DE2725146A1 - DIURETHANE AND HERBICIDES - Google Patents

Description

-υ - ο. ζ. ys 617

Diurethanes and Herbalcides 2725146

The present invention relates to new valuable sulfur-containing diurethanes with excellent herbicidal action, herbicides which contain these compounds, and methods for controlling undesired plant growth using these compounds.

It is known that methyl-N- (3- (N '- (V -fnothy lphenylcarbamoyloxy) - phenyl ) -carbamate, ethyl-N- (N'-phenylcartamoyloxy) -phenyl) -car - bamate , methyl-N- ( 3-N'-methy1-N-phenylcarbamoyloxy) phenyl) -carbonyl Bamat (DT-AS 15 67 151) or 3-isopropyl-1,3 ?, benzothiadiazinon- (O-2,2-dioxide (DT -AS 15 ¹ 12 836) to be used as herbicides.

It has now been found that the new piurethanes of the general formula

R ¹ A R ² E

in which Z denotes ^{the remainder -NCBR 3} and Y denotes the remainder -NCDR ^,

1 2

wherein Z is always different from Y and R and R are each independently hydrogen, alkyl (for example methyl, ethyl, iso-propyl), alkoxyalkyl (eg iMethoxymethyl, 2-methoxyethyl) alkoxy- carbonylalkyl (eg, methoxycarbonylmethyl), haloalkyl (such as chloromethyl) or optionally sub-

3 ^
stituiertes benzyl, R and R each independently represent unsubstituted alkyl or substitu iertes by halo or alkoxy or alkoxy carbonyl, or substituted or unsubstituted aryl alkyl (eg methyl, ethyl, 2-Chlora "thyl, 2-methoxyethyl, methoxycarbonylmethyl, benzyl, Isopropyl, n-propyl, ^ -chlorobenzyl, η-butyl, sec-butyl, tert-butyl, iso-butyl, 2, ^/ <-dichlorobenzy1, 2-ethylhexyl, n-decyl, 2-phenylethyl) or alkenyl which is optionally substituted by halogen (for example allyl, 2-chloropropene (DyI (3), buten (1) yl (3), 2,3-dichloroallyl, 3,3-dichloro-2-N'ethylally 1) or optionally alkynyl substituted by halogen or alkoxy

809850/0238

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2725H6

(e.g. propargyl, butin (1) yl (3), 1-chlorobutin (2) yl (4)) or optionally substituted cycloalkyl (e.g. cyclopentyl, cyclohexyl, 3-methylcyclohexyl, 2,6-dimethylcyclohexyl, cycloheptyl, 4- tert-butylcyclohexyl, cyclooctyl, cyclododecyl, 3,5-dimethylcyclohexyl) or bicycloalkyl (e.g. norbonyl) or tricycloalkyl (e.g. tricyclo (4,3,1, ^{> D} 0 ') -decyl), a phenyl radical with a fused ring system (zoB " Naphthyl or indyl), phenyl or a mono- or polysubstituted phenyl radical, with the substituents alkyl, haloalkyl, alkoxyalkyl, cycloalkyl, halogen, alkoxy, haloalkoxy, alkoxycarbonylalkoxy, nitro, amino, aryl, aryloxy, thiocyanato, cyano, ς 5 5

N g, NH-CR ⁵ , NHCON ^ g, COOR ⁵ , CON _g , SR ⁵ , SO ₂ R ⁵ , OSO ₂ R ⁵ , Rg RR

-CO-R ⁵ , SO ₂ M g, (e.g., phenyl, 4-fluorophenyl, 2-methoxyphenyl,

3-methylphenyl, 2-fluorophenyl, 3-methyl-5-isopropylphenyl, 3-ethylphenyl, 3-chlorophenyl, 2,4,6-trimethylphenyl, 3-fluorophenyl, 3-chloro-4-fluorophenyl, 3,4-dimethylphenyl, 3-trifluoromethylphenyl, 4-methylphenyl, 3, ^ - difluorophenyl, 3-chloro-4-methylphenyl, 3-bromophenyl, 4-iodophenyl, 4-chlorophenyl, 2-chlorophenyl, 3-N, N-dimethylaminophenyl, 2-chloro ⁱ l-fluorophenyl, 3-isopropylphenyl, 4-ethylphenyl, 3-methoxycarbonylaminophenyl, 4-ethoxyphenyl, 2-methylphenyl, 3-methoxyphenyl, 4-cyanophenyl, 2,6-dimethylphenyl, 2,4-dichlorophenyl, 3-methyl-4 -chlorphenyl, 2-trifluoromethylphenyl, 2,4-dibromophenyl, 4-trifluoromethylphenyl, 4-methoxyphenyl, 3- (l'-ethoxycarbonyl-ethoxy) -phenyl), 2,3,6-trimethylphenyl, 3-tert.-butylphenyl, 3-trifluoromethoxyphenyl, 3-c «-, dl, ß, ß-tetrafluoroethoxyphenyl, 3,5-dichlorophenyl, 2-methyl-6-ethylphenyl, 2,3-dimethylphenyl, 2-methyl-4-chlorophenyl, 2,4 , 5-trichlorophenyl, 2,3,6-trichlorophenyl, p-chlorophenoxyphenyl, where R and R are each independently hydrogen or egg nen optionally mono- or polysubstituted aryl radical or one of the two substituents has the meanings given for R, X is hydrogen, alkyl (ζ.Β. Methyl), haloalkyl (e.g. tri fluorine thy 1), alkoxy (e.g. methoxy), halogen (e.g. fluorine, chlorine, bromine or iodine),

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2725U6

Nitro or amino, η the numbers 1-4 and A, B, D, E each independently from one another are oxygen or sulfur, with not all radicals A, B, D, E simultaneously being oxygen and at least one of these residues always means sulfur, a good herbicidal action against numerous important undesirable plants and at the same time are well tolerated by many cultivated plants »These effects are better than those of the known active ingredients.

The new connections can, for example, according to the following

1 2 drive are produced, with the radicals A, B, D, E, R, R, R,

R, R, X and η have the meaning given above «If in the following When speaking of urethanes and chloroformic acid esters, thiono-, thio- and dithiourethanes as well as chloroformic acid thioesters, chloroformic acid thioesters and dithioester chloroformate are understood.

809850/0238 - 9 -

O.Z. 32

YEAR

Cl

A = C reduction
(H ² = Η)

^^^ HER X

Cl

NO,

X 1) A = C = B
\ (B = S
j A = O / S)
'2) alkylation

1) D-C = E (D = S, E = O / S)

2) alkylation

Cl

(R ² = H)

R ^ -DH

NHR D

¹ = Η)

R ⁵ -BH

H ¹

SO- BR ⁵ II A

NCE
G

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2725U6

From the reaction scheme shown, the reciprocal ones are clearly evident Relationships between the starting materials. Farther it becomes clear that depending on the nature of the substitutes A, B, D,

12 3 4
E, R, R, R, R and X as well as the availability of the respective reactants one way or the other can be advantageous. The conversion from F to H is preferred.

Meta-nitrophenyliso (thio) cyanates (B) can be prepared from known meta-nitroanilines (A) (W. Siefken, J, Liebigs Annalen der Chemie, 562 , 75 ff, (1949), which in turn are made with the components R- BH smoothly to the nitro (thiourethanes (C) react (S. Petersen in Methods of Organ. Chemistry, Volume VIII, page 131> Georg Thieme-Verlag, Stuttgart, 4th edition, (1952), which, however, also directly from the meta -Nitranilines (A) with chloroformic acid esters (R ³ B-CA-Cl) (DT-OS 16 43 763) or with carbon disulfide or carbon oxysulfide, base and alkylating agent (Methods of Organic Chemistry, Volume IX, page 831 ff, Georg Thieme- Verlag, Stuttgart, 4th edition, 1955) «The following reduction leads to the amino compounds (E, R = H) (S. Schröter in Methods of Organic Chemistry, Volume XI / 1, page 360 ff., Georg Thieme-Verlag , Stuttgart, 4th edition, 1957), which either directly or after conversion into the product monosubstituted on the amino nitrogen (E, R = H) (Methods of Organic Chemistry, Volume XI / 1, page 24 ff., Georg Thieme-Verlag, Stuttgart, 4th edition 1957) with chloroformic acid esters (R D-CE-Cl) (DT-OS 16 43 763) or with carbon disulfide or Carbon oxysulfide, base and alkylating agent; (Methods of Organic Chemistry, Volume IX, page 831 ff, Georg-Thieme-Verlag, Stuttgart, 4th edition, 1955) are converted into the desired diurethanes (H). The aminourethanes E can also be obtained by reacting meta-phenylenediamines (D) with chloroformic acid esters. Another synthesis possibility is the reaction of Ary 1-1,3-diiso (thio) cyanates (E) with only one mole of R-BH component belonging to the iso (thio) cyanatourethanen (performed (YES Parker, Thomas JJ and CL . Zeise, J. org. Chem. 22_ _t 594 to 596 (1957)), which also by (thio) phosgenation of aminourethanes (F)

809850/0238

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- Il - 0.7 ,. 3? .6l7

are available (DT-OS 19 I ¹ »270, page 5, example 8). Subsequent reaction with the component R DH leads to the desired

End products. Basically it should be noted that the order

"5 H

the -CABR or -CEDR groupings are arbitrary.

The preferred synthesis steps are described in more detail below:

a) The reaction of 3-nitrophenyl iso (thio) cyanates (B) takes place with or without a catalyst commonly used for iso (thio) cyanate reactions, eg tert. Amines (triethylamine, 1,4-diazabicyclo- (2.2.2) -octane), nitrogen-containing heterocycles (pyridine, 1,2-dimethylimidazole) or organic tin compounds (dibutyltin diacetate, dimethyltin dichloride) optionally in a solvent which is inert under the reaction conditions, e.g. hydrocarbons ( Ligroin, petrol, toluene, pentane, cyclohexane), halogenated hydrocarbons (methylene chloride, chloroform, dichloroethane, chlorobenzene, o-, m- or p-dichlorobenzene), nitro hydrocarbons (nitrobenzene, nitromethane), nitriles (acetonitrile, butyronitrile), benzotonitrile Diethyl ether, tetrahydrofuran, dioxane), esters (ethyl acetate, methyl propionate), ketones (acetone, methyl ethyl ketone) or amides (dimethylformamide, formamide) (DT-OS 15 68 138) at temperatures in the range from 0 to 150 ° C, preferably in the range of 40 to 100 C ₀

b) 3-Nitranilines (A) are mixed with chloroformic acid ester in a suitable solvent, e.g. water, alcohols (methanol, ethanol, isopropanol) or as indicated under a), with the aid of a customary acid binder, e.g. alkali hydroxides, carbonates, bicarbonates, alkaline earth oxides , hydroxides, carbonates, hydrogen carbonates, tertiary organic bases (e.g. triethylamine, pyridine, N, N-dimethylaniline, N, N-dimethylcyclohexylamine, quinoline, tributylamine) or starting product 3-nitroaniline, at temperatures from -20 ° to 150 ⁰ C, preferably in the range from 20 to 80 ° C.

809850/0238 ~ ¹² ~

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7 7 ~) ^ 1 A R

c) The reduction of the nitro urethanes (Q) can be carried out by one of the known processes, for example by catalytic hydrogenation, by a metal-acid combination, for example an iron-acid combination, by a metal-alcohol combination, for example aqueous zinc dust Alcohol, ferrous alcohol.

d) Comparable ones apply to the implementation of m-phenylenediamines (D) Conditions as for b), but it can be advantageous to work with an excess of m-phenylenediamines.

e) The reaction of aminourethanes F. with chloroformic acid esters takes place analogously to b), whereby the solution obtained, for example, by catalytic hydrogenation of the nitro urethanes C, is also used without can use further cleaning directly.

The following examples are intended to illustrate the preparation of the new diurethanes and explain their preliminary products:

I. Nitro urethanes Example A

A solution of 6Ί, 3 parts by weight of I-chlorophenol and 3 parts by weight Triethylamine in 430 parts by weight of toluene (absolute) a mixture of 85 parts by weight of 3-nitrophenyl isocyanate and 13 parts by weight was obtained with stirring at 20 to 25 ° C Toluene (absolute) metered in.

To complete the reaction, the mixture was subsequently stirred at room temperature for 1 hour. After cooling to 0 C, the reaction product was filtered off with suction:
Mp. 137-138 ⁰ C.

The compound has the following structural formula:

NO ₂

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Example B.

- 13 - O.Z. 32 617

To 138 parts by weight of m-nitroaniline in 500 parts by weight
Tetrahydrofuran (THF) is added to 87 parts by weight of sodium hydrogen carbonate. 120 parts by weight of thiomethyl chloroformate are added dropwise with stirring at room temperature
Stir for 16 hours at room temperature, filtered, the solvent is distilled off on a rotary evaporator and stirred
the oil obtained in toluene. The separating
Crystals are sucked off and dried:
M.p .: 137-138 ° C.

The compound has the following structural formula:

NO ₂
Example C

To 26 parts by weight 3-nitro-N-methylaniline in 320 parts by weight of ethyl acetate are 17, J ² parts by weight
Given sodium hydrogen carbonate. 33 parts by weight of m-tolyl chloroformate are slowly added with stirring, the mixture is stirred for 20 hours at room temperature, filtered, and the mixture is drawn off
The solvent is removed in vacuo and the residue that remains is recrystallized from toluene / cyclohexane.
M.p .: 114 to 116 ° C.

The compound has the following structural formula:

The following nitro urethanes (C) produced:

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2725H6

A. B. X R ¹ methyl Pp. ° C S. 0 H H 4-fluorophenyl 0 O H H 2,4-dichlorophenyl 166-167 0 0 H H methyl O O H H methyl 153-155 0 O 6-Cn ₃ H 4-chlorophenyl 152-153 0 0 H Benzyl Phenyl 0 0 H H 3-Hethoxyphenyl 123-125 0 0 Ή H Phenyl ο · 0 H CH ₅ - 2-fluorophenyl 69-70 0 0 - H H Phenyl I45-I4O 0 0 6-F H 3-bronphenyl 158-140 " 0 0 H H 5-methylphene y1 130-131 0 0 H CH ₅ OCH ₂ 5,4-dinethylphenyl 0 0 H H 130-131

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B. X K ¹ - 15 - o.a. 32 617 A. O 5-CF ₃ H R ⁵ O O H H methyl 86-87 O O 6-Cn ₃ H 4-methoxyphenyl 132-153 O O H H ethyl 131-133 O O H H 3-fluorophenyl 123-130 O O 2-CH ₃ H ethyl 64-66 O O H Π Phenyl 112-114 O O H H 2-chloro-4-fluorophenyl 146-147 O O 4,6-F ₂ H 2-chlorophenyl 136-138 O O H C ₂ H ₅ methyl O O 4-CH ₃ H 4-cyanophenyl O O H H methyl 114-117 O O 2,5-Cl ₂ CH ₃ " 3-trifluorocethylphenyl 119-120 O O H H 2-methoxyethyl O O H CH ₃ 4-trifluoromethylphenyl O O H H Cyclododecyl O O 4-ci H 4-ethylphenyl 80-88 O O H H Phenyl 125-127 O O 6-CH ₅ 4-ethyl
benzyl 3-chloro-4-fluoro-henyl O O H H methyl O O 4-CI H 2,4,6-triraethylphenyl 212-213 C. O H H methyl 122-124 O O 6-UO ₂ C ₂ H ₅ 314-difluorophenyl O O H H 2,5-dichlorber.7, yl O O 4-Cn ₃ H 171-175 O O H H ethyl 60-61 O O H H Cyclododecyl ο. 3-Isropyl p ^ yl 93-100 - 16 -

809850/0238 ORK3 / NAL INSPECTED

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A. B. X R ¹ R ⁵ Mp ° C S. O H C ₂ H ₅ OCH ₂ n-butyl 2725H6 O O H H 2-triiluone ethylphenyl O O H H Cyclooctyl O O H H 4-ethyl phenyl 138-139 O O H H 2,4-dibromophenyl O O Π H 3-methyl-5-ethylphenyl 115-117 O O H H Methoxycarbonylethyl 123-125 O O H H tert-butyl 97-99 ο ■ O H H 4-ethoxyphenyl O O H H 3-ethylphenyl 85-86 O O H CH, Cycloheptyl O O H H 2,6-dimethylphenyl 165-167 O O 5-CF ₅ H Isopropyl 121-123 O O 6-F H 4-diflucmethoxyphenyl O
O O
O H
H H
H 3-methoxycarbonyl
aminophenyl
2-Ke thoxyphenyl 172-174 O O H H Tricyclo [4.3.1 ² ' ⁵ 0 ¹ · ⁶ ] 103-105 O O H H 2-methylphenyl 126-128 O O H H 4-iodophenyl O O H CH ₃ methyl 54-56 O O 4,6-Cl ₂ H 2-cyclohexylphenyl O O H H 3-methyl-4-chlorophenyl O O H H 3 1 5-kinethylcyclohexyl O O K H 1-ila? Hthyl 141-142 O O H H Isopropyl 86-63 O O 6-Br H Ethy] O O H H 4-i »i trophenyl O O 6-F H Ke thy? 116-113

- 17 -

809850/0238

U.Z. 32 6l ";

A. B. X R ¹ R ⁵ Pp. ° C O O 2-CH, Benzyl ethyl 2725U6 O O 5-c? ₃ H Phenyl 133-135 O O 4-3r CH, methyl O
O O
O H
K H
CE, OCH, - 2,6-dinethylcyclo
hexyl
3-fluorophenyl 121-123 O O 6-0CH ₇ H methyl 131-132 O O 2-CH ₃ CH ₃ Benzyl O O 5-CF ₃ CH, Phenyl O O H H Cycloheptyl 102-104 O O H H Benzyl 113-115 O O 4-CH, H methyl O O 6-OCiL H Phenyl 209-211 O O E. H 4-bronphenyl 136-137 S. O H H Phenyl O
O O
S. H
H H
Benzyl 3-methyl-5-iso-
propyl-phenyl
n _T butyl O O H H Norbomyl 118-120 O O II H 2-sewn ethyl S. S. 5-NO ₂ C ₂ H ₅ 3-kethylphenyl O O H H Cyclopentvl 110-112 O O 6-Cl H methyl 136-138 O S. H iso-propyl 4-methylthiophenyl O O H E. 3-nothylcyclohexyl 120-122 S. S. H H Kethyl S. O H CH ₃ Phenyl O S. H Π Phenyl 156-158

- 18 -

809850/0238

B. X R ¹ - 18 - CZ. 32 617 O H H 2725H6 A. S. H H R ³ Mp. ⁰ C S. O H C ₂ H ₅ ethyl S. O H C ₂ H ₅ Phenyl O O H H Phenyl 56-58 O O H H 3-methylphenyl 75-77 O O H H Hexahydrobenzyl O O H H 3,3,5-trimethylcyclohexyl 79-82 O Aminourethanes 3- (N, N-dimethylamino) -
phenyl 126-127 O Example D 3, ¹ J- (tetramethylene) -
phenyl 164-166 II

A solution of 135 parts by weight of N- (3-nitrophenyl) carbamic acid - ^ - chlorophenyl ester in 900 parts by weight of tetrahydrofuran (absolute) were treated with 3 parts of hydrogenation catalyst (palladium
on animal charcoal, 10 %) and at room temperature and
Hydrogenated to constancy at 0.02 bar Hp pressure. For work-up
was freed from the catalyst and dried with MgSO ^
Solution freed from the solvent to such an extent that the crystalline reaction product could be easily suctioned off: 186 - 187 C.
Structure:

Cl

/ Public transport

OCNH

^w 5

Example E.

To a solution of 10 8 parts by weight of m-phenylenediamine in
1000 parts by weight of water were very slowly added dropwise to 25.2 parts by weight of phenyl chloroformate with vigorous stirring. After the reaction had ended, the solid was filtered off with suction

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2725U6

washed several times with dilute hydrochloric acid, the combined acidic solutions neutralized with ammonia and filtered off with suction. The dried product obtained in this way melts at 178 to 180 ° C. with decomposition.
Structure:

Example F

52.1 parts by weight of phenyl chloroformate are slowly added dropwise with vigorous stirring to 51 parts by weight of 2,4-diaminonitrobenzene and 3 parts by weight of sodium hydrogen carbonate in 600 parts by weight of tetrahydrofuran. After stirring for 14 hours, the mixture is filtered and washed with tetrahydrofuran. The solution is freed from the solvent to such an extent that the crystalline crude product can be easily suctioned off; after washing with diethyl ether and drying, the substance melts at 223 to 225 ^° C. According to the NMR spectrum and elemental analysis, it has the following structure:

Example G

To a mixture of 33 parts by weight heated to 80 C. Iron powder, 75 parts by weight of alcohol, 60 parts by weight of water and 3 parts by weight of conc. Hydrochloric acid is given under intense Stir 40 parts by weight of 3 (S-methylthiocarbamoyl) -nitror benzene in such portions that the temperature without additional

809850/0238 -20-

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2725H6

Lent heating is kept at 80 C. The mixture is then refluxed for a further 1 hour, filtered off with suction while hot, the residue and the piltrate are digested with about 1000 parts by weight of methylene chloride, dried over sodium sulfate, concentrated and recrystallized from toluene
Structure:

Toluene: m.p. 101-103 ° C

0
NH-C-SCH-

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The following aninourethanes (?) Can be produced using the appropriate processes will:

- C - 3R ⁵

7251

A. B. X R ¹ 4-fluorophenyl M.p. C O O H H 2,4-dichlorophenyl 166-167 O O H H methyl O O H H methyl 87-89 O O 6-CH ₃ H 4-chlorophenyl O O H Benzyl methyl O O 4-KO ₂ H 3-methoxyphenyl 187-189 O O H H Phenyl O O H CH ₃ 2-fluorophenyl 70-72 O O H H Phenyl 172-173 O O 6-F H 3-bromophenyl O O H H 3-methylphenyl O O H CH ₃ OCH ₂ methyl S. O H H Phenyl S. S. H CH ₃ ethyl O S. H H 3-methylphenyl O S. H H 4-chlorophenyl S. O H H Phenyl S. O H H 3,4-dinethylphenyl O * O H H methyl 155-157 O O 5-CF ₃ H 4-methoxypheny1 O O H H ethyl 146-149 O O 6-CH ₃ Π 3-fluo '; Sicvyl O O H E. Decomp.

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B. X R ¹ - 22 - 0.Z • 32 617 A. O H E. 2725H6
M.p. C O O 2-CH, E. ethyl thick oil O O Ώ E. Phenyl 131-133 O O H H 2-chloro-4-fluorophenyl Decomp. O O 4,6-P ₂ E. 2-chlorophenyl Decomp. O S. E. C ₂ B ₅ methyl O O 4-CH ₅ E. 4-cyanophenyl O O H E. methyl O O 2.5-Ci ₂ CH ₃ 3-tri fluomethylphenyl 126-123 S. O H E. 2-methoxyethyl O O H CE, 4-tri fluomethylphenyl O O H E. Cyclododecyl O O 4-C1 E. 4-ethylphenyl I6O-I6I O O H H Phenyl 215-217 O S. 6-CH ₃ 4-methyl-
benzyl 3-chloro-4-fluorophonyl S. O H E. methyl O O 4-ci E. 2,4,6-trinethylphenyl 150-152 O O H E. methyl O S. 6-KO ₂ C ₂ H ₅ 3,4-difluorophenyl O O Π E. 2,4-3ichlorobenzyl O O 4-CH ₃ E. 5-indanyl YqV ^ \ j 184-185 O O H E. ethyl O O E. B. Cycloaodecyl O O E. E. 3-isopropylphfer.yl 68-70 O S. E. E. 3-ethyl-5-methylphenyl IO2-IO4 S. O E. E. Phenyl O O E. E. 3,3,5-i'rinethyloyolohev yl 100-102 O O E. C ₂ K ₅ 2-methylcyclohexyl O O Π C ₂ H ₅ 3-kethylphenyl IO4-IO5 O Phenyl IO4-IOu

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3 χ R ¹ - 23 - O.Z. , 32 617 A. O H C ₂ H ₅ OOH ₂ - R ⁵ Mp ° C S. O H H n-butyl 2725H6 O O H H 2-trifloromiethylphenyl O O II H Cyclooctyl O O H H 4-lic thy! Phenyl 158-162 O O H H 2, / - dibronphenyl O S. π H tert-butyl 109-110 O O π H 4-ethoxyphenyl O O H CH ₅ 5-ethylphenyl 112-114 O O H H Cycloheptyl O O 5-CF ₅ H 2,6-diraethylphenyl 160-161 O O 6-F H Isopropyl 102-104 S. O Π H 4-difluoroetho: cyphenyl O O H H 3- (0-Kethyl-c? -Rba3oyl) -
phenyl 149-151 O O H H 2-methoxyphosyl O O H H Tricyolo [4.3.1 ² ' ⁵ 0 ¹ ' ⁶ ] -
decyl 130-131 O O H H 2? -Methyl phenyl 170-172 O O Π CH ₅ 4-iodophenyl O S. 4,6-Cl ₂ H methyl O O H H 2-cyclohexylphenyl O O H H 3_T.iothyl-4-chlorophenyl O O H Π 3, 5-DiniPthylcyclohc "yl O O H H 1-naphthyl 146-148 O S. 6-3r F. Ieopropyl 66-68 O O Π H Xthyl S. O 6-P H 4-nitrophenyl O O 2-CH ₇ Benzyl methyl O ethyl

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A. B. X H ¹ - 24 - OZ
R ⁵ 32 617
2725146
M.p. C * thick oil O O 5-CF ₅ H Phenyl 214-216 S. S. 4-3r CH ₅ methyl O O H H 2,6-dimethylcyclohexyl O O H H Hoxahydrotenzyl O O H H 2-ethylhexyl O S. H H Phenyl 86-88 S. O H CH ₅ OCH ₂ - 5-fluorophenyl O O ß-OCH, H methyl O S. 2-CH ₅ CH ₅ Benzyl 84-86 O S. 5-CF ₃ CH ₅ Phenyl O O E. H Cycloheptyl O O H H Benzyl 155-155 S. O 4-CH
6-HO ^ H methyl O O 6-OCH, H Phenyl O O H H 3-Kethyl-5-isopropyl-
phenyl O S. H Benzyl n-butyl O O H H Norbomyl O O H H 2-naphthyl 95-97 O S. 5-HO ₂ C ₂ H ₅ 5-methylphenyl 112-115 O O H H Cyclopentyl 132-155 * O O 6-Cl H methyl 181-185 S. S. H iaopropyl 4-kethylthiophenyl O ο H H 5-kethylcyclohexyl O O H CH ₅ 5-methylphenyl O O H H 5- (N, lI-Dinethyla3iino) - O O H H pnenyj.
5, 't (Totraiaethylene) phenyl O O H H Methr.ic-'carbonylcothyl S. S. H H methyl

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III. Diurethane Example 1

11 parts by weight of sodium bicarbonate were added to a solution of 22.8 parts by weight of N- (3-aminophenyl) carbamic acid phenyl ester in 200 parts by weight of tetrahydrofuran (absolute) and then 13> 3 parts by weight of chloroformic acid thiomethyl ester were metered in at 20 to 25 ° C. with cooling. To complete the reaction, the mixture was stirred at room temperature for 1 hour. The reaction mixture was then filtered and the filtrate was concentrated in vacuo. The oily residue was made to crystallize by adding toluene. Mp. 155-157 ° C (No. I) ₀ The compound has the following structural formula:

Example 2

A mixture of 20 parts by weight of N- (3-isothiocyanatophenyl) -0-methylcarbamate (available from N- (3-aminophenyl) -0-methylcarbamate and thiophosgene, mp. 99 - 100 ⁰ C), 20 parts by weight of methanol, 3 parts by weight of triethylamine and 150 parts by weight of toluene is heated to boiling for 6 hours. After concentration, it is recrystallized from toluene: mp 147-179 ° C. (No. 2). The compound has the following structural formula:

NHCOOCH,

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2725U6

Example 3

To a solution of 16.6 parts by weight of N (3-aminophenyl) -0-methyl urethane and 10.1 parts by weight of triethylamine in 300 parts by weight of diethyl ether are allowed to 10 parts by weight at room temperature Carbon disulfide drop- After stirring for 20 hours, the mixture is filtered off with suction, the residue in 120 parts by weight Suspended water and stirring with 9 ^ 1 parts by volume of diethyl sulfate added «After 20 hours of stirring, the mixture is filtered off with suction, washed with water and air-dried: melting point 122.degree (No. 3). The compound has the following structural formula:

NHCOOCH ₃

NH-C-SC ₀ H,

809850/0238

Ir. the following connections can be established accordingly:

MCBR ³

\ A

^N C - D - ΈΤ

No. Λ < B. 5 D. E. X R ¹ R ² R ³ R ⁴ Mp ° C I.
-j CT5
I. 4th 0 S. 0 0 H H H ethyl Phenyl 162-164 809850/02 5
6th
7th
8th
9 ο ο ο ο ο S.
0
0
S.
S. 0
S.
S.
0
0 ο ο ο ο ο 2-CK,
H
H
H
H H
H
H
H
H ■ H
Π
H
H methyl
methyl
Fnenyl
methyl
methyl Phenyl
Phenyl
n-propyl
4-chlorophenyl
3-methylphenyl 180-182
155-157
120-122
197-198
118-120 QO 10
11 0
S. S.
S. 0
0 0
0 H
E. H
H H
H 3,5-dichloro-2-methyl-
allyl
methyl Phenyl
3-ethylphenyl 220-222
135-138 13th 0 S. 0 0 5-CF ₃ II H methyl Phenyl • 60-71 O 13th 0 0 S. 0 H H H methyl methyl 144-146 14th 0 0 S. 0 E. CHj H 3-methylphenyl ethyl 120-121 ro 15th 0 0 S. S. H H H methyl Mothyl I4Q-I5O 16 0 S. 0 0 K H H n-butyl Phenyl 127-129 .17
I. S. S. 0 0 H H CH ₅ methyl 3-methylphenyl tough Cl ro
OO
I. •

H ¹

R ²

Pp- ⁰ C

I. 18th • ο S. 0. 0 4-OCE ₅ H II methyl ro
•O 19th 0 0 0 S. H II II methyl 20th 0 0 S. 0 6-Cl H H Phenyl 21 0 S. S. 0 H H H methyl 22nd 0 S. 0 0 H H H 2,3-dichloroallyl 25th 0 S. 0 0 H H H methyl OO
O 24 0 S. 0 0 H H H Phenyl co
00 25th 0 S. 0 0 π H Benzyl methyl cn
O 26th 0 S. 0 0 H H CH ₅ ethyl -ν
O 27 0 0 S. 0 5-CP H H Ioopropyl IS>
Ul 20th 0 0 S. 0 K CH ₅ OCH ₂ H 5-methylphenyl 29 0 S. 0 0 Ii H H methyl 50 0 S. 0 0 H H H 2-phenylethyl 31 0 0 0 S. H H H ethyl 52 0 S. 0 0 H H H methyl 55 0 0 S. 0 6-OCII ₅ K H methyl 54 0 S. 0 0 II Π Π methyl 35 0 S. 0 0 II . H Il ethyl 36 O
VJ S. 0 0 π H CH ₅ methyl

Phenyl 125-125

4-chlorophenyl 156-156

Methyl 183-185

Methyl 186-108

Phenyl 137-139

5-methoxyoarbonylaminophenyl

Phenyl 158-159 4-chlorophonyl

Phenyl 151-155

Phenyl 155-157 '

methyl

2, l (-Dichlorophynyl

Phenyl 129-151

5-bromophenyl

5-bromophenyl

Ethyl 115-117?

3-Mo thoxyphenyl

3-ethylphenyl 130-152

Phenyl 96-97

ro

cn

No. Λ B. D. E. X R ¹ R ^ R ⁵ R ⁴ Mp. ⁰ C I. I52-I54 KJ 37 '0 0 s. 0 H H H 4-methylphenyl ethyl 167-169 -3
ISJ 30th 0 S. 0 0 H H H - methyl 4-cyanophenyl I4O-I5O Cn
Cn 39 S. S. 0 0 H H H methyl 4-methylphenyl 142-144 O 40 S. 0 . 0 0 3,5-Cl ₂ H CHj 1-naphthyl 2-methoxyethyl • 41 S. 0 0 0 H H Π Phenyl methyl 164-167 ro 42 0 0 S. 0 H C ₂ H ₅ Ξ 3-methylphenyl ethyl 103-105 co 43 0 0 S. S. H H II methyl Phenyl 148-150 O
co 44 S. 0 0 0 H H H 4-trifluonethyl methyl 00
cn 45 0 0 S. S. H H E. 4-fluorophenyl methyl 135-133 0/0238 AC
47
48 S.
C.
0 O CO CO S.
0
S. S.
0
0 H
H
H Π
H
H H
H
H methyl
methyl
Methoxycarbonylmethyl Phenyl
Phenyl
Phenyl 49 0 S. 0 0 H H H ethyl 4-fluorophynyl 50 0 S. 0 0 H II Π methyl Cyclododecyl 51 0 0 0 S. H H H methyl 4-methylphenyl 52 0 0 S. 0 H H H 3-chloro-4-fluorophenyl Mothy.1 53 0 S. 0 0 H II H methyl 4-tcrt.Butycyclohexyl 54 0 0 S. 0 H K K gate i. Butyl ethyl I.
O
I. 55
56 0
0 S.
S. 0
0 0
0 II
H M.
II 4-methyl-methyl
benzyl
II ^J Λ thyl Phenyl
4-tcrt.Butylcyclo-
hcxyl

Ur,

,1

P.

Mp- ⁰ C

57 53 59 60 61 62 63 64 65 cc

σ
co co cn ο

ro 67 co oo Ce

69 70 71 72 73 74 75 76

0 0 0 0 0 0 0 0 0 S 0 0 0 0 3 0 0 S 0 0

0 0 0 S S 0 S 0 0 0 S 0 S S S S 5 0 3 S.

S 0 0 S S S S 0 0 S 0 0 S 0 0 S 0 0

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 S 0 S 0 0

4-Cl

II

4-CH ₃

6-CH

2-CH

H H 4-methylthiophenyl

H H norbornyl

H H cyclooctyl

CH ₃ H methyl

H CH ₃ methyl

H H 3,4-difluorophenyl

Π Η phenyl

H H methyl

H H methyl

H H methyl

H CH ₁ , methyl

H H phenyl

H H methyl

H H methyl

H H methyl

H H phenyl

H H methyl

H E propargyl

Π Η · Ethyl

H H methyl

methyl

Methyl 139-141

Methyl phenyl phenyl methyl methyl 2,4-chlorobenzyl Benzyl Cyclododecyl 3 ->! Ethylphenyl Benzyl Cyclopentyl tcrt.Butyl Phenyl Phenyl 1-Naphthyl methyl

4-tert-butylphynyl <

2-fluorophenyl 183-105

118-120 148-150 117-119

12 8-130 'ο

Previous year

7p. ⁰ C

OO O CD OO cn ο

CD

77 0 S. s S. H E. H n-propyl Phenyl 78 0 0 S. 0 E. II H 3-fluorophynyl methyl 79 3 0 0 S. II H H methyl Phenyl 80 0 S. . 0 0 H Π H methyl 4-fluorophenyl 31 S. S. 0 S. H H H methyl Phenyl 82 0 0 3 0 H H H 2-chlorophenyl methyl 83 3 S. S. 0 H H H methyl Phenyl 84 0 S. 0 0 4-CH ₅ H H methyl 4-methylphenyl 05 0 0 S. 0 H H Π 2-methylphenyl methyl QG S. 0 0 S. H Π H methyl 2-methylphenyl 07 0 S. 0 0 H H H methyl 4-methylphenyl «3 0 3 0 S. H H π Phenyl methyl 09 0 S. S. S. Π H H 4-chlorophenyl methyl 90 C. S. 0 0 H II II methyl 3-ethylphenyl 91 0 S. S. S. 6-CH ₅ H Π 4-chlorophenyl ethyl 92 0 S. 0 0 Π H H methyl 4-ethylphenyl 53 0 S. 0 S. H H H methyl 4-chlorophenyl 94 0 0 S. 0 H H H 3-trifluoromethylphynyl methyl ΟΓ,
I " S. 0 0 0 4-NH ₂ H H Bee. Butyl Propargyl 0 S.
0 0 0 II II H methyl 4-methoxyphynyl

161-162

160-182

183-184

176-177

118-120

186 - F83 _O

Previous year

IV)

KJ

cn

-P-CD

185-186

I. No. Λ 3 D. E. X R ¹ R ^ R ³ methyl Mp. ⁰ C • Previous year 97 S. 0 0 S. H H H sec.-amyl 314-dimethylphenyl 93 0 S. 0 0 H H H methyl methyl 180-182 99 S. 0 S. 0 H H H 4-methylphenyl methyl 100 0 0 S. 0 H 'II H 2-chloro-4-fluorophenyl Phenyl 183-184 101 S. S. S. 0 4-OCH, II H methyl 3-Iaopropylphenyl 102 C. S. 0 0 H H II ethyl methyl 107-109 co
σ 103 0 0 S. 0 H H H 2,6-dimethylphenyl ethyl 110-112 co
co 104 0 S. S. S. H H H Cyclododccyl 2,4 »6-trimethylphenyl cn
O 105 0 S. 0 0 H H K methyl ethyl 18Q-190 CD 106 0 0 S. 0 H CH ₅ H 4-methylphenyl 5-indanyl CO 107 0 S. 0 0 H H Π methyl methyl 193-194 ^ ₄ QO 108 S. S. 0 S. 4-NO ₂ H H methyl ethyl 109 0 0 S. 0 II H II 3- (lI, N-dimethylamino) -
phenyl Methoxycfirbonylmethyl 110 S. 0 0 0 H II H Phenyl 3,4- (tetramethylcn) -
phenyl 111 0 S. 0 0 K H H methyl Mothyl 163-165 112 0 0 0 S. H Π Ξ 2-cyclohoxylphenyl methyl O 113 0 0 S. S. H II H 3,4- (Tetrareethylcn) -
phonyl 2-naphthyl Previous year
ro
μ-ι 114 0 S. 0 S. II II H methyl 3-methyl-5-ethylphenyl 115 0 S. 0 0 H H II Methyl 120-122

Mp- ⁰ C

VJ
t 116 0 0 S. 0 H II H 3 »4- (tetramethylene) -
phenyl ethyl 117 S. 0 S. S. H H H methyl Phenyl 118 0 S. 0 0 H H H methyl 3-isopropylphenyl 119 S. S. 0 S. 6-NO ₂ Π H methyl 4-methylphenyl 120 0 0 S. 0 H H Π 3-Mo thyl-5-ethylphenyl ethyl 121 0 0 0 S. H H H 2-naphthyl methyl 608 122 0 S. 0 0 H H H methyl 3- (N ₁ N-diaothylanino) -
phcnyl QO
cn 123 0 S. 0 S. 4-Br H H methyl 2-rifluoromethylphynyl CD 124 0 S. 0 0 H II H methyl Methoxycarbonylmothyl O
Κ » 125 S. S. S. 0 H K H methyl 4-methylphenyl GJ
α » 126 S. S. 0 0 H H IT methyl tort.Butyl 127 0 S. 0 S. 6-Br Π Π Allyl tert-butyl 120 0 S. S. 0 H CH, H Phenyl ethyl 129 0 0 S. 0 Π H E. 3.3 »5-trimethylcyclo-
hexyl ethyl 130 S. 0 0 0 H H H Phenyl tert-butyl 131 0 0 S. 0 H Inopropyl H Phenyl methyl 132 0 S. 0 0 II H II methyl Cyclohexyl 133 0 S. O 0 II CII ₅ Π methyl Phenyl i 13-1 0 S.
O 0 0 II Γ. H methyl 3, J-Dime.thylcyelo-
liexyl

163-165

ro

-J

KJ

cn

rp. C.

135 0 C. S ' S. H E. H tcrt.Butyl Phenyl 155-157
tr 136 S. S. O S. 4-F H H methyl Benzyl 137 0 S. 0 0 H H II ethyl Tricyclo (4.3.1 ^{2> 5} 0 ¹ ' ⁶ ) -
decyl 133 0 0 S. 0 H H H 3-methylcyclohexyl ethyl 139 S. S. S. 0 H II H methyl n-butyl O IF 140 0 S. 0 0 K II Benzyl methyl 4-fluorophenyl t-v- 09850/0238 141
142
143 0
S.
0
0
0 S.
0
0
S.
S. S.
S.
S.
0
0 S.
S.
0
0
0 H
H
H
Π WWWWW WWWWW methyl
4-iodophenyl
tert-butyl
methyl
ethyl Phenyl
methyl
Phenyl
3-methyl-4-chlorophonyl
2,6-dinothyloyclohexyl Γυ 146 ο · Γ » 3 0 Π cn. U Phenyl methyl 147 0 S. 0 0 H H H methyl 4-difluoromethoxyphynyl 1-58 0 0 S. 0 H H H 2-ethylhexyl ethyl 149 0 S. 0 0 H H H methyl 2,6-Dinethylcyclohxyl 150 0 S. 0 0 H H H methyl 3,3,5-trimethylcyclo-
hcxyl 151 0 Crt 0 0 H K II methyl 3-methylcyclohexyl ι 152 0 S. 0 0 H II II methyl Cycloheptyl ^ 153
ι 0 S.
t 0 0 H H H ethyl Cyclohcptyl

1 54 ■ S 0 G Q H H II Kethyl W (CH,) ₂ :; o0,) pher ::; l .146-148 OJ ZLZ 155 C. S. 0 0 E. CH- τ »
11 methyl ! • Ic thyl 186-183 I. (Jl
λ 156 S. 0 S. S. 6-F ii. H 4-lic thylthiophenyl n-? ro? yl cn 157 S. S. S. S. H K K 5-Isothiocya.nr.to 2-chloroethyl 152 0 0 S. 0 H CU, τ: methyl Phenyl 140-142 159 Ξ Q S. 0 4-NO ₂ H H 4-benzoylphenyl Allyl C- OO 160 0 S. S. S. H H H Isopropyl Phenyl 0985 162 S. S.
S. S.
0 0
S. H
H H
H H
H methyl
! ■! Ethyl methyl
3-phenoxyphonyl ro ο 163 S. 0 S. 0 H H H Phenyl methyl . 191-193 I-t O
IN THE 164 S. 0 0 S. 6-F H H methyl 4-chlorobutin-2-yl-1 to
CO 165 S. 0 5 0 II II Π methyl 3- (i'Athoxycarbonyl-
rithoxy) phenyl 104-105 166 η S. 0 0 II H G ₂ H ₅ ethyl Phenyl 167 ο 0 0 S. II Π II methyl Cyclohexyl 16G S. S. S. S. H H H n-decyl methyl 169 0 0 S. 0 H ClCH ₂ - H Phenyl methyl 170 0 S. 0 Π II H A -Methylphenyl methyl 171 0 3 0 0 H II II 3-acetylphenyl 2-methoxyethyl ι
OJ
σ \ 172 0 S. 0 0 II H II methyl Propargyl

Mp. ⁰ C

173 S. 0 0 0 H H H Propargyl 174 0 S. 0 0 H H H methyl 175 S. 0 S. S. H H K sec.Butyl 176 0 0 S. 0 H C ₂ H ₅ H Phenyl 177 0 0 S. 0 4-P H H 4 (CH ₅ 30 ₂ ) phenyl 178 0 S. 0 0 H H H Phenyl OD
CD 179 S. 0 C. 0 H H H Phenyl CO
OO 180 S. 0 0 0 H H H Phenyl o / os 101
102 0
S. S.
S. 0
S. 0
S. H
II H
H H
H methyl
3-methylphenyl u> 103 0 S. 0 0 H H CH ₅ OCH ₂ methyl 104 0 S. 0 0 H CH ₅ H Phenyl 105 0 0 S. 0 H π H 3-arainophenyl 186 S. 0 0 0 II II H 4-ethylphenyl 137 0 S. ο. 0 H H Cn ₅ methyl 160 0 0 S. 0 • H CHj II 4-methylphenyl 1C9 0 0 S. 0 H H CH ₅ methyl 190 0 S. S. 0 H Π CII ₅ Phenyl 191
I. 0 0 S. 0 H IT CiI ₅ Phenyl —J «

3 (CH ₅ SO ₅ ) phenyl

2-ethylhexyl

n-butyl

methyl

methyl

ethyl

ethyl

Iaopropyl

Isopropyl

Allyl

Phenyl

methyl

methyl

ethyl

4-chlorophenyl

methyl

4-chlorophonyl

ethyl

ethyl

HJO-1142

CN I

cn

No. A. B. D. E. X R ¹ R ² H R ³ Xthyl methylphenyl 2,3,5-trimethylphenyl Pp. ⁰ C 192 0 S. 0 0 H H CH, Phenyl 4-phenoxyphenyl methyl 2,3,6-trimethylphenyl 193 S. 0 S. S. 4-OC ₂ H _t - H H Xthyl 4-fluorophenyl methyl 2,4,6-trimethylphenyl 194 S. S. S. S. H H H methyl 4-methylphenyl methyl 2,4,6-trimethylphenyl 195 0 0 S. 0 H H CH ₃ methyl methyl methyl Xthyl 196 0 0 0 S. H H H Phenyl methyl methyl methyl 155 197 S. 0 0 0 6-Cl H H Phenyl Xthyl methyl 135-137 198 0 S. 0 0 H H H methyl 2,3,6-trimethylphenyl 199 0 S. 0 0 H H H methyl methyl 200 0 S. 0 0 H H CH, methyl methyl 149-151 ° 201 0 0 S. 0 H H H 2,3,5-tri- CO cn 202 0 S. 0 0 H H CH ₃ > ■ ». 203 0 S. 0 0 H H CH ₃ O 204 0 S. 0 0 H H CH ₃ CD 205 S. S. 0 0 H H CH ₃ 206 0 0 S. S. H H H 207 0 0 0 S. H , H

IO ON -J

KjI CO

2725U6

- 38 - 0.1 . 32 617

Known herbicidal active ingredients were used for comparison in the following experiments. Methyl N- (3- (N ¹ - (3'-methylphenylcarbamoyloxy) -phenyl) -carbamate and Ethy1-N- (N'-phenylcarbamoyloxy) phenyD-carbamate (DT-AS 15 67 151) are characterized by their, Although it has different effects against unwanted broad-leaved plants with a considerable degree of tolerance for sugar beet. Here, however, as is known, differences are to be recorded, since methyl N- (3- (N '- (3'-methylphenylcarbamoyloxy) -phenyD-carbamate) still has a 3-Isopropyl-2, 1,3-benzothiadiazinon (10-2,2-dioxide (DT-AS 15 ^ ^{2836) has a completely different field of application.} This compound is used to combat various broad-leaved weeds in soybeans, peanuts, cereals, maize and some vegetables. However, there are still ^{gaps in effectiveness. Methyl-N- (3-N 1} -methy1-N ¹ -phenyl-carbamoyloxy) -phenyl) - carbamate shows hardly any crop selectivity with herbicidal activity which is good for its class, which is why the compound was only recommended for sub-leaf spraying (post-directed), e.g. for soybeans (Arndt, F. and G. Boroschewsky: New Selective Herbicides - VIII International Plant Protection Congress, Reports and Information, Section III Chemical Control, Part I, Moskow 1975 , pp. 42- ^ 9). In this case, the young shoot parts and leaves of the crop plants should not be hit by the spray mixture, but undesirable plants that are among them should be.

Examples of the herbicidal effect of new sulfur-containing diurethanes

Numerous test results prove the good herbicidal properties of the new compounds. With regard to their herbicidal potency and their selectivity in cultivated plants, they are tested on the basis of the biological action in the following experiments
characterizes:

809850/0238

2725U6

- 39 - O ₀ line 52 617

Greenhouse trials

Plastic flower pots with a capacity of 300 cm were made with loamy sand filled and equipped with the test plants separated by species. This is mainly about the sowing of seeds or also about transplanting vegetatively propagated species. The active ingredients were suspended or in water as a distributing agent emulsified and by means of finely distributing nozzles for post-emergence application on the leaves of the test plants and those that are still bare Splashed earth surface. For leaf treatment, the plants were first grown up to in the test pots, depending on how they were grown a height of 3 to 10 cm and then treated it. The temperature requirements the test plants were accommodated in that they were placed in cooler or warmer sections of the greenhouse put up »The test period lasted 2 to 4 weeks. While During this time, the plants were tended and their reaction to the individual treatments was evaluated. The application rates of the Test substances count as kg / ha of active substance. For the evaluation a rating scale from 0 to 100 was used. 0 = no damage, 100 = death of the plants.

Result

The figures in the attached tables illustrate the effect of the active ingredients on foliar treatment after emergence of crop plants and unwanted plants (Tab. 2 to 7). It is noteworthy that the new compounds with respect to the herbicidal activity and the spectrum of activity tend towards the diurethanes used as comparison agents. the However, the focus in selectivity for crops is different. The example of soybeans and cereals is an excellent example of this demonstrate. In these cultures, levels of tolerance are achieved which are similar to the 3-isopropyl-2,1,3-benzothiadiazinon (4) -2,2-dioxide, which is known for this are equal (Tab. 5, 6). There are also a number of cultivated plants whose tolerance is just now stands out compared to the compounds according to the invention, while the comparative agents tested are unsuitable (Tab. 2, * », 5).

809850/0238 - io -

2725U6

- HO - 0.Z ₀ i) 2 617

As an application method, the introduction into the soil or the treatment of the soil surface can be considered, but treatment of emerged plants deserves preference. Special applications such as under-leaf spraying (post directed, lay-by) come into question «, Here the spray jet is directed in such a way that the leaves of emerged, sensitive cultivated plants if possible not be taken while the funds are growing on the underlying floor area or there unwanted plants enter.

In view of the versatility of the application methods, the compositions according to the invention or mixtures containing them can be used in addition to the useful plants listed in the tables, in a further large number of crops to eliminate undesirable Plant growth are used. The application concentrations can be from 0.1 to 15 kg / ha and more, depending on the object to be controlled.

The following crops are specifically mentioned:

809850/0238

Botanical name

German name

English name

Allium cepa Pineapple comosus

Asparagus officinalis Avena sativa Beta vulgaris spp. altissima Beta vulgaris spp. rapa Beta vulgaris spp. esculenta Brassica napus var. napus Brassica napus var. napobrassica Brassica napus var. rapa Brassica rapa var. silvestris Camellia sinensis Citrus limon Citrus maxima Citrus reticulata Citrus sinensis

Coffea arabica (Coffea canephora, Coffea liberica) Cucumis melo Cucumis sativus Cynodon dactylon Elaeis guineensis Pragaria vesca

Kitchen onion onions I. pineapple pineapple -Cr asparagus asparagus ' oats oats sugar beet sugarbeets Fodder beet fooder beets Red beet table beets, red beets Rapeseed rape Turnip White turnip turnips O Turnips Ls,
O Tea bush tea plants lemon lemon σ \ Grapefruit grapefruits 1-"
—0 tangerine Orange, orange orange trees coffee coffee plants melon melons cucumber cucumber Bermuda grass Bermuda grass in turfs and lawn ιό oil palm oil palms isj strawberry strawberries ^<J1

Botanical name

German name

English name

Gossypium hirsutum (Gossypium arboreum Gossypium herbaceum Gossypium vitifolium) Helianthus annuus Helianthus tuberosus Hevea brasiliensis Hordeum vulgar Humulus lupulus Ipomoea batatas Lactuca sativa Lens culinaris Linum usitatissimum Lycopersicon lycopersicum Malus spp. Manihot esculenta Medicago sativa Mentha piperita Musa spp.

Nicotiana tabacum (N. rustica) Olea europaea Oryza sativa Panicum miliaceum

cotton

Sunflower

Jerusalem artichoke

Paracaut s chukb aum

barley

hop

Sweet potatoes

Lettuce

lens

Fiber flax

tomato

Apple

manioc

alfalfa

peppermint

Fruit and plantain

tobacco

Olive tree

rice

Millet

cotton

sunflowers

rubber plants barley

sweet potato lettuce lentils flax

tomato apple trees cassava alfalfa (lucerne) peppermint

banana plants tabacco

olive trees rice

O 0 Cx ro -J ro ro σ
t— » cn —J

CD

Botanical name

German name

English name

Phaseolus lunatus Phaseolus mungo Phaseolus vulgaris

Pennisetum glaucum

Petroselinum crispum spp. tuberosum

Picea abies Abies alba Pinus spp.

Pisum sativum Prunus avium Prunus domestica Prunus persica Pyrus communis Ribes sylvestre Ribes uvxa-crispa Ricinus communis Saccharum officinarum Secale cereale Sesamum indieum Solanum tuberosum Sorghum bicolor (see vulgar) Sorghum nochna

Moon bean

Urd Bean

French beans

Pearl or cattail millet

Root parsley

Red spruce

Silver fir

jaw

Garden pea

sweet cherry

plum

peach

pear

Red currant

Gooseberry

Castor oil

Sugar cane

rye

sesame

potato

Carrot millet

Millet

limabeans
mung beans

snap beans, green beans, dry beans

parsley

Norway spruce
fire

pine trees
English peas
cherry trees
plum trees
peach trees
pear trees
red currants

sugar cane

Sesami

Irish potatoes

grain sorghum

ho

-j

KJ

cn

cn

Botanical name German name English name

Spinacia oleracea Spinach Spinach

Theobroma cacao cocoa tree cacao plants

Trifolium pratense red clover red clover

Vaccinium corymbosum cultivated bilberry blueberry

Vaccinium vitis-idaea Blackberry cranberry

Vicia faba horse beans tick beans

Vigna sinensis (V. unguiculata) cow beans

Vitis vinifera grapevine grapes ο

CO OO cn O "> v O K> Ca »

J = - I

cn

2725U6

To further broaden the spectrum of activity of the new individual substances, to achieve synergistic effects or to improve the residual effect on the ground, the Mix new compounds with one another or numerous other herbicidal or growth-regulating compounds as mixture and Use combination partners. Depending on the area of application and control plan, the following compounds are available or chemically similar derivatives as a partner to:

809850/0238

O.Z,} 2 617

2725U6

CHF ₂ CF ₂ O

-NHCH

-NH-CH.

NH

H
H
H
H

R '

H and salts Cl and salts F and salts CH, and salts

H ϊ

809850/0238

H N

so ₂

and salts

U.Z. 32 017

2725H6.

R "

2 R '

N.

NO,

R-

CF.

cf!

η. C ₃ H ₇ η. C ₃ H ₇ η. C ₃ H ₇ CH ₂ -CH ₂ Cl η. C ₃ H ₇ η. C ₃ H ₇

CH.

CH.

Cl Cl

LC ₃ H ₇

'CH

-N = C.

CH,
-Ch-C-NH-C ₀ H ₁ .

I! <- J

'7

809850/0238

- 148 -

^ NCOR ³

o.z. : -2 617

2725U6

Cl

R 'H R-

CH ₂ -C = C-CH ₂ Cl

Cl

CH -CH-CSCH

Cl

Cl

CH.

CH.

CH

CF-

NH-CO tt

NH-C-OCH,

It J

Il

R ²

CH, CH ₇

809850/0238

FT R ¹ ^ -N-CO

Il

NH-C-O-R-

It

2725U6

R-

CH.

CH

N-C-S-R-O

R-

1-C ₃ H ₇ XC ₃ H ₇ CH ₂ -CCl = ChCl nC H ₇ nC H ₇ C ₀ H. η.C ₃ H ₇ η.C ₃ H ₇ η.C ₇ H_
3 7 sec. C ₄ H ₉ sec. C ₄ H ₉ C ₂ H ₅ C ₂ H ₅ C ₂ H ₅ C ₂ H ₅ C ₂ H ₅ ^C 2 ^H 5 C ₂ H

809850/0238

.C, H "

2 \ _

Ql-CSC ₂ H ₁ 0

.ζ. 52 617

2725Η6

R-C-C-O-R

ι η

Y 0

CH _:
Cl '

Cl
Cl
Cl

Cl Cl Cl Na Na Na

Cl

^ Vc-NO-η
0

H and salts

Cl

Cl NH ₁

ti

or *

Cl

CH-C ₂ H ₅

809850/0238 - 51 -

-11

R-C-C-O-R

Y

O.Z. j> 2 617

2725U6

f> C - N- o ii

Cl

CH.

Cl

^ -χ ⁰ C ^

Oh

> 0-

Cl

CH,

F ₃ C <> 0

\ o-CH-C-O-Na

Il

O-CH-CO-Na »ι O

809850/0238

0.2.

6: 7

R NH

N

2725U6

Cl Cl Cl Cl Cl Cl

Cl

Cl OCH, sch! sh 'sh'

C ₂ H ₅

-C (CH) ₂ CN -CH-CH-OCH.

CH -CH-C = CH

CH

-C (CH ₃ ) ₂ -CN

C ₂ H ₅ C ₂ H ₅ tert.

H F

CH

CH ₃

- 53 -

809850/0238

CZ. 32 617

N-C-R-O

R-

CH -CH-C2CH

CH-

CH -CH-CH ₂ -OCH

CH,

-CH ₂ -CH ₂ -OCH CH ₂ Cl

C ₂ H ₅

-CH ₂ -OCH

C ₂ H ₅

C ₂ H ₅

-CH ₀ -C-OC ₀ H, _{-CH 0} Cl

η CH ₂ Cl

-CH.

COOH

809860/0238

2725U6

N-C-R-

Il

OZ $ 2,617

2725H6

Cl

Cl
Cl

C ₂ H ₅

^H 3 ^C ) =

F ₃ CSO ₂ NH

.CH.

F ₃ CSO ₂ HN

-C (CH ₃ J ₂ -C ₃ H ₇

CH ₃

HCsC-C- H CH,

Cl

Cl

- 55 -

809850/0238

. Line 52 617

2725U6

Br

Br H and salts
H and salts
-C- (CH -) .- Ci

ti CO

⁰ 2 ^N "v3" ° ~ ^{N = CH}

and salts

X = NO,

CN

Cl Cl Cl NO, H H Cl

Cl Cl Cl CF Cl

Cl

Cl

Cl

Cl

Cl

COOH

COOCH

OC ₂ H ₅

OCH,

809850/0238 - 56 -

R ² R

NCN
R ¹ OR

O. Z. 32 Γ.17

2725U6

H ₃ CO

Cl '

R-

CH-

CH.

CH. CH.

tertH _n C, .HN-CO

CH.

CH.

CH. CH.

CH-CH

CH.

CH- -CH-CaCH CH.

3 ^C W

CH-

CH. OCH.

CH.

CH. OCH.

- 57 -

809850/0238

N-C-M

R ^A O R-

OZ J> 2 6-7

2725U6

ClCF ₂ S ₁ . _
Cl

CH. CH-

CH-

CH-

CH.

CH.

CH.

CH.

CH.

CH OCH.

CH, OCH.

OCK.

CH.

CH.

-NH-C-N;

Il

CH

CH

NHN-C
T °

-C-NH-CH ₂ -CH

CH

CH.

8098S0 / 0238 - 58 -

FC 3

"0

u.z. 32 617

2725H6

^N V ^ R ²

tert.CjjH

NH

NS

CH

-N = CH-CH ^y SCH

CH

.ιΑνΛ

H ° R ^ R ² sec. C ₄ H ₉ Br tert.C ₄ H _g Cl 9 Cl CH ₂ -CH ₂ -CH ₂ -

809850/0238

- 59 -

O. Z. 32,617

2725H6

CH,

C-CH,

Il J

H ₃ CS- Ö

f ^H

CH,

OC ₂ H ₅

Ο, Ν-Κ-

0R ^J

-C-CH,

Il -5

-C-CH,

Il J

O
-C-CH,

Il 5

O
H
H
H
H

tert.

tert.

CH

tert.C ₁₄ Hg tert.C ,, H _n

H
CH,

H salts and esters H salts and esters H salts and esters CH salts and esters

- 60 -

• 09850/0231

o.z. 32 r.i7

Cl

V-HN-CO 0

-J-HN-CO

If

R ^x -N 0

⁰ CH, ⁰

2725U6

NH-

Cl *** COOH

and salts, esters

H CH ₃ OSO ₃ Br CH ₃ OSO ₃ CH,
CH ₃ CH OSO
CF ₃ SO ₃

- 61 -

809850/0238

OZ J2

C-NH-2725U6

^N O? 3 ^H 7

H ₃ C
H ₃ C

C - NH - O - CH ₂ - CH

η V:

H ₃ C

H, CT "0
^J COOCH,

OCH ₂ - CH = CH ₂ and Na salt

'3 3

^ CH ₃

CH

CH

- CH., -

C- N η

Il \ /

⁰ ΓΗ '

CH

+ 2

2 cl

^ = N N

+ Br

COOCH. ^j

Cl
Cl

Cl ι

COOCH.

- 62 -

809850/0238

O. L. 32

Cl

CN

Cl 2725U6

Cl

CSNK,

Cl

COOH

and salts, esters

R-

Cl

Cl

Cl

Cl H Cl

Cl

OCH.

Cl

OCH.

R- ^ O-CH-C-OR ³ η 0

Cl

Cl

CH.

CH.

H salts, esters, amides

H salts, esters, amides

H salts, esters, amides

809850/0238

O.Z. 32 617

R ¹ -O-CH-C-OR ³

ti

2725U6

R-

CK.

CH. H salts, esters, amides

Cl

H salts, esters, amides

Cl

CH, H salts, esters, amides

CH_-0C-H _c 0
NC-CH.-OS-CH ^

ti <- η J

0 0

N-C-CH ^ -O-S-NHCH.

Il <- Il

0

and salts, esters

and salts, esters

HO COOH 809850/0238

- 61 »-

O.Z. 32 6i7

H-N N

NH,

2725U6

P-CH ₀ -NH-Ch ₀ -C-OH and salts

HO O

N-

Cl

Cl

J \ • J

COOH salts and esters

H, C O

As-ONa

R ¹
OH
CH.

809850/0238

- 65 - CZ. 32 617

HC-CO-NH 272 5 U

HC-CO-NH

HO-P-CH ₀ -CH ₀ -Cl
OH

0-CH ₂ -CH ₂ -CH ₂ -COOH and salts and esters

0-CH ₂ -CH ₂ -CH ₂ -COOH and salts and esters

CH,

F ₂ CHCF ₂ O

NH-CN
dd
O

NO ₀

^ - CH
NH-CH

-C ₂ H ₅

It is also possible to apply the new compounds according to the invention alone or in combination with other herbicides, also mixed with other crop protection agents. Think of means for combating pests or phytopathogenic fungi or bacteria. The miscibility with mineral salt solutions , which are used to remedy nutritional or trace element deficiencies, is also of interest.

To activate the herbicidal effect, wetting agents and adhesives as well as non-phytotoxic oils can be added.

The application takes place e.g. in the form of directly sprayable solutions, Powders, suspensions or dispersions, emulsions, oil dispersions, Pastes, dusts, grit, granulates

- 66 809850/0238

- 66 - O.Z. 32 617

2725H6

by spraying, atomizing, dusting, scattering or pouring, the application forms depend entirely on the intended use; In any case, they should have the finest possible distribution
ensure the active ingredients according to the invention =

Medium-sized mineral oil fractions are used for the production of directly sprayable solutions, emulsions, pastes and oil dispersions to a high boiling point, such as kerosene or diesel oil, also coal tar oils, etc., as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, for example methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, Cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., strongly polar solvents, e.g. Dimethylformamide, Dimethyl sulfoxide, N-methylpyrrolidone, water, etc. into consideration.

Aqueous application forms can be obtained from emulsion concentrates, pastes or wettable powders (wettable powders), oil dispersions by addition be prepared by water. For the production of emulsions, pastes or oil dispersions, the substances can be used as such or dissolved in an oil or solvent, using wetting, adhesive, dispersing or emulsifiers are homogenized in water. However, wetting, adhesive, dispersing agents can also be used from active substances. or emulsifying agents and possibly concentrates consisting of solvents or oil are produced which are suitable for dilution with water are.

The following surface-active substances should be mentioned:

Alkali, alkaline earth, ammonium salts of lignosulfonic acid, naphthalene sulphonic acid, phenolsulphonic acids, alkylarylsulphonates, alkylsulphates, alkylsulphonates, alkali and alkaline earth salts of dibutylnaphthalenesulphonic acid, Lauryl ether sulfate, fatty alcohol sulfates, fatty acid alkali and alkaline earth salts, salts of sulfated hexadecanols, Heptadecanols, octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated Naphthalene and naphthalene derivatives with formaldehyde, condensate

809850/0238

- 67 - O.Z. 22 61?

2725U6

products of naphthalene or naphthalene sulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, Tributylphenyl glycol ether alcohols, isotridecyl alcohol, Fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, Lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulphite waste liquors and methyl cellulose.

Powder, grit and dust can be mixed or mixed together Milling the active substances with a solid carrier material »

Granules, for example _o coated, impregnated and homogeneous granules, can be prepared by binding the active compounds to be prepared to solid carriers "Solid carriers are mineral earths such as silica gel, silicic acid, silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, talc , Bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as grain flours, tree bark -, wood and nut shell flour, cellulose powder and other solid carriers.

The formulations contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90 percent by weight.

Example * J

90 parts by weight of compound 2 are mixed with 10 parts by weight of N-methyl-fluoropyrrolidone and a solution which is suitable for use is obtained in the form of the smallest drops is suitable.

- 68 809850/0238

- 68 - C.E. 32 617

2725Ί46

Example 5

20 parts by weight of compound 8 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide with 1 mol of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of ¹ JO mol Ethylene oxide consists of 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02 percent by weight of the active ingredient.

Example 6

20 parts by weight of compound 13 are dissolved in a mixture that of 40 parts by weight of cyclohexanone, 30 parts by weight Isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of the adduct consists of 40 moles of ethylene oxide in 1 mole of castor oil. By pouring the solution into and finely distributing it 100,000 parts by weight of water give an aqueous dispersion which contains 0.02 percent by weight of the active ingredient.

Example 7

20 parts by weight of compound 23 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction boiling from 210 ° to 280 ° C. and 10 parts by weight of the adduct of ¹ JO mole of ethylene oxide with 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02 percent by weight of the active ingredient.

Example 8

20 parts by weight of the active ingredient 7 with 3 parts by weight of the sodium salt of diisobutylnaphthalene-OU-sulfonic acid, 17 parts

- 69 -

809850/0238

- 69 - ο Ζ. 32 617

parts by weight of the sodium salt of a lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel mixed well and ground in a hammer mill. Obtained by finely distributing the mixture in 20,000 parts by weight of water a spray mixture containing 0.1 percent by weight of the active ingredient.

Example 9

3 parts by weight of compound 46 is 97 parts by weight finely divided kaolin intimately mixed. In this way, a dust containing 3 percent by weight of the active ingredient is obtained.

Example 10

30 parts by weight of compound 2 are mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil, which is applied to the surface of this silica gel was sprayed, intimately mixed. In this way, a preparation of the active ingredient with good adhesion is obtained.

Example 11

40 parts by weight of the active ingredient 7 are mixed with 10 parts of the sodium salt a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water are intimately mixed. You get a stable aqueous dispersion. By diluting with 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.04 percent by weight of active ingredient.

Example 12

20 parts of active ingredient 8 are mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenol sulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil intimately mixed. A stable oily dispersion is obtained.

- 70 -

809850/0238

Table 1 - List of test plants

Botanical name

Abbreviation in tables

German name

English name

O CO OO

Amaranthus retroflexus

Apium graveolens Arachis hypogaea Carthamus tinctorius Centaurea cyanus Daucus carota Datura stramonium Desmodium tortuosum

Euphorbia helioscopia Euphorbia geniculata Glycine max Lamium spp.

Matricaria spp. Mercurialis annua

Sesbania exaltata Setaria spp. Sinapis alba Stellaria media Solanum nigrum Triticum aestivum Xanthium pensylvanicum Zea mays

Amar. ret.

Apium gray. Arach. hyp. Carth. tinct. Cent. cyan. Daucus carot. Datura stram. Desmod. tort.

Euphorb "
heliosCo
Euphorb "genic.

G Iy c c, max Lamium spp.

Matric. spp »Mercury ₀ annua

Sesb. exalt. Setaria spp. Sinap »alba Stell, media Solan, nigr. Tritic. aest. Xanth. pens-zea mays

curved back

Foxtail

celery

Peanut

Safflower

Cornflower

common thorn apple

Sun wolf milk

south american

Milkweed chart

Dead nettle species

Chamomile species

annual ringelkraut

Turi tree

Millet species

white mustard

Chickweed

black nightshade

wheat

Pointed burdock

-j redroot pigweed

celery

peanuts (groundnuts)

safflower

cornflower

carrots

Jimsonweed

Florida beggarweed

wait weed

South American member of the spurge family soybeans

dead-nettle

chamomile
annual mercury

hemp sesbania (coffeeweed)

foxtail sppo

white mustard

chickweed

black nightshade

wheat

common cocklebur ^rs - ⁾

Indian corn "^

ro

cn

CD

Table 2 - Selective effects on vegetable crops when used post-emergence in the greenhouse

Effective

material-

No.

kg / ha of test plants and % damage

Apium Daucus Euphorbia Datura Lamium spp » graVo carota heliosc. stram.

O
CO
OO
Oil

1.0 2.0 4.0

10 20

100 100

100 100

100 100

1.0
2.0
4.0

0 0 0

75 80

100 90

13th

53

100

1.0
2.0
4.0

100 100 100

0 10

100 100

30 85

known

1.0
2.0
4.0

100 100 100

100 100

100 100

100 100

NHCOOCH.

known

= no damage

= total damage to Setaria spp.

Table 3 - Selective herbicidal activity of new compounds in cereals and maize Machauflaufanwendunp; in the greenhouse

Active ingredient no. Kg / ha test plants and % damage

Tritic. Zea cents. Datura Lamium Matric. Mercury. SinaD. Place aest. mays cyan, stram. purp. spp. annua alba media

90

98

96

NH-C-0

known

0.5 1.0 2.0

0 0 0

15th
25th

90

100
100
100

100
100
100

100
100
100

0.5 1.0 2.0

0 0 0 10
20th
30th

100

100

100
100
100

50
50
50

2.0 50

100

0.5 1.0 2.0

10 30
30th
HO

85

90

100

100
100
100

100
100
100

63
63
63

75
75
80

50
50
95

100

17th
67
77

92
92

95

90
90
95

90

95
97
99

0 = no damage

100 = total damage

Vyy I

Table Ί - Effect of New Compounds in Selective Weed Elimination in oilseeds for post-emergence applications; in greenhouse

V / irkstoff- Kr. Kg / ha test plants and % Schadip; us Arach. Carth. Olyc. Amar. Desired. Euphorb. Sesb. Solan. Xanth. hyp. ink. max ret. tort. genius. exal. nif-r. pens.

98

105

107

7 11

88 90

QP

98

98

100

57 57 67

0 0

0 15 30

100 100 100

100 100 100

90 95 95

0 0

100 100 100

10

30th

100

100 100 100

0 0 0

10

100 100 100

10 10 60

50 100 100

100

20th

90

97

100

100 100 100

100 100 100

100 100 100

100

50

60 60

50

70

100

100 100 100

50 50

60

100 100 100

100 100 100

'! 0 10

/ to

30 30

30th

-J -C-

₇ NHCOOCH,

^J known

10 10

30th 50 100 100 100 40 30th O he; 30th 60 100 100 100 60 100 CI
• 35 60 100 100 ICO 60 100 \ ■ Ό-
ιυ

ι C = partial damage, 100 = total damage

O (D CD

Table 5 - Selective weed control with new compounds in cereals Post-emergence application in the greenhouse

Active kg / ha test plants and % damage

fabric- Triticum Mercurialis Sinapis Stellaria

No. aestivum annua alba media

9 1.0 - 100 100 100 2.0 0 100 100 100 Ik 1.0 - - 100 100 2.0 0 - 100 100 17th 1.0 - 100 100 100 2.0 0 100 100 100 37 1.0 - 0 * 100 100 2.0 0 0 100 100 35 1.0 - 0 100 100 2.0 '0 0 100 100 39 1.0 - 0 100 100 2.0 0 80 100 100 1.0 - 10 70 100 2.0 0 80 90 100

Table 5 - continued

Active ingredient

kg / ha of test plants and % damage

Triticum Mercurialis Sinapis Stellaria aestivum annua alba media

1.0 2.0

100
100

W /

2.0

100

known NC-OC ₂ H ₅

CH,

0
known

1.0 2.0

= J 0

NH-C-OCH.

1.0 2.0

38
55

known

100 100

100

100

100

100 100

100 100

100 100

= no damage

= total damage

-j
he"

Table 6 - Post-emergence control of broad-leaved weeds in peanuts in greenhouse

OO O CO 00

O ro u> αο

V.'irk-

material-

No.

C /

₃ ν

kg / ha of test plants and d % damage

Arachys Amaranthus Desmodiurr, Sesbania Xanthium
hypog. retro. tort. exalt. pensyl.

90 0.5 5 100 100 100 50 2.0 20th 100 100 100 50 103 0.5 0 100 90 95 50 2.0 0 100 90 95 50 9 0.5 10 100 90 95 80 2.0 10 100 90 95 90 Ik 0.5 0 20th 20th PO 0 2.0 0 50 90 95 20th 17th 0.5 0 10 90 85 0 2.0 0 30th 90 85 25th

0
10

known

0
0

0 = little damage

100 = total damage

0
20th

60
100

O NHCOOCH, 0.5 0 0 100 100 0 NJ <-> 2.0 0 0 100 100 20th NJ
cn / -
CH ₃ known

Table 7 - Effect of new compounds on post-emergence application in the greenhouse

or

; Bodies of the molecule

f J _ (·> _ C _ Γ U

η ^fabric -

o No.

■ β ο

Substituents

kg / ha

0 r no. Damage, g

CH.

2.0

2.0

2.3

Test plants and % damage

Cer.taurea. Lamiun Sinapis Stellaria cy-nu3 3PP. alba media

100 = plants dead

100

100

100

100

■ üu

100

: on

100

"00

100

ICO

100

K)

K)

cn

cn

Claims (1)

Claims (\ ./ Oi urethane of the general formula R ² E ι Ii τ ι η U in which Z denotes the remainder -N-C-B-R ^ and Y denotes the remainder -N - C-D-R- 1 2 tet, where Z is always different from Y and R and R are each independently hydrogen, alkyl, alkoxyalkyl, alkoxycarbonylalkyl, Haloalkyl, optionally by alkyl or 3 k halogen substituted benzyl, R and R each independently alkyl unsubstituted from one another or alkyl substituted by halogen or alkoxy or substituted or unsubstituted aryl; Alkenyl optionally substituted by halogen, alkynyl optionally substituted by halogen or alkoxy; cycloalkyl optionally substituted by alkyl; Bicycloalkyl; Tricycloalkyl; a phenyl ring with a fused ring system, phenyl, mono- or polysubstituted phenyl, with the substituents alkyl, haloalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkoxy, cycloalkyl, halogen, alkoxy, haloalkoxy, nitro, amino, aryl, aryloxy, thiocyanato, cyano, NH- COR ⁵ , NHCOOR ⁵ , NHCONR ⁵ R ⁶ , ^ -R COOR ⁵ , N ,, CONR ⁵ R ⁶ , SR ⁵ , SO ₅ R ⁵ , OSO ₅ R ⁵ , COR ⁵ , SO ₅ NR ⁵ R ⁶ , where R and R are each independently hydrogen or an optionally mono- or polysubstituted aryl radical or one of the two substituents has the meanings mentioned for R and X is hydrogen, alkyl, halo _{l6o / 77} 809850/0238 _ ₂ _ ORIGINAL! NSPECTED OZ 617 2725U6 Genalkyl, alkoxy, halogen, nitro or amino, η the numbers 1 - h and A, B, D, E each independently represent oxygen or sulfur, whereby not all A, B, D, E radicals are simultaneously oxygen and at least one of these radicals always means sulfur. 2. Herbicide containing a diurethane ^r ? ^r ^ ro claim 1 " H N-C-S-CH. 0 " ¹¹ / Γ ~ \ CH, NCS-CH ₃ 0 " 0-C-N CH, TT ^ η Ii N-C-S-CH- N-C-S-CH- O-C-N N-C-S-CH- 8. Cl-C ⁷ Vo-CN ^{V / x} 809850/0238 -WHERE N-C-S-CH-o_z. 32 617 2725H6 ft o-C-N CH- NCSC ₂ H ₅ CH ν Η ti
NCS-CH, f \ ., H /:
^V V OCNT V / NCSC ₂ -H NCSC ₂ H CH- CH ₃ ^Λ NCS-CH ₃ CH N-C-S-CH O ^CH 3 \ / -Λ? " CH ₃ - C- / H Vo-CN CH '0 N-C-S-CH ti 8098 5 0/0238 H CH, -S-C-N J It NCS-CH, »t j N-C-S-CH- O.Z. ^ 2 2725H6 HC = C-CH ₅ -OCN £ tt 0 N-C-S-CH, Il J N-C-S-CH, ti J CH ^ -CH-, 7 N-C-S-CH, Il J N-C-S-CH, Il J N-C-S-CH, It ■> 80 9 ° 8 50/0238 0.Z. 32 2725U6 N-C-S-CH, I! J 809850/0238