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Ep 0557122 B1 Patentamt Europaisches |||| ||| 1 1|| ||| ||| || || |||| || || || |||| || (19) J European Patent Office Office europeen des brevets (1 1 ) EP 0 557 122 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) int. CI.6: C07C 307/04, C07D 207/26, of the grant of the patent: C07D 207/12, C07D 501/04, 15.01.1997 Bulletin 1997/03 C07D 477/00 (21) Application number: 93301235.3 (22) Date of filing : 1 9.02.1 993 (54) A production method for sulfamide Verfahren zur Herstellung von Sulfamic! Methode de production de sulphamide (84) Designated Contracting States: • Nishino, Yutaka AT BE CH DE DK ES FR GB GR IE IT LI LU MC NL Neyagawa-shi, Osaka (JP) PTSE (74) Representative: Nash, David Allan et al (30) Priority: 21.02.1992 JP 35366/92 Haseltine Lake & Co. 08.07.1992 JP 180930/92 28 Southampton Buildings 20.08.1992 JP 221767/92 Chancery Lane London WC2A1 AT (GB) (43) Date of publication of application: 25.08.1993 Bulletin 1993/34 (56) References cited: EP-A- 0 050 927 (73) Proprietor: SHIONOGI SEIYAKU KABUSHIKI KAISHA • CHEMICAL ABSTRACTS, vol. 85, no. 5, 1976, trading under the name of Columbus, Ohio, US; abstract no. 3331 3n, SHIONOGI & CO. LTD. GRYNKIEWICZ, GRZEGORZ 'Reaction of 1,2:3,4 Osaka 541 (JP) -di-O-isopropylidene-alpha-D-galactopyrano se with dialkyl azodicarboxylate in the presence of (72) Inventors: triphenylphosphine' • Sendo, Yuji • CHEMICAL ABSTRACTS, vol. 103, no. 17, 1985, Itami-shi, Hyogo-ken (JP) Columbus, Ohio, US; abstract no. 142095d, • Kii, Makoto OSIKAWA, TATSUO. 'Dialkyl phosphonate- Amagasaki-shi, Hyogo-ken (JP) promoted reaction of alcohols with diethyl • Nishitani, Yasuhiro azodicarboxylate and triphenylphosphine: Izumi-shi, Osaka (JP) preparation of diethyl 1 -substituted-1 ,2- • Irie, Tadashi hydrazinedicarboxylate.' Suita-shi, Osaka (JP) CO CM CM LO Note: Within nine months from the publication of the mention of the grant of the European patent, give LO any person may notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in o a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. Q_ 99(1) European Patent Convention). LU Printed by Rank Xerox (UK) Business Services 2.13.13/3.4 EP 0 557 122 B1 Description 1 . Field of the Invention: 5 The present invention relates to a production method of sulfamides which are useful for producing medicaments, medicines for plants and animals, polymers and stereoisomer alcohol compounds. 2. Description of the Related Art: 10 The production of sulfamides from alcohol generally includes 4 to 5 steps: Alcohol is converted into a halogen com- pound or sulfonyl ester, the halogen or the sulfonyl ester group is substituted with an azido group to obtain an azide compound, and the azido group is reduced to an amino group. Alternatively, alcohol is converted into a halogen com- pound or sulfonyl ester, the halogen or the sulfonyl ester group is substituted with a phthalimido group, and a phthaloyl group in the phthalimido group is removed with hydrazine to obtain an amino group. The amine produced in either of 15 the above described methods is reacted with a sulfamoylating agent, thereby obtaining a sulfamide. The resultant sul- famide is deprotected, if necessary. The above-mentioned production steps are disclosed in R. Kuhn, and W. Jahn, Chem. Ber., 98, 1699(1965); W. Jahn, Chem. Ber., 98, 1705(1965); M. G. Stout et al, J. Med. Chem., 12, 658(1969); D. A. Shuman at al, J. Am. Chem. Soc, 92, 3434(1970); Richard C. Larock, 'Comprehensive Organic Transformations: A Guide to Functional Group Prep- 20 arations' VCH Publishers, Inc., New York, 1989; G. W. Muller and G. E. DuBois, J. Org. Chem., 54, 4471(1989); B. Unterhalt and G. A. Hanewacker, Arch. Pharm., 321, 375(1988); and C.-H. Lee, Bull. Korean Chem. Soc, 14, 762(1993)). This method has the following problems: the above-mentioned steps are complicated; it is necessary to introduce or remove a protecting group which is adaptable to the reaction condition in each step when the compound to be 25 reacted has a functional group which may generate a side reaction in its molecule; and the azide compound and hydra- zine, which are highly explosive and toxic, are required. SUMMARY OF THE INVENTION 30 The method for producing a sulfamide of this invention comprises the steps of: conducting a condensation reaction between an alcohol and an oxycarbonysulfamide compound in the presence of a trivalent phosphorus compound and an azodicarboxylic acid derivative, wherein the sulfamide is represented by Formula I, the alcohol is represented by Formula II, and the oxycarbonylsulfamide compound is represented by Formula III: 35 R3NHS02NR1R2 (I) wherein R1 and R2 are independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, a heterocyclic group, and alkyl substituted with the heterocyclic group, respectively, said heterocyclic group 40 being selected from the group consisting of pyranosyl, furanosyl, piperidinyl, pyrrolidinyl, an azetidinone ring, a cephem ring, a penem ring, and a carbapenem ring; R3 is selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, a heterocyclic group, alkyl substituted with the heterocyclic group, and pyrrolidinyl-methyl, said heterocyclic group being selected from the group consisting of pyranosyl, furanosyl, piperidinyl, pyrrolidinyl, an azetidinone ring, a cephem ring, a penem ring, and a carbapenem ring; 45 R3OH (II) wherein R3 is defined as above; so R4OOC-NHS02NR1R2 (III) wherein R1 and R2 are defined as above; and R4 is a carboxy protecting group; and subjecting the resulting compound (IV) to a deprotection reaction: 55 R3N(COOR4)S02NR1R2 (IV) wherein R1, R2, R3 and R4 are defined as above. According to another aspect of the present invention, there is provided a method for producing a sulfamide com- prising the step of: 2 EP 0 557 122 B1 conducting a condensation reaction between an alcohol and an oxycarbonylsulfamide compound in the pres- ence of a trivalent phosphorus compound and an azodicarboxylic acid derivative, wherein the sulfamide is represented by Formula IV, the alcohol is represented by Formula II, and the oxycarbonylsulfamide compound is represented by For- mula III: 5 R3N(COOR4)S02NR1R2 (IV) wherein R1 and R2 are independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, a heterocyclic group, and alkyl substituted with the heterocyclic group, respectively, said heterocyclic group 10 being selected from the group consisting of pyranosyl, furanosyl, piperidinyl, pyrrolidinyl, an azetidinone ring, a cephem ring, a penem ring, and a carbapenem ring; R3 is selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, a heterocyclic group, alkyl substituted with the heterocyclic group, and pyrrolidinylmethyl, said heterocyclic group being selected from the group consisting of pyranosyl, furanosyl, piperidinyl, pyrrolidinyl, an azetidinone ring, a cephem ring, a penem ring, and a carbapenem ring; and R4 is a carboxy protecting group; 15 R3OH (II) wherein R3 is defined as above; 20 R4OOC-NHS02NR1R2 (III) wherein R1, R2 and R4 are defined as above. Thus, the invention described herein makes possible the advantages of (1) providing a production method for a sul- famide comprising two steps of a condensation reaction and a deprotection reaction both of which can be conducted 25 under a mild and neutral condition, which requires 4 to 5 steps in conventional methods; (2) providing a simple method for producing sulfamides useful as materials for synthesizing physiologically active materials such as antibacterial agents, antipyretics, analgesics, sweetners, sleeping agents and anticonvulsants; and (3) providing a method for pro- ducing such sulfamides in a high yield. These and other advantages of the present invention will become apparent to those skilled in the art upon reading 30 and understanding the following detailed description. DESCRIPTION OF THE PREFERRED EMBODIMENTS The following are abbreviations used herein: Ac : acetyl Boc : t-butoxycarbonyl Bz : benzene DCM : dichloromethane EtOAc : ethyl acetate Et : ethyl Me : methyl PMB : p-methoxybenzyl PNB : p-nitrobenzyl Ph : phenyl THF : tetrahydrofuran To : toluene t-Bu : t-butyl so In the production method for sulfamides (I) according to the present invention, an alcohol (II) and an oxycarbonyl- sulfamide compound (III) are reacted in the presence of a trivalent phosphorus compound and an azodicarboxylic acid derivative. The method of the present invention is exemplified by the following scheme: 3 EP 0 557 122 B1 RlR2NS02NR3 RlR2NS02NH + HOR3 r!r2nS02NR3 COOR4 H 5 COOR4 (1) (TV) (I) 10 wherein R1 and R2 are, for example, one independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, a heterocyclic group such as pyranosyl, furanosyl, piperidinyl, pyrrolidinyl, an azetidinone ring, a cephem ring, a penem ring and a carbapenem ring, and alkyl substituted with such a heterocyclic group, respectively; R3 is, for example, one selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, a hete- 15 rocyclic group such as pyranosyl, furanosyl, piperidinyl, pyrrolidinyl, an azetidinone ring, a cephem ring, a penem ring and a carbapenem ring, and alkyl substituted with the heterocyclic group, and R3 is preferred to be pyrrolidinylmethyl; and R4 is a carboxy protecting group. The method will now be described concretely.
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