CA1221971A - Sulfonylimido-carbonic acid diesters - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Sulfonylimido-carbonic acid diesters of the formula in which A is an aromatic group chosen from derivatives of phenyl, napthyl, or in which Y is oxygen, sulphur or the grouping -C=N-in which R6 is hydrogen, methyl, fluor-ine, or methoxy, together with processes to prepare these diesters are described. These compounds find use as inter-mediates in the preparation of known sulfonylureas, having herbicidal and plant growth regulatory action, of the formula

Description

-1- 21489~6380D

This Application i5 a divisional application from Application 439,511, filed October 21, 1983.
The present inven-tion relates to sulphonylimido-carbonic acid diesters useful as intermediates in the prep-aration of the related sulfonylureas.
Application 439,511 relates to a novel process for p~oducing sulfonylureas having a herbicidal action and an action regulating plant growth.

The sulfonylureas, with which Application 439,511 is concerned, correspond to the general formula (I) / ~a N ~

-~/

Rb (I) wherein A is a radical of the formula ~ // \\ R ~ ~ 5 Rl 5 R6 Y is oxygen, sulfur or -C=N-, Rl is hydrogen, halogen, nitro, trifluoromethyl, Cl C5-alkyl, Cl-C5-alkoxy, -COR7, -S(O)mCl-C5-alkyl 5-14164/Div I

~,i" L~

S02Rlo, ~S2Cl-C5-alkyl, or Rll, R2 is hydrogen, fluorine, chlorine, bromine, nitro, Cl-C5-alkyl, Cl-C5-alkoxy, trifluoromethyl, Cl-C5-haloalkoXy or -COR7, R3 is hydrogen, fluorine, chlorine, bromine, nitro, methoxy or trifluoromethyl, R4 is hydrogen, halogen, nitro, Cl-C5-alkyl, methoxy, -COR7 or -S02NR8Rg/
R5 is hydrogen, fluorine,chlorine, bromine, nitro, Cl-C5-alkyl, Cl-C5-alkoxy, trifluoromethyl, -S(O)mCl-C5-alkyl, -COR7 or -SO2NR8R9, R6 is hydrogen, fluorine, methyl or methoxy, R7 is hydrogen, Cl-C5-alkyl, Cl-C5-haloalkyl, Cl-C5-alkoxy, Cl-C5-ha].oalkoxy, C2-C10-alkoxyalkoxy, C3-C5-alken-yloxy, C3-C5-alkynyloxy, phenoxy, benzyloxy, Cl-C5-alkylthio or -~R8Rg, R8 is hydrogen, Cl-C5-alkyl, cyanoalkyl having a maximum of 5 carbon atoms, methoxy, ethoxy or C3-C5-alkenyl, Rg is hydrogen, Cl-C5-alkyl or C3-C5-alkenyl, or 2a R8 and Rg together with the nitrogen atom binding them form a 5- or 6-membered, saturated heterocycle which can contain an oxygen or sulfur atom as ring member, Rlo is Cl-C5-haloalkoxy or -NR8Rg, Rll is Cl-C5-alkyl which is substituted by halogen, Cl-C5-alkoxy, -S(O)mCl-C5-alkyl, -S(O) Cl-C -haloalkyl or C2-C5 alkenyloxy, or C2-C5-haloalkyenyloxy, i~ ~ J

r~ ~

m is zero, one or two, E is the methine group or nitrogen, Ra is hydrogen, halogen, Cl-C5-alkyl, Cl-C5-haloalkyl, Cl-C5-alkoxy, Cl-C5-haloalkoxy, Cl-C5-alkylthio, C2-Clo-alkoxy-alkyl or C2-Clo-alkoxyalkoxy, / Rc Rb is the same as Ra or is an amino gro~p -N \ , wherein Rd Rc is hydrogen, methyl or ethyl, and Rd is hydrogen, methyl, ethyl or methoxy, Application 439,511 also includes the salts of these compounds.
By halogen is meant within the scope of the above definition in general: fluorine, chlorine, bromine or iodine, fluorine and chlorine being preferred.
Examples of alkyl are: methyl, ethyl, n-propyl, i-propyl or the isomeric butyl groups. Alkyl itself is to be understood as being a substituent or a part of another sub-stituent, for example alkoxy or alkylthio. Preferred alkyl groups are in each case unbranched alkyl chains, especially however methyl and ethyl.
By alkenyl is meant as a rule: allyl, 2-butenyl, 3-butenyl, 2-isobutenyl, isopropenyl, 2-pentenyl, 3-pentenyl, and 4-pentenyl, particularly allyl and 4-pentenyl.
By alkynyl is meant in general: propargyl, 2-butynyl, 3-butynyl, methylpropargyl, 2-pentynyl, 3-pentynyl and 4-pentynyl.

,A 7 i ~ 4~

The lleterocycles which are covered by the definition of the radical A are: thiophene, furan and pyridine.
The sulfonylureas to be produced by the process of Application 439,511 are described, together with their prop-erties,for examplein theUnited States PatentSpecifications Nos. 4,301,286 and 4,302,241, in the published European Patent Applications Nos. 23422, 44807, and 44808 or in the German Offenlegungsschrift No. 2,715,786.
These sulfonylureas have hitherto been produced either by reaction of a corresponding sulfonylisocyanate with an appropriate amine, or by reaction of a sulfonylamide with a carbamic acid ester derived from the respective amine to be used, especially a phenylcarbamate.
The known processes are disadvantageous in that the reaction has to be performed either with isocyanate derivatives or with isothiocyanate derivatives, the handling of which is difficult on account of the high reactivity of this class of compounds; or in that the synthesis from phenylcarbamates ecologically unfavourable by-products, for example phenols, are formed. In addition, a number of ortho-subs-tituted aryl-sulfonylamides are difficult to produce or cannot be produced.
In the process of the present invention sulfonamides are not needed as intermediates.
Thus Application 439,511 seeks to provide a process which avoids the use of compounds difficult to handle or difficult to produce, and which also avoids the occurrence of ~' ~~

--5~

by-products damaging to the environment.
It is dlsclosed in Application 439,511 that the sulfonylureas corresponding to the formula(I)which have a herbicidal action and an action regulating plant growth can be produced by a novel process.
The process according to Application 439,511 pro-ceeds in several stages. In the first stage, a sulfonyl chloride of the formula (II) A - SO2Cl (II) wherein A has the meaning defined above, is condensed in an inert phase system or solventl in the presence of at least the equimolar amount of a base as acid-blnding agent and at a temperature of between 0 and 100C, with an imidocarbonic acid ester of the formula (III) O-R
HN = C

x (III) in which Rx is Cl-C5-alkyl, to form a sulfonylimidocarbonic acid diester of the formula (IV) OR
A-SO2N=C
x (IV) in which A and Rx have the meanings defined above.
The imidocarbonic acid esters of the formula(III) are known: cp. for example Liebigs Ann. Chem. 287, 310 (1895) and Chem. Ber. 19, 862 (1886).
Some N-benzenesulfonylimido-carbonic acid esters eorresponding to the formula(IV)(those wherein A is the phenyl, para-tolyl or para-chlorophenyl group) are known and were produeed from the corresponding benzenesulfonylamide (cp.
Arch, Pharmaz. 300 (1967) 553; J. Org. Chem. 28 (19h3) 2902 and Chem. Ber. 99 (1966) 2200).
The synthesis procedure aceording to Applieation 439,511 renders possible the production of sulfonylimido-earbonie acid esters of the formula(IV)direetly from the sulfonyl chloride, with by-passing of the sulfonamide. The sulfonylimido-carbonic aeid esters of the formula(IV)aecord-ing to the invention are novel compounds.
Thus in a first broad aspeet this invention pro-vides a sulfonylimido-earbonie aeid diester of the formula (IV) ORx

2 C ~

x (IV) in whieh A is a radieal of the formula R2 Rl R5 R

Y is oxygen, sulfur or -C-N-, Rl is halogen, nitro, trifluoromethyl, Cl-C5-alkyl, Cl-C5-alkoxy, -COR7, -S(O)m-Cl-C5-alkyl, -SO2Rlo, Rll, or '7~

.7_ -oso2cl-c5-alkYl, R2 is hydrogen, fluorine, chlorine, bromine, nitro, Cl-C5-alkyl, Cl-C5-alkoxy, trifluoromethoxy, Cl-C5-haloalkoxy or -COR7, R3 is hydrogen, fluorine, chlorine, bromine, nitro, methoxy or trifluoromethyl, R4 is hydrogen, halogen, nitro, Cl-C5-alkyl, meth-oxy, -COR7 or -SO2NR8Rg, R5 is hydrogen, fluorine, chlorine, bromine, nitro Cl-C5-alkyl, Cl-C5-alkoxy, trifluoromethyl, -S(O)mCl-C5-alkyl, -COR7 or -SO2NR8Rg, R6 is hydrogen, fluorine, methyl or methoxy, R7 is hydrogen, Cl-C5-alkyl, Cl-C5-haloalkyl, Cl-C5 alkoxy, Cl-C5-haloalkoxy, C2-C10-alkoxyalkoxy, C3-C5-alkenyl-oxy, C3-C5-alkynyloxy, phenoxy, benzyloxy, Cl-C5-alkylthio or R8Rg, R8 is hydrogen, Cl-C5-alkyl, cyanoalkyl having a maximum of 5 carbon atoms, methoxy, ethoxy or C3-C5-alkenyl, Rg is hydrogen, Cl-C5-alkyl or C3-C5-alkenyl, or R8 and R9 together with the nitrogen atom binding them form a 5- or 6-membered, saturated heterocycle which can contain an oxygen or sulfur a-tom as ring member, Rlo is Cl-C5-haloalkoxy, or -NR8Rg, Rll is Cl-C5-alkyl which is substitu-ted by halogen, C -C -alkoxY, -S(O)mCl-C5-alkyl, -S(O)mCl C5 h y C2-C5-alkenyloxy or C2-C5-haloalkenyloxy, 7:~

R i Cl-C -alkyl; and m is zero, one, or two provided that when A represents phenyl, then:
(i) at least one of R2, R3 and R5 is other than h~drogen;
(ii) if R3 and R5 are bo-th hydrogen, then R2 is other than either a 4-methyl, or a 4-chloro group.
In a second broad aspect this invention provides a process to prepare the compounds of formula (IV) ~ORX
A-S02N=C
x (IV) 10in which A is a radical of the formula R2 ~ ' ~ or Y is oxygen, sulfur or -C=N-, Rl is halogen, nitro, trifluoromethyl, Cl-C5-alkyl, Cl-C5-alkoxy, -COR7, -S(O)mCl-C5-alkyl, -SO2Rlo, .Rll or -oso2cl-C5-alkYl, R2 is hydrogen, fluorine, chlorine, bromine, nitro, Cl-C5-alkyl, C~-C5-alkoxy, trifluoromethoxy, Cl-C5-haloalkoxy or -COR7, R3 is hydrogen, fluorine, chlorine, bromine, nitro, methoxy or trifluoromethyl, '7~
_9_ R~ is hydrogen, halogen, nitro, Cl-C5-alkyl, me-thoxy, -COR7 or -SO2NR8Rg R5 is hydrogen, fluorine, chlorine, bromine, nitro Cl-C5-alkyl, C1-C5-alkoxy, trifluoromethyl, -S(O)mCl-C5-alkyl, -COR7 or -SO2NR8Rg, R6 is hydrogen, fluorine, methyl or methoxy, R7 is hydrogen, Cl-C5-alkyl, Cl-C5-haloalkyl, Cl-C5-alkoxy, Cl-C5-haloalkoxy, C2-C10-alkoxyalkoxy, C3-C5-alkenyl-oxy, C3-C5-alkynyloxy, phenoxy, benzyloxy, Cl-C5-alkylthio or 8 9' R8 is hydrogen, Cl-C5-alkyl, cyanoalkyl having a maximum of 5 carbon atoms, methoxy, ethoxy or C3-C5-alkenyl, Rg is hydrogen, Cl-C5-alkyl or C3-C5-alkenyl, ox R8 and Rg together with the nitrogen atom binding them form a 5- or 6-membered, saturated heterocycl~ which can contain an oxygen or sulfur atom as ring member, Rlo is Cl-C5-haloalkoxy, or -NR8Rg, Rll is Cl-C5-alkyl which is substituted by halogen, Cl-C5-alkoxy, -S(O)mCl-C5-alkyl~ -S(O) Cl-C5-haloalkyl or C2-C5-alkenyloxy or C2-C5-haloalkenyloxy, R is C -C -alkyl; and m is zero, one or two, which process comprises condensing a sulfonyl chloride of the formula (II) A - SO2Cl (II) wherein A has the meaning defined above in an inert ~'7~l 3a-phase system or organic solvent, in the presence o~ at leastthe equimolar amount of a base as acid-binding agent and at a temperature of 0 to 100C, with an imidocarbonic acid ester of the formula (III) OR
HN=C

x (III) in which Rx is Cl-C5-alkyl; and recovering the formed sulfonyl-imidocarbonic acid diester of the formula (IV).
Suitable solvents for this process stage are hydro-carbons, such as benzene, toluene and exylene; ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and dioxane; ketones, such as acetone, ethyl methyl ketone and cyclohexanone; nit-riles, such as acetonitrile and propionitrile; and dimethyl sulfoxide. The reaction is performed in the presence of at least equimolar amounts of a base, or in an at least molar excess of the irnino derivative to be used. Suitable bases are carbonates, such as sodium and potassium carbonate, hydro-gen carbonates, such as sodium and potassium hydrogen carbon-ate, oxides, such as calcium and magnesium oxide, and tertiary amines, such as trimethylamine, triethylamine, quinuclidine, quinoline, pyridine and tripropylamine. The base is advan-tageously used in excess. There are thus preferably used l to 5 mols of base, especially l.l to 1.5 mols, per mol of sulfonyl chloride. Larger excesses of base are used in part--9b-icular when the reaction is performed without solvent, and the base, preferably a liquid tertiary amine, serves simultane-ously as the reaction medium. I'he reaction temperatures are between 0 and 100C, preferably between 10 and 80C.
In the second stage of the process which is more fully described in Application 439,511 the sulfonylimido-carbonic acid diester of the formula (IV), obtained from the first stage, is reacted in an inert solvent in the presence of a strong base, at a temperature of between 0 and 100C, with a 2-aminopyrimidine or a 2-amino-1,3,5-triazine of the formula (V) H2N-- ~ E
\ N=. /

b (V) wherein E, Ra and Rb have the meanings defined above, to form a sul-fonylisourea.
In the final stage of the process more fully des-cribed in Application 439,511 the sulfonylisourea of the formula (VI) obtainedin the second stage R

, a IORx N--' S2N C NH-~ E
N- /

.b (VI) ,6P~

- 9c~

wherein A, E, Ra, Rb and Rx have the meanings defined above, is reacted in an organic solvent, in the presence of a hydrogen halide and at a temperature of 0-100C, to give the sulfonyl-urea of the formula (I), and this urea is then isolated as such or as a salt.
A preferred embodiment of the process according to Application 439,511 comprises reacting a sulfonyl chloride of the formula (II) with the imidocarbonic acid die-thyl ester in the presence of a tertiary amine inan organic solvent, isola-ting the resulting sulfonylimidocarbonic acid ester of the formula (IV) by concentrating the mother liquor by evaporation, and, if necessary, purifying the product by chromatography through a silica gel column, and then reacting the product, in an ethereal solvent in the presence of sodium hydride or potassium tert-butylate, with a 2-aminotriazinyl or 2-amino-pyrimidine of the formula (V), isolating the sulfonylisourea of the formula (VI) by concentration by evaporation, and washing the residue with dilute acid, then reacting it further as crude produce, by heating in an organic solvent, with hydrochloric acid at 50C to give the sulfonylurea of the formula (I), and isolating this as such or as a salt. The hydrochloric acid can be used, depending on whether the solvent is miscible with water or not, as an aqueous solution or in the gaseous form. The initial steps of this process represent a preferred feature of this invention, up to the step where ;~
-:9d-the compound o:E formula (IV) is isolated.
The starting compounds of the formula (II) are known and can be produced by known methods.
The sulfonylimidocarbonic acid diesters of the formula (IV) as well as certain isoureas of the formula (VI) are novel and were developed specifically for carrying out the process according to the invention described in Appli-cation 439,511.

~lZ,~ 3'7~

The follow;ng Examples serve to further illustrate the invention.
Example 1: Pro_uction of N-(2-difluoromethoxybenzene-sulfonyl)-im _ ocarbonic acid dieth~l ester 02N C ( oc 2ll5 ) 2 ¦ 1I m.p. 80-81C
~ / \OCHF

11.1 g (0.11 mol) of triethylamine are added dropwise at room ternperature, with stirring, to a solution of 24.3 g (0.1 mol) of 2-difluoromethoxy-benzenesulfonyl chloride and 11.7 g (0.1 mol) of imidocarbonic acid diethyl ester in 70 ml of acetone. The reaction proceeds slightly exothermically. The reaction mixture is stirred for some hours at room temperature, and the triethylamine hydrochloride is then filtered off. The mother liquor is concentrated by evaporation, and the oil remaining is chromatographed by means of chloroform/e~her/petroleum ether (3:3:2) on a silica gel column. After the eluate has been evaporated, there remain 23 g of the above ester, which crystallise (72% of theory), m.p. 80-81C.
Analysis:
calculated: C 44.58% H 4.68% N 4.33% S 9.92% F 11.75%
found: C 44.5 % H 4.6 % N 4.3 % S 10% F 11.9 % .

'7~

The following benzenesulfonyl-imidocarbonic acid esters are obtained in a manner analogous to that described in Example 1:
Table 1 ~OR
~ /;-so2-N=c X
2 ~1 x 1 2 R I Physical data . . . .. _ -COOCH3 H C2H5 m.p.: 92-94c -COOCH3 H C4Hg -Cl H ~ 6 1 3 ~ m.p.: 73-75C
-cooc2H5 H C2H5 -CON(CH3)2 H C2H5 Table 1 (continuation) _. _ Rl R2 R Pbysical data _...... ._ -Br H C2H5 -C_N H C2H5 m.p.: 78-80C
-N02 H c~3 -S2cH3 H C2H5 -S02CH(CH3)2 H C2H5 -S02N(CH3)2 H C2H5 -OCHF2 H C2H5 m.p.: 80-81C

2 2 2~ HC2H5 Table 1 (continuation) _ _ .
Rl R2 Rx Physical data . ___ _ ._ -OCCl=CHCl H C2H5 -OCH2CH=CH2 H C2H5 -OCH2c-cH H C2H5 -SCHF2 H C2H5 m.p. 72-74C

-Cl 6-Cl C2H5 -OCHF2 6-Cl C2H5 .
Table 2 --- OR
~ ~S02~=C/ x R X.y./ OR

Rl R YPosition of Physical data group- -_ .

3-COOCH2 C2H5 S 2

4-COOCH3 C2H5 S 3 Table 2 (continuation) R Y Position of _ _ ~ the sulfonyl P~,s~c~l d~.

2-Cl C2H5 s 3 3-Cl C2H5 S 2 2-s02N(CH3)2 C2H5 S 3 3-So2N(CH3)2 C2H5 S 2 H C2H5 C=N 2 2-Cl C2H5 C=N 3 2-OCH3 C2H5 C=N 3 2-F C2H5 C=N 3 2 3 C2H5 C=N 3 , . .

Table 3 ~R5 -S02N=C~
~ R x . ~
4 R5 Rx Physical data Cl HC2H5 Cl ClC2H5 . CH3 HC2H5 CH3 ClC2H5 OCH3 CH3 2 5 _ _ -- 15 ~
Exa~ple 2: Production_of N-(2-difluoromethoxY-benzene-sulfonyl)-N'-(4-metho y-6-met~lpyr-imidin-2-yl)-0-ethyl-isourea ~-~ ~S02N=C-N~ CH3 i OC H N~ ~-~- bC~F2 C~13 To a solution of 11.2 g (0.1 mol) of potassium tert-butylate in 125 ml of tetrahydrofuran are added at room temperature, with stirring, 13.9 g (0.1 mol) of 2-amino-4-methoxy-6-methylpyrimidine. Stirring is maintained for 2 hours at room temperature, and 32.3 g (0.1 mol) of N-(2-difluoromethoxy-benzenesulfonyl)-imido carbonic acid diethyl ester (obtained according to Example 1) are then added, the reaction mixture being stirred for a further 20 hours. The mixture is subsequently concentrated by evapor-ation, and the residue is taken up in water and rendered acid with hydrochloric acid. The acid solution is extracted with ethyl acetate; the organic phases are then collected, dried, and concentrated by evaporation to leave a solid residue, which is suspended in ether and again filtered off.
The yield is 34.5 g (83% of theory) of the above sulfonyl-isourea, m.p. 131-133C.
Analysis:
calculated: C 46.15% H 4.36% N 13.46% S 7.70% F 9.13%
found: C 46.4 % H 4.4 % N 13.4 % S 7.7 % F 9.2 % .

Table 4 -.=. N_ / a So2N=c-Nl~ E
\R C2H5 1 Ra Rb E Phys i cal data _ .. _ . .
-coocH3 -OCH~2 -CH3 CH
-coocH3 -OCHF2 -OCH3 CH
-COOCH3 -OCHF2 -Cl CH
-COOCH2 -OCHF2 -N(CH3)2 CH

-OCHF2 -OCH3 -OCH3 N m.p.: 83-87C
-OCHF2 -CH3 -CH3 CH m.p.: 112-114C

--OCHF2 -CH3 -OCH3 CH m.p.: 131-133C

-OCH2CH20cH2 -CH3 -OCH3 N

-OCH2CH20CH2 -CH3 -CH3 Cll -SCHF2 -CH3 -OCH3 _ ~ 17 -Table 4 (continuati.on) . _ ._ Rl _ E ¦ Physical data -SCHF2 -OCHF2 -OCH3 Cll 2 2Cl -CH3 -OCH3 N

2 2Cl -CH3 -CH3 CH
-OCH2cH2cl -CH3 -OCH3 CH

-OCCl=CHCl -CH3 -OCH3 N
-OCCl=CHCl -OCH3 -OCH3 N
-OCCl=CHCl -CH3 -CH3 CH
-OCCl=CHCl -CH3 -OCH3 CH .
-OCCl=CHCl -OCHF2 -CH3 CH :
-OCCl=CHCl -OCHF2 -OCH3 CH
-OCH=CH2 -CH3 -OCH3 N
-OCH=CH2 -OCH3 -OCH3 N .
-OCH=CH2 -CH3 -CH CH
-OCH=CH2 -CH3 -OCH3 Cll -OCH=CH -OCHF2 -CH3 CH ¦.
l ._ ... _ . ~

~ ~ f5d ~

Table 4 (continuation) _ E ¦ Physical data ' I~ . .
2 ¦ OCHF2 -OCH3 CH
-OCF3 ¦ -CH - -OCH3 N
-OCF3 . -OCH3 -OCH3 N

-OCF3 ~ -CH3 -OCH3 CH

-Cl -OCHF2-OCH3 CH
-Cl -OCHF2-N ( CH3)2 CH
-Cl -OCHF2 -CH3 CH
-COOCH3 -CH3 -CH3 CH m.p.: 85-88 -COOCH3 -CH3 -OCH3 CH m.p.: 96-98 -CONH2 -OCHF2-N(CH3)2 CH

_ -OCHF2-OCH3 CH .

Table 4 (continuation) _ ~ R¦ ~ ~ E ¦ Physical data . _ _. .
-CONHCH3 -OCIIF2-N(CH3)2 Cll -CON(CH3)2 -OCHF2 -OCH3 CH
-CON(CH3)2 -OCHF2 -N(CH3)2 CH
-CON(CH3)2 -OCHF2 -C~3 C~i -NO2 -OCHF2-N(CH3)2 CH
-NO2 -OCHF2 -C~13 CH

-CF3 -OCHF2-N(CH3)2 CH

-OCH3 -OCHF2-N(CH3)2 CH

-SCH3 -OCHF2-N(CH3)2 CH

3 7 -OCHF2-N(CH3)2 CH

. ..

7~

Example 3: Production of N-(2-difluoromethyl-benzene-sulfony~ N'-(4,6-dimethyl-~yrimidin-2-yl) urea ~S02NllCONH~ C~I

~ / \OCHF CH3 To a solution of 10 g of hydrogen chloride in 100 ml of dioxane are added at room temperature, with stirring, 8.0 g (0.02 mol) of N-(2-difluoromethoxybenzenesulfonyl)-N'-(4,6-dimethyl-pyrimidin-2-yl)-0-ethyl-isourea (obtained according to Example 2). The reaction mixture is then stirred at 50C for 12 hours, and subsequently concentrated by evaporation; the solid substance remaining is suspended in water and the suspension is filtered. The yield is 7.2 g (97% of theory) of the above urea, m.p. 190-195C.
Analysis:
calculated: C 45.16% H 3.79% N 15.05% S 8.61% F 10.21%
found: C 44.8 % H 3.9 % N 15 % S 8.6 % F 10.2 % .

Claims (8)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A sulfonylimido-carbonic acid diester of the formula in which A is a radical of the formula Y is oxygen, sulfur or -C=N-, Rl is halogen, nitro, trifluoromethyl, Cl-C5-alkyl, Cl-C5-alkoxy, -COR7, -S(O)m-Cl-C5-alkyl, -SO2Rl0, -0S02Cl-C5-alkyl, or R11, R2 is hydrogen, fluorine, chlorine, bromine, nitro, Cl-C5-alkyl, Cl-C5-alkoxy, trifluromethoxy, Cl-C5-haloalkoxy or -COR7, R3 is hydrogen, fluorine, chlorine, bromine, nitro, methoxy or trifluoromethyl, R4 is hydrogen, halogen, nitro, Cl-C5-alkyl, methoxy, -COR7 or -SO2NR8Rg, R5 is hydrogen, fluorine, chlorine, bromine, nitro Cl-C5-alkyl, Cl-C5-alkoxy, trifluoromethyl, -S(O)mCl-C5-alkyl, -COR7 or - SO2NR8R9, R6 is hydrogen, fluorine, methyl or methoxy, R7 is hydrogen, C1-C5-alkyl, C1-C5-haloalkyl, C1-C5-alkoxy, C1-C5-haloalkoxy, C2-C10-alkoxyalkoxy,C3-C5-alkenyloxy, C3-C5-alkynyloxy, phenoxy, benzyloxy, C1-C5-alkylthio or -NR8R9, R8 is hydrogen, C1-C5-alkyl, cyanoalkyl having a maximum of 5 carbon atoms, methoxy, ethoxy or C3-C5-alkenyl, R9 is hydrogen, C1-C5-alkyl or C3-C5-alkenyl, or R8 and R9 together with the nitrogen atom binding them form a 5- or 6-membered, saturated heterocycle which can contain an oxygen or sulfur atom as ring member, R1o is C1-C5-haloalkoxy, or -NR8R9, R11 is C1-C5-alkyl which is substituted by halogen, C1-C5-alkoxy, -S(O)mC1-C5-alkyl, -S(o)mC1-C5-halOalkyl; or C2-C5 alkenyloxy, or C2-C5-haloalkenyloxy;

Rx is C1-C5-alkyl; and m is zero, one, or two;
provided that when A represents phenyl, then:
(i) at least one of R1, R2 and R3 is other than hydrogen;
(ii) if R2 and R3 are both hydrogen, then R1 is other than either a 4-methyl, or a 4-chloro group.

2. N-(2-Difluoromethoxybenzenesulfonyl)-imidocarbonicc acid diethyl ester.

3. N-(2-Chlorobenzenesulfonyl)-imidocarbonic acid diethyl ester.

4. N-(2-Methoxycarbonyl-benzenesulfonyl)-imidocarbonic acid diethyl ester.

5. N-(Difluoromethylthio-benzenesulfonyl)-imidocarbonic acid diethyl ester.

6. A process for producing the sulfoimido-carbonic acid diester of the formula (IV) (IV) in which A is a radical of the formula Y is oxygen, sulfur or , R1 is halogen, nitro, trifluoromethyl, C1-C5-alkyl, C1-C5-alkoxy, -COR7, -S(O)m-C1-C5-alkyl, -S02R10, -OSO2C1-C5-alkyl, or R11' R2 is hydrogen, fluorine, chlorine, bromine, nitro, C1-C5-alkyl, C1-C5-alkoxy, trifluoromethoxy, C1-C5-haloalkoxy or -COR7, R3 is hydrogen, fluorine, chlorine, bromine, nitro, methoxy or trifluoromethyl, R4 is hydrogen, halogen, nitro, C1-C5-alkyl, methoxy, -COR7 or - SO2NR8R9, R5 is hydrogen, fluorine, chlorine, bromine, nitro C1-C5-alkyl, C1-C5-alkoxy, trifluoromethyl, -S(O)mC1-C5-alkyl, -COR7 or -SO2NR8R9, R6 is hydrogen, fluorine, methyl or methoxy, R7 is hydrogen, C1-C5-alkyl, C1-C5-haloalkyl, C1-C5-alkoxy, C1-C5-haloalkoxy, C2-C10-alkoxyalkoxy, C3-C5-alkenyl-oxy, C3-C5-alkynyloxy, phenoxy, benzyloxy, C1-C5-alkylthio or -NR8R9, R8 is hydrogen, C1-C5-alkyl, cyanoalkyl having a maximum of 5 carbon atoms, methoxy, ethoxy or C3-C5-alkenyl, R9 is hydrogen, C1-C5-alkyl or C3-C5-alkenyl, or R8 and R9 together with the nitrogen atom binding them for a 5- or 6-membered, saturated heterocycle which can contain an oxygen or sulfur atom as ring member, R10 is C1-C5-haloalkoxy, or -NR8R9, R11 is C1-C5-alkyl which is substituted by halogen, C1-C5-alkoxy, -S(O)mC1-C5-alkyl, -S(O)mC1-C5-haloalkyl; or C2-C5-alkenyloxy or C2-C5-haloalkenyloxy, Rx is C1-C5-alkyl, and m is zero, one, or two;
which process comprises condensing a sulfonyl chloride of the formula (II) A - SO2C1 (II) wherein A has the meaning defined in claim 1, in an inert phase system or organic solvent, in the presence of at least the equimolar amount of a base as acid-binding agent and at a temperature of 0 to 100°C, with an imidocarbonic acid ester of the formula (III) (III) in which Rx is C1-C5-alkyl; and recovering the formed sulfon-ylimidocarbonic acid diester of the formula (IV).

7. A process according to claim 6, which process com-prises reacting a sulfonyl chloride of the formula (II) A - SO2C1 (II) in which A has the meaning defined in claim 1, in an inert phase system or organic solvent, in the presence of a tert-iary amine, with the imidocarbonic acid diethyl ester of the formula HN=C(OC2H5)2 to give a sulfonylimido-carbonic acid diethylester of the formula A-SO2N=C(OC2H5)2

8. A process according to claim 6 or 7, wherein the reaction of the compounds II or III is performed in an inert phase mixture or organic solvent, and in the presence of triethylamine.