Patent GB-906183-A (GB)
Title: New esters of n-substituted carbamic acids
IPC: C07C271/06
Filed: 1959-12-04
Abstract: Esters of mono-N-substituted carbamic acids of the general formula <FORM:0906183/IV (b)/1> wherein R stands for a phenylene group substituted with one or more lower alkyl, hydroxy, or acylamino groups or halogen atoms, or R is a naphthylene or quinonylene group, R1 and R2 are lower alkyl groups, R3 is a lower alkyl or an unsubstituted or chloro- or alkoxy-substituted phenyl group, or a lower alkylene or phenylene group substituted by another <FORM:0906183/IV (b)/2> and n is 1, 2 or 3, at least one dialkylaminomethyl group being in the ortho- or paraposition to the carbamate group, are prepared by reacting a Mannich-type dialkylaminomethyl phenol, naphthol or hydroxyquinoline with (i) an isocyanate or di-isocyanate, (ii) N-substituted carbamyl chloride, or (iii) phosgene followed by a primary amine.  In Example 1, an acetone solution of 2,4,6 - tri(dimethylaminomethyl) phenol is reacted at room temperature with phenyl isocyanate whereby the 2,4,6-tri(dimethylaminomethyl)phenyl ester of N-phenyl carbamic acid is obtained.  Example 4 refers to the reaction of 3,5-dimethyl-6-(dimethylaminomethyl)-phenol with 3,4-dichlorophenyl isocyanate to give the compound <FORM:0906183/IV (b)/3> Example 7 describes the reaction of 4-acetylamino - 6 - (dimethylaminomethyl)phenol with 3,4-dichlorophenyl isocyanate. Example 8 refers to reaction of 4-chloro-6-(dimethylaminomethyl)-phenol with ethyl isocyanate to give the compound <FORM:0906183/IV (b)/4> Example 10 describes the reaction of 1-(dimethylaminomethyl) - 2 - naphthol with ethyl isocyanate to give the compound <FORM:0906183/IV (b)/5> Example 11 describes the reaction of 2,5-bis-(dimethylaminomethyl)-hydroquinone with 1 molecular equivalent of phenyl isocyanate to give the compound <FORM:0906183/IV (b)/6> or with 2 molecular equivalents of phenyl isocyanate to give the compound <FORM:0906183/IV (b)/7> Example 13 describes the reaction of 7-dimethylaminomethyl-8-hydroxy-quinoline with phenyl isocyanate to give <FORM:0906183/IV (b)/8> In Example 15 a solution of 1-(dimethylaminomethyl)-2-naphthol in acetic acid is reacted with phenyl isocyanate to yield the acetate of the carbamic ester.  These carbamic esters and their salts have use as herbicides (see Group VI).ALSO:Herbicidal or fungicidal compositions comprise a carbamic ester of the general formula <FORM:0906183/VI/1> wherein R stands for a phenylene group substituted with one or more lower alkyl, hydroxy, or acylamino groups or halogen atoms, or R is a naphthylene or quinonylene group, R1 and R2 are lower alkyl groups, R3 is a lower alkyl or an unsubstituted or chloro- or alkoxy-substituted phenyl group, or a lower alkylene or phenylene group substituted by another <FORM:0906183/VI/2> group, and n is 1, 2 or 3, at least one dialkylaminomethyl group being in the ortho- or paraposition to the carbamate group, admixed with an inert solid extender or a liquid diluent. Suitable solid extenders are: talc, chalk, bentonite, clay, fuller's earth and silica.  Liquid formulations are mainly of an aqueous nature; but auxiliary solvents, such as dimethyl formamide or acetone, may be used, if necessary. Emulsifiers, such as nonyl phenyl polyglycol ether, may be added. There are three Examples (Nos. 18, 19 and 20) relating to the use of aqueous emulsions containing 0.05% or 0.1% of the 2,4,6-tri-(dimethylaminomethyl)-phenyl ester of phenyl carbamic acid as a herbicidal spray.  For the preparation of the carbamic esters-see Group IV(b).