IE46905B1 - Sulfurous diurethanes - 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 present invention relates to new and valuable sulfurous diurethanes having an excellent herbicidal action, herbicides containing these compounds, and processes for controlling the growth of unwanted plants with these compounds.

It is known to use methyl-N-(3-(N'-(3'-methylphenyl)-carbaraoyloxy)-phenyl)-carbaraate, ethy1-N-(Ν'-phenylcarbamoy1oxy)-pheny1-carbamate,.methy1-N-(3-N’-methy1-N *-phenylcarb amoy1oxy)-phenyl-carbamate (German Printed Application DAS 1,567,151) and 3-isopropyl-2,l,3-t>en20thiadiazInone-(4)-2,2-dioxide (German Printed Application DAS 1,542,836) as herbicides.

We have now found that the new diurethanes of the formula I H Tt where Z denotes the radical -N - C-B-RJ and Y denotes the R2 E radical -N - C-D-R , 2 always being different from Y and R1 and 2 R being identical or different and each denoting hydrogen, alkvl - 2 46905 of 1 to 4 carbon atoms (e.g. methyl, ethyl, isopropyl), alkoxyalkyl of 2 to 4 carbon atoms (e.g. methoxymethyl, 2-methoxyethyl), alkoxycarbonylalkyl of 3 to 5 carbon atoms (e.g. methoxycarbonylmethyl), haloalkyl of 1 to 4 carbon atoms (e.g. chloro5 methyl), unsubstituted benzyl, or benzyl substituted by alkyl of 1 to 4 carbon atoms or halogen, R3 and R4 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 or 2 carbon atoms, halogen-substituted phenyl or unsubstituted phenyl (e.g. methyl, ethyl, 2-chloroethyl, 2-methoxyethyl, benzyl, isopropyl, n-propyl, 4-chlorobenzyl, n-butyl, sec-rbutyl, tert-butyl, isobutyl, 2,4-dichlorobenzyl, 2-phenylethyl), alkenyl of 2 to 4 carbon atoms (e.g. allyl, buten-(l)-y1-(3)), alkynyl of 3 or 4 carbon atoms (e.g. propargyl, butyn-(l)-yl-(3)), unsubstituted or C^-C^-alkylsubstituted cycloalkyl of 5 to 8 carbon atoms (e.g. cyclopentyl, cyclohexyl, 3-methylcyclohexyl, 2,6-dimethylcyclohexyl, cycloheptyl, 4-tert-butylcyclohexyl, cyclooctyl, 3,5-dimethylcyclohexyl), bicycloalkyl of 7 or 8 carbon atoms (e.g. norbornyl) , tricycloalkyl of 10 to 15 c'arbon atoms (e.g. tricyclo-(4,3.12*^. 01’®)-decyl), phenyl with a fused ring system (e.g. naphthyl, indyl), phenyl or mono- or polysubstituted phenyl with the substituents alkyl of 1 to 4 carbon atoms, halogen or alkoxy 46395 (e.g. phenyl, 4-fluorophenyl, 2-methoxyphenyl, 3-methylphenyl, 2- fluorophenyl, 3-methyl-5-isopropyIphenyl, 3-ethyIphenyl, 3chlorophenyl, 2,4,6-trimethyIphenyl, 3-fluorophenyl, 3-chloro4-fluorophenyl, 3,4-dimethylphenyl, 4-methylphenyl, 3,4-di5 fluorophenyl, 3-chloro-4-methyIphenyl, 3-bromophenyl, 4-iodophenyl, 4-chlorophenyl, 2-chlorophenyl, 2-chloro-4-fluorophenyl, 3- isopropylphenyl, 4-ethyIphenyl, 4-ethoxyphenyl, 2-methylphenyl, 3- methoxyphenyl, 2,6-dimethylphenyl, 2,4-dichlorophenyl, 3-methyl 4- chlorophenyl, 2,4-dibromophenyl, 4-methoxyphenyl, 2,3,6-tri10 methylphenyl, 3-tert.-butyIphenyl, 3,5-dichlorophenyl, 2-methyl6-ethyIphenyl, 2,3-dimethyIphenyl, 2-methyl~4-chlorophenyl, 2o4,5-trichlorophenyl, 2,3,6-trichlorophenyl), and A, B, D and E being identical or .different and each denoting oxygen or at least sulfur (with the proviso that/one of the radicals-always-denotes sulfur), X denotes hydrogen, alkyl of 1 to 4 carbon atoms (e.g. methyl), haloalkyl of 1 to 3 carbon atoms (e.g. trifluoromethyl), alkoxy of 1 or 2 carbon atoms (e.g. methoxy), halogen (fluoro, chloro, bromo or iodo), nitro or amino, and n denotes 1,2,3 or 4, have a good herbicidal action on numerous important unwanted plants and are also excellently tolerated by many crop plants. These effects are better than those achieved by prior art active ingredients. - 4 4 6 a 0 s The new compounds may for instance be prepared by the follow12 3 1) ing methods, the radicals A,B,D,E,R ,R ,R ,R and X and n having the above meanings. Where mention is made in the following of urethanes and chloroformic acid esters, these two terms are also intended to cover thiono-, thio- and dithiourethanes and chloroformic acid thionoesters, chloroformic acid thioesters and chloroformic acid dithioesters. 43905 The interrelationships between the starting compounds will be readily apparent from this reaction scheme. It will also be clear that the one or the other route may be more advantageous, depending on the nature of the substituents A,B,D,E,R1,R2,R^,R2t and X, and on the availability of the reactants. The reaction of F to H is preferred.

Starting from prior art m-nitranilines (A), m-nitropheny1iso(thio)cyanates (B) may be produced (W. Siefken, J. Liebigs Annalen der Chemie, 562, 75 et sea., 1949), which in turn smoothly react with the components R^-BH to give nitro(thio)urethanes (C) (S.Petersen,· Methoden der Organ. Chemie, VIII, 131, Georg Thieme-Verlag, Stuttgart, 4th edition, 1952), which are, however, also accessible direct from m-nitranilines (A) with chloroformic acid esters (R^-B-CA-C1) (German Laid-Open Appli)θ cation DOS 1,643,763), or with carbon disulfide or carbonyl sulfide, base and alkylating agent (Methoden der Organ. Chemie, IX, 831 et seq., Georg Thieme-Verlag, Stuttgart, 4th edition, 1955). Subsequent reduction gives the amino compounds (F; R =H) (S. Schroter, Methoden der Organ. Chemie, XI/1, 360 et seq., Georg Thieme-Verlag, Stuttgart, 4th edition, 1957), which are reacted direct, or after conversion into the product monosubο stituted on the amino nitrogen (P; R =H) (Methoden der Organ. Chemie, Xl/1, 24 et seq., Georg Thieme-Verlag, Stuttgart, 4th edition, 1957), with chloroformic acid esters (R^D-CE-Cl) (German Laid-Open Application DOS 1,643,763) or with carbon disulfide or carbonyl sulfide, base and alkylating agent (Methoden der Organ.

Chemie, IX, 831 et seq., Georg Thieme-Verlag Stuttgart, 4th edition, 1955) to give the desired diurethanes (H). The aminourethanes (F) may also be obtained by reaction of m-phenylenediamines (D) with ehloroformic acid esters. Λ further synthesis route is the reaction of aryl-l,3-diBo(thio)cyanates (£) with only one mole of component R^-BH; this reaction gives the iso(thio)cyanatourethanes (G) (J.A. Parker, J.J. Thomas and C.L. Zeise, J. Org. Chem., 22, 594-596, 1957), which are also obtainable by (thio)phosgenation of aminourethanes (F) (German Laid-Open Application DOS 1,914,270, p. 5, Ex. 8). Subsequent 4 reaction with the component R DH gives the desired end products. 4 It should be noted that the -CABR and -CEDR groupings may be in any order.

The preferred synthesis steps are described in more detail below: a) The 3-nitrophenyliso(thio)cyanates (B) are reacted with or without a catalyst conventionally used for iso(thio)cyanate reactions, e.g., tertiary amines (triethylamine, 1,4-diazabicyclo-(2,2,2)-octane), nitrogenous heterocycles (pyridine, 1,2-dimethylimidazole) or organic tin compounds (dibutyl tin diacetate, dimethyl tin dichloride) if desired in a solvent inert under the reaction conditions, e.g., hydrocarbons (ligroin,gasoline, toluene, pentane, cyclohexane), halohydrocarbons (methylene chloride, chloroform, dichloroethane, chlorobenzene, 0-, m- and p-dichlorobenzene), nitrohydrocarbons (nitrobenzene, nitromethane), nitriles (acetonitrile, butyronitrile, benzonitrile), ethers (diethyl ether, tetrahydrofuran, dioxane), esters - 7 46905 (ethyl acetate, methyl propionate), ketones (acetone, methyl ethyl ketone) and amides (dimethylformamide, formamide) (German Laid-Open Application DOS 1,568,138) at from 0° to 150°C, preferably from 40° to 100°C. b) 3-nitranilines (A) are reacted with chlorcforraic acid esters in a suitable solvent, e.g. water, alcohols (methanol, ethanol, isopropanol), or as under a), with the aid of a conventional acid binder, e.g., alkali metal hydroxides, carbonates, bi carbonates, alkaline earth metal oxides, hydroxides, carbonates, bicarbonates and tertiary organic bases (e.g., triethylamine, pyridine, N,N-dimethylaniline, Ν,Ν-dimethylcyclohexylamine, quinoline, trihutylamine), at from -20° to +150°c, preferably from +20° to 80°C. ' c) Nitrourethanes (C) may be reduced by a prior art process, e.g., catalytic hydrogenation, a metal-acid combination such as iron-acid, or a metal-alcohol combination such as zinc dust-aqueous alcohol or iron-aqueous alcohol. d) For the reaction of m-phenylenediamines (D), conditions comparable to those for b) apply; it may be advantageous to employ an excess of m-phenylenediamine. e) Aminourethanes (F) are reacted with chloroformic acid esters analogously to b); the solution obtained for instance by catalytic hydrogenation of nitrourethanes (C) may also be used direct without further purification.

The following examples are intended to illustrate the production of the new diurethanes and their precursors. - 8 46905 I. Nitrourethanes Example A While stirring and at 20° to 25°C, a mixture of 85 parts by weight of 3-nitrophenyl isocyanate and 43 parts by weight of absolute toluene was metered intc a solution of 64.3 parts by weight of 4-chlorophenol and 3 parts by weight of triethylamine in 430 parts by weight of absolute toluene.

To complete the reaction, the mixture was stirred for 1 hour at room temperature. After cooling to 0°C, the reaction product was suction filtered; m.p,: 137°-138°C.

The compound has the following structural formula: ΟΙΝΟ.

Example B parts by weight of sodium bicarbonate is added to 138 parts by weight of m-nitraniline in 500 parts by weight of tetrahydrofuran (THF). At room temperature and while stirring, 120 parts by weight of chloroformic acid thiomethyl ester is dripped in, the mixture is stirred for 16 hours at room temperature and then filtered, the solvent is distilled off in a rotary eva20 porator, and the oil which is obtained is stirred into toluene. The crystals which separate out are suction filtered and dried; m.p.: 137°-138°C.

The compound has the following structural formula: Example C 17.4 parts by weight of sodium bicarbonate is added to 26 parts by weight of 3-nitro-N-methylaniline in 320 parts by’weight of ethyl acetate .· While stirring, 33 parts by weight of chloro5 formic acid m-tolyl ester is slowly added, the mixture is stirred for 20 hours at room temperature and filtered, the solvent is removed in vacuo, and the residue is recrystallized from toluene/cyclohexane.

The compound has the following structural formula: The following nitrourethanes (C) may be prepared analogously: A Β X R1 R5 m.p.°C S 0 Η Η methyl 0 0 Η Η 4-fluorophenyl 166-167 0 0 Η - Η 2,4-dichlorophenyl 150-151 0 0 Η Η methyl 153-155 0 0 6-CH3 Η methyl 132-133 0 0 Η benzyl 4-chlorophenyl 0 0 Η Η phenyl 123-125 0 0 Η Η 3-methoxyphenyl 0 0 Η ch3 phenyl 69- 70 0 0 Κ Η 2-fluorophenyl 145-146 0 0 6-F Η phenyl 138-140 0 0 Η Η 3-bromophenyl 130-131 0 0 Η CH3OCH2 3-methylphenyl 0 0 Η Η 3,4-dimethylphenyl 130-131 0 0 5-CP3 Η methyl 86- 87 0 0 Η Η 4-methoxyphenyl 132-133 0 0 6-CH3 Η ethyl 131-133 0 0 Η Η 3-fluorophenyl 128-130 0 0 Η Η ethyl 64- 66 0 0 2-CH3 Η phenyl 112-114 0 0 Η Η 2-chloro-4-fluorophenyl 146-147 0 0 Η Η 2-chlorophenyl 136-138 0 0 4,6-Ρ2 Η methyl _ η 4 6905 A B X R1 R3 m.p.°C 0 0 il-CH5 H methyl 114-117 0 0 2,5-diCI ch3 2-methoxyethyl 0 0 H H 4-ethylphenyl 86- 88 0 0 4-Cl K phenyl 125-127 0 0 K H 3-chloro-4-fluorophenyl 0 0 6-CH3 4-methyl benzyl methyl 0 0 H H 2,4,6-trimethylphenyl 212-213 0 0 4-Cl H methyl 122-124 0 0 H H 3,4-difluorophenyl 0 . 0 6-NO2 . H5 2,5-dichlorobenzvl 0 0 H , H 5-indanyl 171-173 0 0 4-CH- 9 H- ethyl 80- 81 0 0 H H 3-isopropylphenyl 98-100 s 0 H C2h5och2 n-butyl 0 0 H H cyclooctyl 103-105 0 0 H H 4-methylphenyl 138-139 0 0 H H 2,4-dibromop'neny 1 0 0 H H 3-methy1-5-ethyl- 115-117 phenyl 6905 A Β X R1 nup °C 0 0 H H tert.-butyl 97- 99 0 0 H H 4-ethoxyphenyl 0 0 K H 3-ethylphenyl 85- 86 0 0 H CHj cycloheptyl 0 0 H H 2,6-dimethvIphenyl 1(=5-167 0 05~CF3 II isopropyl 121-123 0 0 H H 2-methoxyphenyl 0 0 H H tricyclo [A-lAo1’® decyl L ]103-105 0 0 H H 2-methylphenyl 126-128 0 0 H H 4-iodophenyl 0 0 H ch3 methyl 54- 56 0 0 H H 3-methyl-4-chlorophenyl 137-138 0 0 H H 3,5-dimethylcyclo- hexyl 128-129 0 0 H H 1-naphthyl 141-142 0 0 H H isopropyl 86- 89 0 0 6-Er H ethyl 0 0 6-F H methyl 116-118 55 S Ο 5 A B X R1 R^ m.p.°C 0 0 2-CH3 benzyl ethyl 0 0 5-C?3 H phenyl 133-135 0 0 4-Br ch3 methyl 0 0 H H 2,6-dimethylcyclohexyl 121-123 0 0 H CH,OCHn* 3-fluorophenyl 0 0 6-OCH3 H methyl 131-132 0 0 2-CH5 ch3 benzyl 0 0 5-CF3 CH3 phenyl 0 0 H H cyeloheptyl 102-104 0 0 H H benzyl 113-115 0 0 4-CH, 6-NO^ H methyl 0 0 6-OCH3 H phenyl 209-211 0. 0 H : h 4-bromophenyl 136-137 s 0 H H phenyl 0 0 H H 3-methy1-5-isopropylphenyl 0 s. H benzyl n-butyl 0 0 H H norbornyl 118-120 0 0 H H 2-naphthyl s s 5-NO2C2H5 3-methylphenyl 0 0 H R eyclopentyl 110-112 0 0 6-C1 H methyl 136-138 0 0 H . H 3-methylcyclohexyl 120-122 s 5 H H methyl 6905 A B X R1 R3 m.p.°C S c H CH^ phenyl 0 s H H phenyl 156-1=8 S 0 H H ethyl S s H H phenyl 0 0 HC2H5 phenyl 56- 58 0 0 HC2H5 3-methylnhenvl 75- 77 0 0 H H 3,3,5-trimethyΙον clohexyl 79- 82 0 0 H H 3,4-(tetramethylene)- phenyl 160-166 0 0 H H cyolohexyl 117-118 0 0 H H 2-methyIcyclohexyl 100-102 0 0 H H 1,3-dimethoxyisopropyl 95- 96 0 0 H .H tert.-amyl 62- 63 0 0 H H 2,3,6-trimethyl- phenyl 180-182 0 0 H H 2,3,5,6-tetramethy1phenyl 237-238 0 0 H H 0-tert.-butylpheny1 113-115 0 0 H H 2,3,5-trimethylpheny1 IO5-IO7 0 0 H H 2-isopropyl-5-methyl- phenyl 103-105 0 0 H H 2-tert.-butyl-0-methy1phenyl 154-156 0 0 H H 2,6-dimethoxyDhenyl 155-157 4S90S v_.

A B X R1 R3 m.p.°C 0 0 H H 3-methylphenyl 106-108 0 0 HC2K5 3-methylphenyl 75- 77 0 0 H H . 2-methy1-6-isopropyl- phenyl 122-12** 0 0 H H 3,5-diethylphenyl 128-130 0 0 H H 1-adamantyl 113-115 0 0 H H 1-me thy1cy clop enty1 57- 59 Q 0 H CHj 4-chlorophenyl 99-103 0 0 H H 3}4;5-trimethoxy- 173-175 phenyl 0 0 H H 2-methoxy-4-tert.- butyl-phenyl 151-153 0 0 H ft 2,4-ditert.-butyl- phenyl 186-187 0. 0 H ch3 2,4,6-trimethylphenyl 75- 77 0 0 H H 2,6-di chlorophenyl 156-158 0 0 H H 2,3-dichlorophenyl 166-168 0 0 H H 2,4,6-trichloropheny1 171-173 0 0 H ch3 4-chlorophenyl 94- 96 0 0 H H 2-s e c,-b utylphenyl 72- 74 0 0 H - H 2-ethylphenyl 115-117 0 0 H H 2,5-dimethylphenyl 127-128 0 0 H H 2-methy1-5-isooropyl- phenyl 146-147 0 0 H H 2-isopropylphenyl 85- 87 0 0 H H 4-tert.-butylphenyl 84- 86 0 0 H H 4-methylcyclohexyl 122-126 - 16 46905 II. Aminourethanes Example D parts of a hydrogenation catalyst (palladium on animal charcoal, 10%) was added to a solution of 135 parts by weight of N-(3-nitrophenyl)-carbamic acid-4-chlorophenyl ester in 900 parts by weight of tetrahydrofuran (absolute); the mixture was then hydrogenated to constant weight at room temperature and a hydrogen pressure of 0.02 bar. The solution was freed from catalyst, dried with MgSO^ and freed from solvent to such an extent that the crystalline reaction product was readily able to be filtered; l86°-l87°C.

Structure: NH0 Example E While stirring intensively, 25.2 parts by weight of phenyl chloroformate was dripped very slowly into a solution of 108 parts by weight of m-phenylenediamine in 1,000 parts by weight of water. After completion of the reaction, the mixture was suction filtered, the solid was washed several times with dilute hydrochloric acid, and the combined acidic solutions were neutralized with ammonia and suction filtered. The dried product thus obtained melts with decomoosition at 178° to l80°C Structure NH - 17 4690S Example F While stirring intensively, 52.1 parts by weight of phenyl chloroformate is slowly dripped into 51 parts by weight of 2,4-diaminonitrobenzene and 43 parts by weight of sodium bicarbonate in 600 parts by weight of tetrahydrofuran. After the mixture has been stirred for 14 hours it is filtered and washed with tetrahydrofuran. The solution is freed from solvent to such an extent that the crude crystalline product can readily be filtered; after washing with diethyl ether and drying, the compound melts at 223° to 225°C. According to the nmr spectrum and elemental analysis, it has the following structure: Example G While stirring intensively, 40 parts by weight of 3-(S-methylthiocarbamoyl)-nitrobenzene is added to a mixture, heated at 80°C, of 33 parts by weight of powdered iron, 75 parts by weight of alcohol, 60 parts by weight of water and 3 parts by weight of concentrated hydrochloric acid in such portions that the temperature is-kept at 80°C without additional heating. The mixture is refluxed for 1 hour and suction filtered while hot, the residue and the filtrate are digested with about 1,000 parts by weight of methylene chloride, followed by drying over sodium sulfate, concentration, and recrystallization from toluene; m.p.: 101°-103°C.

Structure: tt The following aminourethanes (F) may be prepared by analogous processes: A B X R1 R3 m.p.°C 0 0 H H 4-fluorophenyl 166-167 0 0 H H 2,4-dichlorophenyl 126-128 0 0 H H methyl 87- 89 0 0 6-CH3 H methyl 0 0 H benzyl 4-chlorophenyl 0 0 4-N02 H methyl 187-189 0 0 H H 3-methoxyphenyl 0 0 H ch3 phenyl 70- 72 0 0 H H 2-fluorophenyl 172-173 0 0 6-F H phenyl 0 0 H H 3-bromophenyl 0 0 H ch3och2 3-methylphenyl s • 0 H H methyl s s H ch3 phenyl 0 s H K ethyl 0 s H H 3-methylphenyl s 0 H H 4-chlorophenyl 469θ5 A B X R1 R3 m.p.°C S 0 H H phenyl 0 0 H H 3,4-dime thylphenyl 155-157 0 0 5-CF3 H methyl 0 0 H H 4-methoxyphenyl 146-149 0 0 6-CHj H ethyl 0 0 H H 3-fluorophenyl decomposes 0 0 H H ethyl viscous oil 0 0 2-CH3 H phenyl 131-133 0 0 H H 2-chloro-4-fluorophenyl decomposes 0 0 H H 2-chlorophenyl decomposes 0 0 4,6-diF H methyl 0 0 4-CH3 H methyl s 0 2,5-diF . ch3 2-methoxyethyl 0 0 H H 4-ethylphenyl 160-161 0 0 4-C1 H phenyl 215-217 0 0 H H 3-chloro-4-fluorophenyl s s 6-CH3 4-methyl benzyl methyl 0 0 H H 2,4,6-trimethylphenyl 150-152 0 0 4-C1 H methyl 469 05 A B X R1 R3 m.p.°C 0 0 H H 3,4-difluoropheny1 0 s 6-fJO, C?H, 2,5-dichlorobenzyl 0 0 H H 5-i ndany 184-186 0 0 4-CHj H ethyl 0 0 . H H 3-isopropylphenyl 68- 70 0 0 H H 3-ethyl-5-methyl- phenyl 102-104 s s H H phenyl 0 0 H H 3,3,5-trimethylcyclo- hexyl 100-102 0 0 H H 2-methylcyclohexyl 0 0 HC2H5 3-methylphenyl 104-105 0 0 HC2H5 phenyl 104-106 s 0 H C2H5OCH2- n-butyl 0 0 H H cyclooctyl 77- 79 0 0 H H 4-methylphenyl 158-162 0 0 H H 2,4-dibromophenyl 0 0 H H tert,-butyl 109-110 0 s H H 4-ethoxyphenyl 0 0 H H 3-ethylphenyl 112-114 0 0 H ch3 cycloheptyl 0 0 H H 2,6-dimethylphenyl I6o-l6l 0 0 5-CFj H isopropyl 102-104 _ 21 _ A B X R1 R3 m.p.°C 0 0 H H 2-methoxyphenyl 0 0 H ‘ H tricyclo [ϋ .3 J· decyl 130-131 0 0 H H 2-methylphenyl 170-172 0 0 H H 4-iodophenyl 0 0 H ch3 methyl 0 0 H H 3-methy1-4-ehiorophenyl 181 0 0 H H 3,5-dimethyIcyclohexyl 80- 82 0 0 H H 1-naphthy1 146-148 0 0 H H isopropyl 66- 68 0 s δ-Br H ethyl 0 0 6-F H methyl 0 0 2-CH, benzyl ethyl 0 0 5-CP3 H phenyl 214-216 s s li-Br ch3 methyl 0 0 H H 2,6-dimethyIcyclohexyl 0 0 H H 2-ethylhexyl viscous 0 s H H phenyl s 0 H CH,0CH„ 3 2 3-fluorophenyl 0 0 6-OCH3 H methyl - 22 _ A B X R1 R3 m.p.°C 0 s 2-CHg ch3 benzyl 0 s 5-CF3 CHj phenyl 0 0 H ' ' H cycloheptyl 86- 88 0 0 H H benzyl S 0 4-CH, 6-N°2 H methyl 0 0 6-OCHj H phenyl 84- 86 0 0 H • H 3-methyl-5-isopropyl- phenyl 0 s H 'benzyl n-butyl 0 0 H - H norbornyl 133-135 0 0 H H 2-naphthyl 0 s 5-NO2C2H5 3-methylphenyl 0 0 H H cyclopentyl 0 0 6-C1 H methyl 0 0 H H 3-methyIcyclohexyl 95- 97 0 0 H CHj 3-methylphenyl 112-115 0 0 H H 3,4(tetramethylene) phenyl 181-183 s s H H methyl 0 0 H H 2-isopropyl-5-methyl- phenyl 122-123 0 0 H H 3-methylphenyl 142-144 0 0 H H 2-tert.-butyl-t-methy1phenyl 89- 91 6905 A Β X R1 R5 m.p.°C 0 0 · Η Η tert.-amyl 65- 67 0 0 Η Η 4-tert.-hutylphenyl 175-177 0 0 Η Η 2,3,5-trimethylphenyl 152-154 0 0 Η ‘ Η 2,3,6-trimethylphenyl 155-156 0 0 Η Η 3,5-diethylphenyl 121-123 0 0 Η . Η cyclohexyl 122-124 0 0 Η Η . 2-methylcyelohexyl 0 0 Η Η 1,3-dimethoxyis opropy1 0 0 Η Η 2-methyl-6-is opropy1phenyl 133-135 0 0 Η ch3 2,4,6-trimethylphenyl 0 0 Η Η 4-methyley clohexy1 73- 75 0 0 Η Η 1-adamantyl 158-16I 0 0 Η Η 1-methylcyclopentyl 0 0 Η ch3 4-chlorophenyl 88- 90 ό 0 Η Η 3,4,5-trimethoxyphenyl 146-148 0 0 Η Η 2-methoxy-4-methyl 110-112 phenyl 0 0 Η Η 2-methy1-4-tert.hutylphenyl 185-186 0 0 Η ch3 2,4,6-trimethylphenyl 0 0 Η Η 2,4-di-tert.-butylphenyl 195-197 0 0 Η Η 2-sec.-butylphenyl 75- 77 0 0 Η Η 2-ethylphenyl 74- 75 0 0 Η CH^ 4-fluorophenyl 123-125 A B X R1 R3 m.p.°C 0- O H H 2,5-dimethylpheny1 142-144 0 . 0 H H 2-methyl-5-isopropyl- phenyl 139-141 0 0 H H 2,3-dime thylpheny1 184-186 0 0 H H 2-isopropylphenyl 80-82 III. Diurethanes Example 1 parts by weight of sodium bicarbonate was 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); at 20° to 25°C and with cooling, 13.3 parts by weight of thiomethyl chloroformate was then metered in. To complete the reaction, the mixture was stirred for 1 hour at room temperature. The reaction mixture was then filtered and the filtrate concentrated in vacuo. The oily residue was crystallized by adding toluene; m.p.: 155°-157°C (No.l). The compound has the following structural formula: It J 0 Example 2 A mixture of 20 parts by weight of N-(3-isothiocyanatophenyl)-O-methylcarbamate (obtainable frcm N-(3-aminophenv1)-0-methylcarbamate and thiophosgene, m.p. 99°-100°C), 20 parts by 469 0 5 weight of methanol, 3 parts by weight of triethylamine and 150 parts by weight of toluene is boiled for 6 hours. After concentration, the residue is recrystallized from toluene; m.p.: 147°-i49°C (No.2). The compound has the following structural formula: S Example 3 At room temperature, 10 parts by weight of carbon disulfide is dripped into a solution of 16.6 parts by weight of N'-(3“aminophenyl)-0-mefchyl urethane and 10.1 parts by weight of triethylamine in 300 parts by weight of diethyl ether. After the mixture has been stirred for 20 hours it is suction filtered, the residue is suspended in 120 parts by weight of water, and 9.1 parts by volume of diethyl sulfate is added while stirring. After this mixture has been stirred for 20 hours, it is suction filtered, washed with water and air-dried; m.p.: 122°-124°C (No.3). The compound has the following structural formula: S The following compounds may be prepared analogously: 46flos l-k r— ro O CO Co CO Co Ο O Co Co C3 VJ » ro 3 3 3 3 3 Ό 3 3 Φ Φ Φ Φ Φ Φ O' Φ Φ ct ct ct ct ct ct Φ ct S' a O' ST 3* a 3 S' a < *<?< < W μ-» M f-* w H H* 3 *0 OJ VJ 3 Ό *3 Ό Φ sr 1 t 1 I S' S' 3* ct Φ Φ 3 o σ Φ Φ Φ S* 3 ct Φ a 3 3 3 3 «< a . μ-» O «< *<2 '< M xj a O 3 M H M 3 << 0 f—1 o f—1 S’ 3 σ Φ □* a 3 Φ φ 3 3 h-* < I J~k cr σ\ o\ DO I ->] v* I t-* OJ co »~l 1—» H* H* H* I-* X5 M 'JT CO 0\ CO | | o | Oi | O ro f-k h-k t-k 1 V-k μ* H-k ro Ό JO CO C\ O 00 ro -0 ?\ί Jsr *3 O .468 Ο 5 V.· ΓΟ 3 Ό •σ χ=· *3 Μ φ 3 3 1 3* ΧΓ ct φ φ ο Φ I zr □ 3 3* □ Q, Μ Η* «< Η· Μ Η* W Ο 1—· ο 3* W ο 3 ο ό 3 ' Φ □ ►3 Ο Ό Φ Μ w 3 J5T Ό VJ Ό 3 Φ Φ 1 3* 1 3 Φ ct C+ Ο Φ· 3 Φ ct 3 3* 3* 3 Φ 3 3 «< Η* ct «< «< Η Η Ο Η* 3 W Η» 3 Ο Ι-» *3 •d 3 3 Φ φ 3 3 «< Μ Μ μ* σ\ —3 I μ* ο% Η» μ* V4 VI μ* I t μΑ μ* VI VI -< VI μ^ νι ΊΟ μΑ VI •Ο α U 3 00 \ VI I μ* ο co ρ VI μΑ μ νι ro σ\ ν 5 I μΑ μ*· V ΓΟ 00 VI Ο I I I ο μΑ μ* μι £ !\3 VI W W Ό Ο Ι-Α Ο Η· Η Ό Ο Ο 46305 Λ* fir fi· ί~ JS· ’U4 Ό4 SM oj V4 Ό4 Ό4 U4 σ\ σι V4 ι\> μ* Ο <ο •ri σ\ \.η V4 \5 μΑ Ο 03' Ο Ο ο 03 03 03 Ο 03 Ο Ο Ο Ο Ο ο 03 Ο Ο ο Ο Ο 03 Ο 03 03 03 ο ο: Ο 03 03 03 03 03 Ο ο Ο 03 ο ο Ο 03 Ο Ο ο 03 03 03 ο ο ο ο ο ο ο ο Ο Ο 03 ο X X X X X S.M X X X X X OS X X X V 1 νπ ο 1 Q ο. 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H 3 3 a^ Φ Φ Φ Φ H ft ct ft 3 I a a a M -tr «< «< h-> 1 Η μ» 3 *3 *3 Φ a a a 4 φ φ φ ct 3 3 3 t «< Μ Μ 1 H Η Η rv Φ I Cfr H· a « νή O H3 Ό 4 a ο Φ XJ 3 Μ Η Η I νη ι Φ C+ a «< Η α rv Η· I 2 φ a ctK a ο Μ 4 Η Ο 3 I a -tr φ W 3 νη << I tv Φ w ft VI a* kn H* 3 cn a ι φ ct 3 Φ M ft μ 3 » 3 3 3 tv 3 rv 3 3 3 ΓΟ 3 rv Φ Φ V I a* Φ Φ 1 Φ i ct ct O 3 Φ Jr ft ft 0 3 ft ct a a *3 Φ 3 1 a a 3 Φ a φ M M ct M 0. e< M << ct tj fi fi fi a Η H* fi fi fisr fi ct 3 I 3 3 · a h ft a μ a a Φ t Φ Φ 1 Φ a 3 kn d 3 σ> 3 a Μ I ft Μ 1 ς< «< j_» μ. μ μ· Μ H ω a ω 1 0 3 0 xr 1 ct 1 1 Φ ft a << Η }-» μ μ rv μ μ μ σ\ VO -t vn co IV rv • rv t O vO 1 kJI j | 1 μ I μ tv μ μ μ 3\ VO Xr o\ oo rv jr . jr μ μ vo μ μ μ μ μ μ kn kn Vi vn —j σ\ *4 O | rv |. rv μ I rv 1 1 μ 1 μ 1 μ μ μ μ vn vi Vi vn σ\ co rv Vi Vi -t- X Ο > α Μ X X tv W Vi X JT ΰ 3 Ο Q ro ro w ro ro ro IO IO ro ro V VI Jr Jr Jr xx jr Jr jr Jr μ O kO 00 -4 os VI 4Sr Vi t-k O CO O o CO co o o O o co Co CO' co CO co co co O co o o co Q o o o o CO o o o o O o O o o o o X X X X X X X X X X Ο > ω ο W X χ ο χ χ w χ α κ χ VJ α ΓΟ X VI ο Ο ο χ χ χ νι vi νΓ X ΓΟ 3 § 3 3 3 3 3 3 3 ro 3 Φ n> 0 0 0 0 0 0 a* 0 ct ct et ct ct ct ct ct 0 4r rt a a a a a a a a 3 * a «4 «4 «4 «4 **4 <4 «4 *4 <4 OS <4 H H H H H H H H Η 1 H et Ρ· Ο a Η Ο Ο I Jr 1 3 a 3 0 Jr 1 Jr 1 Jr 1 ro 3 IO a* 3 0 3 ΓΟ 0 1 ω 0 ct »3 »3 o VJ 0 Jr ct ct 3 0 3 a t—· H a 1 3* a a 0 o <4 a a H Cb =4 VI «4 «4 ct • H H o 0 O P· Ρ* I (—* h a 1 3 3 3 o a 3 0 a O O O a 3 a x a 3 3 3 H P* 0 =4 ct a a a 0 o 3 1 *•4 0 0 0 3 a <4 Jr H 3 a 3 0 t—* H 1 O * «4 *4 3 0 a H H H a 3 0 0 . 0 3 3 1 «4 «4 H H ο G? I Η Ο σ\ vs •ο I Η Η Η νι Ο co vi νι οο I I I Η H VI 0 VO VI -4 o I SO t-k *4 Vi I H VI t-k I t-k Vi Xr O I H J=r IO O rv ΓΟ IV IV IV ΓΟ IV ΓΟ ΓΟ IV σ\ σ\ VI VI VI VI VI V VI VI μ* ο \ο co —4 σν VI jr VI ΓΟ Ο Ο Ο ο ο ο ο ο ο ο co ω ω ω co co co ο CQ ο ο ο ο to ο ο ο co ο co ο ο Ο ο ο σ ο ο ο co X X X X X X X X X X 3 ct ct X X X φ φ Φ Φ Φ Φ ct Ί X ct ct X X X <<; β « • 0 * X X X X X έ 3 £ ff ff ct X X X X << << << w H w H . H X Q X X X Μ X Ο VI =< Η O o X X CV X tv | o 1 o X o rv o I Q o X μι VI Q o o X X X VI VI V4 3· νι φ w X VI X I << ft μ* Η· ι 3 Ο Φ Μ X Ο X Η<< Ο. Η χ r Φ νι X I << Μ 3 3 3 3 ο 3 X 3 ο X 0 X Φ X ΓΟ X φ X X Φ Φ ct Φ X Φ 3 φ VI □ X □ 3* 3 ν 3 X 3 o «< «< • μ* 3 3 μ» μ* μ« μι X μ» Η· IV μ^ μ»· μ^ kA ΗΑ μ* VI Ο 4=Γ VI VI ν© VI μ. -C 03 VI 00 ΓΟ Ό ι σ\ I Υ VI I V | μΐ I ΓΟ μ* ι μ>· I μ* μ* μ* μ* 2Τ Ο VI VI OS V3 VI Μ -Er Ο -4 Ο -Cr μ- co VI -3 X Ο » CD Ο Μ X X μ* X ΓΟ Q-PJ I α χ -fir /46905 In the following experiments, prior art herbicidal active ingredients were used for comparison purposes.

Methyl-N-(3—(N * — (3’-methylphenyl)-carb amoyloxy)-phenyl)-carbamate and ethyl-N-(N'-phenylcarbamoyloxy)-phenyl-carbamate (German Printed Application DAS 1,567,151) are characterized by their - albeit different - action on broadleaved unwanted plants and are well tolerated by sugarbeets. However, as is known, the selectivity of the former compound is better in this crop than that of the latter. The range of application for 3-isopropy1-2,1,3-benzothiadiazinone-(4)-2,2-dioxide (German Printed Application 1,5^2,836) is completely different. This compound is used to combat various broadleaved weeds in soybeans, groundnuts, cereals, Indian corn and some vegetable species. However, there are gaps in the action. Methyl-N-(3—Ν’— -methyl-N'-phenylcarbamoyloxy)-phenyl-carbamate has a herbicidal action good for its class, but hardly any crop plant selectivity; for this reason, the compound has only been recommended for instance in soybeans for post-directed use (Arndt, F. and G. Boroschewsky: New Selective Herbicides, VIII International Plant Protection Congress, Reports and Information, Section III, Chemical Control, Part I, Moscow, 1975, pp. 42-49). In this method, the young shoots and leaves of the crop plants are not contacted by the spray liquor, which is used to treat the unwanted plants growing beneath them. 469 0 5 Examples demonstrating the herbicidal action of the novel sulfurous diurethanes Numerous test results give proof of the good herbicidal properties of the novel compounds. Their herbicidal potency and their selectivity in crop plants are demonstrated in the following examples.

Greenhouse experiments Plastic flowerpots having a volume of 300 cm3 were filled with a sandy loam and test plants, separated by species, were placed therein. Predominantly, seeds were sown or vegetatively reproducing species were transplanted. The active ingredients were suspended or emulsified in water as vehicle and sprayed (postemergence treatment) by means of finely distributing nozzles on to the leaves of the test plants and the surface of the soil. For the postemergence treatment, the plants were grown in the· pots to a height of from 3 to 10 cm, depending on habit, before being treated. Depending on the temperature requirements of the plants, they were placed in either cooler or warmer sections of the greenhouse. The experiments were run for from 2 to 2Q 4 weeks. During the experimental period, the plants were tended and their reaction to the individual treatments was evaluated. The application rates of the compounds are given in kg/ha of active ingredient. The scale for assessment of the activity was 0 to 100, 0 denoting no damage, and 100 complete destruction of the plants.

Results The figures in the- following tables illustrate the action of the active ingredients on treatment after emergence of the crop and unwanted plants (Tables 2 to 18). It is worthy of note that the herbicidal effectiveness and spectrum of action of the new compounds tend toward those of the diurethanes used for comparison purposes. However, their selectivity in crop plants is not the same. This can be excellently exemplified by the results in soybeans and cereals. These crops tolerate the new compounds to the same extent as 3-isopropyl-2,l,3-benzothiadiazinone-(4)-2,2-dioxide, which is known to be well tolerated in these crops (Tables 5,6). In addition, there are a number of crop plants whose tolerance precisely of the compounds according to the invention is conspicuous, whereas the comparative agents are unsuitable (Tables 2, 4, 5).

Possible application methods are soil incorporation or treatment of the soil surface, but the treatment of emerged plants is preferred. Special applications, such as post-directed or lay-by spraying, are also suitable. The jet is directed here in such a manner that the leaves of the sensitive crop plants are if possible not contacted; the agents thus reach the surface of the soil or the unwanted plants growing there.

In view of the variety of application methods, the agents according to the invention or compositions containing them may be used for removing unwanted plants from a much larger number of crop plants than those given in the tables. Application rates may be 0.1 to 15 kg/ha and more, depending on the objective to be achieved.

Crop plants in which the compounds according to the invention may be used are as follows: Botanical term Common name Allium cepa onions Ananas comosus pineapples ΐ Asparagus officinalis asparagus 5 Avena sativa oats Beta vulgaris spp. altissima sugarbeets Beta vulgaris spp. rapa fodder beets Beta vulgaris spp. esculenta table beets, : Brassica napus var. napus rape 10r Brassica napus var. napobrassica Brassica napus var. rapa turnips Brassica rapa var. silvestris Camellia sinensis tea plants Citrus limon lemons 15 Citrus maxima grapefruits Citrus reticulata Citrus sinensis orange trees Coffea arabica (Coffea canephora, Coffea liberica) coffee plants η 20 Cucumis melo melons Cucumis sativus cucumbers Cynodon dactylon Bermudagrass ί Elaeis guineensis oil palms Fragaria vesca strawberries 25 Gossypium hirsutum (Gossypium arboreum Gossypium herbaceum Gossypium vitifolium) cotton Botanical term Common name Helianthus annuus sunflowers Helianthus tuberosus Hevea brasiliensis rubber plants 5 Hordeum vulgare barley Humulus lupulus hops Ipomoea batatas sweet potatoes Lactuca sativa lettuce Lens culinaris lentils 10 Linum usitatissimum flax Lyeopersicon lycopersicum tomatoes Malus spp. apple trees Manihot esculents cassava Medieago sativa alfalfa (lucerne) 15 Mentha piperita peppermint Musa spp. banana plants Nicotiana tabacum (N. rustica) tobacco Olea europaea olive trees 20 Oryza sativa rice Panicum miliaceum Phaseolus lunatus limabeans Phaseolus mungo mungbeans Phaseolus vulgaris snapbeans, green 1 dry beans 25 Pinnisetum glaucum Petroselinum crispum spp. tuberosum parsley Picea abies Norway SDruce - 49 Botanical term Common name 46305 Albies alba fir Pinus spp. pine trees Pisum sativum English peas 5 Prunus avium cherry trees Prunus domestica plum trees Prunus persica peach trees Pyrus communis pear trees Ribes sylvestre redcurrants 10 Ribis uva-crispa Ricinus communis Saccharum officinarum sugar cane Secale cereale rye Sesamum indicum Sesame 15 Solanum tuberosum Irish potatoes Sorghum bicolor (s. vulgare) Sorghum dochna grain sorghum Spinacia oleracea spinach Theobroma cacao cacao plants 20 Trifolium pratense red clover Vaccinium corymbosum blueberries Vaccinium vitis-idaea cranberries Vicia faba tick beans Vigna sinensis (V. unguiculata) cow beans 25 Vitis vinifera grapes 5C 469 0 5 To broaden the spectrum of activity of the new individual compounds, to achieve synergistic effects or to improve the residual action in the soil, the new compounds may be intermixed, or numerous other herbicical or growth-regulating compounds may be employed in compositions and combinations. Depending on the area of use and the objective, the following compounds or chemically similar derivatives are suitable for admixture with the compounds according to the invention: - 51 46305 QCHF2CF2<3 NH2 -HHCHj -NH-CH3 nh2 R R1 R2 n —( . H and salts K -< Cl • and salts H -< F 'and salts K CH, H -and salts CHoOCK5 —( SO-, ✓ 2 and salts C?3 n.C,H_ J 7 n.CjHy CF3 n. C ch2-ch2ci S02NH2 n.C3H? n.C3Hy Xl-C-O-R3 il R2 CHCH.

Cl Cl & ooi-C3H7 -NsC.

/CH CH CK, -CH-C-NH-C„Ht II ¢:5 i-C,H =Τ N-C-O-R' RR3 CK2-CSC-CH2ci CH3 -CH-CsCH C1 Cl· CH Cl 2»-0-s HON< >S02 . a CK & CF30 I MH-C-OCHΙΓ b ,1' R2 rM-co·/-^ NH-C-O-Rσ oR K CH, R CH, -5446305 NK-C-O-R3 If RJ CH, H3C pC^Kg CH, n3c C2H5 n-c-s-r1/ II 1 0 i-C3H? n.CjH? n.C3H? Se.O.CyHg c2h5 σ i-C3H7 n.CjH? n.C3H? sec.CjjHg C„H..

C,H, 3 CH2-CC1=CKC1 C,H2 3 n.CjHy c2K5 CH.

^•Cl C,K_ 2 3 c2h5 Oc-s-c2i<; 0M-S-R CH3 0 C2K5 n.CjHy J^-C-C-O-R2 ι n Y 0 R1 X Y R2 CH, Cl Cl Na ci3 Cl Cl NaC2K5 Cl Cl Nac1-£^-ch2 Cl H CH. H ©=c4-o- H H H· 0 O™- H Cl NH(j Cl f%C-N- \w/ u t H CK, J c2h. °(ίη •'-A Cl Cl H · and. salts _ 56 X Ί ’ 9 r-.C-C-O-R^ II ϊ Ο CECH Cl X η ΐ^ίίγ Cl -C2H5 · ί~(^Κγ. Cl 4 Cl i-CjKy C2h5 Cl c2h5C2H5 Cl -C(CH3)2CN c/5 Cl -CH-CH,-OCH, t CH. 2 c2h5 Cl -CH-C5CH t CH, 3 S}“ Cl -c(ch3)2-cn i°C,K_ OCH3 i-CjH?i“C3H7 C2H5 C2H5 SCHj SCHj c2h5 c2h5 SCH3 tert.CjjHg ο X ο CFj Η Κ F CH, CH - 58 46305 ,Ν-C-R R·^ 0 ch3 · -CH-CaCH ch3 , -ch-ch2-och3 -CH2-CH2-OCH3 -CH2-0CH3 -CH2-C-OC2H5 CH2-O-C4H9n ch2ci CH2C1 CH2C1 ch2ci ch2ci ch2ci ch2ci -p COOH 469 Ο 5 R R1 R2 R3 Cl Cl Cl K F Cl Cl H Cl Cl H H Cl CF, H COOK Cl Cl H cooch3 N02 CF, H H ' H c.?3 Cl H H CFj Cl oc?h5 Cl 'Cl · a OCHj 6 8 0 5 R1 ' R2 R3 H ch3 Η,ΟΟ-θ· H ch3 oi tertHgC^HM· QH -CO It 0 CH3 o- H CH,ciO CI · · H CHj C1-Q H CH3 £> P3c H CH3 HCH3 •vp H CH, J CIci*czy H ch3 CH, J CHj CHCH CH ch3 -CH-CsCH CH, OCH, J CH, OCH) n-c-m: H CH NH N-C-NK-CH.-CK ' η ώ \ CF Ϊ0 ~3 ;n ?h3 ' N-C-NECH, .P3C R - R1 R2 tert.C.jjflg NH2 SCH, 3 tert.CjjHg ^-•CH, -N=CH-CH 3 SCH, ^CK- ✓ o- NK2 CH- R1 R2 CH, Br CH- Cl 3 CH, Cl.

-CH2-CH2-CH2R3 sec;. C4H9 tert.C^Hg Q -© s2 N’-S-O· CH3 CHj it ο R\,n°202H\/-OR1 \,2 46305 R1 -C-CH, ir / 0 sec.C^Hg H -C-CH, « J 0 tert.CjjHg H -C-CKII J 0 tert.C^Hg ch3 H ch3 H . salts and esters H ses.CjjKg tert.C^Hg tert.CjjHg H - salts and esters H H '' salts and esters HCH3 salts and -esters 69 0 5 11¼-0 ο “F'HN—CO esters R x Η CHjOSO. 3r CHjOSCX CH, CH-OSO 2 CH3 CFjSOj θ2Η5 σ - NH - OC,H_ 2 □ “sc2 Ο ?3Η7η H-C h3c - ΝΗ - 0 - CH2 - CH = CK2 η’Λ J COOCH., QH ?3H7n £ = N - 0CH2 - CH = CH2 and_Na salt HjC· ,CH3 +2 CHjOSOCH, Q - s - “2 -'OO'- CHa - ί - £} ra.° 0 chO «Ο rt® +2 Br +2 Cl 4 6 9 0 5 Η Η Cl Cl Cl Cl I H Cl Cl Cl· Cl CH, - and saltss esters HH2 Cl H Cl R’-O-CH-C-OR5 It Cl I OCH2 Cl OCHH salts, esters, amides H •salts-, esters, amides H salts, esters, amides 469ύΰ f^-C-CK-C-OR3 Η Ο Cl CH Cl· Cl Cl Cl· CH R3 H -salts, esters, amides H salts, _esters, amides H salts, estersr amides Cl ch3 ch2-oc2h5 0 -N-C-CH2-O-S-CH3 0 CxCH, p ^CH, N-C-CH.-O-S-NKCH, ' ι» & it 3 0 0 and salts, esters and- salts, esters - 69 463 05 NHg HO HO ‘P-CH-»NH-CH,-C-OH ' n · 2 . 2 n '0 0 and salts H_C ;As-ONa OH CH 8 9 0 5 HC-CO-NH HC-CO-NH HO-P-CH2-CH2-C1 OH Cl-c y-O-CH2-CH2“CH2-COOK and salts and esters Cl Cl-^Jy-O-CHg-CHg-CHg-COC. and salts and esters CH, 'CH, H,C- -NH-CH^ d 5 3 It is also possible to apply the new compounds according to the invention, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combatting pesto or phytopathogenic fungi or bacteria. Of further interest is the fact that the compounds according to the invention may be mixed with mineral salt solutions used to overcome nutritional or trace element deficiencies. / ! 6 9 0 5 To ensure the herbicidal action sets in, spreader-stickers and non-phytotoxic oils may be added.

Application may be effected for instance in the form of directly sprayable solutions, powders, suspensions, disper5 sions, emulsions, oxi dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used; in any case they should ensure a fine distribution of the active ingre10 dient.

Por the preparation; of solutions, emulsions, pastes' and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, etc. and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., ’20 and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, 469 05 adhere ;s or =. ulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sufonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ether, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated_nonylphenol, alkylphenol polygiycoi ethers, tributylphenol polygiycoi ethers, alkylaryl polyester alcohols, isotridecyl alcohols, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polygiycoi ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier. 469 0 5 Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic oowders, etc.

The formulations contain from 0.1 to 95, and preferably 0.5 to 90, ί by weight of active ingredient.

. EXAMPLE 4 parts by weight of compound 2 is mixed with 10 parts by 15 weight of N-methyl-oZ-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops. EXAMPLE 5 parts by weight of compound 8 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole 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 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight oi* water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient . ~ 74 4ϋ9υ EXAMPLE 6 parts by weight of compound 13 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil.

By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 7 parts by weight of compound 7 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthal ene-a-sulfonic acid, 17 parts by weight of the sodium salt of a ligninsulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 --75469 ύ 5 parts by weight of water, a spray liquid is obtained containing 0.155 by weight of the active ingredient.

EXAMPLE 8 parts by weight of compound 46 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3? by weight'of the active ingredient.

• EXAMPLE 9 parts by weight of compound 2 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

EXAMPLE 10 parts by weight of cpmpour.d 7 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. Dilution in 100,000 parts by weight of water gives an aqueous dispersion containing 0.04 wti of active ingredient.

EXAMPLE 11 parts of compound 8 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained. 3 P W Φ X P μι* P w to φ ω σ » Η· Ρ exaltata Sesb. exalt. hemp sesbania (coffeeweed) 3 Si o · ra w γ/ X Ο α Ο >» > > Φ P 9) w 2 3 Φ Ρ Ρ φ Ρ 3 93 3 4 X 3 4 93 93 ρ X 3 3 3 Ρ Μ· Ρ o 4 H· o X 3* 3 3 Ο X X Ω 3 4 c H· 3 W 0 0 0 ►S 3 Ρ 3* 3* 3 Ρ ►3 Ω 3 3 4 4 α Ρ Μ 3 Ρ μ»· 3 M· P Φ x x μ. *1 3 Μ C1 X P *3 a Η· μ Ρ Ω Φ £ 4 X 9-> W *3 3 P Ρ 3 X Ρ Ρ Ρ 3 Ρ 3 H· P 93 P •3 4 < Μ 03 • X 01 X X Ρ 0 Ω X 93 Φ CO Φ φ 0 3 X 4 Η· Ο 0 P 93 3 Η* 4 Ο Ρ Ρ 3 01 Μ Φ 3 93 Η» Η· X 3 3 Ω Ρ Φ X 3 • ω 0 μ) Η· 3 X Φ □ 4 £ c ω 0 3 Ρ 0 Ρ ω 0 93 t-i ο ω 3 *1 X P 0 3 ρ. μ-ι X •σ 3 3 Φ P Η· ω κ Ρ 3 ω 3 Φ 3 Ρ χ Ρ Q W ra 3 ra 3 σ ο σ Ρ σ Ρ α φ Ο Ρ ϊ» 91 3» Ό > 3 *3 X 3 4 93 Ό ω X 3 3 τ Ρ μμ Ρ Ω 4 Μ· Ω 3* X 3 3 Ω X X Ω 3 »3 3 Η» C • 0 0 ο 4 3 • X X 3 • Ω 3 4 α Ρ W • « • 3 X σ • Ω 01 4 Ρ Ρ a • Ρ Ω 4 X X 4 Φ & Μ Ό X χ X Ρ Ρ Η· 4 Ρ X 3 93 93 31 X 0 4 4 3 3 93 < • 3 93 Φ Φ 4 ρ Ο • ο a • 3 Η» X 3 X X Ρ Η· Η· • a • Ω 0 ο Ρ Ω Ω. ω ρ to ί ra C-i Ω Ω Ρ 93 Ω 4 3 3* Φ ο 93 0 Ρ Μ Η« Ρ Ο Ρ Φ Φ Φ 3 Ρ Ρ 4 3 3 φ 0 3 4 91 *Φ Ρ W Ω 3 3 Ω χ 3 X X 4 Ρ 4 3 >Φ 3 Φ 4 Ρ 0 1 φ Cl X Η· Ο Ο »Φ Μ 3 4 Ο X 3 3 Ρ Φ £ & 3 X Η» Ο X 4 Ο Η· Φ □ > φ Ρ £ Ρ Ο £ Ρ X 3 Η» X co ►Φ 3 φ Φ £ Φ Φ Φ X Ρ Φ α X Φ Φ 4 93 ι~» 3 4 φ Ω 91 Ώ μ·· Ω φ μΐ· Μ« C1 »3 01 3 Η Ω 01 Ο £ »3 4 Ρ Ρ Μ Φ 4 3 4 3 Φ £ Ω Ω φ Φ 3 3 Ω X X Ρ Φ ν-*' ο 4} X 3* Φ Botanical term Abbreviation in tables Common 6 3 0 5 .3 a μ O W ο Ο X o 4 3 o O' 3* 3 -Φ φ Ρ μ M Q - co 3- Φ 4 ¢+ Ρ 3 «< N 3 CO μ 3 «< . Ρ 3 OQ P o 3 Ο co 3 3* o Φ 3 0 Ό Ρ < Ρ μ» 3 CO P H* o Ο 3 3 3 £ 03 c 3* CL 3 «-j 3 ΓΙ 3 3 CO 3 μ Η· 3* CQ Η» 3 O 3 Φ Ρ *3 3 < 3 3* P 3 3 4 Φ Φ P • μ 3 μ 3 3 4 O - Ρ 3 ω co CQ ca 4 μ <4 H· 3 3 3 Μ μ a 3 co .3 Φ < P 3 3 CQ Ρ 3 3 . CQ Φ 3 H· P 3 μ P μ 3 ο μ 3 3 μ 3 3 ο Η Q W Ο ο CD Ν X ο 4 3 Ο ο 3 3 Φ Φ Ρ μ '< Ο ω 3* Φ 4 3 Ρ 3 Ν 3 co μ 3 << Ρ 3 CQ . Ρ • . «< 3 • co 3 3 3 • « •4 Ρ • 3 co Μ • Ρ 3 Φ Ρ 3 Ο μ co μ co 3 4 3 3 3 ♦ 3 φ CQ Φ ω • • μ .· QQ • 3 • 4 CQ co CQ » • μ Ρ a «< 0J 3* ‘ί Η· Ο Φ ο Η» -¾ 0Q GQ μ ο Μ ο 3 μ Ο co ο Ρ Ρ 0 3 3 4 3 4 CQ 3 3 3 3 Ρ 0 η 4 3 Ρ Δ 3 3 4 3 Ρ Φ a -Ρ 4 Φ CQ 4 μ. 3 4 3 CQ CO Ρ Φ Ο co 4 μ CO CO a Η Ο 3 Ο te § Η* 3 Ρ Ο Triticum aestivum Tritic. aest. wheat 0Q Ο Ο ω φ *-* ο ο 3 φ Ο μ. φ ο CQ a ο 3 X 3 μ ω φ 3 3 Ρ 3 a 4 φ Table ? - Selective action in vegetable crops; postemergence application in tiie greenhouse kg/ha Teet Diants and % damageCompound Apium Daucus Euphorbia Datura Lamium spp. no. gray. carota heliosc. strain.

O Ti m ro o I η in o Ή o Ch in o I b* CO o o o n c\j o o o • t a H CM -=r Ο Ο I I T< ο ο o • · » r4 cm Jio c r-< o o f4 ο ο o KO OS Os o O I •rt 000 τ-t CM CM σ\ no damage 100 = complete destruction Setaria spp ll o ^SSO.S r-4 fl, r-f «Η CO co CO ς> Ό CY C\ c\ 45 Cl w ε d d C £t 04 CM in •H r-f co a c\ σ\ Cl p 3 d O 3 tn m ό P S c— c— co Q) G E CO. O »rt U · -45 & o o o 53 · ;« ο. o o o „ Ξ to r< r-f vt C d to dg to S3 · r-f QJ qf-H P- O O O d vr φ 2 G 0 —* E ρ d s O ΓΗ O 5“1 o rf viP & □ C On! · - 0) ct. ε β Φ »13S o O o «rf £f 45 £< o © o to- £Q d 45 r-l r4 r4 ol j3O ra 53 0) G G Si d . . 3 4* c O ftc (0 i o Gs G ci £ ‘ri 450 Q O ra Φ 45 Φ , « C £ Φ o s Cj d r? H o rt in in in b3 E t4 CM G-P dα a 0 & •ri « 45 45 45 G •ri « o o o σ o •Η ϋ &4 OJ Ch d 45 C d Ο 0) j-· d ω **» - m o o β h5 e r-f Q) 54 o T-1 CM ο ο ο ο ο ο τ-* . t-f *Ί cc co co c\ ον σ» in ο- σι o\ ci σ\ r— f— ¢fi M3 C*m m m l£3 IG MO o o o o o o τ-ί ν» rf moo cc σι o rf ό vo o vH c o •H C in M Φ Ό V Φ r4 d s Ό φ •Η & ϋ W •Η Ο Χί Ρ. •S4 .0) ·*% χ: £ & •ρ c α d <υ «Η W <0 Ο C Μ Μ I fn Φ r-i Ό C 3 . O JO & d E • O o 5P £ ιη Ο Ο Ο cm Q.

£ O o II O O rf Φ ω ¢3 £ d Ό o β II O 469 0 5 φ ϋ £ φ bO rtφ ε φ Ρ « Ο ft ft γη W (0 Φ X W Φ ft rt · ο ο ft ·Η c. c 4) ui ω s ω ο σ> σ. ο T*t όΛ ΙΓ. '<3 Ο Ο ΤΗ ο ο rt Ο C rt Ο ο rt ο Λ it* ο\ ο\ ο*. ο ο ο ο u-% ο ο <τ Φ ·*. bO ω fi ε Φ fi , Φ fi 1 ω rrt w. •rH ο •σ £ ε Φ 0 rt w <Η Ρ £ W «3 fi rrt φ : ft φ W Ρ Φ rt< , Φ ° £η rH ια. > 0 6 Φ rt •σ ο · ε ρ Vi rt Φ Ο G Ρ rt · Λ Ρ Η Ο < rt υ >, χ r—j ίΤ3 Ο β rt £ <ΰ ·η Ο Ρ cc co Ο C σ\ Ο co ο co co c\ σ\ ί— Ti τ-ι ο ο rt ο m Ο ri μ ο ο ο α rt rt \β C4 ο ο rt ο ο rH ο ο σ rt Ο Ο; Ο Ο irt Κ\ νά κ\ £ Ο •Η Ρ Q φ c η •rt 3 ο η ft fi £ £ Φ 3 φ Ο rt ft bO α η. rt >, < JZ Ο Ο xrt ο ο C rt m ο C • · ·» Ο rt Γυ Ο Ο Ο t-t tr, ο ο • « ♦· Ο τμ CM ο . rt ιη Ο Ο Ο • ♦ # * Ο η Μ (Μ irt Ο ο r- · » Ο η oj κΛ IQ Φ fi Φ Ρ Φ rH & Ο ο £ «Η Ρ Ο £ Φ £ ε Ο Ρ •η α Ρ Φ ο rt < Ρ t φ rrt ft Ρ *§ £ u ft £ Ο U CC 0' GJ ff Ο £ fi Φ Φ a •Φ' ff μ fi «Η ff fi Φ ’ 3 ;ff ff ' Φ ?4 ff S φ fcd φ '. ε φ 'ff ff •Η h ff ΪΛ’Η ft »rt <0 ff β fiff aj*HΉ CO Cj ta fi w ff*H -* d α, co *ri 4-3 ff ίΰ φ a ff £. fi C φ c S ff o o o o vi vt o o c o v< vi o o o o vt vt o o o o vi vt o o o o vt vt o o o o vt ff o o o o vt vt o o o c vt vi o o o c vt vt o o σ o Vi vt o o co o o o o vi vt o o t*- o\ o o -=r co ε ε σ α a > •ff Ή ff ff •Η 03 fi Φ e* d ff χ (—5 0‘ ?4 ff '§ ο ’ φ, Φ' o o * * vt CV o o < · vt CV o o « 9 vt CM o o 9 vt rv Φ | > { •Η -μ ο Φ r-ί . φ , co φ ι—I ff «3 &4 fi ffl ig t o ϋ c\ fA 463U5 rt (rt cd μ ·Η φ *σ -Ρ Φ w ε o o rt w •rt & a) Κΰ j «rt «rt w rt w •rt (rt rt •rt (4 3 rt ft 3 £ C Φ 3 rt £ ε 3 3 ft > •rt •rt +> 4J •rt rt o EM rt rt bC ^4 o o tk o o th o o • * rt CM O Q rt O O rt O CU o « cu **CM ϋ o ι 0=0 I -2’.

Table 5 - eonfcd o I = 0 t .rZ -P k rt £ •rt ft -p o a * & P 'CO Λφ τ? P Φ (rt I .ft ft It O o rt no damage II Ο '1 Table 5 j- contd •H Πί r-5 (tf ι—ϊ t-J 3} 3 4J •rl a nJ C AS •H «Η CO nJ σι •Ή i3 nJ - V 3 to c o c.

S nJ Ξ Ξ 3 3 U > •H -ri •ri 53 £. 0) gn nJ AS ο C* ο <Ώ ο ο ε* ο Ο Ο ιη ο ιη Ο mo ιη ο 4 « - · » « « * 4 A Α 03 CM ο 03 Ο CM Ο 03 Ο CM ιη cu οι ΚΩ ο m rn ω rt •rt £ rt r—j rt rrt »rt 0 Ό +i 0 CO S •rt ft rt rt 1 CX» •rt rrt i co rt O in c-σ' O O COO ε ε 3 Ο > •rt »rt qj 40 •rt 03 £ 0 E-< rt OO Table 5 - eontd rt Λ x. hO Λ4 mo mo * * » · ON ON t— i“—l N no damage - _ 1o0 = ' lapmplete destruction (( O <46905 ω_ AZ g •rl ε s · •H rf X >> *ύ n c c ai in o in CO o o m in cc cs O C 04 S <3 ,n$ :φ :g QJ to tt Φ s Q) IS O P. a -d G O G to a •rl (ti •rl IQJ§ 40 fcQo r-i CjW O s Ο $3 -Ρ C nJ ec r-ljj cue t-pE · ‘ra« o 0)3 *5 r > (ti 4^ ε·*ε a < E o o tH in in cs Ct in in o in CS CS CC OS in in co oo C O νί o © rl o o o © C» CS CS OS o o rl o o r-i o o o o Oi os cs cs o o o o 04 in π m ω Ό cti ¢) JO Ol χ ώ o o <3 Q. «c e in O rl O rl in o * O oj in o < t © oi in o O Oi in O < 1 o 04 in © Λ V O 04 in o t r O Ol in o O Oi > d QJ r4 Ό ni tr & a c o ♦,-f -P ϋ < ϊ vc Φ .3 O 0) M to •rl >. Pf X CU cn 1 o o oz“X.= o=u o •rl ti 5 1 P· w |o| -r \A5 Φ r-i AS d Ό C O i* o o o ςη Ct = no damage' - - 100 = complete destruction Table 7 - Action of new compounds; postemepgeBC£rtr§afcStgllfc. in-^he greenhouse rt tc rt g cu Ό rt •rt rt •rt rt «rt .rt O «3 P rt w ε « .M P. rt rt £ A •rt rrt co rt Ό £ rt η •p £ •rt rt _3 Ω. o. η ..•p « ‘Eh rt a rt ρ c rt o rt Λ · ^co ω . ptf rt '*rt £ § I*·o· © -o ci o o o » * * cu cu cu vo m co tn tn 4680S •H i¢0 r-i kJ μ ·Η Ο Ό fi <0 CQ g· Λ •Η a. d d β-Ο •ri μ •co d Ο tn Ο σ* d χ ν to ε μ d >4 a a Ο σ' tn «τ ο tn σ» co Table 7 - cor. id o in t « r- O 0-5 95 . - 95 100 c\ rH f OJ OJ o co bX*\ OI vo Oi 469U5 Λ •rt (5 •rt (ΰ rrt *rt 0 Ό JP 0 CO S rt •rt CU. rt rt C Λ •rt rrt co rt c o •rt 4P ϋ s •rt · g ft rt ft J n rt u rt P c Q n c rt >* υ in co in in £ •P co Ό •P rt ft g o Table 7 - eontd rt Λ *>» to o CM o CM to rt g rt Ό o £ rrt o \o CM O rrt rrt rrt rrt CJ CM CM CM 469^5 to £ *3 Ο to to · ΛΛ 0) C 3 (ti & X o.

CM OJ β · (ti £4 rf bfl Ο i4 <0 d C ‘ o •H O rf to (ti O X «3 Q 00 σιο S O fi. fi. fi. d Φ Ό Φ 60 · •H 09 rf e O 3 •Η O E-d rf-g w 05 03 Oa 0 £ Φ Φ 02 Φ • σ ·α Φ to c S > <” n £ •Η Φ 0 a .«P 02 Oi3 n O 40 43 ΦC- H C rf 5» • Φ ·Η nJ; s 03 &3 aj 0 ω co Cl O cn cn CM O •τ o <· oo· 00 00 •S’ kfl T* < t 1 it d £ Φ h0£ 40 •H nJ > Φ d Pf Λ40 co f $QI Φ (ti 4 S I 0. 1” to Φ TJ 0 £ £ 3 Φ 0 to CLPf S Φ 0 ε Ο Φ 40 03 **. 60 3 « φ 0 2 a O · cti fi. to S «3 03 in 0 • « O OJ in in 0 0 CM ° 0 00 00 in 0 0 CM in 0 in 0 < » «. < O CM Ο CM 0) HI JS £ Ό C s* Ch ir\ Ch Ch G\ «=r co 6905 Ρ V) c c fi OJ X fi. o ft fi · fi fi Ο Ή ft fi Φ bO «3 β Φ fi e · O Q. fi. fi. w « ft ft » I o ft fi £ φ ft M o · fi tx V fi. fi fi RJ · fi 3 3 fi P fi RJ P fi fi ρ ϋ ε< ii. i · ft CM ft o — o o Ιft o · fi a I- X Ό P £ o o I co Φ td ft ¢6 e·* fi ft x ft a in o o oj xn CM « o o Λ CM •o £ P a β o o CM '0 c in no -damage _ 100 = Complete destruction>1 O ο Ο fi c φ φ φ fi 4-5 cd Φ Sμ C φ to ίφ § μ Ο ft Φ ω ca ε cd fi ίο ο C φ «Η Ό C ff C cd co ff cd φ μ φ ο C Ό C TO μ fi cd ff ft Φ Φ ϊft Ο Ο ίμ C Ο ο φ ff μ Φ Φ ff Φ CQ o fi C O ft E O Q ε- cd cd ff ff 3 ff Φ φ ε μ w ff φ ftfi cd ff C cd ff Φ CS3 TO >> ca ε c > μ μ Φ cd fi V) -hi 95 CO σχ o ox 100 100 o OX in o 1 o o I ox ox o ox ff o o o o Q o o «κ O ff o ff 00 ιοτ a ff o in o in in o ff ff ff ff ff 10 o ff o o o 10 in 0.2 1.0 2.0 1.0 0.5 1.0 222 235 111 o in ff m ff CO AT OJ Φ O fi μ TO Φ b> ff Φ ft ε o a μ C cd Φ b0 cd O s II O C d L. rH bO 0 r+ w C 4) VI 3 0 fi d d c ·»-< 4J 4J C d d d fi L fi rH bO w d d X 4> CQ d β P d c 4> £ μ (ϋ l> L. μ 4) _ *3 d *h t« o Ό rH c d d «0 o >> η fi z a c d U £ P w to a a χ β <υ fi rH a K C a o L, bO d 93 4) ή d Λ bO □ 0 d a u >» < β d fi c o ε o o O o o O o o rH rH rH o o o o o o rH »H fH o O o O 1 rH rH o o o o o o »H »H rH o o in Ui in o o O rH o 00 CM CM O m CM CM CM Ό 4) >3 L. ft £ O 4* hO d £ d T3 Table 15 Control of Euphorbia genleulata In soybeans; postemergence treatment In the greenhouse Compound no. Test plants and % damage kg/ha Glycine max Euphorbia genleulata 87 1.0 0 90 2.0 0 90 235 1.0 15 98 222 1.0 15 80 221 1.0 15 80 » no damage 100 » plants completely destroyed Table 16 Destruction of Chenopodium album and Stellarla media in beets; postemergence treatment in the greenhouse Compound no. Test plants and Ϊ damage kg/ha Beta Chenopodium Stellarla vulgaris album media 251 0.5 10 94 = no damage 100 = plants completely destroyed 46S05 Table 17 Control of Chenopodium album and Sesbanla exaltata In peppermint; postemergence treatment In the greenhouse Compound no. Teat plants and ί damage kg/ha Mentha piperita Chenopodium album Sesbanla exaltata 215 1.0 0 95 90 258 1.0 0 100 80 0 no damage 100 • plants completely destroyed Table 18 Herbicidal action; postemergence treatment in the greenhouse Compound no Test plants and X damage kg/ha Centaurea cyanus Izpamoea spp. Echlnochloa crus galli 246 3.0 100 100 100 215 3.0 100 100 90 252 3-0 90 70 - 258 3.0 100 100 100 152 3.0 100 100 -

Claims (17)

1. A diurethane of the formula Z R 1 ft where Z denotes the radical -N - C-B-Iv and Y denotes the R e I tt Jr . η radical -N - C-D-R , Z always being different from Y and R p and R 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 A carbon atoms, unsubstituted benzyl, or benzyl substituted by alkyl of 1 to 4 carbon atoms or halogen, 3 4’ R and R. 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 or 2 carbon atoms, halogen-substituted phenyl or unsubstituted phenyl, alkenyl of 2 to 4 carbon atoms, alkynyl of 3 or 4 carbon atoms, unsubstituted or C^- C^-alkyl-substituted cycloalkyl of 5 to 8 carbon atoms, bicycloalkyl of 7 or 8 carbon atoms, tricycloalkyl of 10 to 15 carbon atoms, phenyl with a fused ring system, phenyl or mono- or polysubstituted phenyl being the substituents/alkyl of 1 to 4 carbon atoms, halogen or alkoxy of 1 to 3 carbon atoms, and A, B, D and E being identical or different and each denoting oxygen or sulfur (with at least the proviso that/one of the radicals denotes sulfur), 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, and n denotes 1, 2, 3 or 4.

2. A diurethane as claimed in claim 1 wherein R 1 , R 2 , 3. 4 R , R and X each has one of the individual meanings listed hereinbefore as examples thereof and A, B, D, E and n have the meanings given in claim 1. 96 5 469U5

3. A diurethane identified hereinbefore in any one of Examples 1 to 3 or as any one of compounds Nos. 4-9, 1120, 24-37, 39-43, 45-47, 51-56, 58-65, 67-93, 95-103, 105108, 111, 113-121, 125-146, 149-153, 155, 158, l60, l6l, 163, 166, 167, 169, 170, 172, 175, 176, 178-184, 186-192, 194-208, 210-226, 228-241, 243-261.

4. The diurethane of the formula

5. The diurethane of the formula

6. The diurethane of the formula

7. The diurethane of the formula

8. The diurethane of the formula

9. The diurethane of the formula - 97 4 69θ δ

10. The diurethane of the formula

11. The diurethane of the formula 13. The 3 N-C-S-CHj diurethane of the formula diurethane of the formula 14. The The diurethane of the formula 98 17. The diurethane of the formula 18. A process for preparing a diurethane as claimed in claim 1, wherein a phenylaminourethane of the formula

12. 5 where R , R , R , A, Β, X and n have the meanings given in claim l^is reacted with a haloformic acid ester of the formula E it π Hal - C - D-- R n 10 where R , D and E have the meanings given in claim 1 and Hal denotes a halogen atom, or is reacted with carbon disulfide and an alkylating agent at a temperature of from -20°C to +150°C. 19. A diurethane when prepared by a process as claimed

13. 15 in claim 18.

14. 20. A herbicide containing as active ingredient a diurethane as claimed in any of claims 1 to 17 or 19.

15. 21. A process for combatting the growth of unwanted plants by treatment with a diurethane wherein a diurethane 20 as claimed in any of claims 1 to 17 or 19 is used.

16. 22. A process as claimed in claim 21 wherein the unwanted plants combated are selected from Euphorbia, Echinocloa,Datura, Laminum, Matricaria, Centaurea, Mercurialis, Sinapis, Stellaria, Chrysanthemum, Solarium, Amaranthus and 25 Chenopodium species.

17. 23. A process as claimed in claim 22 wherein the un wanted plants are combated in a crop area, the crop being Indian corn, celery, carrots, wheat, soybeans, safflower, or groundnuts.