Patent GB-1262585-A (GB)
Title: Improvements in or relating to quaternary ammonium steroids
IPC: C07J75/00
Filed: 1969-05-16
Abstract: 1,262,585. Quaternary ammonium steroids. SYNTEX CORP. 16 May, 1969 [8 Aug., 1968], No. 25104/69. Headings C2C and C2U. Novel steroids of the formula (where R<SP>1</SP> is a steroid molecule attached at position -3, -6, -7 or -16, or at the 17-position or to a side chain at this position, including A-, B- and D-homo and A- and B-nor steroids, m is 2, 3, 4, 5, 6 or 7, n is 2, 3 or 4, the wavy line indicates α- or #-configuration for the attached diaza bicycloalkene group, or a mixture of the two epimers, the dotted line indicates resonance in the diazabicycloalkene group, and x# is an anion) are prepared by a displacement reaction in which a halogen atom or a radical such as an alkyl- or aryl-sulphonyloxy group is displaced on the steroid molecule by an appropriate diazabicycloalkene. In most cases, depending on the stereochemistry of the steroid molecule, complete or partial inversion takes place. Anions are exchanged by metathesis. 3# - Halo - androst - 5 - en - 17 - ones are prepared by halogenation of the corresponding 3#- ols. 3# - Bromo - androst - 4 - ene, 3α - bromo - 5α- androstan - 17 - one, 3# - chlorocholest - 4 - ene, the 3-bromo derivatives of diosgenin and tigogenin, 17# - bromo - methyl - 3 - methoxy - estra - 1,3,5(10)- triene, 3 - methoxy 20 - bromo - 19 - norpregna- 1,3,5(10) - triene, 3# - chloro - androst - 1 - en- 17# - ol, 21 - bromo - 3 - methoxy - 19 - norpregna- 1,3,5(10),17(20) - tetraene, 7α - bromo - 3#,17#- diacetoxy - 5α - androstane, and 2# - chloromethyl - 19 - nor - 5α - pregnan - 20 - one and other halo-steroid starting materials, are prepared similarly from the corresponding ols. 7#- Bromo-3#-acetoxyandrost-5-en-17-one is prepared by bromination of the 7-unsubstituted compound. 7# - Bromodiosgenin acetate and other halo-steroid starting materials are prepared similarly.  The 5,6,22,23 - tetrahydro derivative of ergosteryl acetate is prepared by catalytic hydrogenation of the parent compound. 3 - Methoxy - 17# - hydroxymethyl - estra- 1,3,5(10)-triene is prepared from estrone methyl ether via the 17-methylene derivative.  3# - Acetoxy - 17# - hydroxymethyl - 5α - androstane is prepared by reduction of 3#-acetoxy-5α- androstane - 17# - carboxylic acid. 3# - Acetoxypregn - 5 - ene - 20 - carboxylic acid, 3#- acetoxy - 23,24 - bisnor - chol - 5 - ene - 22 - carboxylic acid, 3# - acetoxy - 23,24 - bisnor - 5α- cholane - 22 - carboxylic acid, 3# - acetoxy- 5α - cholanic acid, 3# - acetoxychol - 5 - enoic acid and 3# - acetoxy - androst- 5 - en - 17#- carboxylic acid are similarly converted into the corresponding alcohols. #<SP>7</SP>-Ergostenol 3-acetate is prepared by acetylation of #<SP>7</SP>-ergostenol. 3 - Methoxy - 19 - norpregna = 1,3,5(10),17(20)- tetraen-21-ol is prepared by reduction of the 21 - al. 3 - Methoxy - 19 - nor - -18 - methylpregna- 1,3,5(10),8,17(20) - pentaen - 21 - ol and 3- methoxy - 19 - norpregna - 1,3,5(10),6,8,17(20)- hexaen-21-ol are prepared similarly. 3 - Methoxy - 19 - norpregna - 1,3,5(10) - trien- 21 - one, 3 - methoxy - 18 - methylpregna- 1,3,5(10) - trien - 21 - one and 3 - methoxy - 19 - norpregna - 1,3,5(10),8 - tetraen - 21 - one are prepared by catalytic hydrogenation of the corresponding #<SP>17(20)</SP>-21-als. 17# - Methanesulphonyloxy - 3 - methoxyestra- 1,3,5(10)-triene and the corresponding 17-tosylate are prepared from the free 17#-ol. 7α - Hydroxy - 3#,17# - diacetoxy - 5α - androstane is prepared by reduction of the 7-one. The novel quaternary ammonium steroids are bactericides and fungicides and may be made up into pharmaceutical and veterinary compositions with suitable carriers.