| 摘要 |
Carboxylic esters of polyfunctional hydroxymethyl ethers are prepared by reacting 1 mol of an organic compound containing 2 to 6 primary or secondary alcoholic hydroxyl groups with at least 2 mols of formaldehyde or polymerized formaldehyde at an elevated temperature and treating the resultant hemiacetal with at least 2 mols of an acetylating and/or propionylating agent in the absence of water. The initial polyhydroxy compounds may contain nitrogen, oxygen or sulphur as hetero-atoms. Suitable polyhydroxy compounds include those derived from alkanes, alkenes and alkynes which may also contain aldehyde, ether, thioether, sulphone or amino groups. The products of the formulae <FORM:0913865/IV (b)/1> in which R1 represents an alkyl radical containing 1-20 carbon atoms or a radical of the formula -Z-O-CH2-O-CO-R5, R2 represents an alkyl radical containing 2-4 carbon atoms which may be substituted by a hydroxyl group or by a group of the formula -O-CH2-O-CO-R6, R3, R4, R5 and R6 represent methyl or ethyl radicals, A, B and Z represent alkylene radicals containing 2-4 carbon atoms, and X represents an equivalent of an anion, are claimed per se. The formaldehyde may be added in free form, either anhydrous or in aqueous solution, or in the form of its readily clearable polymers. Inert solvents may be present. The acylation is conducted under anhydrous conditions using acid anhydrides or halides, or ketenes. In Examples (3)-(5), (8), (9) and (12)-(17) using paraformaldehyde and acetic anhydride:- (3) triethylene glycol gives its bis-acetoxymethyl ether; (4) triethanolamine gives the acetate of its triacetyloxymethyl ether; (5) tetraethanolammonium chloride gives its tetraacetyloxymethyl ether; (8) hexaethylene glycol, (9) dihydroxydiethylsulphone, (12) but-2-ene-1, 4-diol, (13) but-2-yne-1,4-diol, (14) n-hexane-1,6-diol and (15) n-hexane-2,4-diol give their respective bis-acetyloxymethyl ethers; (16) and (17) sorbitol gives its tetrahydroxymethyldiacetyloxymethyl and hexaacetyloxymethyl ethers. Using pentaerythritol and acetic anhydride, (1) and (2) formaldehyde, and (7) aqueous formaldehyde, give (1) and (7) the tetraacetyloxymethyl, and (2) the mixed polyacetyloxymethyl, ethers of pentaerythritol. In other examples; (6) paraformaldehyde, propionic anhydride and dimethyldihydroxyethylammonium methosulphate give the bispropionic acid ester of dimethyldihydroxyethylammonium methosulphate bis-hemiacetal; (10) paraformaldehyde and ketene convert ethylene glycol to its bis-acetyloxymethyl ether; (11) paraformaldehyde and acetyl chloride convert butane-1,4-diol to its bis-acetyloxymethyl ether. Many other reagents are specified. The products are used in the treatment of textiles. |
