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

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

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WO1993010086A1
WO1993010086A1 PCT/HU1992/000047 HU9200047W WO9310086A1 WO 1993010086 A1 WO1993010086 A1 WO 1993010086A1 HU 9200047 W HU9200047 W HU 9200047W WO 9310086 A1 WO9310086 A1 WO 9310086A1
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general formula
ar
alkyl
phenyl
meaning
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PCT/HU1992/000047
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German (de)
French (fr)
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Gábor BESENYEI
Sándor NÉMETH
László SIMÁNDI
Mária BELÁK
Éva FISCHER
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MTA Központi Kémiai Kutató Intézete
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    • C07D239/02Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
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    • C07C311/58Y being a hetero atom either X or Y, but not both, being nitrogen atoms, e.g. N-sulfonylurea having sulfur atoms of the sulfonylurea groups bound to carbon atoms of six-membered aromatic rings having nitrogen atoms of the sulfonylurea groups bound to hydrogen atoms or to acyclic carbon atoms
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    • C07C311/52Y being a hetero atom
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    • C07D251/14Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
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    • C07D333/26Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulfur with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07C2601/14The ring being saturated

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 R5¿ can be different aliphatic, cycloaliphatic or aromatic groups. To produce these compounds, arlsulphonylimines having the general formula (II): ArSO¿2?N=XR?1R2R3¿, in which R?1, R2 et R3¿, independently from each other, designate C¿1-12?-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?4R5¿ZH.

Description

PROCESS FOR PRODUCING N- (ARYLSÜLFONYL) -carbamic DERIVATIVES AND IN THIS PROCESS SUITABLE

INTERMEDIEREN

The invention relates to an improved process for preparing known N- (arylsulfonyl) -carbamic acid derivatives (carbamides, carbamates and thiocarbamates) (Method A). The invention further relates to a novel, chemically peculiar process for preparing the Arylsulfonylisocyan usable as Intermediere in the Method A te (Method B), further a novel process for the production of a part of the usable as Intermediere in the methods A and B Arylsulfonylimine (Method C ) and finally new Arylsulfonylimine, which are produced in part by the method in part C by known methods.

Which can be prepared by the method A N- (arylsulfonyl) - carbamic acid derivatives have the general formula

(I)

wherein

Ar is phenyl, benzyl, naphthyl, pyridyl or thienyl

is represented 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, aryl-oxycarbonyl, alkylsulfonyl, arylsulfonyl, alkoxysulfonyl, dialkylamino, dialkylaminocarbonyl, dialkylaminosulfonyl, N, N-dialkylcarbamoyl, N, N-Dialkylthiocarbamoyl and / or halogen may be substituted one or more times, and

R 4 and R 5 is

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 is substituted) 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,

s) pyrimidinyl,

o) Trάazinyl,

with the proviso that R 4 and R 5 do not simultaneously k for group) - can stand o),

p) the groups j) - m) obtained 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 are mono- or polysubstituted,

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

s) hydrogen,

t) are electron pair or

u) R 4 and R 5 together are a α, ω-alkylene chain form having 4-6 carbon atoms which may be interrupted by an oxygen atom, a sulfur atom, a sulphinyl, sulphonyl or C1-4 -alkylimino group, and

Z is a nitrogen, oxygen or sulfur atom

is with the proviso that in the case of Z = O or SR 4 stands for electron pair and R5 one of the meanings a) - m) and p), while in the case of Z = NR 4 and R 5 have a meaning other than electron pair. Among the N- (arylsulfonyl) carbamate derivatives, numerous compounds with beneficial biological effects found. The amide derivatives are characterized by vari able biological effects; while the N- (arylsulfonyl are known as herbicides N'-triazinyl- (or -pyrimidinyl-) compounds primarily have the derivatives instead of an aromatic N-heterocycle, a phenyl group or aliphatic or alicyclic group-containing anti-diabetic, heart rhythm regulating or anti-cancer activity . the O-esters and S-esters exhibit antidote activity against the phytotoxicity of herbicides on triazine and Thiocarbamatbasis or even have a herbicidal effect.

To prepare the derivatives of Arylsulfonylcarbamidsäuren numerous methods have been developed. A comprehensive overview enter the following reference 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 spread applied or procedures not described in the cited literature can be summarized as follows.

Sulfonamides and their alkali metal salts are reacted in mixtures of water and acetone, water and tetrahydrofuran, or in organic solvents, if appropriate in the presence of tertiary amines, with aliphatic isocyanates to form N- (arylsulfonyl) -N'-alkylureas [Ger. 1,201,337, Brit. 808071, US 2371178]

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

The addition reaction of arylsulfonyl isocyanates and primary or secondary amines also provides sulfonylureas [Chem. Rev. 1965, 65, 369-376 and references therein]:

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

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

Also carried out at about 100 ° C conversion of

Aryl sulfonamides and N-substituted carbamates leads to

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

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

In the reaction of carbamoyl chlorides with sulfonamides arise Brit with elimination of hydrochloric acid sulfonylureas [. 538,884 (CA 36, 3511/1942 /), Brit. 604,259 (CA 43

1061B / 1949 /), Swiss 222,077 (CA 13, 821/1949 /)]. The carbamoyl chlorides are generally prepared by the reaction of primary or secondary amines with phosgene and frequently used further without intermediate isolation:

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

abs acetone

In analogous manner, esters of Chlorthioameisensäure- and sulfonamides Arylsulfonylthiocarbamidsäure-S- are prepared ester [DE 2644446].

Arylsulfonylcarbamate are accessible by used as acylating agent carbonic acid esters [US

4,612,385, EP 96,003]:

A simple way of preparing arylsulfonyl fonylcarbamaten is the reaction of arylsulfonyl isocyanates with alcohols or mercaptans [J. Heterocycl. Chem. 1980, 17, 271]:

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

Z = O, S

Sulfonylthiocarbamidsäure-S-ester produced in good yield in the alkaline hydrolysis of N- (arylsulfonyl) - imino-dithiokohlensäuredimethylestern or the modification with H 2 O 2 oxidation of N- (arylsulfonyl) -dithiocarbamidsäuremethylester [Nippon Kagaku Zasshi, 1970. 91 (12 ) 1168-73, CA 75, 19878].

In the thermal rearrangement of N-Tosyliminokohlensäurediethylester arises N-ethyl-N-tosylkarbamidsäureethylester [J. Org. Chem. 1963, 28, 2902].

According to the Hungarian Patent Specifications Nos. 202 487, 203 719 and 204 779 are sulfonylureas, carbamates and -thiocarbamate by catalytic carbonylation of N-Halogensulfonamidaten prepared. Although this method overcomes many disadvantages of the previous method, but its applicability is limited because no against oxidation, acid or alkaline hydrolysis sensitive groups may be present on the aryl group.

The methods described meet the modern requirements of environmental protection, technology and the economy only partially. An important part of the method is based on the direct or indirect use of phosgene, leading to serious environmental and corrosion problems. The nonworking with phosgene methods require the use of other difficult to handle, flammable and / or toxic raw materials, in some cases, the yields are low. For most of the described method is characteristic in that they contain reaction steps that need to be made at relatively high temperatures, which increases the cost of energy. In light of all DIE ser disadvantages there was a need to develop a new and better method for producing Sulfonylcarbamidsäure derivatives.

The invention is based on the finding that the Arylsulfonylimine the general formula (II)

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

Blank carbonylate ArSO 2 NCO (III), when the catalyst used is a transition metal of the 4th, 5th or 6th period of the periodic table, the oxide, salt, carbonyl, or the complex of such a metal, in which the coordination bond by a carbon, tin, nitrogen, phosphorus, arsenic, antimony, oxygen, sulfur, selenium, tellurium and / or halogen atom is formed, and the Arylsulfonylisocya- nate the general formula (III) with compounds of the general formula (IV)

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

Accordingly, the invention is a process for the preparation of N- (arylsulfonyl) -carbamic acid derivatives of general formula (I)

ArSO 2 NHCZR 4 R 5 (I) wherein the meaning of Ar, R 4, R 5 and Z are the same as indicated at the outset the. For the inventive method is characterized in that one (optionally prepared in situ) Arylsulfonylimine the general formula (II)

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 are each independently C 1-12 alkyl,

Cyclohexyl, benzyl, phenyl or naphthyl, which latter two groups with C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy, C 1-4 -haloalkoxy and / or halogen substituted one or more times could not it be electron pair or oxygen atom,

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

R 1, R 2 and R 3 are the coupled to a polymer matrix of the groups listed are related to the limita effect that at least one of the groups R 1, R 2 and R 3 represents a hydrocarbon group, with iodine, sulfur, selenium capable of forming a covalent bond tellurium phosphorus, arsenic or antimony, and

X is phosphorus, arsenic, antimony, sulfur, selenium,

Tellurium or iodine atom,

catalytically carbonylated, wherein the catalyst used is a transition metal of the 4th, 5th or 6th period of the periodic table, the oxide, salt, carbonyl, or the complex of such a metal, in which the coordination bond through a carbon, tin , nitrogen, phosphorus, arsenic, antimony, oxygen, sulfur, selenium, tellurium and / or halogen atom is formed, said catalyst can be pre-prepared or generated in the reaction mixture and homogeneous as a homogeneous, heterogeneous or heterogenized catalyst is present and the Ausgangsimin of the general formula II is present in an Men ge of 10 -3 - 10 mass% is used, 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 performs in a solvent 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) reaction mixture containing 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 is added to, or carries out the carbonylation in the presence of a compound of the general formula IV and the product of general formula I obtained in a known per se as isolated.

The process can be illustrated by the following reaction schemes:

or for the case that in the presence of the compound (IV) is carbonylated:

For the substituent definitions, the following are particularly preferred: 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. Present in the groups Ar aliphatic substituents have most preferably 1-4 carbon atoms.

The synthesis of the compounds of general formula I is carried out in a solvent medium. Suitable solvents are the customary organic solvents, preferably dichloromethane, 1, 2-dichloroethane, acetonitrile or mixtures thereof in question. It has been found that a small amount of a nitrile (acetonitrile, benzonitrile) enhances the reaction. therefore it is preferably used as a solvent, a nitrile or another of the solvents mentioned, the slightly nitrile was added.

The carbonylation of the compounds II is carried out in the presence of a catalyst. As a catalyst, the transition metals of the 4th, 5th and 6th period of the periodic table are, their oxides, salts, carbonyls or those complexes in question, as donor atom a carbon, tin, nitrogen, phosphorus, arsenic antimony, oxygen, sulfur, selenium, tellurium and / or halogen atom. Mixtures of these catalysts can be used.

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

The catalyst may be homogeneous, heterogeneous or heterogeneous form (immobilized) to be. He may have been prepared in advance, or you can generate it in situ. As carriers of heterogeneous catalysts and immobilized, for example, are aluminum oxide, silica gel, activated carbon and organic polymers.

The catalyst is used in an amount of from 10 to Ausgangssulfonylimin -3 - used 10% by weight.

The carbon monoxide used for the carbonylation reaction may come as a pure gas or gas mixture used. As a diluent component all gases and vapors out of the question, which are inert to the catalyst and the reactants. Examples are: nitrogen, oxygen, noble gases, air, carbon dioxide, hydrogen, water vapor, vapors of organic solvents. However, some catalysts or reactants can be sensitive to the diluent gas, therefore, allowed for the individual catalysts and reactants diluent gases may be different. 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, especially at temperatures between 20 ° C and 100 ° C. The temperature is selected depending on the activity of the catalyst and the thermal stability of the reactants.

The carbonylation is carried out either in the presence of compound IV, or after completion of the carbonylation, the compound IV is added to give the target product I is formed.

However, since the phosgene carbonylation is new and valuable under the specified conditions, is also a need to protect the taking place in this way making the Arylsulfonylisocyanate. When adding no reagent IV after the carbonylation, the reaction in the isocyanate III stops.

For the production of sulfonyl successful attempts have been made as early as the turn of the century, and since then numerous pathways have been worked out. The following is a brief overview is given.

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

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

Although the yield of this reaction could be significantly improved later, the procedure has not been used in practice found.

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

(Ar = substituted phenyl), the yields were about

50%.

Significantly better results were obtained when instead of the sulfonamide its derivatives, for example N- (arylsulfonyl) -N'-butylharnstoffe, were reacted with phosgene [J. Org. Chem. 1966. 31, 2658-61; Angew. Chem. Int.

Ed. 1966. 5, 704-12]:

The two isocyanates can be separated easily by distillation from each other, the yield is over 80%.

Variations of this method are the method in which the phosgenation of the sulfonamide is carried out in the presence of lower aliphatic isocyanates or aliphatic amines [Chem. Rev. 1965. 65, 369-76; DE 2152971 / CA 79 18 386].

In several publications it was reported that the preparation of aromatic or aliphatic sulfonyl iso cyanate instead of phosgene and oxalyl chloride can be used [J. Org Chem 1964, 29, 2592-5..; J. Med. Chem. 1965, 8, 781-4]. The yields depend strongly on the bound to the sulfonyl hydrocarbon group. .

R = phenyl, p-tolyl, piperidyl

According to a Stauffer registration sulfonamides with thionyl chloride and Chlorcarbonylsulfonylchlorid can be reacted in the presence of pyridine to sulfonyl [US 4835053 / CA 10278564]:

After JP 70/19 893 (CA 73 98607) a product obtained by the reaction of sulfonamides with N, N-carbonyldiimidazole intermediate can be reacted by method practiced in the presence of P 2 C 5 Heating to sulfonyl isocyanate:

be prepared from N-sulfonyldithiocarbamaten can in a multistep synthesis sulfonyl [Nippon Kagaku Zasshi 1970, 91, 1168-73 / CA 75 19878 /]:

The last step is either heating in xylene or chlorination.

The chlorosulfonyl isocyanate proved to be identical in two different ways for the preparation of sulfonyl isocyanates to be suitable [DE 3132944 / CA 98.215319 /; Ger 1289526 / CA 70 87312 /].:

From this review, it is apparent that the production of sulfonyl isocyanates is no easy task for the chemist. Judging from sulfonamides, so the phosgenation gives the best yields. If no phosgene ver be spent, so other very reactive compounds must be used, in some cases, it is multi-level, complex reaction pathways.

The invention is therefore also a process (Process B) for preparing arylsulfonyl isocyanates of the general formula (III)

ArSO 2 NCO (III)

(Wherein the meaning of Ar is the same as above). For the method is characteristic in that Arylsulfonylimine 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, is carbonylated under the conditions given for the method A conditions.

The required as starting materials in the process of the invention A and B Arylsulfonylimine of the general formula II are partly known, partly new. As examples from the literature can be mentioned:

X = I; R 1 = (substituted) phenyl, R 2 = R 3 = electron pair, 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 789th

The known processes for preparing the compounds (II) assume a Sulfonamidkomponente and compounds of general formula (V)

from wherein 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. It is either the Sulfonylstickstoff the sulfonamide in 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 references therein.

MHal

X = S, Chem Rev. 1978, 78, 65-79 and references therein. tl

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

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

i

)

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

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

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

MeOH / KOH

)

Chem. Lett., 1975, 361-362.

All these methods have some one or other disadvantage. N-Halogensulfonamidate can be formed only from relatively little sulfonamides, ie the number of producible from these sulfonylimines is necessarily limited. For some reaction types are aggressive (highly alkaline or strongly acidic) media used, for example, acetic anhydride, or they run only at high temperatures (see. For example, the equations (22), (24), (25)), and these circumstances limit the number of producible sulfonylimines. Many of the operations are very time consuming, and its yield is low.

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

The invention therefore also provides a method (Method C) for preparing a narrower group of the compounds of the general formula (II) forming compounds of the general formula (IIa)

ArSO 2 N = IR 1 'R 2 R 3 (IIa), wherein the meaning of Ar is the same as above, R 1' stands for an optionally substituted phenyl or naphthyl group and R 2 and R 3 are electron pairs.

Since two substituents R represent electron pair, one can 1 'write the compounds (IIa) and ArSO 2 N = IR.

The compounds of general formula (Ha) may be prepared according to the invention, by aryl sulfonamides of the general formula (VI)

ArSO 2 NH2 (VI),

wherein the meaning of Ar is the same as above, preferably prepared 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 having 1-4 carbon atoms, at temperatures between -20 ° C and 80 ° C for one minute to 2 implements hours.

The substituents of the optionally substituted phenyl bzw- naphthyl Rl'sind preferred: C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 haloalkoxy, C 1-4 alkylsulfonyl, phenyl sulfonyl and / or Halogen.

not dissected in general, but prepared from the corresponding alcohols Jodosylaromaten and in situ:

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 expedient to work in the presence of a dehydrating agent. Suitable such organic and inorganic dehydrating agents usually used in laboratory practice, for example, magnesium sulfate, magnesium perchlorate, natural or synthetic zeolites, Ortoameisensäureester, 2,2-dimethoxypropane and dicyclohexylcarbodiimide in question. The selectivity of the process is generally better when the reaction mixture is anhydrous.

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

The compounds of general formula (IIa) are prepared from the reaction mixture by filtration, evaporation and / or precipitation with a solvent isolated. As the solvent for precipitating is preferably an inert solvent which does not contain alcoholic hydroxyl groups used.

To prepare the compounds of general formula (Ila), it is, for example, as before, that the Jodosylverbindung R 1 'l = O in the presence of an equivalent amount of aryl sulfonamide of general formula (VI) (in the corresponding alcohol AlkOH, for example in methanol Alk = Me), stirred for a short period and then the solvent removed in vacuo.

It is also possible to prepare the first Dialkoxyjodverbindu and to give to the solution of the sulfonamide.

According to a preferred variant of the process C, the organic iodine compound is R 1 'I (OAlk) 2 coupled to a polymer matrix, or other solid support. These carrier-bound iodine compound can then make the filling of a reactor, through which flows the solvent with the remaining components of the reaction. The removal of the water can be done here outside the reactor. It is furthermore advantageous with this solution is that the organic iodine compound, after the arylsulfonylamine the general formula (IIa) reacted further (carbonylated) was, can be easily recovered.

Finally, the invention also relates to novel Arylsulfonylimine the general formula (IIb)

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

Ar 'is 2-halophenyl, 2- (2-chloroethoxy) phenyl, 2- (C 1-4 - alkoxycarbonyl) phenyl, 2- (C 1-4 alkoxycarbonyl) - benzyl, 3- (dimethylaminocarbonyl) -pyrid -2-yl or

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

This closer group of compounds of general formula (II) forming new compounds may be both by literature methods [s. the reaction equations (19) - (25), s. the Embodiments] as well as - if X is iodine - are produced by the inventive method C. They can, as well as the known compounds (II) in the pharmaceutical industry as un pesticides Intermediere for Arylsulfonylisocyanate, ureas, carbamates and -thiocarbamate, as an oxidizing agent or taking place in the presence of a catalyst geeigne-th synthesis of the amino and imino derivatives of hydrocarbons be used.

The advantages of the invention can be summarized as follows:

1) The methods A and B do not require phosgene, it is therefore safer and more environmentally friendly than the currently accepted method in practice.

2) The Intermedieren of the general formula II may be prepared as the N-Halogensulfonamidate under milder reaction conditions, and thereby the circuit of the isocyanates or obtainable by carbonylation of the compounds II can be prepared from these compounds I is substantially greater than that on N-Halogensulfonamida - ten the case. Since the organic iodine compounds used according to the method C dissolve well in organic solvents, the reaction proceeds rapidly.

According to the method C, the reaction proceeds to Arylsulfonylimid even at room temperature, which means a reduced energy expenditure.

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

4) The method is easily inserted into known technological processes and provides a result of his good nuclear utilization level the opportunity to develop an environment friendly technology. A Realisierungsmög- friendliness shown in the following series of reactions:

NaCl + AE - - - - - - -> Na + ½ Cl 2

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

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

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

R 1 R 2 R 3 X (OCH 3) 2 + NH 2 ArSO 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 overall reaction can in principle also be designed so that the only by-product

Hydrogen is formed.

The invention is described below with reference to exemplary embodiments.

method A

example 1

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

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

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

example 2

1.6 g (4 mmol) Np-Tosyl-Se, Se-diphenyl-selenylimin

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

example 3

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

example 4

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

example 5

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

Analogously to Examples 1-5 are carbonylating sulfonyl imines of the general formula (II) and reacting the resultant sulfonyl Intermediere as the compounds of general formula (I) listed in Table 1 (IV) with compounds of the general formula prepared.

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 were charged. The reactor is filled with pressurized under 3.5 MPa carbon monoxide. The reaction mixture is stirred at room temperature for 16 hours. After blowing off the gas phase the solvent is evaporated and the residue washed with hexane. This gives the N- (2-methoxycarbonyl-phenyl¬sulfonyl) -N '- (4-methy1-6-methoxytriazine-2-yl) -urea in 80% yield (HPLC).

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

summarized in the following Table 2. carbamates and thiocarbamates are produced on the specified in Example 1.

method B

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

example 22

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

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

example 23

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

The physical data are consistent with those reported in Example 22nd

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

method C

example 37

1.3 g (5.9 mmol) Jodosylbenzol 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 for 15 - minutes stirring. Then the solvent is removed in vacuo, the solid residue is triturated with 4 ml of dichloromethane and then filtered. After washing with dichloromethane and subsequent drying,

2.0 g of 2- (methoxycarbonyl) phenylsulfonyl-imino-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 location of many bands depends on the moisture content of the product.)

example 38

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

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

example 39

2.20 g (10 mmol) Jodosylbenzol are suspended in 30 ml of methanol and treated with approximately 3 g of molecular sieve type 4A. The reaction mixture is an absence of air

stirred for an hour, then the molecular sieve is filtered off and the filtrate was treated with 2.35 g (10 mmol) of 2- (2-Chloreth oxy) benzenesulfonamide was added. Stirring is continued for half an hour, then the methanol is stripped off and the solid residue treated with 10 ml of dichloromethane. After filtration and drying, 3.24 g (74%), 2- (2-chloroethoxy) phenylsulfonyl-iminojodbenzol

[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 sets in when the sulfonamide vm beginning of the reaction in the reaction mixture is present.

summarized in the following Table 4 Arylsulfonylimine be prepared in the manner indicated in Example 37.

Preparation of further compounds (IIb)

example 51

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

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

example 52

To the solution of 4.016 g (12.5 mmol) in 50 ml of acetic anhydride are Triphenylarsinoxyd 2.39 g (12.5 mmol) of 2-chloro-benzenesulfonamide given. The reaction mixture is held for 5 minutes at reflux temperature and then rapidly cooled. The product is filtered and washed with ether. This gives 4.78 g (80%) of 2-Chlorphenylsulfonyltriphenyl-arzinimin.

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

example 53

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

(84%) of 2-methoxycarbonyl-thien-3-yl-sulfonyl-Se, Se-diphenyl-selenylimin.

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

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

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

from 2-Methoxycarbonylbenzolsulfonamid in 80% yield 2-methoxycarbonyl-phenylsulphonyl-Se, Se-diphenylselenylimin,

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

Claims

claims
1. A process for the preparation of N- (arylsulfonyl) -carbamic acid derivatives of the general formula I
wherein
Ar is phenyl, benzyl, naphthyl, pyridyl or thienyl
is represented 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-dialkylcarbamoyl, N, N-Dialkylthiocarbamoyl and / or halogen may be substituted one or more times, and
R 4 and R 5 is
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 is substituted by halogen,
j) benzyl,
k) phenyl,
l) naphthyl,
m) pyridyl,
n) Pyrimidiny1,
o) triazinyl,
may be o) - with the proviso that R 4 and R 5 do not simultaneously k for group). p) the groups j) - m), the alkyl with C 1-4 alkyl, C 1-4 -Halo-, C 1-4 alkoxy, C 1-4 haloalkoxy oxyalkoxy, alkoxyalkyl, alk, C 1 -4 alkylamino and / or halogen singly or multiply substituted,
r) indicated the groups n) and o), which are substituted as described under p),
s) hydrogen,
t) are electron pair or
u) R 4 and R 5 together form an α, o-alkylene chain having 4-6 carbon atoms, the imino group by an oxygen atom, a sulfur atom, a sulfinyl, sulfonyl or C 1-4 ~ alkyl can be interrupted, and
Z is a nitrogen, oxygen or sulfur atom
is with the proviso that in the case of Z = O or SR 4 stands for electron pair and R 5 is one of the meanings a) - has m) and p), while in the case of Z = NR 4 and R 5 have a meaning other than electron pair, characterized in that (optionally prepared in situ) Arylsulfonylimine the general formula (II)
ArSO 2 N = XR 1 R 2 R 3 (II) wherein the meaning of Ar, the same R 2, and R 3 is as above and R 1, independently of one another C 1-12 alkyl,
Cyclohexyl, benzyl, phenyl or naphthyl, which latter two groups with C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy, C 1-4 -haloalkoxy and / or halogen substituted one or more times could not it be electron pair or oxygen atom,
R 1 and R 2 together form a divalent hydrocarbon group, or
R 1, R 2 and R 3 are the coupled to a polymer matrix of the groups listed are related to the limita effect that at least one of the groups R 1, R 2 and R 3 represents a hydrocarbon group, with iodine, sulfur, selenium , can tellurium phosphorus, arsenic or antimony to form a covalent bond, and X is phosphorus, arsenic, antimony, sulfur, selenium,
Tellurium or iodine atom,
catalytically carbonylated, wherein the catalyst used is a Öbergangsmetall 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 coordination bond through a carbon, tin , nitrogen, phosphorus, arsenic, antimony, oxygen, sulfur, selenium, tellurium and / or halogen atom is formed, said catalyst can be pre-prepared or generated in the reaction mixture and homogeneous as a homogeneous, heterogeneous or heterogenized catalyst is present and the Ausgangsimin of the general formula II in an amount of 10 -3 - 10 mass% is used, 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 performs in a solvent 0.1-10 hours, and after. Completion of the carbonylation which the arylsulfonyl isocyanate of the general formula (III)
ArSO 2 NCO (III)
(Wherein the meaning of Ar is the same as above) reaction mixture containing 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 is added to, or carries out the carbonylation in the presence of a compound of the general formula IV and the product of general formula I obtained in a known per se as isolated.
2. A process for preparing arylsulfonyl isocyanates of the general formula III
ArSO 2 NCO (III) wherein
Ar is phenyl, benzyl, naphthyl, pyridyl or thienyl, which, by C 1-12 alkyl, C 1-4 alkenyl, C 1-12 haloalkyl, C 1-4 haloalkenyl, C 1-12 alkoxy C 1-12 -Haloalk- oxy, C 3-6 cycloalkyl, aryl, aryloxy, nitro, cyano, aliphatic acyl, aromatic acyl, alkoxycarbonyl, aryl-oxycarbonyl, alkylsulfonyl, arylsulfonyl, alkoxysulfonyl, dialkylamino, dialkylaminocarbonyl, dialkylaminosulfonyl, N, N-dialkylcarbamoyl, N, N-Dialkylthiocarbamoyl and / or halogen may be substituted one or more times,
characterized in that the Arylsulfonyimine
ArSO 2 NX = R 1 R 2 R 3 II wherein the meaning of Ar is the same as above and R 1, R 2 and R 3 are each independently C 1-12 alkyl,
Cyclohexyl, benzyl, phenyl or naphthyl, which latter two groups by C 1-4 -Alky C 1-4 -haloalkyl, C 1-4 -alkoxy, C 1-4 -haloalkoxy and / or halogen be mono- or polysubstituted can, or Elektrόnenpaar or oxygen atom are,
R 1 and R 2 together form a divalent hydrocarbon group, or
R 1, R 2 and R 3 are the coupled to a polymer matrix of the groups listed with the proviso that at least one of the groups R 1, R 2 and R 3 represents a hydrocarbon group with iodine, sulfur, selenium, tellurium capable of forming a covalent bond phosphorus, arsenic or antimony,
X is phosphorus, arsenic, antimony, sulfur, selenium,
Tellurium or iodine atom,
catalytically carbonylated using as catalyst a
Transition metal of the 4th, 5th or 6th period of the periodic table, the oxide, salt, carbonyl, or the complex of such a metal is used in which the coordinate bonding through a carbon, tin, nitrogen, phosphorus, arsenic is formed, antimony, oxygen, sulfur, selenium, tellurium and / or halogen atom, wherein the Ka talysator may be previously prepared or generated in the reaction mixture and is present as a homogeneous, heterogeneous or homogeneous catalyst and heterogenized on the Ausgangsimin - general formula II in an amount of 10 -3 - 10 mass% is used, and the carbonyl nylierungsreaktion at -20 ° C to 200 ° C, preferably -20 ° C to 120 ° C and a CO partial pressure of 10 5 - performs 10 7 Pa in a solvent 0.1-10 hours.
3. A process for preparing Arylsulfonyliminen the general formula (Ila)
ArSO 2 N = IR 1 'R 2 R 3 (IIa), wherein the meaning of Ar is the same as in claim 1, R 1' stands for an optionally substituted phenyl or naphthyl group and R 2 and R 3 are electron pairs, characterized in that aryl sulfonamides of the general formula (VI)
ArSO 2 NH2 (VI),
wherein the meaning of Ar is the same as in claim 1, produced in situ with, preferably, 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 having 1-4 carbon atoms, at temperatures between -20 ° C and 80 ° C for one minute to 2 hours implement long.
4. New Arylsulfonylimine the general formula (IIb) wherein
Ar'SO 2 N = XR 1 R 2 R 3 (IIb), wherein
Ar 'is 2-halophenyl, 2- (2-chloroethoxy) phenyl, 2- (C 1-4 - alkoxycarbonyl) phenyl, 2- (C 1-4 alkoxycarbonyl) - benzyl, 3- (dimethylaminocarbonyl) -pyrid -2-yl or
2- (Cι-4-alkoxycarbonyl) is thien-3-yl, and the meaning of R 1, R 2, R 3 and X as in claim. 1
5. The method according to claim 1, characterized in that the compound of general formula (II) in
Versus waiting a compound (IV) is carbonylated 4 in which R stands for Trazinyl and R 5 is hydrogen or methyl.
6.A 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 Arylsulfonyliminverbindung the general formula (II) or Jodimine Selenylimine are.
8. The method according to claim 3, characterized in that a compound (VII) is used, is on the Alk is methyl.
9. Arylsulfonylimine the general formula (IIb) wherein X is iodine or selenium.
10. Arylsulfonylimine the general formula (IIb) wherein Ar 'is 2-chlorophenyl, 2-methoxycarbonylphenyl, 2-ethoxycarbonylphenyl, 2- (2-chloroethoxy) -phenyl, 2-methoxycarbonylbenzyl, methoxycarbonyl-3-thienyl, 3- (dimethylaminocarbonyl ) -2-pyridyl stands.
PCT/HU1992/000047 1991-11-13 1992-11-12 Process for preparing n-(arylsulphonyl)-carbamide acid derivates and intermediates useful for carrying out this process WO1993010086A1 (en)

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HUP9201169 1992-04-07

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US7109337B2 (en) 2002-12-20 2006-09-19 Pfizer Inc Pyrimidine derivatives for the treatment of abnormal cell growth
US7145008B2 (en) 2004-05-14 2006-12-05 Pfizer Inc Pyrimidine derivatives for the treatment of abnormal cell growth
US7208499B2 (en) 2004-05-14 2007-04-24 Pfizer Inc. Pyrimidine derivatives for the treatment of abnormal cell growth
US7235562B2 (en) 2004-05-14 2007-06-26 Pfizer Inc Pyrimidine derivatives for the treatment of abnormal cell growth
US8945884B2 (en) 2000-12-11 2015-02-03 Life Technologies Corporation Methods and compositions for synthesis of nucleic acid molecules using multiplerecognition sites
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Cited By (14)

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US5633287A (en) * 1993-05-14 1997-05-27 Warner-Lambert Company N-acyl sulfamic acid esters (or thioesters), N-acyl sulfonamides, and n-sulfonyl carbamic acid esters (or thioesters) as hypercholesterolemic agents
US5491172A (en) * 1993-05-14 1996-02-13 Warner-Lambert Company N-acyl sulfamic acid esters (or thioesters), N-acyl sulfonamides, and N-sulfonyl carbamic acid esters (or thioesters) as hypercholesterolemic agents
US6171861B1 (en) 1995-06-07 2001-01-09 Life Technologies, Inc. Recombinational cloning using engineered recombination sites
US9309520B2 (en) 2000-08-21 2016-04-12 Life Technologies Corporation Methods and compositions for synthesis of nucleic acid molecules using multiple recognition sites
US8945884B2 (en) 2000-12-11 2015-02-03 Life Technologies Corporation Methods and compositions for synthesis of nucleic acid molecules using multiplerecognition sites
US7109335B2 (en) 2002-12-20 2006-09-19 Pfizer Inc Pyrimidine derivatives for the treatment of abnormal cell growth
US7109337B2 (en) 2002-12-20 2006-09-19 Pfizer Inc Pyrimidine derivatives for the treatment of abnormal cell growth
US7741336B2 (en) 2002-12-20 2010-06-22 Pfizer Inc. Pyrimidine derivatives for the treatment of abnormal cell growth
US7351712B2 (en) 2002-12-20 2008-04-01 Pfizer Inc Pyrimidine derivatives for the treatment of abnormal cell growth
US7674796B2 (en) 2002-12-20 2010-03-09 Pfizer Inc. Pyrimidine derivatives for the treatment of abnormal cell growth
US9534252B2 (en) 2003-12-01 2017-01-03 Life Technologies Corporation Nucleic acid molecules containing recombination sites and methods of using the same
US7208499B2 (en) 2004-05-14 2007-04-24 Pfizer Inc. Pyrimidine derivatives for the treatment of abnormal cell growth
US7145008B2 (en) 2004-05-14 2006-12-05 Pfizer Inc Pyrimidine derivatives for the treatment of abnormal cell growth
US7235562B2 (en) 2004-05-14 2007-06-26 Pfizer Inc Pyrimidine derivatives for the treatment of abnormal cell growth

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