# US 11,111,197 B2 · Process for the preparation of alpha, beta unsaturated aldehydes by oxidation of alcohols in the presence of a liquid phase > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,111,197 B2 - Document ID: US11111197B2 - Status: Granted - Kind: B2 - Application number: 16/956,972 - Filed: 2018-12-05 - Published: 2020-12-17 - Granted: 2021-09-07 - Earliest claimed: 2017-12-21 - Assignees: BASF SE - Applicants: BASF SE - Inventors: Michaela Fenyn; Joseph John Zakzeski; Nicolas Vautravers; Joaquim Henrique Teles - Web page: https://patentgrep.com/patent/US11111197B2 ## CPC - C07C 45/38: being a primary hydroxyl group - B01J 23/42: Platinum - B01J 23/44: Palladium - B01J 23/52: Gold - C07C 47/21: with only carbon-to-carbon double bonds as unsaturation - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS ## Abstract Process for the preparation of alpha, beta unsaturated aldehydes by oxidation of alcohols in the presence of a liquid phase. ## Claims ### Claim 1 A process for the preparation of alpha, beta unsaturated aldehydes of general formula (I) wherein R1, R2 and R3, independently of one another, are selected from hydrogen; C1-C6-alkyl, which optionally carry 1, 2, 3, or 4 identical or different substituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (C1-C6-alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; and C2-C6-alkenyl, which optionally carry 1, 2, 3, or 4 identical or different substituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (C1-C6-alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; by oxidation of alcohols of general formula (II) wherein R1, R2 and R3 have the meaning as given above in the presence of a catalyst and in the presence of a liquid phase, wherein the liquid phase contains at least 25 weight-% water based on the total weight of the liquid phase, determined at a temperature of 20° C. and a pressure of 1 bar and wherein the oxidant is oxygen, and wherein the catalyst comprises a catalytically active metal on a support and the catalytically active metal is located mainly in the outer shell of the catalyst, wherein the outer shell of the catalyst is the space from the outer surface of the catalyst to a depth of X from the outer surface of the catalyst, wherein X is 15 % of the distance from the outer surface of the catalyst to the center of the catalyst. ### Claim 2 A process for the preparation of alpha, beta unsaturated aldehydes of general formula (I) wherein R1, R2 and R3, independently of one another, are selected from hydrogen; C1-C6-alkyl, which optionally carry 1, 2, 3, or 4 identical or different substituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (C1-C6-alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; and C2-C6-alkenyl, which optionally carry 1, 2, 3, or 4 identical or different substituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (C1-C6-alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; by oxidation of alcohols of general formula (II) wherein R1, R2 and R3 have the meaning as given above in the presence of a catalyst and in the presence of a liquid phase, wherein the liquid phase contains at least 25 weight-% water based on the total weight of the liquid phase, determined at a temperature of 20° C. and a pressure of 1 bar and wherein the oxidant is oxygen, and wherein a catalyst is used which is obtainable by a) providing a support b) providing a metal compound c) depositing the metal compound on the support d) optionally calcinating the so obtained catalyst precursor e) reducing the catalyst precursor, by treatment of the catalyst precursor with a solution of a reducing agent f) optionally recovering the catalyst. ### Claim 3 (depends on 1) The process according to claim 1, wherein an alcohol according to formula (II) is used, wherein R1, R2 or R3, independently of one another, are selected from H and CH3. ### Claim 4 (depends on 1) The process according to claim 1, wherein an alcohol according to formula (II) is used, wherein R3 is H and R2 and R1 are CH3. ### Claim 5 (depends on 1) The process according to claim 1, wherein the liquid phase contains at least 50 weight-%, water based on the total weight of the liquid phase. ### Claim 6 (depends on 1) The process according to claim 1, wherein the oxidation is carried out at a temperature of 20° C. to 100° C. ### Claim 7 (depends on 1) The process according to claim 1, wherein the oxidation is carried out under a partial pressure of oxygen between 0.2 and 8 bar. ### Claim 8 (depends on 1) The process according to claim 1, wherein the catalytically active metal is selected from elements selected from the group consisting of platinum, palladium and gold. ### Claim 9 (depends on 1) The process according to claim 1, wherein the support is selected from the group consisting of carbonaceous materials and oxidic materials. ### Claim 10 (depends on 1) The process according to claim 1, wherein the support is selected from the group consisting of alpha aluminium oxide (α-Al2O3), beta aluminium oxide (ß-Al2O3) and gamma aluminium oxide (γ-Al2O3). ### Claim 11 (depends on 2) The process according to claim 2, wherein an alcohol according to formula (II) is used, wherein R1, R2 or R3, independently of one another, are selected from H and CH3. ### Claim 12 (depends on 2) The process according to claim 2, wherein an alcohol according to formula (II) is used, wherein R3 is H and R2 and R1 are CH3. ### Claim 13 (depends on 2) The process according to claim 2, wherein the liquid phase contains at least 50 weight-% water based on the total weight of the liquid phase. ### Claim 14 (depends on 2) The process according to claim 2, wherein the oxidation is carried out at a temperature of 20° C. to 100° C. ### Claim 15 (depends on 2) The process according to claim 2, wherein the oxidation is carried out under a partial pressure of oxygen between 0.2 and 8 bar. ### Claim 16 (depends on 2) The process according to claim 2, wherein the catalytically active metal is selected from elements selected from the group consisting of platinum, palladium and gold. ### Claim 17 (depends on 2) The process according to claim 2, wherein the support is selected from the group consisting of carbonaceous materials and oxidic materials. ### Claim 18 (depends on 2) The process according to claim 2, wherein the support is selected from the group consisting of alpha aluminium oxide (α-Al2O3), beta aluminium oxide (ß-Al2O3) and gamma aluminium oxide (γ-Al2O3). ### Claim 19 (depends on 1) The process according to claim 1, wherein the liquid phase contains at least 70 weight-% water based on the total weight of the liquid phase and the oxidation is carried out at a temperature of 20° C. to 70° C. ### Claim 20 (depends on 2) The process according to claim 2, wherein the liquid phase contains at least 70 weight-% water based on the total weight of the liquid phase and the oxidation is carried out at a temperature of 20° C. to 70° C. ### Claim 21 (depends on 1) The process according to claim 1, wherein the outer shell of the catalyst is the space from the outer surface of the catalyst to a depth of X from the outer surface of the catalyst, wherein X is 30 % of the distance from the outer surface of the catalyst to the center of the catalyst. ### Claim 22 (depends on 2) The process according to claim 2, wherein the liquid phase contains at least 95 weight-% water based on the total weight of the liquid phase. ### Claim 23 (depends on 2) The process according to claim 2, wherein the catalyst comprises Pt and Bi.