GB2036742A - Peroxide complexes of platinum and palladium, their production and their use as selective oxidation and oxidative dehydrogenation reagents - Google Patents

Peroxide complexes of platinum and palladium, their production and their use as selective oxidation and oxidative dehydrogenation reagents Download PDF

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GB2036742A
GB2036742A GB7941206A GB7941206A GB2036742A GB 2036742 A GB2036742 A GB 2036742A GB 7941206 A GB7941206 A GB 7941206A GB 7941206 A GB7941206 A GB 7941206A GB 2036742 A GB2036742 A GB 2036742A
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0013—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
    • C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

Peroxide complexes have the general formula: <IMAGE> in which [A] is an anion of a carboxylic or sulphonic acid containing from 2 to 20 carbon atoms in the molecule, M is palladium or platinum, R is an alkyl, aryl, aralkyl or alkylaryl hydrocarbon radical containing from 3 to 20 carbon atoms and n is 1, 2 or 3. They are prepared by reaction of a salt MA2 with an organic hydroperoxide R-O-OH. They can be used to convert olefins to ketones and for the oxidative dehydrogenation of cyclic ketones.

Description

SPECIFICATION Peroxide complexes of platinum and palladium, their production and their use as selective oxidation and oxidative dehydrogenation reagents The present invention concerns novel peroxidic complexes of palladium and platinum, their preparation and their use as selective oxidation catalysts and reagents for converting olefins into ketones and for the conversion of cyclic ketones into oxidative dehydrogenation products.
The crude general formula of the complexes is as follows:
\)(A) x -0-0- a) in which [A] is the anion of a carboxylic acid or a sulphonic acid containing from 2 to 20 carbon atoms per molecule, M is a metal such as palladium or platinum and R is an alkyl, aryl, aralkyl or alkylaryl hydrocarbon radical containing from 3 to 20 carbon atoms, e.g. t-butyl, isopentyl, cumyl, ethylbenzyl or menthyl and n is 1, 2or3.
The anion [A] is conveniently derived from an acid preferably containing from 2 to 20 carbon atoms per molecule, for example, acetate, propionate, butyrate, benzoate, monochloroacetate, dichloroacetate, trichloroacetate, monofluoroacetate, difluoroacetate, trifluoroacetate, methanesulphonate, trifluoromethanesulphonate or paratoluenesulphonate.
The complexes are preferably produced by reacting an organic hydroperoxide with a palladium or platinum compound in accordance with reaction (1) where M, A and R are as defined above: MA2+ROOH- > AM-O-OR+AH ROOH AM - 0 - OR + AH (1) The compound MA2 may if desired be prepared in situ, as indicated hereinafter.
An example of reaction 1 is the reaction of t-butyl hydroperoxide with palladium trifluoroacetate, which results in the formation of palladium t-butyl peroxide trifluoroacetate in accordance with reaction 2 (where tBu denotes the t-butyl radical): (CF3CO2)2 Pd + tBu - O2H CF3CO2Pd - 0 - O-tBu + CF3CO2H (2) Reaction 1 is generally effected at a moderate temperature of from 0 to 80 C and preferably from 20 to 40 C. Operation may be effected in the absence or presence of a solvent, for example an aromatic hydrocarbon, an ether or a chlorinated solvent.
In most cases, the peroxide complexes are precipitated from the reaction medium in the form of yellow or orange crystals.
In order to promote substitution of the hydroperoxide radical for the anion [A], it is often advantageous to operate not only in the presence of the desired hydroperoxide but also in the presence of an alkali metal salt of the hydroperoxide used. Thus for example, adding t-butyl hydroperoxide to a compound MA2 may be accompanied by the addition of the sodium salt of formula tBu - 0 - O Na which is produced for example by dissolving metallic sodium in the hydroperoxide.
The palladium and platinum carboxylates which can be used in reaction 1 can be prepared in accordance with the method described by G Wilkinson and his collaborators [J Chem. Soc. 3632 (1965)] from the metal and carboxylic acid. They can also be produced by reacting the carboxylic acid on a palladium salt such as the nitrate.
The hydroperoxides which can be used for the synthesis of peroxide complexes in accordance with reaction 1 therefore have the general formula ROOH in which R is a hydrocarbon radical, preferably a tertiary radical, containing from 4 to 20 carbon atoms.
The following may be mentioned as examples of the complexes [A] MOOR and more particularly those which can be produced in accordance with reaction 1: - palladium t-butyl peroxide acetate (abbreviated to P.P.A.), which has the crude formula CH3CO2 Pd - 0 O - tBu and which is produced directly from palladium acetate and t-butyl hydroperoxide; - palladium t-butyl peroxide trifluoroacetate (abbreviated to P.P.T.), which has the crude formula CF3CO2 Pd - 0 - 0 - tBu and which can be produced from palladium trifluoroacetate and t-butyl hydroperoxide but which can also be prepared from a solution of palladium acetate in trifluoroacetic acid (production in situ of palladium trifluoroacetate) to which an excess of t-butyl hydroperoxide is added.
The following complexes can also be produced by the same mode of operation: CCI3 CO2 Pd - 0 - 0 - tBu from palladium trichloroacetate and t-butyl hydroperoxide; CF2 CO2 Pd - 0 - 0 - C(CH3)2 C6H5from palladium trifluoroacetate and cumyl hydroperoxide; CH3 CO2 Pt - 0 - 0 - tBu from platinum acetate and t-butyl hydroperoxide; CF3 CO2 Pt - 0 - 0 - tBu from platinum trifluoroacetate and t-butyl hydroperoxide.
Platinum trifluoroacetate, which has not been previously described in the literature, was produced by the action of siiver trifluoroacetate on the complex PtC12.(norbornadiene).
The complexes in accordance with the present invention have been found to be selective oxidation reagents. They selectively convert olefins into ketones in accordance with equation 3:
in which reaction the olefins comprise from 2 to 20 carbon atoms per molecule and have the general formula R3CH = CHR4 where each of R3 and R4, which are similar or different, is a hydrogen atom ora hydrocarbon radical containing from 1 to 18 carbon atoms. However, in the process of the present invention, preferred olefins are the terminal olefins, that is to say, those in which R4 is a hydrogen atom, e.g. ethylene, propylene, but-1-ene, but-2-ene, hex-1-ene, oct-i -ene, oct-2-ene, dec-1 -ene, dodec-1 -ene and styrene.All these olefins are selectively oxidised to form corresponding ketones.
Reaction 2 is effected at a temperature of from 0 to 10000 but more particularly from 20 to 60"C. The solvent used may be either the olefinic substrate or a chlorinated solvent, for example chloroform, dichloromethane or chlorobenzene, or an aromatic solvent such as benzene, toluene, xylene or nitrobenzene. The ratio olefin/peroxidic complex may be from 0.1 to 10,000 but is preferably greater than 2.
The peroxidic complexes of platinum or palladium also make it possible to effect oxidising dehydrogenation in respect of cyclic ketones having the formula
where m is an integer of from 4 to 11, and particularly cyclopentanone, which is selectively oxidised to form cyclopent-i-en-3-one in accordance with equation 4:
and cyclohexanone, which is selectively oxidised to form cyclohex-1-en-3-one in accordance with equation 5:
In this case, cyclohex-1-en-3-one can be consecutively oxidised to form phenol (equation 6)::
The oxidising dehydrogenation reaction is effected at a temperature of from 0 to 100"C and more particularly from 20 to 40"C, either in the absence of any solvent or in the presence of a solvent such as an aromatic hydrocarbon (for example benzene or toluene) or a chlorinated solvent, for example dichloromethane, dichloroethane or chlorobenzene. The ketone/complex molar ratio is in the range 0.1:1 to 10,000:1.
The present invention is illustrated by the following examples.
Example 1 - Synthesis of palladium t-butyl peroxide acetate.
1 g (4.5 millimoles) of palladium acetate is dissolved in 8 cc of t-butyl hydroperoxide at ambient temperature (2000) with magnetic stirring for a period of 12 hours in a glass reaction vessel. An orange precipitate is gradually formed. This is collected at the end of the reaction, filtered and washed several times with pentane. Evaporation under a high vacuum of the filtrate results in the production of a supplementary amount of the complex. 3.82 millimoles of complex is produced, giving a total yield of 85% of the complex, elementary analysis of the complex corresponding to the formula CH3CO2 Pd-O-O-C(CH3)3 (abbreviated to PPA).
The infra-red spectrum of this complex has the characteristic bands of t-butyl (2900 - 3000 cm-'), acetate (1400- 1550 cam~1) and peroxide (860 cm-1) groups.
Example 2 - Synthesis of palladium t-butyl peroxide trifluoroacetate 1 g (4.5 millimoles) of palladium acetate is dissolved at a temperature of 20"C in 1 cc of trifluoroacetic acid.
8 cc of t-butyl hydroperoxide is added to the resulting solution. An orange precipitate is then formed. The mixture is stirred for 2 hours at ambient temperature (20"C) and then the complex is fiitered and washed several times with pentane. 4 millimoles is obtained, giving a yield of 88% of a complex in respect of which elementary analysis corresponds to the formula CF3CO2 Pd - 0 - 0 - C(CH3)3 (abbreviated to PPT). The infra-red spectrum of this complex shows the characteristic bands of trifluoroacetate (1630 and 1200 cm-'), t-butyl (3000 cm-1) and peroxide (856 cm~1) groups.
The same complex can be produced directly from palladium trifluoroacetate and t-butyl hydroperoxide.
Example 3 10 millimoles of oct-i -ene, 15 ml of benzene and 1 millimole of PPA prepared as described in Example 1 are introduced into a heat-insulated glass reaction vessel, at a temperature of 20"C. After 1 hour, by gas-phase chromatography, the formation of octan-2-one (0.45 millimole, i.e. a molar yield of 4.5% with respect to the PPA) and 2-acetoxy-l-octene (0.4 millimole) is noted. The palladium is precipitated in the form of metal at the end of the reaction. Substantially the same yields would have been obtained by using much less oct-i -ene, for example 5 millimoles of oct-1-ene.
Example 4 10 millimoles of oct-l-ene, 15 ml of benzene and 1 millimole of PPT prepared in accordance with Example 2 are introduced into a glass reaction vessel, at a temperature of 20"C. After 15 minutes, gas-phase chromatography shows the exclusive formation of 0.98 millimole of octan-2-one (molar yield of 98% with respect to PPT) without the precipitation of metallic palladiu m at the end of the reaction. Infra-red analysis of the final complex shows that the perioxide band has disappeared.The following reaction has therefore been effected: CF3CO2Pd-O-O-tBu + oct-1 -ene ~ CF3CO2 Pd-O-tBu + octan-2-one Examples 5 to 10 These Examples show that PPT, one mode of preparation of which is set forth in Example 2, is a highly selective reagent for the oxidation of terminal olefins to form methyl ketones. Internal olefins such as cyclohexene are oxidised less selectively. Operation is effected as described in Example 4; the solvent is benzene and 1 millimole of PPT is used. Operation is at a temperature of 20"C.
Example Olefin Products obtained and Reaction No. (lOmmoles) molaryields time 5 hex-i-ene hexan-2-one 98% 15 minutes 6 dec-l-ene decan-2-one98% 20 minutes 7 dodec-1-ene dodecan-2-one 98% 20 minutes 8 styrene acetophenone 97% 40 minutes 9 octa-1,7-diene oct-i-en--7-one70% 40 minutes 10 cyclohexene cyclohexanone 30% cyclohex-l-en3-one 20% 4 hours phenol = 40% The yields are expressed in moles with respect to the starting complex.
Example 77 10 millimoles of cyclopentanone and 1 millimole of PPT are introduced into a heat-insulated glass reaction vessel, at a temperature of 20"C. After 20 minutes, the exclusive formation of 0.45 millimole of cyclopent-1-en-3-one is observed.
Example 12 Operation is as in Example 1, and 10 millimoles of cyclohexanone and 1 millimole of PPTare introduced.
After 20 minutes, the formation of 0.2 millimole of cyclohex-1-en-3-one and 0.25 millimole of phenol is observed.

Claims (23)

1. A peroxide complex having the general formula:
Aj H - O - O - nS in which [A] is an anion of a carboxylic or sulphonic acid containing from 2 to 20 carbon atoms in the molecule, M is palladium or platinum, R is an alkyl, aryl, aralkyl or alkylaryl hydrocarbon radical containing from 3 to 20 carbon atoms and n is 1,2 or 3.
2. A complex in accordance with Claim 1 in which, in the formula, [A] is an acetate, propionate, butyrate, benzoate, monochloroacetate, dichloroacetate, trichloroacetate, monofl uoroacetate, difl uoroacetate, trifluoro-acetate, methanesulphonate, trifluoromethanesulphonate or paratoluenesulphonate anion and R is a t-butyl, isopentyl, cumyl, ethylbenzyl or menthyl radical.
3. A complex in accordance with Claim 1 or 2, in which M is palladium.
4. A complex in accordance with Claim 1 having the crude formula: CH3CO2 Pd - 0 - 0 - C(CH3)3.
5. A complex in accordance with Claim 1 having the crude formula: CF3CO2 Pd - 0 - 0 - C(CH3)3.
6. A complex in accordance with Claim 1 having the crude formula: CF3CO2 Pt - 0 - 0 - C(CH3)3.
7. A method of producing a complex in accordance with Claim 1 comprising reacting a platinum or palladium carboxylate or sulphonate with an organic hydroperoxide in accordance with the reaction M A2 f ROOH AM -O-O-R + AH where M, A and R are as defined in Claim 1.
8. A method in accordance with Claim 7 in which the reaction is effected at a temperature in the range 0 to 80 C.
9. A method in accordance with Claim 8 in which the reaction is effected at a temperature in the range 20 to 40"C.
10. A method in accordance with Claim 7, 8 or 9 in which an alkali metal salt of the hydroperoxide used is added to the reaction medium.
11. A process in accordance with Claim 10 in which the alkali metal salt is a sodium salt
12. A process in accordance with Claim 10 or ii in which the alkali metal salt of the hydroperoxide is produced by dissolving an alkali metal in the hydroperoxide.
13. A method in accordance with any one of Claims 7 to 12 in which the compound MA2 is prepared in situ, that is to say, simultaneously with the addition of the compound ROOH.
14. A method in accordance with Claim 7 substantially as hereinbefore described in any one of Examples 1 to 4.
15. A peroxide complex obtained by a method in accordance with any one of Claims 8 to 14.
16. A method of producing ketones by the oxidation of an olefin containing from 2 to 20 carbon atoms in the molecule and having the formula R3CH = CH R4 where each of R3 and R4, which are identical or different, is a hydrogen atom or a hydrocarbon radical containing from 1 to 18 carbon atoms, at a temperature of from 0 to 100"C in the presence of at least one peroxide complex in accordance with Claim 1, the olefin:peroxidic complex molar ratio being from 0.1:1 to 10,000:1.
17. A method in accordance with Claim 16 carried out at a temperature of from about 20 to 60 C.
18. A method in accordance with Claim 16 or 17 in which R4 is a hydrogen atom.
19. A method in accordance with Claim 16 substantially as hereinbefore described in any one of Examples5to 10.
20. A method for the oxidative dehydrogenation of a cyclic ketone having the formula:
where m is an integer of from 4 to 11, at a temperature of from 0 to 100 C, in the presence of the complexes in accordance with Claim 1, the ketone/complex molar ratio being from 0.1 to 10,000.
21. A method in accordance with Claim 19 as applied to the oxidative dehydrogenation of cyclopentanone or cyclohexanone.
22. A method in accordance with Claim 20 substantially as hereinbefore described in Examples 11 or 12.
23. Ketones obtained by a method in accordance with any one of Claims 16 to 22.
GB7941206A 1978-11-30 1979-11-29 Peroxide complexes of platinum and palladium their production and their use as selective oxidation dehydrogenation reagents Expired GB2036742B (en)

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FR7834052A FR2442835A1 (en) 1978-11-30 1978-11-30 NOVEL PEROXIDE PLATINUM AND PALLADIUM COMPLEXES, PROCESS FOR THEIR MANUFACTURE AND THEIR USE AS SELECTIVE OXIDATION AND OXIDANT DEHYDROGENATION REAGENTS

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