Olefin epoxidation using a perrhenate catalyst and an organic hydroperoxide

Claim 2

A process for epoxidizing an olefin comprising contacting the olefin with an organic hydroperoxide in the presence of an amount of a rhenium catalyst comprised of a perrhenate anion and an organopnicogen-containing cation effective to form an epoxide of the olefin.

Claim 3

The process of claim 1 wherein the pnicogen of the organopnicogen-containing cation is N, P, or As.

Claim 4

The process of claim 1 wherein the organopnicogen-containing cation has the general formula RR.sup.1 R.sup.2 R.sup.3 Pn wherein R, R 1 , R 2 and R 3 are the same or different and are selected from the group consisting of hydrogen, C 1 -C 20 linear, branched, or cyclic alkyl, C 6 -C 20 aryl, and C 7 -C 20 aralkyl, with the proviso that not all of R, R 1 , R 2 , and R 3 are hydrogen, and Pn is N, P, or As; or the general formula R.sup.4 R.sup.5 R.sup.6 Pn.sup.2 --R.sup.7 --Pn.sup.3 R.sup.3 R.sup.9 R.sup.10 wherein R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are the same or different and are selected from the group consisting of hydrogen, C 1 -C 20 linear, branched, or cyclic alkyl, C 6 -C 20 aryl, and C 7 -C 20 aralkyl, with the proviso that R 7 is not hydrogen, and Pn 2 and Pn 3 are the same or different and are N, P, or As.

Claim 5

The process of claim 1 wherein the olefin is an alkenyl aromatic compound.

Claim 6

The process of claim 1 wherein the organic hydroperoxide is a secondary or tertiary hydroperoxide having the general structure ##STR4## wherein R 11 , R 12 , and R 13 are the same or different and are selected from the group consisting of hydrogen, methyl, ethyl, and phenyl.

Claim 7

A process for epoxidizing an olefin wherein at least one of the ethylenically unsaturated functional groups of the olefin bears an aromatic substituent, said process comprising contacting the olefin with a secondary or tertiary hydroperoxide having the general structure ##STR5## wherein R 11 , R 12 , and R 13 are the same or different and are selected from the group consisting of hydrogen, methyl, ethyl, and phenyl in the presence of a rhenium catalyst having the general formula [RR.sup.1 R.sup.2 R.sup.3 Pn][ReO.sub.4 ] wherein R, R 1 , R 2 , and R 3 are the same or different and are selected from the group consisting of hydrogen, C 1 -C 20 linear, branched, or cyclic alkyl, C 6 -C 20 aryl, and C 7 -C 20 aralkyl, with the proviso that not all of R, R 1 , R 2 , and R 3 are hydrogen, and Pn is N, P, or As, effective to form an epoxide of the olefin.

Claim 8

A process for epoxidizing an olefin wherein at least one of the ethylenically unsaturated functional groups of the olefin bears an aromatic substituent, said process comprising contacting the olefin with a secondary or tertiary hydroperoxide having the general structure ##STR5## wherein R 11 , R 12 , and R 13 are the same or different and are selected from the group consisting of hydrogen, methyl, ethyl, and phenyl in the presence of a rhenium catalyst having the general formula [RR.sup.1 R.sup.2 R.sup.3 Pn][ReO.sub.4 ] wherein R, R 1 , R 2 , and R 3 are the same or different and are selected from the group consisting of hydrogen, C 1 -C 20 linear, branched, or cyclic alkyl, C 6 -C 20 aryl, and C 7 -C 20 aralkyl, with the proviso that not all of R, R 1 , R 2 , and R 3 are hydrogen, and Pn is N, P, or As, effective to form an epoxide of the olefin.

Claim 9

The process of claim 6 wherein the olefin has the general structure ##STR6## wherein at least one of R 14 , R 15 , R 16 , or R 17 is an aromatic substituent and the remaining R substituents are the same or different and are selected from the group consisting of hydrogen and C 1 -C 8 alkyl.

Claim 10

The process of claim 6 wherein the secondary or tertiary organic hydroperoxide is selected from the group consisting of t-butyl hydroperoxide, t-amyl hydroperoxide, cumene hydroperoxide, and ethyl benzene hydroperoxide.

Claim 11

The process of claim 6 wherein none of R, R 1 , R 2 , or R 3 is hydrogen.

Claim 12

The process of claim 6 wherein the molar ratio of olefin:organic hydroperoxide is from about 100:1 to 1:100.

Claim 13

The process of claim 6 wherein the molar ratio of olefin:rhenium is from about 10,000:1 to 1:1.

Claim 14

The process of claim 6, wherein said contacting is carried out at a temperature of from about 0° C. to 150° C.

Claim 15

The process of claim 6 wherein said contacting is carried out for a time of from about 10 minutes to 48 hours.

Claim 16

The process of claim 6 wherein an organic solvent is additionally present during said contacting.

Claim 17

A process for epoxidizing an olefin comprising contacting the olefin with an organic hydroperoxide in the presence of catalytically effective amounts of an alkali metal perrhenate and an organopnicogen halide salt.

Claim 18

A process for epoxidizing an olefin comprising contacting the olefin with an organic hydroperoxide in the presence of catalytically effective amounts of an alkali metal perrhenate and an organopnicogen halide salt.

Claim 19

The process of claim 15 wherein the alkali metal perrhenate is lithium perrhenate, sodium perrhenate, or potassium perrhenate.

Claim 20

The process of claim 15 wherein the organopnicogen halide salt has the general formula RR.sup.1 R.sup.2 R.sup.3 PnX wherein R, R 1 , R 2 , and R 3 are the same or different and are selected from the group consisting of hydrogen, C 1 -C 20 linear, branched, or cyclic alkyl, C 6 -C 20 aryl, and C 7 -C 20 aralkyl, with the proviso that not all of R, R 1 , R 2 , and R 3 are hydrogen, Pn is N, P, or As, and X is Cl, Br, or I; or the general formula X.sup.2 R.sup.4 R.sup.5 R.sup.6 Pn.sup.2 --R.sup.7 --Pn.sup.3 R.sup.8 R.sup.9 R.sup.10 X.sup.3 wherein R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are the same or different and are selected from the group consisting of hydrogen, C 1 -C 20 linear, branched, or cyclic alkyl, C 6 -C 20 aryl, and C 7 -C 20 aralkyl, with the proviso that R 7 is not hydrogen, Pn 2 and Pn 3 are the same or different and are N, P, or As, and X 2 and X 3 are the same or different and are N, P, or As.

Claim 21

The process of claim 15 wherein an organic solvent is additionally present.

Claim 22

The process of claim 15 wherein water is additionally present.

Claim 23

The process of claim 15 wherein both water and an organic solvent are additionally present.

Claim 24

The process of claim 15 wherein the organic hydroperoxide is a secondary or tertiary hydroperoxide having the general structure ##STR7## wherein R 11 , R 12 , and R 13 are the same or different and are selected from the group consisting of hydrogen, methyl, ethyl, and phenyl.

Claim 25

The process of claim 15 wherein the olefin is an alkenyl aromatic compound.

Claim 26

A process for epoxidizing an olefin wherein at least one of the ethylenically unsaturated functional groups of the olefin bears an aromatic substituent, said process comprising contacting a secondary or tertiary hydroperoxide having the general structure ##STR8## wherein R 11 , R 12 , and R 13 are the same or different and are selected from the group consisting of hydrogen, methyl, ethyl, and phenyl with the olefin in a biphasic reaction mixture containing water, a water-immiscible organic solvent, and catalytically effective amounts of an alkali metal perrhenate and an organopnicogen halide salt.

Claim 27

A process for epoxidizing an olefin wherein at least one of the ethylenically unsaturated functional groups of the olefin bears an aromatic substituent, said process comprising contacting a secondary or tertiary hydroperoxide having the general structure ##STR8## wherein R 11 , R 12 , and R 13 are the same or different and are selected from the group consisting of hydrogen, methyl, ethyl, and phenyl with the olefin in a biphasic reaction mixture containing water, a water-immiscible organic solvent, and catalytically effective amounts of an alkali metal perrhenate and an organopnicogen halide salt.

Claim 28

The process of claim 23 wherein the alkali metal perrhenate is lithium perrhenate, sodium perrhenate, or potassium perrhenate.

Claim 29

The process of claim 23 wherein the organopnicogen halide salt has the general formula RR.sup.1 R.sup.2 R.sup.3 PnX wherein R, R 1 , R 2 , and R 3 are the same or different and are selected from the group consisting of hydrogen, C 1 -C 20 linear, branched, or cyclic alkyl, C 6 -C 20 aryl, and C 7 -C 20 aralkyl, with the proviso that not all of R, R 1 , R 2 , and R 3 are hydrogen, Pn is N, P, or As, and X is Cl, Br, or I; or the general formula X.sup.2 R.sup.4 R.sup.5 R.sup.6 Pn.sup.2 --R.sup.7 --Pn.sup.3 R.sup.8 R.sup.9 R.sup.10 X.sup.3 wherein R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are the same or different and are selected from the group consisting of hydrogen, C 1 -C 20 linear, branched, or cyclic alkyl, C 6 -C 20 aryl, and C 7 -C 20 aralkyl, with the proviso that R 7 is not hydrogen, Pn 2 and Pn 3 are the same or different and are N, P, or As, and X 2 and X 3 are the same or different and are N, P, or As.

Claim 30

The process of claim 23 wherein the water-immiscible organic solvent is selected from the group consisting of halogenated aliphatic hydrogens, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, and aromatic hydrocarbons.

Claim 31

The process of claim 23 wherein the olefin has the general structure ##STR9## wherein at least one of R 14 , R 15 , R 16 , or R 17 is an aromatic substituent and the remaining R substituents are selected from the group consisting of hydrogen and C 1 -C 8 alkyl.

Claim 32

The process of claim 23 wherein R 11 , R 12 , R 13 are each methyl.

Claim 33

The process of claim 23 wherein the molar ratio of alkali metal perrhenate:organopnicogen halide salt is from 4:1 to 1:4.