Cycloalkane oxidation catalysts and method to produce alcohols and ketones

Abstract

The present invention concerns a method of oxidizing a cycloalkane to form a product mixture containing a corresponding alcohol and ketone, said method comprising contacting a cycloalkane with an oxidant agent in the presence of catalytic effective amount of metal triflates or metal triflimidates catalysts.

Claims

1. A method of oxidizing a cycloalkane to form a product mixture containing a corresponding alcohol and ketone, comprising contacting a cycloalkane with an oxidant agent in the presence of at least a catalyst of formula (I) as follow: ##STR00002## wherein: Y is N or O; X=1 when Y═O or 2 when Y═N; M is a metal selected from the group consisting of transition metal, post transition metal, and lanthanide; and Z is valency of the metal M; and wherein the oxidant agent is a hydroperoxide compound corresponding to formula (II):
R—O—O—H  (II) wherein R is a hydrocarbon group comprising from 3 to 15 carbon atoms.

2. A method according to claim 1, wherein cycloalkane is selected from the group consisting of cyclopentane, cyclohexane, cycloheptane, and cyclooctane.

3. A method according to claim 1, wherein hydroperoxide compounds are selected from the group consisting of tert-butyl hydroperoxide, tert-amyl hydroperoxide, cumene hydroperoxide, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, methylcyclohexyl hydroperoxide, tetralin hydroperoxide, isobutylbenzene hydroperoxide, and ethylnaphthalene hydroperoxide.

4. A method according to claim 1, wherein Y is an oxygen atom.

5. A method according to claim 1, wherein Y is a nitrogen atom.

6. A method according to claim 1, wherein M is selected from the group consisting of Fe, Y, Cu, Cr, Bi, In, Nd, and Ce.

7. A method according to claim 1, wherein the at least one catalyst of formula (I) is selected from the group consisting of Fe(OTf).sub.3, Cu(OTf).sub.2, Y(OTf).sub.3, Fe(TSIF).sub.3, Cu(TFSI).sub.2, Ce(TFSI).sub.3, In(TFSI).sub.3, and Bi(TFSI).sub.3.

8. A method according to claim 1, wherein at least one catalyst of formula (I) is used in a range of between 0.0001 wt % to 10 wt. %, in relation of metal weight to the total weight of the reaction medium.

9. A method according to claim 1, wherein the cycloalkane is contacted with an oxidant agent in the presence of at least a catalyst of formula (I) in a reaction medium that comprises a polar aprotic or a polar protic solvent.

Description

EXPERIMENTAL PART

Example 1

(1) Several catalysts have been used to catalyze the oxidation of cyclohexane using t-butyl hydroperoxide (TBHP) at 80° C. for 1.0 h with 0.02 g catalyst and 7.7 wt. % TBHP in cyclohexane. Molar ratio TBHP/catalyst is 79.3. Results are mentioned in Table 1.

(2) TABLE-US-00001 TABLE 1 TBHP Conversion KA Selectivity KA Yield Trials Catalyst (%) (%) (%) C1 None 0.7 98.0 0.7 C2 Co(NO.sub.3).sub.2 49 44 — C3 Triflic acid 99.7 4.2 4.2 1 Fe(OTF).sub.3 100 30.2 30.2 2 Cu(OTf).sub.2 75 30.0 22.5 3 Y(OTf).sub.3 55.8 27.2 15.2 4 Fe(TSIF).sub.3 100 23.1 23.1 5 Cu(TFSI).sub.2 84.7 29.8 25.2 6 Ce(TFSI).sub.3 72.4 14.1 10.2 7 In(TFSI).sub.3 81.6 12.6 10.3 8 Bi(TFSI).sub.3 91.3 11.8 10.8

(3) Trial C2 is using Co(NO.sub.3).sub.2 catalyst as mentioned in EP 0768292 A1.

(4) It appears then that without any catalysts, TBHP conversion and KA yield are less than 1%, while with the catalysts of the present invention a high conversion of TBHP with important KA yields and KA selectivities can be obtained.