# US 5,349,088 A · Oximation process > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,349,088 A - Document ID: US5349088A - Status: Granted - Kind: A - Application number: 08/087,828 - Filed: 1993-07-07 - Granted: 1994-09-20 - Earliest claimed: 1993-07-07 - Assignees: Henkel Corporation - Inventors: Leroy O. Krbechek - Web page: https://patentgrep.com/patent/US5349088A ## CPC - C07C 249/08: by reaction of hydroxylamines with carbonyl compounds - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS ## Abstract An improved process for oximation of carbonyl compounds, such as ketones and aldehydes by oximation with hydroxylamine including oximation processes carried out in the presence of a catalytic amount of an alkyl phenol phase transfer catalyst, such as nonylphenol or dodecylphenol and the presence of an alkali metal or alkaline earth metal compound. The resulting oximes are useful as metal extractants. ## Claims ### Claim 1 In a method of preparing aromatic oximes by reaction of an aromatic ketone or aldehyde carbonyl compound with hydroxylamine the improvement which comprises conducting the reaction in the presence of a catalytic amount of an alkyl phenol, and an alkali metal or alkaline earth metal hydroxide, carbonate or bicarbonate, the alkyl phenol being present in an amount effective to act as a phase transfer catalyst. ### Claim 2 (depends on 1) A method as defined in claim 1 wherein the carbonyl compound is selected from the group consisting of heptylsalicylaldehyde, octylsalicylaldehyde nonylsalicylaldehyde and dodecylsalicylaldehyde. ### Claim 3 (depends on 1) A method as defined in claim 1 wherein said phenol phase transfer catalyst is an alkyl phenol in which the alkyl group has from about 6 to about 20 carbon atoms. ### Claim 4 (depends on 3) A method as defined in claim 3, wherein said alkyl phenol contains from about 8 to about 18 carbon atoms in the alkyl groups. ### Claim 5 (depends on 3) A method as defined in claim 3, wherein the alkyl phenol phase transfer catalyst is present in an amount of about 0.05 to about 0.3 moles of phenol per mole of carbonyl. ### Claim 6 (depends on 5) A method as defined in claim 5 wherein the alkyl phenol catalyst is present in an amount of about 0.15 to about 0.2 moles of phenol per mole of carbonyl. ### Claim 7 (depends on 1) A method as defined in claim 1, wherein said carbonate is sodium carbonate. ### Claim 8 (depends on 7) A method as defined in claim 7, wherein said carbonate is present in at least a stoichiometric amount to the hydroxylamine. ### Claim 9 (depends on 8) A method as defined in claim 8 wherein said carbonate is present in an amount of 1.1 equivalents of carbonate to 1 equivalent hydroxylamine. ### Claim 10 (depends on 1) A method as defined in claim 1, wherein said carbonyl compound is dodecylsalicylaldehyde and said alkyl phenol phase transfer catalyst is dodecylphenol. ### Claim 11 (depends on 1) A method as defined in claim 1, wherein said carbonyl compound is nonylsalicylaldehyde and said alkylphenol phase transfer catalyst is nonylphenol. ### Claim 12 (depends on 1) A method as defined in claim 1, wherein the water content is from about 0.1 to about 10 moles of water per mole of carbonyl. ### Claim 13 (depends on 12) A method as defined in claim 12, wherein said reaction is conducted in a non-alcoholic media containing water in an amount just sufficient to wet the surfaces of the hydroxylamine and carbonate reactants. ### Claim 14 (depends on 12) A method as defined in claim 12, wherein the media further comprises a hydrocarbon solvent. ### Claim 15 (depends on 14) A method as defined in claim 14, wherein said hydrocarbon solvent is toluene. ### Claim 16 (depends on 12) A method as defined in claim 12, wherein said carbonyl compound is selected from the group consisting of 2-hydroxy-5-octylacetophenone, 2-hydroxy-5-nonylacetophenone, 5-nonylsalicylaldehyde, 5-octylsalicylaldehyde and 5-dodecylsalicylaldehyde and 2-hydroxy-5-dodecylacetophenone. ### Claim 17 (depends on 8) A method as defined in claim 8, wherein the carbonyl compound is or 5-nonylsalicylaldehyde or 5-dodecylsalicylaldehyde, said alkyl phenol phase transfer catalyst is an alkyl phenol in which the alkyl group contains from about 8 to about 12 carbon atoms present in an amount of about 0.15 to about 0.2 moles of phenol per mole of carbonyl, the hydroxylamine is hydroxylammonium sulfate present in an amount of about 1.1 equivalents to 1 equivalent carbonyl, said carbonate is sodium carbonate present in an amount of about 1.1 equivalents carbonate to 1 equivalent of hydroxylamine and the reaction is conducted at a temperature of greater than about 35.degree. C. up to about 90.degree. C. ### Claim 18 A method of preparing a hydroxy oxime having the formula ##STR3## in which R and R.sub.a may be individually alike or different and are saturated aliphatic hydrocarbon different and are saturated aliphatic hydrocarbon groups of 1-25 carbon atoms or ethylenically unsaturated groups of 3-25 carbon atoms and Y is H or R.sub.b where R.sub.b is an aliphatic hydrocarbon group containing from 1 to about 10 carbon atoms; ##STR4## in which R.sub.a and Y are as defined with respect to Formula I, comprising (a) reacting a carbonyl compound corresponding to the hydroxy oxime defined above with hydroxylamine in the presence of (1) a catalytic amount of an alkyl phenol phase transfer catalyst and (2) an alkali metal or alkaline earth metal hydroxide, carbonate or bicarbonate whereby the carbonyl group of the carbonyl compound is converted to the oxime group; and (b) recovering the resulting oxime from the reaction mixture. ### Claim 19 (depends on 18) A method as defined in claim 18 wherein said phase transfer catalyst is an alkyl phenol containing from about 6 to about 20 carbon atoms in the alkyl group and the alkyl phenol is present in an amount of about 0.05 to about 0.5 moles of phenol per mole of carbonyl, the hydroxylamine reactant is hydroxylammonium sulfate present in an amount of about 1.1 equivalents per equivalent of carbonyl, said carbonate is sodium carbonate present in an amount cf about 1.1 equivalents carbonate to 1 equivalent of hydroxylamine, and the reaction is conducted at about 50.degree. to about 90.degree. C. in the presence of water in a sufficient amount to wet the surfaces of the hydroxylammonium sulfate and the carbonate. ### Claim 20 (depends on 19) A method as defined in claim 19, wherein the phase transfer catalyst is an alkyl phenol having from about 8 to about 12 carbon atoms in the alkyl group present in an amount of about 0.1 to about 0.2 moles of phenol per equivalent of carbonyl, and in which the alkyl group of the alkylphenol is the same as, or different from, R.sub.a and the reaction is conducted with agitation at a temperature of about 90.degree. C. in a non-alcoholic, hydrocarbon solvent reaction media for at least about 1 hour. ### Claim 21 (depends on 20) A method as defined in claim 20, wherein said hydrocarbon solvent is toluene.