Patent GB-938424-A (GB)
Title: Improvements in or relating to substituted oxazolidin-2-ones
IPC: C07D/
Filed: 1959-12-09
Abstract: Aryloxymethyl oxazolidinones of the general formula <FORM:0938424/IV(a)/1> wherein R is hydrogen or a C1-6 alkyl radical or an aralkyl radical and wherein the aryloxymethyl is in the 5-position and R1 is hydrogen in the 5-position or the aryloxymethyl radical is in the 4-position and R1 represents hydrogen or a C1-6 alkyl radical in the 4-position, the aryl group being mono- or di-nuclear and if, desired, substituted, are prepared by reacting a metal phenolate Aryl-O-M with an oxazolidinone of the general formula <FORM:0938424/IV(a)/2> wherein B is halogen or an aryl sulphonyloxy radical and when BCH2 is in the 5-position, R1 is hydrogen in the 5-position and when BH2 is in the 4-position, R1 is hydrogen or a C1-6 alkyl radical in the 4-position, the reaction preferably being effected under anhydrous conditions; when R is hydrogen, the product may be alkylated to convert R into a C1-6 alkyl or an aralkyl radical, for example by the method described in Specification 894,198.  The 4-(aryloxymethyl)-oxazolidinones are claimed per se. The first step of the process is preferably effected under anhydrous conditions in an organic solvent for example an alcohol or ether. The metal phenolate is desirably mononuclear and may be substituted by halogen, C1-6 alkyl or C1-6 alkoxy groups; the metal may be an alkali metal, alkaline earth metal or silver, B in the oxazolinone reactant may be chlorine or bromine or an aryl sulphonyloxy group introduced into methylol oxazolidinone by means of for example p-toluenesulphonyl chloride; the phenyl, p-bromo-phenyl and p-methoxyphenyl sulphonyloxy groups are also mentioned.  Examples describe the preparations of (1) 5-(o-methoxyphenoxymethyl), (3) 5-(o-chlorophenoxymethyl), (4) 5-(o-toloxymethyl), (5) 5-phenoxymethyl (6) 5-(m-methoxyphenoxymethyl), (7) 5-(o-ethoxyphenoxymethyl), (8) 5-(p-bromophenoxymethyl), (9) 5-(p-isopropyl phenoxymethyl), (10) 5-(o-methoxyphenoxymethyl)-3-methyl, (11) 5-(o-methoxyphenoxymethyl)-3-ethyl, (12) 5-(o-methoxyphenoxymethyl)-3-benzyl, (13) 4-phenoxy methyl-4-methyl, (14) 4-(o-toloxy-methyl)-4-methyl, (15) 4-(o-chlorophenoxy-methyl)-4-methyl, (16) 4-(o-methoxyphenoxy-methyl)-4-methyl, (18) 4-(o-methoxy phenoxy-methyl)-4-ethyl, (19) 4-(o-methoxyphenoxy-methyl), and (20) 4-(o-toloxymethyl) oxazolidinones-2 by the one step method. In Examples (3) copper powder is used as a catalyst.  The preparation of certain starting materials is described.  Thus (21) 5-bromo-methyl-3-methyl-oxazolyidinone-2 is prepared by reacting bromine with N-methyl-N-carbethoxyalkyl amine in chloroform and cyclising the product at 180-190 DEG C.; (22) 5-bromomethyl-3-benzyl-oxazolidinone and (23) 5-chloromethyl-3-ethyl oxazolidinone are similarly prepared; (24)- (27), 4-methyl-4-chloromethyl oxazolidinone, 4-methyl-4-p-toluene sulphonyloxymethyl oxazolidinone, 4-p-toluenesulphonyloxymethyl and 4-ethyl-4-p-toluene sulphonyloxymethyl oxazolidinones are similarly prepared from toluene sulphonyl chloride and the appropriate 4 - methylol oxazolidinones; (28) 4-methylol oxazolidinone is prepared by refluxing diethyl carbonate with the oxalate of 2-amino-1,3-propane-diol in the presence of NaOCH3 in ethanol; (29) 4-ethyl-4-methylol oxazolidinone is prepared by heating diethyl carbonate with 2-amino-2-ethyl-1,3-propane-diol in the presence of NaOCH3.  Reference has been directed by the Comptroller to Specification 838,759.