# US 4,393,253 A · Hydroxylation of olefins

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- Number: US 4,393,253 A
- Document ID: US4393253A
- Status: Granted
- Kind: A
- Application number: 06/310,099
- Filed: 1981-10-09
- Granted: 1983-07-12
- Earliest claimed: 1980-11-24
- Assignees: Exxon Research & Engineering Co.
- Inventors: Robert C. Michaelson; Richard G. Austin
- Web page: https://patentgrep.com/patent/US4393253A

## CPC

- C07C 29/03: by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 (by simultaneous introduction of -OH groups and halogens C07C29/64)
- C07C 29/132: by reduction of an oxygen containing functional group
- C07C 29/48: by oxidation reactions with formation of hydroxy groups
- Y02P 20/52: using catalysts, e.g. selective catalysts
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A method for preparing polyols such as diols by catalytic hydroxylation of an olefinic compound by reacting the olefinic compound with an organic hydroperoxide and water in the presence of a catalyst comprising osmium compound and a specific halide co-catalyst is disclosed.

## Claims

### Claim 1

A process for hydroxylating olefins which comprises reacting at least one olefinic compound having at least one ethylenic unsaturation with water and at least one organic hydroperoxide in the presence of a catalyst composition under conditions and in a manner sufficient to convert at least one of said ethylenic unsaturation to its corresponding diol said catalyst composition comprising:
(a) Osmium tetroxide; and
(b) at least one co-catalyst selected from the group consisting of alkali metal halide, alkaline earth metal halide, hydrogen halide, quaternary hydrocarbyl phosphonium halide, halogen, and transition metal halide said transition metal being selected from the group consisting of Fe, Co, Ni, Cu, V, Cr, Mn, Sc, Ti, Mo, Ru, Rh, Pd and W.

### Claim 2 (depends on 1)

The process of claim 1 wherein the transition metal is selected from the group consisting of Cu, Fe, Ni, Co, and Mn.

### Claim 3 (depends on 1)

The process of claim 1 wherein the catalyst composition possesses a molar ratio of halide species in the co-catalyst to osmium metal in the OsO.sub.4 of from about 2:1 to about 100:1.

### Claim 4 (depends on 1)

The process of claim 1 wherein the quaternary hydrocarbyl phosphonium halide is represented by the structural formula
(R).sub.4 P.sup.+ X.sup.-
wherein each R is independently selected from the group consisting of substituted and unsubstituted alkyl, aryl, aralkyl and alkaryl, and X is selected from the group consisting of Cl, F, Br, and I.

### Claim 5 (depends on 1)

The process of claim 1 wherein the co-catalyst is selected from the group consisting of sodium iodide, sodium bromide, potassium iodide, hydrogen iodide, hydrogen bromide, tetraethyl phosphonium chloride, tetra ethyl phosphonium bromide, tungsten hexachloride and mixtures thereof.

### Claim 6 (depends on 1)

The process of claim 1 wherein the organic hydroperoxide is selected from the group consisting of t-butyl hydroperoxide, ethyl benzyl hydroperoxide, t-amyl hydroperoxide and cumene hydroperoxide.

### Claim 7 (depends on 1)

The process of claim 1 wherein the olefinic compound is selected from the group consisting of ethylene, propylene and mixtures thereof.

### Claim 8

A process for hydroxylating olefins which comprises admixing to form a liquid reaction mixture, at least one olefinic compound having at least one ethylenic unsaturation, at least one organic hydroperoxide, water in at least a stoichiometric molar ratio with the moles of ethylenic unsaturation to be hydroxylated, and a catalyst composition, under conditions and in a manner sufficient to convert at least one of said ethylenic unsaturation to its corresponding diol hydroxylation product, said catalyst composition comprising:
(a) osmium tetroxide; and
(b) at least one co-catalyst selected from the group consisting of alkali metal halide, alkaline earth metal halide, hydrogen halide, quaternary hydrocarbyl phosphonium halide, halogen, and transition metal halide said transition metal being selected from the group consisting of Fe, Co, Ni, Cu, V, Cr, Mn, Sc, Ti, Mo, Ru, Rh, Pd, and W.

### Claim 9 (depends on 8)

The process of claim 8 wherein the liquid reaction mixture additionally comprises at least one inert organic solvent.

### Claim 10 (depends on 9)

The process of claim 9 wherein the inert organic solvent is the hydroxylation product.