Process for preparing an arylpropene

Patent metadata

Field	Value
Publication number	US-10308580-B2
Application number	US-201615744474-A
Country	US
Kind code	B2
Filing date	Jul 15, 2016
Priority date	Jul 15, 2015
Publication date	Jun 4, 2019
Grant date	Jun 4, 2019

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.

First claim

The invention claimed is:

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;
R 1 is, independently from each other, hydroxy, C 1 -C 6 alkoxy, di(C 1 -C 6 -alkyl) aminyl;
wherein the catalyst has a pore volume of at least 0.5 cm 3 /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 NH 3 -TPD.

2. The process of claim 1 , wherein the catalyst has a pore volume in the range of from 0.5 to 2.0 cm 3 /g.

3. The process of claim 1 , wherein the catalyst has a pore volume in the range of from 0.7 to 1.1 cm 3 /g.

4. 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).

5. 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).

6. The process of claim 1 , wherein at least 75 weight-% of the catalyst consist of silica.

7. The process of claim 1 , wherein at least 99 weight-% of the catalyst consist of silica.

8. 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 cm 3 /g and an acidity characterized by an amount of adsorbed ammonia in the range of from 0.02 to 0.05 mmol/g(catalyst).

9. 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.

10. The process of claim 1 wherein C 1 -C 6 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(C 1 -C 6 -alkyl) aminyl, the C 1 -C 6 -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.

11. 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

12. 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.

13. 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.

14. 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.

15. 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.

16. 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.

17. 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.

18. 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.

19. 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.

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;
R 1 is, independently from each other, hydroxy, C 1 -C 6 alkoxy, di(C 1 -C 6 -alkyl) aminyl, which comprises utilizing a solid porous catalyst comprising silica, wherein the catalyst has a pore volume of at least 0.5 cm 3 /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 NH 3 -TPD.

21. 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.

Assignees

• Basf Se

Inventors

• Rüdenauer Stefan
• Lanver Andreas
• Pelzer Ralf
• Ebel Klaus
• Fenlon Thomas
• Parvulescu Andrei-Nicolae
• Chaturvedula Sumana

Classifications

• C07C41/18 Primary

  by reactions not forming ether-oxygen bonds · CPC title

• C07C43/215

  having unsaturation outside the six-membered aromatic rings · CPC title