Reduction of carbonyl-containing dialkyl peroxides to hydroxy-containing dialkyl peroxides
AssigneePennwalt Corporation
InventorsWilbur H. McKellin, William A. Swarts
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Abstract
A method of producing hydroxy-containing dialkyl peroxides of the formula ##STR1## by either heterogeneously catalytically reducing or homogeneously, non catalytically chemically reducing carbonyl-containing dialkyl peroxides of the formula ##STR2## R, R.sub.1, R.sub.2 and R.sub.3 are aliphatics. This invention also concerns novel hydroxy-containing dialkyl peroxide compounds having the structure of formula I.
Claims13
A process of reducing carbonyl-containing dialkyl peroxide of the formula ##STR17## to the corresponding hydroxy-containing dialkyl peroxide of the formula ##STR18## which comprises reacting II in the temperature range of -20.degree. to 100.degree. C and a pressure range of 0-200 psig with a member selected from the group consisting of (A) hydrogen gas in the presence of a promoter and a catalyst selected from the group consisting of (i) platinum, palladium, rhodium or ruthenium on a carrier, (ii) platinum oxide and (iii) Raney nickel wherein the concentration of said catalyst is in the range of 0.5-30% on the carrier and 0.1-3% without the carrier and (B) a hydride selected from the group consisting of an alkali metal aluminum hydride and an alkali metal borohydride wherein the hydride to peroxide ratio is in the range of 1 mole to 0.5-4 moles, wherein:
- n is 1 to 3 with provisos (a) through (n) below:
- a. when n is 1, R is selected from the group consisting of tertiary alkyl of 4-10 carbons, tertiary bicycloalkyl of 8-10 carbons, tertiary cycloalkyl of 6-10 carbons and tertiary aralkyl of 9 carbons;
- b. when n is 2, R is selected from the group consisting of ditertiary alkylene diradical of 8-20 carbons, ditertiary alkynylene diradical of 8-20 carbons, and ditertiary aralkylene diradical of 12 carbons;
- c. when n is 3, R is selected from the group consisting of tri-tertiary alkyl triradical of 10-21 carbons and tri-tertiary-aralkyl triradical of 15 carbons;
- d. R.sub.1 is a tertiary alkyl or cycloalkyl diradical of 3-15 carbons having the tertiary carbon attached to the peroxy oxygen;
- e. R.sub.2 and R.sub.3 are selected from the group consisting of --R.sub.1 --OO--R, alkyl of 1-15 carbons, cycloalkyl of 3-15 carbons, and hydrogen;
- R.sub.2 can also be selected from the group consisting of a hydroxyl and lower alkoxy of 1-5 carbons;
- f. R.sub.1 can be linked with R.sub.2 or R.sub.3 to form a cycloalkyl triradical of 3-10 carbons;
- g. when n is 1, R can be linked to R.sub.1 to form an alkyl triradical of 6-20 carbons;
- and
- h. when n is 1, R can be linked to R.sub.2 or R.sub.3 to form an alkyl diradical of 3-10 carbons.
Hydroxy-containing dialkyl peroxide compound of the formula:
- ##STR19## wherein:
- n is 1 to 3 with provisos (a) through (d) recited below,
- a. when n is 1, R is selected from the group consisting of tertiary alkyl radical of 4-10 carbons, tertiary bicycloalkyl radical of 8-10 carbons, tertiary cycloalkyl radical of 6-8 carbons and tertiary aralkyl radical of 9 carbons and R.sub.3 is selected from --R.sub.1 --OO--R;
- and R.sub.1 and R.sub.3 can join to form a cycloaliphatic triradical of 3-10 carbons;
- b. when n is 2, R is selected from the group consisting of ditertiary alkylene diradical of 8-20 carbons, ditertiary alkynylene diradical of 8-20 carbons and ditertiary aralkylene diradical of 12 carbons and R.sub.3 is selected from the group consisting of hydrogen, alkyl of 1-15 carbons, cycloalkyl of 3-15 carbons;
- c. when n is 3, R is selected from the group consisting of tri-tertiaryalkyl triradical of 10-21 carbons and tri-tertiary-aralkyl triradical of 15 carbons and R.sub.3 is selected from hydrogen, alkyl of 1-15 carbons, and cycloalkyl of 3-15 carbons;
- and
- d. R.sub.1 is a tertiary alkyl or cycloalkyl diradical of 3-15 carbons having a tertiary carbon attached to the peroxy oxygen.
Dependencies are inferred from the claim text.