Process for preparing perhydrofluorene or alkyl-substituted perhydrofluorene

Patent metadata

Field	Value
Publication number	US-10233135-B2
Application number	US-201615536569-A
Country	US
Kind code	B2
Filing date	Jul 11, 2016
Priority date	Mar 22, 2016
Publication date	Mar 19, 2019
Grant date	Mar 19, 2019

Abstract

The present invention discloses a process for preparing perhydrofluorene or alkyl-substituted perhydrofluorene, comprising the steps of: (1) reacting a phenolic compound or an aromatic hydrocarbon compound or an aromatic ketone compound or an aromatic ether compound with a benzyl compound to carry out an alkylation reaction in the presence of a first catalyst, thereby to produce substituted or unsubstituted diphenyl methane, wherein the first catalyst is an acidic catalyst; and (2) reacting the substituted or unsubstituted diphenyl methane with hydrogen gas to carry out an hydrogenation reaction or a hydrodeoxygenation reaction, thereby to produce perhydrofluorene or alkyl-substituted perhydrofluorene, wherein the second catalyst is a physical mixture of a metal catalyst and an acidic catalyst or a metal catalyst loaded on an acidic catalyst.

First claim

The invention claimed is:

1. A process for preparing perhydrofluorene or alkyl-substituted perhydrofluorene, characterized in that the process comprises steps of:
(1) reacting a phenolic compound or an aromatic hydrocarbon compound or an aromatic ketone compound or an aromatic ether compound with a benzyl compound to carry out an alkylation reaction in the presence of a first catalyst, thereby to produce substituted or unsubstituted diphenyl methane, wherein the first catalyst is an acidic catalyst; and
(2) reacting the substituted or unsubstituted diphenyl methane with hydrogen gas in the presence of a second catalyst to carry out a hydrogenation reaction or a hydrodeoxygenation reaction, thereby to produce perhydrofluorene or alkyl-substituted perhydrofluorene, wherein the second catalyst is a physical mixture of a metal catalyst and an acidic catalyst or is a metal catalyst loaded on an acidic catalyst;
wherein the metal catalyst is one or more selected from the group consisting of Cu, W, Mo, Ni, Pd, Pt, Ru, Ir, Rh, Zn, PtNi, CoNi, CoMo, IrFe, PdPt, or RuCu, and the acidic catalyst is one or more selected from the group consisting of SiO 2 —Al 2 O 3 , HZSM-5, Al-MCM-41, Hβ, MMT-K10, SAPO-34, USY, H 3 O 40 PW 12 .xH 2 O, Amberlyst-15, Nafion, AlCl 3 , FeCl 3 , ZnCl 2 , CuCl 2 , metal-modified HPW, Nb 2 O 5 , WO 3 or liquid phosphoric acid;
wherein when the metal catalyst and the acidic catalyst are physically mixed, a mass ratio of the metal catalyst to the acidic catalyst is 0.02% or above; and when the metal catalyst is loaded on the acidic catalyst, the mass ratio of the metal catalyst to the acidic catalyst is from 0.02 to 10%.

2. The process for preparing perhydrofluorene or alkyl-substituted perhydrofluorene according to claim 1 , characterized in that the first catalyst is one or more selected from the group consisting of SiO 2 —Al 2 O 3 , HZSM-5, Al-MCM-41, Hβ, MMT-K10, SAPO-34, USY, H 3 O 40 PW 12 .xH 2 O, Amberlyst-15, Nafion, AlCl 3 , FeCl 3 , ZnCl 2 , CuCl 2 , metal-modified HPW, Nb 2 O 5 , WO 3 or liquid phosphoric acid, wherein the first catalyst is added in an amount of 0.5-26% by weight of the benzyl compound.

3. The process for preparing perhydrofluorene or alkyl-substituted perhydrofluorene according to claim 2 , characterized in that the metal modified HPW is Sn 0.5 TPA or HfTPA.

4. The process for preparing perhydrofluorene or alkyl-substituted perhydrofluorene according to claim 1 , characterized in that the phenolic compound is selected from the group consisting of phenol, guaiacol, 3-methylphenol, 2-methylphenol, 3-methoxyphenol, 4-ethylphenol, catechol, 4-vinylphenol, 3-methoxycatechol, 4-ethyl-2-methoxyphenol, 2-methoxy-4-vinylphenol, 2,6-dimethoxyphenol, 4-methyl-2,6-dimethoxy-phenol or 4-allyl-2,6-dimethoxyphenol; the aromatic hydrocarbon compound is selected from the group consisting of benzene, toluene, ethylbenzene, xylene, trimethylbenzene, 2-allylbenzene, 1-ethyl-2-methylbenzene, 1,2,4,5-tetramethylbenzene, naphthalene, and 1-methylnaphthalene; the aromatic ketone compound is selected from the group consisting of benzophenone, acetophenone, propiophenone or 3,4-dimethoxy-1-acetophenone; the aromatic ether compound is selected from the group consisting of anisole, 1-ethyl-4-methoxylbenzene; and the benzyl compound is selected from the group consisting of benzyl alcohol, 2-methylbenzyl alcohol, 4-methylbenzyl alcohol or dibenzyl ether.

5. The process for preparing perhydrofluorene or alkyl-substituted perhydrofluorene according to claim 1 , characterized in that the alkylation reaction is carried out under the following conditions: reaction temperature is from 50 to 200° C., reaction time is 0.5 to 24 h, and molar ratio of the phenolic compound or the aromatic hydrocarbon compound or the aromatic ketone compound or the aromatic ether compound to the benzyl compound is from 2:1 to 30:1; the hydrogenation reaction is carried out under the following conditions: mass ratio of the second catalyst to the substituted or unsubstituted diphenyl methane is from 0.01% to 23%, hydrogen gas pressure is from 3 to 8 MPa, reaction temperature is from 120° C. to 250° C., and reaction time is from 2 to 40 h.

6. The process for preparing perhydrofluorene or alkyl-substituted perhydrofluorene according to claim 1 , characterized in that a proportion of the metal catalyst in the second catalyst is increased so as to enhance a selectivity of the perhydrofluorene and/or the alkyl-substituted perhydrofluorene.

Assignees

• Univ Tianjin

Inventors

• Zou Jijun
• Pan Lun
• Zhang Xiangwen
• Wang Qingfa
• Wang Li

Classifications

• C07C45/61

  by reactions not involving the formation of >C = O groups · CPC title

• C07C2/865

  the non-hydrocarbon is an ether · CPC title

• C07C2/864 Primary

  the non-hydrocarbon is an alcohol · CPC title

• C07C13/567

  with a fluorene or hydrogenated fluorene ring system · CPC title

• C07C2603/10

  containing five-membered rings · CPC title