DE2348487A1 - NEW SUBSTITUTED CROTONANILIDES, PROCESS FOR THEIR PRODUCTION AND COMPOSITIONS CONTAINING THESE COMPOUNDS - Google Patents

Description

Dr. F. Zumstein Sr. - Dr. E. Assmsnr Df. R. Koenlgsberger - Dlpl.-Phys. R. Holzhauer - Dr. F. Zumstein Jun.

. - PATENT ADVOCATE =.

TELEPHONE: COLLECTIVE NO. 2253 41

TELEX 529979 TELEGRAMS: ZUMPAT

CHECK ACCOUNT: MUNICH 91139-809. BLZ 70O10O80

BANK ACCOUNT: BANKHAUS H. AUFHÄUSER ACCOUNT NO. 397997. BLZ 70030600

8 MUNICH 2.

BRÄUHAUSSTRASSE 4

97 / N Cas 1557 D

ROUSSEL-UCLAF, Paris / France "

New substituted crotonanilides, processes for their preparation and compositions containing these compounds

The invention relates to new substituted crotonanilides Formula I.

MHCOC = C-A

ι ι

E ₁ R ₂

wherein

A denotes the radical ZR, where Z denotes an oxygen or sulfur atom and R denotes an alkyl radical having 1 to 6 carbon atoms or represent an optionally substituted aryl radical,

X and Y are hydrogen, a halogen atom, one optionally , denote by "one or more halogen atoms substituted alkyl radical with 1 to 6 carbon atoms or

X and Y are an alkyloxy radical whose alkyl radical has 1 to 3 carbon atoms contains an alkylthio radical or alkyl

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sulfinyl radical, the alkyl radical of which has 1 to 6 carbon atoms contains an acyl radical with 1 to 6 carbon atoms, a nitro group or a trxfluoromethyl radical,

R. hydrogen, a chlorine or bromine atom, an alkyloxycarbonyl radical, whose alkyl radical contains 1 to 6 carbon atoms, one. Nitro group or an alkylthio, Alkylsulfinyl or alkylsulfonyl groups, their alkyl radical Contains 1 to 3 carbon atoms, means and

R ₂ denotes an alkyl radical with 1 to 6 carbon atoms,

where these compounds of the formula I are in the form of the isomer E or the isomer Z. or in the form of a mixture of these isomers are present.

The methyl, ethyl, propyl and butyl radicals may be mentioned in particular among the alkyl radicals.

Among the compounds of the formula I, those described in the examples may be mentioned in particular.

The invention also relates to a process for the preparation of compounds of the formula I in which R ^ = H, Rp - alkyl with 1 up to 6 carbon atoms and A = ZR, where R is an alkyl radical with Represents 1 to 6 carbon atoms, which is characterized in that one is based on a substituted anilide of formula

γ ^ / rr \

IiHCOCH ₂ COE ₂

wherein X and Y are as defined above, either allows an O-alkylating agent to act in order to obtain a compound of the formula I in which R. = H, R ₂ = alkyl having 1 to 6 carbon atoms and A = OR, where R is a Represents an alkyl radical having 1 to 6 carbon atoms, or allows hydrogen sulfide to act in the presence of gaseous hydrogen chloride and

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and then the compound of formula obtained

IiCOCLC-H ₅

² II ² s

treated with an S-alkylating agent to obtain a compound of formula I wherein R. = H, R ₂ = alkyl having 1 to 6 carbon atoms and A = SR, where R is an alkyl radical having 1 to 6 carbon atoms.

The O-alkylating agents that are used on the substituted anilide let act, can, can under the alkyl-ortho-formates, alkyl halides and diazoalkanes. Either an alkyl halide is used as the O-alkylating agent of the formula Hal-R, in which Hal represents a halogen atom, or an alkyl ortho formate of the formula H-C (ORK preferred.

With the alkyl ortho formates, the reaction is preferably carried out in In the presence of an acidic agent such as sulfuric acid. These reagents lead in two stages to the derivatives of the formula I, wherein the first acetalization to derivatives of the formula

"OR

™ ₂ CR ₂ 0 OR

which leads, spontaneously or by heating, into derivatives of the formula

0 OR

convert.

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In general, the use of an alkyl ortho formate as O-alkylating agent leads to the Ε-isomers of the compounds of the formula I _1, whereas the use of a diazoalkane leads to the corresponding Z-isomers.

The S ^ alkylating agents that can be used on the substituted anilide can act can be chosen from alkyl halides and diazoalkanes. Pas preferred S-alkylating agents is an alkyl halide of the formula HaI-R, where Hai represents a halogen atom and R represents an alkyl radical.

The compounds of the formula I for which R ^ = H, Rp = CH ₃ and A a ZR, where Z and R have the meaning given for the formula I, can be prepared by a process which is characterized in that one a -ß-chlorocrotonyl chloride to a substituted aniline of the formula

in which X and Y have the above meaning, to a compound of the formula '

I] HCOCH = C-CH

Cl

to obtain, which is treated either with an alkali metal alkylate or arylate or with an alkali metal thioalkylate or thioarylate to obtain a compound of the formula I in which R ₁ = H, R ₂ = CH ₃ and A = ZR.

The compounds of formula I in which R ^ = COO-alkyl or NO ₂ , R ₂ = CH ₃ and A = OR, where R is an alkyl radical, can be prepared by a process which is characterized in that one Compound of formula

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where X and Y have the above meaning and R ^, COO-alkyl or NOp means with an alkyl-ortho-acetate

the formula

CH-C (OR) ₅

in which R is an alkyl radical, in order to obtain the desired compound of the formula I.

The compounds of the formula I in which R ^, = Cl, Br, alkylthio or alkylsulfinyl, Rp = CH ₃ and A * = OCHU can be prepared by a process which is characterized in that one reacts to a compound of the formula

NHCOCHCOCe

Shark

wherein Hal is a chlorine or bromine atom and X and Y are as defined above, either diazomethane, to obtain a compound of the formula I in which R ₁ = chlorine or bromine, Rp = CHL and A = OCH-, or a sodium - Or potassium thioalkylate to act to a compound of the formula

I] HCOCHCOCH,

to obtain in which Alk is an alkyl radical having 1 to 3 carbon atoms means which one treats with methyl ortho formate, to obtain a compound of formula I in which R ^ = alkylthio, R- = CHo and A = OCHo, which one desires, if necessary with a

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Treated oxidizing agent to obtain a compound of formula I wherein R ^, = alkylsulfinyl, R ₂ = CH ₃ and A = OCH ₃ .

The compounds of the formula I in which R ^, = alkyl sulfonyl, R ₂ = CH ₃ and A = OR, where R is an alkyl radical, can be prepared by a process which is characterized in that an isocyanate of the formula

IT = C = O

wherein X and Y are as defined above, an alkylsulfonylacetone the formula

AIkSO ₂ CH ₂ COCH ₃

wherein Alk is an alkyl radical with 1 to 3 carbon atoms, lets act and then the product of the formula obtained

-MHCOCHCOCJL

ίΛ / f-JNhUÜUhUUUIi-

SO ₂ AIk

with an alkyl ortho formate of the formula HC (OR) ₃ , in which R is an alkyl radical, to obtain a compound of the formula I in which R = alkylsulfonyl, R ₂ = CH ₃ and A = OR, where R represents an alkyl radical.

The compounds of the formula I have remarkable herbicidal properties which make them useful in agriculture make useful of weeds. The herbicidal properties of pre-emergence or post-emergence can be proven are made through experiments on representative plants of the large botanical families, such as bluegrass (agrostis), oats, Wheat, corn, barley, ryegrass, foxtail grass, beetroot, goosefoot (goosefoot plants) (chenopod), chrysanthemum (wicker

409814/1237

flowering plants), bedstraw, mustard, dock and clover. 2348487 Details of these experiments are given below.

The invention also relates to herbicidal compositions which contain at least one of the compounds as the active ingredient of the formula I contain, optionally together with one or several pesticidal agents or with one or more agents influencing the growth of the plants.

These compositions can be in the form of powders, granules, suspensions, emulsions, solutions, in particular In addition to the active ingredients, cationic, anionic or nonionic surface-active agents, inert powders such as talc, Clays, silicates, diatomaceous earth, etc., a carrier such as water, alcohol, hydrocarbons or other organic solvents, contain a mineral oil, an animal or vegetable oil, etc.

For herbicidal uses, for example, a wettable one is used Powder, ^ which contains 25% by weight of 3-methoxycrotonanilide or N- (m-Tolyl) -3-methoxycrotonamide, 15% by weight Ekapersol "S" (condensation product of sodium naphthalene sulfonate), 0.5% by weight Brecolane NVA (sodium alkylnaphthalene sulfonate), 34.5% by weight Zeosil 39 (synthetic hydrated silica obtained by precipitation) and 25% by weight Vercoryl "S" (colloidal kaolin).

The herbicidal compositions according to the invention contain generally 10 to 80% by weight and preferably 10 to 50% by weight of the active ingredient.

The various compounds used as starting materials for the above processes are prepared as follows:

The substituted anilides of the formula

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NTICGH ₀ CR ₀

Ij * Ίί ² ο ο

can R-COCH-COO-alkyl by the action of an alkylacylacetate to a substituted aniline according to one in "J.Pharm.Soc.Japan", 1949, 6j9_, 126 described procedure can be obtained.

The substituted anilides of the formula

HHCCH ₀ -R. II ^{2 1} 0

wherein R ^, an alkyloxycarbonyl radical, a nitro group or a Cyano group means, can by the action of a chlorocarbonyl alkyl acetate, a Nitroäthylacetats or a Cyanäthylacetats to a substituted aniline of the formula

after one for the last connection in "J. Indian Chem. Soc", 1927, 4_, 548 described procedure can be obtained.

The substituted anilides of the formula

■ MHCCH-COGBL

Ii I ³

γ 0 shark

where Hai is a chlorine or bromine atom, according to the in "J. Indian Chem. Soc", 1943, 2 £, 3 84 for the production of a-chloroacetoacetanilide produced will.

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The following examples are intended to explain the invention further without, however, restricting it.

example 1

3-methoxycrotonanilide

Stage A: N-phenyl-3,3-dimethoxybutyramide

43 g of methyl orthoformate and 5 drops of concentrated sulfuric acid are introduced into 70.8 g of acetoacetanilide. The mixture is stirred for 3 hours at 20 ° C and a solution, allowed to stand to the 20 hours at 20 ⁰ C, cooled and filtered off with suction and the precipitate formed from the one. It crystallizes from isopropyl ether and receives 54 g of N-phenyl-3,3-dimethoxybutyramide, which can be recrystallized from isopropyl ether, F = 80 C.

Analysis: C ₁ ,, H _-1 ^

i.e. ι. Ι

Calculated: C 64.57 H 7.62 N 6.28 % Found: 64.3 7.3 6.4%

Level B: 3-methoxycrotonanilide

558 g of N-phenyl "-3, 3-dimethoxybutyramide are under a vacuum heated from 60 mm Hg to 195 ° C for 1 hour. It is then cooled to 60 ° C. and 500 ecm of isopropyl ether are added. One cools down and sucks off the precipitate formed. This gives 226 g of 3-methoxycrotonanilide in the form of white crystals from F = 111 to

Analysis: C ₁₁ H ₁₃₂

Calculated: C 69.09 H 6.85 N 7.32% Found: 69.0 6.5 7.2%

Example 2 2-ChlQr-3-methoxycrotonanilide

In 500 cc of methylene chloride 52.9 g of a-chloroacetoacetanilide, and then at 0 ⁰ C over 4 hours 725 cc of a methylene chloride solution of diazomethane with a titer of 17.4 g / l was added.

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2348-87

The mixture is stirred for 16 hours at 0 ° C and then 1 hour at 20 ⁰ C. The mixture is concentrated under reduced pressure to dryness, is added isopropyl ether, the precipitate is isolated by suction, recrystallised from isopropyl ether and 12 g of 2-chloro-3 -methoxycrotonanilide from F = 100 ° C.

Analysis: C ^ H ^ Cl N0 "

Calculated: C 58.53 H 5.36 Cl 15.71 N 6.20% Found: 58.4 5.4 15.9 6.2 %

Example 3

N- (3 ', 4' -Dichlorophenyl ) -3-ethoxycrotonamide

98.4 g of 3,4-dichloroacetoacetanilide and 6 drops of concentrated sulfuric acid are introduced into 60 g of ethyl orthoformate. The mixture is stirred for 3 hours at 20 ° C, the solution is stirred for 16 hours at 20 ° C., are added 12 drops of quinoline, heated for 2 hours under reduced pressure at 90 ⁰ C, is added isopropyl ether and obtains 40 g of N- (3 ', 4'-dichlorophenyl) -3-ethoxycrotonamide, melting point 126 ° C, which can be recrystallized from methanol, melting point 126 ° C.

Analysis: C ₁₂ H ₁₃ CIpNO ₂ *

Calculated: C 52.57 H 4.78 Cl 25.87 N 5.11% Found: 52.4 4.8 25.7 5.2%

Example 4 N- (m-Trifluoromethylphenyl) -3-methoxycrotonamide

98 g of m-trifluoromethylacetoacetanilide and 6 drops of concentrated sulfuric acid are introduced into 44 g of methyl orthoformate. It is stirred for 3 hours at 20 ⁰ C, stirred for 16 hours at 20 ⁰ C are, are 12 drops of quinoline, and 500 cc of toluene added, heated to 150 ⁰ C, which was added dropwise distilled within 1 1/2 hours, remove the remaining toluene by Distillation under reduced pressure, the residue is chromatographed on silicon dioxide gel, eluting with a mixture of methylene chloride and ethyl acetate (8/2), giving 55 g of N- (m-trifluoromethylphenyl) -

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3-methoxycrotonamide of F = 90 C. ^ o A Ο / O · 7

Analysis: C ₁₂ H ₁₂ F ₃₂

Calculated: C 55.60 H 4.67 F 21.99 N 5.40 % Found: 55.4 4.7 21.8 5.1%

Example 5 N- (3 *, 4'-dichlorophenyl) -3-methoxycrotonamide (Z-isotneres)

50 g of 3,4-dichloroacetoacetanilide are introduced into 200 ecm of methylene chloride. The mixture is stirred, cooled to 0 ° C., 450 ecm of a solution of diazomethane in methylene chloride (titer 2%) is added, the mixture is stirred for ^{3 hours at 0 ° C., left at 0} ° C. for 16 hours, and the methylene chloride is removed by distillation under reduced pressure , adds isopropyl ether, cools, isolates the precipitate formed by suction and receives 18 g of N- (3 ', 4'-dichlorophenyl) -3-methoxycrotonamide, which can be recrystallized from isopropyl ether, mp = 123.degree.

Analysis: ^c n ^H ₁ i ^cl 2 ^NO 2

Calculated: C 5.0.79 H 4.26 Cl 27.26 N 5.39%

Found: 50.8 4.3 '27, 0 5.5%

Example 6 N— (3 ', 4'-dichlorophenyl) -3-methoxycrotonamide (Ε-isomer)

98 g of 3,4-dichloroacetoacetanilide are added to 44 g of methyl orthoformate and 6 drops of concentrated sulfuric acid were added. The mixture is stirred for 3 hours. left for 16 hours at 20 ° C., cooled, and the precipitate formed was isolated by suction filtration 40 g N- (3 '^' - dichlorophenyD-S-methoxycrotonamide with a temperature of 156 ° C, which can be recrystallized from methanol, mp = 156 ° C.

Analysis: ^C ₁₁ ^H ₁₁ ^C1 ₂ ^NO 2

Calculated: C 50.79 H 4.26 Cl 27.26 N 5.39%

Found: 50.9 4.2 26.8 5.4%

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N ~ (o-Tolyl) -3-methoxycrontonamide

80 g of trimethyl orthoformate, 110 g of o-methylacetoacetanilide and 6 drops of concentrated sulfuric acid are mixed together. The mixture is stirred for 8 hours, left for 16 hours at 20 ° C., 12 drops of quinoline are added, an insoluble substance is removed by filtration, concentrated by distillation to dryness under reduced pressure, add xylene, reflux for 5 hours, remove the xylene by concentration under reduced pressure, add isopropyl ether, isolate the precipitate formed by suction, purify it by chromatography on silica gel while eluting with a mixture of methylene chloride and ethyl acetate (δ / 2) and 30 g N-Co-S-TolyD methoxycrotonamid from F = 101 ⁰ C.

Analysis: ^c i2 ^H 15 ^NO 2

Calculated: C 70.23 H 7.36 N 6.82% Found: 70.2 7.6 6.9 % '

Example 8

3-methoxy-2-hexenanilide

Grade A: 3,3-dimethoxyhexananilide

10 drops are concentrated in 80 g of methyl orthoformate Sulfuric acid and 68 g of butyrylacetanilide introduced. The mixture is stirred for 3 hours, left to stand for 16 hours, cooled, and the formed is isolated Precipitate by suction, washes it, dries it to obtain 66 g of 3,3-dimethoxyhexananilide. F = 88 ° C.

Stage B: 3-methoxy-2-hexenanilide

The mixture is heated 60 g of 3,3-Dimethoxyhexananilid to 145 ° C until completion of methanol distillation, cooled, added isopropyl ether, isolated by filtration with suction and the precipitate formed and 24 g of 3-methoxy-2-hexenanilid, F = 104 ⁰ C.

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Calculated: C 71.19 H 7.82 N 6.39% Found: 71.4 7.9 6.4%

Example 9

3- (methylthio) crotonanilide

Level A: thioacetoacetanilide

500 ecm of ethanol are cooled to -30 ° C., hydrogen chloride gas is passed in until saturation and then hydrogen sulfide at -10 ° C. for 30 minutes a, gives 35.5 g of acetoacetanilide while passing in hydrogen sulfide, stirs while passing in Hydrogen sulfide for 16 hours at OC, concentrated under reduced Pressure to dryness, the residue chromatographed on silica gel while eluting with a mixture from acetone and chloroform (l / l) and receives 13 g of thioacetoacetanilide from F = 125 ° C.

Level B: 3- (methylthio) crotonanilide

To 60 cc of ethanol is added 11.6 g Thioacetoacetanilid and then a solution of 3.4 g of potassium carbonate in 35 cc of ethanol is added, stirred for 1 hour at 20 ⁰ C and is added 8.5 g methyl iodide. It is poured into 300 ecm of water, the precipitate formed is isolated by suction, dissolved in chloroform, the chloroform solution is dried, concentrated to dryness under reduced pressure and 12 g of 3- (methylthio) ~ crotonanilide with a melting point of 175 ° C. is obtained , which is recrystallized from acetone, F = 178 ° C.

Analysis: C ₁₁ ^ ₁₃ NO S

Calculated: C 63.73 H 6.32 N 6.75 S 15.47% Found: 63.5 6.1 6.7 15.5%

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N- (m-Tolyl) -3-methoxycrotonamide

A mixture of 80 g of N- (m-tolyl) acetoacetamide, 80 g of methyloithoformate, 100 ecm of methanol and 1 g of p-toluenesulfonic acid is refluxed with stirring for 6 hours. The volatile constituents are removed under reduced pressure, 300 ecm of toluene and 1.5 ecm of quinoline are added, the mixture is heated at about 140 C for 3 hours and the remaining toluene is then evaporated off. The residue is chromatographed on silica gel while eluting with a mixture of methylene chloride and ethyl acetate (9/1) and 40 g of N- (m-tolyl) -3-methoxycrotonamide, melting point = 106 ^° C., are obtained.

Analysis: ^c ip ^H 15 ^IiiO 2

Calculated: C 70.23 H 7.37 N 6.82%

Found: 70.4 7.3. 6.6% '·'

Example 11

By proceeding as in Example 10, the following connections are obtained:

N- (2 ', 6'-dimethylphenyl) -3-methoxycrotonamide, m.p. 163 ° C N- (4'-nitrophenyl) -3-methoxycrotonamide, F = IQO C

N- (3 ^f -chloro-4'-methy! Phenyl) -3-methoxycrotonamide, 'F = 118 ° C

N- (3 ·, S'-dichlorophenyl I-S-methoxycrotonamide, m.p. '139 ° C

N- (3'-chloro-4'-methoxyphenyl) -3-methoxycrotonamide, m.p. 136 ° C

N- (3'-nitrophenyl) -3-methoxycrotonamide, m.p. 187 ° C N- (3'-methylsulfinylphenyl) -3-methoxycrotonamide, m.p. 157 ° C 3-n-propoxycrotonanilide, m.p. 75 ° C

3-n-butoxycrotonanilide, m.p. 102 ° C

N- (4'-methoxyphenyl) -3-methoxycrotonamide, m.p. 104 ° C N-ip-TolyD-S-methoxycrotonamide, m.p. 109 ° C

N- (2 ^L -chlorophenyl) -3-methoxycrotonamide, m.p. 72 ° C. 3-ethoxycrotonanilide, m.p. 118 ° C

N- (4'-Bromophenyl) -3-methoxycrotonamide, m.p. 152 ° C. N- (4'-Chlorophenyl) -3-methoxycrotonamide, m.p. 124 ° C. N- (3'-chlorophenyD-S-methoxycrotonamide, F = 104 ⁰ C

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N- (5'-chloro-2'-methylphenyl) -3-methoxycrotonamide, m.p. 150 ° C N- (4'-chloro-2'-methylphenyl) -3-methoxycrotonamide, m.p. 157 ° C N- (5'-chloro-2'-methoxyphenyl) -3-methoxycrotonamide, m.p. 134 ° C N- [3 '- (3 ", 3" -Dimethyl-n-butoxy) -phenyl] -S-methoxycrotonamide, M.p. = 94 ° C.

Example 12

3-methoxy-2-methylthiocrotonanilide

By the action of diazomethane on 2-methylthioacetoacetanilide (obtained by the action of the sodium salt of methyl mercaptan on oc-chloroacetoacetanilide) one obtains the 3-methoxy-2-methylthiocrotonanilide, m.p. 155 ° C.

Example 13 3-Phenoxycrotonanilide

By the action of phenol in a basic medium on 3-chlorocrotonanilide (obtained by condensation of aniline with ß-chlorocrotonyl chloride) one obtains the 3-phenoxycrotonanilide, F = 145 ° C.

Example 14

Investigation of the herbicidal properties of 3-methoxycrotonanilide and N- (m-tolyl) -3-methoxycrotonamide in pre-emergence and Post-emergence

The plants used (bluegrass, oats, wheat, corn, barley, ryegrass, foxtail grass, beetroot, goose foot (goosefoot plants), chrysanthemum, bedstraw, mustard, dock and clover) are in culture dishes (23 χ 14 χ 4 cm) with a double bottom and Irrigation grown from below. The different varieties are placed in rows of 20 grains per variety at a distance of 3 cm from each other in a single bowl - four times for each concentration. The culture conditions are: temperature 20 ° C ± 2 ^P C, humidity about 6O%, fluorescent lighting (daylight + bright white light) of 6 to 22:00 daily. The soil mixture used consists of 10 parts by volume of potting soil, 10 parts by volume of river sand and

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For the pre-emergence examinations, the treatment is 24 hours carried out after sowing, and the first watering is carried out by sprinkling in such a way that you get part of the product holds at the level of the grains.

For post-emergence attempts, the "treatment after 21 days." Culture time on the parts in the air. guided.

In both cases, the product to be examined is poured into the The amounts given in the tables below and applied in a dilution corresponding to 560 l / ha.

Comparative experiments without treatment and comparative experiments with METOXURON [(N-dimethyl-N ¹ -3-chloro-4-methoxyphenyD-urea], LINURON [N- (3,4-dichlorophenyl) -N '-methoxy-N «- methyl urea], NITROFEN [(2,4-dichlorophenyl) -4 «-nitrophenyl ether] and METABENZTHIAZURON [1-methyl-3- (2-benzothiazolyl) urea].

The final inspection is carried out by weighing the plants after 21 days of treatment for the pre-emergence attempts and 1.5 days after

Treatment carried out for the post-emergence attempts.

The results are expressed as a percentage of the decrease in plant growth P expressed:

Weight of control plants - weight of treated plants

P ₌ x ₁₀ 0

Weight of the comparison plants

The following tables give those obtained with 3-methoxycrotonanilide experimental results again.

4098U / 1 237

A) Results of the pre-emergence tests with 3-methoxycrotonanilide

3 meth
oxy-
croton
anilide dose
kg / ha ^v j. Ris
pen
grass Ha
fer White
Zen Corn Ger
ste Ray
grass Fox
tail
grass run
kel
turnip , Goose
se
foot Chrys
anthe
mum Lab
herb mustard Dock clover • NITRO
FEN 100 83 58 0 41 100 100 100 ioo 100 45 100 100 100 META-
BENZ-
THIAZ-
URON 0.625 100 43 20th 0 0 100 80 100 100 100 0 100 100 100 0.312 100 25th 0 0 0 100 82 95 100 63 0 100 100 100 0.156 90 72 0 0 34 25th 43 0.625 • 60 0 0 0 0 0 0 0.312 0 0 0 0 0 0 0 0.156 89 100 100 33 .100 100 100 0.625 35 97 100 35 100 100 100 0.312 0 ■ 48 94 36 92 90 87 0.156

CO OO 00

B) Test results of the post-emergence experiments with 3-methoxycrotonanilide

NJ CaJ

dose
kg / ha Ris
pen
grass Ha
fer White
Zen Corn Ger
ste Ray
grass Fox
tail
grass run
kel
turnip Goose
se
foot Chrys
anthe
mum Lab
herb mustard Dock clover 100 92 34 0 62 100 100 100 ioo 100 0 100 ■ 88 100 3 meth
oxy-
croton
anilide 0.625 100 54 0 0 0 82 57 98 100 100 0 • 57 64 100 METOX
URON 0.312 100 0 0 0 0 50 36 85 100 86 0 0 30th 94 LINURON 0.156 82 0 0 41 0 52 68 0.625 70 0 0 0 0 0 0 0.312 44 0 0 0 0 0 0 0.156 100 100 100 45 100 100 100 0.625 100 100 100 0, 1.00 100 100 0.312 80 100 70 0 96 79 91 0.156

CjO 00 OO

N- (m- C) test results Ha
fer White
Zen the pre-emergence experiments with N ~ (m-tolyl) -3-methoxycrotonamide Corn Ris
pen
grass, Ray
grass Fox
tail
grass run
kel
turnip Goose
se
foot Chrys
anthe
mum t. mustard Dock clover ToIyI) -
'3-meth- dose
kg / ha 100 0 0 100 100 83 loo ' 100 100 Lab
herb 100 100 100 oxy-
croton— 100 0 Ger
ste 0 100 100 67 100 100 100 100 100 100 100 amide 5 78 0 59 0 100 100 81 100 100 34 100 100 100 100 2.5 51 0 47 0 100 86 69 40 10 0 100 88 36 100 σ NITRO 1.25 69 25th 0 0 100 59 100 72 co
OO FEN 0.625 31 0 0 0 100 68 57 5 31 0 0 " 0_ 100 47 . 45 co META-
BENZ-
THIAZ-
URON 2.5 24 0 0 0 60 0 51 CO
-J 1.25 0 100 100 100 100 100 100 0.625 0 100 100 100 100 100 100 100 5 100 100 100 ■ ioo 100 100 100 2.5 .100 100 100 100 100 100 ! Op;! 1.25 100 0.625

N- (m- D) test results Ha
fer White
Zen the post-emergence experiments with N- (m-tolyl) -3-methoxycrotonamide Corn Ris
pen
grass Ray
grass Fox
tail
grass run
kel
turnip Goose
se
foot Chrys
anthe
mum Lab
herb mustard Dock clover ToIyI) -
3-meth- dose
kg / ha 100 100 100. 100 100 100 100 100 100 - 100 100 100 oxy-
croton 100 100 Ger
ste 100 100 100 100 100 100 100 - 100 100 .100 ami d 5 100 75 100 45 100 100 100 100 100 100 - 100 100 100 METOX
URON 2.5 92 0 100 0 100 100 36 100 100 100 - 100 100 ioo O 1.25 100 0 100 71 100 100 100 OO
_1 LINURON 0.625 46 0 53 0 100 100 80 -C-
"» Χ 5 29 0 60: 0 70 20th 0 1 237 2.5 0 0 0 0 0 36 0 " ^: 1.25 0 100 100 100 100 100 100 ■ ico 0.625 0 100 100 100 100 100 100 10G-. 5 100 100 100 100 100 100 100 " 2.5 .100 100 100 100 100 100 100 1.25 0.625

Conclusion; Both pre-emergence and post-emergence have the 3-methoxycrotone

anilide and N- (m-tolyl) -3-methoxycrotonamide have remarkable herbicidal properties.

Claims (10)

wherein A denotes a group ZR, where Z is an oxygen or Sulfur atom and R is an alkyl radical having 1 to 6 carbon atoms or an optionally substituted one Represent aryl radical, X and Y are hydrogen, a halogen atom, one optionally by one or more halogen atoms substituted alkyl radical with 1 to 6 carbon atoms or X and Y are an alkoxy radical, the alkyl radical of which is 1 to 3 carbon contains atoms, an alkylthio or alkylsulfinyl radical, whose alkyl radical contains 1 to 6 carbon atoms, an acyl radical with 1 to 6 carbon atoms, denote a nitro group or a trifluoromethyl radical, R ^, hydrogen, a chlorine or bromine atom, an alkyloxycarbonyl radical, whose alkyl radical contains 1 to 6 carbon atoms, a nitro group or an alkylthio, alkylsulfinyl or alkylsulfonyl group, whose alkyl radical contains 1 to 3 carbon atoms, and Rp denotes an alkyl radical with 1 to 6 carbon atoms, where these compounds of the formula I are in the form of the E isomer or the Z-isomer or in the form of a mixture of these Isomers exist. 4098 14/1237 2.) 3-methoxycrotonanilide. 3.) N- (m-Trifluoromethylphenyl) -3-methoxycrotonamide. 4.) N- (o-Tolyl) -3-methoxycrotonamide. 5.) N- (m-Tolyl) -3-methoxycrotonamide. 6.) N- (3'-Chlorophenyl) -3-methoxycrotonamide. 7.) Process for the preparation of the compounds of the formula I according to claim 1, wherein R ^, = H, R "- alkyl having 1 to 6 carbon atoms and A = ZR, where R represents an alkyl radical with 1 to 6 carbon atoms, characterized in that that one on a substituted anilide of the formula NHCOCH ₂ COR ₂ wherein X and Y have the meaning given in claim 1, either an O-alkylating agent to a compound of the formula I, wherein R ₁ = H, Rp = alkyl with 1 to 6 carbon atoms and A = OR, where R is an alkyl radical with 1 represents up to 6 carbon atoms, to obtain, to act, or Hydrogen sulfide in the presence of gaseous hydrogen chloride allows acid to take effect and then the compound of formula obtained NHCOCH "CR_ " ² treated with an S-alkylating agent to give a compound of formula I wherein R ₁ = H, Rp = alkyl with 1 to 6 409814/1237 2348A87 Carbon atoms and A = SR, where R is an alkyl radical represents having 1 to 6 carbon atoms. 8.) Herbicidal compositions containing as active ingredient at least one compound of the formula I according to claim 1, 9.) Herbicidal compositions containing 3-methoxycrotonanilide as the active ingredient. 10.) Herbicidal compositions containing the active ingredient N- (m-Tolyl) -3-methoxycrotonamide. 4098 U / 1237