Patent GB-776776-A (GB)
Title: Manufacture of new dioxypropane compounds containing mercury
IPC: C07F3/10
Filed: 1952-09-26
Abstract: The invention comprises organo-mercury compounds of the general formula <FORM:0776776/IV(b)/1> wherein Y represents the residue of N-theophylline or a carboxyalkylmercapto or polyoxyalkylmercapto group, and Z represents a b  : g -dioxypropyl group of which the hydroxyl group in the g -position is etherified with a carbohydrate of the general formula <FORM:0776776/IV(b)/2> wherein n is 1, 2, 3 or 4, and of which the hydroxyl group in the b -position is etherified (a) with an alcohol group of the carbohydrate group in the g -position which is vicinal to the alcohol group forming the ether linkage with the g -position of the b  : g -dioxypropyl group, and (b) with an aliphatic alcohol, and the preparation thereof by reacting mercuric oxide and/or a mercuric salt of an inorganic or organic acid with an ether of allyl alcohol and a carbohydrate of the above general formula in the presence of water (for compounds (a) above) or an aliphatic alcohol (for compounds (b) above) to bring about addition of the group Z and the group -HgX at the double bond of the allyl grouping (X representing a free hydroxyl group or a hydroxyl group esterified with an organic or inorganic acid), and the resulting product is reacted with a compound of the formula H-Y, wherein Y has the above significance.  The carboxyalkylmercapto group preferably contains a lower alkylene residue such as the carboxymethylmercapto group or a salt thereof, and the polyoxyalkylmercapto group is preferably of the formula <FORM:0776776/IV(b)/3> wherein n is 1, 2, 3 or 4 such as the d-glucopentaoxypentylmethylmercapto or d-xylotetroxybutylmethylmercapto group.  The g -position of the b -g -dioxypropyl group may be etherified with a pentitol or hexitol, the ether bridge being in the 3-position of the pentitol or in the 3- or 6-position of the hexitol, e.g. in the 3-position of d-xylitol or d-mannitol or in the 6-position of d-sorbitol, or with an aldohexose, the ether bridge being in the 3-position such as in the 3-position of d-glucose.  The aliphatic alcohol is preferably a lower alkanol such as methanol or ethanol or a lower oxy-alkanol.  The mercuric salt, which may be used in the presence of alkali, is preferably derived from nitric acid or a lower aliphatic carboxylic acid such as acetic acid.  A metal salt of the reactant H-Y may also be used in the above process. Organo-mercury compounds of the above general formula containing salt-forming groups, for example, carboxyl groups, salts such as alkali metal salts may be prepared.  In the examples: (1) 1-S-(61-hydroxymethyl-21-p-dioxanylmethylmercuri) -1-thiosorbitol is prepared by reacting mercuric acetate and 2 : 3-dioxy-propyl-allyl ether in the presence of water to form 6 - acetoxymercurimethyl - 2 - hydroxy - methyl-p-dioxane which is then reacted with 1-d-thiosorbitol; (2) similar series of reactions are carried out as in (1) using mercuric acetate, 3(o)-allyl-d-mannitol and 1-thio-2,3-dioxpropane, mercapto-acetic acid or 1-d-thiosorbitol; using mercuric acetate, 3(o)-allyl-d-xylitol and 1-d-thiosorbitol; using mercuric acetate, 3(o)-allyl-d-glucose and mercapto-acetic acid or 1-d-thiosorbitol; and using mercuric acetate, 6(o)-allyl-d-sorbitol and 1-d-thioxylitol or 1-d-thiosorbitol; (3) a -(d-gluco-pentaoxypentyl-methylmercaptomercuri)-b , g -dioxypropane of which the hydroxyl group in the g -position is etherified with d-mannitol in the 3-position of the latter and the hydroxyl group in the b -position is etherified with methanol is prepared by reacting 3(o)-allyl-mannitol with mercuric acetate in the presence of methanol to form 3(o)-(21-methoxy-31-acetoxymercuripropyl)-d-mannitol which is then reacted with 1-thio-d-sorbitol; the methanol may be replaced by ethanol to form the corresponding ethyl ether in each step; (4) a -[11,31-dimethylxanthyl-(71)-mercuri]-b ,g -di oxypropane of which the hydroxyl group in the b -position is etherified with methanol and the hydroxyl group in the g -position is etherified with d-mannitol in the 3-position of the latter is prepared by reacting 3(o)-(21-methoxy-31-acetoxymercuri-propyl)-d-mannitol prepared by the method of the previous example with theophylline; (5) a -(d-gluco-pentaoxypentylmethyl-mercaptomercuri)-b , g -dioxypropane of which the hydroxyl group in the g -position is etherified with d-mannitol in the 3-position of the latter and the hydroxy group in the b -position is etherified with b -oxyethanol is prepared by reacting 3(o)-allyl-mannitol with mercuric acetate in the presence of ethylene glycol to form 3(o) - [31 - acetoxymercuri - 21 - (b  - oxyethoxy) - propyl]-d-mannitol which is then reacted with 1-d-thiosorbitol.  Starting compounds.  3-(o)-Allyl-d-xylitol is prepared by reacting 1,2,4,5-diacetone-d-xylitol and allyl bromide to form 3(o)-allyl-diacetone-d-xylitol which is then heated with aqueous concentrated sulphuric acid, and 3(o)-allyl-d-glucose is prepared by reacting 1,2,5,6-diacetone-d-glucose with allyl bromide to form 3(o)-allyl-1,2,5,6-diacetone-d-glucose which is then heated with aqueous concentrated sulphuric acid.