FR2469392A2 - Carbonyl cpds. prodn. - by liq. phase oxidn. of olefin(s) with hydrogen peroxide or organic hydroperoxide using palladium complex catalyst (BE 12.6.80) - Google Patents

Carbonyl cpds. prodn. - by liq. phase oxidn. of olefin(s) with hydrogen peroxide or organic hydroperoxide using palladium complex catalyst (BE 12.6.80) Download PDF

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Publication number
FR2469392A2
FR2469392A2 FR7928154A FR7928154A FR2469392A2 FR 2469392 A2 FR2469392 A2 FR 2469392A2 FR 7928154 A FR7928154 A FR 7928154A FR 7928154 A FR7928154 A FR 7928154A FR 2469392 A2 FR2469392 A2 FR 2469392A2
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Prior art keywords
hydrogen peroxide
prodn
liq
olefin
complex catalyst
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FR7928154A
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French (fr)
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FR2469392B2 (en
Inventor
Michel Roussel
Hubert Mimoun
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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Priority to FR7928154A priority Critical patent/FR2469392A2/en
Priority to CH1095879A priority patent/CH643226A5/en
Priority to DE19792949847 priority patent/DE2949847A1/en
Priority to IT28027/79A priority patent/IT1126576B/en
Priority to GB7943413A priority patent/GB2037768B/en
Priority to US06/104,941 priority patent/US4310704A/en
Priority to US06/265,488 priority patent/US4379942A/en
Publication of FR2469392A2 publication Critical patent/FR2469392A2/en
Application granted granted Critical
Publication of FR2469392B2 publication Critical patent/FR2469392B2/fr
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    • 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

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

Abstract

Carbonyl cpds. are produced in the liq. phase by oxidn. of olefins R-CH=CH-R' in which R and R' are each H or 1-20 C hydrocarbyl, or together form an alkylene gp. The reaction is carried out in the presence of (a) A catalyst of formula PdAA'Lm in which A and A' may be the same or different, A is fluoroborate, acetate or trifluoroacetate and A' is as for A or pi-allyl or OOR1 in which R1 is a hydrocarbon gp., m = O or 2, and L is a ligand chosen from amine, phosphine, arsine, stibine and amide; and (b) an oxidising agent chosen from H2O2 and organic peroxides R2OOH in which R2 is a tert. hydrocarbon gp., alkyl, aralkyl or alkylaryl with 4-20 C. Process is carried out in the absence of Cl ion, so that problems of corrosion are avoided. The process uses salts and complexes of a single metal (Pd) and gives high selectivity to the prodn. of the desired carbonyl cpds. with a wide range of olefin starting materials.

Description

Le brevet principal concerne un procédé de fabrication de dérivés carbonylés, par oxydation d'oléfines, en phase liquide, par l'eau oxygénée, en présence d'au moins un catalyseur soluble constitué par un sel ou complexe de palladium. Il a été à présent découvert que l'utilisation d'un alcool ou d'un acide monocarboxylique comme tiers solvant 9 la fois de l'oléfine et de l'eau oxygénée, permet d'obtenir une amélioration importante de la vitesse de réaction. The main patent relates to a process for the production of carbonyl derivatives, by oxidation of olefins, in the liquid phase, with hydrogen peroxide, in the presence of at least one soluble catalyst consisting of a palladium salt or complex. It has now been discovered that the use of an alcohol or a monocarboxylic acid as a third solvent for both olefin and hydrogen peroxide allows a significant improvement in the reaction rate to be obtained.

A titre d'exemples non limitatifs d'alcools utilisables selon l'invention, on peut citer : l'alcool tertio butylique, l'alcool tertio amylique, le diméthyl phényl carbinol et l'ethylène glycol. As nonlimiting examples of alcohols which can be used according to the invention, there may be mentioned: tertiary butyl alcohol, tertiary amyl alcohol, dimethyl phenyl carbinol and ethylene glycol.

Comme acides monocarboxyliques, on peut citer l'acide acétique, l'acide propionique et l'acide butyrique. As monocarboxylic acids, there may be mentioned acetic acid, propionic acid and butyric acid.

EXEMPLE 1
Dans un réacteur en verre calorifugé, on introduit 37,3 g de dodécène -1 > 233 g de tertio-butanol comme solvant et 80 mg d'acétate de palladium. L'ensemble est brassé énergiquement au moyen d'un agitateur magnétique. On verse alors peu à peu 130 g d'une solution aqueuse a 30 % en poids d'eau oxygénée Le mélange est maintenu ensuite à reflux.EXAMPLE 1
37.3 g of dodecene -1> 233 g of tert-butanol as solvent and 80 mg of palladium acetate are introduced into a heat-insulated glass reactor. The whole is stirred vigorously by means of a magnetic stirrer. Then gradually poured 130 g of an aqueous solution at 30% by weight of hydrogen peroxide The mixture is then maintained at reflux.

Au bout de 3 heures, on constate que 89,5 % du dodécène-l ont été transformés. La sélectivité molaire en dodécanone -2 est de 77 %. After 3 hours, it is found that 89.5% of the dodecene-1 has been transformed. The molar selectivity for dodecanone -2 is 77%.

EXEMPLE 2
On opère comme décrit dans l'exemple 1 mais avec 33,6 g d'octène-l, 176 g de tertio-butanol, 45 mg d'acétate de palladium et 130 g d'une solution aqueuse d'eau oxygénée à 30 %.EXAMPLE 2
The procedure is as described in Example 1 but with 33.6 g of octene-l, 176 g of tert-butanol, 45 mg of palladium acetate and 130 g of an aqueous solution of hydrogen peroxide at 30% .

Apès 6 heures de réaction, on observe que 95,2 % de l'octène -1 ont été transforms. After 6 hours of reaction, it is observed that 95.2% of the octene -1 have been transformed.

la séle-tivité molaire en octanone-2 est de 80 %.  the octanone-2 molar selectivity is 80%.

EXEMPlE 3
Dans un réacteur en verre calorifugé, on introduit 66 g de dodécène -1, 225 g de tertio butanol, 22,5 g d'acétate de palladium puis, goutte à goutte et sous violente agitation magnétique, 55 g d'une solution aqueuse à 70 % en poids d'eau oxygénée. On porte ensuite avec précaution à température de reflux.EXAMPLE 3
66 g of dodecene -1, 225 g of tert-butanol, 22.5 g of palladium acetate are then introduced into a heat-insulated glass reactor, then 55 g of an aqueous solution at 70% by weight of hydrogen peroxide. It is then brought carefully to reflux temperature.

En 6 heures de réaction, on convertit 62 % de dodécène -1. La sélectivité molaire en dodécanone -2. est de 84,5 %. In 6 hours of reaction, 62% of dodecene -1 is converted. Molar selectivity for dodecanone -2. is 84.5%.

EXEMPLE 4
On opère comme précédemment mais avec 33,6 g d'octène -1, 176 g de tertio butanol comme solvant, 45,5 mg d'acétate de palladium et 73 g d'eau oxygénée à 70 %.EXAMPLE 4
The procedure is as above, but with 33.6 g of octene -1, 176 g of tert-butanol as solvent, 45.5 mg of palladium acetate and 73 g of 70% hydrogen peroxide.

Après 6 heures de réaction, 91,6 % de l'octène -1 ont été convertis. La sélectivité en octanone-2 est de 91 %. After 6 hours of reaction, 91.6% of octene -1 was converted. The selectivity for octanone-2 is 91%.

EXEMPLE 5
On opère comme dans l'exemple 2 mais avec 236 g d'acide acétique à 100 % comme solvant.EXAMPLE 5
The procedure is as in Example 2 but with 236 g of 100% acetic acid as solvent.

Après 4 heures de réaction,on on constate que 96,7 % de l'octène -1 ont été transformés. La sélectivité molaire en octanone-2 est de 94,8 %.  After 4 hours of reaction, it is found that 96.7% of the octene -1 have been transformed. The molar selectivity for octanone-2 is 94.8%.

Claims (3)

REVENDICATIONS 1/ Procédé selon la revendication 6 du brevet principal dans lequel1 / Method according to claim 6 of the main patent in which l'oléfine est diluée dans un solvant organique choisi parmi les the olefin is diluted in an organic solvent chosen from alcools et les acides monocarboxyliques. alcohols and monocarboxylic acids. 2/ Procédé selon la revendication 1 dans lequel l'alcool est choisi2 / A method according to claim 1 in which the alcohol is chosen parmi l'alcool tertiobutyliqueD l'alcool tertioamylíque, le diméthyl-  among tertiary butyl alcohol, tertiary amyl alcohol, dimethyl- phénylcarbinol et l'éthylène glycol. phenylcarbinol and ethylene glycol. 3/ Procédé selon la revendication 1 dans lequel l'acide monocarboxylique3 / A method according to claim 1 wherein the monocarboxylic acid est choisi parmi l'acide acétique, l'acide propionique et I'acide is chosen from acetic acid, propionic acid and acid butyrique.  butyric.
FR7928154A 1978-12-18 1979-11-13 Carbonyl cpds. prodn. - by liq. phase oxidn. of olefin(s) with hydrogen peroxide or organic hydroperoxide using palladium complex catalyst (BE 12.6.80) Granted FR2469392A2 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
FR7928154A FR2469392A2 (en) 1979-11-13 1979-11-13 Carbonyl cpds. prodn. - by liq. phase oxidn. of olefin(s) with hydrogen peroxide or organic hydroperoxide using palladium complex catalyst (BE 12.6.80)
CH1095879A CH643226A5 (en) 1978-12-18 1979-12-11 PROCESS FOR THE MANUFACTURE OF CARBONYL COMPOUNDS BY OXIDATION OF OLEFINIC COMPOUNDS.
DE19792949847 DE2949847A1 (en) 1978-12-18 1979-12-12 METHOD FOR PRODUCING CARBONYL COMPOUNDS BY OXIDATION OF OLEFINS
IT28027/79A IT1126576B (en) 1978-12-18 1979-12-17 CARBONYLATE COMPOUNDS MANUFACTURING PROCESS FOR OXIDATION OF OLEFINIC COMPOUNDS
GB7943413A GB2037768B (en) 1978-12-18 1979-12-17 Manufacture of carbonyl compounds
US06/104,941 US4310704A (en) 1978-12-18 1979-12-18 Process for manufacturing methyl ketones by oxidation of terminal olefins
US06/265,488 US4379942A (en) 1978-12-18 1981-05-20 Process for manufacturing methyl ketones by oxidation of terminal olefins

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR7928154A FR2469392A2 (en) 1979-11-13 1979-11-13 Carbonyl cpds. prodn. - by liq. phase oxidn. of olefin(s) with hydrogen peroxide or organic hydroperoxide using palladium complex catalyst (BE 12.6.80)

Publications (2)

Publication Number Publication Date
FR2469392A2 true FR2469392A2 (en) 1981-05-22
FR2469392B2 FR2469392B2 (en) 1983-04-15

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FR7928154A Granted FR2469392A2 (en) 1978-12-18 1979-11-13 Carbonyl cpds. prodn. - by liq. phase oxidn. of olefin(s) with hydrogen peroxide or organic hydroperoxide using palladium complex catalyst (BE 12.6.80)

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