JPS5811855B2 - Novel method for producing substituted crotonanilide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the following formula I [where A represents a ZR group [wherein Z represents an oxygen or sulfur atom and R represents an alkyl group containing 1 to 6 carbon atoms] represents, and X and Y are hydrogen, halogen, 1-
represents an alkyl group containing 6 carbon atoms, or X and Y represent an alkyloxy group in which the alkyl group contains 1 to 3 carbon atoms, or a trifluoromethyl group; Object of the invention is a process for the preparation of novel substituted crotonanilides (representing an alkyl group containing a carbon atom, and the compound of formula I is present in the form of isomer E or isomer Z or in the form of a mixture of these isomers) shall be.

Among the alkyl groups, methyl, ethyl, propyl and butyl groups may be mentioned in particular.

Among the products of formula I, mention may be made in particular of those described in the examples.

The process for preparing compounds of formula I, which is the object of the present invention, comprises reacting a substituted anilide of formula I (wherein X, Y and R1 have the meanings given above) with an O-alkylating agent. or react with hydrogen sulfide in the presence of gaseous hydrochloric acid and then react the resulting product of formula S- Treatment with an alkylating agent gives formula I (where A
=SR (R has the meaning given above).

O-alkylating agents that can be reacted with the substituted anilides can be selected from alkyl orthoformates, alkyl halides and diazoalkanes.

As the 0-alkylating agent, formula Hal-R (where Ha
Alkyl halides of the formula H-C(OR)3 (l represents a zsogen atom) are preferred.

According to alkyl orthoformates, the reaction preferably takes place in the presence of an acidic reagent such as sulfuric acid.

These reagents lead to the derivatives of formula I in two steps: a first acetalization step leading to derivatives of formula I, followed automatically or by heating to lead to derivatives of formula I.

In general, the use of alkyl orthoformates as O-alkylating agents leads to the E isomer of the product of formula I, whereas the use of diazoalkanes leads to the corresponding two isomers.

S-alkylating agents that can be reacted with substituted anilides can be selected from alkyl halides and diazoalkanes.

Preferred S-alkylating agents have the formula Hal-R, where H
al represents a halogen atom and R represents an alkyl group).

As a variant of the process according to the invention, formula I (R1=CH3°A=
The product of ZR) is obtained by reacting β-chlorocrotonyl chloride with a substituted anilide of the formula (wherein X and Y have the meanings given above) to obtain a product of the formula or by treatment with an alkali thioalkylate to obtain the desired product.

The compounds of formula I are endowed with significant herbicidal properties which make them useful for controlling weeds in the agricultural field.

Its pre-emergence treatment or post-emergence herbicidal properties include bentgrass (Branch genus), oats, wheat, corn, barley,
ryegrass, hoxtailgrass, beet, boothfoot, chrysanthemum, yellow bed
This can be revealed by tests on plants representative of macroflora such as straw), mustard, rumex and clover.

Details of these tests are provided below.

The compound of formula (III) can be used in herbicidal compositions containing at least one of them as an active substance and optionally containing one or more pesticides and one or more substances that influence plant growth. Can be used for manufacturing.

The present invention also provides herbicidal compositions containing at least one compound of formula I as an active substance, optionally mixed with one or more pesticides and one or more substances that affect plants. Regarding.

These compositions contain, in addition to the active ingredients, in particular cationic, anionic or nonionic surfactants, inert powders such as talc, clays, silicates, diatomaceous earth, etc., water, Alcohols, hydrocarbons or other organic solvents, mineral oils,
They may be provided in the form of powders, granules, suspensions, emulsions, solutions containing vehicles such as animal or vegetable oils.

For example, for herbicide applications, 25% by weight of 3-methoxycrotonanilide or N-(m-)lyl)-3-methoxycrotonamide, 15% of Ekapersol 5 (Ekaper
sol S, condensation product of sodium naphthalene sulfonate), 0.5% Brecol NVA (Brecol
ane NVA, sodium alkylnaphthalene sulfonate), 34.5% Zeosil 39 (Zeosi
139, synthetic hydrated silica obtained by precipitation method) and 2
Hydrated silica containing 5% Velchoryl S (colloidal kaolin) may be used.

Herbicidal compositions according to the invention generally contain from 10 to 80% by weight of active substance, preferably from 10 to 50% by weight.

The substituted anilides of the formula used at the start of the process of the invention are J, Rharm, Soc, Japa
alkyl acylacetate R2COCH2C00 to the substituted aniline according to the method described in N69.126 (1949).
It can be produced by reacting with alkyl.

The following examples illustrate the invention without limiting it.

Example 1 3-methoxycrotonanilide Step A: N-phenyl-3,3-dimethoxybutyramide 43 g of methyl orthoformate and 5 drops of concentrated sulfuric acid were introduced into 70.8 g of acetoacetanilide, and the mixture was stirred at 20°C for 3 hours. A solution was obtained, which was stirred at 20° C. for 3 hours, cooled with ice, and the resulting precipitate was vacuum filtered and crystallized in isopropyl ether to obtain 54 g of N-phenyl-3,3-dimethoxybutyramide. This is recrystallized in isopropyl ether.

MP=80°C Analysis: Cl2H17NO3 Calculation: 6%64.57H%7.62N%6.28 Actual measurement:
64.3 7.3 6.4 Step B: 3-
Methoxycrotonanilide 558 g of N-phenyl-3,3-dimethoxybutyramide are heated at 195° C. for 1 hour under a vacuum of 60 mm Hg.

Then cool to 60° C. and add 500 cc of isopropyl ether.

Cool and vacuum filter the formed precipitate.

226 g of 3-methoxycrotonanilide to 111-1
It is obtained in the form of white crystals that melt at 12°C.

Analysis” C11H13NO2 Calculation = C%69.09H%6.85N%7.32 Actual measurement:
69.0 6.5 7.2 Example 2 N-(3',4'-dichlorophenyl)-3-ethoxycrotonamide To 60 g of ethyl orthoformate, 98.4 g of 3,4-dichloroacetoacetanilide and Introducing 6 drops of concentrated sulfuric acid,
Stir at 20°C for 3 hours, leave the solution at 20°C for 16 hours, add 12 drops of quinoline, heat at 90°C under reduced pressure for 2 hours, add isopropyl ether and remove the N-( of 4(Bi'). 3'4'-dichlorophenyl)-3-ethoxycrotonamide is obtained.

MP=126°C. This is recrystallized in methanol.

MP=156°C. Analysis: Cl2H03C12NO2 Calculation: C%52.57 H%4.78 C13%25.
87 N%5.11 Actual measurement: 52.4 4.8
25.7 5.2 Example 3 N-(m-)')fluoromethylphenyl)-3-methoxycrotonamide To 44 g of methyl orthoformate were added 98 g of m-trifluoromethylacetoacetanilide and 6 drops of concentrated sulfuric acid. introduced, stirred at 20°C for 3 hours, left at 20°C for 16 hours,
Add 2 drops of quinoline and 500 CC of toluene, heat at 150°C for 1 hour and 30 minutes while distilling drop by drop, remove the remaining triene by vacuum distillation, and chromatograph the residue on silica gel and dilute with methylene chloride. Elution with a mixture (8-2) with ethyl acetate yielded 55 g of N-(m
-trifluoromethylphenyl)-3-methoxycrotonamide is obtained.

MP=90°C. Analysis: Cl2H82F3NO2 Calculation: C%55.60 H%4.67 F%21.99
N%5.401 actual measurement: 55.4 4.7 21
．． 8 5.1 Example 4 N-(3',4'-dichlorophenyl)-3-methoxycrotonamide (isomer Z) Introducing "50 g of 3,4-dichlororuace" toacetanilide into 200 ee of methylene chloride 1st, stir, ′θ
℃, 450 CC of diazomethane in methylene chloride (concentration 2%) was introduced, stirred for 3 hours at 0℃, then left at 0℃ for 16 hours, methylene chloride was removed by vacuum distillation, and isopropyl ether was removed. The precipitate was isolated by vacuum filtration and 18.9 N-(3',4'
-dichlorophenyl); -3-methoxycrotonamide is obtained, which is recrystallized in isopropyl ether.

MP=123°C.

Analysis 2 C11H11C12NO2 Calculation = C%50.79 H%4.26 C1%27.2
6 N%5,392 Actual measurement: 50.8 4.3
27.0 5.5 Example 5 N-(3',4'-dichlorophenyl)-3-methoxycrotonamide (isomer E) 98 g of 3,4-i dichloroacetoacetanilide in 44 g of methyl orthoformate and 6 drops of concentrated sulfuric acid were added, stirred for 3 hours, left at 20° C. for 16 hours, cooled, and the precipitate was isolated by vacuum filtration to give 40 g of N-(3',4'-dichlorophenyl)- 3-methoxycrotonamide is obtained.

MP=156°C. This ν is crystallized in methanol.

MP=156°C. Analysis: C11H1, Cl2N02 Calculation 20% 50.79 H% 4.26 C1% 27.2
6 N%5.39 actual measurement: 50.9 4.2 2
6.8 5.4 Example 6 N-(0-tolyl)-3-methoxycrotonamide 80 g of trimethyl orthoformate, 110 g of 〇-methylacetoacetanilide and 6 drops of concentrated sulfuric acid were mixed and stirred for 8 hours. : Leave at 20°C for 16 hours, add 12 drops of quinoline, filter out insoluble matter, concentrate and dry by distillation under reduced pressure, add xylene, heat under reflux for 5 hours, and concentrate ζ xylene under reduced pressure. was removed, isopropyl ether was added, the resulting precipitate was isolated by vacuum filtration, and purified by chromatography on silica gel, then eluting with a mixture of methylene chloride and ethyl acetate, giving 30.9 N-( 0-)lyl)-3-methoxycrotonamide is obtained.

MP=101'C0 analysis: Cl2H1,N02 Discretion: 0%70.23 H%7.36N%6
．． 82 actual measurement: '70.2 7.6 6,. 9 Example 7 3-Methoxy-2-hexaneanilide Step A: 10 drops of concentrated sulfuric acid and 68g of butyryl acetanilide were introduced into 80g of 3,3-dimethoxyhexaneanilide and 68g of butyryl acetanilide, and stirred for 3 hours. After standing for an hour and cooling, the precipitate formed is isolated by vacuum filtration, washed and dried to obtain 66 g of 3,3-dimethoxyhexaneanilide.

MP=86°C. ■Process B: 3-Methoxy-2-hexenanilide 60 g of 3,3-dimethoxyhexaneanilide was heated at 145°C until the distillation of methanol was completed, and then cooled.
Isopropyl ether is added and the resulting precipitate is isolated by vacuum filtration to obtain 24 g of 3-methoxy-2-hexenanilide.

MP=86°C.

Analysis” 13H17NO2 Calculation = C%71.19H%7.82N%6.39 Actual measurement:
71.4 7.9 6.4 Example 8 3-(Methylthio)crotonanilide Step A: Thioacetoacetanilide - Hydrogen chloride gas was blown into 500 cc of ethanol cooled to 30°C to the saturation point, and then hydrogen sulfide was blown for 30 minutes. 35.5 g of acetoacetanilide was introduced while blowing in hydrogen sulfide, and after blowing in hydrogen sulfide, the mixture was stirred at 0°C for 16 hours, concentrated and dried under reduced pressure, and the residue was chromatographed on silica gel. , eluting with a mixture of acetone and chloroform (1-1) to obtain 13 g of thioacetoacetanilide.

MP = 125°C Step B: 3 one step ruthio)crotonanilide 11.6.9 thioacetoacetanilide in 60 cc of ethanol, then 3.4 g of caustic potassium in 35 c
A solution prepared by dissolving c in ethanol was introduced and heated to 20°C.
Stir for 1 hour, introduce 8.5 g of methyl iodide,
The precipitate formed is isolated by vacuum filtration, dissolved in chloroform, the chloroform solution is dried, and concentrated to dryness under reduced pressure to obtain 12 g of 3-(methylthio)crotonanilide.

MP=86°C. This is recrystallized with acetone.

MP=86°C. Analysis: C11H13NO8 Calculation = C%63.73 H%6.32 N%6.758
%15.47 actual measurement: 63.5 6.1 6.7
15.5 Example 9 N-(m-tolyl)-3-methoxycrotonamide 80 g of N-(m-tolyl)acetoacetamide, 80
g of methyl orthoformate, 100 cc of methanol and 1
6 g of p-toluenesulfonic acid with stirring.
Reflux for an hour.

The volatiles are removed under reduced pressure, 300 cc of toluene and 1.5 cc of quinoline are added and heated at about 140° C. for 3 hours, then the remaining toluene is evaporated.

The residue was chromatographed on silica gel, eluting with a methylene chloride-ethyl acetate mixture (9-1),
g of N-(m-tolyl)-3-methoxycrotonamide are obtained.

MP=86°c. Analysis: C1°Hf, NO2 Calculation: 0%70.23H%7.37N%6.82 Actual measurement:
70.4 7.3 6.6 Example 10 By working in an analogous manner to Example 1O, the following product is obtained.

N-(2',6'-dimethylphenyl)-3-methoxycrotonamide MP=163°C N-(3'-chloro-47-methylphenyl)-3-methoxycrotonamide MP=118°0N-(3 ',
5'-dichlorophenyl)-3-methoxycrotonamide MP=86°C N-(3'-chloro-4'-methoxyphenyl)-3-
Methoxycrotonamide MP=86°C3-n-propoxycrotonanilide MP=75°C 3-n-butoxycrotonanilide MP=102°C N-(4'-methoxyphenyl)-3-methoxycrotonamide MP=104° CN-(p-tolyl)-3-methoxycrotonamide MP=109°C N-(2'-chlorophenyl)-3-methoxycrotonamide MP=72°C 3-ethoxycrotonanilide MP=118°0N-
(4'-bromphenyl)-3-methoxycrotonamide MP=152°C N-(4'-chlorophenyl)-3-methoxycrotonamide MP=124°C N-(3'-/yot lephenyl)-3 -Methoxycrotonamide MP=104°C N-(5'-chloro-27-methylphenyl)-3-methoxycrotonamide MP=150°C N-(4'-chloro-2'-methylphenyl)-3-methoxy Crotonamide MP=157℃N-(5'-chloro-2'-methoxyphenyl)-3-methoxycrotonamide MP
=134℃N-C5'-(3",3"-dimethyl-n-
butoxy)phenylcou 3-methoxycrotonamide M
P=94℃ 3-methoxycrotonanilide and N-(m-tolyl)
-3-Methoxycrotonamide pre-emergence treatment and post-emergence herbicidal study on plants used (bentgrass, oats, wheat, corn, barley, ryegrass, hoxtailgrass, beets, boothfoot, chrysanthemums, yellow pine) (23 x 14 x 4 cm) with a double bottom and water supply from the bottom.
) to cultivate.

These are planted in one half box in a line with a spacing of 3 cIIL at a rate of 20 seeds per plant and repeated 4 times for each concentration.

The cultivation conditions are as follows.

Temperature: 20±2℃, approximately 60% temperature, illuminated with fluorescent lights (daylight color and bright daylight color) from 6:00 to 10:00 every day.

The soil mixture used consisted of 10 volumes of top layer, 10 volumes of river sand and 2 volumes of beet.

For pre-emergence treatment tests, the treatment is done 24 hours after sowing and the first watering is done by watering to bring some of the compound to the seed level.

For the post-emergence treatment test, the treatment is applied to the above ground portion after 21 days of cutting culture.

In each case, the surfactant compounds are applied using a microsprayer under standard conditions at the doses indicated in the table below and at a dilution corresponding to 5601/ha.

Control tests were also conducted without treatment and comparative tests were conducted with METOXURON (METOXURON, N-dimethyl-N'
-3-chloro-4-methoxyphenyl)urea), LTNURON (N-(3,4-dichlorophenyl)N/-methoxy-N'-methylurea), nitrofen (NITROFENE, 2,4-dichlorphenyl) phenyl), i/-nitrophenyl ether), metabenzothiazuron (METABENZT-HIAZURO\1
-methyl-3-(2-benzothiazolyl)urea).

The final test is carried out by weighing the plants 21 days after treatment for pre-emergence treatment tests and 15 days after treatment for post-emergence treatments.

The result is the plant reduction rate P The table below illustrates the experimental results obtained.

Conclusion In both pre- and post-emergence treatments, 3-methoxycrotonanilide and N-(m-tolyl)-3-methoxycrotonamide are endowed with interesting herbicidal properties.

Furthermore, the herbicidal activity of the four compounds shown in the table below was examined in post-emergence treatment according to the method described above.

Claims (1)

[Claims] Primary formula ■ [Here, A is a ZR group (here, Z represents an oxygen atom, and R
represents an alkyl group containing 1 to 6 carbon atoms)
, X and Y represent hydrogen, halogen or an alkyl group containing 1 to 6 carbon atoms, or X and Y
represents an alkyloxy group or trifluoromethyl group in which the alkyl group contains 1 to 3 carbon atoms, and R1 is 1
represents an alkyl group containing ~6 carbon atoms and the compound of formula I is present in the form of isomer E or isomer Z or in the form of a mixture of these isomers] In preparation, the substituted anilide of the enemy (where X, Y and R1 have the meanings given above) is reacted with an O-alkylating agent to form A=OR(R
A process for the preparation of substituted crotonanilides of formula I, characterized in that a product of formula (1) is obtained, in which ( has the abovementioned meaning). 2nd Formula I [Here, A is a ZR group (here, Z represents an atom,
R represents an alkyl group containing 1 to 6 carbon atoms), X and Y represent hydrogen, halogen or an alkyl group containing 1 to 6 carbon atoms, or X and Y represent an alkyl group containing 1 to 6 carbon atoms. represents an alkyloxy group containing from 1 to 3 carbon atoms or a trifluoromethyl group, R1 represents an alkyl group containing from 1 to 6 carbon atoms, and the compound of formula I is an isomer E or an isomer. For the preparation of novel substituted crotonanilides, present in the form of isomers Z or in the form of mixtures of these isomers, substituted anilides of the formula (wherein X, Y and R1 have the meanings given above) are reacted with hydrogen sulfide in the presence of gaseous hydrochloric acid,
Substituted crotons of formula I, characterized in that the product of formula I obtained is then treated with an S-alkylating agent to obtain a product of formula Ⅰ, in which A=SR (R has the meaning given above) Production method of anilide.