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WO1993010086A1 - Procede de fabrication de derives d'acides n-(arylsulfonyl)-carbamiques ainsi que des intermediaires utilises dans ledit procede - Google Patents

Procede de fabrication de derives d'acides n-(arylsulfonyl)-carbamiques ainsi que des intermediaires utilises dans ledit procede Download PDF

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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
alkyl
phenyl
meaning
groups
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PCT/HU1992/000047
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German (de)
English (en)
Inventor
Gábor BESENYEI
Sándor NÉMETH
László SIMÁNDI
Mária BELÁK
Éva FISCHER
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MTA Központi Kémiai Kutató Intézete
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Priority claimed from HU355491A external-priority patent/HU209864B/hu
Priority claimed from HU9200895A external-priority patent/HUT64018A/hu
Priority claimed from HU9201169A external-priority patent/HUT64017A/hu
Application filed by MTA Központi Kémiai Kutató Intézete filed Critical MTA Központi Kémiai Kutató Intézete
Publication of WO1993010086A1 publication Critical patent/WO1993010086A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic 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
    • C07D239/28—Heterocyclic 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
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
    • C07C311/52—Y being a hetero atom
    • C07C311/53—X and Y not being nitrogen atoms, e.g. N-sulfonylcarbamic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
    • C07C311/52—Y being a hetero atom
    • C07C311/54—Y being a hetero atom either X or Y, but not both, being nitrogen atoms, e.g. N-sulfonylurea
    • C07C311/57—Y 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
    • C07C311/58—Y 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
    • C07C311/52—Y being a hetero atom
    • C07C311/54—Y being a hetero atom either X or Y, but not both, being nitrogen atoms, e.g. N-sulfonylurea
    • C07C311/57—Y 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
    • C07C311/59—Y 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 carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
    • C07C311/52—Y being a hetero atom
    • C07C311/54—Y being a hetero atom either X or Y, but not both, being nitrogen atoms, e.g. N-sulfonylurea
    • C07C311/57—Y 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
    • C07C311/60—Y 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 carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/65—N-sulfonylisocyanates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/02—Monothiocarbamic acids; Derivatives thereof
    • C07C333/12—Monothiocarbamic acids; Derivatives thereof having nitrogen atoms of thiocarbamic groups bound to other hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C391/00—Compounds containing selenium
    • C07C391/02—Compounds containing selenium having selenium atoms bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic 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
    • C07D251/14—Heterocyclic 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
    • C07D251/16—Heterocyclic 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 to only one ring carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
    • C07D295/215—Radicals derived from nitrogen analogues of carbonic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic 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 sulphur atom
    • C07D333/26—Heterocyclic 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 sulphur atom 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
    • C07D333/30—Hetero atoms other than halogen
    • C07D333/34—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/66—Arsenic compounds
    • C07F9/70—Organo-arsenic compounds
    • C07F9/74—Aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • 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.
  • N- (arylsulfonyl) carbamic acid derivatives which can be prepared by process A correspond to the general formula
  • Ar represents phenyl, benzyl, naphthyl, pyridyl or thienyl
  • C 1-12 alkyl 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 together form an ⁇ , ⁇ -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
  • 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.
  • 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]:
  • 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
  • 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].
  • 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 invention is based on the knowledge that the arylsulfonylimines of the general formula (II)
  • 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 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
  • 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
  • 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
  • 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.
  • 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
  • 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.
  • 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.
  • the two isocyanates can be easily separated from one another by distillation; the yield is over 80%.
  • R phenyl, p-tolyl, piperidyl
  • 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]:
  • 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 /]:
  • the invention therefore also relates to a process (process B) for the preparation of arylsulfonyl isocyanates of the general formula (III)
  • 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.
  • 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:
  • Ph 2 Se (OMe) 2 + ArSO 2 NH 2 - - - - - - - - - - - - - - -> Ph 2 Se NSO 2 Ar (23)
  • N-halosulfonamidates can only be formed from relatively few sulfonamides, ie the number of sulfonylimines which can be prepared from them is necessarily limited.
  • 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.
  • 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.
  • Rl's are preferred: C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 haloalkoxy, C 1-4 alkylsulfonyl, phenylsulfonyl and / or Halogen.
  • R 1 ' I O + 2 AlkOH - - - - - - - - - -> R 1' I (OAlk) 2 + H 2 O (27)
  • a dehydrating agent 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.
  • 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).
  • reaction to the arylsulfonylimide takes place at room temperature, which means less energy consumption.
  • 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.
  • R 1 R 2 R 3 X (OCH 3 ) 2 + ArSO 2 NH 2 - - - - - - - -> R 1 R 2 R 3 X NSO 2 Ar +
  • R 1 R 2 R 3 X NSO 2 Ar + CO - - - - - - - -> ArSO 2 NCO + R 1 R 2 R 3 X
  • 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.
  • 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).
  • 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).
  • 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.
  • the physical data correspond to those given in example 22.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé amélioré de fabrication de dérivés d'acides N-(arylsulfonyl)-carbamiques (carbamide, carbamate et thiocarbamate) connus en soi, de formule générale (I) où Ar représente le groupe aryle, Z représente N, S ou O et R4 ainsi que R5 peuvent désigner divers groupes aliphatiques, cyclo-aliphatiques ou aromatiques. Les composés sont fabriqués en carbonylant de manière catalytique avec du CO les arylsulfonylimines de la formule générale (II): ArSO¿2?N=XR?1R2R3 où R1, R2 et R3¿ représentent, indépendamment les uns des autres, alkyl C¿1-12?, cycloalcényle, benzyle, phényle ou naphtyle éventuellement substitué, et X représente un atome de phosphore, d'arsenic, d'antimoine, de soufre, de sélénium, de tellure ou d'iode, et en faisant réagir l'isocyanate d'arylsulfonyl de formule générale (III): ArSO2NCO pendant ou après la carbonylation avec les composés de la formule générale (IV): R?4R5¿ZH.
PCT/HU1992/000047 1991-11-13 1992-11-12 Procede de fabrication de derives d'acides n-(arylsulfonyl)-carbamiques ainsi que des intermediaires utilises dans ledit procede WO1993010086A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
HU3554/91 1991-11-13
HU355491A HU209864B (en) 1991-11-13 1991-11-13 Process for producing arylsulfonyl isocyanates and solutions thereof
HU9200895A HUT64018A (en) 1992-03-18 1992-03-18 Process for producing n-(arylsulfonyl)-carbamic acid derivatives
HUP9200895 1992-03-18
HU9201169A HUT64017A (en) 1992-04-07 1992-04-07 Process for producing arylsulfonyl imines
HUP9201169 1992-04-07

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
US6171861B1 (en) 1995-06-07 2001-01-09 Life Technologies, Inc. Recombinational cloning using engineered recombination sites
US7109337B2 (en) 2002-12-20 2006-09-19 Pfizer Inc Pyrimidine derivatives for the treatment of abnormal cell growth
US7109335B2 (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
US9534252B2 (en) 2003-12-01 2017-01-03 Life Technologies Corporation Nucleic acid molecules containing recombination sites and methods of using the same
RU2821509C1 (ru) * 2023-12-18 2024-06-25 Акционерное общество "Щелково Агрохим" Способ получения толбутамида

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AUPN193095A0 (en) * 1995-03-24 1995-04-27 Polychip Pharmaceuticals Pty Ltd Potassium ion channel blockers

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT260944B (de) * 1965-03-16 1968-03-25 Boehringer & Soehne Gmbh Verfahren zur Herstellung von Sulfonylurethanen bzw. deren Salzen
DD105215A1 (fr) * 1972-11-09 1974-04-12
US4260824A (en) * 1979-09-21 1981-04-07 Stauffer Chemical Company Sulfonylurea herbicidal antidotes
EP0185227A2 (fr) * 1984-12-06 1986-06-25 Nihon Tokushu Noyaku Seizo K.K. Procédé de préparation de N-(2-biphénylylsulfonyl)-carbamate de phényle
US4600792A (en) * 1984-04-11 1986-07-15 Nihon Tokushu Noyaku Seizo K.K. Preparation of biphenylylsulfonylureas and intermediates therefor
CH662348A5 (de) * 1983-11-23 1987-09-30 Du Pont Verfahren zur herstellung von sulfonylharnstoffen.
DE3919747A1 (de) * 1988-06-17 1989-12-21 Magyar Tudomanyos Akademia Verfahren zur herstellung von n-(arylsulfonyl)-isocyanaten und additionsderivaten
DE3906010A1 (de) * 1989-02-26 1990-08-30 Wuertex Maschinenbau Hofmann G Verfahren zur herstellung einer feuchten mischung aus stuckgips und altpapierfasern
US4990637A (en) * 1986-12-16 1991-02-05 Bayer Aktiengesellschaft 1-benzylsulphonyl-3-heteroaryl-(thio)urea herbicides

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT260944B (de) * 1965-03-16 1968-03-25 Boehringer & Soehne Gmbh Verfahren zur Herstellung von Sulfonylurethanen bzw. deren Salzen
DD105215A1 (fr) * 1972-11-09 1974-04-12
US4260824A (en) * 1979-09-21 1981-04-07 Stauffer Chemical Company Sulfonylurea herbicidal antidotes
CH662348A5 (de) * 1983-11-23 1987-09-30 Du Pont Verfahren zur herstellung von sulfonylharnstoffen.
US4600792A (en) * 1984-04-11 1986-07-15 Nihon Tokushu Noyaku Seizo K.K. Preparation of biphenylylsulfonylureas and intermediates therefor
EP0185227A2 (fr) * 1984-12-06 1986-06-25 Nihon Tokushu Noyaku Seizo K.K. Procédé de préparation de N-(2-biphénylylsulfonyl)-carbamate de phényle
US4990637A (en) * 1986-12-16 1991-02-05 Bayer Aktiengesellschaft 1-benzylsulphonyl-3-heteroaryl-(thio)urea herbicides
DE3919747A1 (de) * 1988-06-17 1989-12-21 Magyar Tudomanyos Akademia Verfahren zur herstellung von n-(arylsulfonyl)-isocyanaten und additionsderivaten
DE3906010A1 (de) * 1989-02-26 1990-08-30 Wuertex Maschinenbau Hofmann G Verfahren zur herstellung einer feuchten mischung aus stuckgips und altpapierfasern

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
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
US7674796B2 (en) 2002-12-20 2010-03-09 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
US7741336B2 (en) 2002-12-20 2010-06-22 Pfizer Inc. Pyrimidine derivatives for the treatment of abnormal cell growth
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
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
US7235562B2 (en) 2004-05-14 2007-06-26 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
RU2821509C1 (ru) * 2023-12-18 2024-06-25 Акционерное общество "Щелково Агрохим" Способ получения толбутамида

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