CS196429B2 - Herbicide - Google Patents

Abstract

1. A diurethane of the general formula see diagramm : EP0000030,P50,F6 where Z denotes the radical see diagramm : EP0000030,P50,F7 and Y denotes the radical see diagramm : EP0000030,P50,F8 Z always being different from Y and R**1 and R**2 being identical or different and each denoting hydrogen, alkyl of 1 to 4 carbon atoms, alkoxyalkyl of 2 to 4 carbon atoms, alkoxycarbonylalkyl of 3 to 5 carbon atoms, haloalkyl of 1 to 4 carbon atoms, unsubstituted benzyl, or benzyl substituted by alkyl of 1 to 4 carbon atoms or halogen, R**3 and R**4 being identical or different and each denoting unsubstituted alkyl of 1 to 6 carbon atoms, alkyl of 1 to 4 carbon atoms substituted by halogen, alkoxy of 1 to 2 carbon atoms, halogen-substituted phenyl or unsubstituted phenyl, alkenyl of 2 to 4 carbon atoms, alkynyl of 3 to 4 carbon atoms, unsubstituted or C1 -C4 -alkyl- substituted cycloalkyl of 5 to 8 carbon atoms, bicycloalkyl of 7 to 8 carbon atoms, tricycloalkyl of 10 to 15 carbon atoms, phenyl with a fused ring system, phenyl or mono- or poly-substituted phenyl with the substituents alkyl of 1 to 4 carbon atoms, halogen or alkoxy of 1 to 3 carbon atoms, X denotes hydrogen, alkyl of 1 to 4 carbon atoms, haloalkyl of 1 to 3 carbon atoms, alkoxy of 1 or 2 carbon atoms, halogen, nitro or amino, n denotes one of the integers 1, 2, 3 and 4, and A, B, D and E are identical or different and each denotes oxygen or sulfur (with the proviso that the radicals A, B, D and E are not simultaneously oxygen and one of the radicals always denotes sulfur).

Description

The invention discloses novel valuable sulfur-containing diurethanes exhibiting excellent herbicidal activity, herbicidal compositions containing these compounds as active ingredients, and a method for controlling unwanted plants using the above-mentioned compounds and compositions. . ·

The use of methyl N-3- [Ν'- (3'-methylphenylcarbamoyloxy) phenyl] carbamate, ethyl N - [(Ν'-phenylcarbamoyloxy) phenyl] carbamate, methyl N - [(3-N ') is already known -methyl-N'-phenylcarbamoyloxy) phenyl) carbamate (DAS No 15 · 67151), or

3-isopropyl-2,1,3-benzothiadiazin-4-one 2,2-dioxide (DAS No. 15 42 836) as herbicides. '

It has now been found that the novel diurethanes of formula (IX) in which,

Z represents the remainder of the formula

R1 A 'I II —N — C — B — R ³ ·

Y represents the remainder of the formula. R2 · E — N — C — D — R4, wherein Ϋ is always different from Z, each of. R @ 1 and R @ 2, which may be the same or different, each represent a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms, each of R @ ³ and R @ 4 which may be the same or different represents an alkyl group; C 1 -C 6 alkyl, C 1 -C 5 alkyl substituted with - halogen, methoxy, Cyclohexyl or phenyl C 4 -alkynyl C 5 -C 8 -cycloalkyl-C 5 -C 8 -alkynyl carbon optionally substituted by methyl; (C7-C9) -cycloalkyl, indanyl or phenyl, optionally substituted with one to five substituents selected from the group consisting of (C1-C5) alkyl, halogen and (C1-C2) alkoxy,

A, B, D and E independently represent oxygen or sulfur, and not all residues A, B, D and E simultaneously represent oxygen, and at least one of these radicals always represents sulfur, show a good herbicidal action against a number of important undesirable plants and at the same time good compatibility for numerous cultivation plants. These effects are better than known active substances.

The novel compounds of the invention may be prepared, for example, by the procedures described below, wherein A, B, D, E, R, R 1, R ² , R ⁵ and R ^{4 are} as defined above in the following formulas. In the following, reference is made to urethanes and chloroformic esters. Thiono-, thio- and dithlourethanes are also included under these group names. as well as esters of thionochloroformic acid, thiochloroformic acid and di-chloroformic acid.

NO _Z

NCA,

^А Я С С1

... _. Ъ ^ NHR ремиксе -: ----- »

U&H.)

NHR ¹

H)

NO _Z

Cl> Cl

.4

... NCE (VI) (R-H) R-DH n - ^ - br '] A (IV)

1) A = C ^S B (B = S # 07 S12) and alkylation

Г.

ClC-Br

NO ₉ ..., ^1,1,1 \

1) D ^and CE (DS, E ^with O / S)

2) AlhflAce

C-W

E (Vlil)

The above reaction scheme clearly shows the relationships between the starting materials. Further, it will be appreciated that depending on the nature of the substituents A, B, p, E, R ¹ , R ² , R 3 and R ⁴ as well as the availability of the respective reactants, one or another route may be preferred in the present case. Reaction VI VIII is preferred.

NCE (R) (R = H)

N-CrBfir

From the known m-nitranins (I), m-nitrophenylsilo (thio) cyanates (II) can be prepared (W. Siefken, J. Liebigs Annaleri der Chemie, 562, p. 75 et seq. (1949)), which react smoothly. with compounds of formula R ³ —BH to give, nitro (thio) ur ethane (III) [S. Petersen, Methoden der Organ. Chemie, Vol. VIII, p. 131, Georg Thieme-Ver1 9, β 4 2 9

SB lag, Stuttgart, 4th edition (1952)], but which can be directly reacted by m-nitranilines (I) with chloro-acetic acid-esters, (R ³ B - ••• CA — Cl) . - (DOS No. 16 43 763) or with carbon-carbon or carbon-oxysulphide; and alkylating. with a reagent [Methoden der Organischen 'Chemie, vol. IX, p. 831.' et al., Georg, - Tieme-Verlag, Stuttgart, 4th edition (1955)]. The subsequent reduction results in -aminoslóufč ^ ^^ M (VI, R ² '= H) [S. -Schroter, Methoden der Organischen · Chemie, Vol. XI / 1, pp. -360 -and-others, - Georg Thieme-Verlag, Stu-tgart, - 4th edition (19 ^^ 7)]. which - either directly or after conversion - into a mono-substituted product on the nitrogen and on the nitrogen group (VI, R ² '= H) [' Methoden der - Organischen Chemie, vol. XI / 1, p. 24 -and others, Georg - Thieme-Verlag, Stuttgart, -4. - edition (195'7)] is reacted with - chloroformic acid esters - (R ⁴ D-CE-Cl) (DOS-No 16 43 763) - or with carbon disulphide, optionally with -oxysulfide-carbon, with a base and an alkylating agent [Methoden der organisohen Chemie, vol. IX,, -p. 831 et al., Georg Thieme-Verlag, Stuttgart, 4th edition - (19515)], suggesting the formation of the desired diurethanes (Vlil ·). Aminourethanes (VI) can, however, also be obtained by reaction of m-phenylenediamines (IV) with chloroformic acid esters. Another possibility for the synthesis is the reaction of -aryl-1,3-diiso (thio) cyanates (V) - only with 1 mole, of the compound R3-BH, leading to isophthiocyanateourethanes (VII) [JA Parker, JJ - Thomas and CL Zeise, J-. org. - Chem. 22, 594-596 (1957), which can also be obtained (gravitated by the oxidation of amineourethanes - (VI) (DOS - No. 19 14 270, p. 5, Example 8)). - sloučeninou- formula R ⁴ DH - vede- to -žádaným - finálním- products. In principle, it should be noted that the order of - introducing group - CAB'R3, -popř. -CEDR4 is arbitrary..

In the following, preferred synthetic procedures are described:

a) The reaction of the 3 - (II -) - (II) - (II) - (4-thio) cyanates (II) - takes place either without the use of a catalyst or with the use of a catalyst used in the reactions of iso (thio) cyanates, for example - tertiary amine [triethylamine, 1,4-diazabicyclo (2,2,2) octane, nitrogenous heterocycle - (pyridine, 1,2-dimethylimidazo-1), or organic tin compounds (dibutyltin diacetate, dimethytin tin dichloride), optionally in a solvent inert under the reaction conditions, for example in a hydrocarbon (ligroin, petrol, toluene, - pentane, -cyclohexane), , o-, m- or p-dichlorobenzene), nitrated hydrocarbon (n-HTobenzene, nitromethane), nitrile (acetonitrile, butyronftril, benzonitrile), - ether (diethyl ether, - tetrahydrofuran, -dioxane), ester - [ethyl acetate, methyl ester of the acid propionic acid), ketone (acetone, methyl ethyl ketone) or amide (dimethylformamide, formamide) - [DOS-No. 15 - 68138), at a temperature in the range of from 0 to 150 ° C, preferably from 40 to 100%.

b) the 3-nitranilines (I) are reacted with chloroformic acid esters in a suitable solvent, for example - water, an alcohol (methanol, ethanol-1, isopropanol) or one of the solvents mentioned in - (a) using conventional acid acceptors, for example hydroxides, carbonates or acidic carbonates of alkali metals, oxides, hydroxides, carbonates or acidic metal carbonates of alkaline earths, tertiary - organic bases - (for example, triethylamine, pyridine, N, N-dimethylaniline, N, N-dimethylcyclohexylamine, - hops - or tributylamine) or - starting 3-nitranilines, at temperatures from -20 ° C to 150% preferably from 20 to 80%. ·

c) Reduction of the dimetromine (IH) can be carried out in a known manner, for example by catalytic hydrogenation, by a combination of a metal and an acid, for example a combination of iron and an acid, or by a combination of a metal and an alcohol, for example a combination of zinc powder and aqueous ·· alcohol or iron and aqueous alcohol.

d) - - The reaction conditions of m-phenylenediamines (IV) are similar to those in the sense of the reaction. - paragraph b), but it may be advantageous to use an excess of -, m-phenylenediamines. ,. .

e) The reaction of the aminourethanes (V) with the acid esters is carried out analogously to (b), whereby, for example, a solution obtained by catalytic hydrogenation of aiseoueethaau (III) can be used directly in the present case, without any direct reaction. another · - cleaned.

The preparation of the novel diurethanes and starting materials is illustrated by the following examples, but the scope of the invention is not limited thereto.

AND.

Example -1 and -d - A

To a solution of -64.3 parts by weight of 4-chlorophenol and 3 parts by weight of Sriethylania in 430 parts by weight of absolute. A mixture of 85 pbw of 3-nitrophenylenyl isocyanate and 43 pbw of absolute toluene was added with stirring at 20-25%. ’

The reaction mixture was stirred at room temperature for 1 hour to complete the reaction, then cooled to 0% and the reaction product was filtered off with suction. The product melting at 137-138% corresponds to the following structural formula:

Ci - <^ y-0CNH- ^ o ^ ^N ° ^Z

Example B

K 138 - parts by weight of m-nitraniline v

87 parts by weight of sodium bicarbonate are added to 500 parts by weight of tetrahydrofuran, and 120 parts by weight of methyl thio-chloroformate are added dropwise at room temperature with stirring. The reaction mixture is stirred at room temperature for 16 hours, the lever is filtered, the solvent is distilled off on a rotary evaporator and the oily residue is stirred with toluene. The precipitated crystals are aspirated and dried. The product melting at 137-138 ° C corresponds to the following structural formula:

of thylaniline in 320 parts by weight of ethyl acetate are added 17.4 parts by weight of sodium bicarbonate. 33 parts by weight of m-tolyl chloroformate are slowly added to the mixture while stirring, the reaction mixture is stirred at room temperature for 20 hours, then filtered, e. the solvent was evaporated in vacuo and the residue was recrystallized from toluene / cyclohexane.

The product melting at 114-116 ° C corresponds to the following structural formula:

Example C

In 26 parts by weight of the 3-nitro-N-me analogous method, the following nitrourethanes (III) can be prepared:

AND в R ¹ R3 Melting point WITH 0 H methyl O 0 H 4-fluorophenyl 166-187 O 0 H 2,4-dichlorophenyl 150-151 O 0 H methyl 153-155 O 0 H phenyl 12'3-125 O 0 • H 3-methoxyphenyl O 0 СНз Цпу1 69-70 O 0 H 2-fluorophenyl 145-146 0 0 H phenyl 138-140 0 0 H 3-bromophenyl 130-131 0 0 H 3,4-Dimethylphenyl 130-131 0 0 H 4-methoxyphenyl 132-133 0 0 H 3-fluorophenyl 128-130 0 0 H ethyl 64 - 66 0 0 H 2-chloro-4-fluorophenyl 146-147 0 0 H 2-chlorophenyl 136-138 0 0 H .alpha.-ethylphenyl 86 -. 88 0 0 H - 3-chloro-4-fluorophenyl 0 0 H 2,4,6-trimethylphenyl 212-213 0 0 H 3,4-difluorophenyl Λ 0 0 H 5-indanyl f 171-173 0 0 H. 3-isopropylphenyl 98-100 0 0 H cyclooctyl 103-105 0 0 H 4-methylphenyl 13 8 - 139 0 0 H 2,4-dibromophenyl

Οβ'42.9

AND в .. ^R1 Rj Melting point 0 0 . H 3-methyl-5-ethylphenyl 115 - 117 0 and H tert-butyl 97 - , 99 0 0 H 4-ethoxyphenyl 0 0 H 3-ethylphenyl 85 - 86 .0 0 СНз cycloheptyl 0 0 · H 2,6-dimethylphenyl 165 - 167 0 0 H 2-methoxyphenyl 0 0 H. , 2-methylphenyl • 126 - 128 0 0 H 4-iodoenyl 0 0 СНз methyl 54— 56 0 0 H 3-methyl-4-aminophenyl 137 - 138 0 0 H 3,5-dimethylcyclohexyl 128 - 129 0 0 H isopropyl 86 - 8'8 0. 0 H 2,6-Dimethylcyclohexyl 121 - 123 0 0 H cyclolheptyl 102 - 104 о 0 H benzyl . 113 - 115 0 0 H. 4-bromophenyl .136 - 137 S. 0 H phenyl 0 0 H 3-methyl-5-isopropylphenyl 0 0 H norbornyl 118 - 120 0 0 H cyclopentyl 110 - 112 0 0 H methyl 136 - 138 0 0 H 3-methylcyclohexyl .120 - 122 with with H methyl ' with 0. -СНз ' phenyl 0 with H phenyl  156 - 158 with 0 H ethyl. with with H phenyl 0 0 C2H5 phenyl 56 - 58 0 0 C2H5 3-methylphenyl 75 - 77 □ 0 H hexahydrobenzyl 127 - 128 0 0 H 3,3,5-trimethylcyclohexyl 79 - 82 0 0 H icyclohexyl 117 - 118 0 0 H 2-methylcyclohexyl IOO - 102 0 0 H 1,3-dimethoxyisopropyl 95 - 96 0 0 , й terc.amyl 62 - 63 0 0 H 2,3,6-trimethylene enyl 1 180 - 182 0 0 H 2, 3,5,6-tetramethylphenyl 237 - 238 0 0, H α-tert-butylphenyl 113 - 115 0 0 H 2,3,5-trimethylphenyl 1'45 - 147 0 0 H 2- (5-methyl-1-methylphenyl) 103 - 105 0 0 H 2-tert-butyl-4-methylphenyl 154 - 1'56 0 0 H 2,6-dimethoxyphenyl 155 - 157 0 0 H 3-methylphenyl. 106 - 108 0 0 C2H5 3-methylphenyl 75 - 77 0 0 H 2-methyl-6-isopropylphenyl 122 - 124 0 0 , H 3,5-diethylphenyl 128 - 130 0 0 H 1-methylcyclopentyl 57 - 59 0 0 СНз 4-chlorophenyl 99 - 103 0 0 H 3,4,5-trimethoxyphenyl 173 - 175 □ 0 H 2-methoxy-4-tert-butylphenyl 151 - 153 0 0 H 2,4-di-tert-butylphenyl 186 - 187 0 0 СНз 2,4,6-trimethylphenyl 75 - 77 0 0. H . 2,6-Dichlorophenyl 156 - 158 0 0 H 2,3-dlchlorophenyl 166 - 168 ' □ 0 H 2,4,6- £ г1с111огГепу1 171 - 173 0 0 СНз 4-chlorophenyl 94 - 9'6 0 0 H 2-sec-butylphenyl 72 - 74 0 0 H 2-ethylphenyl 115 - 117 0 0 H / 2,5-Dimethylphenyl 127 - 128 0 0 H 2-methyl-5-isopropylphenyl 146 - 147 0 0 H 2-isopropylphenyl 85 - 87. 0 0 H 4-tert-butylphenyl 84 - 86 0 0 H 4-ethylcyclohexyl 122 - 126

186429

II. Aminourethany

Example D

To a solution of 135 parts by weight of N- (3-nitrophenyl) carbamic acid 4-chlorophenyl ester in 900 parts by weight of absolute tetrahydrofuran is added 3 parts of 10% palladium on carbon as a hydrogenation catalyst and the mixture is hydrogenated at room temperature under 50 psi of hydrogen. to steady state. The catalyst is filtered off, the filtrate is dried over magnesium sulphate and the solvent is evaporated from the solution to such an extent that the crystalline reaction product can be well aspirated. Product obtained corresponding to the formula

Ct = O-OCNH-O. NH ₂ has a melting point of 186-187 ° C.

Example 1 a d E

Example 1 a. D F

To a mixture of 33 parts by weight of powdered gelatin, 75 parts by weight of alcohol, 60 parts by weight of water and 3 parts by weight of concentrated hydrochloric acid heated to 80 ° C is added with vigorous stirring 40 parts by weight of 3- (S-methylthiocarbamoyl) titrobenzein. 80 DEG C. The reaction mixture is refluxed for 1 hour, filtered off with suction while hot, the residue is digested with about 1000 parts by weight of methylene chloride, the filtrate is dried over sodium sulfate and the solvent is evaporated off. The residue melts after crystallization from toluene at a temperature of 101 to 103%.

To a solution of 108 parts by weight of m-phenylenedlamine in 1000 parts by weight of water, 25.2% by weight were added very slowly with vigorous stirring. % of the formic acid phenyl ester. After completion of the reaction, the reaction mixture is filtered off with suction, the solid product is washed several times with dilute hydrochloric acid, the combined acid solutions are neutralized with ammonia and filtered off with suction. The dried product thus obtained melts at 178-180 ° C with decomposition and corresponds to the formula

The following aminourethanes of formula VI can be prepared in an analogous manner.

AND в Ri R ^! Melting point (' 0 0 H 4-fluorophenyl 166-167 0 0 H 2,4-dichlorophenyl 126-128 0 0 H methyl 87-89 0 0 H 3-methoxyphenyl 0 0 СНз phenyl 70-72 0 0 H 2-fluorophenyl 172 - .173 0 0 H 3-bromophenyl with 0 H methyl with with СНз phenyl with with H ethyl 0 with H 3-Methylphenyl

. Λ (B) Rl R3 Melting point (° C) with 0 H <4-chlorophenyl - ·. ·. - with 0 H phenyl 0 0 H 3,4-dimethylphenyl. 155-157 »0 0  H 4-methoxyphenyl  146-149 0 0 H 3-fluorophenyl. . decomposition 0 ΰ H ethyl . viscous oil ¹ 0 . 0 H 2-chloro-4-fluorophenyl · Decomposition 0 0 H . 2-chlorophenyl decomposition 0 0 H 4-ethyl-phenyl . 160 · 161 0 0 H 3-chloro-4-fluorophenyl 0 0 H 2., 4, S-trimethylphenyl 150-152 0 0 H : 3,4-difluorophenyl.1 0 0 H B-iiditoyi 184-186 0 0 H 3-isopropylphenyl 68 - 70 0 0 H 3-ethyl-5-methylphenyl 102-104 S ·. ·, WITH H Phenyl 0 0 · · H . S-Trimethylcyclohexyl 100-102 0 0 H , 2 ^ ύ ^ 1 € γΜθ11βΧ72 0 0 C2H5 3-methylphenyl, 104 —105 0 0 C2H5 phenyl ' · 104 —106 ' 0 0 H cyclooctyl 77 - 79 0 0 H 4-Methyl; enyl · 158-162 0 0 H  2,4-dibromophenyl 0 0 H tert-butyl 109-110 0 WITH Ή 4-Ethexyphenyl 0 0 H 3-ethylphenyl 112-114 0 0 CH3 cycloheptyl 0 0 H  2,6-dimethylmethylphenyl 160-161 0 0 H 2-Methoxyphenyl 0 0 H 2-methyl · fe ^: nyl · 170-172 0 0  H '· · 4-Joidophenyl 0 0 CH3 methyl 0 0 H 3-Methyl-4-chloro-phenyl 161 · 0 0 H 3,5-dimethylcyclohexyl ... 80 - 82 - 0 o. H isopropyl ·. · - 66 · - 68 0 . ο · H 0 0 H 1 hexahydrobenzyl. 106-108 0 0 H 2-ethylhexyl viscous ^: oil 0 WITH H phenyl ΰ < 0 H ' cycloheptyl _____ 86-88 * 0 0 H benzyl 0 0 H 3-Methyl-5-isopropylphenyl 0 0 H norbořriyl 133-135 0 ' 0 H cyclopentyl 0 0 H 3-methylcyclohexyl 95-97 0 0 CH3 3-Methylphenyl 112-115. WITH WITH H methyl 0 0  H. 2-isopropyl · 5-methylphenyl1 122 - 123 0 0. H 1-S-methylphenyl 142 · 144 1 0, 0 H . 2-tert-butyl-4-methylphenyl . 89-91 0 0 H terc.amyl 65 - 67 0 0 H 4-tert-butylphenyl 175-177 0. 0 H 2,3,5-trimethylphenyl 152-154 0 0 H 2,3,6-trimethylphenyl 155-156 0 0 H 3,5-diethylphenyl 121 - 123 0 0 H cyclohexyl 122-124 O 0 H 2-methyl-cyclic-hexy1 0 0 H 1,3-dimethoxyisopropyl 0 0 H 2-Methyl-6-isopropyl-phenyl 133-135 0 0 CH3 1 ^{2,4,6-tгimethylfe,} NY1 0 0 H 4-methylcyclohexyl ^'S 73-75

198429 '· ’. . . . Ί2

AND R ¹ R ³ . ' Melting point (° C) 0 O H i-methylcyclopeintyl 0 0 СНз 4-chlorophenyl 88-90 0 0 H 3,4,5 - trimethoxyphenyl 146 -. 148 0 0 H 2-methoxy-4-methylphenyl 110-112 0 O H ' 2-methyl-1-tert-butylphenyl 185-180 0 0 CH3 2,4, '6-trimethyl'phenyl' O 0 H 2,4-di-tert-butylphenyl _r 195-197 0 0 H 2-sec-butylphenyl 75-77 0 0 H 2-ethylphenyl 74-75 0 0 CH3 4-fluorophenyl 123-125 0 0  H . 2,5-dimethyl-phenyl 142-144 0 0 H 2-methyl-15-sopropyl-phenyl 139-141 0 0 H 2,3-dimethylphenyl ; 184-186 0 0  H 2-isopropylphenyl 80-82

III. Dlurethany

Example 1

To a solution of 22.8 parts by weight of the phenyl ester of N- (3-aminophenylcarbamic acid) in 200 parts by weight of absolute tetrahydrofuran is added first 11 parts by weight of sodium bicarbonate and then under cooling at 20 to 25 ° C. 13.3 parts by weight of thiomethyl chloroformate To complete the reaction, the mixture was stirred at room temperature for 1 hour, then filtered and the filtrate was evaporated in vacuo. (No · 1) melts at 155 to 157 ^e C and corresponds to the structural formula .....

Example 3

To a solution of 16.6% by weight. 10.1 parts by weight of triethylamine in 300 parts by weight of diethyl ether are added dropwise at room temperature to 10 parts by weight of carbon disulphide at a room temperature, followed by the addition of 10 parts by weight of N- (3-aminophenyl) -O-methylurethane. The mixture is filtered off with suction, the residue is suspended in 120 parts by weight of water, and 9.1 parts by volume of diethyl sulfate are added to the suspension while stirring, and after stirring for 20 hours the mixture is filtered off with suction, the residue on the filtrate is washed with water. The product (No. 3), m.p. 122 DEG-124 DEG C., corresponds to the structural formula

NHCOOCW

i., .'X. v Λ. ' '' Λ

H-C-SC #

WITH

O

Example 2

A mixture of 20 parts by weight of N- (3-isothiocyanatophenyl) -O-methylcarbamate [obtained from N- (3-aminothenyl) O-methylcarbamate and thiophosgene and melting at 99-100 ° C], 20 parts by weight of methanol, 3 parts by weight of triethylamine and 150 parts by weight of toluene are refluxed for 6 hours The residue of evaporation of the solvent is crystallized from toluene, the product obtained having a melting point of 147-149 [deg.] C. (C..2) corresponds to the following: structural formula

The following compounds can be prepared in an analogous manner:

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O // Ύ-ο-ζΛ

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O S O O Η H methyl 3-methyl-5-ethylphenyl '120

S O S S Η H methyl phenyl;

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1 ·· 4> ·

% XX%%%%%%%%%%%%%%%%%%%%% X X д д X Q О UQU у О и Q _л & X £ х Д £ XXX X ХДХ.Д ДДДДДДДД XX ж х Д X Д Д X Д XX Д хд.

198429

Compound '.

ABDE number · R ¹ R 2 R ³ R * Melting point (° G)

151 O S O O Η H ethyl 4-tert-butylphenyl 140-142

152 .... · O S O O, Η H · methyl 2-sec-butyl-phenyl · 127 - 129

O tM -Φ · CO · CO · cm 5 5 ff.tb rd Н .-. Χη XT CČMCp lů

OLDOSiOcooojqoco · 05 · co t>

HrlrHrlrrr ^ drtHrfrl CM rd tH rd rd · rd

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SDCDON · NO - CO cm co in r · qs · co · o · t> n, Η d CM · rd rd rd rd rd

O) hs Id rd rt t> РОЮ tsO / rd 05 rd rd rd rd

OO 00 1 L · CO O) xd Cx oo φ -.irt co O rd · tH rd rH rd

CM. CM

XX XX x XXXXXXX XX x XXX ^and XX x. ^E · X ₄ OQQ of xx T χ χ χ χ χ χ χ χχ T · χ χ.χ X X XXX - £ xx □ OOOOOOQP OQOO O.OO.OOqoOoÓO pwtfOOmwOOmwoowowooQQO _well on gOOwwOOc ^ OO · CN's what What c.cp.w ° n ° o he co

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198428

AND

CQ I ₄ xU

4 * ce

I Q Ujsó et t * -Z

-and

• 8 rH

cn cn ^: Я w

XXSBSx g .. 0 to cx

Κ. following attempts as a ·. the comparators use known herbicides. Methyl N-3- [N'- (3'-methylenenylcarbamoyloxy) phenyl] carbamate and ethyl [N- (N'-phenyl) carbamoyloxy] phenyl] carbamate (DAS No. 15 67 151), are distinguished by their, albeit different, It is known, however, that they occur differently since methyl-N-3- [N '- (3'-methylphenylcarbamoyloxy-phenyl) -carbamate exhibits a different tolerance to sugar beet. even more favorable selectivity in this culture than the other of the above-mentioned compounds A completely different application has 3-isopropyl-2,1,3-benzothiadiazin-4-one 2,2-dioxide (DAS # 15) With this compound, various broadleaf weeds in soybean crops, peanuts, cereals, maize and some vegetable species are combated. · Methyl N- (3- ('N'-methyl-1''-phenylcarbamoyloxy) phenyl) arbamate has a very poor selectivity for crop plants with a good herbicidal effect, characteristic of this group of substances, and therefore, for example in soybean culture, this compound is recommended only for application under the leaf surface (p-ost-directed (See Arndt, F. and G. Boo ^ schoWsky: New Seleotive Herblcldes · - VIII · International Plant Protection Cohgres.s,. Reports and Information, Section III, Chemical Control, Part I, Moscow 1975, pp. 4-49). In this method of application, the young shoots and leaves of the crop plants should not be affected by the spraying of the suspensions, but only the undesirable plants located below the leaves. ·

The good herbicidal properties of the novel compounds show numerous test results. To demonstrate the herbicidal activity of the disclosed compounds and their selectivity in crop plants, the following experiments were carried out:

Experiments in the greenhouse

The 300-cm3 plastic pots are filled with loamy-sand soil and separately occupied by different species of test plants. In the latter case, it is predominantly the sowing of seeds or also the planting of those species which are propagated vegetatively. The active substances are suspended or emulsified in water and, by means of fine dispersion nozzles, applied by post-emergence spraying to the leaves of the test plants and to the soil surface below them. For leaf application, the plants are first grown to a height of 3-10 cm (depending on the species) and then treated. The temperature requirements of the test plants are respected by placing the individual plant species in either the warmer or cooler sections of the greenhouse. The experiments last 2 to 4 weeks. During this time the plants are grown in the usual way and their response to the individual treatments is evaluated. The consumption of test substances is given in kilograms of active substance per hek1> β429 14 taao. Evaluation is carried out using a scale of 0 to 100, where 0 is normal or no damage, and 100 is no plant emergence or death.

Results

Efficacy of individual active substances; when applied to ·. after the emergence of cultural ·. Plants and undesirable plants show the numerical results in the following tables. 12. It is noteworthy that the novel compounds of the invention, in terms of their herbicidal activity and spectrum of action, are close to the diurethanes used as comparators, but the key selectivity values for the crop plants are other. This can be perfectly demonstrated for example on soybeans and grain. In these cultures, ss achieves compatibility values the same as when applied. The known 3-isopropyl-2,1,3-benzothiadiazin-4-one 2,2-dioxide (see Tables 5 and 6). In addition, there are, however, a number of crop plants that are excellent in tolerating compounds. according to the invention, while the test substances to be tested are unsuitable for application in these crop plants (see Tables 2, 4 and 5). Suitable methods of application of the new active substances are application to the soil, treatment of the soil surface or treatment of already grown plants. However, special applications are also possible, such as spraying under the leaves of plants; (post-directed, lay-by), in which the · -se - stream · · · spray is directed ·. · Tak ,. To avoid contact with the leaves of emerging, susceptible crop plants, as far as possible, but to spray the soil surface underneath the crop plants or growing undesirable plants here. . .

¹ In accordance with the versatility of application methods, · may · the compound of the 'present invention or compositions containing them,' deploy to combat · unwanted plants' only · in crops listed in tables · but in · a large number of crop plants . Depending on the area to be treated, the consumption may be 0.1 to 15 kg / ha or more. Examples of crops are:.

Botanical name Czech name Allium cepa onion · Pineapple comosus pineapple Asparagus officinalis ·· asparagus Avena satiíiva oats. Beta v.ulgaris spp. altissima • sugar beet

Beta vulgaris spp. rapa; fodder beet

Beta vulgaris spp. esculenta beetroot

Brassica napus var. napus rape

Brassica napus var.

napobrassica:, turnip

Brassica napus var. rapa · · · white beets · ..

Brassica napus var. з ^ евШе · oilseed rape

8 4 '2 9

Botanical · name /

Czech name

Botanical "name."

Czech name

Camellia slunensis Citrus Hmon. ·. Citrus maxima Citrus- retlculata teapot lemon lemon tree, the largest tangerine orange coffee tree Citrus slunensis Coffea. arabica (COffea cane- phora, Coffea liberica Cucumís melo · melon Cucumts sativus cucumber Cynodon dactylon troskot · Elaeis guineensts coconut tree. · · · · Fragaria vešca Strawberry Gossy.pium hirsutum cotton Gossypium arboreum cotton Gossy.pium herbaceum cotton Gossyplum vitifoíium) cotton Helianthus annuus · ·. · sunflower HeUanťhus tuberosus; toplnambuř Hevea brasilie ^ nssis kuačukoivník Hordeum vulgare barley. Humulus Jupulus hops ¹ · Ipomoea · batatas sweet potato Lactuca sativa salad Lens culinarls. edible lentils Linum usitatisa ^ ittum only Lycoperslcon Lycopersic-m Maus · spp. - apple tree apple tree Manihot esculenta tapioca Medlcago sativa lucerne Mentha plperita peppermint Musa spp. banana tree Nicotiana tabacum (N. ru-stica) tobacco Olea europaea olive Oryza sativa - rice Panicum millaceaum millet Phaseolus lunatus. bean '·. Phaseolus mungo bean. Phaseolus vulgaris, grilled bean ¹ Pěnnisetum glaucum. Petroseinium crispum spp. parsley tuberosum root Pice and tt ^ lies spruce Ables alba. Fir Pinus spp. pine ^ Plsum sativum pea Prunus avium cherry Prunus doméstlca , plum Prunus persica. peach Pyrus commuhla pear Rlbes sylvestré redcurrant Ríbes uva-crlspa gooseberry Riclnus communis castor Saccharum officinarum Secale · céreale sugarcane rye Sesamum indicum sesam Solar. potatoes

Sorghum biOolor ·· (p. Vulgare) 'Sorghum dochna

Spinacia oleracea Theobroma cacao

Trffolium pratense

Vaccinium corymbósum Vaccinium vitis-idaea Vícia faba

Vigna slunensis' (V. ungulculata) ... Vitls vinifera. . ^! sorghum: bicoloured sorghum · spinach cacao .jetel blueberries cranberries ·: · bob bean grapevine

In order to further extend the spectrum of action of the individual new active substances, to achieve synergistic effects or to improve the duration of action in the soil, the compounds according to the invention can be mixed with one another and, moreover, they can be mixed. combine or mix with numerous other herbicides or plant growth regulators. Depending on the area of use and the intended use, the following substances or similar derivatives may be used,

RR ¹

NH 2 - NHCH 3 - NH - CH 2

ŇH2

198'429

AT

Ø R1 R1 R2

H -of H and salts H . ·. Cl and salts H «Яиппз ^ F and salts H -of СНз and salts CH2OCH3 au III H

«I

H

Rl

'Rl _ / ^ я * NOj R2 R3 CF3 CF3 SO2NH2 П-С3N7 П-С3N7 П-С3Н7 OH2 — CH2Cl П.-С3Н7 n-CsH7 Rl N — C — O — R ³ Z II R 2 O R2 R ³

CHs

H 1-C 5 H 7 • CH 3 z- ··

H = N = C

Z- VCHS СНз ι zH —CH — C — NH — C2H5 'II. .. -.

^ ZZ ^; o ·.

H 1-8N7

H CH2 — C ^ C — СН2С1

CHs č

H — CH — CsCH

H .. CHs

H ... CHs

AND

181438

R ⁵

C2H5

СНз

С2Н5

СНз

CsHs

Ø ^x

I-C3H7 I-C3H7 CH2-CCl = CHCl П-CH H-CsH7 ČžHS П-С3Н7. H-C3H7. П-С3Н7 ' sec.-CHs . sec.-СШэ C2Hs CHs C2Hs 0- CaHs C2Hs & CaH  . ' - -CaHS ’

198419

C> -cs- ^c ₂ H _S

R

C2H5 П-С3Н7

R ²

Na Na Na

СНз

H and the salts of NH 3

C2H9

СНз

11843 ·

18842 »| R1 XR ²

1ЧЗЗН7 С1 С2Н5 1-СзН7 С1 1-СзН7 С2Н5 C2H5 CZH5 \ С1 С1. 01 С1 HC3H7 С2Н5 —С (СНз) гСЫ —СН — СНз — ОСНз Сз (Нз Cl. 1 ’ СНз —CH — CsCH 1 СНз £> -— Cl —О (СНз) 2 — CN 1-СзН7 I-C3H7 С2Н5 С2Н5 ОСНз ЗСНз ЭСНЗ ЗОНз UC3H7 \ С2Н5 С2Н5 terc.CáHg

X, __________ Y Y

CF 3 H (CHS • H F, CH 3,:>

R2

N ^С-R / R ^{1 11} О R1 R ² R ³

CHs

I - CH - C = CH

СНз —CH — CHz — ОСНз —СНг — СНг — ОСНз —СНз — ОСНз снгС1

СНгС!

CH2C1 снзС1

Ri

186429

R ²

R3

CH 2 —C — OC 2 H 5 II o

CH2-O-C1HWi

CH2Cl

I WANT

CHaCl

COOH

Cl

4 ' ¹ <

C2H5-C (CHS) 2-C5H7

CH 3 fSO 2 HN

. . CHí

I HGsC — C. Ϊ.

CHí

1ЯВ42Я

p

Ha so li H a salts —C— (CH3Je ^ CHe ·

ir

R ^s

Cl Cl F Cl Cl Cl Cl CFs Cl Cl NO2 CF3 H CF3 H CF3 Cl Cl

H H

H СООН СОООНз

H

OC2H5 ОСНЗ%

R ¹

tert -HjC ^-CO

O

Cl o-

a-Q-

Cl

У,>

111429

R ²

RS _R 4

H СНз СНз н ... СНз СНз H СНз • . СНз

н СНз СНз Н · - СНз, 1, · СНз н СНз СНз 1 —СН — С = СН н. СНз СНз н СНЗ Сснз в СНз СНз - ’· '· н СНз ОСНз н СНз / СНз н СНз сн $ » н СНз ОСНз н сш ( СНз

R 2 R 3. . / R4

CHs

CH 2 OCH 3

CHs · OCHS

CHs' CHs | —П

TO · ..... CHi

O

R1

^ егс.СШэ iterc.CáHe

.... NHz. SCH3

CHs - .. '.

' OF . --N = CH - CH3: SCH3

ΓΖΖ

u /. ··>. ·: - снз - ’*

- · · W ^ · - ''

...... ’

NHaCHs.

, R1

CHs Br

CHs Cl

CH 2 Cl - CH 2 - CH 2 - CH 2 -;

188421

Rl __________ R ²

CHs CHS

CHs —С — СНз

R1 R2 (R5

—С — СНз II of ..: < 0 A sec.-CiHe H. —C — CHs II. · 0 tarc.-CiHg H —С — СНз II 0 tert-C 1 H 6 CHs H CHs · .: H. salts and esters H sůk.CíHe H salts and esters H. ' tert.-CiHff H salts and esters H tetc.-CiHe CHs salts and esters

p-1-HN-CO

191429

Ří

CH3OS03

CH3OS03 CH3OSO3 ČFsSOj

186418

and salts, esters

R ¹ . - RZ '-RS. ;  R4 Ή 'Cl NHa' - Cl iH Cl . ··· J 'j - H. Cl J OCHS Cl Cl 1 H Cl Cl Cl Cl OCHs · ' ^R - - - -. R = O-CH-C-O-R3. II. 0 ^R1 . Rž. RS

Salts, esters, amides

CHs

H salts, esters, amides

Soli H · salts, esters, amides chs' h salts, esters, amides

Η / H salts, esters, amides

CH 3 H salts, esters, amides.

} ·

O-c-e ^ o-fо о

136429

^ к = .О Д *? Ц / esters

J J? OF- *

СООН solid · esters

J. +. '- / · 2

НзС О · '; . \ ||; ·> -

As — ONa - ’

но

'. х ... . . .

Р — СН _{2 —} NH — СН2 — С — ОН • - ··. ... II.

но о о

-; R1

ОН СНз

НС — СО — NH

II · · Л -. ·

НС — СО — NH

О '; ·'

НО — Р — СН2 — СН2 — С1 он

Cl— / у — О-СН £ СН ^ СН ^ СООН And salts and esters

In addition, the novel compounds of the invention, either alone or in combination with other herbicides, can be applied as mixtures with other plant protection agents, which are meant herein combating pests or phytopathogenic fungi or bacteria. Also of interest is the possibility of mixing with mineral salt solutions which are used to eliminate nutrient or trace element deficiencies. .

Wetting agents and adhesives as well as non-phytotoxic oils may be added to activate the herbicidal effect; .... ... '

The application takes place in the form of, for example, directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, spreads, granulates, by spraying, misting, dusting, spreading or watering. The application forms of the compositions are entirely, according to the purpose of use; in any case, they are intended to ensure the finest possible distribution of the active compounds according to the invention.

For the production of directly sprayable solutions, emulsions, pastes and oil dispersions, suitable fractions of medium to high boiling mineral oil, such as kerosine or diesel oil, tar oils, etc., as well as 1 oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof such as methanol, ethanol, propanol, hutanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone. • halobenzene, isophorone, etc., strongly polar solvents, for example dlmethylformamide; dimethylsulfoxide, N-methylpyrrolidone, water, etc.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders or oil dispersions by the addition of water. For the preparation of emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent may be homogenized with wetting agents, adhesives, dispersing agents or emulsifiers in water. However, it is also possible to prepare concentrates consisting of the active ingredient, a wetting agent, an adhesive, a dispersing or emulsifying agent and, optionally, a solvent or a solvent. oils which are suitable for dilution with water. (The surfactants include: ligninsulfonic acid salts with alkali metals, alkaline earth metals and ammonium salts, corresponding salts, naphthalenesulfonic acids, phenolsulfonic acids, allylaryl sulfonates, alkylisulfates, alkylsulfonates, dibutylnaphthalenesulfonic acid salts, alkaline alkaline earth metals, lauryl ether sulphate, sulphated fatty acids, alkali metal salts of alkaline metals and alkaline earth metals, sulphated hexadecanols, heptadecaolols, octadecanols, salts of sulphated fatty alcohol glycol ethers, condensation products of sulphonated naphthalene and der! .

1Я9429 naphthalene with formaldehyde, condensation products of naphthalene and / or naphthalenesulphonic acids, · phenolihi and formaldehyde, ··. polyoxyethylene ethylphenofethetes, ethoxylated; isococylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyluolyglycol ethers,. alkylaryl polyether alcohols, isotridecyl alcohol, condensation products of fatty alcohols with. ethylene oxide, ethoxylated castor oil, polyoxyethylenaphthyl ethers ethoxylated polyoxyprbpyfen ,. · Esters · · sorbitol, · lignin, · sulphite waste liquors and · · methylcellulose.

Powders, dusts and dusts can be produced by mixing or grinding the active ingredients with a solid carrier.

Granules, for example coated granules, impregnated with granules. and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are, for example, mineral. clays, such as silica gel, silicas, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, silica, calcium sulfate. and magnesium sulphate, · magnesium oxide, ground plastics, fertilizers such as · ammonium sulphate, ammonium phosphate, ammonium nitrate, ureas and plant products such as · cereal flour, tree bark flour, · wooden · · flour and nutshell meal, powdered cellulose and other solid carriers.

The compositions according to the invention contain between 0.1 and 95% by weight of active substance, preferably between 0.5 and 90% by weight. and

^Example:.

parts by weight of compound 2 are mixed with 10 parts by weight of N-methyl-.alpha.-pyrrolidine to give a solution which is suitable for application in the form of as small droplets as possible.

Example 5 parts by weight of compound · 8 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of addition product 8-10 moles of ethylene oxide per 1 mol of N-monoethanolamide oleic acid, 5 parts by weight of calcium, % of dodecylbenzenesulfonic acid and 5 parts by weight of an addition product of 40 moles of ethylene oxide per 1 mol. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of active ingredient.

Example 6. parts by weight of compound 13 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight are mixed positively with -97 parts by weight. • ground kaolin. In this way, a dust containing 3% by weight of the active ingredient is obtained; ..,

An example of 10 parts by weight of compound 2 is intimately mixed with the mixture. 92 parts by weight of powdered silica and 8 parts by weight of paraffin oil which has been sprayed onto the surface of the silica gel. In this way, an effective formulation with good adhesion is obtained.

Example 11 parts by weight of the active compound 7 are intimately mixed with 10 parts by weight of the sodium salt of the condensation product of phenolsulphonic acid, urea and formaldehyde, 2 parts of silica gel and 48 parts of water to obtain a stable aqueous dispersion whose dilution is 100,000 by weight. Aqueous parts containing 0.04% by weight of the active ingredient are prepared in parts of water.

Example 12 parts of active substance 8 are thoroughly mixed with 2 parts of calcium dodecylbenzene sulphonic acid, 8 parts of polyglycyl ether of fatty alcohol, 2 parts of sodium salt of phenolsulphonic acid condensation product, urea and formaldehyde, and díly8 parts of paraffinic mineral Oils to obtain a stable oil dispersion.

Table 1 gives an overview of the test plants:

of the addition product of 7 moles of ethylene oxide: 1 mole of isooctylphenol and 10 parts by weight of the addition product, 40 moles of ethylene oxide per mole of sulfuric acid. oils. by "emerging" and finely "dispersing" the solution in 100 parts by weight of water. an aqueous dispersion containing 0.02% by weight of the active ingredient is obtained. . '.

For example, 7 parts by weight of compound 23 are added in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point of 210 to 280% and 10 parts by weight of an addition of a product of 4.0 moles of ethylene oxide per 1 mol of castor oil. By pouring and finely distributing the solution in 100000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

Example. 8 parts by weight of the active substance 7 are intimately mixed with 3 parts by weight of sodium salt of diisobutylnaphthalene-α-sultphonic acid, 17 parts by weight of sodium salt of ligeiesulfoeic acid from waste sulphite lye and 60 parts by weight of powdery silica gel; the resulting mixture is ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray suspension is obtained which contains 0.1% by weight of active ingredient;

Example 9 parts by weight of compound 46 is shown in TABLE 1

Botanical name Abbreviation in tables Czech name

Amaran-thus retroflex-p Amiar. 'ret. Kindweed bent Aplum gravedens Apium grav: celery Arachis hypogaea Arach. hyp. peanut Carthamus tiectorius Cárth. tinct. Safflower Centaurea cyanus Cent. cyan. cornflower · blue Daucus carota • Daucus · carot. carrot Datu-ra stramonium Ďatura stram. durman Desm-odium tortuosum Desm-od. tort. - Euphorbia helioscopia Euphorb. heliosc. ".Pryš-ec spinning wheel Euphorbla geniculata Euphorb. genie.  - · · Glycine max Glyc. max soya. Lamium spp. Lamlu-spp. deafness Matricaria spp. Matrices, spp. chamomile Mercurialis annu Mercur, annua annual pheasant Sesbania exaltata Sesb. exalt. . - Setaria spp. Setaria spp. bér Sinapis alba Slnap. Albums , mustard white Stellaria media Stell, media chickweed frog Solanum nigrum Solan. nigr. aubergine black Tritlcum aestivum Tritic. aest. wheat Xánthium pensylvanicum ' Xanth. · Pens. beet Zea mays Zea mays maize

В 429

Botanical name Abbreviation in tables Czech name

Beta vulgaris Beta vulg. . sugar beet Chrysanthemum segetum Chrys. seg _v daisy. Echinochloa crus galii Echln. c.g / hedgehog corns the leg Chenopodium album Fire. alb. White goosefoot Gossypium hlrsutum Gossyp. hlťs. ba waves к Ipomoea spp. Ipom. spp. povíjníce Oryza sativa Oryza suck. rice Polygonům persicaria Polyg. pers. rdesno wormwood

· Setaria spp. 92 O = no damage 100 = plants destroyed

TABLE 3

Selective herbicidal effect of new compounds in corn and maize in post-emergence application in greenhouse

Active substance kg / ha Test plants and damage in%

Tritic. Zea Cent. Datura Lamium Matric. Mercur: Sinap. Stell, aest. mays cyan. stram. purp. spp. annua alba media

WHAT WHAT WHAT IN IN WHAT WHAT WHAT

w) O to o 05 O to o 05 cm (Μ ιη o O in o iq o to o CD 05 to o to o o

to o eo to q

what

§§§§ ¹¹ i §§§

I S I g? Sg§ in in ф O O to it O

HflHNCO I СО 0П o to o o q to o * 0 .0 o.

in O to ^ in <to in to in to Q OHeÍQHwtf toríéa

13В423 oooaoogqqooo © ‘qoo '<© © ©. © © Φ · · · © © ©. © oo rH 'rH ·· τΗ W rH tH' 'W - W

<5 ο OQooogqoOQo cogg:) ^^ © (οίδΐ4θοοο · νιηιή · ©.

rH rH rH rH 'v' ^ss §§§§§§§i§§§8§§ t> bbO © G G0QQQO OO OO ..OO © © © OO o o X H ri

8888 ^ 88 ° 8 8® N 8 ^Q 888 r * Ψ 'υΉ vH ⁷ ^ 4 oo 8 8 888888 8888Φ г § гйгНгНтНгНгНгйгНгНтН bx Q © O © © © © © q © rH rH © rH CM © ©

IOO | .0O | 96 © o © 'I | , ₍

© οποοοοβοοοο ©

Ut © q 1Λ © _ q ιη ®. © ιη Q ο. · Ο «© <© rH CM of the Д ^'N' of rT cM © · H * Q © CM HT

£ , g Д φ > Q and; X ti ^ti X MJ y a three three • iM .i p > o ©

Legend:.

- without damage

1QQ = complete destruction of plants

188429

TABLE 5

Effect of new compounds on selective weed control in post-emergence application in greenhouse

Active substance kg / ha Test plants and damage in%

Trlticum Mercu-Slnapls Stellaria aesthum; rialtš: ΐ · media annua albums

100 ALIGN!

100 ALIGN!

100 ALIGN!

8 1.0 - 100 ALIGN! 100 ALIGN! 10Ó 2,0 Os 100 ALIGN! 100 ALIGN! 100 ALIGN! 11 Г У. '1.0 ~' ·. ... ·:. · Λ — i ': 100 ALIGN! 100 ALIGN! 2,0 · · '·· <0. · <· ' 100 ALIGN! 100 ALIGN! 14 1.0 -, 100 ALIGN! 100 ALIGN! 100 ALIGN! 2,0 0 100 ALIGN! 100 ALIGN! 100 ALIGN! 26 1.0 - 0 100 ALIGN! 100 ALIGN! 2,0 O. ’100 100 ALIGN! 24 1.0 _ 0 100 ALIGN! 100 ALIGN! 2,0 0 0 100 ALIGN! 100 ALIGN! 27 Mar: 1.0 - 0 100 ALIGN! 100 ALIGN! 2,0 • 0 80 . Ί00. 100 ALIGN! 32 1.0 -. 70  100 ALIGN! 2,0 O 80 90 100 ALIGN! 58 1.0 - 100 ALIGN! 100 ALIGN! 100 ALIGN! 2,0 0 100 ALIGN! 100 ALIGN! - O from - · .- <· W n á, o 20 May 100 ALIGN! óóó 1O0

(zaarna) CHx (zaana)

100 ALIGN!

100 ALIGN!

22nd 2,0- 0 - 100 ALIGN! 100 ALIGN! 152 2.0 30 70 100 ALIGN! 100 ALIGN! 134 ' 0.5 . - 100 ALIGN! 100 ALIGN! 100 ALIGN! 2,0 0 100 ALIGN! 100 ALIGN! 100 ALIGN! 157 0.5 - 70 100 ALIGN! 100 ALIGN!  , . 2,0 0 100 ALIGN! , 100 109 159.. 0.5 - - 100 ALIGN! 100 ALIGN! 2,0 0 - 100 ALIGN! 100 ALIGN! 94 0.5 0 100 ALIGN! -. · 100 ALIGN! 2,0 0 100 ALIGN! '- 100 ALIGN! 167 0.5 0 100 ALIGN! : - 100 ALIGN! 2,0 0 1Ů0 -. 100 ALIGN! 144 0.5 0 30 70 . -. 2,0 0 ÍOO 95 -

Legend:

= without damage

100 = plants destroyed

1 »84? 9

TABLE 6

Effect on the control of broadleaf weeds in peanut culture by moderate application in a greenhouse. Test plants and damage in%,

Active substance

Arachils hypog. Ama • ranthus retro. Desmodium tort, Sesbania ěxalt. Xanthium pensyl. 63 0.5 , 5 Z 100 ALIGN! 100 ALIGN! 100 ALIGN! 50 2,0 20 May 100 ALIGN! 100 ALIGN! 100 ALIGN! 50 7'2 0.5 0 100 ALIGN! 90 ^; 95 50 2,0 0 100 ALIGN! 90 95 50 8 0.5 10 100 ALIGN! 90 95 80 2,0 10 <10O 90 :. '> 95 90 11 0.5 0 20 May 20 May 80 0 2,0 0 50 90 95 20 May 14 0.5 0 10 90 85 0 2,0 0 30 90 85 25

10Q

100 ALIGN!

.

100 ALIGN!

O

Legend:

O · = 100 = 100 = without destroying the plant destroyed the complete destruction of the plants

TABLE

Effect of new compounds in post emergent application in greenhouse

Active substance' > kg / ha Test plants and damage in% Centaurea cyanus Lamium ^from spp. Sinapis - Albums Stellaria media 81 2,0 100 ALIGN! 100 ALIGN! 100 ALIGN! 1Q0 53 2,0 100 ALIGN! 10Ó 100 ALIGN! 100 ALIGN! 58 2,0 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 214 1.0 90 . -. - 100 ALIGN! 100 - 239 1.0 45 '- 100 ' 100 ALIGN! 80 1.0 90 - 100 ALIGN! 100 ALIGN! 237 0.5 85 - 95 100 ALIGN! 4'2 - 2,0 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 27 Mar: 2,0 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 14'2 1.0 90 - · 100 ALIGN! 100 ALIGN! 165 1.0 45 —- ‘ 100 ALIGN! 100 ALIGN! 54 1.0 90 - 100 ALIGN! 100 ALIGN! 163 . 0.5 85 - 95 100 ALIGN! 162 0.5 95 - 95 100 ALIGN! 139 1.0 85 - 100 ALIGN! 100 ALIGN! 138 2,0 55 '- 70 : 100 . 143 2,0 90 : - 95, 100 ALIGN! 140 ' 1.0 55 - 100 ALIGN! 100 ALIGN!

Legend:

= no damage • 100 · »plants destroyed

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О = no damage 100 = plants destroyed

plants destroyed

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196428

24 object of the invention

Claims (1)

A herbicidal composition, characterized in that it contains a solid or liquid carrier and, as active ingredient, a diurethane of the formula IX Z. represents the remainder of the formula R ¹ A I II —N — С — B — R ³ ,. Y represents a radical of formula R ² E Wherein Y is different from Z, each of R ¹ and R ² , which may be the same or different, each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms each of R ³ and R ⁴ , which may be the same or different, each represents an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 5 carbon atoms, substituted by halogen, methoxy, cyclohexyl, or phenyl; (C 4 -C 8) alkynyl, (C 5 -C 8) -cycloalkyl, optionally substituted by methyl, (C 7 -C 9) bicycloalkyl, indanyl, or phenyl, optionally substituted by one to five substituents selected from the group consisting of C 1 -C 8 alkyl C 1 to C 5, halogen atoms and C 1 -C 2 alkoxy; A, B, D and E are each independently oxygen or sulfur, and not all of A, B, D, and E are simultaneously oxygen, and at least one of these is always sulfur. Severography, et al., Gívod 7, Maet