Patent GB-812480-A (GB)
Title: Thio- and dithio-carbonic acid esters
Filed: 1956-12-06
Abstract: The invention comprises thio- and dithiocarbonic esters of the formula <FORM:0812480/IV (b)/1> where A represents the non-carboxylate portion of a dicarboxylic acid which may be aliphatic, having a chain of 2 or 3 carbon atoms between the carboxyl groups, which chain may be substituted by an alkyl group or by an hydroxyl group and a further carboxyl group, or interrupted by hetero atoms such as O, S or N; or aromatic, hydroaromatic or heterocyclic, which may be further substituted with halogen atoms or alkyl, alkoxy or nitro groups; X and Y are O or S, at least one being S, and R is an alkyl or aryl radical. They may be prepared by reacting cyclic oximides with mono- or dithiocarbonic acid ester halides, especially chlorides.  The oximides may be reacting as such in the presence of an acid-binding agent such as NaOH, Na2CO3, K2CO3, ammonia or a tertiary base, as a salt, especially the sodium salt, in aqueous solution or dissolved in an aqueous solution of a base.  Inert organic solvents may be present such as alcohols or ketones.  Room temperature or slightly above is usual, but temperatures from about 0-100 DEG  C. may be used. Specified oximides include those of the following acids: succinic, propane-1,3-dicarboxylic, thiodiglycollic, imino diacetic, citric, hexane - 1,2 - dicarboxylic, pentane - 1,2-dicarboxylic, phthalic, homophthalic, tetrahydrophthalic, naphthalic, pyridine - 2,3 - dicarboxylic and substituted phthalic acids such as chloro-, bromo- and nitrophthalic acids.  Thiocarbonic acid ester chlorides may be prepared by reacting thiophosgene with alcohols or phenols or phosgene with mercaptans or thiophenols for the monothio compounds, and with mercaptans or thiophenols for the dithio compounds.  Specified groups R include C1-6 alkyl, cycloalkyl, phenyl, chloro- and nitrophenyl, and naphthyl.  The products are fungicides.  In examples, esters are prepared by reacting thionocarbonic acid ethylester chloride with D 4 - tetrahydrophthaloxime, phthaloxime, D 4 - tetrahydroendomethylene - phthaloxime, naphthaloxime, hexahydrophthaloxime, D 2 - tetrahydrophthaloxime and homophthaloxime, by reacting thionocarbonic acid phenylester chloride with D 4-tetrahydro-endomethylene - phthaloxime and D 4 - tetrahydrophthaloxime, by reacting thionocarbonic acid methylester chloride with D 4-tetrahydrophthaloxime and by reacting thionocarbonic acid propylester chloride with D 4-tetrahydro-endomethylenephthaloxime; acid binding agents used are sodium hydroxide, sodium carbonate, pyridine and hexahydrodimethylaniline; solvents used are dioxan and acetone.ALSO:Fungicidal compositions comprise thio- and dithiocarbonic acid esters of formula <FORM:0812480/VI/1> where A represents the non-carboxylate portion of a dicarboxylic acid which may be aliphatic, having a chain of 2 to 3 carbon atoms between the carboxyl groups, which chain may be substituted by an alkyl group or by an hydroxyl group and a further carboxyl group, or interrupted by hereto atoms such as O, S or N; or aromatic, hydroaromatic or heterocyclic, which may be further substituted with halogen atoms or alkyl, alkoxy or nitro groups; X and Y represent O or S, at least one being S, and R is an alkyl or aryl radical.  Specified acids from which A may be derived are succinic, propane-1,3-dicarboxylic, thiodiglycollic, imino diacetic, citric, hexane-1,2-dicarboxylic, pentane-1,2-dicarboxylic, phthalic, homophthalic, tetrahydrophthalic, naphthalic, pyridine-2,3-dicarboxylic, chloro-, bromo- and nitrophthalic, D 4- and D 2-tetrahydrophthalic, D 4 - tetrahydroendomethylene - phthalic and hexahydrophthalic acids. Specified groups R include C1-6 alkyl, cycloalkyl, phenyl, chloro- and nitrophenyl, and naphthyl.  Other substances which may be present include water, lower aliphatic alcohols, hydrocarbons, chlorinated hydrocarbons, talc, chalk, bentonite, clay and emulsifiers. Generally 0.1 to 1 per cent by weight of active ingredient is used but up to 50 per cent may be used.