Patent GB-553578-A (GB)
Title: Manufacture of dioxyacetone mono ethers or their esters with phosphoric acid or low molecular fatty acids
IPC: C07C49/17
Filed: 1941-12-16
Abstract: 553,578. Dioxyacetone ethers and esters. GEIGY AKT.-GES., J. R. Dec. 16, 1941, No. 16210. Convention date, Dec. 17, 1940. [Class 2 (iii)] Esters of dioxyacetone mono ethers are prepared by reacting a 1-oxy-3-halogen-2- propanone with a salt of a carboxylic acid to effect a substitution of the halogen by an ester residue. The ester so produced may if desired be treated with an alcohol to displace the 3- ester group by hydroxyl, which may itself in turn be re-esterified by treatment with an inorganic or organic acid. The first two steps for the formation of the mono-ether of dioxyacetone may be carried out in one operation by treating the halogen parent material with a mixture of the salt of the carboxylic acid and an alcohol. In this case the temperature should be 100‹-150‹C. In examples (1) 1- Ethoxy - 3 - chloro - propanone - 2 is added to a solution of potassium formate in methanol to give ethoxy-acetol (1-ethoxy-3-hydroxypropanone-2) ; (2) 1-Propanoxy-3-chloro-propanone-2 is reacted with methyl alcoholic potassium formate solution as in example (1) to give allyloxy acetol; (3) 1-Phenoxy-3-bromopropanone-2 is reacted with alcoholic potassium formate or acetate to give phenoxy-acetol; (4) 1-o-methoxyphenoxy-3-chloro-propanone-2 when treated with alcoholic potassium formate as above gives o-methoxyphenoxy acetol; (5) 1-Amyl-phenoxy-3-chloro-propanone-2 when treated as above gives amyl-phenoxy-acetol; (6) 1 - α - Naphthoxy - 3 - chloro - propanone - 2 treated as above gives α-naphthoxy acetol. The #-naphthol derivative may be similarly obtained ; (7) 1-Meta-diethylamino-phenoxy-3- chloropropanone-2 gives on the above treatment 1 - (3<SP>1</SP> - diethylaminophenoxy - 11) - 3 - hydroxypropanone-2. Other basic substituted phenols which may be used instead of diethylamino phenol are dimethylaminophenols and cresols, dimethylamino-methyl phenols and cresols, piperidylmethyl phenol, morpholinyl methyl phenol and cresol; (8) Dry potassium acetate is added to 1 guaiacoxy-3-chloro-propanone-2 to give 1-(21-methoxyphenoxy)-3-acetoxy-propanone-2. This is converted into o-methoxyphenoxy-acetol by boiling with absolute methyl alcohol; (9) Phenoxy-acetol produced as in example (1) is treated with acetyl chloride in the presence of pyridine to give 1-phenoxy-3- acetoxy-propanone-2 ; (10) Phenoxy acetol is treated with phosphorus oxychloride in chloroform solution. The ester dichloride so produced is hydrolyzed with ice water to produce the secondary phosphoric acid ester of phenoxy acetol. The starting materials used in the above examples are prepared as follows:- 1-Ethoxy-3-chloro-propanone-2. by the oxidation with sulphuric acid and bichromate of glycerine monochlorhydrin-ethyl ether. 1-Propenoxy-3-chloro-propanone-2. by the oxidation with sulphuric acid and bichromate of glycerine chlorhydrin alkyl ether. 1 - ortho - methoxyphenoxy - 3 - chloro - propanone-2 by reaction of glycerine-α, γ-dichlorohydrin with guaiacolate, or as a purer product by reacting epichlorhydrin with potassium guaiacolate and splitting the epiguaiacoline so obtained by means of hydrochloric acid. 1- Amylphenoxy-3-chloro-propanone-2 by the reaction of amylphenol with epichlorhydrin, treatment with hydrochloric acid and oxidation. 1-α-naphthoxy-3-chloro-propanone-2, by passing dry hydrochloric acid into epihydrin-α- naphthyl ether, followed by oxidation. 1 - meta - diethylaminophenoxy - 3 - chloro - propanone - 2 by reacting N-diethyl-metaaminophenol with epichlorhydrin in alkaline solution, followed by treatment with hydrochloric acid and oxidation.