# US 9,518,001 B1 · High purity 1,1-dicarbonyl substituted-1-alkenes and methods for their preparation > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,518,001 B1 - Document ID: US9518001B1 - Status: Granted - Kind: B1 - Application number: 15/159,185 - Filed: 2016-05-19 - Granted: 2016-12-13 - Earliest claimed: 2016-05-13 - Assignees: Sirrus, Inc. - Applicants: Sirrus, Inc. - Inventors: Jeffrey M. Sullivan; Kevin Powers; William Barrett - Web page: https://patentgrep.com/patent/US9518001B1 ## CPC - C07C 67/333: by isomerisation; by change of size of the carbon skeleton (introduction or elimination of carboxyl groups C07C67/313, C07C67/32) - C07C 51/377: by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups {(C07C51/36 - C07C51/373 take precedence)} - C07C 57/13: Dicarboxylic acids - C07C 67/343: by increase in the number of carbon atoms - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS ## Abstract A composition comprising about 97 mole percent or greater of one or more 1,1-dicarbonyl substituted-1-ethylenes and about 3 mole percent or less of one or more 1,1-dicarbonyl substituted-methanes. A process comprising: contacting in a fluid state one or more 1,1-dicarbonyl substituted-1,1 hydroxymethyl-methanes and greater than 200 ppm to about 1000 ppm of one or more strong acids based on the weight of the one or more 1,1-dicarbonyl substituted-1,1 hydroxymethyl-methanes with a zeolite catalyst at a temperature of about 180° C. to about 220° C. for a sufficient time to convert about 96 percent or greater of the one or more 1,1-dicarbonyl substituted-1,1 hydroxymethyl-methanes to one or more 1,1-dicarbonyl substituted-1-ethylenes. ## Claims ### Claim 1 A process comprising: contacting in a fluid state one or more 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl)-methanes and greater than 200 ppm to about 1000 ppm of one or more strong acids based on the weight of the one or more 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl)-methanes with a zeolite catalyst at a temperature of about 180° C. to about 220° C. for a sufficient time to convert about 96 percent or greater of the one or more 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl)-methanes to one or more 1,1-dicarbonyl substituted-1-ethylenes. ### Claim 2 (depends on 1) A process according to claim 1 wherein the one or more 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl)-methanes and the one or more strong acids are passed through a fixed bed of zeolite catalyst, a reaction effluent containing one or more 1,1-dicarbonyl substituted-1-ethylenes exits the fixed bed of zeolite catalyst and the one or more 1,1-dicarbonyl substituted-1-ethylenes are isolated from the reaction effluent. ### Claim 3 (depends on 1) A process according to claim 1 wherein the zeolite catalyst contains acid groups. ### Claim 4 (depends on 1) A process according to claim 1 wherein the strong acid is present in an amount of about 300 ppm to 900 ppm and about 98 percent or greater of the one or more 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl)-methanes are converted to one or more 1,1-dicarbonyl substituted-1-ethylenes. ### Claim 5 (depends on 1) A process according to claim 1 wherein the pKa of the strong acid is about 3 to about −12. ### Claim 6 (depends on 1) A process according to claim 1 wherein the strong acid is one or more mineral acids. ### Claim 7 (depends on 2) A process according to claim 2 wherein the one or more 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl)-methanes and the strong acids are contacted with the bed of the zeolite catalyst at a pressure of about 50 to about 200 mmHg. ### Claim 8 (depends on 1) A process according to claim 1 wherein the one or more 1,1-dicarbonyl substituted-1-ethylenes is isolated by separating the reaction effluent into three streams, a light stream comprising water, formaldehyde and one or more 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl)-methanes; a heavy stream containing oligomers and polymers and an intermediate stream containing one or more 1,1-dicarbonyl substituted-1-ethylenes and one or more 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl)-methanes; distilling the intermediate stream and isolating a product containing 1,1-dicarbonyl substituted-1-ethylenes. ### Claim 9 (depends on 1) A process according to claim 1 wherein the one or more 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl)-methanes are prepared by contacting one or more 1,1-dicarbonyl substituted-methanes with formaldehyde or a source of formaldehyde in the presence of a catalytic amount of one or more trialkylene amines under conditions to prepare a reaction mixture containing one or more 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl)-methanes and the trialkylene amines are removed from the reaction mixture by evaporation. ### Claim 10 (depends on 9) A process according to claim 9 wherein the concentration of the trialkylene amine in the one or more 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl)-methanes is less than 1 ppm after the trialkylene amines are removed by evaporation. ### Claim 11 (depends on 9) A process according to claim 9 wherein the one or more 1,1-dicarbonyl substituted-methanes is one or more malonates and the one or more 1,1-dicarbonyl substituted-1-ethylenes is one or more methylene malonates. ### Claim 12 (depends on 1) A process according to claim 1 wherein the product isolated comprises about 97 mole percent or greater of one or more 1,1-dicarbonyl substituted-1-ethylenes and about 3 percent mole percent or less of one or more 1,1-dicarbonyl substituted-methanes. ### Claim 13 (depends on 12) A process according to claim 12 wherein the product isolated comprises 99 percent by weight or greater of one or more 1,1-dicarbonyl substituted-1-ethylenes and 1 percent by weight or less of one or more 1,1-dicarbonyl substituted-methanes. ### Claim 14 (depends on 12) A process according to claim 12 wherein the isolated product contains 1 mole percent or less of an impurity containing a dioxane group, about 1 mole percent or less of any impurity having the alkene group replaced by an analogous hydroxyalkyl group wherein the mole percent is based on the total moles in the 1,1-disubstituted alkene compound.