Patent GB-716126-A (GB)
Title: Process of producing compounds of metal alcoholate type
IPC: C07F19/00
Filed: 1951-07-19
Abstract: Compounds of metal alcoholate type of the metals titanium, iron, and aluminium are obtained by reacting a substituted or unsubstituted alkylene oxide with anhydrous titanic, ferric, or aluminium chloride or bromide in solution in ethyl alcohol or carbon tetrachloride. Suitable alkylene oxides include ethylene oxide, propylene oxide, epichlorhydrin, cyclohexene oxide and phenoxy propylene oxide.  The process may be carried out by dissolving the metallic chloride in ethyl alcohol or carbon tetrachloride and gradually adding thereto the alkylene oxide which may also be dissolved in ethyl alcohol or carbon tetrachloride.  The reaction of at least three mols. of alkylene oxide per mol. of ferric or aluminium chloride and the reaction of at least 4 mols. of alkylene oxide with 1 mol. of titanium tetrachloride yields neutral products but when smaller amounts of alkylene oxide are used the product still contains a chlorine atom attached to the metal atom, thus 3 mols. of ethylene oxide reacts with 1 mol. of titanium tetrachloride to yield the compound Ti(O.CH2.CH2.Cl)3Cl.  The products may be treated with water to yield the corresponding metallic hydroxides (see Group III) and may find application as intermediates in the manufacture of organometallic compounds.  In examples (1) anhydrous titanium tetrachloride is dissolved in carbon tetrachloride in a flask fitted with a reflux condenser and dry ethylene oxide introduced whilst cooling the reaction vessel to prevent the temperature exceeding 50 DEG  C., the ethylene oxide being added until a sample shows a neutral reaction to wet titmus paper; (2) cyclohexene oxide is added to a solution of titanium tetrachloride in carbon tetrachloride and after distilling off the solvent a colourless viscous liquid is obtained which is soluble in acetic ester, benzene, gasoline and alcohol, and on adding water yields a precipitate of titanium hydroxide; (3) ethylene oxide is introduced into a solution of anhydrous ferric chloride in dry alcohol with cooling until a sample shows an almost neutral reaction to wet indicator paper.  A deep brown solution is formed from which ferric hydroxide precipitated on adding a little water. Reference is also made to the reaction of ferric chloride with propylene oxide and aluminium chloride with epichlorhydrin.ALSO:Metal alcoholate type compounds of titanium, iron, and aluminium obtained by reacting a substituted or unsubstituted alkylene oxide with anhydrous titanic, ferric, or aluminium chloride or bromide in solution in ethyl alcohol or carbon tetrachloride (see Group IV (b)) are stated to yield the corresponding metallic hydroxides on admixture with water. Suitable alkylene oxides include ethylene oxide, propylene oxide, epichlorhydrin, cyclohexene oxide and phenoxy propylene oxide. In examples:-(1) cyclohexene oxide is added to a solution of titanium tetrachloride in carbon tetrachloride and after distilling off the solvent a colourless viscous liquid is obtained which on adding water yields a precipitate of titanium hydroxide; (2) ethylene oxide is introduced into a solution of anhydrous ferric chloride in dry alcohol, with cooling, until a sample shows an almost neutral reaction to wet indicator paper.  A deep brown solution is formed from which ferric hydroxide precipitates on adding a little water. On adding a further quantity of water a colloidal solution is formed.