Modulators of the complement system

A process for the preparation of compounds of the formula:

• ##STR6## wherein M is a nontoxic pharmaceutically acceptable cation salt, wherein the salt forming moiety is selected from the group consisting of alkali metal, alkaline earth metal, aluminum, ammonia and substituted ammonia selected from the group consisting of trialkylamine (C.sub.1 -C.sub.6), piperidine, pyrazine, alkanolamine (C.sub.2 -C.sub.6) and cycloalkylamine (C.sub.3 -C.sub.6);
• B is selected from the group consisting of --NHCO--, --NHSO.sub.2 --, --NHCH.sub.2 --, and --NH--;
• and Z is a straight or branched chain alkylidene group --(CH.sub.2).sub.m --, where m is an integer 0-12, inclusive, with the proviso that when m is zero or one, B cannot be --NHSO.sub.2 --;
• which comprises reacting 4-aminothiophenol in dimethoxyethane and sodium hydride in oil with a solution of acetobromo-.alpha.-D-maltose or cellobiose in dimethoxyethane, under an inert atmosphere, for 18 hours, subjecting the mother liquor to dry column chromatography on silica gel using the solvent system ethyl acetate:hexane (1:1) giving 4-aminophenyl 2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-.alpha.(or .beta.)-D-glucopyranosyl)-1-thio-.alpha. (or .beta.)-D-glucopyranoside;
• then reacting with an appropriate acid chloride of the formula X--(CH.sub.2).sub.m --X, where X is COCl or SO.sub.2 Cl and m is an integer 0-12 (with the proviso that when m is zero or one X cannot be SO.sub.2 Cl), in dry pyridine:acetonitrile (1:1) under an inert atmosphere for 18-36 hours, extracting from a suitable organic solvent, giving a compound of the formula:
• ##STR7## where B and Z are as hereinabove defined, treating this acetylated derivative in ammonia saturated methanol at 0.degree. C., or sodium in methanol, for 18-24 hours;
• extracting from absolute ethanol, giving the corresponding deacetylated derivative of the formula:
• ##STR8## where B and Z are as hereinabove defined, then converting to the tetradecatriethylammonium sulfate derivatives of the formula:
• ##STR9## where B and Z are as hereinabove defined and Y is NH.sup.+ (C.sub.2 H.sub.5).sub.3, by treating with triethylamine-sulfur trioxide complex in N,N-dimethylacetamide, under an inert atmosphere at 60.degree.-65.degree. C., for 66 hours;
• reacting with a cation-containing compound wherein the salt forming moiety is selected from the group consisting of alkali metal, alkaline earth metal, aluminum, ammonia and substituted ammonia selected from the group consisting of piperidine, pyrazine, alkanolamine (C.sub.2 -C.sub.6) and cycloalkylamine (C.sub.3 -C.sub.6), and thereafter precipitating in ethanol, giving the desired products.