1} - 5- (4-pyridyl) pyrazole

3- (2-Carboxy-5-butoxyphenyl) -4-methyl-5-phenylpyrazole

3- (2-carboxyphenyl) -5- (1,1-dimethylhexyl) -pyrazole

3- (2-carboxyphenyl) -5- (Ί, 1-diinethyldecyl) pyrazole

3- (2-Carboxypheny 1) -5- (4-butyl-1-naphthyl ) -pyrazole

example 1 anhydride - Ketone 45 -Cr Phthalic acid 2-acetylphenanes anhydride 46 Phthalic acid
anhydride 9-Acetylphenanthrene 47 Phthalic acid 3-acetylindole anhydride 48 Phthalic acid 4-hydroxyacetophenone anhydride ro 49 Phthalic acid 3-n-butylthioaeto- ο anhydride phenone co co
—J fO Ca »

product

3- (2-carboxyphenyl) -5- (2-phenanthry1) -pyras oil

3- C 2-carboxyp3ienyl) -5- (9-pb e aanthryl) -pyrazo.1

3 - C 2 »carboxyplienyl) - 5- (3-indolyl) pyrazole

3- (2-car doxyplienyl) -? 5- (4-hydroxyplienyl) pyrazole

3- (2- C art »oxypheny 1) - 5- C 3-n-" b uty 1 thi oplaeny 1) -py r az ο 1

Example 50 2- (4-methoxyphenyl) pyrazolo / 5, ia / isoindol-8-one

A mixture of 62.00 g of 2- (4-methoxyphenyl) -3,3a-dihydro-8H-pyrazoloZ5,1-jg / isoindol-8-one, 1100 ml of benzene and 27/2 g of 2,3-dichloro-5 6-dicyanobenzoquinone is heated under a nitrogen atmosphere at reflux conditions for 2 hours, a further 27.2 g of 2,3-rDiehlor-5,6-dicyanobenzoquinone are added, then heating is continued for a total of 8 hours, after cooling to 25 ° C the solid residue is filtered off and the Filtrag evaporated to dryness in vacuo. The combined solids from the filter and from the vapors are mechanically stirred for 1 hour with a mixture of 20 g of 85% strength potassium hydroxide solution and 1500 g of water, whereupon the mixture is filtered and the yellow solid is extracted twice in succession with 500 ml . Sodium bicarbonate and washed twice with 500 ml of water and air-dried and the yellow residue is now recrystallized from JOOO ml of acetone. Here, fall 55 g (80%) of 2- (4-methoxyphenyl) -pyrazolo / 5 "1-a / isoindol-8-one _i F. 180-181 ° C, to.

Example 51

5- (2-carbomethoxyphenyl) - 5- (4-methoxyphenyl) pyrazole and its hydrochloride

A mixture of 100 mg of 2- (4-methoxyphenyl) pyrazolo- / 3> 1-δ / isoindol-8-one, 10 ml of methanol and 0.1 g of sodium is stirred at 25 ° C. overnight. The evaporation of the
Methanol leads to the remaining 120 mg (96 %) of a colorless, gummy substance, the ester 5- (2-carbomethoxyphenyl) -5- ( ^/ 4-me, thoxyplienyl) -pyrazole. The crude ester is dissolved in benzene and stirred overnight with 2 g of magnesium silica gel (Florisil). Filtration and

- 25 -2098A7 / 123 1

194-9-1 / 2-G

Evaporate the benzene solution and then recrystallize from hexane-ethyl acetate (1: 1) provide 3- (2-carbomethoxypheny ^^ - ^ - methoxyphenyl ^ pyrazole, F. 92 to 93 °

The ester, 3- (2-carbomethox; 7phenyl) -5- (4-methoxyphenyl) pyrazole, is now dissolved in ether, cooled to ⁰ ° C., the solution is saturated with gaseous hydrogen chloride, and the colorless one is filtered off Precipitate of 3- (2-carbomethoxyphenyl) -5- (4-methoxyphenyl) pyrazole hydrochloride, rinsed with ether and dried by suction, whereby 105 mg (85 %) of product are obtained. The crude hydrochloride of 3- (2-carbomethoxyphenyl) -5- (4-methoxyphenyl) pyrazole is recrystallized from 10 ml of acetone, 43.9 mg being obtained after drying at 25 ° C. (0.1 mm). F. 187 to 189 ° C.

Analysis: Calculated for Found:

By replacing the hydrogen chloride in Example 51 with 100 % phosphoric, sulfuric or nitric acid, the following salts are formed:

example

52 phosphoric acid oil of 3- (2-carbomethoxyphenyl) -5- (4-methoxypheiiyl) -pyrazole,

53 sulfuric acid salt of 3 ~ (2-carbomethoxyphenyl) -5- (4-methoxyphenyl) pyrazole,

54 Nitric acid salt of 3- (2-carbomethoxyphenyl) -5- ( 4-ni e thoxyphenyl) -ijyrazole s.

B ice ρ i e l 5 5

^, (. 2 "J? / ^ Hpäthoxypheny3j-5-X4 ~ mothoxyphenyl A mixture of 100 mg of 2 ~ (4-Hethoxyphenyl) -pyrazo] o-

C. , 70 H N 62 , 71 4.97 8.15 62 4.86 7.99

2098A7 / 1231

_Z5,1-a7isoindol-8-.one and 20 ml of ethanol is overnight at 25 ° G stirred. The dissolution occurs slowly, so one adds a chip of sodium metal, judging by that Disappearance of the yellow color of 3- (2-carboethoxyphenyl) -5- (4-methoxyphenyl) pyrazole leads to an almost instant response. Remains when the solvent evaporates the colorless, rubbery 3- (2-carboethoxyphenyl) ~ 5- (4-methoxyphenyl) pyrazole back, which is recrystallized from hexane-ethyl acetate; .F. 99.5 to 101 ° G.

Using the method of example 55 UEd use Using the following starting materials and reactants, the following pyrazoles are made:

209847/1231

at
game From gang mat eri al Eeactants HO-CH ₀ -CE ₀ OH 56 2- (4-methoxyphenyl) -pyra- / ^ tTT ^ 1TT ^ tTT ATJ
. 3 3 2 C- C. 57 2- (4-methoxyphenyl) -pyra- CH ^ CH ₀ CH ₀ CHoOE QCH-, ) _O CH-OE zolo / 3i1-a7isoindol-8-one 3 c. d. C- 58 2- (4-Mettioxyphenyl) -pyra- CH ₅ CH ₂ CH ₂ Ch ₂ CH ₂ OH C ^ Ec-CE ₀ OH 59 2- (3-Ni tropheny 1) -5-methyl- (CH ₃ ) ₂ CH-OH 8-pn ro
<—> 60 2-phenylpyrazolo / 5 j 1 - & 7- CE ^ OE isoindol-8-one location 61 2-phenylpyrazoio3? 1-a / - CE _x CH ₉ CE ₀ OE ^ - j isoindol-8-one Ρ «- c. 62 2- (3,4-dichlorophenyl) - ' CE ₀ ClCE ₀ CH ₀ OH Λ /
CO 4j 7-di ^ hlorpyrazolo- £. C. C, / 3,1-a7isoindol-8-one CE ^ SH 63 2-phenylpyrazolo / 5,1-§7- isoindol-8-one 64 2-phenylpyrazolo / 5 »1-a7- isoindol-8-one 65 2-Pheny lpyr az 01 oZ5, .1 - a7 isoindol-8-one 66 2- C 3-Keth ^ lOhenvl) -pyrä-

C 3ypy) py zolo / 3,1-a7isoindole-8-oii product

3- (2-Carbopropoxyphenyl) -5 - "( 4-methoxyphenyl) pyraz ο 1

■ 3- (2-Carbobutoszyp'henyl) - 5- • (4-methoxyphenyl; -pyrazOl

3- (2-carbopentopcyphenyl) - 5- (4-methoxyphenylj-pyrazole

107 92 - 94 - 82 - 83.5

3- (2-Carboisopropoxy-5- ■ me _; thy! Phenyl) -5- (3- ^ i trophehylj-pyrazole

-3- / 5- (2-Eydroxyäthoxycarb- 94- - 95 _s 5

.onyl) -phenyl7-5-phenylpyrazole · ■. ·

3- (2-Carboisopropoxyphenyl) -5-phenylpyrazole

3- (2-Carbobenzyloxy-3 _? 6 ~ dichlorophenyl) - 5- (3 »^ * - & i chi orphenyl) pyrazole

3- (2-carbomethoxyphenyl) -5-103.5 phenylpyrazole ■ ·

3- (2-carbopropoxyphenyl) -5-. 64 phenylpyrazole

3-Z5- (J-Chlorprop oxycarbonyl) -phenyl / -5-pfc-eD.y lpyraz 01

3- (2-methylthiocarbonylphenyl) -5- (3-m ethy! phenyl) pyraz oil

ro

(S3

- *

CO

example

57 68

69

From gangsniat eri al

Reactant product

2-Ph.enylpyrazolo / 5? 1 ~ isoindol-8-one

2-phenylpyrazolo / 5 »1-17-isoindol-S-one

, i-i7-

_r (CH ₂ ) ^ - SH

I _C -CH _O SH

^ ypy isoindol-8 ~ on J- (2-Buty 1 ttd ο carbony lphenyl) .- ^ -piienylpyrazole

3- (2-hexyl thiocarbonyl phenyl) -5-pii.enylpyrazole

3- C 2-benzyl thiocarbonyl phenyl) -5-phenylpyrazole

Example 70

5- (2-carboxyphenyl) -5- (4-methoxyphenyl) ~ pyrazole

A mixture of 100 mg 2- (4-methoxyphenyl) -pyrazolo- ^ 5i1- ^ isoindol-jB-one, 5 DiI water and 5 ^ l methanol is stirred with 0.5% sodium hydroxide for 1 hour. A colorless solution forms within 5 minutes. The mixture is then acidified to pH 3 with concentrated hydrochloric acid, cooled to 0 ° C. and filtered. The colorless, crystalline residue is rinsed with water and air-dried and then ^{recrystallized from 15 μl of 35% is em} »aqueous ethanol, giving 80.7 mg (79 %) of colorless crystals, P. 223 to 225 ° C (decomp.) , of 3- (2-carboxyphenyl) -5- (4 - methoxyphenyl) -pyrazole wins.

Analysis: CHK

Calculated for C ₁₇ H ₁₄ N ₂ O ₅ : 69.37 4.80 9.52

Found: 69.19 4.68 9.43

Following the procedure of Example 70 and employing the following starting materials, the following are made Pyrazole produced:

~ ko

209847/1231

Example starting material

product

4 =

71 ·

72

73

'74

75

76

- 3-methoxy-11 H-naolite-

O-/

5_i3 y11

/ 1 ', 2': 3.4 / pyrazoloZ5,1-a7isö-

indol-11-on ^

3-Metho ^ -i iH-naphth / i ', 2': lZ5 ^ iidl

2- (2-thienyl) -8H-pyrazolo / B> isoindol-8-one

2- (2-? Uryl) -8H-pyrazolo / 5ί1-isoindol-8-one

2- (4-331 troplienyl) -pyrazolo- / 3 »1 ~ §7i soindo1-8-one

2- (3j4,5-trimetiloxyplienyl) -pyrazolo / 5> 1-§7isoindol-8-one 2- (4,5-pihydro-7-metlioxy-2H-benzZg7indaz oil-3-yl) - "b enz ο es acid

2- (7-methoxy-2H-benz / gzindazol-) Ä

F., ⁰ C ι vD 228 - 230 ro 270 - 274

3- (2-carboxyplieryl) -5- (2-part eny 1) -py raz ο 1

3- (2-carboxypiienyl) - 5- (2- f ury 1) -. pyrazole

3- (2-carboxypiienyl) -5- (4-nitro-, phenyl) pyrazole

3- (2-carboxyphenyl) -5t (3 »^» 5-trimethoxyplienyl ) -pyrazole

Example 77

A mixture of 2- (4-methoxyphenyl) -pyrazolq / 5,1-a7-isoindol-8-one and an excess of concentrated hydriodic acid is heated for 6 hours at reflux conditions and then poured onto ice. The crude solid material is recrystallized 3/1/1-ethylene / dimethylsulfoxide / v / ater, wherein the 5- (4-hydroxyphenyl) -3- (2-carboxyphenyl) pyrazole, mp 260-264 ⁰ C, is obtained.

Example 78 .

A mixture of 1.0 g • 2- (4-methylphenyl) -pyrazolo- / 3,1-a7isoindol-8-one, 2.0 g sodium hydrogen sulfide and 25 ml of dimethyl formamide is stirred at 40 ° C. overnight. The reaction mixture is then treated with concentrated hydrochloric acid acidified to pH 3, diluted with ice and water and filtered, the 3- (2-! EhiocarbQs? phenyl) -5- (4-methylphenyl) pyrazole accrues.

Example 79

5 '& 2- (4 ~ methoxyphenyl) pyrazolo / 5,1-a / isoindol ~ 8 ~ one are stirred in 50 ml of liquid ammonia (-33 ° C.) for 5 hours. After the ammonia has been allowed to evaporate, the residue is recrystallized from ethanol-water, with 2.8 g of 3- (2-carboxamidophyl) -5- (4-methoxyphenyl) pyrazole,. F., 205 to 207 ° C.

Example 80

A mixture of 20.0 g of 3- (2-carboxyphenyl) -5-phenylpyrazole and 125 ml of pyridine is treated at 25 ° C. with 13.5 g of thionyl chloride. After stirring for 2 hours, the mixture is added 55 »0 6 2-aminobutane and the reaction mixture is stirred for 3 hours. whereupon the reaction mixture between water and methylene

209847/1231

chloride and split the organic layer with water washed and evaporated. The recrystallization of the The residue from kitromethane yields 16.0 g of 3- / 2- (N ~ sec-butylcarboxamido) -phenyl7-5-phenylpyrazole, F. 174 bia

175 ⁰ c. ·

Following the procedure of Example 79 or 80 and using the. The following participants become the following Pyrazole produced:

2098Λ7 / 1231

Example starting material

Participant Product

81 82

83 84-

85 86

87

88

^ ypy / ^ - a / - HH isoindol-8-one

2- (2,4-dimethylphenyl) -. CH

pyrazolo / ^ ji-fV'isoin- ..

dol-8-on

/ Bi-a / - HH

^ ypy isoindol-8-one

2- (4-n-butoxyplienyl) -

pyrazoloZBii - ^ / iso-

indol-8-one

2- (4-trifluoromethylph.enyl) -6-liromopyrazolo-. / ^ iidlS

CH ₁ - (CHp) ₁ -HHp

3 - ^ - Carboxy ^ -tri fluorine thy (phenyl) -5- (3-m ethyl thiophenyl) pyrazole

3- (2-carboxyphenyl) -5-phenylpyrazole

3- (2-carboxyphenyl) -5- (CH,), C-phenylpyrazole ^^

3- (2-carboxamidophenyl) -5-phenylpyrazole ·

3- / 2- (N-methylcarboxamido) p3ienyi7-5- (2,4-dimethylphenyl) pyrazole

3- (2-carboxamidophenyl) -5-p-tolylpyrazole

196-198

3Z ^ - (N, K-Dimethylcarboxamido ) -phenyl7-5- (4-butoxyphenyl) pyraz oil

3- / 4-Bromo-2- (N-hexylcarboxanido) phenyl / -5- (4-trifluoromethylphenyl) pyrazole

3- / 2- (N-Ethy1-N-methylcarbox-_ amido; -5-trifluoromethylphenyi7-5- (3-methy1thi ophenyl) pyraz oil

y / 2- (N, N-Dip entylcarboxamido) -pheny y- 5-pheny lpy raz ο 1

3- / 2- (N-neopentylcarboemido) -phenyi7-5-phenylpyrazole

co - »J

Example 89

5- (2-carboxyphenyl) - 5- (4-methoxyphenyl) pyrazoline

A mixture of 0.50 S 2 ~ (4-metho: xyphenyl) -3., 3a-di-. hydro-8H-pyrazolo / 5 »1 ~ a? isoindol-8 ~ one and 50 ml of 10% aqueous sodium hydroxide solution are stirred overnight at 25 °. Somewhat undissolved pesticide that is still present in the morning is completely dissolved by adding 30 ml of ethanol. After a further hour, the mixture is adjusted to pH 5 with hydrochloric acid and cooled to 0 ° G, and the pale brown precipitate, 3- (2-carboxyphenyl) -5- (4-methoxyphenyl) pyrazoline, is filtered off, rinsed with water and air-dried . Yield 0.4095 g (77 %), ϊ ¹ x 139 to 176 ° C (dec.) '.

Following the procedure of Example 89 and using of the following reaction participants, the following products are produced, omitting the acidification step the said product is obtained in the form of the salt. ' ·

45 ~

209847/1231

Example starting material reactant product

90

91 92

93

. 94 f 95

96 97

98

99

2- (4-methoxyplienyl) -3, 3a ~ di-

3iydro-8H-pyrazoloZ5 »1-§7 ~ isoindol-8-one

2- (4-kethoxyplienyl) -3 i.e. hydro-SE-pyrazolo / i5.1 isoindol-8-one

2- (4-methoxypnenyl) -3, 3a-dihydro-8E-pyrazole / B, 1-a7-isoindol-8-one CH ₂ OH + CH ₂ ONa

2-Phenyl-3, 3a-dihydro-8E-prazlo ^ 1a7isoiiLdol8

2-phenyl-3, 3a-dih.ydro-8H-pyrazoloZB> 1-a7isoindol-8-one

2- (4-Ätlioxyplienyl) -3, 3a-di-

hydro-8H-pyrazolo.Z51 Λ- £ / ~ isoindol-8-one

2- (4 ~! Thiioxyp3ienyl) -3, 3a-di

h.ydro-8H-pyrazolo / 5 »1-§7-

isoiD.dol-8-on

2- (2,5-dicliloxp] aenyl2-3, 3a

di33.ydro-8H-pyrazolo / 5 1-a7 isoindol-8-one

2- (2,5-diciloip3ienyl) -3, 3a

diliydro-8H-pyrazolo / 3 ·> 1 -§ / isoindol-8-one

2- (^ -MethoxyphenylT- 3, dihydro-SH-pyrazolo / ^, 1-isoinaol-8-one ^r

H ₀ O + C ₀ H ₁ -OH + ■ N&OH. . ·?

CH ₂ OH + CH ₂ ONa

+ H ₀ O +

CH ₂ CH ₂ CH ₂ OH + CH ₂ CH ₂ CH ₂ ONa
C ₂ H ₅ OH +
C ₂ H ₅ ONa

CpH ₁ -OH + EpO, NaOH

3- (2-cartoniet3ioxyphenyl) -5- ( 4-methoxyp] ieny 1; -py r az olin

3- (2-CarT-doethoxyphenyl) -5- (4-methoxypnenyl ) -pyrazoline

3- (2-.carboisopropoxyphenyl) -5- (4-metho: xyphenyl) -pyrazoline

3- (2-carboxypheny1) -5-pneny1-pyrazoline '

3- (2-carbometiioxyphenyl) -5-phenylpyrazoline

3 ~ (2-carboxy-nyl) -5- (4-ethoxy) phenyl) pyrazoline

3- (2-Carbopropoxyp] ienyl) -5- (4-ethoxyphenyl) pyrazoline

3- (2-Carboethoxyphenyl) -5- (2,5-diciilorpnenyl) pyrazoline ■

3- (2-Car "boxyp3aenyl ') - 5- (2,5-dicjb.lorp] ienyl} -pyrazoline

3- (2-carboxamidophenyl) -5 methoxyphenyl) pyrazoline

Example starting material reactant product

100

101 102 103 104

105

106

107 108

109

2- (4-methoxyphenyl-3, 3a-di-3iydro-8H-pyrazolo23 ? 1 ~ ^ 7 ~ isoindol-8-one

2-Piienyl-3, 3a-dinydro ~ 8H-pyrazolo ^ 3,1-a7isoindol-8-one

2-phenyl-3, 3a-dihydro-8H-pyrazolo / 3,1-a7isoindol-8-one

2-phenyl-3, 3a-dihydro-8H ~

2- (4 ~ F1 aorplienyl)

hydro-SH-pyrazole q isoindol-8-one

2- (4-? Luophenyl) -3 ₅ 3a-dihydro-8H-pyrazolo / 3,1- ^ a7 * -isoindol-8-one

2- (2,5-dichlorophenyiQ-3, 3jadihydro-SH-pyrazolo ^, 1 - £ [- isoindol-8-one.

2-Ph.enyl-3j 3a-dihydro-8H-pyraz.olo- ^ 5,1-a7isoindol-8-one

2-phenyl-3, 3a-_dihydro-8E-pyrazolo ^ 5, i-a / isoindol-8-one

2- (4-Ät3ioxypiienyl) -3 j 3a-dihydro-8H-pyrazolo / 2, i-ä ^ - isoindol-8-one

Ba (OH) ₂

KOH
Hg (OH) ₂

3- (2-DiethylcarTDOxaraidoplienyl) -5- (4-meth.oxyph.enyl) -pyrazoline

.3- (2-Dimethylcarboxamidoplienyl) -5-piienylpyrazoli B. ■

3- / 2- (N-methyl-N-ethylcarlDOX-amido ; -phenyl ^ - ^ -pkeB-ylpy ^ zolin

3- (2-Dipentyloarboxamido) -5-phenylpyrazoline ■

3- (2-carboxamidophenyl) -5- (4-f 1 uorptLenyl) pyrazoline

3- / 2- (N-ethyl-N-propylene carboxamido) phenyl7-5- (4-fluorophenyl) pyrazoline

3- (2-Carboxyph.enyl) -5- (2,5-dichlorophenyl) pyrazoline, ' Barium salt

3- (2-carboxyphenyl) -5-phenylpyrazoline, E-SaIz

3- (2- * Carb oxypheny 1) - 5-phenyl pyrazoline, Mg salt

3- (2-carboxyphenyl) -5- (4-ätiioxyphenyl) pyrazoline, Ietramethylammonium salt.

"Example starting material

Reactant product

110

111

112

113

O 1 114 co 4 = co CD -C- 1 115 116 117 118 119

2- (4-thiomethylphenyl) -3, 3a-

dihydro-8H-pyrazolo ^ 3> 1-§ / -isoindol-8-one

2- (2-nitrophenyl) -3,3a-di ~ hy dr ο - 8H-pyr az ο 1 o / J »1 -Jä7-isoindol-8-one ~ *

2- (4-cyanophenyl) -3 _? 3 ^a -dihydro-SH-pyrazolc ^, 1-aZisoindol-8-one

2- (3-2) ri f 1 ummethylphenyl) 3j 3a-dihydro-8H-pyrazolo- / 5,1-a7isoindol-8-one ,

2- (4-methylsulfonylphenyl) -. 3, ^ a-dihydro-SE-pyrazolo- / 5 ? 1 -.§7i s ο indo 1- 8- on

2-C2,4,6-trimethylphenyl) -

yroSpyra 1- a / i s ο indo 1-8- on

2- (2-thienyl) -3, ^ a-dihydro-8H-pyrazolo / 3,1-a / isoindol-8-one

2- (2-furyl) -3, Ja-dihydro-8E-pyrazoloZ5 ₅ 1-a / isoindol-8-one

2-phenyl-5,3a-dihydro-8H-pyrazolo23,1-a / i soindol-8-one

2- (4-Methxyphenyl) -8H-pyrazolo / 5j1-.a / isoindol-8-one LiOH
H ₂ O

Ca (OH).

CH-, ΟΕ + CH _z OITa

.N ⁺ OH "

C ₂ H ₅ OH + C ₂ H ₅ ONa

H ^ O + C ₀ Hj-OH +
TTaOH ^ ^?

CH ₃ NH ₂ , H ₂ O
NaOE, H ₂ O

3- (4-thiomethrlphenyl) -5- (2-carboxyphenyl ; -pyrazoline, lithium salt

3- (2-nitrophenyl) -5- (2-carboxy- ^ phenyl) pyrazoline, calcium salt ro

3- (2-Diethylcarboxamidophenyl) -5- (4-cyanophenyl) pyrazoline

3- (2-carbomethoxyphenyl) -5- (3-trifluoromethylphenyl) -pyrazoline

3- (4-methylsulfonylphenyl) -5- (2-carboxyphenyl) -pyrazoline, tetraethylammonium salt

3- (2,4,6-trimethylphenyl) -5- (2-car "doxyphenyl > -pyrazoline, sodium salt

3- (2-Carboethoxyphenyl) -5- (2-thienyl) pyrazoline

3- (2-carboxyphenyl) -5- (2-furyl) pyrazoline

3- (2-carboxyphenyl) -5-phenylpyrazoline, Methylammonium salt

3- (2-carboxyphenyl) -5- (4-methoxyphenyl) pyrazole, Sodium salt

Example starting material Reaction participant product

120 121 122

123 124

125

<o 126

2-rphenyl ~ 5:, 3a-dihydro-8H-pyra ~ olZ51ä / iidl8

• 127 , Ξ _ρ Ο

(CH ₅ J ₃ IT, H ₂ O

CH ^ SH,
CH ^ OITa

CH _x CH ₀ CH ₀ SH,
CH ^ OIfö r

CH ₂ ONa

3- (2-carboxyphenyl) -5-phenylpyrazoline, Dimethylammonium salt

3- (2-carboxyphenyl) -5-phenylpyrazoline, Irimethylammonium salt

3- (2-carboxyphenyl) -5-phenylpyrazoline, Dodecyl ammonium-: salt

3- (2-Garboxyphenyl) -5-phenylpyrazoline, Benzylammonium Salζ

3- (2-methylthiocarbonylphenyl) -5-ph'enylpyraz olin

3- (2-propylthiocarbony! Phenyl) 5-phenylpyrazoline

3- (2-hexylthiocarbonylphenyl) -5-phenylpyraz olin

3- (2-Benzylthi ο carbony! Phenyl) 5-phenylpyrazoline

Example 128

A mixture of 30 g of 3- (2 ~ CarbGmethoxyplienyl) -5- (4-methoxyphenyl) -pyrazole, O.3O Sodium hydride and 0.8 g Acetyl chloride in 50 ml anhydrous tetrahydrofuran (THF) is stirred overnight at reflux conditions, whereupon the reaction mixture is filtered and the tetrahydrofuran is removed the oil removed to give a mixture of 1-acetyl-5- (2-carbomethoxyphenyl) -3- (4 ~ methoxyphenyl) pyrazole and 1-acetyl-3- (2-carbomethoxyphenyl -5- (4-methoxyphenyl) -pyrazole to 'win.

For example 129

Using dimethylcarbamoyl chloride instead of the Acetyl chloride in Example 128 is a mixture of 1 -Dime thy 1 carbamoyl 3- (2- carbon methoxyphenyl) -5- (4-methoxyphenyl) pyrazole and 1-dimethylcarbamoyl-3- (4-iaethoxyphenyl) -5- (2-carbomethoxyphenyl) pyrazole educated.

example

A mixture of 100 ml of dimethylformamide, 13.0 g of 5-methoxyphenyl) -3- (2-carboxyphenyl) pyrazole, 9 »36 g of sodium carbonate and 25 ml of methyl iodide is heated for 6 hours under reflux conditions, then poured into 500 ml of water , acidified to pH 3 and extracted with chloroform. The yellow oil obtained from the extracts is placed in 100 g of silicate CC-4. Chromatograph, whereby 200 ml fractions are obtained. Fractions 1 to 6 (2/1 cyclohexane / ethyl acetate) contain 6.04 g of a mixture of 1-methyl-3- (4-methoxyphenyl) -5- (carbomethoxyphenyl) -pyrazole and 1-methyl-3- ( 2-carbomethoxyphenyl) -5- ( ^/ + -methoxyphenyl) -pyrazole.

«50 -

209847/1231

Example 151

Treatment of the disodium salt of 2-benzoylacetylbenzoic acid with methylhydrazine (as in Example 20) and then recrystallization of the product from -ethanol-water gives the X-methyl-3- (or 5) - (2-carbo2cyphenyl) -5 ~ (or 3 ) -phenylpyrazole _t F. 163 to 165 ° 0 (decomp.)

After the operation of Example 131, the following become Pyrazole produced:

2098A7 / 1231

Example starting material

133

134

2- (3,4-Mae uhyrbenzoylac e ty 1) -4,5- <ii chi ο rb enz ο esäure, Disodium salt

2- (4-cyanobenzoylacetyl) -3-bromobenzoic acid, ■ disodium salt

2- (2-Carboxyb enzylac etyl) - "benzoic acid, Disodium salt

Reactant CH ₂ CH _{0 NHHH 0}

CH ₅ (GH ₂ ) -

product

1-Ethyl-3- (or 5) - (2-carboxy-4-, 5-dichlorophenyl) -5- ^: (or 3) - (3,4-dimethylphenyl) -pyrazole

1-Isopropyl-3- (or 5) - (3 2-carboxyphenyl) -5- (or 3) - (4-cyanophenyl) -pyrazo1

1-butyl-3,5-di-C2-carboxyphenyl) pyrazole

2949-1 / 2- G 53

Example 153

A mixture of 5.0 g of 3- (4-methoxyphenyl) -5- (2-carbomethoxypheriyl) pyrazole, 3 »5 g of acetic anhydride and 25 ml of pyridine is stirred overnight at -25 ° C, the mixture then in 100 ml poured into ice water and the product extracted with benzene. recrystallization from 2/1-hexane lthylacetat 119 provides the 1-acetyl-3- (2-carbomethoxyphenyl) -5- (4-methoxyphenyl) pyrazole, i. ¹ to 121 ° C.

Following the procedure of Example 135 and using of the following starting materials and reactants the following pyrazoles are produced:

. - 55 -209847/1231

Example starting material

Respondents

product

P.,

136

137

138

139

3- (4-methoxyphenyl) -5- (2-carbomethoxyphenyl) pyrazole

3- (4-methoxyphenyl) -5- (2-carbomethoxyphenyl; -pyrazole

3- (3-Hydroxyphenyl) -5- (2-carboethoxy-4,5-difluorophenyl) pyrazole

3- (2-carbobutoxyphenyl) -5- (4-carboprapoxypb.enyl) pyrazole

Butyric anhydride

Propionic acid eanhy dri d

Ethyl chi or f ο xmi at

Butyl chlorofonate

1-butyryl-3- (or (2-carbomethoxyphenyl) ~ 5- (or 3) - (4-methoxyphenyl} pyrazole ·

1-propionyl-3- (or 5 ~) - (2-carb ⁱ omethoxyphenyl) -5- (or 3) - (4-methoxypheny1) -pyrazole

i-Carboathoxy-3- (or 5) - (2- carb ο ä thoxy-4 ·, 5-difluorophenyl) -5- (or 3) - (3-ethylcarbonyldioxyphenyi; ~ pyrazole

1-carbobutoxy-3- (or 5) - (2-carbobutoxypheny1) -5- (or "3) - (4-carbopropoxyphenyl) pyrazole

) - 65 -

2949-1 / 2-G
Example 140

A mixture of 15.0 S 3- (2-carboxy-1- (cyclohexen-i-yl) ~ 5-phenylpyrazole and 125 ml pyridine "is treated at 25 ° C with 13> 5 S thionyl chloride, after 2 hours. 40.0 g of ethanol are added to the stirring, the mixture is then stirred for 3 hours and then partitioned between water and methylene chloride, whereupon the organic layer is washed with water and evaporated to remove the 3- (2-carboethoxy-1-cyclohexene-1 ^w yl) 5-phenylpyrazole

Following the procedure of Example 140 and using the reaction product of thionyl chloride with 3- (2-carboxy-1-cyclohexen-1yl) -5-phenylpyrazole and the following reactants, the following pyrazoles are made:

«55 ~

209847/1231

; isl Seaktionteilnaiijiie .-, - product

141

C ₆ H ₅ CE ₂ OH 3- (2-Garbobenzyloxy-1-cycloiiexen-i-yl) -5-pjb.enylpyrazole

142 CE ^ OH 3- (2-CarboELethoxy-1-cyclohexen-1-yl) -5-plienylpyr'azOl

143 (CH ₃ ) gCHOE 3- (2-0 arboi sop-rop oxy-1 -cyclohexen-1 -yl) - 5-ph.enylpyrazole

3- (2-Carbopentoxy-1-cyclc3iexen-1-yl) -5-plienylpyrazole

3- (2-Garbocyclohexyloxy-1-cycloliexerL-1-yl) -5-pii.enylpyrazole

146 EOCHpCEpOH '3 - /. 2- (2-Hydroxyätlioxyc & rbcnyl) -1-cyclo] iexeii-1-yi7-5 - pti.enyl-

pyrazole

OH

14? CH ^ CH-CH ₀ CH ₀ OH. . 3 ~ / ^ - (3-Hydroxybutoxycarbonyl) -1-cycloliexen-1-yl7-5 ~ piienyl

· *. pyrazole

148 Ci-CHpCH ^ CE ₂ OH 3- / 2- (3-chloropropoxycarbonyl) -1-cycloh.exeii-1-yl7-5-plienyl-

^ pyrazole

155 (CH *) 0CE-CHoKH ₀ 3-Z2- (K-isobutylcarboxamido) -1-cycloliexerL-1-yi _: / -p] ienyl-

• f «

3- (2-carboxamido) -1 -cyclohexen-1 -yl / -5-ph.enylpyrazol

ro ¹ ^ 150 CH ^ KH ₂ 3-Z2- (K-Metliylcarboxamido) -1-cyclo3iexen-1-yl / -5-piienylr-

^α * ^; ί ^ pyrazole '. % i

* ^ phenylpyrazole

152 / X CH ^) ^ EfW-UH 3- / 2- (K, K-Diisopropylc .irboxami do) -1-cycloiiexeii-1 -yl7-

^ phenylpyrazole

153 (C ₅ H,.) PM 3-Z2- (K, K-Dipentylcarboxamido) -1-cycloliexe2i-1-yl / -piienyl ~

^ pyrazole

3-Z2- "(K-ethyl-K-methylcarboxamido) -1-cycloh.exen-1-yi7-phenylpyrazole I ^

pyrazole ^ ₃

CD

Example of a reactant product

CJEUSE ~ "3 ~ (2-Keth7ltMocar" bonyl-1-cycloliexen-1-yl) -5 - plieiiylpyi ⁱ azole

157 CH ₅ CH ₂ CH ₂ GH ₂ SH, 5- (2-Butylthiocar "borLyl-1-cyclo] iexen-1-yl) -5-plienylpyrazol

158 CHx (CH ₂ ) CSH 3 ~ (2-hexyltliiocarbonyl-1-cyclolieis: en-1-yl) -5-pheiiylpyrazole Ί59 CgHc-CH ₂ SH 5- (2-benzylt32iocarbonyl-1-cyclohexerL-1 ~ yl) - 5-piienylpyrazole

Example 160

A mixture of 24.0 g of acetophenone, 19-2 g of a slurry of 50 % sodium hydride in mineral oil and 170 ml of dimethylformamide is stirred for 2 hours or until the evolution of hydrogen has ceased. ' · ·

A solution of 50.4 g of 3,4,5,6-tetrahydrophthalic anhydride in 150 ml of dimethylformamide is mixed with 11 jO g of sodium methoxide added and after half an hour into the iodine-acetophenone solution introduced. The resulting mixture is stirred for 3 hours at 120 ° G, the solid precipitate is filtered off, washes. with acetone and ether and dries to the crude disodium salt of 2-benzoylacetyl ~ 1-cyclohexenecarboxylic acid.

A suspension of 31.6 g of the disodium salt of 2-benzoylacetyl-1-cyclohexenecarboxylic acid in 150 ml of methanol is mixed with 12 g of concentrated hydrochloric acid and then 12 g of hydrazine hydrate. The reaction mixture is refluxed for 2 hours, cooled to 5 ° C., acidified to pH 3 and diluted with 150 ml of water, and the solid is collected and recrystallized from acetic acid-water, with 11.4 g of 3- (2-carboxy-1-cyclohexene -1-yl) -i? -Phenylpyrazole, t. 207 to 209 ° C.

Following the procedure of Example 160 using 3,4,5,6-tetrahydrophthalic anhydride and the following Ketones made the following pyrazoles:

209847/1231

Example ketone product

161 162

163

164 165 166 167

168 ο 169 «a 170

j. ^ 171 173

175 176

177 178

Methyl tert-butyl ketone 3,3-dimethyl-2-dodecanone

3 _? 3-diethyl-3-pentanone

1-acetyl naphthalene

2-acetylnaphthalene

2-acetylphenanthrene

9-acetylphenanthrene.

2-acetylfuran

2 ~ acetylthiophene

2-acetyl pyridine

4-acetyl pyridine

3-acetylindole

^ -Ciilozpropioplienon

Pentyl phenyl ketone 1 ~ indanon

a-tetralone

3 ~ bromoacetoplie: n.on, 2 ~ fluoroacetoptLenon 3- (2-Carboxy-1-cyclohexen-1-yl) -5-tert-butylpyrazole 3- (2-Carboxy-1-cyclohexen-1-yl) -5- (1,1-dimethyldecyl) pyrazole

3- (2-Carboxy-1-cyclohexen-1-yl) -5- (i, 1-diethylpropyl) pyraz oil

3- (2-Carboxy-1-cyclohexen-1-yl) -5- (i-naphthyl) -pyrazole 3- (2-Carboxy-1-cyclohexen-1-yl) -5- (2-naphthyl) -pyrazole 3- (2-0arboxy-1-cyclohexen-1-yl) -5- (2-phenaathryl) -pyrazole 3- (2-carboxy-1-cyclohexen-1-yl) -5- (9-ph.enanthryl) -pyrazole 3- (2-Carboxy-1-cyclohexen-1-yl) -5- (2-furyl) -pyrazole 3- (2-Carboxy-1-cyclohexen-1-yl) -5- (2-thienyl) -pyrazole 3- (2-carboxy-1-cyclohexen-1-yl) -5- (2-pyridyl) -pyrazole 3- (2-carboxy-1-cyclohexen-1-yl) -5- (4-pyridyl - pyrazole 3- (2-carboxy-1-cyclohexen-1-yl) -5- (3-i ^: n-dolyl) pyrazole

3- (2-Carboxy-1-cyclohexen-1-yl) -4-methyl-5- (4-chlorophenyl) = pyrazole

3- (2-Carboxy-1-cyclohexen-1-yl) - ^ - butyl - ^ - phenylpyrazole 2- (2,4-Dihydroindeno-3, 2-c7pyrazol-3-yl) -1-cyclohexen-1- ■ carboxylic acid

2- (4,5-pihydro-2H-benz / g / indazol-3-yl) -1-cyclohexen-1 = - carboxylic acid

3- (2- Carboxy-1 -cyelohexen-1 -yl) -5- (3-bromophenyl) -pyrasol 3 »(2-carboxy ~ 1-cyclohexen-1 -yl) -5» (2- f 1 uophenyl) -pyrasol

Example ketone

product

179 180 181 182 183 184

185

186 187

189 190

191 192

193

4-methyl acetophenone 3-butylacetophenone 4-hydroxy acetophenone 3-methoxyacetophenone ^ -butoxyacetophenone

2- (Methyl thio ^ acetophenone 3- (2-Carboxy-1-3- (2-Garboxy-1-3- (2-Carboxy-1
3- (2-carboxy-1-

cyclohexene-1 cyclohexene-1 -cyclohexenecyclohexene-1 cyclohexene-1 cyclohexene-1

-yl) -

■ yi) - ■ yi) · -yi) ·

- (4-methylphenyl) pyrazole 5- (3-butylphenyl) pyraz ol -5- (4-hydroxyphenyl) -pyrazole 5- (3-methoxyphenyl) -pyrazole 5- (4-butoxyphenyl) -pyrazole 5- / 2- (methylthio) -phenyI7-

(Butylthio) acetophenone

3-nitroacetophenone

4-Kethylsulfonylacetophenon

2- (trifluozmethyl) -

acetophenone

4-cyanoacetophenone 3-carboxyacetophenone

4- Garbomethoxyacetophenone

3-carboprop oxyac eto-

phenone

3,4-dichloracetophenone

2,5-dimethoxyacetophenone 3- (2-carboxy-1- <

pyrazole

3- (2-Carboxy-1-cyclohexen-1-yl) -5- / Ä- (butyl thi ο) -pheny £ 7-pyrazole

3- (2-carboxy-1-cyclohexen-1-yl)

3- (2-Carboxy-1-cyclohexen-1-yl) -pyraz "ol

5- (2-Carboxy-1-cy c 1 ohexen-1-yl) - 5- / 2- (tri f 1 uorm e thy 1) -phenyl7 ~ pyrasol

3- (2-Carboxy-1-cyclohexen-1-yl) 3- (2- Ca.rboxy-1-cyclohexen-1-yl)

3- (2-Carboxy-i -cyclohexen-1 -yl) pyrazole

5- (3-nitrophenyl) pyrazole 5 ~ ( ^z <-methylsulfonylphenyl) -

5- (4-cyanophenyl) ~ pyrazole 5- (3-carboxyphenyl) -pyrazole 5- (4-carboxyphenyl) -

3- (2-Carbox | j7-1-cyclohexen-1-yl) -5- (3-carbopropoxyphenyl) ~

pyrazole

3- (2-carboxy-1-

3- (2-carboxy-1-pyrazole

cyclohexen-1-yl) cyclohexen-1-yl)

5- (3,4-dichlorophenylpyrazole 5- (2,5-dimethoxyphenyl) -

CQ -J O

-eispiex
^:

196

197

198

199
200

Ketone

product

£} 201

phenone

2,6-2iethylacetophenone

3,4-di (tert-butoxy) acetophenone

2,6-difluoroacetophenone

3,4,5-phencn

3,4,5-phenone

3,4,5-trimethylacetophenone

3- (2-Carboxy ~ 1-cyclohexen-1 -yl) - 5- (3 j 5-ö-i ^ e thylphenyl) -pyrazole

3- (2-Carboxy-1-cyclohexen-1-yl) -5- (2,6-diethylphenyl) pyrazole

3- (2-Carboxy-1-cyclohexen-i-yl) -5- / 3 »^ di- (tert-butoxy) -phenyl-7-py3-azole

3-C2-carboxy-1-cyclohexen-1-yl) -5 -. (2,6-difluorophenyl) -

pyrazole

3- (2-Carboxy-1-cyclohexen-1-yl) -5- C 314.5-trichlorophenyl) pyrazole

3- (2-Carboxy-i - cyclohexen-1 -yl) - 5- (3> 4-, 5-trimethoxyphenyl) pyrazole

3- (2-Carboxy-1-cyclohexen-i-yl) -5- (3 A? 5- "toimethylphenyl) pyrazole.

Example 202

I- (2-Carboxy-i-cycloliexeii-i-yl) -5- (4-metlioxyphenyl) pyrazole is dissolved in hot water, treated with sodium hydroxide solution and cooled to 5 ° C., a precipitate of the Na salt of 3- (2-Carboxy- ^/ 1-cyclohexen-1 ~ yl) - ⁱ -5-C ^ - ^nl ethoxyphenyl) pyrazole is obtained.

Following the procedure of Example 202 using 3- (2-Cai ^v boxy ~ 1-cyclohexen-1-yl) -5 ^ phenylpyrazole and the following reactants, the following salts of the

3- (2-Carboxy-1-cyclohexen ~ 1-yl) -5-phenylpyra2iols produced:

- 62 -

2G9847 / 1231

2949-V 2-G ; Respondents product example LiOH Lithium salζ $ 20 KOH EaIiumsalζ 204 Ca (OH) ₂ Calcium salt 205 Ba (OH) ₂ Barium salt 206 (CH ₃ ) ^ N ⁺ OH " Tetramethylammonium salt 207 (GHj) ₅ NV H ₂ O Trimethylammonium salt 208 (CEL) ₂ NH, H ₂ O Dimethylammonium salt 209 CH ₃ NH ₂ , H ₂ O .Methylammonium salt 210 C ₁₂ H ^ NHp, H ₂ O. Dodecylammonium salt 211 (C ₄ H ₉ ) ^ OH " Tetrabuty ammonium salt 212 Example 213

3- (2-Carbomethoxy-1-cyclohexen-i-yl) -5-phenylpyrazool is dissolved in ether and treated with gaseous hydrogen chloride, a precipitate of 3- (2-carbomethoxy-1-cyclohexen-1-yl) -5-phenylpyrazole hydrochloride get vjird.

By exchanging the hydrogen chloride in Example 213 for 100 % phosphoric, sulfuric or nitric acid, the following salts of 3- (2-carboethoxy-1-cyclohexen-1-yl) -5-phenylpyrazole are formed.

example

214-

215 216

Salt with

Phosphoric acid sulfuric acid nitric acid

Example 217

A mixture of 3.0 g of 3- (2-carbomethoxy-1-cyclohexen-1-yl) ~ 5-phenylpyrazole, 0.3 g of a suspension of 50 % sodium hydride in mineral oil and 1.0 g of methyl iodide in 50 ml of wa, os free a total hydrofuran is observed with stirring

- 63 "

2098A7 / 1231
BA13

2949-1 / 2-G ^WT

refluxed, whereupon the reaction mixture is filtered, and the solvent evaporates from the filtrate. Here a mixture of 1-methyl-3- (2-carbomethoxy-1-cyclohexen-1-yl) -5-phenylpyrazole falls and 1-methyl-5- (2-carbomethoxy-1-cyclohexen-1-yl) -3-phenylpyrazole at.

Using the following reactants instead of the methyl iodide with J-CS-carbomethoxy-i-cyclohexeri-i-yl) -5-phenylpyrazole the procedure of Example 217 produces the following pyrazoles:

209SA7 / 1231

Promotion part & iiier product

218

219

220

221

222

ro

CE- ^ COCl
0

COCl

C ₂ H ₅ OCOCl

₂ CHCH ₂ OCO Cl

yp (5) - (2-cartometlioxy-1- ⁱ c.ycloiiexen-1-yl) -

5 (or 3) -piienylpyrazole · 'v8

1-Ethyl-3 (or 5) - (2-carbomethoxy-1-cycloliexen-1-yl) -5 (or 3) ~ ^ ⁰ piLeay'lpyrazol '^

1-Acetyl-3 (or 5) - (2-carbometlioxy-1-cycloliexen-1-yl) -5 (or 3) - V piienylpyrazole q

1-Butyryl-3 (or 5) - (2-carbomethoxy-1-cycloliexen-1-yl) -5 (or 3) -piLenylpyraz oil

1 - (! Thoxyoarbo; ayl) -3 (or 5) - (2-car "bometlioxy-1-cycloh.exen-1 ~ yl) -5 (or 3) -piienylpyrazole.

1- _r (Iso'butoxycarbonyl) -3 (or 5) ~ (2-carbomet3ioxy - 1- (cycloliexen-1-yl) -5 (or 3) -phenylpyrazole, ·

1-Dimethylearbamoy. L ~ 3 (or 5) - (2-carboEiet} ioxy-1- (cycloliexen- ^

1-yl) -5 (or 3) -plieiiylpyrazole

Claims (1)

tfc 2949-1 / 2-G Claims i compound of the formula wherein
D. or H
-C CH or is, X 'is hydrogen, fluorine, chlorine or bromine, Y ^{1 is} hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or irifluoro methyl, η is an integer from 1 to 3, R is hydrogen, alkyl having 1 to 4 carbon atoms or a group from the class -CH ₀ -, -CH ₀ CH ₀ - and -CH = CH-, the group being in the 4-position - 66 ~ 209 8 47 / 12-31 294-9-1 / 2-G * Connects pyrazole ring with the 2-position of the substituent 1L ,
tert-alkyl with 4 to 12 carbon atoms, / tv or Hydrogen, halogen, alkyl with 1 to 4 carbon atoms, hydroxy, alkoxy with 1 to 4 carbon atoms, Alkylthio with 1 to 4 carbon atoms, nitro-methy! Sulfonyl, Trifluoromethyl, cyano, carboxy or Carbalkoxy with 1 to 4 carbon atoms, hydrogen, halogen, alkoxy with 1 to 4 carbon atoms or alkyl with 1 to 4 carbon atoms, hydrogen, halogen, alkoxy with 1 to 4 carbon atoms or alkyl having 1 to 4 carbon atoms, hydrogen, alkyl having 1 to 4 carbon atoms or O ' Il ^u 4 ' Alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or B -OM, -SM or -N M is hydrogen, benzyl, alkyl of 1 to 6 carbon atoms on, where desired, with hydroxy or halogen sub- - 6? -2098A7 / 1231 2949-1 / 2-G substituted, sodium, lithium, potassium, calcium, magnesium, barium or where, in the case of M being hydrogen, benzyl or alkyl having Λ to 6 carbon atoms which, if desired, is substituted by hydroxy or halogen, the compounds can also be present in the form of their salts with strong acids in which the acid part of the group Belongs to phosphoric, sulfuric, hydrochloric and nitric acid,
Eo and R ₃ , each hydrogen or alkyl having 1 to 6 carbon atoms, E (- hydrogen or alkyl with 1 to 4 carbon atoms, Jt- hydrogen or alkyl with 1 to 4 carbon atoms, Rn is hydrogen or alkyl having 1 to 4 carbon atoms and Eg hydrogen, alkyl with Λ to 12 carbon atoms or benzyl, 2. A compound according to claim 1, characterized in that E ^. p-methoxyphenyl, p-methylphenyl, p-chlorophenyl or Is phenyl. 5. A compound according to claim 2, characterized in that E is hydrogen. 4. A compound according to claim 1, characterized in that E is hydrogen and B is hydroxy. 5. Plant growth regulating agent characterized by - 68 ~
209847/1231 2949-1 / 2-G a content of inert diluent and a compound according to one or more of the claims 1 to h, in particular claim j5 6. A method for regulating the Pf larizenwax turns, characterized in that a growth-regulating amount of a compound according to one or more of claims 1 to 4, in particular claim 3, is applied at the location of the plant growth. " 2098A7 / 1231