WO1993010086A1

WO1993010086A1 - Process for preparing n-(arylsulphonyl)-carbamide acid derivates and intermediates useful for carrying out this process

Info

Publication number: WO1993010086A1
Application number: PCT/HU1992/000047
Authority: WO
Inventors: Gábor BESENYEI; Sándor NÉMETH; László SIMÁNDI; Mária BELÁK; Éva FISCHER
Original assignee: MTA Központi Kémiai Kutató Intézete
Priority date: 1991-11-13
Filing date: 1992-11-12
Publication date: 1993-05-27
Also published as: AU2954992A

Abstract

An improved process is disclosed for preparing known N-(arylsulphonyl)-carbamic acid derivates (carbamide, carbamate and thiocarbamate) having the formula (I), in which Ar can be an aryl group, Z can be N, S or O and R<4> and R<5> can be different aliphatic, cycloaliphatic or aromatic groups. To produce these compounds, arlsulphonylimines having the general formula (II): ArSO2N=XR<1>R<2>R<3>, in which R<1>, R<2> et R<3>, independently from each other, designate C1-12-alkyl, cyclohexyl, optionally substituted benzyl, phenyl or naphthyl; and X stands for an atom of phosphorus, arsenic, antimony, sulphur, selenium, tellurium or iodine, are catalytically carbonylated with CO and the resulting arylsulphonyl isocyanate having the formula (III): ArSO2NCO is reacted during or after carbonylation with compounds having the general formula (IV): R<4>R<5>ZH.

Description

METHOD FOR PRODUCING N- (ARYLSÜLFONYL) -CARBAMIC ACID DERIVATIVES AND THE USES THEREOF

INTERMEDIATE

The invention relates to an improved process for the preparation of known N- (arylsulfonyl) carbamic acid derivatives (carbamides, carbamates and thiocarbamates) (process A). The invention further relates to a new, chemically peculiar process for the preparation of the arylsulfonyl isocyanates which can be used as intermediates in process A (process B), furthermore to a new process for the preparation of some of the arylsulfonylimines which can be used as intermediates in processes A and B (process C ) and finally new arylsulfonylimines, some of which are prepared by process C, some of which are known processes.

The N- (arylsulfonyl) carbamic acid derivatives which can be prepared by process A correspond to the general formula

(I)

wherein

Ar represents phenyl, benzyl, naphthyl, pyridyl or thienyl

stands by C _1-12 alkyl, C _1-4 alkenyl, C _1-12 haloalkyl, C _1-4 haloalkenyl, C _1-12 alkoxy, C _1-12 haloalkoxy, C _3-5 -Cycloalkyl, aryl, aryloxy, nitro, cyano, aliphatic acyl, aromatic acyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulfonyl, arylsulfonyl, alkoxysulfonyl, dialkylamino, dialkylaminocarbonyl, dialkylaminosulfonyl, N, N-dialkyl-halocarbamoyl can be mono- or polysubstituted, and

R ⁴ and R ⁵ for

a) C _1-6 alkyl,

b) C _1-6 haloalkyl,

c) alkoxyalkyl, d) aryloxyalkyl,

e) C _3-6 alkenyl,

f) C _3-6 haloalkenyl,

g) C _3-6 alkynyl,

h) C _3-8 cycloalkyl,

i) C _3-8 cycloalkyl which is substituted by C _1-4 alkyl, C _1-4 haloalkyl or by halogen,

j) benzyl,

k) phenyl,

l) naphthyl,

m) pyridyl,

n) pyrimidinyl,

o) trάazinyl,

with the restriction that R ⁴ and R ⁵ cannot simultaneously stand for groups k) - o),

p) the groups j) - m) by C _1-4 alkyl, C _1-4 haloalkyl, C _1-4 alkoxy, C _1-4 haloalkoxy, alkoxyalkyl, alkoxyalkoxy, Cι-4-alkylamino and / or halogen is mono- or polysubstituted,

r) the groups n) and o) which are substituted as indicated under p),

s) hydrogen,

t) electron pair are standing or

u) R ⁴ and R ⁵ together form an α, ω-alkylene chain with 4-6 carbon atoms, which can be interrupted by an oxygen atom, a sulfur atom, a sulfinyl, sulfonyl or C _1-4 alkylimino group, and

z for a nitrogen, oxygen or sulfur atom

stands with the restriction that in the case of Z = O or SR ⁴ stands for electron pair and R5 has one of the meanings a) - m) and p), while in the case of Z = NR ⁴ and R ^{5 have} a different meaning than electron pair. Among the N- (arylsulfonyl) carbamic acid derivatives, there are numerous compounds with advantageous biological effects. The amide derivatives are characterized by vari discard biological effects; While the N- (arylsulfonyl-N'-triazinyl (or -pyrimidinyl)) compounds are primarily known as herbicides, the derivatives containing a phenyl group or an aliphatic or alicyclic group instead of an aromatic N-heterocycle have an antidiabetic, cardiac rhythm-regulating or cancer-inhibiting effect The O-esters and S-esters show an antidotum activity against the phytotoxicity of herbicides based on triazine and thiocarbamate or have a herbicidal action themselves.

Numerous methods have been developed for the preparation of the derivatives of arylsulfonylcarbamic acids. The following reference gives Chem. Rev., 1952. 50, 1-46; Houben-Weyl, Methods of Organic Chemistry, Volume E4, 267-272, 332, 400-402, Georg Thieme Verlag, Stuttgart, New York, 1983.

The methods used widely or not described in the cited literature can be summarized as follows.

Sulfonamides and their alkali salts are reacted in mixtures of water and acetone, water and tetrahydrofuran or in organic solvents, optionally in the presence of tertiary amines, with aliphatic isocyanates to form N- (arylsulfonyl) -N'-alkylureas [Ger. 1,201,337, Brit. 808 071, US 2,371,178]:

ArSO ₂ NH ₂ + RNCO - - - - - - -> ArSO ₂ NHC (0) NHR (1)

The addition reaction of arylsulfonyl isocyanates and primary or secondary amines also gives sulfonylureas [Chem. Rev. 1965, 65, 369-376 and the literature given there]:

ArSO ₂ NCO + NHR ¹ R ² - - - - - - -> ArSO ₂ NHC (O) NR ¹ -R ² (2).

In the aminolysis of N-sulfonylcarbamic acid esters, the corresponding ureas are formed in good yield. The reaction can be carried out in a solvent or by pyrolysis of the ammonium salt of the carbamate [J. Org. Chem. 1958, 23, 923-929]:

Also the conversion of at about 100 ° C

Arylsulfonamides and N-substituted carbamates lead to

N- (arylsulfonyl) ureas [Brit. 604 259 (CA 421061b

/ 1949 /), monthly Chem. 1972, 103, 1377]:

When carbamoyl chlorides are reacted with sulfonamides, sulfonylureas are formed when hydrochloric acid escapes [Brit. 538 884 (CA 36, 3511/1942 /), Brit. 604 259 (CA 43

1061b / 1949 /), Swiss 222077 (CA 13, 821/1949 /)]. The carbamoyl chlorides are generally produced by the reaction of primary or secondary amines with phosgene and are often used without isolation in the meantime:

N- (Arylsulfonyl) carbamic acid esters are generally prepared by reacting arylsulfonamides with chloroformic acid esters [J. Org. Chem. 1958, 23, 923; US 3 799 760, US 3 933 894, EP 101 407]:

abs acetone

Arylsulfonylthiocarbamic acid esters can be prepared in an analogous manner from chlorothio formic acid esters and sulfonamides [DE 2 644 446].

Arylsulfonyl carbamates can be obtained by using carbonic acid esters as the acylating agent [US

4,612,385, EP 96 003]:

An easy way to make arylsul fonylcarbamate is the reaction of arylsulfonyl isocyanates with alcohols or mercaptans [J. Heterocycl. Chem. 1980. 17, 271]:

ArSO ₂ NCO + RZH - - - - - - -> ArSO ₂ NHC (O) ZR (8)

Z = O, S

S-sulfonylthiocarbamic acid esters are produced in good yield in the alkaline hydrolysis of N- (arylsulfonyl) imino-dithiocarbonic acid dimethyl esters or in the oxidation of N- (arylsulfonyl) -dithiocarbamic acid methyl ester (12 Nippon Kagaku 91) with H ₂ O ₂ ) 1168-73, CA 75, 19878].

The thermal rearrangement of diethyl N-tosyliminocarbonate produces ethyl N-ethyl-N-tosylcarbamate [J. Org. Chem. 1963, 28, 2902].

According to Hungarian Patent Nos. 202 487, 203 719 and 204 779, sulfonylureas, carbamates and thiocarbamates are produced by catalytic carbonylation of N-halosulfonamidates. While this method overcomes many of the disadvantages of the previous methods, its applicability is limited because the aryl group must not contain any groups sensitive to oxidation, acidic or alkaline hydrolysis.

The described processes only partially meet the modern requirements of environmental protection, technology and economy. A significant part of the processes are based on the indirect or direct use of phosgene, which leads to serious environmental and corrosion problems. The processes that do not work with phosgene require the use of other difficult to handle, flammable and / or toxic starting materials, in some cases the yields are only low. It is characteristic of most of the processes described that they contain reaction steps which have to be carried out at relatively high temperatures, which increases the costs for energy sources. Because of all this There were a need to develop a new, better process for the preparation of sulfonylcarbamic acid derivatives.

The invention is based on the knowledge that the arylsulfonylimines of the general formula (II)

ArSO ₂ N = XR ¹ R ² R ³ (II) catalytically to the arylsulfonyl isocyanates of the general formula (III)

ArSO ₂ NCO (III) can be carbonylated if a catalyst is used as a transition metal from the 4th, 5th or 6th period of the periodic table, the oxide, salt, carbonyl or the complex of such a metal in which the coordinative bond by a carbon, tin, nitrogen, phosphorus, arsenic, antimony, oxygen, sulfur, selenium, tellurium and / or halogen atom is formed, and the arylsulfonyl isocyanates of the general formula (III) with compounds of the general formula (IV)

R ⁴ R ⁵ ZH (IV) react to the desired N- (arylsulfonyl) carbamic acid derivatives of the general formula (I).

The invention accordingly relates to a process for the preparation of N- (arylsulfonyl) carbamic acid derivatives of the general formula (I)

ArSO ₂ NHCZR ⁴ R ⁵ (I) in which the meaning of Ar, R ⁴ , R ⁵ and Z is the same as stated at the beginning. It is characteristic of the process according to the invention that arylsulfonylimines of the general formula (II) (optionally prepared in situ)

ArSO ₂ N = XR ¹ R ² R ³ (II) wherein the meaning of Ar is the same as above and

R ¹ , R ² and R ³ independently of one another are C _1-12 -alkyl,

Cyclohexyl, benzyl, phenyl or naphthyl, the latter two groups being substituted by C _1-4 alkyl, C _1-4 haloalkyl, C _1-4 alkoxy, C _1-4 haloalkoxy and / or Halogen can be mono- or polysubstituted, or represent a pair of electrons or an oxygen atom,

R ¹ and R ² together form a divalent hydrocarbon group, or

R ¹ , R ² and R ³ for the forms of the groups listed coupled to a polymer matrix stand with the restriction that at least one of the groups R ¹ , R ² and R ^{3 represents} a hydrocarbon group which is mixed with iodine, sulfur, selenium, Tellurium, phosphorus, arsenic or antimony can form a covalent bond, and

X for phosphorus, arsenic, antimony, sulfur, selenium,

Tellurium or iodine atom,

catalytically carbonylated, the catalyst used being a transition metal from the 4th, 5th or 6th period of the periodic system, the oxide, salt, carbonyl or the complex of such a metal, in which the coordinative bond by a carbon, tin or , Nitrogen, phosphorus, arsenic, antimony, oxygen, sulfur, selenium, tellurium and / or halogen atom is formed, where the catalyst can be prepared beforehand or generated in the reaction mixture and as a homogeneous, heterogeneous or heterogenized homogeneous Catalyst is present and is used in a quantity of 10 ^-3 - 10 mass% based on the starting imine of the general formula II, and the carbonylation reaction at -20 ° C to 200 ° C, preferably -20 ° C to 120 ° C, and a CO partial pressure of 10 ⁵ - 10 ⁷ Pa in a solvent for 0.1-10 hours, and after completion of the carbonylation, the arylsulfonyl isocyanate of the general formula (III)

ArSO ₂ NCO (III)

(wherein the meaning of Ar is the same as above) containing reaction mixture a reagent of the general formula (IV)

R ⁴ R ⁵ ZH (IV) wherein the meaning of R ⁴ , R ⁵ and Z is the same as above, or the carbonylation is carried out in the presence of a compound of the general formula IV and the product of the general formula I obtained is isolated in a manner known per se.

The process can be illustrated by the following reaction schemes:

or in the event that carbonylation is carried out in the presence of the compound (IV):

The following are particularly preferred for the substituent meanings: Ar: 2-chlorophenyl, 2-methoxycarbonylphenyl, 2-ethoxycarbonylphenyl, 2- (2-chloroethoxy) phenyl, 2-methoxycarbonylbenzyl, methoxycarbonyl-3-thienyl, 3- (dimethylaminocarbonyl) -2 -pyridyl; Z: nitrogen; R ⁴ and R ⁵ : 4-ethyl-6-methoxy-2-triazinyl, hydrogen, methyl, 4, 6-dimethyl-2-pyrimidinyl, 4, 6-bis (difluoromethoxy) -2-pyrimidinyl, 4, 6-dimethoxy -2-pyrimidinyl, 4-chloro-6-methoxy-2-pyrimidinyl, 4-ethoxy-2-pyrimidinyl, 4-methylamino-6-ethoxy-2-thiazinyl. The aliphatic substituents present in the groups Ar particularly preferably have 1-4 carbon atoms.

The synthesis of the compounds of general formula I is carried out in a solvent medium. The usual organic solvents, preferably dichloromethane, 1, 2-dichloroethane, acetonitrile or, come as solvents their mixtures in question. A small amount of a nitrile (acetonitrile, benzonitrile) has been found to improve the reaction. A nitrile or another of the solvents mentioned, to which some nitrile has been added, is therefore preferably used as the solvent.

The carbonylation of the compounds II takes place in the presence of a catalyst. The transition metals of the 4th, 5th and 6th period of the periodic system, their oxides, salts, carbonyls or those complexes which as a donor atom have a carbon, tin, nitrogen, phosphorus, arsenic, Contain antimony, oxygen, sulfur, selenium, tellurium and / or halogen atom. Mixtures of these catalysts can also be used.

It is particularly preferred to use palladium as the metal component of the catalyst.

The catalyst can be homogeneous, heterogeneous or heterogenized (immobilized). It can have been prepared beforehand, or it can be generated in situ. For example, aluminum oxide, silica gel, activated carbon and organic polymers can be used as carriers for heterogeneous and immobilized catalysts.

The catalyst is used in an amount of 10 ^-3-10 mass% based on the starting sulfonylimine.

The carbon monoxide used for the carbonylation reaction can be used as a pure gas or as a gas mixture. All gases and vapors which are inert to the catalyst and the reactants are suitable as dilution components. Examples include: nitrogen, oxygen, noble gases, air, carbon dioxide, hydrogen, water vapor, vapors from organic solvents. However, some catalysts or reactants can be sensitive to the diluent gas, which is why the diluent gases permitted for the individual catalysts and reaction components can differ. The CO partial pressure in the reactor is between 10 ⁵ and 10 ⁷ Pa.

The carbonylation reaction is carried out at temperatures between -20 ° C and 200 ° C, preferably between 20 ° C and 120 ° C, in particular at temperatures between 20 ° C and 100 ° C. The temperature is chosen depending on the activity of the catalyst and the thermal stability of the reactants.

The carbonylation is either carried out in the presence of the compound IV, or after the carbonylation has ended, the compound IV is added, the target product I being formed.

However, since the phosgene-free carbonylation is new and valuable under the stated conditions, there is also a need to protect the arylsulfonyl isocyanates produced in this way. If no reagent IV is added after carbonylation, the reaction with isocyanate III stops.

Successful attempts have been made to produce sulfonyl isocyanates around the turn of the century, and numerous reaction routes have been developed since then. A brief overview is given below.

Billeter [Reports 1903, 36, 3213; 1904. 37, 690; 1905, 38, 2013] prepared sulfonyl isocyanates by reacting sulfonyl chlorides and silver cyanate in 5-38% yield:

RSO ₂ Cl + AgOCN - - - - - - - -> RSO ₂ NCO + AgCl. (10)

Although the yield of this reaction could later be improved significantly, the process has not been put into practice.

Krzikalla observed that the sulfonamides, like the primary aromatic and aliphatic amines, react with phosgene at high temperatures to form sulfonyl isocyanates [GB 692 360 (CA 47 8771)]:

(Ar = substituted phenyl), the yields were about

50%.

Much better results were achieved if instead of the sulfonamide, its derivatives, for example the N- (arylsulfonyl) -N'-butylureas, were reacted with phosgene [J. Org. Chem. 1966. 31, 2658-61; Appl. Chem. Int.

Ed. 1966. 5, 704-12]:

The two isocyanates can be easily separated from one another by distillation; the yield is over 80%.

Modifications to this method are the processes in which the sulfonamide is phosgenated in the presence of lower aliphatic isocyanates or aliphatic amines [Chem. Rev. 1965. 65, 369-76; DE 2 152 971 / CA 79 18386].

In several publications it has been reported that oxalyl chloride can also be used instead of phosgene for the production of aromatic or aliphatic sulfonyl isocyanates [J. Org. Chem. 1964, 29, 2592-5; J. Med. Chem. 1965, 8, 781-4]. The yields depend strongly on the hydrocarbon group attached to the sulfonyl group.

.

R = phenyl, p-tolyl, piperidyl

According to a Stauffer application, sulfonamides can be reacted with thionyl chloride and chlorocarbonylsulfonyl chloride in the presence of pyridine to give sulfonyl isocyanates [US 4,835,053 / CA 10278564]:

According to JP 70/19 893 (CA 73 98607), an intermediate product obtained by the reaction of sulfonamides with N, N-carbonyldiimidazole can be converted to sulfonyl isocyanate by heating in the presence of P ₂ C ₅ :

Sulfonyl isocyanates can be prepared from N-sulfonyldithiocarbamates in a multi-stage synthesis [Nippon Kagaku Zasshi 1970. 91, 1168-73 / CA 75 19878 /]:

The final step is either heating in xylene or chlorination.

The chlorosulfonyl isocyanate proved to be suitable in two ways for the preparation of sulfonyl isocyanates [DE 3 132 944 / CA 98.215319 /; Ger. 1 289 526 / CA 70 87312 /]:

From this overview it can be seen that the preparation of sulfonyl isocyanates is not an easy task for the chemist. If one starts from sulfonamides, phosgenation gives the best yields. Should no phosgene ver other, very reactive compounds must be used, in some cases it is a multi-stage, complicated reaction pathways.

The invention therefore also relates to a process (process B) for the preparation of arylsulfonyl isocyanates of the general formula (III)

ArSO ₂ NCO (III)

(wherein the meaning of Ar is the same as above). It is characteristic of the process that arylsulfonylimines of the general formula (II)

ArSO ₂ N = XR ¹ R ² R ³ (II) wherein the meaning of Ar, R ¹ , R ² and R ³ and X is the same as above, under the conditions given for process A, carbonylated.

Some of the arylsulfonylimines of the general formula II required as starting materials in processes A and B according to the invention are known, some are new. Examples from the literature include:

X = I; R ¹ = (substituted) phenyl, R ² = R ³ = pair of electrons, Chem. Lett. 1975, 361;

X = S, Se, Te; R ¹ = R ² = (substituted) phenyl; R ³ =

Electron pair, Zh. Org. Khim. 1979, 15, 896-899 Zh. Org. Khim. 1974. 10, 807-810;

X = P, As, Sb; R ¹ = R ² = R ³ = (substituted) phenyl,

Reports 1964. 97, 747, 769 and 789.

The processes known from the literature for the preparation of the compounds (II) are based on a sulfonamide component and compounds of the general formula (V)

from where R ⁶ and R ^{7 are} leaving groups or electron pairs and R ¹ , R ² and R ^{3 have} one of the meanings given above for these groups. Either the sulfonyl nitrogen of the sulfonamide is in the oxidized state and the heteroatom X of compound V in a reduced state: (19)

X = P, As, Sb, Chem. Rev. 1978. 78, 65-79 and the literature cited therein;

MHal

X = S, Chem. Rev. 1978, 78, 65-79 and the literature given there; t l

Here the oxidized state of the sulfonyl nitrogen is caused by azide formation [Synthesis 1979, 596-597].

The second possibility is that the sulfonamide nitrogen is in a reduced state and the heteroatom X of compound V is in an oxidized state:

i

)

J. Chem. Soc. Perkin I, 1974. 460-70.

Ph ₂ Se (OMe) ₂ + ArSO ₂ NH ₂ - - - - - - - - - - - -> Ph ₂ Se = NSO ₂ Ar (23)

Zh. Org. Khim. 1987. 23, 2242-2243.

MeOH / KOH

)

Chem. Lett., 1975. 361-362.

All of these methods have one or two consequences. part. N-halosulfonamidates can only be formed from relatively few sulfonamides, ie the number of sulfonylimines which can be prepared from them is necessarily limited. For some types of reactions, aggressive (strongly alkaline or strongly acidic) media, for example acetic anhydride, are used, or they only run at high temperatures (see, for example, equations (22), (24), (25)), and these circumstances also limit the range of sulfonylimines that can be prepared. Many of the methods listed are very time consuming and their yield is low.

In our own experiments for the production of arylsulfonylimines it has now surprisingly been found that the I, I-dimethoxyiodobenzene forms aromatic arylsulfonylimines quickly and in good yield with aromatic sulfonamides under mild reaction conditions:

The invention therefore also relates to a process (process C) for preparing the compounds of the general formula (Ha) which form a narrower group of the compounds of the general formula (II)

ArSO ₂ N = IR ^{1 '} R ² R ³ (IIa), in which the meaning of Ar is the same as above, R ^{1' represents} an optionally substituted phenyl or naphthyl group and R ² and R ^{3 are} electron pairs.

Since two substituents R represent a pair of electrons, the compounds (IIa) can also be written ArSO ₂ N = IR _{1 '} .

The compounds of the general formula (Ha) are prepared according to the invention by using arylsulfonamides of the general formula (VI)

ArSO ₂ NH ₂ (VI),

wherein the meaning of Ar is the same as above, with I, I-disubstituted preferably prepared in situ organic iodine compounds of the general formula (VII)

R ^{1 '} -I (OAlk) ₂ (VII) in which the meaning of R ^{1' is} the same as above and Alk is alkyl with 1-4 carbon atoms, at temperatures between -20 ° C and 80 ° C for one minute to 2 Implemented for hours.

The substituents of the optionally substituted phenyl or naphthyl group Rl's are preferred: C _1-4 alkyl, C _1-4 haloalkyl, C _1-4 haloalkoxy, C _1-4 alkylsulfonyl, phenylsulfonyl and / or Halogen.

generally not prepared but made in situ from the corresponding iodosyl aromatics and alcohols:

R ^{1 '} I = O + 2 AlkOH - - - - - - - -> R ^1' I (OAlk) ₂ + H ₂ O (27)

Inorg. Chem., 1983. 22, 1563-5

In this case it is advisable to work in the presence of a dehydrating agent. The organic and inorganic dehydrating agents usually used in laboratory practice, for example magnesium sulfate, magnesium perchlorate, natural or synthetic zeolites, orthoformate, 2,2-dimethoxypropane and dicyclohexylcarbodiimide, are suitable as such. The selectivity of the process is generally better if the reaction mixture is anhydrous.

The reaction is carried out in a solvent. Lower aliphatic alcohols, preferably methanol, furthermore hydrocarbons, chlorinated hydrocarbons, ethers, esters, nitriles, aliphatic or aromatic nitro compounds or mixtures of lower aliphatic alcohols and the other solvents listed are suitable as solvents.

The compounds of the general formula (Ha) are isolated from the reaction mixture by filtration, evaporation and / or precipitation with a solvent. A solvent is preferably used as the precipitation solvent inert solvent that does not contain alcoholic hydroxyl groups.

To prepare the compounds of the general formula (Ila), the procedure is, for example, that the iodosyl compound R ^{1 '} l = O in the presence of an equivalent amount of arylsulfonamide of the general formula (VI) in the corresponding alcohol AlkOH, for example in methanol ( Alk = Me), stirred for a short time and then the solvent was removed in vacuo.

It is also possible to first prepare the dialkoxy iodine compound and to add the sulfonamide to its solution.

According to a preferred variant of process C, the organic iodine compound R ¹ 'I (OAlk) _{2 is} coupled to a polymer matrix or another solid support. This carrier-bound iodine compound can then form the filling of a reactor through which the solvent flows with the other components of the reaction. The water can be removed here outside the reactor. It is also advantageous with this solution that the organic iodine compound can be easily recovered after the arylsulfonylamine of the general formula (Ila) has been reacted further (carbonylated).

Finally, the invention relates to new arylsulfonylimines of the general formula (IIb)

Ar ^, SO ₂ N = XR ¹ R ² R ³ (Hb), wherein

Ar 'for 2-halophenyl, 2- (2-chloroethoxy) phenyl, 2- (C _1-4 alkoxycarbonyl) phenyl, 2- (C _1-4 alkoxycarbonyl) benzyl, 3- (dimethylaminocarbonyl) pyride -2-yl or

2- (C _1-4 -alkoxycarbonyl) -thien-3-yl and the meaning of R ¹ , R ² , R ³ and X is that given for the general formula (II).

These new compounds, which form a narrower group of the compounds of the general formula (II), can be prepared by processes known from the literature [s. the reaction equations (19) - (25), see. the exemplary embodiments] as well - if X is iodine - can be produced by means of the method C according to the invention. Like the known compounds (II) in the pharmaceutical and crop protection industry, they can be used as intermediates for arylsulfonyl isocyanates, ureas, carbamates and thiocarbamates, as oxidizing agents or for the synthesis of the amino and imino derivatives of hydrocarbons in the presence of a suitable catalyst be used.

The advantages of the invention can be summarized as follows:

1) Methods A and B do not require phosgene, so it is safer and more environmentally friendly than the methods currently used in practice.

2) The intermediates of the general formula II can be prepared under gentler reaction conditions than the N-halosulfonamidates, and as a result the range of isocyanates obtainable by carbonylation of the compounds II or of the compounds I which can be prepared from them is considerably larger than is the case with N-halosulfonamida - is the case. Since the organic iodine compounds used in process C dissolve well in organic solvents, the reaction proceeds quickly.

According to process C, the reaction to the arylsulfonylimide takes place at room temperature, which means less energy consumption.

3) The carbonylation can be carried out at low to medium pressure and temperatures between 20 ° C and 100 ° C, in a homogeneous phase, which enables simple and energy-saving technology.

4) The process is easy to insert into known technological processes and, due to its good degree of atomic utilization, offers the possibility of developing an environmentally friendly technology. A realization possibility the following series of reactions shows:

NaCl + ΔE - - - - - - -> Na + ½ Cl ₂

Na + CH3OH - - - - - - -> NaOCH ₃ + ½ H ₂

R ¹ R ² R ³ X + Cl ₂ - - - - - - -> R ¹ R ² R ³ XCl ₂

R ¹ R ² R ³ XCl ₂ + ₂ NaOMe - - - - - - -> R ¹ R ² R ³ X (OCH ₃ ) ₂ + 2

R ¹ R ² R ³ X (OCH ₃ ) ₂ + ArSO ₂ NH ₂ - - - - - - -> R ¹ R ² R ³ X = NSO ₂ Ar +

Cat.

R ¹ R ² R ³ X = NSO ₂ Ar + CO - - - - - - -> ArSO ₂ NCO + R ¹ R ² R ³ X

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

ArSO ₂ NH ₂ + CO + E - - - - - - -> ArSO ₂ NCO + H ₂

This means that the gross reaction can in principle also be carried out in such a way that it is the only by-product

Hydrogen is created.

The invention is explained in more detail below on the basis of exemplary embodiments.

Procedure A

example 1

1.86 g (5 mmol) of Np-tosylimino-iodobenzene (4-CH ₃ C ₆ H ₄ - SO ₂ N = IC ₆ H ₅ ) are dissolved in 10 ml of dichloromethane in the presence of 37.3 mg of PdCl ₂ (PhCN) 2 as a catalyst Carbonylated at an initial CO pressure of 3.7 MPa at 25 ° C for one hour.

The homogeneous reaction mixture is transferred to a glass apparatus under a nitrogen atmosphere. 0.64 g (5 mmol) of 2-chloroaniline are added there with stirring and external cooling. A white precipitate begins to separate after 1-2 minutes. The reaction mixture is concentrated, treated with diethyl ether and then filtered. 1.0 g (62%) of N- (4-methylphenylsulfonyl) -N '- (2-chlorophenyl) urea are obtained.

IR: 1698, 1599, 1547, 1444, 1353, 1160 cm ^-1

Example 2

1.6 g (4 mmol) of N-p-tosyl-Se, Se-diphenyl-selenylimine

[4-CH ₃ C ₆ H ₄ SO ₂ N = Se (C ₆ H ₅ ) 2] in 10 ml dichloromethane in the presence of 50 mg PdCl ₂ (PhCN) ₂ and 0.2 ml benzonitrile carbonylated at an initial pressure of 3.6 MPa at 45-50 ° C for 4 hours. The procedure below is as in Example 1 and 0.83 g (64%) of N- (4-methylphenylsulfonyl) -N '- (2-chlorophenyl) urea is obtained.

Example 3

1.11 g (2.63 mmol) of N- (2-chlorophenylsulfonyl) -Se, Se-diphenyl-selenylimine [2-ClC ₆ H ₄ SO ₂ N = Se (C ₆ H ₅ ) ₂ ] are in the presence of 45 , 5 mg PdCl ₂ (PhCN) ₂ as a catalyst in a mixture of 5 ml dichloromethane and 0.2 ml acetonitrile at a pressure of 4.1 MPa and a temperature of 60 ° C for 2 hours carbonylated. After the reactor has cooled and the gas phase has been blown off, 0.33 g of 2-amino-4-methyl-6-methoxytriazine is added to the mixture and the mixture is stirred at room temperature for a further 14 hours. The mixture is evaporated, filtered and the product washed with petroleum ether. The N- (2-chlorophenylsulfonyl) -N '- (4-methyl-6-methoxy-triazin-2-yl) urea is obtained in 52% yield.

Example 4

2.36 g (5.66 mmol) of N- (2-methoxycarbonyl-phenylsulfonyl) -imino-iodobenzene (2-CH ₃ O ₂ CC ₆ H ₄ SO ₂ N = IC ₆ H ₅ ) are in the presence of 63 mg of PdCl ₂ (PhCN) ₂ carbonylated in a mixture of 10 ml dichloromethane and 0.2 ml acetonitrile at room temperature for 15 minutes (P ° CO = 4.0 MPa). After the gas phase had been blown off, 0.7 g (5 mmol) of 2-amino-4-methyl-6-methoxytriazine were added to the reaction mixture and the mixture was stirred for one night with the exclusion of air. After working up the reaction mixture, 1.8 g of N- (2-methoxycarbonyl-phenylsulfonyl) -N '- (4-methyl-6-methoxytriazin-2-yl) urea of 80% purity, corresponding to a yield of 66 ,8th %.

Example 5

3.8 g (10 mmol) of Np-tosyl-imino-iodobenzene) 4-CH ₃ C ₆ H ₄ -SO ₂ N = IC ₆ H ₅ ) are mixed out in the presence of 46 mg of PdCl ₂ (PhCN) ₂ 10 ml dichloromethane and 0.2 ml acetonitrile carbonylated at a CO pressure of 4.0 MPa and room temperature for 45 minutes. After the gas phase has been blown off, the reaction mixture is mixed with 1.23 g of 2-amino-4,6-dimethylpyrimidine and stirred for a further hour. The reaction mixture is evaporated and the product washed with petroleum ether. 2.45 g of Np-tosyl-N '- (4,6-dimethyl-pyrimidin-2-yl) urea are obtained with a purity of 85%, which corresponds to a yield of 65%.

Analogously to Examples 1-5, the compounds of the general formula (I) listed in Table 1 are prepared by carbonylating sulfonylimines of the general formula (II) and reacting the sulfonyl isocyanates formed as intermediates with compounds of the general formula (IV).

Example 16

In a pressure-resistant reactor of 45 ml volume, 1.1 g (2.6 mmol) of 2- (CH ₃ OC (O) C ₆ H ₄ SO ₂ N = IPh, 0.4 g

(2.85 mmol) 2-amino-4-methyl-6-methoxytriazine, 49 mg

PdCl ₂ (PhCN) ₂ complex and 10 ml of acetonitrile. The reactor is filled with carbon monoxide under a pressure of 3.5 MPa. The reaction mixture is stirred at room temperature for 16 hours. After the gas phase has been blown off, the solvent is drawn off and the residue is washed with hexane. The N- (2-methoxycarbonyl-phenylsulfonyl) -N '- (4-methy1-6-methoxytriazin-2-yl) urea is obtained in 80% yield (HPLC).

In the same way, but starting from 2-amino-4-methyl-6-methoxyethoxytriazine, N- (2-methoxycarbonyl-phenylsulfonyl) -N '- (4-methyl-6-methoxyethoxy-triazine) is obtained in 71% yield. 2-yl) urea.

The carbamates and thiocarbamates summarized in Table 2 below are prepared in the manner given in Example 1.

Procedure B

The qualitative identification of the sulfonyl isocyanates is carried out by IR analysis of the diluted reaction mixture (presence of the bands _as NCO, _as SO ₂ , _s SO ₂ and optionally _as NO ₂ , _s NO ₂ and CO). For quantitative analysis, the isocyanates are reacted with 2-chloroaniline to give the corresponding N- (arylsulfonyl) -N '- (2-chlorophenyl) ureas. The components of the reaction mixture are identified by means of IR (KBr), MS and HPLC.

Example 22

1.86 g (5 mmol) of 4MePhSO ₂ N = IPh are dissolved in 10 ml of dichloromethane in the presence of 37.3 mg of PdCl ₂ (PhCN) ₂ catalyst with an initial CO pressure of 3.7 MPa at 25 ° C. for one hour carbonylated. The homogeneous reaction mixture is transferred to a glass apparatus under a nitrogen atmosphere, the supernatant (0.2 ml) is diluted with 50 times the amount of dichloromethane. In the cuvette an intense IR absorption can be observed at 2220 cm ^-1 , which indicates the presence of the sulfonyl isocyanate group. 0.64 g (5 mmol) of 2-chloroaniline are added to the remaining reaction mixture with nitrogen, stirring and external cooling. A white precipitate precipitates after 1-2 minutes. The reaction mixture is evaporated, treated with diethyl ether and the product is filtered off. 1 g (62%) of N- (4-methylphenylsulfonyl) -N'- (2-chlorophenyl) urea is obtained.

IR: 1698, 1599, 1547, 1444, 1353, 1160 cm ^-1 .

Example 23

1.6 g (4 mmol) of 4-MePhSO ₂ N = SePh ₂ are dissolved in 10 ml of dichloromethane in the presence of 50 mg of PdCl ₂ (PhCN) ₂ catalyst and 0.2 ml of benzonitrile with an initial CO pressure of 3.6 Pa Carbonylated at 45-50 ° C for 4 hours. The further working up is carried out according to Example 22. 0.83 g (64%) of N- (4-methylphenylsulfonyl) -N '- (2-chlorophenyl) urea is obtained.

The physical data correspond to those given in example 22.

The arylsulfonyl isocyanates of the general formula ArSO ₂ NCO listed in Table 3 above are prepared in the manner described in Examples 22 and 23.

Procedure C

Example 37

1.3 g (5.9 mmol) of iodosylbenzene and 1.25 g (5.8 mmol) of 2- (methoxycarbonyl) -benzenesulfonamide in a mixture of 20 ml of methanol and 0.8 ml of 2,2-dimethoxypropane at room temperature 15 - Stirred for minutes. The solvent is then removed in vacuo, the solid residue is triturated with 4 ml of dichloromethane and then filtered off. After washing with dichloromethane and then drying, is obtained

2.0 g of 2- (methoxycarbonyl) phenylsulfonylimino-iodobenzene

[2- (CH ₃ O ₂ C) C ₆ H ₄ SO ₂ N = IC ₆ H ₅ ]. The iodometrically determined purity of the product is 98%, which corresponds to a yield of 82.7%.

IR: 1721, 1267, 1128, 1108, 1058, 982 cm ^-1

(The position of some gangs depends on the moisture content of the product.)

Example 38

A mixture of 2.2 g (10 mmol) of iodosylbenzene, 30 ml of methanol and 1.5 ml of 2,2-dimethoxypropane is stirred at room temperature for 20 minutes. 2.35 g (10 mmol) of 2-bromo-benzenesulfonamide are added in small portions and the reaction mixture is stirred for a further 12 minutes. After removal of the solvent, 4.15 g of 2-bromophenylsulfonylimino-iodobenzene (2-BrC ₆ H ₄ SO ₂ N = IC ₆ H ₅ ) with a purity of 98% are obtained. Yield: 95%.

IR: 1282, 1272, 1141, 1120, 1093, 880 cm ^-1

Example 39

2.20 g (10 mmol) of iodosylbenzene are suspended in 30 ml of methanol and about 3 g of type 4A molecular sieve are added. The reaction mixture becomes a in the absence of air

Stirred for one hour, then the molecular sieve is filtered off and the filtrate with 2.35 g (10 mmol) of 2- (2-chloroeth oxy) -benzenesulfonamide added. Stirring is continued for half an hour, then the methanol is removed and the solid residue is treated with 10 ml of dichloromethane. After filtering and drying, 3.24 g (74%) of 2- (2-chloroethoxy) -phenylsulfonyl-imino-iodobenzene are obtained

[2- (ClCH ₂ CH ₂ O) C ₆ H ₄ SO ₂ N = IPh].

IR: 1275, 1115, 1055, 880, 870 (doublet) cm ^-1

The same result is obtained if the sulfonamide is present in the reaction mixture from the start of the reaction.

The arylsulfonylimines summarized in Table 4 below are prepared in the manner given in Example 37.

Production of further connections (Ilb)

Example 51

2.38 g (10 mmol) of diphenylselenide and 2.65 g (10 mmol) of potassium N, 2-dichlorobenzenesulfonamidate are refluxed in 12 ml of acetonitrile for 12 hours. After cooling, the reaction mixture is mixed with 10 ml of diethyl ether. The unreacted potassium salt and the potassium chloride are filtered off. Evaporation of the filtrate gives 1.54 g (36%) of N- (2-chlorophenylsulfonyl) Se, Se-diphenyl-selenimine.

IR: 1262, 1141, 1125, 1105, 1044, 969, 956 (d) cm ^-1

Example 52

2.39 g (12.5 mmol) of 2-chlorobenzenesulfonamide are added to the solution of 4.016 g (12.5 mmol) of triphenylarsine oxide in 50 ml of acetic anhydride. The reaction mixture is kept at reflux temperature for 5 minutes and then rapidly cooled. The product is filtered and washed with ether. 4.78 g (80%) of 2-chlorophenylsulfonyltriphenyl-arzinimine are obtained.

IR: 1435, 1260, 1135, 1120, 1045, 1005, 985, 740 cm ^-1

Example 53

1.5 g (5 mmol) of diphenylselenide dichloride are suspended in 10 ml of methanol, and 0.54 g (10 mmol) of Na methylate in 5 ml of methanol are added dropwise to the suspension. The mixture is stirred for 30 minutes and then 1.1 g (5 mmol) of 2-methoxycarbonylthiophene-3-sulfonamide are added. After stirring for a further 30 minutes, the reaction mixture is concentrated to half its volume. The product is filtered off and washed with a little hexane. 1.9 g are obtained

(84%) 2-methoxycarbonylthien-3-yl-sulfonyl-Se, Se-diphenyl-selenylimine.

IR: 1708, 1271 (br), 1119, 981, 969 cm ^-1 .

In the same way, 2- (2-chloroethoxy) benzenesulfonamide is obtained in 2- 70% yield from 2- (2-chloroethoxy) phenylsulfonyl-Se, Se-diphenyl-selenylimine,

IR: 1474, 1264, 1112, 1070, 954 cm ^-1 , and

from 2-methoxycarbonylbenzenesulfonamide in 80% yield 2-methoxycarbonyl-phenylsulfonyl-Se, Se-diphenylselenylimine,

IR: 1721, 1267, 1259, 1125, 1114, 953 cm ^-1 .

Claims

1. Process for the preparation of N- (arylsulfonyl) carbamic acid derivatives of the general formula I

wherein

Ar represents phenyl, benzyl, naphthyl, pyridyl or thienyl

stands by C _1-12 alkyl, C _1-4 alkenyl, C _1-12 haloalkyl, C _1-4 haloalkenyl, C _1-12 alkoxy, C _1-12 haloalkoxy, c _3-6 -Cycloalkyl, aryl, aryloxy, nitro, cyano, ali phatic acyl, aromatic acyl, alkoxycarbonyl, aryl-oxycarbonyl, alkylsulfonyl, arylsulfonyl, alkoxysulfonyl, dialkylamino, dialkylaminocarbony1, dialkylaminosulfonyl, N, N-dialkylthoylamoylamoylamoyl / nylkylcarbam Halogen can be mono- or polysubstituted, and

R ⁴ and R ⁵ for

a) C _1-6 alkyl,

b) C _1-6 haloalkyl,

c) alkoxyalkyl,

d) aryloxyalkyl,

e) C _3-6 alkenyl,

f) C _3-6 haloalkenyl,

g) C _3-6 alkynyl,

h) C _3-8 cycloalkyl,

i) C _3-8 cycloalkyl substituted by C _1-4 alkyl, C _1-4 haloalkyl

or is substituted by halogen,

j) benzyl,

k) phenyl,

l) naphthyl,

m) pyridyl,

n) pyrimidiny1,

o) triazinyl,

with the restriction that R ⁴ and R ⁵ cannot simultaneously stand for groups k) - o). p) the groups j) - m), which are substituted by C _1-4 alkyl, C _1-4 haloalkyl, C _1-4 alkoxy, C _1-4 haloalkoxy, alkoxyalkyl, alkoxyalkoxy, C _{1 -4-} alkylamino and / or halogen are mono- or polysubstituted,

r) the groups n) and o) which are substituted as indicated under p),

s) hydrogen,

t) electron pair are standing or

u) R ⁴ and R ⁵ together form an α, o-alkylene chain with 4-6 carbon atoms, which can be interrupted by an oxygen atom, a sulfur atom, a sulfinyl, sulfonyl or C _1-4 ~ alkyl imino group, and

z for a nitrogen, oxygen or sulfur atom

stands with the restriction that in the case Z = O or SR ⁴ stands for an electron pair and R ^{5 has} one of the meanings a) - m) and p), while in the case Z = NR ⁴ and R ^{5 have} a different meaning than an electron pair, characterized in that arylsulfonylimines of the general formula (II) (optionally prepared in situ)

ArSO ₂ N = XR ¹ R ² R ³ (II) in which the meaning of Ar is the same as above and R ¹ , R ² and R ³ independently of one another for C _1-12 -alkyl,

Cyclohexyl, benzyl, phenyl or naphthyl, the latter two groups being substituted one or more times by C _1-4 alkyl, C _1-4 haloalkyl, C _1-4 alkoxy, C _1-4 haloalkoxy and / or halogen can be, or are electron pair or oxygen atom,

R ¹ and R ² together form a divalent hydrocarbon group, or

R ¹ , R ² and R ³ stand for the forms of the groups listed coupled to a polymer matrix with the restriction that at least one of the groups R ¹ , R ² and R ^{3 stands} for a hydrocarbon group which is mixed with iodine, sulfur, selenium, Tellurium, phosphorus, arsenic or antimony can form a covalent bond, and X for phosphorus, arsenic, antimony, sulfur, selenium,

Tellurium or iodine atom,

catalytically carbonylated, the catalyst used being a transition metal from the 4th, 5th or 6th period of the Periodic Table, the oxide, salt, carbonyl or the complex of such a metal, in which the coordinative bond by a carbon, tin , Nitrogen, phosphorus, arsenic, antimony, oxygen, sulfur, selenium, tellurium and / or halogen atom is formed, wherein the catalyst can be prepared beforehand or generated in the reaction mixture and as a homogeneous, heterogeneous or heterogenized homogeneous Catalyst is present and is used in an amount of 10 ^-3 - 10 mass% based on the starting imine of the general formula II, and the carbonylation reaction at -20 ° C to 200 ° C, preferably -20 ° C to 120 ° C, and a CO -Partial pressure of 10 ⁵ - 10 ⁷ Pa in a solvent for 0.1-10 hours, and after. Completion of the carbonylation of the arylsulfonyl isocyanate of the general formula (III)

ArSO ₂ NCO (III)

R ⁴ R ⁵ ZH (IV) in which the meaning of R ⁴ , R ⁵ and Z is the same as above, or the carbonylation is carried out in the presence of a compound of the general formula IV and the product of the general formula I obtained is known per se Way isolated.

2. Process for the preparation of arylsulfonyl isocyanates of the general formula III

ArSO ₂ NCO (III) wherein

Ar represents phenyl, benzyl, naphthyl, pyridyl or thienyl stands by C _1-12 alkyl, C _1-4 alkenyl, C _1-12 haloalkyl, C _1-4 haloalkenyl, C _1-12 alkoxy, C _1-12 haloalkoxy, C _{3 -6} -cycloalkyl, aryl, aryloxy, nitro, cyano, aliphatic acyl, aromatic acyl, alkoxycarbonyl, aryl-oxycarbonyl, alkylsulfonyl, arylsulfonyl, alkoxysulfonyl, dialkylamino, dialkylaminocarbonyl, dialkylaminosulfonyl, N, N-dialkylthoylamoylamoylamoyl / nylkyloylamoylamoylamoyl / nylkyloylamoylamoyl / nylkyloylamoylamoyl / nylkyloylamoylamoyl / nylkyloylamoylamoyl / nylkylcarbam or halogen can be mono- or polysubstituted,

characterized in that the arylsulfonyimines

ArSO ₂ NX = R ¹ R ² R ³ II in which the meaning of Ar is the same as above and R ¹ , R ² and R ³ independently of one another for C _1-12 alkyl,

Cyclohexyl, benzyl, phenyl or naphthyl, the latter two groups being mono- or polysubstituted by C _1-4 -alky C _1-4 -haloalkyl, C _1-4 -alkoxy, C _1-4 -haloalkoxy and / or halogen can stand, or pair of electrons or oxygen atom,

R ¹ and R ² together form a divalent hydrocarbon group, or

R ¹ , R ² and R ³ for the forms of the groups listed coupled to a polymer matrix stand with the restriction that at least one of the groups R ¹ , R ² and R ^{3 stands} for a hydrocarbon group which contains iodine, sulfur, selenium, tellurium , Phosphorus, arsenic or antimony is able to form a covalent bond,

X for phosphorus, arsenic, antimony, sulfur, selenium,

Tellurium or iodine atom,

catalytically carbonylated, one being a catalyst

Transition metal from the 4th, 5th or 6th period of the periodic table, which uses oxide, salt, carbonyl or the complex of such a metal, in which the coordinative bond through a carbon, tin, nitrogen, phosphorus, arsenic -, Antimony, oxygen, sulfur, selenium, tellurium and / or halogen atom is formed, the Ka can be prepared beforehand or generated in the reaction mixture and is present as a homogeneous, heterogeneous or heterogenized homogeneous catalyst and is used in an amount of 10 ^-3 - 10 mass%, based on the starting imine of the general formula II, and the carbonylation reaction 20 ° C to 200 ° C, preferably -20 ° C to 120 ° C, and a CO partial pressure of 10 ⁵ - 10 ⁷ Pa in a solvent for 0.1-10 hours.

3. Process for the preparation of arylsulfonylimines of the general formula (Ila)

ArSO ₂ N = IR ^{1 '} R ² R ³ (IIa), in which the meaning of Ar is the same as in claim 1, R ^{1' represents} an optionally substituted phenyl or naphthyl group and R ² and R ^{3 are} electron pairs, thereby characterized in that arylsulfonamides of the general formula (VI)

ArSO ₂ NH ₂ (VI),

wherein the meaning of Ar is the same as in claim 1, preferably with in-situ, I, I-disubstituted organic iodine compounds of the general

Formula (VII)

R ¹ '-I (OAlk) ₂ (VII) wherein the meaning of R ^{1' is} the same as above and Alk is alkyl with 1-4 carbon atoms, at temperatures between -20 ° C and 80 ° C for one minute to 2 hours implemented for a long time.

4. New arylsulfonylimines of the general formula (Ilb), in which

Ar'SO ₂ N = XR ¹ R ² R ³ (Ilb), wherein

2- (-C-4-alkoxycarbonyl) -thien-3-yl and the meaning of R ¹ , R ² , R ³ and X is as in claim 1.

5. The method according to claim 1, characterized in that the compound of general formula (II) in

A compound (IV) is carbonylated in which R ^{4 is} trazinyl and R ^{5 is} hydrogen or methyl.

6.The method according to claim 1 or 2, characterized in that the metal component of the catalyst

Is palladium.

7. The method according to claim 1 or 2, characterized in that the arylsulfonylimine compound of the general formula (II) are iodimines or selenylimines.

8. The method according to claim 3, characterized in that a compound (VII) is used in which Alk is methyl.

9. Arylsulfonylimines of the general formula (Ilb), in which X represents iodine or selenium.

10. Arylsulfonylimines of the general formula (Ilb), in which Ar 'is 2-chlorophenyl, 2-methoxycarbonylphenyl, 2-ethoxycarbonylphenyl, 2- (2-chloroethoxy) phenyl, 2-methoxycarbonylbenzyl, methoxycarbonyl-3-thienyl, 3- (dimethylaminocarbonyl ) -2-pyridyl.