CA1139777A - N-sulfenylated diurethanes - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE: Diurethanes of the formula I, where R denotes unsubstituted or halogen- or alkoxy-substituted alkyl, alkenyl or alkynyl, each of up to 5 carbon atoms, and X
and Y are identical or different and each denotes hydrogen, halogen, alkyl, haloalkyl, alkoxy or alkylthio, each Or up to 4 carbon atoms, nitro or cyano.
Herbicides containing these diurethanes as active ingredients are suitable for combating broadleaved weeds in numerous crops.

Description

3'~ 7 .

O.Z. 0050/033621 N~SULFENYLATED DIURETHANES
The present application relates to novel diurethanes, a process for their manufacture, herbicides containing these com-pounds as active ingredients, and a process for controlling un-wanted plant growth with these compounds.
It has been disclosed (German Printed Application DE-AS 1,567,151) that methyl N-(3~(N'-3'-methylphenylcarbamoyloxy)--phenyl)-carbamate may be used as a postemergence herbicide for combating broadleaved weeds in sugarbeets. Although the compound is generally well tolerated by this crop, selectivity difficulties may occur if treatment is effected during emergence or development of the cotyledons.
Al~ylation of the acidic NH groups of this active ingredient gives carbamates having relatively poor herbicidal properties (German Laid-Open Application DE-OS 1,567,163). For instance, methylation of both nitrogens results in a considerable decrease in photosynthesis inhibition activity (Z. Naturforsch., 23b~
342-348, 1968).

~, ~ 35~D ~

We have now found that new N sulfenylated diurethanes of the formula X ~ / SCFC12 I, y~= / \COO~

COOR

where R denotes unsubstituted or halogen- or alkoxy-substituted alkyl, alkenyl or alkynyl, each of up to 5 carbon atoms, and X and Y are identlcal or different and each denotes hydrogen, halogen, alkyl, haloal]cyl, alkoxy or alkylthio, each of up to 4 carbon atoms, nitro or cyano, have a good herbicidal action and are excellently tolerated by crop plants.
R in formula I denotes linear or branched alkyl, alkenyl or alkynyl, each of up to 5 carbon atoms, e.g., methyl, ethyl, isomeric propyl, butyl and pentyl, allyl, l-methylpropen-

2-yl~ propargyl, and 1-methylpropen-2-yl.
These radicals may be substituted by halogen, e.g.~
chlorine, or by alkoxy of up to 2 carbon atoms. Examples are 2-chloroethyl, 2-methoxyethyl, 2-chloroallyl, 4-chlorobutyn-2-yl, and 2-ethoxy-n-propyl.
X and Y in formula I may be identical or different and denote hydrogen; halogen, e.g., fluorine, chlorine, bromine and iodine; linear or branched alkyl of up to 4 carbon atoms, e.g., methyl, ethyl, isopropyl and tert-butyli linear or branched haloalkyl of up to 4 carbon atoms, e.g., trifluoromethyl and l-chloroisopropyl; linear or branched alkoxy of up to 4 carbon atoms, e.g., methoxy, ethoxy and tert~b~toxy; linear or branched alkylthio of up to 4 carbon atoms, e.g., methylthio and ethylthio; and nitro or cyano.

~139 ~ 7 7 Preferred diurethanes of the formula I are those in which R is methyl or ethyl, X is hydrogen, chlorine, fluorine, methyl or ethyl, and Y is hydrogen.
The N-sulfenylated diurethanes of the formula I may be obtained by reaction of diurethanes of the formula ~NHCOO--~ ` II, NH-COOR
where R, X and Y have the meanings given for formula I, with dichlorofluorosulfenyl chloride in the presence of an acid binder and in a solvent or diluent.
The reaction may be illustrated by the following equation:

2 CL ~ C12 ~ N-COO
Y .~ ~ y ~ 12 ~ICOOR
COOR
Suitable organic binders are organic bases, such as tertiary amines, e.g., trialkylamines such as triethylamine, dialkylcyclohexylamines, quinoline or pyridine, and inorganic bases~ such as hydroxides, bicarbonates or carbonates of alkali metals and alkaline earth metals, e.g., potassium carbonate, sodium bicarbonate, calcium carbonate and potassium hydroxide.
The acid binder i5 employed in at least molar amounts, based on the compound of the formula II, or on dichlorofluorosulfenyl chloride.
The reaction is carried out in the presence of a solvent or diluent. Suitable examples are, in addition to water, organic solvents r such as optionally chlorinated aliphatic and ~39~t~

aromatic hydrocarbons, ketones, ethers, esters or nitriles, for example methylene chloride, toluene, chlorobenzene, cyclohexane, petroleum ether, acetone, tetrahydrofuxan, dioxane, ethyl acetate~ and acetonitrile, and dimethyl sulEoxide, sulfolane, hexamethylphosphoric triamide and dimethylformamide.

.

- 3a -~39 ~ ~
0. Z ~ 0050/033621 The reaction is carried out at from -20 to +110C and at atmospheric or superatmospheric pressure. Preferably, the di chlorofluorosulfenyl chloride is used in excess, based on the diurethane of the formula II.
The diruethanes o~ the ~ormula II used as starting materials are known and may be manufactured by conventional processes (German Printed Applications DE-AS 1,568,138, 1,657gl51; 1,567,163;
and 2,638,897). The manufacture of dichlorofluorosulfenyl chloride is disclosed in J. Gen. Chem~ USSR 1959, p. 3362~
The following example illustrates the manufacture of the compounds according to the invention.

143 g of methyl-N-( 3-N ' -phenylcarbamoyloxy)-phenyl-carbamate and 250 g of dichlorofluorosulfenyl chloride in 750 ml o~ toluene are placed in a receiver. At room temperature, a mixture of 177 g o~ triethylamine and 500 ml of toluene is dripped in and the resultant mixture is stirred for 3 hours. The reaction mixture is extracted by shaking first with 400 ml of ice water, then

3 times with 250 ml of ice-cold 20% strength h~drochloric acid, 20 and again with water. After drying over sodium sul~ate and con-centration, 100 ml of diethyl ether and 400 ml o~ petroleum ether are added to the residue and the mixture is filtered after having been allowed to stand briefly, ~here is obtained 233 g of a crystalline product of melting point 88 to 89C.
Analysis calc.: C 37.0 H 2.2 N 5.1 S 11.6 Cl 25.7 F 6.9 found: C 37.1 H 2.~ N 5.2 S 11.6 Cl 25.7 F 6.o

- 4 -~35a~7~7 The compound has the :Eollowing structural formula:

jCFC12 \ COO ~

COOC~3 The following compounds for instance may be prepared analogously:

X SCFCl ~ N /

N \
COOR

No. R X Y m.p.~bC~

7 CH2CE~2OCH3 3-CH3O H

9 CH2CH=CH2 3 C2H5 H

13 CH(CH3)C_CH 4-Br H
14 CE~3 3-CN H
CH3 3-Cl H

3~ ~

No . R X Y m.p . LcJ
16 CH3 3 C?H5 H
17 CH3 3-i-C3H7 H
18 CH3 3-F 4-Cl 19 CH3 3-C1 4-Cl - 5a V~9~ , O.Z. 0050/033621 The active ingredients according to the invention may be applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering~ The forms of applic~
ation depend entirely on the purpose for which the agents are being used; in any case they should ensure as fine a distribution of the active ingredient as possible.
For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed directg mineral oil fractions of medium to high boillng point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene~ xyleneg paraffin, tetrahydronaphthalene, al~ylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclo-hexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suit~ble.
Aqueous formulations may be prepared from emulsion con--centrates, 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 ma~J be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. 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.

~ 3L3~
O.Z. 0050/033621 Examples of sur~actants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalene-sulfonic acids 3 phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sul~ate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, neptadecanols, and octadecanols, salts of sulfated fatty alco-hol glycol ethersg condensation products of sulfonated naphtha-lene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxyl-ated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethersg alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxy-propylene, lauryl alcohol polyglycol ether acetal, sorbitol es~ers, 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.
Granules, e.gO, coated, impregnated or homogeneous gra-nules, 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, mag-nesium oxide, ground plastics, fertili~ers such as ammonium sulfate~ ammonium phosphate, ammonium nitrate3 and ureas, and 3~ vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

3t~
0.~. 0050/033621 The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % by weight of active ingredient. Application rates are from 0.1 to 15 kg of active ingredient per hectare.
Examples of formulations are given below.
I. 90 parts by weight of compound 1 is mixed with 10 parts by weight of N-methyl~ pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops II. 20 parts by weight of compound 2 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 with 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by wei.ght; o~
the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dis-persion is obtained containing 0.02% by ~eight of the active ingredient.
III. 20 parts by weight of compound 6 is dissolved in a mix-ture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weigh-t of the adduct of 7 moles of ethylene oxide with 1 mole of isooctyl-phenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solu-tion into 100,000 par-ts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02%
by weight of the active ingredient.
IV. 20 parts by weight of compound 2 is dissolved in a mix-ture consisting of 25 parts by weight of cyclohexanol, 65 par~s by weight of a mineral oil fraction having a boiling point bet-ween 210 and 280C, and 10 parts by weight of the adduct of ~3~ ~
O.Z. 0050/033621 40 moles of ethylene oxide with 1 mole of caskor 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.
. 20 parts by weight of compound 6 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene--~sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. B~ uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1% by weight of the active ingredient.
VI. 3 parts by weight of compound 1 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containin~ 3~ by weight of the active ingredient.
VII. 30 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.
VIII. 40 parts by weight of compound 11 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-form-aldehyde 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 wt$ of active ingredient.
IX. 20 parts of compound 2 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 ob-tained.

O.Z. 0050/033621 The influence of various representatives of compounds according to the invention on the growth of unwanted plants in comparison with prior art active ingredients is demonstrated by the following greenhouse experiments and e~periments in the open.
I. Greenhouse experiments The vessels employed were plastic ~lowerpots having a volume o~ 300 cm3 and which were filled with a sandy loam containing about 1.5% humus. For the postemergence treatment, the plants were : first grown to a height of 3 to 10 cm, depending on growth shape.
The active ingredients were then suspended or emulsified in water as vehicle, and sprayed onto the leaves of the test plants and the soil by means of ~inely distributing nozzles. The test plants were set up in cooler or warmer sections of the greenhouse J depen-ding on their temperature requirements. The experiments were run ~or ~rom 2 to 4 wee~s. During this period the plants were tended and their reaction to the individual treatments was assessed.
II. Experiments in the open These results were obtained ~rom very early postemergence treatments on small plots. The active ingredients, emulsified or suspended in water as vehicle 3 were applied with the aid o~ a motor~driven plot spray mounted on a tractor, as soon as the cotyledons of the crop plants and weeds became visible.
The scale used for assessment of the greenhouse experiments and the `experiments in the open was 0 to 100~ 0 denoting no damage or normal emergence, and 100 denoting nonemergence or complete destruction of at least the visible plan-t parts.
The plant species used in the experiments are listed in Table 1. The results obtained are given in Tables 2 and 3; they show that the compounds according to the invention have, compared with prior art diurethanes, a good herbicidal action on a number of broadleaved weeds and are better tolerated by certain crop plants.

39 ~ni~
O O Z . ()050/0 3362 1 Table 1 - List of plant names Botanical name Common name Arachas hypogaea peanuts (groundnuts) Beta vulgaris sugarbeets Chenopodium album lambsquarters (goosefoot) Euphorbia geniculata South American member of the spurge family Galinsoga spp. gallant soldier Glycine max~ soybeans Lamium amplexicaule henbit ~3~
O. Z . 0050/033~i21 d al o~ ~ ~
o~
G~rl ~0 Ei ~: 3 C O ~ J O
.~ ~L ~ Cr~ I O
O ~1 ~ ~ ~ t S ' ~d V ~ .
~d a h ~ X ~ .
blJ ~ , a~ ~

. ... ~ ~ ~ I O

~¢~
S ~ .
, .
.~~
.
O h O I O
S:: S ~ I
h r~ ~ ~U ~ I C~
v ~ ~ ~ 7 ' o o ¢ ~ '~ =o, C~ =o ~3~
0. Z. 0050/033621 t~ O 8 1 00 ~ E~ X O ~1 1 ~ .~

0 u7 ~

C~ ~ ,1 o ~ ~ .
c~ a ~ .
hO ~, e ~D ~! 1 ~; 1 ~ 8 cr~
a~ , Ir~3 i ~
O ~ :~ ~I t~J I
' ) t~
r, 1 15-\
~ O ~ I ~ O
S
O ~ V I O i D O Q. bO O
P~ ~ O - C~ I ~1 0 S S I I h ~ -O

~ U o~
t/~ 3 C~_O ~ =O

O.Z. C050/033621 In addition to the crops mentioned in Tables 2 and 3, the compounds according to the in~ention may be used for com-bating unwanted plants in numerous other crops such as the following:
Botanical name Common name Allium cepa onions Ananas comosus pineapples Arachis hypogaea peanuts (groundnuts) 10 Asparagus o~ficinalis asparagus Avena Yativa oats Beta vulgari~ spp. altissima sugarbeets Beta vulgaris spp. rapa ~odder beets Beta vulgaris spp. esculenta table beets, red beets Brasslca napus var, napus rape Brassica napus var. napobrassica Brassica napus var~ rapa turnips Brassica rapas var. silvestris Camellia sinensis tea plants 20 Carthamus tinctorius sa~flo~er Carya illinoinensis pecan trees Citrus limon lemons Citrus maxima grapefruits Citrus reticulata Citrus sinensis orange trees Co~ea arabica (Coffea canephora, Coffea liberica) coffee plants Cucumis melo melons Cucumis sativus cucumbers Cynodon dactylon Bermudagrass in turf and lawns Daucus carota carrots 0 . Z . 0050/03362 Botanical name Common name Elais guineensis oil palms Fragaria vesca strawberries Glycine max soybeans Gossypium hirsutum (Gossypium arboreum cotton Gossypium herbaceum Gossypium vitifolium) Helianthus annuus sun~lowers Helianthus tuberosus 10 Hevea brasiliensis rubber plants Hordeum vulgare barley Humulus lupulus hops Ipomoea batata~ sweet potatoes Juglans regia ~alnut trees Lactuca sativa lettuce Lens culinaris lentils Linum usitatissimum ~lax Lycopersicon lycopersicum tomatoes Malus spp. apple trees 20 Manihot esculenta ca~sava Medicago sativa al~al~a (lucerne) Mentha piperita peppermint Musa spp. banana plants Nicothiana tabacum tobacco (N. rustica) Olea europaea olive trees Oryza sativa rice Panicum miliaceum Phaseolus lunatus limab eans Phaseolus mungo mungbeans 3o Phaseolus vulgaris ~napbeans, green beansS
dry beans O.Z. 0050/033621 80tanical name Common name _ _ _ Pennisetum glaucum Pe~roselinum crispum parsley spp. tuberosum Picea abies Norway spruce Abies alba ~ir trees Pinu~ spp. pine trees Pisum ~ativum English peas Prunus avium cherry trees 10 Prunus domestica p~um trees Prunus dulcis almond trees Prunus p~rsica peach trees Pyrus communis pear trees Ribes sylve~tre redcurrants Ribes uva-crispa Ricinus co~munis Saccharum of~icinarum sugar cane Secale cereale r~e Sesamum indicum se~ame 20 Solanum tuberosum Irish potatoes Sorghum bicolor ~s. vulgare) grain sorghum Sorghum dochna Spinacia oleracea spinac~
Theobroma cacao cacao plants Tri~olium pratense red clover Triticum aestivum ~heat Vaccinium cor~mbosum blueberries Vaccinium vitis-idaea cranOerries Vicia faba ti~ck beans Vigna sinensis (V. unguiculata) cow peas Vitis vini~era grapes Zea mays Ind~an corn, sweet corn, maize - 16 ~

O.Z. 0050/033621 The new herbicidal active ingredients according to the in-vention may be mixe~ and applied together with numerous represent-ati~e~ of other herbicidal or growth-regulating ackive ingredient groups. Examples of suitable mixture components are diazines, benæo-thiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates~ thiol-carbamates, halocarboxylic acid~ triazines, amides, ureas, di phenyl ekhers, triazinones, uracils, ben~ofuran derivatives, etc.
Such combinations broaden the spectrum o~ actionO A number of active ingredients whichg when combined with the new compounds, give mixtures useful for widely varying applications are given below by way of example:

7 ~ , O . Z . 0050/033621 R--N~ F~ 1 R \2 O
~ =
NH2 Cl (~ ~H2 ~r ~ O~H3 OCH3 N(CH3)2 Cl ~} OCH3. . OC~I3 NH2 Cl ~ N(CH3)2 Cl C~3 ~ NHCH3 Cl ~ OCH3 Cl C~3 ~} NH2 Br ,--~
~ OCH3 OCH3 C~3 ;~Q3~
0. Z . 0050/033621 ~ NHCH3 C l -R2 ~,N -R R

H 3 7 H H ( salts ) H i-C3H7 H CH3 ( sal~s ) H i C3H7 H Cl ( salts ) CH2~0CH3 3 7 H H
H 3 7 H F t salts ) CH2-OCH3 3 7 H Cl CN i 3 7 H Cl . - 19 -~3~

0 . Z . 0050/033621 Rl ~ ~

H3CS02 H n-C~;H7 3 7 3 H C2~ C4Hg H F3 n~( 3H73 7 H F3C H CH?`cH2cln~C3H7 Htert-C4Hg H ~ecwC4~g~e~-C4~Ig E~ S02NH2 :~ n C3H7 n-C3~7 3 ~ C3H7 CH2~a H H ~ec-C4Hg H ~jC H3C H H-CH ( C2H5 ) H F3C ~H2 3 7 3 7 H H ~C H n-C3~I7 n--C3H7 H i-C3H7 H n-C3H7 n-C3H~

. - 20 -O.Z. 0050/033621 --N C ~ 0 ~ R~
F~ / "

R Rl R2 ~. .

C~3 ~I ` C~2 Cl ~ . ~ CH3 CH C- CH
Cl Cl -~ ; C-C-CH Cl Cl~ J . i~C3~7 CH3 ' O
Cl~ . H CH3 C~

? ~so2_ H CH3 CH3 H tert,-HgC~--CH
tert.-HgC4 3 ~CH3 H ~CH

0. Z . 0050/033621 R
R - N - C ` O 4 8 ~ 2 NH r c o -- R
O

R R~ R;~
. ~ .
~ ~ C~5 C~3 r~
~ ~ C2X~
~H3 ~
~ H C~H5 C~3 ~ CH3 C~13 F~ H CH3 F-~_ H C2H~

~ I C2H5 Cl ,.~

F~ H CX 5 F

H ~3 Cl ~3~
0 . Z . 0050/033621 ~3 NH - C ~ O - ~

CF3 N~C-0C~3 ~~ - G - S ~ R2 R/

R. . . Rl . R2 i -C3E~7 i ~C3~7 C~2~CCl-CCl~

~ C3 7 i-C3X7 -CH;2- CCl-CHCl n- ~3H7 3 7 C2~5 ~} 2 5 2 ~

sec-C4Hg ~ec-C4Hg C2H5 ~l-G3H7 3 7 n-C3H
c~s C2X~ -CX~,l -~ec-~C4Hg sec-C4Hg , -CH2~>
Q C2H5 c2H5 i-C3H7 i-C3E~7 CE~ ~C 3 _ 23 _ O.Z. oo50/03362~
i i-C3~I7 i~C3H7 CH2~ C2~5 ~~C~S R
X n -{}I2 CCl=CHCl ~CH;2~CCl-CC12 CN; C S C;2H5 x R ~ C C - O -O

Na Na C1~CH2~ C1 H C~ 3 ~C~ O- H H
H ~alts ) O
, . .
C1~0~0 H CH3 ~C~3 7t~

0 . ~ . 0050/033621 R X ~ Rl ~C-N H CH3 C2H5 [~ =
Cl Cl 2 5 Cl Na ~n ~ ~I CH3 i^C3H7 0~
~, Cl (~C N- H CH3 CH3 [~ .
F Cl Cl~0~0- H CH3 -CH2-C~3 ( CH3 ~ 2 Cl . . -. Cl~0~0- H CH3 Na 20F~C~o~0- H CH3 Na ~1 3 ~ ~ H CH3 CH3 O . Z 1 0050/033621 .

Rl N~ /R2 R N ~R 3 tert-C4Hg SCH3 H C 2H5 HC2H~ SCH3 H C2 Hi-C3H7 SCH3 H C2~
HCH3 SCH3 H i-C3H7 Hi G H Cl H C~H~;
Hi C3 7 Gl H _ KC2H5 Cl H C 2~5 H C2H5 Cl ~ -C-C;I

K i C H7 Cl H i C3H7 H i 3 7 OCH3 H i-C3H7 N ~ 3 Cl H

H C2H5 Cl H -CH-CH2-OCH3 H C2H5 Cl H -CH~C-CH

O. Z . 0050/033621 --N C ~ R 2 R ~ Q

CH3 C~3 CH(C6H~;)2 <~ ' COOH

lO Cl~
Cl Cl~ ~ ~ 2 H~
Cl Cl~S~L H C2~5 , 3 Cl~ H . -C~ CX2-~X2-CH3 C}I3 t--\ 7 ~ -CH-C-CH C~2Cl ~ .
CH-C~I2-OCH3 CH2 Cl C2~5 ' , -Cx2-ocH3 CX2Cl C2H,5 ~:~L3~"~
O.Z. 0050/033621 C~
~C -~H2 C-OC2~5 CH2Cl <~ iCX CX2C

~ 3 -CH2 0-CH2CH ( C~ 3 ) 2 CH2 C~X5 H2-O~n~C~Hg CH2C~
C2H~

~3 -C~I2-0-C2H5 CH2Cl G2H~

CH

~ CH2-<~ C~2t C~
~_ 3 -CH2-CH2-OCH3 ~H2Cl 2 N~-- CH2Cl ~L~3~'~7~

O, Z . 0050/033621 R Rl R2 C. H 3 - CH~ ~N~ CH2 Ci CH ~ OCH 3 CH

~X3 -C~2~N l C~2 ~ H3 CH2 ~ C~2 CH ~ CH3 3 3 t 3~N~
. CH-N~
Br ~r CH
C2H5 ~2~5 ~C~I-O~

CH2-CH-CH2 CX2-CH-CH2- C~2Cl 3 -CH2~ CH2 ,3 CH3 ~CH~ -N~ CH2 Cl u c2~5 ~L~3~
O . Z . 0050/033621 CH3 Cl HC_C~C- H ~Cl H3C~ H 3 CS02~

H3C~ H CH~5 F3CS02}~

. . .
NC--~/~0 - R
' X Y R
Br ar E ( salts 3 H ~ ~alts ) Br Br ~ C-(CH2) 6-CH3 Br 02N ~-O-N=CH-~-C)EI salts, esters N02 Br Br 02N ~-O-N=CH-~-OH ~al-ts, esters CN Br 30~ 30 -'Y

O.Z.0050/033621 R 1 ~R2 N ~ C - N
~/ 0 R 3 .

i-H7C3~ ~ CH3 CX3 H3 ~ H CH3 CH3 Cl H C~3 CH3 tert -~19 C 4 HN- C0 O

[~ />~ H CH3 H
~_ CH3 CH3 H

Cl~ H CH 3 C~3 Cl~ H CH3 3 Cl ~ H ~ H
C~3 ~ . H C~3 C~3 O. Z . 0050/033621 CH
Cl~ H CH3-CH-C--CH

Br~ H CH3OCH3 H3 ~ H C~ 5CH3 Cl CH
H3C~ H -C~ H

Cl~ H CH3OCH3 ClF2C~ . H - C~I3CH3 Cl ~ H CX3CH3 Cl~ H CX3C~3 ~~~
U H C~3CH3 Cl~ E~ CH3OCH3 Cl Br~ H CH3oc~3 Cl '7~ o . z . 0050J03362~

R Rl R2 R3 Cl~ H CH3 H
Cl N--N
tert~HgC4 ~S~L CH3 CH3 H

N--~t F 5C I~SJL CX3 c~3 EI

Cl~ H C2H5 c2 .~;;1 . .
.

~C~
Cl Cl H3C0~ 3 CH3 Cl ~ n NX CH2 - CH(CH3)2 ~ 33 ~

~L~3~'~"7~
oOZ. 0050/033621 }~2 R 1 ~O~N02 -C1 Cl Cl H

C1 CF3 HCOOH ~ salts ) C1 C1 ~ }I
~1 Cl HOCH3 Cl C1 H~C~OCH3 O
H ~ c~3 Cl H CF3 C1OC 2~5 O
R~N -N~l R2 tert-C4Hg NH2 SCH3 tert-C4H~ N=CH-CH(CH3) 2 SCH3 ~ NH2 CH3 0 . Z . 0050/033621 R~X~N ~ ~.3 H CH3 Br -CE-C~H5 H CH3 3r i-C3H7 ~ c~3 Cl tert-C4Hg H CH3 Cl C~\

O

O
, ~ .

R NC~2 02N ~0 - R

-C-CH3 sec C4H H H.

H CH3 H H~salts, esters ) H sec-C4H~3- H H(salts, esters ) -C-CH3 tert C4H9 H H

~3~
0 . Z . 0050/033621 n 3 tert-C 4E~9 E3: CH3 H i-G3H7 CH3 H ~alts, esters ) H tert-C4Hg H H ( salts) o ~N~N R
J~,o X O

~ 1~' O . C~

~-s-~oC~3 ~ ..
J'CH C2H5 H C
3 ~ N C~H5 o C2H5 0 . Z O 0050/033621 O l O

'~ _ Cl~ CX3 ~J
Cl ~)~ CH3 i H7 3 ,.

.. ~ C~I3 tert; C4Hg-~N C0 o ~2 N <~

R R.l R2 X

CH3 CH3 H ~3C~s_o O
~H3 CH3 Br CX30S020 O tC2H5 ~C-NX O-C2H5 ~3~
O . Z . 0050/03362~1 O n-C3~17 H3C>~ N~-O~CH2 C~=CH2 OH n-C3H7 H3 >(~-N~O-CH2-C~-C~I2 ONa n C H
H3C~¢~G N O CHz CX CH2 n 3 OH H.
~__~ Cl ~esters, salts) Cl Cl N COOH ~alts, ester C~I3 .~ --N- C - CH 2-N~ \C 2 E5 ]

0 . Z . 0050/033621 ~13C~N~4~N CH3] . 2CH30S03 (3 L ~2 /

2~

o <_C_CH2_N~N-CH2-C-~ 2CI(~) ~-CH3 0 _~-C~3 COOCX
C~Cl3 C~l Cl COOC}~3 ,, <~1 .

Cl p~ . .
CN
CSNH;~

~L~3~
O.Z. 0050/033621 COOR
R~,R~
Rl~R2 H C1 NH2 C~ ~salts~ esters, amides ) Cl Cl H C1 Na H

Cl Cl H Cl (CH3)2N~2 Rl .
R O - C~ - C ~ O o R2 ~ .
_~ .
Cl~ )~ CX3 H (s&:~ts, esters, ami-des ) C1~ H H " ,t .t fcl C 1~ ~ H n tt rt Cl Cl~ H H ~ n n ., 3~

O.Z. 0050~033621 C ~ CH3 ~ (salts, esters, amides) Cl Cl ~ c~3 ~ (salts, esters~ amides) ~H3 ~ ~2 n 3 Cl ~ O (CH2)3 ~(salts, esters, amides) o Cl ~ O-(CX2)3-C-OH (salts, esters, amides) C ~ -CH2-C-OH (salts, e~ters, amides) -- -Rl o ~,1 R2 OH CH3 Na CH3 CH3 Na ONa c~3 Na 0 . Z . 0050/033621 Ps~ O
R N C CH2 ~ R
O O

,~CH3 ~C -CH;2~ H~; CH 3 3 i-C3~-0-CH2 3 C~I3 ~H3 CH CH -0-C;2H~ CH3 C~3 C~I-C=CH - O
N- C-CH2-0 -S -MH- i C3 7 ~N C CH2 0 S 3 7 Ol-C -C~I2 -O-S -NH- C~ 3 o ~ n CH2 0-S-NH-i-C3H7 7~
.

O . Z . 0050/0~3621 CH~-C-OE~ ( salk s ) [~ =

( salts, esters ) HO COOE~

H - N--N
~ 2 <~S02~NH-S02CF3 c~3 HO~O
n p -- CH2 ~ ~H ~ CH2 n ( salts) HO

~1 N--N~3H7i t~rt -C4Hg (g>-S02NEI-C2X4-S ~ 3 7 ~COONa ~COONa (and other salts) 3 ~L3 O.Z. 0050/033~2 ~S~,S
H3C ~ N N CH3 O O
CH~ - CH2 - O - P ~ C - NH2 NHL~

NHCL~Ign (,~,,OC 4Hgn 0 OC4Hgn, n P-CH2) N-CH2-C ;OH ( salts ) [~

~ (~) C1 (3 c~3 O O

~S~CX3 0 ~0 ~I4 Cg~ 3 OH

~IL3~
O.Z. 0050/033621 o HN - C - CX
HN C - CH (salts) CX3--N - NH - C GH2 ~ CX2 ~ COOH
CH~/ o o Cl GX ~H2 , OH

[c~ 2-cH2-~-cx~ Cl~) r Vc~ 1~
lC~ X2-P(c4Xg)3 ~

~(~ ClO

. .

COOE~ ( salts ~ esters, amides ) O.Z. 0050/033621 HO ~ NH
~ NH
Ho_c.H2C~ ~
o N - CH2 ~ C~ ~ Br J oc~2-cH-cH~
N

N~,N
/

B ~

CH
Cl- ~ ~O-CH-CO~C-C~

It may also be useful to apply the new compounds, elther alone or in combination with other herbicides, in admixture wlth other crop protectlon agents, e.g., agents for combating pests or phytopathogenic fungi or bacteria. The compounds may also be mixed with solutlons o~ mineral matters used to remedy nutrltional or trace element deficiencies. Oils o~ various types, wetting agents, spreader-stickers and antifoams may also be added to the lndividual active ingredients or mixtures thereof.

Claims (5)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. An N-sulfenylated diurethane of the formula I, where R denotes unsubstituted or halogen- or alkoxy-substituted alkyl, alkenyl or alkynyl, each of up to 5 carbon atoms, and X
and Y are identical or different and each denotes hydrogen, halogen, alkyl, haloalkyl, alkoxy or alkylthio, each of up to 4 carbon atoms, nitro or cyano.

2. The compound of the formula

3. The compound of the formula

4. A process for the manufacture of N-sulfenylated diurethanes of the formula I as claimed in claim 1, wherein a diurethane of the formula II, where R, X and Y have the meanings given in claim 1, is reacted with dichlorofluorosulfenyl chloride in the presence of an acid binder in a solvent or diluent.

5. A process for the control of unwanted plants, wherein the soil or the unwanted plants are treated with a herbicidally active amount of an N-sulfenylated diurethane of the formula I as claimed in claim 1.