Methods for selectively hydrogenating substituted arenes with supported organometallic catalysts

Patent metadata

Field	Value
Publication number	US-2016159709-A1
Application number	US-201414559380-A
Country	US
Kind code	A1
Filing date	Dec 3, 2014
Priority date	Dec 3, 2014
Publication date	Jun 9, 2016
Grant date	—

Abstract

Methods for selectively hydrogenating substituted arenes with a supported organometallic hydrogenating catalyst are provided. An exemplary method includes contacting a substituted arene-containing reaction stream with hydrogen in the presence of a supported organometallic hydrogenating catalyst under reaction conditions effective to selectively hydrogenate the substituted arenes to the cis isomer with high selectivity. In this method, the supported organometallic hydrogenating catalyst includes a catalytically active organometallic species and a Brønsted acidic sulfated metal oxide support.

First claim

What is claimed is:

1 . A method for hydrogenation of substituted arenes comprising the step of:
contacting a reaction stream comprising one or more substituted arenes with hydrogen in the presence of a supported organometallic hydrogenating catalyst under reaction conditions effective to deliver hydrogen selectively to one face of the one or more substituted arenes yielding a product stream selective to cis-substituted cyclohexanes, wherein the supported organometallic hydrogenating catalyst comprises a catalytically active organometallic species and a Brønsted acidic sulfated metal oxide support.

2 . The method of claim 1 , wherein the substituted arenes are selected from the group consisting of di-alkyl arenes, tri-alkyl arenes, bicyclic arenes, and/or mixtures thereof.

3 . The method of claim 2 , wherein the substituted arenes are selected from the group consisting of xylenes, trimethylbenzenes, naphthalenes, and/or mixtures thereof.

4 . The method of claim 1 , wherein the cis-substituted cyclohexanes are selected from the group consisting of cis-di-alkylcyclohexanes, cis-tri-alkylcyclohexanes, cis-bicyclic cyclohexanes, and/or mixtures thereof.

5 . The method of claim 1 , wherein the supported organometallic hydrogenating catalyst comprises a supported organo-zirconium catalyst.

6 . The method of claim 1 , wherein selectivity to cis-substituted cyclohexanes is greater than about 90%.

7 . The method of claim 6 , wherein the selectivity to cis-substituted cyclohexanes is greater than about 95%.

8 . The method of claim 7 , wherein the selectivity to cis-substituted cyclohexanes is essentially 100%.

9 . The method of claim 1 , wherein the supported organometallic hydrogenating catalyst is a supported version of an unsupported organo-zirconium catalyst with the general formula of Cp # c ZrR r , where Cp # indicates a cyclopentadienyl ligand selected from the group consisting of cyclopentadienyl (Cp), pentamethylcyclopentadienyl (Cp*), a cyclopentadienyl radical substituted with alkyl or trimethylsilyl groups such as 1,2-dimethylcyclopentadienyl (Cp″), or a fused cyclopentadienyl radical; c is from 0 to 2; Zr is zirconium; R is an alkyl or aromatic ligand selected from the group consisting of methyl or substituted methyl (Me), benzyl or substituted benzyl (Bz), phenyl or substituted phenyl (Ph), 2,2-dimethylpropyl (also known as neopentyl, Np) or substituted 2,2-dimethylpropyl, trimethylsilylmethyl (also known as neosilyl, Ns) or substituted trimethylsilymethyl, and 2,2-dimethylethylbenzyl (also known as neophyl, Nph) or substituted 2,2-dimethylethylbenzyl; and r is determined by the equation r=4-c.

10 . The method of claim 1 , wherein the supported organometallic hydrogenating catalyst comprises one or more selected from the group consisting of Cp*ZrBz 2 /ZrS and Cp*ZrMe 2 /ZrS,
where: Cp* is a pentamethylcyclopentadienyl, Me is a methyl or substituted methyl, Bz is a benzyl or substituted benzyl, Zr is zirconium, and ZrS is a sulfated zirconia support.

11 . A method for stereoselective hydrogenation of substituted arenes comprising the step of:
contacting a reaction stream comprising one or more substituted arenes with hydrogen in the presence of a supported organozirconium hydrogenating catalyst under reaction conditions effective to selectively hydrogenate the substituted arenes to cis-substituted cyclohexanes, wherein the supported organozirconium hydrogenating catalyst comprises a catalytically active organozirconium species and a Brønsted acidic sulfated metal oxide support.

12 . The method of claim 11 , wherein the substituted arenes are selected from the group consisting of di-alkyl arenes, tri-alkyl arenes, bicyclic arenes, and/or mixtures thereof.

13 . The method of claim 12 , wherein the substituted arenes are selected from the group consisting of xylenes, trimethylbenzenes, naphthalenes, and/or mixtures thereof.

14 . The method of claim 11 , wherein selectivity to cis-substituted cyclohexanes is greater than about 90%.

15 . The method of claim 14 , wherein the selectivity to cis-substituted cyclohexanes is greater than about 95%.

16 . The method of claim 15 , wherein the selectivity to cis-substituted cyclohexanes is essentially 100%.

17 . A method for stereoselective hydrogenation of substituted arenes comprising the step of:
contacting a reaction stream comprising one or more substituted arenes with hydrogen in the presence of a heterogeneous hydrogenating catalyst under reaction conditions effective to deliver hydrogen selectively to one face of the substituted arenes, yielding a product stream comprising cis-substituted cyclohexanes, wherein selectivity to cis-substituted cyclohexanes is greater than about 95%.

18 . The method of claim 17 , wherein the heterogeneous hydrogenating catalyst is a supported version of an unsupported organo-zirconium catalyst with the general formula of Cp # c ZrR r , where Cp # indicates a cyclopentadienyl ligand selected from the group consisting of cyclopentadienyl (Cp), pentamethylcyclopentadienyl (Cp*), a cyclopentadienyl radical substituted with alkyl or trimethylsilyl groups such as 1,2-dimethylcyclopentadienyl (Cp″), or a fused cyclopentadienyl radical; c is from 0 to 2; Zr is zirconium; R is an alkyl or aromatic ligand selected from the group consisting of methyl or substituted methyl (Me), benzyl or substituted benzyl (Bz), phenyl or substituted phenyl (Ph), 2,2-dimethylpropyl (also known as neopentyl, Np) or substituted 2,2-dimethylpropyl, trimethylsilylmethyl (also known as neosilyl, Ns) or substituted trimethylsilymethyl, and 2,2-dimethylethylbenzyl (also known as neophyl, Nph) or substituted 2,2-dimethylethylbenzyl; and r is determined by the equation r=4-c.

19 . The method of claim 17 , wherein the heterogeneous hydrogenating catalyst comprises one or more selected from the group consisting of Cp*ZrBz 2 /ZrS and Cp*ZrMe 2 /ZrS,
where: Cp* is a pentamethylcyclopentadienyl, Me is a methyl or substituted methyl, Bz is a benzyl or substituted benzyl, Zr is zirconium, and ZrS is a sulfated zirconia support.

20 . The method of claim 17 , wherein the selectivity to cis-substituted cyclohexanes is essentially 100%.

Assignees

• Uop Llc

Inventors

• Delferro Massimiliano
• Stalzer Madelyn Marie
• Nicholas Christopher P
• Marks Tobin Jay
• Bhattacharyya Alakananda

Classifications

• C07C5/10 Primary

  of aromatic six-membered rings · CPC title

• C07C2531/12

  containing organo-metallic compounds or metal hydrides · CPC title

• C07C2527/04

  Sulfides · CPC title

• B01J2231/646

  of aromatic or heteroaromatic rings · CPC title

• B01J2531/48

  Zirconium · CPC title