Patent GB-745900-A (GB)
Title: Acylaminodiols and method for preparing same
Filed: 1952-06-24
Abstract: The invention comprises threo-acylaminodiols of the general formula <FORM:0745900/IV(a)/1> (wherein R represents a hydrocarbon radical of 1-7 carbon atoms, X represents S or SO2, and Y represents an aliphatic carboxylic acylamino radical), and the manufacture thereof by: (a) acylating the corresponding free aminodiols (Y = NH2); (b) (when X is S) reducing compounds of the general formula <FORM:0745900/IV(a)/2> (preferably by means of an oxidizable aluminium alkoxide containing not more than 4 carbon atoms in each alkyl group); (c) (when X is SO2) oxidizing the corresponding compounds in which X is S (preferably with a percompound under acidic conditions).  The starting materials for processes (a) and (b) are obtainable by the processes of Specifications 746,015 and 746,016 respectively.  The radical represented by R in the general formula may be benzyl, a cycloalkyl or alkenyl radical, or especially an alkyl or aryl radical, whilst that represented by Y may be, for example, alkanoylamino, nitroalkanoylamino, alkylmercaptoalkanoylamino, or especially haloalkanoylamino, and preferably contains 1-4 carbon atoms.  The products, which may exist in racemic or in optically active forms, are useful as antibiotic agents, especially in their dextro-rotatory forms, or as intermediates therefor.  In examples (in which all acylaminodiols and aminodiols are threo forms) (1) a -acetylamino-b -hydroxy-4 -methylmercaptopropiophenone is reduced with aluminium isopropoxide in isopropanol to 2-acetylamino - 1 - (4 - methylmercaptophenyl)-1 : 3 - propanediol, which is oxidized with peracetic acid in acetone to the corresponding 4-methylsulphonyl compound; (2) 2-amino-1-(4-methylmercaptophenyl) - 1 : 3 - propanediol or either of its optically active isomers is dichloracetylated by heating with ethyl dichloracetate or by treatment with chloral cyanhydrin and triethylamine, and the products are oxidized as in (1) to the corresponding 2-dichloracetylamino-1 - (4 - methylsulphonylphenyl) - 1 : 3 - propanediols; the same products are obtained by dichloracetylation of the corresponding 2-amino-1 - (4 - methylsulphonylphenyl) - 1 : 3 - propanediols; chloral hydrate and an alkali metal cyanide may be used instead of chloral cyanhydrin, and calcium carbonate, sodium carbonate or pyridine instead of triethylamine.  By analogous process are prepared: (3) 2-dibromacetylamino - 1 - (4 - methylmercapto - and 4 - methylsulphonyl - phenyl) - 1 : 3 - propanediols; (4) the racemic products of (2) by the process of (1); (5)-(7), (9) and (10) racemic 2-dichloracetylamin - 1 - (4 - ethyl -, - n propyl-, -n-butyl-, -benzyl- and -phenyl-mercapto-and - sulphonylphenyl) - 1 : 3 - propanediol; (8) racemic 2 - acetylamino - 1 - (4 - benzylmercapto - and - sulphonyl - phenyl) - 1 : 3-propanediol. Further products and the corresponding starting materials and intermediates are listed in which R and Y have the following additional meanings: p-tolyl, cyclohexyl, methallyl, iso - and tert. - butyl; iodoacetylamino, b  - chloropropionylamino, trifluoracetylamino, a  - methylpropionylamino and a  : b -dichloropropionylamino.  Still further radicals which may be represented by R and Y are: n-heptyl, isoamyl, allyl, cyclopentyl, o- and m-tolyl; mono- and di-bromacetylamino, difluoracetylamino, a - chloropropionylamino, trichloracetylamino, nitroacetylamino, methyl-and ethylmercaptoacetylamino, methylsulphonylacetylamino, butyrylamino, a  : a  - dichloropropionylamino, cyanoacetylamino, methoxyacetylamino, acrylylamino and a  - hydroxypropionylamino.