Transalkylated cyclohexylbenzyl and biphenyl compounds

Patent metadata

Field	Value
Publication number	US-10017433-B2
Application number	US-201515554211-A
Country	US
Kind code	B2
Filing date	Dec 16, 2015
Priority date	Mar 31, 2015
Publication date	Jul 10, 2018
Grant date	Jul 10, 2018

Abstract

Processes for selectively alkylating and/or dealkylating one ring of cyclohexylbenzyl and/or biphenyl compounds are provided. Such selective alkylation and/or dealkylation takes place through a transalkylation reaction between the cyclohexylbenzyl compound and a substituted or unsubstituted benzene, which replaces the phenyl moiety of the cyclohexylbenzyl compound. The transalkylated cyclohexylbenzyl may be dehydrogenated to give a corresponding biphenyl compound. The same reaction steps can be utilized with respect to biphenyl compounds by first partially hydrogenating one phenyl ring of the biphenyl compound, thereby obtaining a corresponding cyclohexylbenzyl compound, which may undergo the transalkylation and, optionally, subsequent dehydrogenation. Combinations of any two or more of partial hydrogenation, transalkylation, and dehydrogenation enable targeted substitution (or de-substitution) of only one ring of cyclohexylbenzyl and/or biphenyl compounds, thereby providing superior control in designing the synthesis of these compounds.

First claim

What is claimed is:

1. A process for forming cyclohexylbenzyl and/or biphenyl compounds, the process comprising:
(a) contacting a first cyclohexylbenzyl compound with a substituted or unsubstituted benzene in the presence of a transalkylation catalyst, thereby obtaining a transalkylated cyclohexylbenzyl compound,
wherein the transalkylation catalyst comprises a solid acid catalyst;
wherein the first cyclohexylbenzyl compound has the structural formula (I)

where each R 1 -R 10 is independently H or a C 1 -C 10 alkyl group;
wherein the substituted or unsubstituted benzene has the structural formula (II)

where each R 6* -R 10* is independently H or a C 1 -C 10 alkyl group, and further provided that one or more of the following is true: R 6* is different from R 6 , R 7* is different from R 7 , R 8* is different from R 8 , R 9* is different from R 9 , and R 10* is different from R 10 ; and
wherein the transalkylated cyclohexylbenzyl compound has the structural formula (III)

or a positional isomer thereof in which the cyclohexyl ring has each R 1 -R 5 covalently bonded thereto, and the phenyl ring has each R 6* -R 10* covalently bonded thereto.

2. The process of claim 1 , further comprising partially hydrogenating a precursor biphenyl compound having the structural formula (IV)

thereby obtaining the first cyclohexylbenzyl compound contacted with the substituted or unsubstituted benzene in (a).

3. The process of claim 2 , further comprising:
(a) dehydrogenating the transalkylated cyclohexylbenzyl compound to obtain a ring-replaced biphenyl compound having the structural formula (V)

or a positional isomer thereof in which one phenyl ring has each R 1 -R 5 covalently bonded thereto, and the other phenyl ring has each R 6* -R 10* covalently bonded thereto;
(b) partially hydrogenating the ring-replaced biphenyl compound in the presence of a hydrogenation catalyst to obtain a ring-replaced cyclohexylbenzyl compound having the formula (VI)

or a positional isomer thereof in which the phenyl ring has each R 1 -R 5 covalently bonded thereto, and the cyclohexyl ring has each R 6* -R 10* covalently bonded thereto;
(c) and contacting the ring-replaced cyclohexylbenzyl compound with an additional substituted or unsubstituted benzene in the presence of a second transalkylation catalyst, thereby obtaining a further transalkylated cyclohexylbenzyl compound,
wherein the additional substituted or unsubstituted benzene has the structural formula (VII)

or a positional isomer thereof, where any one of R 1* -R 5* is a C 1 -C 10 alkyl group, and the rest of R 1* -R 5* are each independently selected from H and C 1 -C 10 alkyl groups, and further provided that one or more of the following is true: R 1* is different from R 1 , R 2* is different from R 2 , R 3* is different from R 3 , R 4* is different from R 4 , and R 5* is different from R 5 ; and
wherein the further transalkylated cyclohexylbenzyl compound has the structural formula (VIII)

or a positional isomer thereof in which the phenyl ring has each R 1* -R 5* covalently bonded thereto, and the cyclohexyl ring has each R 6* -R 10* covalently bonded thereto.

4. The process of claim 3 , further comprising dehydrogenating the further transalkylated cyclohyexylbenzyl compound in order to obtain a double ring-replaced biphenyl compound having the structural formula (IX)

or a positional isomer thereof in which one phenyl ring has each R 1* -R 5* covalently bonded thereto, and the other phenyl ring has each R 6* -R 10* covalently bonded thereto.

5. The process of claim 1 , wherein R 1 -R 5 are each H.

6. The process of claim 5 , wherein R 6 -R 10 are each H.

7. The process of claim 1 , wherein one of R 1 -R 5 is a C 1 -C 5 alkyl group, and the rest of R 1 -R 5 are each H; and further wherein R 6 -R 10 are each H.

8. The process of claim 1 , wherein the substituted or unsubstituted benzene and the additional substituted or unsubstituted benzene are each independently selected from the group consisting of toluene, xylene, and ethylbenzene.

9. The process of claim 1 , wherein R 1* -R 5* and R 6* -R 10* each comprise the same five substitutions.

10. The process of claim 3 , wherein the transalkylation catalyst and the second transalkylation catalyst are each independently selected from molecular sieves having a large pore molecular sieve having a Constraint Index less than 2.

11. The process of claim 3 , wherein a single catalyst composition is both the transalkylation catalyst and the second transalkylation catalyst.

12. The process of claim 1 , wherein:
the cyclohexylbenzyl compound is cyclohexylbenzene (CHB);
the substituted or unsubstituted benzene is a substituted benzene selected from the group consisting of toluene, xylene, ethylbenzene, and mixtures thereof; and
the transalkylated cyclohexylbenzyl compound comprises one or more isomers of cyclohexyltoluene, cyclohexylxylene, cyclohexylethylbenzene, or mixtures thereof, respectively.

13. A process for forming cyclohexylbenzyl and/or biphenyl compounds, the process comprising:
(a) providing to a combined hydroalkylation and transalkylation reaction zone a hydroalkylation feed comprising (i) hydrogen, (ii) a substituted or unsubstituted benzene, and (iii) one or both of a cyclohexylbenzyl compound and a precursor biphenyl compound;
wherein the combined hydroalkylation and transalkylation reaction zone comprises (A) a hydrogenation catalyst and an alkylation catalyst, or (B) a bifunctional catalyst comprising (i) a hydrogenation metal selected from group 10 of the Periodic Table of the Elements and (ii) a molecular sieve;
further wherein the substituted or unsubstituted benzene has the structural formula (II)

where any one of R 6* -R 10* is a C 1 -C 10 alkyl group, and the rest of R 6* -R 10* are each independently selected from H and C 1 -C 10 alkyl groups, and further provided that one or more of the following is true: R 6* is different from R 6 , R 7* is different from R 7 , R 8* is different from R 8 , R 9* is different from R 9 , and R 10* is different from R 10 ;
further wherein the cyclohexylbenzyl compound has the structural formula (I)

where each R 1 -R 10 is independently H or a C 1 -C 10 alkyl group; and
further wherein the precursor biphenyl compound has the structural formula (IV)

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Salciccioli Michael
• Sangar Neeraj
• Chen Tan-Jen
• De Smit Emiel
• Kheir Ali A
• Pavlish Aaron B

Classifications

• C07C2529/12

  Noble metals · CPC title

• C07C2/74 Primary

  by addition with simultaneous hydrogenation · CPC title

• C07C6/126 Primary

  of more than one hydrocarbon · CPC title

• C07C2601/14

  The ring being saturated · CPC title

• C07C5/11

  Partial hydrogenation · CPC title