# US 10,308,580 B2 · Process for preparing an arylpropene > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,308,580 B2 - Document ID: US10308580B2 - Status: Granted - Kind: B2 - Application number: 15/744,474 - Filed: 2016-07-15 - Published: 2018-07-26 - Granted: 2019-06-04 - Earliest claimed: 2015-07-15 - Assignees: BASF SE - Applicants: BASF SE - Inventors: Stefan Rüdenauer; Andreas Lanver; Ralf Pelzer; Klaus Ebel; Thomas Fenlon; Andrei-Nicolae Parvulescu; Sumana Chaturvedula - Web page: https://patentgrep.com/patent/US10308580B2 ## CPC - C07C 41/18: by reactions not forming ether-oxygen bonds - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS ## Abstract A process for preparing an arylpropene from a diarylpropane by gas phase thermolysis in the presence of solid porous catalyst comprising silica having large pore volume and low acidity. ## Claims ### Claim 1 A process for preparing a compound of formula (I) comprising contacting a compound of formula (II) in the gas phase with a solid porous catalyst comprising silica, wherein k is, independently from each other, 0, 1, 2 or 3; R1 is, independently from each other, hydroxy, C1-C6 alkoxy, di(C1-C6-alkyl) aminyl; wherein the catalyst has a pore volume of at least 0.5 cm3/g as determined by Hg porosimetry according to DIN 66133, and an acidity characterized by an amount of adsorbed ammonia of at most 0.1 mmol/g(catalyst) as determined by NH3-TPD. ### Claim 2 (depends on 1) The process of claim 1, wherein the catalyst has a pore volume in the range of from 0.5 to 2.0 cm3/g. ### Claim 3 (depends on 1) The process of claim 1, wherein the catalyst has a pore volume in the range of from 0.7 to 1.1 cm3/g. ### Claim 4 (depends on 1) The process of claim 1, wherein the catalyst has an acidity characterized by an amount of adsorbed ammonia in the range of from 0.01 to 0.09 mmol/g(catalyst). ### Claim 5 (depends on 1) The process of claim 1, wherein the catalyst has an acidity characterized by an amount of adsorbed ammonia in the range of from 0.01 to 0.06 mmol/g(catalyst). ### Claim 6 (depends on 1) The process of claim 1, wherein at least 75 weight-% of the catalyst consist of silica. ### Claim 7 (depends on 1) The process of claim 1, wherein at least 99 weight-% of the catalyst consist of silica. ### Claim 8 (depends on 1) The process of claim 1, wherein at least 99.5 weight-% of the catalyst consist of silica and wherein the catalyst has a pore volume in the range of from 0.8 to 1.0 cm3/g and an acidity characterized by an amount of adsorbed ammonia in the range of from 0.02 to 0.05 mmol/g(catalyst). ### Claim 9 (depends on 1) The process of claim 1, wherein the catalyst is in the form of moldings, having an essentially circular cross section, wherein the cross section has a diameter in the range of from 1 to 5 mm. ### Claim 10 (depends on 1) The process of claim 1 wherein C1-C6 alkoxy is selected from the group consisting of methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, n-hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy and 1-ethyl-2-methylpropoxy, and wherein in di(C1-C6-alkyl) aminyl, the C1-C6-alkyl is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl and 1-ethyl-2-methylpropyl. ### Claim 11 (depends on 1) The process of claim 1, wherein the compound of formula (I) is a compound of formula and the compound of formula (II) is a compound of formula wherein the compound of formula (I) is a compound of formula and the compound of formula (II) is a compound of formula ### Claim 12 (depends on 1) The process of claim 1, wherein contacting the compound of formula (II) with the solid porous catalyst comprising silica is carried out under thermolytic conditions at a temperature of the gas phase in the range of from 250 to 650° C., and at an absolute pressure of the gas phase in the range of from 0.1 to 2.0 bar. ### Claim 13 (depends on 1) The process of claim 1, wherein contacting the compound of formula (II) with the solid porous catalyst comprising silica is carried out under thermolytic conditions at a temperature of the gas phase in the range of from 300 to 400° C., and at an absolute pressure of the gas phase in the range of from 0.8 to 1.1 bar. ### Claim 14 (depends on 1) The process of claim 1, wherein contacting the compound of formula (II) with the solid porous catalyst comprising silica is carried out in the presence of water, and wherein the gas phase further comprises nitrogen. ### Claim 15 (depends on 1) The process of claim 1, wherein contacting the compound of formula (II) with the solid porous catalyst comprising silica is carried out in continuous mode. ### Claim 16 (depends on 1) The process claim 1, wherein contacting the compound of formula (II) with the solid porous catalyst comprising silica is carried out at a catalyst load in the range of from 0.01 to 5 kg(compound of formula (II))/kg(catalyst)/h. ### Claim 17 (depends on 1) The process claim 1, wherein contacting the compound of formula (II) with the solid porous catalyst comprising silica is carried out at a catalyst load in the range of from 0.1 to 0.5 kg(compound of formula (II))/kg(catalyst)/h. ### Claim 18 (depends on 1) The process of claim 1, further comprising cooling the reaction mixture, obtained from contacting the compound of formula (II) in the gas phase with the solid catalyst, to a temperature in the range of from 0 to 40° C. ### Claim 19 (depends on 1) The process of claim 1, wherein the compound of formula (I) comprises a compound of formula (I-a) and a compound of formula (I-b) said process further comprising separating the compound of formula (I-a) from the compound of formula (I-b), by distillation. ### Claim 20 A process for increasing the selectivity of solid catalyst gas-phase thermolysis of a compound of formula (II) with respect to the compound of formula (I-a) wherein k is, independently from each other, 0, 1, 2 or 3; R1 is, independently from each other, hydroxy, C1-C6 alkoxy, di(C1-C6-alkyl) aminyl, which comprises utilizing a solid porous catalyst comprising silica, wherein the catalyst has a pore volume of at least 0.5 cm3/g as determined by Hg porosimetry according to DIN 66133, and an acidity characterized by an amount of adsorbed ammonia of at most 0.1 mmol/g(catalyst) as determined by NH3-TPD. ### Claim 21 (depends on 1) The process of claim 1, wherein the catalyst is in the form of strands having an essentially circular cross section, wherein the cross section has a diameter in the range of from 1 to 5 mm.