DE2235811A1 - DERIVATIVES OF 5-METHYLPYRROL-2-CARBONIC ACID, THE PROCESS FOR THEIR MANUFACTURING AND HERBICIDES CONTAINING THIS - Google Patents

Description

LAWYERS DR. JUR. DIPL-CHEAL WALTER BEIL 19. Ml 1972

ALFRED HOPPS

ALFRED cPPSNES

SÄ ^Wlff 2235811

⁶²³ & £ "" !! ^{AT THE}

Our no. 18 018

The Upjohn Company Kalamazoo, Mich., V.St.A.

Derivatives of 5-methylpyrrole-2-carboxylic acid, method too their preparation and herbicides containing them.

The invention relates to new ^ -Methylcarbamoyl-J-substit.-5-methylpyrrole-2-carboxylic acid ester and 4-substit-carbonyl-3-substituted; .- 5 "niethylpyrrole-2-carboxamides, a new and improved method for making substituted Pyrroles by in situ hydrogenation of an a-oximinoacetoacetamide or a hydrocarbyl-a-oximinoacetoacetate in Presence of a hydrocarbylacetoacetate, an acetoacetamide or a substituted β-diketone as well as new ones Herbicides containing the new compounds and one or more auxiliary substances.

The 4-methylcarbamoyl-3-substit.-5 ~ methylpyrrole-2-carboxylic acid esters and ^ -substit.-carbonyl-3-substit.-5-methylpyrrole-2-carboxamides own the formulas

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CH, N-C

³ Il

and

fi)

do)

in which an alkyl group or a haloalkyl group with 1 to 10 carbon atoms, an alkenyl group or a haloalkenyl group with 3 to 8 carbon atoms, an alkynyl group with 3 to 10 carbon atoms, a cycloalkyl group with 3 to 6 ring carbon atoms, a cycloalkenyl group with ¹ I to 6 ring carbon atoms, a cycloalkyl radical with 4 to 12 carbon atoms substituted by alkyl radicals or halogen atoms, a cycloalkenyl radical substituted by alkyl radicals or halogen atoms with 5 to carbon atoms, a lower alkyl radical substituted by cycloalkyl or cycloalkenyl radicals with * J to 12 carbon atoms or a lower alkyl radical substituted by alkoxy radicals a total of 3 to 9 carbon atoms, R _{1 is} a hydrogen atom, a lower alkyl or a lower haloalkyl radical with 1 to ¹ carbon atoms, η zero or 1 and R _{2 is} a methyl, ethyl, trifluoromethyl, methoxy or methylamino radical.

The compounds of the invention (i.e. the compounds of formulas I and II) are biologically active as herbicides and can be used to control weeds in crops

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use plants. For this purpose, the compounds in pure or technically pure form can be applied to the Apply the desired location. In general, however, the compounds are mixed with one or more auxiliaries formulated to better handle, sell and use.

Among the typical herbicidally active substances according to the invention Compounds include the Ethyl-iJ-Cmethylearbamoyl) -} ^ -

2 2 4 dimethylpyrrole-2-carboxylate; N, N, N, 3,5-pentamethylpyrrole-2,4-dicarboxamide; Methyl 1-5- (ethylmethylcarbamoyl) -2,4-dimethylpyrrole-3-carboxylate; Methyl 5- (dimethylcarbamoyl) · 2,4-dimethylpyrrole-3-carboxylate; Methyl 1-5- (methylpropy1-carbamoyl) -2,4-dimethylpyrrole-3-carboxylate; Methyl 1-5- (methylpropylcarbamoyl) -2,4-dimethylpyrrole-3-carboxylate; Methyl 1-5- (methylisopropylcarbamoyl) -2,4-dimethylpyrrole-3-carboxylate; Methyl 1-5- (allylmethylcarbamoyl) -2,4-dimethylpyrrole-3-carboxylate; Methyl-5- (cyclopentylmethylcarbamoyl) -2,4-dimethylpyrrol- ⁱ 3-carboxylate and 4-propionyl-N, N, 3 '5 ~ Tetramethylpyrrol-2-carboxamide. The above compounds are preferred compounds of the invention and can be applied to farmland, roadsides, railroad areas, golf courses, wet areas, shrubbery areas, pasture land, parks or public facilities or similar areas (places or locations) before the weed seeds germinate or after Apply seedlings to the emergence of the weed in order to inhibit, suppress or interrupt their growth and normal development.

It has been found, for example, that the inventive, herbicidally active compounds against grass-like and broad-leaved weed species, e.g. Digitaria sanguinalis and Digitaria ischaemum, Setaria lutescens, Convolvulus

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arvensis, Avena fatua, Sorghum halepense L., Plantago lanceolata L. and Rumex crispus. Numerous other weed species are also ^{combated with the 1} -methylcarbamoyl-3-substit.-5-diethylpyrrole-2-carboxylic acid esters and 4-substit.-carbonyl-3-substit.-5-methylpyrrole-2-carboxamides according to the invention. In some cases it is advantageous to incorporate the herbicidally active compounds according to the invention into the soil surface, ie into the germination zone of the weed seeds.

After the herbicidal activity of the compounds according to the invention (i.e. the compounds of the aforementioned Formulas I and II), it was also found that there were certain limited subclasses of the claimed compounds are, which have a particularly good effectiveness and are preferred. For example weäum the compounds of formula II, in the Rp one Methoxy radical and η are zero, particularly preferred. Within of this subclass those compounds in which R denotes an alkyl or alkenyl radical are particularly preferred. Compounds in which R is ethyl are most preferred.

A further preferred subclass are those compounds of the formulas I and II in which R- is a Means methyl radical, and in particular those compounds in which R represents an alkyl or alkenyl radical. These preferred classes appear to have properties that make them potent or potent are more beneficial than other tested compounds of the present invention.

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The new inventive ⁱ l-methylcarbamoyl-3-substit.-S-methylpyrrole-S-carboxylic acid esters and iJ-substit.-carbonyl-3-substit.-5-methylpyrrole-2-carboxamides (ie the compounds of formulas I and II) can be produced by known synthetic processes. For example, the compounds according to the invention can easily be obtained by reacting a 4-substit.-carbonyl-3-substit.-5-methylpyrrole-2-carbonyl chloride with a corresponding selected alcohol or secondary amine by conventional methods.

Another method (namely, the new and improved method of the present invention) is an extension that of Ochiai et al. in Chem. Ber. 68B, p. 17IO - 1716 (1935) described the "isonitrosoketone + ketone" reaction. According to their method, an ee-oximinoacetoacetamide of the formula is applied to the compounds according to the invention

(III)

in which R, η and R _{1 have} the meanings given above for formulas I and II, with methyl acetoacetate, N-methylacetoacetamide or a substituted β-diketon of the formula

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\ ^<IV)

in which R _{2 has} the meaning given above for formula II. The reaction includes a reduction step which is a critical factor in the process of the invention. It has been found that the c-oximinoacetoacetamide obtained as an intermediate can be prepared and hydrogenated in situ, so that the new end products, namely the Ί-substit.-carbonyl-3-substit, -5-methylpyrrole-2-carboxamides of the formula II , in which R is an alkyl radical, a haloalkyl radical, a cycloalkyl radical, a cycloalkyl radical substituted by alkyl radicals or halogen atoms, a lower alkyl radical substituted by cycloalkyl radicals or a lower alkyl radical substituted by alkoxy radicals, are advantageously obtained by simple precipitation and filtration at the end.

It is assumed that the crOximinoacetoacetamides obtained as intermediates are new; they are formed according to the new process by reacting an acetoacetamide with sodium nitrite in an aqueous organic acidic solution. This nitrosation is rapid and is carried out at temperatures in the range from -10 ⁰ C to 25 ⁰ C.

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The aqueous organic acidic solution of the ct-Oximinoacetoacetaraids is with methylacetoacetate, N-methylacetoacetamide or a substituted ß-diketone of the formula IV as well a base metal or noble metal catalyst. (+ Hydrogen under pressure) added to the reduction, whereby the reductive cyclization stage is initiated. The catalytic hydrogenation is carried out in the presence of a hydrogenation catalyst, e.g. a Raney nickel, Raney cobalt, Platinum, palladium or rhodium catalyst, and in the presence an inert diluent, e.g. methanol, ethanol, dioxane, a lower alkanecarboxylic acid, e.g. acetic acid, or ethyl acetate carried out. Palladium on charcoal is preferred as the catalyst. The hydrogen pressures can

ρ in the range from atmospheric pressure to 70.3 kg / cm and the hydrogenation temperatures in the range from 10 C-100 ⁰ C. If palladium on charcoal is used as a catalyst, a

2
Hydrogen pressure of 3 »52 kg / cm and a ·. Temperature of 25 ° C preferred. Hydrogenation with a Raney nickel catalyst under similar conditions is also advantageous.

The desired herbicidally active products according to the invention are isolated after the reductive cyclization stage, the catalyst being filtered off and then the piltrate being washed with water. The products are in 'general, or crystallize and are recovered by filtration. They can be purified by recrystallization.

The new 4H-methylcarbamoyl) -3-substit.-S-carboxylate of the general formula I with a saturated radical R are produced in a similar manner by reacting N-methyl-

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acetoacetamide made with an R-ct-oximinoacetoacetate,

In addition to the processes described above for the preparation of the compounds according to the invention, some of them can also be produced by other methods. In one of these processes, an N, 5-dimethyl-N-R-3-substit.-2-carboxamide is used subjected to a Friedel-Crafts reaction with an alkanoyl halide to produce various il-acyl-N, 5-dimethyl-N-R-3-substit.-2-carboxamides der to produce general formula II.

The following examples are the preferred embodiments represent serve to explain the invention. Unless otherwise specified, parts refer to and percentages by weight and solvent ratios on the volume.

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Preparation 1

Acid chloride of 3,5-dimethyl-2,4-pyrroldicarboxylic acid H-methyl ester

A solution of 16.8 g (0.085 mol) of 3,5-dimethyl-2, U-pyrroldicarboxylic acid U-methyl ester and 100 ml of acetyl chloride was heated at reflux temperature for 30 minutes. After cooling the reaction mixture to about 25 ^° C., the precipitate which had formed was filtered off. The filter cake was washed with hexane and dried, 12.7 g of the acid chloride of 3,5-dimethyl-2, H-pyrroldicarboxylic acid U-methyl ester being obtained.

Using the same procedure, but using the 4-methyl-3,5-Dimethy1-2, U-pyrroldicarboxylic acid by the 5-methyl-3-trifluoromethyl-2,4-pyrroldicarboxylic acid 4-methyl ester, 3-ethyl-5-methyl-2, H-pyrroldicarboxylic acid U-methyl ester, 5-methyl-3-propyl-2, U-pyrroldicarboxylic acid - ^ - methyl ester and the methyl 2-isopropyl-5-methyl-2, 4-pyrroldicarboxylic acid was replaced, the corresponding acid 'chlorides of 5-methyl-3-trifluoromethyl-2, U-pyrroldicarboxylic acid 4-methyl ester, 3-ethyl-5-methyl-2,4-pyrroldicarboxylic acid 4-methyl ester, 5-methyl-3-propyl-2, U-pyrroldicarboxylic acid - »* - methyl ester or of 3-isopropyl-5-methyl-2, pyrroledicarboxylic acid 4-methyl ester manufactured.

Preparation 2

Acid chloride of 5-methyl-2, H-pyrroldicarboxylic acid - «» - methyl ester

A solution of 18 g (0.13 mol) of 2-methyl-3-pyrroldicarboxylic acid methyl ester in 150 ml of toluene was admixed with 25 ml of phosgene (liquefied gas). The reaction solution was allowed to stand for 24 hours at 25 ⁰ C and heated to 90 ° C then for 2 hours. The toluene and the volatile constituents were then evaporated, the acid chloride of the 5-methyl-2,4-pyrroldicarboxylic acid - »* - methyl ester being obtained.

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Methyl 5- (dimethylcarbamoyl) -2,4-dimethylpyrrole-3-carboxylate

A solution of 6.5 ml (0.1 mol) of dimethylamine and 25 ml of diethyl ether was a solution of 5.0 g (0.23 mol) of methyl 5- (chlorocarbonyl) -2, ^ - dimethylpyrrole-S-carboxylate in 50 ml of diethyl ether were added dropwise. This reaction mixture was left stirring for 18 hours, after which 100 ml of ethyl acetate was added. The reaction solution prepared in this way was washed with water, 2 η aqueous sodium hydroxide and again with water and finally dried over anhydrous sodium sulfate. The diethyl ether and the ethyl acetate were then evaporated off under reduced pressure, and the remaining solid thus obtained was recrystallized twice from a mixture of methylene chloride and hexane, the methyl 5- (dimethylcarbamoyl) -2, U-dimethylpyrrole ^ -carboxylate with a melting point of 119 - 150.5 ⁰ C was obtained.

58.61; H 7.19; N 12.49 59.01; H 7.15; N 12.35.

Methyl 5- (isopentylmethylcarbamoyl) * 2, ♦ -dimethylpyrrole-3-carboxylate

A solution of 6.0 ml of N-methylisoamylamine in 50 ml of methylene ' chloride was slowly stirred with 4.0 g (0.018 mol) Methyl 5- (chlorocarbonyl) -2, i-dimethylpyrrole-S-carboxylate offset. After 30 minutes, this reaction solution was successively mixed with 50 ml of 2η hydrochloric acid and 50 ml of 2η sodium hydroxide and finally washed with 3 100 ml portions of water. The washed reaction solution became over anhydrous sodium sulfate dried and the methylene chloride was evaporated under reduced pressure. The remaining oil was in hot technical hexane (Skellysolve B, a

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Analysis: 11 ^H 16 ^N 2 ° 3 ^: C. Calculated for C C. Found: Example 2

Dissolved mixture of isomeric hexanes having a boiling range from 61.1 ° C to 6 ⁰ 8.8 C). The solution was quenched and crystals formed. The crystals were filtered off and recrystallized from technical grade hexane, the 5- (isopentylmethylcarbamoyl) -2, U-dimethylpyrrole-S-earboxylate with a melting point of 89-92 ° C. being obtained .

analysis

Calculated for C ₁₅ H ₂₄ N ₂ O _3: C 64.26; H 8.63; N, 9.99 Found: C, 64.29; H 8.56; N 9.90.

Example 3

Methyl 5- (ethylmethylcarbamoyl) -2, '+ - dimethylpyrrole-3-carboxylate

119 ⁰ C prepared - according to the procedure of Example 1, except that dimethylamine was replaced with N-methylethylamine was the methyl 5- (äthylmethylcarbamoyl) -2,4-dimethylpyrrole-3-carboxylate having a melting point of the 115th ■

Analysis ■. ■

Calculated for C ₁₂ H ₁₈ N ₂ O ₃ : C, 60.48 .; H 7.61; N, 11.71 Found: C, 60.29; H 7.58; N 11.87

Example 4

Methyl 5- (methylpropylcarbamoyl) -2,4-dimethylpyrrole-3-carboxyl at

126 ⁰ C prepared - according to the procedure of Example 1, except that dimethylamine was replaced with N-methylpropylamine was the methyl 5- (methylpropylcarbamoyl) -2,4-dimethylpyrrole-3-carboxylate having a melting point of the 124th

analysis

Calculated for C ₁₃ H ₂₀ N ₂ O ₃ : C, 61.88; H 7.99; N, 11.10 Found: C, 61.91; H 8.10; N 11.13.

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Example 5

Methyl 5- (isopropylmethylcarbamoyl) -2, U-dimethylpyrrole-3-carboxylate

Following the procedure of Example 1, except that dimethylamine was replaced with N-methylisopropylamine "was the methyl 5- (isopropylmethylcarbamoyl) -2, 3-Hrdimethylpyrrol- Oarboxylat having a melting point of 158 - 161 C manufactured.

analysis

Calculated for C ₁₃ H ₂₀ N ₂ O ₃ : C, 61.88; H 7.99; N, 11.10 Found: C, 62.16; H 7.98; N 11.19.

Example 6

Methyl 5- (butylmethylcarbamoyl) -2, t -dimethylpyrrole-3-carboxylate

Following the procedure of Example 1, but using the dimethylamine was replaced by N-methylbutylamine methyl 5- (butylmethylcarbamoyl) -2,4-dimethylpyrrole-3-carboxylate with a melting point of 89-92 ° C.

analysis

Calculated for ^C ₁ i ₊ ^H ₂ 2 ^N 2 ° 3 ^{: C 63} » ¹³ 5 ^H 8.33; ^N, 10.52 Found: C, 63.26; H 8.45; N 10.29

■ Example 7 Methyl 5- (allylmethylcarbamoyl) -2, '+ - dimethylpyrrole-S-carboxylate

Following the procedure of Example 1, except that dimethylamine was replaced with N-methylallylamine, the methyl-5- (allylmethylcarbamoyl) -2,4-dimethylpyrrole-3-carboxylate having a melting point of 116.5 to 118.5 ⁰ C manufactured.

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Calculated for C ₁₃ H ₁₈ N ₂ O ₃ : C, 62.38; H 7.25; N, 11.19 Found: C, 62.61; H 7.34; N 11.14.

Example 8

Methyl 5- (dimethylearbamoyl) -2-methyl-4-propylpyrrole-3-carboxylate

Following the procedure of Example 1, except that the methyl 5- (chlorocarbonyl) -2,4-dimethylpyrrole-3-carboxylate by methyl 5- (chlorocarboriyl) -2-methyl-4-propylpyrrole-3-carboxylate was replaced, the methyl-5- (dimethylcarbamoy 1) - 2-methy 1-! ! + - propylpyrrole-3-carboxy lat with a melting point of 127-129 C.

Example 9

Another process for the preparation of methyl 5- (ethylmethylcarbamoyl) -2,4-dimethylpyrrole-3-carboxylate

After a cooled solution of 52.0 g (0.55 mol) of N-methylethylamine hydrochloride and 200 ml of water with an aqueous sodium hydroxide solution, which was prepared by dissolving 22.0 g (0.55 mol) of sodium hydroxide in 200 ml of water, added 50 g (0.60 mol) of diketene were slowly added with stirring over the course of one hour. This reaction mixture was allowed to stand for 18 hours, and then the water turned 100%. ⁰ C and a pressure of 10 mm Hg. In this way, 63.0 g of N-ethyl-N-methylacetoacetamide was obtained. A serving of 31 g (0.22 mol) of N-ethyl-N-methylacetoacetamid was 5 ml in 12 of acetic acid, and this solution was cooled to 10 ⁰ C. A solution of 13.0 g (0.19 mol) of sodium nitrite in 20 ml of water was then slowly added to this cooled solution. The temperature was kept at 10-20 ^° C. during the addition. After this solution ^{has been allowed to warm to about 25 °} C. within 30 minutes and 34 ± 8 g (0.30 mol) of methyl acetoacetate and about 4 ml of a suspension of the Raney nickel catalyst have been added to it

2 the mixture for 30 hours at a ::; Pressure of 3.52 kg / cm

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- 11} -

(50 lbs.) Hydrogenated. About 0.3 moles of hydrogen were adsorbed. The hydrogenated reaction mixture was hydrogenated to remove the catalyst, and the filtrate thus obtained was diluted with water. The desired product, ie methyl 5- (ethylmethylcarbamoyl) -2,4-dimethylpyrrole-3-carboxylate, crystallized out and was filtered off. It had a melting point of 116-119 ⁰ C. The yield was 78%.

Example 10

Methyl 5- (cyclohexylmethylcarbamoyl) -2,4-dimethylpyrrole-3-carboxylate

22.6 g (0.20 mol) of N-methylcyclohexylamine were added dropwise with a portion of 16.8 g (0.20 mol) of diketene over the course of 90 minutes while stirring. The reaction mixture was kept at a temperature in the range of 0-20 ° C. during the addition. After this reaction mixture had been allowed to stand at 25 C for 18 hours, 80 ml of glacial acetic acid were added and the acidified solution was cooled to 10 ⁰ C. Then 13.8 g (0.20 mol) of sodium nitrite were added in small portions over a period of 45 minutes. The temperature was kept in the range of 5-15 ° C. After a further 2 hours, the reaction solution was filtered and the filtrate was admixed with 50 ml (0.46 mol) of methyl acetoacetate and 0.5 g of a catalyst composed of 10% palladium on charcoal. This reaction mixture was ^{hydrogenated at 25 °} C. and a pressure of 3.52 kg / cm (50 lbs.) Until the uptake of hydrogen ceased. The catalyst was filtered off and the filtrate was diluted with water. The desired product, ie the methyl 5- (cyclohexylmethylcarbamoyl) -2, H-dimethylpyrrole-3-carboxylate, precipitated. The precipitate was filtered off; so the filtered solids had a melting point of 190-195 C. After recrystallization from methanol provided an analytical sample was obtained with a melting point of 19 3 ⁰ -'194,5 C.

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; . ■ - 15 -

Calculated for ^C ₁₆ ^H ₂ 4 ^N 2 ^O 3 ^: - ^{C 65} > ⁷² s ^H 8.27; N 9.58 Found; C 65.66 H 8.40; N 9.3.8.

Example 11

Methyl 1-5- (cyclopentyimethylcarbamoyl) -2,4-dimethylpyrrole-3-carboxylate

Following the procedure of Example 10, except that the N-methylcyclohexylamine was replaced by N-methylcyclopentylamine, was the methyl 5- (cyclopentylmethylcarbamoyl) -2,4r dimethylpyrrole-3-carboxylate having a melting point of 165 16 8 ⁰ C.

Analysis "

Calculated for C ₁₅ H ₂₂ N ₃ O _3: C, 64.72; H 7.97; N, 10.07 Found: C, 64.84; H -7.99; N 10.03.

Example 12
4-acetyl-N, N, 3,5-tetramethylpyrrole-2-carboxamide

13.8 g (0.2 mol) of sodium nitrite were within 45 minutes in small portions to a stirred (at -16.1 to -13.9 ⁰ C cooled solution of 25.8 g (0.20 mol) of N, N-dimethylacatoacetamide in 125 ml of glacial acetic acid was added After these participants were allowed to react for a further 45 minutes, the temperature rising to 25 ° C., 20.5 ml (0.20 mol) of 2,4-pentanedione and 0.5 This reaction mixture was then ^{hydrogenated at 25 °} C. and a pressure of 3.52 kg / cm (50 lbs.) until the uptake of hydrogen ceased. The catalyst was then filtered off and the Acetic acid was evaporated off under reduced pressure, the solid residue thus obtained was washed with water and dried over anhydrous sodium sulfate to give 24.0 g of 4-acetyl-N, N, 3,5-tetramethylpyrrole-2-carboxamide with a melting point of 15% -157 C. An analytical sample was obtained by recrystallization from methanol ß

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a melting point of 158 - 160 C.

analysis

For C ₁ .H .. _c N “0 _o : C 63.44; H 7.74; N 13.45 11 Ib LI

Found: C 6 3.56; H 7.88; N 13.54.

Example 13

N, N ^, S-tetramethyl ^ -trifluoroacetylpyrrole ^ -carboxamide

Following the procedure of Example 12, but using the 2,4-pentanedione was replaced by 1,1,1-trifluoro-2,4-pcntandione, became the N, N, 3,5-tetramethyl-4-trifluoroacetylpyrrole-2-carboxamide with a melting point of 152-155 ° C.

analysis

Calculated for ^C ₁₁ ^H ₁₃ ^F 3 ^N ₂ ^O 2 ^{: C 5O} » ³⁸ 5 ^H 5.00; N 10.68;

F 21.74 Found: C 50.53; H 5.35; N 10.87;

F 22.83.

Example 14

2 2 4
N, N, N, 3,5-pentamethylpyrrole-2,4-dicarboxamide

Following the procedure of Example 12, but using the 2,4-pentanedione was replaced by N-methylacetoacetamide

2 2 4
the N, N, N, 3,5-pentamethylpyrrole-2,4-dicarboxamide with

a melting point of 186 - 189 ⁰ C produced.

analysis

For C ₁₁ H ₁₇ N ₃ O: ^{c 59} > l ⁷ i ^{H 7} >68; N, 18.82 Found: C, 59.98; H 7.69; N 18.70

Example 15

4-propionyl-N, N, 3,5-th tramethylpyrrole-2-earboxamide

A solution of 7b g (0.29 mol) of tert-butyl-5- (dimethylcarbamoyl ) -2, 'l-dimo thyli'yrrol-3-carbcixylat and 100 ml tri-

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2 2 3 5 8 Ί1

Fluoroacetic acid was stirred continuously at 25 ° C. for 18 hours. The reaction solution was then with 300 ml Diluted water to form the 5- (dimethylcarbamoyl) -2,4-dimethylpyrrole-3-carboxylic acid to fail. The precipitate was filtered off, washed thoroughly with water and air dried. The washed and dried filter cake (58.5 g) was dispersed in 50 ml of 2-hydroxyethylamine and refluxed for two hours. After cooling, the reaction solution was poured into a mixture of ice and water poured to the formed N, N, 3,5-tetramethylpyrrole-2-carboxamide to fail. This precipitate was filtered off and dried. The amount was 28.0 g. A portion of 5.0 g of the filter cake was dispersed in .1.3 g of propionyl chloride and then U, 3 g of anhydrous Aluminum chloride added. After heating at 45 ° C. for 3 hours, the reaction mixture was poured into a separatory funnel, which contained 100 ml of ethyl acetate and 100 ml of water. The organic layer was separated and dried over anhydrous Dried sodium sulfate. The dried solution was then concentrated to a small volume, whereby Most of the ethyl acetate was evaporated, and the concentrate was poured onto a 100 g silica gel Column applied. After that the chromatogram developed and eluted with ethyl acetate, the eluate collected and the After the ethyl acetate had finally been evaporated, 1.0 g of 4-propionyl-N, N, 3,5-tetramethylpyrrole-2-carboxamide were added a melting point of 139-143 ° C obtained. By recrystallization a mixture of benzene and technical grade hexane became an analytical sample with a melting point from 144 - 146.5 ° C.

analysis

Calculated for ^c i ₂ ^H 18 ^N 2 ^O 2 ^: ° ⁶⁴ > ^{81 |} > ^{H 8} > ¹⁶ > N 12.60 Found: C 64.83; H 8.04; N 12.77.

2 0 9 8 8 6/1310 _{@M) 0} WGMAi-

Example 16

Tert-butyl 4- (methylcarbamoyl) -3,5-dimethylpyrrole-2-carboxylate

A solution of 11.1 g (0.07 mol) of tert-butyl acetoacetate and 100 ml of glacial acetic acid was admixed with +.8 g (0.07 mol) of sodium nitrate in small portions over the course of 30 minutes while stirring at 0 ° C . After the reaction mixture had been left to stand for 1 hour and then allowed to warm to 25 ° C., 11.0 g (0.10 mol) of N-methylacetoacetamide and 0.5 g of a catalyst composed of 10% palladium on charcoal were added . This mixture was hydrogenated at a pressure of 3.52 kg / cm (50 lbs.) Until hydrogen uptake ceased. The catalyst was filtered off and the filtrate was diluted with water to precipitate the reaction product. After filtering off the precipitate and recrystallization from ethanol, the tert-butyl-4- (methylcarbamoyl) -3,5-dimethylpyrrole-2-carboxy was obtained
keep.

carboxylate with a melting point of 209 - 211 C

analysis

Calculated for C ₁₃ H ₂₀ N ₂ O ₃ : C, 61.88; H 7.99; N, 11.10 Found: C, 62.06; H 8.10; N 10.89.

Example 17

Ethyl 4- (methylcarbamoyl) -3,5-dimethylpyrrole-2-carboxylate

Follow the procedure of Example 16, but using the tert-butyl acetoacetate was replaced by ethyl acetoacetate, the ethyl 4- (methylcarbamoyl) -3,5-dimethylpyrrole-2-carboxylate became with a melting point of 218-219 ° C.

Analysis

For C ₁₁ H ₁₆ N ₂ S ^{1 c 58} > ⁹² i ^H 7.19; N, 12.49 Found: C, 58.86; H 7.24; N 12.52.

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Example 15

Isopropyl 4 - :( methylcarbamoyl) -3 _s 5-dimethylpyrrole-2-carboxylate

Following the procedure of Example 16, but using the tert-butyl acetoacetate was replaced by isopropyl acetoacetate, the isopropyl 4- (methylcarbamoyl) -3,5-dimethyl pyrrole-2-carboxylate became with a melting point of 191-194 ° C.

Analysis """*

Calculated for C ₁₂ ^H 18 ^N 2 ° 3 ^{: C '60} ^ ⁸ J ^{H 7} r ⁶¹ i ^N H »7» Found:'"C 60, -39; Ή 7.79; N 11.69

Example 19 · '

Methyl 5- (diethylcarbamoyl) -2, if-dimethylpyrrole-S-carboxylate

Following the procedure of Example 1, except that the Dime thy lamin was replaced by diethylamine, methyl-5- (diethylcarbamoyl) -2 became jU-dimethylpyrrole-3-carboxylate with obtained a melting point of 135-136 ° C.

analysis

Calculated for C ₁₃ H ₂₀ N ₂ O ₃ : C, 61.88; H 7.99; N, 11.10 Found: C, 61.60; H 8.26 '; N 11.28.

Example 20

Following the procedure of Example 16, except that the tert-butyl acetoacetate is replaced by hexyl acetoacetate, octyl acetoacetate, decyl acetoacetate, 2,2,2-trifluoroethyl acetoacetate, 2-chloroethyl acetoacetate ,, 2-bromo ethyl acetoacetate, 2-iodo ethyl acetoacetate, S-chloropropyl acetoacetate, 2,3 -Dibrombutylacetoacotat, 5-Fluorpentylacetoacetat, U-Jodoctylacetoacetat, 3,3-Dibromdecylacetoacetat, 3-Butenylacetoacetat, 5-Hexenylacetoaoetat, l7Heptenylacetoacetat, _{1-methyl-1-heptenylacetoacetat:} 3,3-dichloro-2-methylallylacetoacetat, Cyclohexylacetoacetat, ^ .- Cycloporiten-1-yl-acetoacetate, 1,3-cyclopentadien-1-yl-aceto -. 'Acetate, 1-methyl-2-cyclobuten-1-yl-acetoacetate, 3-bromo-2-cyclc

209 8 86/1310 /

hexen-l-yl-acetoacetate, cyclopropylmethylacetoacetate, 3- (2-cyclohexen-l-yD-butylacetoacetate, 2-methoxyethylacetoacetate or 2-methoxyoctylacetoacetate was replaced, the corresponding hexy1-4- (methylcarbamoy1X-3,5-dimethylpyrrole-2 carboxylate, octyl 4- (methylcarbamoyl) -3,5-dimethylpyrrole-2-carboxylate, decyl 4- (methylcarbamoyl) -3,5-dimethylpyrrole-2-carboxylate, 2,2,2-trifluoroethy1-1- ( ! methylcarbamoyl) -3,5-dime thy pyrrole-2-carboxylate, 2 -Chloräthyl- ¹ + - (methyl lcarbamoyl) -3, 5-dirnethylpyrrol-carboxylate 2, 2-bromoethyl-4- (methylcarba Moyles) -3 , 5-dimethylpyrrole-2-carboxylate, 2-iodoethyl-4- (methylcarbamcyl) -3,5-dimethylpyrrole-2-carboxylate, 3-chloropropyl-4- (methylcarbamoyl) -3,5-dimethylpyrrole-2-carboxylate, 2 , 3-Dibromobutyl-U- (methylcarbamoyl) -3,5-dimethylpyrrole-2-carboxylate, 5-fluoropentyl-4- (methylcarbamoyl) -3,5-dimethylpyrrol2-carboxylate, 4-iodoctyl-i + - (methylcarbamoyl) - 3, 5-dimethylpyrrole-2-carboxylate, 3,3-dibromodecyl-4- (methylcarbamoyD-3,5-dimethylpyrrole-2-carboxylate, 3-butenyl-4- ( methylcarbamoy 3,5-dimethylpyrrole-2-carboxylate, 5-hexenyl-4- (methylcarbamoy 3 j5-dimethylpyrrole-2-carboxylate, 1-heptenyl-4- (methyl-carbamoyl) -3,5-dimethylpyrrole-2-carboxylate, 1-methyl-lheptenyl-4- (methylcarbamoyl) -3,5-dimethylpyrrole-2-carboxyIaI 3 ₅ 3-dichloro-2-methylallyl-14- (methylcarbamoyl) -3,5-dimethylpyrrole-2-carboxylate, cyclohexy1-4 - (methylcarbamoyl) -3,5-dimethylpyrrole-2-carboxylate, 2-cyclopenten-1-yl-U- (methylcarb'imoyl) -3, 5-dimethylpyrrole-2-carboxylate, 1,3-cyclopentadien-1-yl -4- (methylcarbamoyl) -3,5-dimethylpyrrole-2-carboxylate, 1-methyl-2-cyclobutene-ly.1-4 (methylcarbamoyl) -3,5-dimethylpyrrole-2-carboxylate, 3-bromo-2 -cyclohexen-l-yl-4- (methylcarbamoyl) -3,5-dimethylpyrrole-2-carboxylate, cyclopropylmethyl-4- (methylcarbamoyl) -3,5-dimethylpyrrole-2-carboxylate, 3- (2-cyclohexene-1- yl) -butyl - '+ - (methylcarbamoyl) -3,5-dimethylpyrrole-2-carboxylate, 2-methoxyethyl-4- (methylcarbamoyl) -3,5-dimethylpyrrole-2-carboxylate or the corresponding 2-methoxyoctyl-4 - (methylcarbamoyl) -3,5-dimethylpyrrole-2 -carboxylate produced.

209886/1310

BAD ORi3 »NAl.

Following the procedure of Example 2, but using the N-methylisoamylamine each by N-methylhexylamine, N-methyloctylamine, N-ethyldecylamine, N-methyltrifluoromethylamine, M-ethyl trifluoromethylamine, N-ethyl-2-chloroethylamine, N-ethyl-2-bromoethylamine, N-methyl-3,3,3-trifluoropropylamine, N-methyl-3 , 3, 3-triiodopropylamine, N-methyl-4-iodoctylamine, N-methyl-3,3-dibromodecylamine, N-methyl-1-ethylpropenylamine, N-methyl-2-butenyl- (crotylamine), N-methyl-5-hexenylamine, N-ethyl-1-heptenylamine, N-1-dimethyl-l-heptenylaminej N-ethylcyclopropylamine, N-methyl-3-chloro-2-butenylamine, N-methyl-2-chloro-3-fluoroallylamine, N-methyl-M-chloro-2-octenylamine, N-methyl-2-cyclohexen-1-ylamine, N, S-dimethyl ^ -cyclohexen-i-ylamine, N-methyl-3-bromo-2-cyclohexen ~ l-ylamine, N-methyl-2-ethoxymethylamine, N-methyl-2-isopropoxyethylamine, N-methyl-2-cyclopentylethylamine, N-methyl-2-butoxyethylamine, N-methyl-. l-methyl-3-methoxybutylamine, N-methyl-l-ethyl-3-isopropoxybutylamine, N-methyl-3,5-dipropylcyclohexylamine, N-methyl-2,4,6-triethyl-2-cyclohexen-1-ylamine or N-methyl-2-ethyl-4-cyclohexylbutylamine was replaced, the corresponding methyl 5- (hexylmethylcarbamoyl) -2, '+ - dimet.hylpyrrole-S-carboxylate, Methyl 5-cmethyloctylcarbamoyl) -2,4-dimethylpyrrole-3-carboxylate, Methyl-S-CdecyläthylcarbamoyD-S, 4-dimethylpyrrole-3-carboxylate, Methyl 5- [methyl- (trifluoromethyl) carbarnoyl J-2, '+ - dimethylpyrrole-S-carboxylate, methyl-5-ethyl- (trif luoromethyl) -carbamoyl3-2, M - dime thy lpy-rr ο 1-3-carboxy lat, Methyl 5 - [(2-chloroethyl) ethylcarbamoyl3-2,4-dimethylpyrrole-3-carboxylate j methyl-5- [(2-bromoethyl) ethylcarbamoyl3-2, M-- -limethylpyrrQl-3-carboxylate, methyl 5- [methyl- (3, 3, 3-trifluoropropyl) -carbamoyl3-2 , "- f-dimethylpyrrole-S-carboxylate, Methyl 5- [methyl- (3,3,3-triiodopropyl) -carbamoyl3-2 »M-dimo-ethyl pyrrole-3-carboxylate, Methyl 5 - [(4-iodoctyl) methylcarbamoylj-2 , 4-diinethylpyrrole-3-carboxylate, methyl 5- [(3, 3-dibromodecyl) -me thy lcarbamoyl J-2, H-dime thy lpyrrole-3-carboxylate, * methyl-5 - [(l-ethylpropenyl) -mothylcarbamoyl] -2,4-dimethylpyrrole-3-carboxylate, Methyl-5-C (2-butenyl) -methylcarbamoylj-2, H-dimethylpyrrole-3-carboxylate, Methyl-5-C (5-hexenyl) -methylcarba-

209886/1310

SAP ORIGINAL.

moyl] -2,4-dimethylpyrrole-3-carboxylate, methyl 5 - [(1-heptenyl) ethylcarbamoyl3-2,4-dimethylpyrrole-3-carboxylate, methyl 5- [methyl- (l-methyl-1- heptenyl) carbamoyl J-2,4-dimethylpyrrole-3-carboxylate, methyl 5- (cyclopropylethylcarbamoyl) -2, H-dimethylpyrrole-3-carboxylate, methyl 5- [(3-chloro-2-butenyl) methylcarbamoyl ] -2,4-dimethylpyrrole-3-carboxylate, methyl 5 - [(2-chloro-3-fluoroallyl) methylcarbamoyl3-2, »+ - dimethylpyrrole-3-carboxylate, methyl 5 - [(4-chloro- 2-octenyl) methylcarbamoyl} -2, 4-dimethylpyrrole-3-carboxylate, methyl 5- [(2-cyclohexenyl) methylcarbamoyl3-2, 4-dimethylpyrrole-2-carboxylate, methyl 5-cmethyl- ( 5-methyl-2-cyclohexen-1-yl) carbamoyl 3-2,4-dimethylpyrrole-3-carboxylate, methyl 5 - [(3-bromo-2-cyclohexen-1-yl) methyl carbamoyl 3-2 , '+ - dimethylpyrrole-3-carboxylate, methyl 5- [(2-ethoxymethyl) -methylcarbamoyl3-2, U-dimethylpyrrole-3-carboxy lat, methyl-5-t (2-isopropoxyethyD-methylcarbamoyl3-2, U- dimethylpyrrole-3-carboxylate, methyl-5-t (2-cyclopentylethyl) -methylcarbamoyl3-2,4-dimethylpyrrole -3-carboxylate, methyl 5- [(2-butoxyäthyl) -methylcarbamoyl3- 2, ^l-f dimethylpyrrole-3-carboxylate, methyl 5- [methyl- (1-methyl-1-3-methoxybutyl) -carbamoyl3-2 , U-dimethylpyrrole-3-carboxylate, methyl 5 - [(1-ethy1-3-isopropoxybutyl) -methylcarbamoyl3-2,4-dimethylpyrrole-3-carboxylate, methyl-C (3,5-dipropylcyclohexyl) -methylcarbamoyl3-2 , '! - dimethyl pyrrole 3-carboxylate, methyl 5- [methyl- (2,4,6-triethyl-2-cyclohexen-1-yl) carbamoy13-2, U-dimethylpyrrole-3-carboxylate or the corresponding methyl 5-t (2-ethyl-4-cyclohexylbutyl) -methylcarbamoyl3-2, H-dimethylpyrrole-3-carboxylate is produced.

Example 22

Following the procedure of Example 1, except that the methyl 5- (chlorocarbonyl) -2,4-dimethylpyrrole-3-oarboxylate by the acid chlorides of the 5-methyl-2,4-pyiToldicarbonsäure-4-methylester, 5-methyl ^ 3-trifluoromethyl-2, H-pyrroldicarboxylic acid 4-methyl ester, 3-ethyl-5-methyl-2, 4-pyrrole. HiVaT>lM> u acid -! + - methyl ester, 5-methyl-3-propyl-2, ⁱ -pyrix> idicarboxylic acid 4-methyl ester, 3-isopropyl-5-methyl-2, U-pyrroledicarboxylic acid 4-methyl ester and 3-sec-butyl-5-methyl-2, H-pyrroledicarboxylic acid c-H-methyl ester and the dimethylamine durcli

209886/1310

ο ο q er ρ -ι ι

Ethylmethylamine were replaced, the corresponding methyl 5- (äthy lme thylcarbamoyl) -2-methylpyrrole-3-carboxyla ⁺ " _:) Methy1-5- (ethylmethylcarbamoyl) -2-methyl-4-trifluoromethylpyrrole-3-carboxylate, methyl 5- (ethylmethylcarbamoyl) -4 ~ ethyl 2-methylpyrrole-3-carboxylate, methyl 5- (ethylmethylcarbamoyl) 2-methy1-4-propylpyrrole-3-carboxylate, methyl 5 :-( ethylmethylcarbamoyl) -i + -isopropyl -2-methylpyrrole-3-carboxylate or the corresponding methyl 1-5- (ethylmethylcarbamoyl) -2-methyl-4-sec-butylpyrrole-3-carboxylate.

The it-methylcarbamoyl-J-substit.-S-methylpyrrole-2-carboxylic acid esters according to the invention and 4-substit.-carbonyl-3-substit * S-methylpyrrole-S-carboxamide can be used alone for weed control can be used, but if appropriate a mixture of the compounds can also be used. The connections can be in pure or technically pure form, as raw mixtures of one or more compounds or as improved agricultural preparations are used. Such improved preparations are through the present one or more, excipients characterized that the promote effective use of the active ingredient and for economic Application of the invention contribute. In some cases a solvent may be desirable, in others, an aid, such as a fine powdered pesticide. Such liquids and solids for stretching the active ingredients are called carriers. In still other cases Wetting or dispersing agents, adhesives or atomizing agents, or even other active ingredients may be desirable be.

In the context of the present invention, the agricultural preparations include, for example, solutions, liquid Suspensions, emulsions, creams, pastes, wettable powders, dusts, emulsifiable concentrates, granulates, impregnated elastomeric strips, bands or blocks. In general, the active ingredient is preferably dispersed

209886/1310

or easily dispersible form. The dispersibility allows for a thorough and uniform application on any area overgrown with weeds so that the desired control is achieved.

If selective weed control is desired in an area of cultivated land or in the lawn, a non-phytotoxic one becomes Carrier preferred. In this way, the useful plants or desired grass varieties are not damaged, however the weeds through the 4-methy 'used as active ingredients carbamoyl-3-substit.-5-methylpyrrole-2-carboxylic acid ester or ^ -substitute-carbonyl-3-substit.-5-methylpyrrole-2-carboxamide c selectively killed. Water is a non-phytotoxic carrier that occurs everywhere. Certain non-phytotoxic Vegetable oils can be used in small amounts of about 9.35 l / ha (1 gal / acre). Usually in pesticides related to herbicidal preparations are not phytotoxic. On the other hand, the whole fight against the If vegetation is desired, a phytotoxic carrier can be chosen. Suitable phytotoxic carriers are e.g. high-boiling petroleum fractions and tetrachloroethane.

The herbicidal effectiveness of 4-methylcarbamoyl-3-substit. · ■ 5-methylpyrrole-2-carboxylic acid esters and 4-substit.-carbonyl-3-substit .- ^ - methylpyrrole - ^ - carboxamides is very strong, and

2 the compounds can be used in relatively small amounts per m to control the growth of weeds, for example germinating weed seedlings. For example, with the compounds methyl-5- (dimethylcarbamoyl) -2 ^,! 4-dimethylpyrrole-3-carboxylate, methyl 5- (isopropylmethylcarbamoyl) -2, 4-dimethylpyrrole-3-cnrboxylate, methyl ~ 5- (ethy "methylcarbamoyl) -2, ⁱ " -dimethylpyrrole-3-carboxylate and

209886/1310

Ät.hyl-4- (methylcarbamoyl) -3 _J 5-dimethylpyrrole-2-carboxylate, if they were applied in amounts of 0.672 and 0.336 g / m (6 lbs., And 3 lbs. Per acre), a complete or nearly complete Achieve eradication of Amaranthus retroflexus L. Application levels from about 0.112 to about 1.68

2 ·

¹ Regenfall- or irrigation volume and response of the most common species of weeds, are effective g / m under conventional conditions, depending on the particular circumstances, such as soil type. At high application rates, ie at approx. 2.24 to approx. 5.60 g / m 2, the compound acts as a soil sterilant.

For example, excellent weed control in grain fields was possible without any significant damage of cereal plants if one uses the 4-methylcarbamoyl-3-substit.-5-methylpyrrole-2-carboxylic acid ester and 4-substit.-carbonyl-3-substit.-S-methylpyrrole ^ -carboxamides applied in concentrations of about 1000 to about 5000 ppm in amounts of about 0.112 to about 0.336 g / m. in the In general, a desired amount can be applied in such a way that an aqueous spray preparation according to the invention is also used a content of about 700 to about 30,000 ppm active ingredient Distributed over the area to be treated. Of course, the choice of active ingredient concentration depends on both the Application amount as well as the type of preparation and the extent of the desired weed control. In general the concentration within the specified range is not critical, since an effective amount of the Active ingredient on a given area is better with larger amounts at a lower concentration than with smaller amounts can be applied with a higher concentration. The concentration of the active ingredient in the dispersible powder and the emulsifiable concentrates that make up the aqueous

209886/1310

Spray preparations are made, can be up to 99.5 wt .- 5S. The concentration of the active ingredient in the dust and granulate preparations according to the invention can vary between about 0.25 and about 80 % or more, but is preferably 0.50 to 20%.

The granular preparations according to the invention is mixed with about 0.25 to about 80% _t preferably from 0.50 to 20 parts by weight Jt, active ingredient and a granular carrier such as hitzeexpandiertem vermiculite, perlite hitzeexpandiertem, pyrophyllite or attapulgite prepared. The active ingredient can be dissolved in a volatile solvent such as methylene chloride, acetone and the like and sprayed onto the granular carrier in a mixer or drum. The granules are then dried. The granular carriers can have a particle size with a mesh size in the range from about 1.95 to about 0.25, preferably from about 0.59 to about 0.25 mm.

The herbicidal dust preparations according to the invention are prepared by adding about 0.25 to about 80% by weight, preferably 0.50 to 20 %, of active ingredient with a solid, powdery carrier, by means of which the constituents are kept in a dry, flowable state, intimately mixed. The herbicidal dust preparations according to the invention can be prepared by mixing the compound with a solid extender and then grinding it. Preferably, however, the active ingredient is dissolved in a volatile organic solvent of the type mentioned above and then sprayed onto the solid support so that thorough distribution is ensured. The mixture is then dried and ground to the desired size, e.g. less than 60 microns.

209886/1310

Among the solid carriers that are used in the inventive Dust supplements that can be used include natural clays such as kaolin and betonite, minerals in natural Condition such as talc, pyrophyllite, quartz, diatomaceous earth, puller earth, chalk and phosphate rock, as well as chemical modified minerals such as washed betonite, precipitated calcium phosphate, precipitated calcium carbonate, precipitated Calcium silicate and colloidal silica. About the solid extenders that can be used in the preparations, also include solid fertilizer mixtures. Such solid, finely divided preparations can be found on the plants as dust can be applied using conventional equipment.

A preparation preferred according to the invention is in the form of a dispersible powder, for the preparation of which a surface-active agent is incorporated into a dust preparation prepared as described above. Such a dispersible powder can be dispersed in water at any desired concentration and applied to vegetation using conventional spray devices. The dispersible powders are expediently produced with higher concentrations of active ingredient than powder preparations; they can to approximately QO% ■ »preferably about 10 to 80% of active ingredient, for example up. The surface-active agents which are suitable for the production of such dispersible powder preparations include alkyl sulfates and sulfonates, alkylarylsulfonates, sulfosuccinic acid- ^ stor, polyoxyethylene sulfates, polyoxyethylene sorbitan mono-1-urate, / ukylaryl polyether sulfates, alkylaryl alcohol polyether sulfates, alkylaryl polyether sulfates, alkyl aryl alcohol. Ammonium salts, sulfated fatty acids and esters, sulfatuorto Fottsäureamide, glycerin mannitan laurate, the poly-

2 0 9 8 8 6/1 31 0

BATH OFiIQWAL

alkyl ether condensate of pot acids, ligninsulphonates and the like. A preferred class of surface-active agents comprises mixtures of sulphonated oils and polyalcohol carboxylic acid esters (Emcol H-77), mixtures of polyoxyethylene ethers and oil-soluble sulphonates (Emcol H-400), mixtures of alkylarylsulphonates and alkylphenoxyethanols 151, X-161 and X-171), e.g. approximately equal parts of sodium kerylbenzene sulfonate and isooctylphenoxypolyethoxyethanol with about 12 ethoxy groups and mixtures of calcium alkylarylsulfonates and polyethoxylated vegetable oils (Agrimul N ^ S). Of course, the sulfates and sulfonates proposed above as surface active agents are preferably used in the form of their soluble. Salts, for example their sodium salts, related. All of these surfactants have the ability, in concentrations of about 1 % or less, to reduce the surface tension of water to less than about 50 dynes / cm. The dispersible powder preparations can optionally also be produced with a mixture of the surface-active agents mentioned.

Anionic and nonionic surfactants are used preferred. The calcium salts of myristylbenzenesulfonic acid are suitable as anionic surface-active agents and laurylbenzenesulfonic acid. As a nonionic surfactant The oleate ester of a polyoxyethylene glycol with a molecular weight of about is suitable 35O- 500. Other surfactants as disclosed by J. McCutcheon in Soap and Chemical Specialties (Dec. 1957) and (Jan., Feb., March and April 1958), are also suitable.

209886/1310 ¹ ^ ORIGINAL

A suitable dispersible powder preparation is obtained, by adding IO7 kg of Georgia clay ,. 2.5 kg of isooctylphenoxypolyethoxyethanol (Triton X-IOO) as a wetting agent j 4.3 kg of a polymerized sodium salt einor substituted benzenoid long-chain sulfonic acid (Daxad 27) as a dispersant and 113 kg of active ingredient mixed and ground. The preparation obtained in this way has the following percentage composition (where parts are expressed in parts by weight unless otherwise specified are).

Active ingredient 50 %

Tsooctylphenoxypolyethoxy-

ethanol 1.1 %

polymerized sodium salt

the substituted benzoids

long chain sulfonic acid "1.9 %

Goorgia tone hj%

When dispersed in water in a Monge of ea. 12 g / l ^1, this preparation results in a spray preparation containing about 0.6 % (60000 ppm) of active ingredient, which is applied to the soil, other plant growth medxes, growing plants, for example lawns, in an amount of approx. 373 l / ha can be applied, resulting in a total amount of active ingredient applied of 0.224 g / m ² ,

Bio compounds according to the invention can be sprayed onto the soil, plants, Plant growth media and growing plants, ζ / B. Lawn. As the connections as such

209886/1 310

are relatively insoluble in water, they are preferably dissolved in a suitable inert organic solvent. It is beneficial to use the solvent
Water is not miscible, so that an emulsion of the solvent in water can be produced. For example, if a water-miscible solvent such as acetone is used, the solvent dissolves in water and any excess of the compound of formula I precipitates out of solution. In an emulsion, the solvent phase is dispersed in the aqueous phase and the active ingredient is kept in solution in the dispersed phase. In this way, a uniform distribution of the active ingredient can be achieved with the aid of an aqueous spray solution.

It is desirable to use a solvent in which the compounds are very soluble so that relatively high concentrations of active ingredient can be achieved.
Sometimes it is possible to use one or more solvents
to use with odor without co-solvents in order to obtain concentrated solutions of the active ingredient, but the main requirement remains to use a water-immiscible solvent for the active ingredient that contains the compound within the concentration range that is used to prevent the germination of unwanted seeds and suitable for controlling plant growth, keeps in solution.

The emulsifiable concentrates according to the invention are
produced by adding <ion active ingredient and a surface-active agent in a solvent which is essentially immiscible with water as a carrier (ie a solution which at temperatures in the range from 20 to 30 ° C. only up to 2.5 vol Water soluble), e.g. cyclohexanone,

209886/1310 'β / Φ OFUGWAL

Methyl propyl ketone, summer oils, ethylene dichloride, aromatic Hydrocarbons such as benzene, toluene or xylene, and high-boiling petroleum fractions such as heavy aromatic Naphtha rosin, diesel oil, and the like., Dissolves. Possibly A co-solvent such as methyl ethyl ketone, acetone and the like can also be used together with the solvent to increase the solubility of the active ingredient. Aqueous emulsions are then produced in that one water up to any desired concentration of active ingredient inflicts. The surfactants that are in the Allow aqueous emulsions according to the invention to be used have already been mentioned above. If necessary, can mixtures of the surfactants can also be used. , -

The concentration of the active ingredient in the emulsifiable concentrates can be in the range from about 5 to about 50% by weight , preferably about 10 to 40%. A concentrate which contains 20 % by weight of the compound which is dissolved in a water-immiscible solvent of the type mentioned above can be mixed with an aqueous medium in a ratio of approx. 3.4 ml of concentrate per 1 liter of medium, whereby a mixture of 700 parts of active ingredient per million parts of liquid carrier is obtained. Similarly, about 0.94 l of a 20% concentrate mixed with 151 l of water give a solution with about 1200 ppm of active ingredient. More concentrated solutions of the active ingredient can be prepared in the same way.

The concentrates according to the invention which are for use in Pf) HTi of aqueous dispersions or emu! si uiteii boBLninni fvind, may also contain a Fouchth-aJt / -Gini "Ltel, i.

ORIGINAL

209 886/1310

an agent which involves drying an aqueous spray preparation delayed on the material to which it was applied. Examples of suitable humectants are 'soluble' made lignins such as calcium lignosulfonate and the like.

According to the invention, certain preparations of ^ -Methyl-carbamoyl ^ -substit .- ^ - methylpyrrole - ^ - carboxylic acid ester and the Jl-substit.-carbonyl - ^ - substit .- ^ - methylpyrrole · ^ - carboxamide with oil particularly effective, with the herbicides Effectiveness of the compound is increased. A petroleum with a viscosity in the range of 70-100 seconds (Sayboldt) is satisfactory. Such non-phytotoxic vegetable oils are advantageous when they are in the ratio of about 0.9 ^ to about 1.88 ccm / m (1 to 2 gals per acre) related will. Apparently they encourage the herbicide to penetrate the weeds or maybe make the surface of the weeds susceptible to the penetration of the herbicide.

Preferably a 50 / K-strength wettable powder of the herbicidal Active ingredient with about 144 l of water and 7.6 l of oil for Preparing a spray solution mixed. But it is also possible to start with about 7.6 liters of oil and a 50 # wettable Premix the powder and then disperse it in about 14-1 of water to make a spray solution. In field trials oil preparations of the type mentioned above have shown improved herbicidal effectiveness.

The amount that is present on soils, plant growth media and growing plants, e.g. lawns that need to be protected against harmful weeds, must be applied

209886/1310

on the type of plants to be controlled, the presence or absence of desirable types of tarpaulin, the time of year in which the treatment is carried out, and the method and effectiveness of the application. In general, a selective herbicidal activity is achieved if the active ingredients are applied in a ratio of about 0.112 to about 1.68 g / m ² , preferably about 0.112 to about 0.896 g / m 2.

The preparations containing the 4-methylcarbamoyl-3-substit.-5-methylpyrrole-2-carboxylic acid ester and the 4-substit.-carbonyl Contain 3-sufostit.-5-methylpyrrole-2-carboxamide Apply to soil, plant growth media, and growing plants such as lawns using conventional methods. For example, a floor area can be before or after dr-m sowing are treated, with wettable powder suspension, -emulsions or solutions. with the help of motor-driven Boom-type power sprayers or hand-operated backpack sprayers can be. Dusts can be applied by motorized or hand-operated atomizers. Dusts and granulates can also be applied on both sides of the occupied rows during the sowing season.

The following examples serve to illustrate the process according to the invention and that according to the invention Preparations.

209886/1310

A dispersible powder concentrate with the following percentage composition

Methy1-5- (dialkylcarbamoyl) -

2, H-dimethylpyrrole-S-carboxylate 45.8%

polymerized sodium salt of a substituted long-chain benzo-.iden Sulfonic acid 9.2%

Kaolinite 4 5.0%

was prepared by adding 250 g of methyl 5- (dialkylcarbamoyl) -2, ^ - dimethylpyrrole-a-carboxylate, 50 g of a polymerized sodium salt of a long chain benzoid sulfonic acid (Daxad 27) and 245 g of kaolinite were mixed. The mixture was reduced to an average particle size Grind 5 to 30 microns. It was suspended in 38 l of water, an aqueous spray preparation being obtained, which contained about 500 ppm active ingredient.

Example 24

A fine-grained preparation with the following percentage composition

Alkyl 4- (methylcarbamoyl) -3,5-dimethylpyrrole-2-carboxylate 3.7%

Vermiculite (with a clear

Mesh size from 0.59 - 0.25 mm) 96.3%

was prepared by adding a solution of 220 g of alkyl M - (methylcarbamoy 1) - 3, 5-dimethyl pyrrole-2-carboxylate in 1000 ml of methylene chloride to 5780 g of vermiculite (with a mesh size of 0.59-0.25 mm) sprayed on, w'ihreml i \; ^: I & vermiculite kept in motion and stirred

2 0 9 8 8 6 / I 3 1 0 BAD U

Vermiculite was left adsorbed, and the vermiculite was pulverized.

Example 2 5

An emulsifiable concentrate with the following percentage composition

-S, 5-dimethylpyrrole-2-carboxamide 15.0%

technical alkylnaphthalene with a boiling range of 2 38 -

293 ° C (Velsicol AR50) 19.7%

Xylene 17.4%

Acetone 17.4%

Ethylene dichloride 2 5.4%

Mixture of alkylarylsulfonates and alkylphenoxypolyethoxy-

Ethanols (Triton X-151) 5.1%

was prepared by mixing 6.8 kg 4-propionyl-N, N-dialkyl-3,5-tetramethylpyrrol-2-carboxamide, 8.9 kg technical alkylnaphthalene (boiling range 2 38-29 3 ⁰ C; commercial product Velsiccl AR50), 7 , 9 kg of xylene, 7.9 kg of acetone, 11.6 kg of ethylene dichloride and 2.3 kg of a mixture of alkylarylsulfonates and alkylphenoxypolyethoxyethanols (commercial product Triton X-151) were mixed together.

3j0 kg of this concentrate were mixed with 38 l of water, whereby a spray emulsion was obtained which contained about 11,000 ppm of active ingredient.

Example 2 6

An emulsifiable concentrate with the following percentage composition

Methyl 5- (dialkylcarbamoyl) -2,4-dimethylpyrrole-3-carboxylate 40.0%

209886/1310

technical alkylnaphthalene with a boiling range of 2 38 -

233 ⁰ C (Velsicol AR50) 13.7%

Xylene 12.3 %

Acetone 11.3 %

Ethylene dichloride 17.7 %

Mixture of alkylarylsulfonates and alkylphenoxypolyethoxy-

Ethanols (Triton X-151) 5.0%

was prepared by adding 18.1 kg of methyl 5- (dialkylcarbamoyl) -2, + - dimethylpyrrole-3-carboxylate, 6.2 kg technical alkylnaphthalene (boiling range: 2 38-293 ⁰ C; commercial product Velsicol AR50)!, 5, 5 kg of xylene, 5.1 kg of acetone, 8.0 kg of ethylene dichloride and 2.3 kg of a mixture of alkylarylsulfonates and alkylphenoxypolyethoxyethanols (commercial product Triton X-151) were mixed with one another.

7.6 kg of this concentrate were mixed with 38 l of water, a spray emulsion was obtained which was about 8,000 ppm Active ingredient contained.

Example 27

A dispersible powder concentrate with the following percentage composition

Methyl 5- (ethylmethylcarbamoyD-2, U-dimethylpyrrole-3-carboxylate 50%

(finely divided) kaolinite clay t6%

Sodium salt of a condensed mononaphthalene sulfonic acid (Lomar D) Ί%

was prepared by adding 50 g of methyl 5- (äthylmothylcarbamoy1) -2, H-dimethylpyrrole-S-carboxylate, »+6 g of kaolinite clay and 4 g of the sodium salt of a condensed mononaphthalenesulfonic acid.

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(Hand product Lomar D) were mixed together. That Mixture was ground to an average particle size of 5-30 microns.

Example 28

A granulate with the following percentage composition

Methyl 5- (allylmethylcarbamoy1) -2 ,! + - dimethylpyrrole-3-carboxylate Ί%

Pyrophyllite (with a mesh size of 0.59-0.25mm) 99%

was prepared by adding 0.45 kg of methyl 5- (allylmethylcarbamoyl) -2, H-dimethylpyrrole-3-carboxylate were dissolved in 10 1 of ethylene dichloride and the solution was sprayed onto 44.9 kg of pyrophyllite. The granules were dried and then packaged for use.

Example 29

In a test different amounts of methyl 5- (ethylmethylcarbamoyl) -2,4-dimethylpyrrole-3-carboxylate were used in practically equal parts by volume of a pond, which was separated with plastic separation devices, introduced. Each Compartment had a surface area of 1.86 m and a water depth of 0.9 m, in each compartment was about the same There is an association between aquatic plants and organisms, especially plankton and thread algae. The connection was added in such amounts by underwater injection that concentrations of 2 ppm, 1 ppm, 0.5 ppm and Gave 0.25 ppm.

After 6 weeks in the middle of summer, a 100 %, 90 SS, 30 # or imperceptible control of the plankton and the paden algae could be determined.

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Example 30

In a field test, the methyl 5- (ethylmethylcarbamoyl ^v 2, ¹ 4-dimethylpyrrole-3-carboxylate in an amount of 0.22 * 1

g / m worked into the surface of the soil before planting. Four test areas with a size of 3.0 × 4.5 m each were laid out, one of which was untreated was. Three days after the herbicide had been incorporated, the areas were covered with a row of corn, a row of sweet corn, planted a row of sorghum, a row of sunflowers and a row of peanuts. Then weed species became such as Chenopodium album L., Amaranthus retroflexus L., Amaranthus albus L., Ambrosia artemisiifolia, Ipomoea purpurea and other types of weeds applied naturally to the surfaces. It became so common and in such Quantities watered by sprinkling ensure near optimal seed germination and near optimal plant growth were maintained. After five weeks it was found that all treated areas a commercially interesting weed control had been achieved and that the useful plants had been achieved by the herbicide had not been harmed. The corn plants, sorghum and sunflowers were with the untreated Plants comparable.

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Claims (30)

- 39 - claims . ^ ο OO Ί I <1 ■ ML / i-methylcarbamoyl-3-substit. -5-metliyli) yi'i-ol -2-carlic acid esters and 4-substit.-carbonyl-3-substit.-5-methylpyrrole-2-carboxamides of the formulas 2 η 3 Il I and CHJM-C ^ R. 3 j, 1 (I) (II) in which R is an alkyl radical or a Halogpnalkylrosl with 1 to 10 carbon atoms, an alkenyl radical or a haloalkenyl radical having 3 to 8 carbon atoms, a Alkynyl radical with 3 to 10 carbon atoms, a cycloalkyl radical with 3 to 6 ring carbon atoms, a cycloalkenyl radical having 4 to 5 ring carbon atoms, a cycloalkyl radical substituted by alkyl radicals or halogen atoms with 4 to 12 carbon atoms, one by alkyl radicals or Halogen atoms substituted cycloalkenyl radical with 5 to carbon atoms, one by cycloalkyl or cycloalkenyl radicals substituted lower alkyl radical with 4 to 12 carbon atoms or one substituted by alkpxy radicals lower alkyl radical with a total of 3 to 9 carbon atoms R. a hydrogen atom, a lower alkyl or a lower haloalkyl radical with 1 to 4 carbon atoms, η zero or 1 and R »a methyl, ethyl, trifluoromethyl methoxy or methylamino radical. 2. 4-substit. -Carbonyl-3-substit. -S-methylpyrrole ^ -carboxamides according to claim 1. 209886/1310 3. 4-Substitute-carbonyl-3-substit.-5-methylpyrrole-2-carboxy-j Amides according to claim 2, wherein R is an alkyl radical with 1 to> Means 10 carbon atoms. 4. 4-Substit.-Carbonyl-S-lower-alkyl-S-methylpyrrole ^ - carboxamides according to claim 3. 5. 4-Substitute carbonyl-3,5-dimethylpyrrole-2-carboxamides according to claim 4. 6. methyl-5- (alkylmethylcarbamoyl) -2,4-dimethylpyrrole-3- / carboxylates according to claim 5. ^ 7. 4-carbomethoxy-3-substit.-5-methylpyrrole-2-carboxamides according to claim 2; 8. methyl 5- (dimethylcarbamoyl) -2,4-dimethylpyrrole-3-carboxylate, a compound according to claim 6. 9. methyl 5- (ethylmethylcarbamoyl) -2,4-dimethylpyrrole-3-carboxylate, a compound according to claim 6. 10. methyl 5- (methylpropylcarbamoyl) -2,4-dimethylpyrrole-3-carboxylate, a compound according to claim 6. 11. methyl 5- (isopropylmethylcarbamoyl) -2,4-dimethylpyrrole-3-carboxylate, a compound according to claim 6. 12. methyl 5- (butylmethyIcarbamoyl) -2,4-dimethylpyrrole-3-carboxylate, a compound according to claim 6. 13. Methyl 5- (alkenylmethylcarbamoyl) -2,4-dimethylpyrrole- 3-carboxylate according to claim 7. j 14. Mothyl 5- (allylmethylcarbamoyl) -2,4-dimethylpyrrole-3-carboxylate, a compound according to claim 13. 209886/1310 15. Methyl 5- (cycloalky lmethylcarbamoyl) -2, 4 ^ dimethylpyrrole-3-carboxylate, a compound according to claim 7. 16. Methy 1-5- (cyclopenty lmethyl carbamoy I) -2, 4-dimethylpyrrole-3-carboxylate, a compound according to claim 15. 17. Methyl 5- (dimethylcarbamoyl) -2-methyl- ^1- t-propylpyrrole- ^ carboxylate, a compound according to claim 4. 18. 4-Propionyl-N, N, 3,5-teframethylpyrrole-2-carboxamidi one Compound according to claim 5, 19. Herbicidal agent containing one or more compounds according to claim 1 as active ingredient (s), 20. Herbicidal agent according to claim 1, characterized in, that it also contains a finely divided solid. . ■ 21. Herbicidal agent according to claim 20, characterized in that that it additionally contains a surfactant. 22. Herbicidal agent according to claim 21 »characterized in that that it also contains a liquid extender for the active ingredient. 23. Herbicidal agent according to claim 22, characterized in that that there is also a. surfactant contains. .. \ .., - .. _. 24. Herbicidal agent according to one of claims 19 to 23, characterized in that there is also water for dilution contains. ■ '■ - ■■ ..- 25. ■ Process for the production of the 4rstxbstit.-carbonyl-3-substit.-S-methylpyrrole-i-carboxamides according to claim 1 by reductive cyclization, characterized in that one . 2 0 9 88 6/1310 - 1 + 2 - an α-oximinoacetoacetamide of the formula ⁰ im, ι « HO H / ^ ^L Vn ^U Ή _ν .CN
C \ _D in which R is an alkyl radical or a haloalkyl radical having 1 to 10 carbon atoms, an alkenyl radical or a Haloalkenyl radical with 3 to 8 carbon atoms, a Alkynyl radical with 3 to 10 carbon atoms, a cycloalkyl radical with 3 to 6 ring carbon atoms, a cycloalkenyl radical with 4 to 6 ring carbon atoms, a cycloalkyl radical substituted by alkyl radicals or halogen atoms with 4 to 12 carbon atoms, a cycloalkenyl radical with 5 to 12 substituted by alkyl radicals or halogen atoms Carbon atoms, a lower alkyl radical with 4 to 12 carbon atoms substituted by cycloalkyl or cycloalkenyl radicals or a lower alkyl radical with a total of 3 to 9 carbon atoms substituted by alkoxy radicals, R .. a hydrogen atom, a lower alkyl or a lower haloalkyl radical with 1 to 4 carbon atoms and η mean zero or 1, in the presence of methyl acetoacetate, N-methylacetoacetamide or a substituted ß-diketone the formula CH ₂ in the R "a methyl, ethyl, trifluoromethyl, methoxy or methylamino radical means hydrogenated in situ. 209 8 86/1310 - M-3 - 26. The method according to claim 25, characterized in that that the hydrogenation is carried out in the presence of a base or noble metal catalyst and an inert diluent carried out with hydrogen under pressure. 27. The method according to claim 26, characterized in that that the catalyst used is palladium on charcoal. 28. The method according to claim 26, characterized in that the catalyst used is Raney nickel. 29. Process for the preparation of the ^ -Methylcarbamoyl-S-substit.-5-methylpyrrole-2-carboxylic acid ester and 4-substit.-Carbonyl-3-substit.-5-methylpyrrol-2-carboxanu.de according to claim 1, characterized in that a corresponding Alcohol or a corresponding secondary amine with the underlying H-substit.-carbonyl-3-substit.-5-methylpyrrole-2-carbonyl chloride implements. 30. Process for the preparation of the i-methylcarbamoyl-S-substit.-S-methylpyrrole-2-carboxylic acid ester and 4-substit.-carbonyl-3-substit.-5-methylpyrrole-2-carboxamides according to claim 1, characterized in that a corresponding 3-oximinoacetoacetamide in the presence ^ of methylacetoacetate, N-methylacetoacetamide or a substituted one ß-Diketcns reduced using zinc dust in a lower alkanecarboxylic acid. For The Upjohn Company Kalamazoo, Mich., V. St. A. CDr. H. J. Wolff) Lawyer 209886/1310 V ¹ " SAD ORIGINAL