# US 9,434,671 B2 · Nitrogen monoxide as cis/trans isomerization catalysts for unsaturated compounds > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,434,671 B2 - Document ID: US9434671B2 - Status: Granted - Kind: B2 - Application number: 14/652,286 - Filed: 2013-12-18 - Published: 2015-11-12 - Granted: 2016-09-06 - Earliest claimed: 2012-12-18 - Assignees: Dsm IP Assets B.V. - Applicants: Dsm IP Assets B.V. - Inventors: René Tobias Stemmler; Nadine Greiner; Angela Wildermann - Web page: https://patentgrep.com/patent/US9434671B2 ## CPC - C07C 43/313: containing halogen - C07C 29/56: by isomerisation - C07C 33/02: Acyclic alcohols with carbon-to-carbon double bonds - C07C 45/67: by isomerisation; by change of size of the carbon skeleton - C07C 49/203: with only carbon-to-carbon double bonds as unsaturation - C07B 2200/09: Geometrical isomers - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - C07B: GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR (preparation of carboxylic acid esters by telomerisation C07C67/47; telomerisation C08F) ## Abstract The present invention relates to a process of a cis/trans isomerization of an unsaturated compound A being selected from the group consisting of unsaturated ketones, unsaturated ketals, unsaturated aldehydes, unsaturated acetals, unsaturated carboxylic acids, esters of an unsaturated carboxylic acid and amides of an unsaturated carboxylic acid using nitrogen monoxide as cis/trans isomerization catalyst. It has been observed that the isomerization is very efficient and fast. ## Claims ### Claim 1 A process of a cis/trans isomerization of an unsaturated compound A having at least one but not more than two conjugated carbon-carbon double bonds, the compound A being selected from the group consisting of unsaturated ketones, unsaturated ketals, unsaturated aldehydes, unsaturated acetals, unsaturated carboxylic acids, esters of an unsaturated carboxylic acid, amides of an unsaturated carboxylic acid and unsaturated alcohols, wherein the process comprises the steps of: a) providing a cis or a trans isomer of the unsaturated compound A; b) adding nitrogen monoxide to the cis or trans isomer of the unsaturated compound A of step a) to form a mixture thereof; c) heating the mixture of nitrogen monoxide and cis or trans isomer of the unsaturated compound A to a temperature of between 10° C. and the boiling point of the unsaturated compound A, thereby leading to a mixture of cis/trans isomers of the unsaturated compound A. ### Claim 2 (depends on 1) The process according to claim 1, wherein the unsaturated compound A is an unsaturated ketone, an unsaturated ketal, an unsaturated aldehyde, an unsaturated acetal or an unsaturated alcohol. ### Claim 3 (depends on 1) The process according to claim 1, wherein step b) comprises including nitrogen monoxide to the cis or trans isomer of the unsaturated compound A at atmospheric pressure or up to 1 MPa over-pressure. ### Claim 4 (depends on 3) The process according to claim 3, wherein the over-pressure is from 10 to 300 kPa. ### Claim 5 (depends on 1) The process according to claim 1, wherein step b) comprises adding nitrogen monoxide as a gas mixture with at least one other gas. ### Claim 6 (depends on 5) The process according to claim 5, wherein the amount of nitrogen monoxide in the gas mixture is in the range of 10-60% by weight. ### Claim 7 (depends on 1) The process according to claim 1, wherein the unsaturated compound A is of formula (I), (II), (IID) or (IIE): wherein Q stands for H or CH3 and m and p stand independently from each other for a value of 0 to 3 with the proviso that the sum of m and p is 0 to 3; and wherein a wavy line represents a carbon-carbon bond which is linked to the adjacent carbon-carbon double bond so as to have said carbon-carbon double either in the Z or in the E-configuration, and wherein the substructures in formula (I), (II), (IID) and (IIE) represented by s1 and s2 can be in any sequence; and wherein the double bond having dotted lines () in formula (I), (II), (IID) and (IIE) represent either a single carbon-carbon bond or a double carbon-carbon bond; and wherein the symbol represents a stereogenic centre. ### Claim 8 A process of producing a respective specific cis or trans isomer of an unsaturated compound A having at least one but not more than two conjugated carbon-carbon double bonds, the compound A being selected from the group consisting of unsaturated ketones, unsaturated ketals, unsaturated aldehydes, unsaturated acetals, unsaturated carboxylic acids, esters of an unsaturated carboxylic acid, amides of an unsaturated carboxylic acid and unsaturated alcohols from a mixture of cis and trans isomers thereof, wherein the process comprises the steps of: i) providing a mixture of cis isomers in an amount of weight wcis and trans isomers in an amount of weight wtrans of the unsaturated compound A; ii) adding nitrogen monoxide to the mixture of cis and trans isomers provided by step i); iii) heating the mixture of the nitrogen monoxide and cis and trans isomers obtained from step ii) to a temperature Tiso1, which is the boiling point of the isomer Ilbp having a lowest boiling point of the mixture of the cis/trans isomers of step i); iv) distilling off the isomer Ilbp and collecting the isomer Ilbp; v) conducting cis/trans isomerization of the isomer Ilbp having a higher boiling point than the isomer Ilbp in the presence of nitrogen monoxide being added in step ii); wherein step ii) can take place before, during or after steps iii) and/or iv); and wherein after the step v), the steps ii) and iii) and iv) and v) are repeated subsequently; and wherein a sum of the weight of all the collected isomer Ilbp is either (1) more than the weight wcis in the case the collected isomer Ilbp is a cis isomer of said unsaturated compound A or (2) more than the weight wtrans in the case the collected isomer Ilbp is a trans isomer of the unsaturated compound A; and wherein the weight wcis and the weight wtrans are each 0 grams to 10 tons, with the proviso that the ratio of wcis and wtrans is larger than 70/30 or smaller than 30/70 with the proviso that wcis and wtrans are not both 0 grams. ### Claim 9 (depends on 8) The process of claim 8, wherein the weight of the collected isomer Ilbp is more than 80% by weight of the sum of the weight wtrans and the weight wcis. ### Claim 10 A process of producing a respective specific cis or trans isomer of an unsaturated compound A having at least one but not more than two conjugated carbon-carbon double bonds, the compound A being selected from the group consisting of unsaturated ketones, unsaturated ketals, unsaturated aldehydes, unsaturated acetals, unsaturated carboxylic acids, esters of an unsaturated carboxylic acid, amides of an unsaturated carboxylic acid and unsaturated alcohols from a mixture of cis and trans isomers thereof, wherein the process comprises the steps of: a) providing a mixture of cis isomers in an amount of weight wcis and trans isomers in an amount of weight wtrans of the unsaturated compound A; b) adding nitrogen monoxide to the mixture of cis and trans isomers provided by step i); c) heating the mixture of the nitrogen monoxide and cis and trans isomers obtained from step ii) to a temperature Tiso1, which is the boiling point of the isomer Ilbp having a lowest boiling point of the mixture of the cis/trans isomers of step a); d) distilling off the isomer Ilbp; e) isolating the specific isomer Ihbp which has a higher boiling point than the isomer Ilbp from a remainder of step d) and collecting the isomer Ihbp; f) conducting cis/trans isomerization of the isomer Ihbp and a remainder of step e), if any, in the presence of nitrogen monoxide being added in step b); wherein step b) can take place before, during or after steps c) and/or f); and wherein after the step f), the steps b) and c) and d) and e) and f) are repeated subsequently, and wherein the weight of the collected isomer Ihbp is either (1) more than the weight wcis in the case the collected isomer Ihbp is a cis isomer of the unsaturated compound A or (2) more than the weight wtrans in the case the collected isomer Ihbp is a trans isomer of said unsaturated compound A; and wherein the weight wcis and the weight wtrans are each 0 grams to 10 tons, with the proviso that the ratio of wcis and wtrans is larger than 70/30 or smaller than 30/70 with the proviso that wcis and wtrans are not both 0 grams. ### Claim 11 (depends on 8) The process according to claim 8, wherein step b) comprises introducing nitrogen monoxide to the mixture of cis and trans isomers of the unsaturated compound A at atmospheric pressure or up to 1 MPa over-pressure. ### Claim 12 (depends on 5) The process according to claim 5, wherein the at least one other gas is an inert gas. ### Claim 13 (depends on 12) The process according to claim 12, wherein the inert gas is nitrogen. ### Claim 14 (depends on 9) The process of claim 9, wherein the weight of the collected isomer Ilbp is more than 90% by weight of the sum of the weight wtrans and the weight wcis. ### Claim 15 A composition comprising: (a) nitrogen monoxide; and (b) an unsaturated compound A of the formula (I), (II), (IID) or (IIE): wherein Q stands for H or CH3 and m and p stand independently from each other for a value of 0 to 3 with the proviso that the sum of m and p is 0 to 3; and wherein a wavy line represents a carbon-carbon bond which is linked to the adjacent carbon-carbon double bond so as to have said carbon-carbon double either in the Z or in the E-configuration, and wherein the substructures in formula (I), (II), (IID) and (IIE) represented by s1 and s2 can be in any sequence; and wherein the double bond having dotted lines ()in formula (I), (II), (IID) and (IIE) represent either a single carbon-carbon bond or a double carbon-carbon bond; and wherein the symbol represents a stereogenic centre. ### Claim 16 A ketal or acetal which is selected from the group consisting of 2-(4,8-dimethylnona-3,7-dien-1-yl)-2,5,5-trimethyl-1,3-dioxane, 2,6-dimethyl-10,10-bis(2,2,2-trifluoroethoxy)undeca-2,6-diene, 2-(4,8-dimethylnon-3-en-1-yl)-2,5,5-trimethyl-1,3-dioxane, 6,10-dimethyl-2,2-bis(2,2,2-trifluoro-ethoxy)undec-5-ene, 2,5,5-trimethyl-2-(4,8,12-trimethyltridec-3-en-1-yl)-1,3-dioxane, (R)-2,5,5-trimethyl-2-(4,8,12-trimethyltridec-3-en-1-yl)-1,3-dioxane, 6,10,14-trimethyl-2,2-bis(2,2,2-trifluoroethoxy)pentadec-5-ene, (R)-6,10,14-trimethyl-2,2-bis(2,2,2-trifluoroethoxy) pentadec-5-ene, 2,5,5-trimethyl-2-(4,8,12trimethyltrideca-3,7,11-trien-1-yl)-1,3-dioxane, 2,6,10-trimethyl-14,14-bis(2,2,2-trifluoroethoxy)pentadeca-2,6,10-triene, 2,5,5-trimethyl-2-(4,8,12-tri-methyltrideca-3,7-dien-1-yl)-1,3-dioxane, 6,10,14-trimethyl-2,2-bis(2,2,2-trifluoroethoxy) pentadeca-5,9-diene, 2-(2,6-dimethylhept-1-en-1-yl)-5,5-dimethyl-1,3-dioxane, 3,7-dimethyl-1,1-bis(2,2,2-trifluoroethoxy)oct-2-ene, 3,7-dimethyl-1,1-bis(2,2,2-trifluoroethoxy)octa-2,6-diene, 2,6-dimethyl-8,8-bis(2,2,2-tri-fluoro-ethoxy)-oct-2-ene, (R)-2,6-dimethyl-8,8-bis(2,2,2-trifluoroethoxy)oct-2-ene, 2-(4,8-di-methylnona-1,3,7-trien-1-yl)-2,5,5-trimethyl-1,3-dioxane, 2,6-dimethyl-10,10-bis(2,2,2-trifluoroethoxy)undeca-2,6,8-triene, 2,5-dimethyl-2-(4,8,12-trimethyltridec-3-en-1-yl)-1,3-dioxane, (R)-2,5-dimethyl-2-(4,8,12-tri-methyltridec-3-en-1-yl)-1,3-dioxane, 6,10,14-trimethyl-2,2-bis(2,2,2-trifluoro-ethoxy)pentadec-5-ene and (R)-6,10,14-trimethyl-2,2-bis(2,2,2-trifluoro-ethoxy)pentadec-5-ene and all possible E/Z-isomers thereof. ### Claim 17 A method for the cis/trans isomerization of an compound A having at least one but not more than two conjugated carbon-carbon double bonds, the compound A being selected from the group consisting of unsaturated ketones, unsaturated ketals, unsaturated aldehydes, unsaturated acetals, unsaturated carboxylic acids, esters of an unsaturated carboxylic acid and amides of an unsaturated carboxylic acid, wherein the method comprises subjecting the unsaturated compound A to cis/trans isomerization conditions in the presence of nitrogen monoxide as a catalyst.