Patent GB-395003-A (GB)
Title: The manufacture of metal-organic complex compounds
IPC: C07F19/00
Filed: 1932-01-07
Abstract: Basic, water-insoluble (or difficulty water-soluble) alkaline earth metal salts of complex compounds of aliphatic polyhydroxy compounds with trivalent iron, aluminium, trivalent chromium or bismuth are manufactured by reacting upon an alkaline-reacting aqueous solution of an aliphatic polyhydroxy compound with a salt or hydroxide of trivalent iron, aluminium, trivalent chromium or bismuth and precipitating the complex metal compound formed by the addition of an alkaline earth metal salt or hydroxide.  The aliphatic polyhydroxy compounds may be polyvalent alcohols, e.g. glycerine, erythrite, xylite, sorbite, dulcite, or mannite, or polyhydroxycarboxylic acids, e.g. glyceric, tartaric, arabic, p  mucic, saccharic, glucoheptonic, mannoheptonic or lactobionic acids.  The process may be carried out by adding at most one molecular proportion of a water-soluble salt or of a hydroxide of one of the complex-forming metals to an aqueous solution containing about one molecular proportion of the aliphatic polyhydroxy compound and a caustic alkali, which, when using a salt of the metal, should be in excess, e.g. 5-8 molecular proportions, and, after filtration if necessary, adding about one molecular proportion of a water-soluble alkaline-earth metal salt or hydroxide, which may be in slight excess.  When employing a calcium salt or calcium hydroxide, heating of the solution is generally necessary in order to precipitate the complex compound. The process may also be performed by first mixing an alkaline reacting solution of the aliphatic polyhydroxy compound with the alkaline-earth metal salt or hydroxide and then adding the salt or hydroxide of the complex-forming metal.  Neutral water-soluble salts of the metal complex compounds are manufactured by reacting upon the alkaline-earth metal salts with the calculated quantity of an alkali metal, magnesium, ammonium or amine salt, the anion of which forms alkaline earth metal salts insoluble or sparingly soluble in water, e.g. salts of sulphuric, oxalic or carbonic acid such as sodium or potassium sulphate or bisulphate, carbonate or bicarbonate, or oxalate, or the corresponding salts of magnesium, ammonia or amines. The metal complex compounds from polyhydric alcohols are capable of forming salts only with strong bases, e.g. alkalies, tetraalkylammonium and alkylene diamines, whereas those from polyhydroxycarboxylic acids yield water soluble salts also with weak bases, e.g. ammonia and monoamines.  The water-insoluble basic alkaline-earth metal salts of metal complex compounds from aliphatic polyhydroxycarboxylic acids are also converted into neutral water-soluble salts by reaction with one equivalent of the free polyhydroxycarboxylic acid.  In examples: (1) to a solution of mannite in aqueous caustic soda are added barium chloride solution and and ferric chloride solution, yielding basic barium ferric mannite of the probable formula Ba [O2C6H8.(OH).O3Fe] aq.; by treating an aqueous suspension of this compound with a solution of ethylene diamine sulphate or tetramethyl- or tetraethylammonium sulphate or bisulphate the corresponding salts are obtained; (2) to a solution of mannite in aqueous caustic soda are added precipitated ferric hydroxide and calcium chloride solution, yielding the ferric calcium compound of mannite, of the probable formula Ca [C6H9O6Fe] aq.; (3) to a solution of sorbite in aqueous caustic soda are added ferric chloride solution and barium chloride solution, producing barium ferric sorbite of the probable formula Ba (C6H9O6Fe) aq.; the barium chloride may be replaced by strontium chloride; by treating an aqueous suspension of the barium salt with sodium sulphate solution there is obtained sodium ferric sorbite of the probable formula Na [O.C6H8(OH)2. O3Fe] aq.; (4) to a solution of glycerine in aqueous caustic soda are added precipitated ferric hydroxide and barium hydroxide solution, yielding barium ferric glycerine of the probable formula Ba2[(C3H5O3)2 FeOH] aq.; (5) erythrite similarly yields barium ferric erythrite of the probable formula C25H50O24Fe2Ba3 aq.; (6) to a solution of mannite in aqueous caustic soda are added powdered bismuth nitrate and barium chloride solution, producing barium bismuth mannite of the probable formula Ba [(C6H11O6)2(Bi OH)2] aq.; (7) to a solution of mannite in aqueous caustic soda are added calcium chloride solution and bismuth trichloride, to yield calcium bismuth mannite of the probable formula Ca [(C6H11O6)2 (BiOH)2)] aq.; (8) to a solution of mannite in aqueous caustic soda are added solutions of barium chloride and of chromium chloride, producing barium chromic mannite of the probable formula Ba [O2.C6H8.OH.O3Cr] aq.; by treating an aqueous paste of this compound with sodium bisulphate solution there is obtained sodium chromic mannite of the probable formula Na [O.C6H8(OH)2O3Cr] aq.; (9) the chromic chloride in (8) is replaced by aluminium chloride to produce barium aluminium mannite of the probable formula C6H9O6Al. Ba. aq., which is similarly converted into sodium aluminium mannite of the probable formula Na [O.C6H8(OH)2.O3Al] aq.; (10) a solution of gluconic acid in aqueous caustic soda is added to a ferric chloride solution, and to the mixture is added a solution of barium chloride, yielding barium ferric gluconate of the probable formula C6H7O7Fe Ba. aq.; by replacing the barium chloride by calcium chloride the corresponding calcium salt is obtained; by employing different proportions of calcium chloride there may be produced a compound of the probable formula C12H17O14Ca2Fe, or a compound containing for 4 molecules of gluconic acid, 3 atoms of iron and 6 atoms of calcium; by treating an aqueous paste of basic barium ferric gluconate with potassium bisulphate solution there is obtained neutral potassium ferric gluconate of the probable formula K[O2C6H6(OH)2.O3Fe] aq.; the potassium bisulphate may be replaced by ammonium or dimethylamine bisulphates, yielding analogous compounds, or by magnesium bisulphate, yielding neutral magnesium ferric gluconate of the probable formula (C6H8O7Fe2) Mg.4H2O; by introducing basic barium ferric gluconate into gluconic acid solution there is obtained neutral barium ferric gluconate of the probable formula Ba[C12H19O18Fe]aq., which with calcium sulphate yields the corresponding calcium salt; if the basic calcium ferric gluconate C12H17O14Ca2Fe is added to gluconic acid solution there is obtained a neutral salt of the probable formula [C24H41O28Fe] Ca2 aq. (11) to a solution of mucic acid in aqueous caustic soda are added solutions of ferric chloride and of barium chloride, to yield a compound of the probable formula [C12H13O16Fe] Ba2 aq. the mucic acid may be replaced by saccharic or galactonic acid; (12) to a solution of gluconic acid in aqueous caustic soda are added bismuth trichloride and a solution of barium chloride, yielding barium bismuth gluconate; on adding this to gluconic acid solution a soluble compound is obtained; (13) solutions of gluconic acid and chromic chloride are mixed and to the mixture are added solutions of caustic soda and barium chloride, producing basic barium chromic gluconate of the probable formula C6H7O7CrBa. aq.; on adding this to gluconic acid solution there is obtained neutral barium chromic gluconate of the probable formula C12H19O14Cr.Ba. aq.; (14) the chromic chloride in (13) is replaced by aluminium chloride to produce basic barium aluminium gluconate of the probable formula C6H7O7Al. Ba.aq.; on treating an aqueous paste of this with tetraethylammonium bisulphate there is obtained neutral tetraethylammonium aluminium gluconate of the probable formula C6H8O7Al.N (C2H5)4 aq. Specification 335,965, [Class 2 (iii), Dyes &c.], is referred to.