Analogifremgangsmåde til fremstilling af 4-amino-spiro-[cyclohexan-1,9'-thioxanthen]-forbindelser eller syreadditionssalte eller kvartære ammoniumsalte deraf

1289209 Spirothioxanthenes MERCK PATENT GmbH 8 Oct 1970 [15 Nov 1969] 47849/70 Heading C2C Novel compounds of Formula I in which R1 is H or an alkyl group with up to 6 carbon atoms, R2 is H or an alkyl group with up to 3 carbon atoms, or R1 and R2, together with the nitrogen atom to which they are attached, form a morpholine ring or a pyrrolidine, piperidine or piperazine ring which may, if desired, be substituted by a methyl or ethyl group, and R3 and R4 are H or Cl, or a physiologically acceptable acid addition salt or quaternary ammonium salt thereof, are prepared by one of the following methods: (a) reducing an enamine of formula in which the dashed line denotes an optional bond, (b) reacting a compound of Formula IV in which Y is Cl, Br, I, OH, or a reactively esterified OH group, and R3 and R4 have the meanings specified above, with a base of the formula, R1R2NH, in which R1 and R2 have the meanings specified above, or with a reactant that yields such a base, (c) reducing a compound of formula in which the dashed line in the cyclohexane ring represents a double bond that may, if desired, be present in this position in the compound of Formula II, X is =NOH, =NR1, (H,NR2Ac1) or (H,NR1Ac2) or another group which can be converted by reduction to the group NR1R2, Ac1 is an acyl radical with up to 6 carbon atoms, Ac2 is an acyl radical with up to 3 carbon atoms, and R1 , R2, R3 and R4 have the meanings specified above, (d) an organometallic compound of Formula VI in which M is-Li or MgHal, Hal is Cl, Br or I, and R3 and R4 have the meanings specified above, with a hydroxylamine derivative of the formula, R1R2NA, in which A is an alkoxy group having 1 to 4 carbon atoms or Hal, (e) by hydrogenolysing, hydrolysing, alcoholysing or aminolysing a compound corresponding to Formula I and in which the amino group is present in a functionally modified form, in order to liberate the amino group, and (f) by reacting a compound of formula with a thioether-bridge forming reactant in order to obtain intramolecular cyclization and, in each case, the product obtained may be converted into a salt. 21 - Chloro - spiro[cyclohexane - 1,91 - thioxanthene] - 4 - one is obtained by oxidation of 2-chlorothioxanthene to the sulphoxide which is converted successively to 9,9 - bis - (2 - cyanoethyl - 2 - chlorothioxanthioxanthene sulphoxide, 9,9 - bis - (2 - cyanoethyl) - 2 - chlorothioxanthene, hydrolysed to the dipropionic acid, esterified to the dimethyl ester which is cyclized t