| 摘要 |
<p>1,221,738. Propynyl phosphonic acid and salts thereof. MERCK & CO. Inc. 12 May, 1969 [15 May, 1968], No. 23964/69. Heading C2C. A salt of 1-propynyl phosphonic acid is prepared by treating a mono- or diester of the formula or mixture thereof with a base, R being a straight or branched chain alkenyl or alkynyl group having 2 to 7 carbon atoms or a substituted or unsubstituted monocyclic aryl group and R<SP>1</SP> is hydrogen or is a group as defined for R. Preferably R and R<SP>1</SP> are 2-propynyl groups. The treatment is usually effected by contacting the ester in a solvent with the base for sufficient time to cleave the ester. The base used may be a strong inorganic or organic base, e.g. an alkali or alkaline earth metal oxide or hydroxide, a basic quaternary ammonium type anion exchange resin, triethylamine, trimethylamine, triethanolamine, an N-alkylpiperidine or tetramethyl ammonium hydroxide. The salts may be converted to the free 1-propynyl phosphonic acid by treating with a mineral acid, e.g. HCl or H 2 SO 4 . Suitable solvents for the main reaction include water, alcohols, dimethylsulphoxide, N,N<SP>1</SP>-dimethyl formamide and sulpholane or an excess of the base (when appropriate) may be used as solvent. The sodium salt of 1-propynyl phosphonic acid may be converted to the sodium salt of cispropenyl phosphonic acid by hydrogenation and the cis-propenylp hosphonicac id may be oxidized with H 2 O 2 to form racemic cis-1,2-epoxypropyl phosphonic acid which may be recovered as the sodium salt and the latter treated with quinine in methanol to yield the quinine salt of (-) (cis- 1,2-epoxypropyl) phosphonic acid which is then converted to the ammonium salt by treating with NH 4 OH in water, details being given for each step of the process. The (-) (cis- 1,2-epoxypropyl) phosphonic acid is an antimicrobial agent and may be administered orally e.g. in the form of its Na, K or Ca salt, or parenterally. Also, salts of (+) (cis-1,2-epoxypropyl) phosphonic acid inhibit undesirable bacterial growth in the white water used in paper mills, or in paints e.g. polyvinyl acetate latex paint.</p> |
