# US 4,391,759 A · Process for the preparation of organothioaldoxime compounds > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,391,759 A - Document ID: US4391759A - Status: Granted - Kind: A - Application number: 06/247,368 - Filed: 1981-03-25 - Granted: 1983-07-05 - Earliest claimed: 1981-03-25 - Assignees: Union Carbide Corporation - Inventors: John K. Chan - Web page: https://patentgrep.com/patent/US4391759A ## CPC - C07C 327/58: Derivatives of thiocarboxylic acids, the doubly-bound oxygen atoms being replaced by nitrogen atoms, e.g. imino-thio ethers - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS ## Abstract An improved process for preparing 1-organothioaldoxime compounds by reacting an aldoxime or .alpha.-hydroxyiminoketone with an alkaline hypohalite in an acidic medium and reacting the resulting 1-haloaldoxime with the alkali metal salt of a mercaptan, said acidic medium comprising an acid added in an amount of from about 0.5 to about 4.0 equivalents for each mole of alkaline hypohalite used. ## Claims ### Claim 1 A process for preparing an organothioaldoxime compound of the formula: ##STR3## by the steps of: (a) reacting an aldoxime of the formula: R.sub.1 CH.dbd.NOH or an .alpha.-hydroxyiminoketone of the formula: ##STR4## with an alkaline hypohalite in an acidic medium to form the corresponding 1-haloaldoxime, said acidic medium comprising an acid added in an amount of from about 0.5 to about 4.0 equivalents for each mole of alkaline hypohalite used; and (b) reacting said 1-haloaldoxime with an alkali metal mercaptide salt of the formula: R.sub.2 SM to form said organothioaldoxime compound, wherein the reactions of said steps (a) and (b) are conducted in an aqueous medium and wherein M denotes an alkali metal cation and R.sub.1, R.sub.2 and R.sub.3 are individually alkyl, alkoxyalkyl, cycloalkyl, phenyl or phenylalkyl, all of which may be either unsubstituted or substituted with one or more alkyl, halo, alkoxy, cyano, nitro or dialkylamino substituents. ### Claim 2 (depends on 1) The process of claim 1 wherein the reactions of steps (a) and (b) are carried out at a temperature or between about -20.degree. C. and about 40.degree. C. ### Claim 3 (depends on 1) The process of claim 1 wherein said acidic medium comprises an acid selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, benzenesulfonic acid, toluenesulfonic acid, acetic acid and propionic acid. ### Claim 4 (depends on 1) The process of claim 1 wherein the acidic medium comprises an acid added in an amount of from about 1 to about 2 equivalents for each mole of alkaline hypohalite used. ### Claim 5 (depends on 1) The process of claim 1 wherein the alkaline hypohalite is selected from the group consisting of sodium hypochlorite, calcium hypochlorite and potassium hypochlorite. ### Claim 6 (depends on 1) The process of claim 1 wherein the alkaline hypohalite is employed in an amount of from about 10 to about 25 percent molar excess based on the total weight of aldoxime or .alpha.-hydroxyiminoketone reactant. ### Claim 7 (depends on 1) The process of claim 1 wherein the alkaline hypohalite is employed in an amount of from about 15 to about 20 percent molar excess based on the total weight of aldoxime or .alpha.-hydroxyiminoketone reactant. ### Claim 8 (depends on 1) The process of claim 1 wherein the aqueous medium is water. ### Claim 9 (depends on 1) The process of claim 1 wherein the aldoxime is acetaldoxime. ### Claim 10 (depends on 1) The process of claim 1 wherein the .alpha.-hydroxyiminoketone is biacetyl monoxime. ### Claim 11 (depends on 1) The process of claim 1 wherein the aldoxime or .alpha.-hydroxyiminoketone is employed in an amount of from about 5 to about 75 weight percent based on the total weight of the aqueous medium. ### Claim 12 (depends on 1) The process of claim 1 wherein the aldoxime or .alpha.-hydroxyiminoketone is employed in an amount of from about 10 to about 25 weight percent based on the total weight of the aqueous medium. ### Claim 13 (depends on 1) The process of claim 1 wherein the 1-haloaldoxime is acetylhydroxamoyl chloride. ### Claim 14 (depends on 1) The process of claim 1 wherein the alkali metal mercaptide salt is sodium methyl mercaptide. ### Claim 15 (depends on 1) The process of claim 1 wherein the alkali metal mercaptide salt is employed in an amount of from about stoichiometric to about 50 percent molar excess based on the total weight of 1-haloaldoxime. ### Claim 16 (depends on 1) The process of claim 1 wherein the alkali metal mercaptide salt is employed in an amount of from about 5 to about 25 percent molar excess based on the total weight of 1-haloaldoxime. ### Claim 17 (depends on 1) The process of claim 1 wherein the organothioaldoxime is S-methyl-N-hydroxythioacetimidate. ### Claim 18 (depends on 1) The process of claim 1 wherein R.sub.1, R.sub.2 and R.sub.3 are individually cyanoalkyl or nitroalkyl having from one to eight carbon atoms. ### Claim 19 (depends on 1) The process of claim 1 wherein R.sub.1, R.sub.2 and R.sub.3 are individually methyl, ethyl or propyl. ### Claim 20 (depends on 1) The process of claim 1 wherein R.sub.1, R.sub.2 and R.sub.3 are methyl. ### Claim 21 (depends on 1) The process of claim 1 wherein the reactions of steps (a) and (b) are carried out at a temperature of between about -10.degree. C. and about 15.degree. C. ### Claim 22 (depends on 1) The process of claim 1 wherein the reaction time of step (a) is 6 hours.