Methods for selectively hydrogenating substituted arenes with supported organometallic catalysts

Patent metadata

Field	Value
Publication number	US-9862657-B2
Application number	US-201414559380-A
Country	US
Kind code	B2
Filing date	Dec 3, 2014
Priority date	Dec 3, 2014
Publication date	Jan 9, 2018
Grant date	Jan 9, 2018

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, wherein the product stream is selective to cis-substituted cyclohexanes when the reaction stream comprises two or more substituted arenes,
wherein the supported organometallic hydrogenating catalyst comprises a catalytically active organometallic species with the general formula of Cp # c ZrR r , and a Brønsted acidic sulfated metal oxide support,

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, and a fused cyclopentadienyl radical; c is from 1 to 2; Zr is zirconium; R is an alkyl or aromatic ligand selected from the group consisting of benzyl or substituted benzyl (Bz), phenyl or substituted phenyl (Ph), 2,2-dimethylpropyl (neopentyl) or substituted 2,2-dimethylpropyl, trimethylsilylmethyl (neosilyl) or substituted trimethylsilymethyl, and 2,2-dimethylethylbenzyl (neophyl) or substituted 2,2-dimethylethylbenzyl; and r is determined by the equation r=4−c.

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 comprises Cp*ZrBz 2 /ZrS
where:
Cp* is a pentamethylcyclopentadienyl,
Bz is a benzyl or substituted benzyl,
Zr is zirconium, and
ZrS is a sulfated zirconia support.

10. 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 produce a product stream, wherein the product stream is selective to cis-substituted cyclohexanes when the reaction stream comprises two or more substituted arenes wherein the supported organometallic hydrogenating catalyst comprises a catalytically active organometallic species with the general formula of Cp # c ZrR r , and a Brønsted acidic sulfated metal oxide support, 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, and a fused cyclopentadienyl radical; c is from 1 to 2; Zr is zirconium; R is an alkyl or aromatic ligand selected from the group consisting of benzyl or substituted benzyl (Bz), phenyl or substituted phenyl (Ph), 2,2-dimethylpropyl (neopentyl) or substituted 2,2-dimethylpropyl, trimethylsilylmethyl (neosilyl) or substituted trimethylsilymethyl, and 2,2-dimethylethylbenzyl (neophyl) or substituted 2,2-dimethylethylbenzyl; and r is determined by the equation r=4−c.

11. The method of claim 10 , wherein the substituted arenes are selected from the group consisting of di-alkyl arenes, tri-alkyl arenes, bicyclic arenes, and/or mixtures thereof.

12. The method of claim 11 , wherein the substituted arenes are selected from the group consisting of xylenes, trimethylbenzenes, naphthalenes, and/or mixtures thereof.

13. The method of claim 10 , wherein selectivity to cis-substituted cyclohexanes is greater than about 90%.

14. The method of claim 13 , wherein the selectivity to cis-substituted cyclohexanes is greater than about 95%.

15. The method of claim 14 , wherein the selectivity to cis-substituted cyclohexanes is essentially 100%.

16. A method for stereoselective hydrogenation of substituted arenes comprising the step of:
contacting a reaction stream comprising substituted arenes selected from the group consisting of di-alkyl arenes, tri-alkyl arenes, bicyclic arenes, and/or mixtures thereof 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%, and
wherein the heterogeneous hydrogenating catalyst comprises Cp*ZrBz 2 /ZrS,
where:
Cp* is a pentamethylcyclopentadienyl,
Bz is a benzyl or substituted benzyl,
Zr is zirconium, and
ZrS is a sulfated zirconia support.

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

18. The method of claim 1 , wherein the Brønsted acidic sulfated metal oxide support is selected from the group consisting of sulfated alumina (AlS), sulfated zirconia (ZrS) and tungstated zirconia (ZrW).

19. The method of claim 10 , wherein the Brønsted acidic sulfated metal oxide support is selected from the group consisting of sulfated alumina (AlS), sulfated zirconia (ZrS) and tungstated zirconia (ZrW).

Assignees

• Uop Llc
• Univ Northwestern

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

• C07C13/50

  Decahydronaphthalenes · CPC title

• B01J27/053

  Sulfates · CPC title

• B01J21/066

  Zirconium or hafnium; Oxides or hydroxides thereof · CPC title

• C07C2601/14

  The ring being saturated · CPC title