EP1467961A1 - Procede de preparation de 3,5,5-trimethylcyclohex-2-ene-1,4-dione - Google Patents

Procede de preparation de 3,5,5-trimethylcyclohex-2-ene-1,4-dione

Info

Publication number
EP1467961A1
EP1467961A1 EP02701264A EP02701264A EP1467961A1 EP 1467961 A1 EP1467961 A1 EP 1467961A1 EP 02701264 A EP02701264 A EP 02701264A EP 02701264 A EP02701264 A EP 02701264A EP 1467961 A1 EP1467961 A1 EP 1467961A1
Authority
EP
European Patent Office
Prior art keywords
process according
catalyst
reaction
solvent
oxygen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02701264A
Other languages
German (de)
English (en)
Inventor
Ralf Maassen
Volker HÄFNER
Steffen Krill
Jürgen Bilz
Georg Markowz
Klaus Huthmacher
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Degussa GmbH filed Critical Degussa GmbH
Publication of EP1467961A1 publication Critical patent/EP1467961A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/603—Unsaturated compounds containing a keto groups being part of a ring of a six-membered ring, e.g. quinone methides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • This invention relates to an improved process for the preparation of 3, 5, 5-trimethylcyclohex-2-ene-l, -dione (ketoisophorone) by oxidation of 3 , 5, 5-trimethyl-cyclohex- 3-en-l-one ( ⁇ -isophorone) .
  • Ketoisophorone is an important intermediate product in the synthesis of trimethylhydroquinone or trimethylhydroquinone esters, which in turn are an intermediate product in the synthesis of vitamin E.
  • KIP is furthermore an intermediate product for the preparation of various carotenoids, such as, for example, astaxanthine, zeaxanthine and canthaxanthine.
  • oxidation of ⁇ -isophorone to KIP is achieved by tert-butyl hydroperoxide in the presence of 10 mol% palladium acetate and an auxiliary base in yields of a maximum of 55%.
  • tert-butyl hydroperoxide makes the process unattractive for an industrial reaction.
  • the selectivity of this process can be increased to up to 96% by employing organic amines or alkali metal salts as additives, in addition to catalytic amounts of phospho- or silicomolybdic acid.
  • the maximum conversion which can be achieved in this way is only 59%, which necessitates a working up of the product solution which is expensive and not very desirable from economic aspects .
  • acetylacetonates of various transition metals can be employed as catalysts of the oxidation of ⁇ -isophorone by molecular oxygen.
  • long reaction times of more than 40 h and high temperatures of 100 2 C to 130 S C are necessary, and only unsatisfactory yields of 20% to 40% are obtained.
  • no economical process is known for the direct oxidation of ⁇ -isophorone to KIP, since the yield of the reaction by the processes described is low.
  • the oxidation of ⁇ -IP which can be obtained from ⁇ -isophorone by known processes, can be carried out considerably more efficiently.
  • the most economical variant of this oxidation also is the procedure using oxygen or an oxygen- containing gas as the oxidizing agent.
  • the yields in the oxidation reaction catalyzed by transition metal acetylacetonate can be increased to up to 56% by prior isomerization, mediated by sodium acetate, of ⁇ -isophorone to ⁇ -IP, at the same time somewhat lower temperatures of 25 9 C - 75 a C and shorter reaction times of > 26 h being necessary. Nevertheless, these results are still unsatisfactory.
  • EP-B 0 311 408 employs Mn tetraphenylporphyrin as the catalyst, in addition to triethylamine as a base and water as an additive. Optimum crude yields of 98% are obtained here using a solvent mixture of ethylene glycol dimethyl ether and methylene chloride. The use of a solvent mixture is not appropriate for an industrial realization both from economic and from safety aspects .
  • DE 26 10 254 discloses the oxidation of ⁇ -IP to KIP using manganese (II) - or cobalt-salen or related compounds as the catalyst.
  • a selectivity of the reaction catalyzed by manganese-salen of 100% is reported here in one example. Under the conditions described, this corresponds to a space/time yield of 0.09 kilograms of KIP per hour-liter (kg/h*l) .
  • hydroxyisophorone Another problem which has so far not been solved satisfactorily is the formation of by-products during the oxidation, in particular hydroxyisophorone, which is formed in an amount of between 5%-20% in the preparation by conventional processes, depending on the reaction procedure. Under optimum conditions, a minimum formation of hydroxyisophorone of 5% (based on the ⁇ -IP employed) can be obtained if manganese-salen is used as the catalyst in the system NEt 3 /water/diglyme. The formation of byproducts in this order of magnitude is not desirable from economic aspects .
  • ethers as the solvent for the oxidation reactions moreover involves the risk of formation of highly explosive peroxides already described.
  • diglyme is a very expensive solvent, which has an adverse effect on the preparation costs of the process, so that the use of diglyme as the solvent for the reaction investigated is not very desirable from economic aspects.
  • the object of the present invention is thus to discover, on the basis of the prior art, a suitable, stable reaction system, in particular solvent, which avoids the disadvantages described for the processes already known, which are in come cases considerable, while retaining or increasing the good selectivities and reaction yields, specifically in the catalyst system manganese-salen / auxiliary base / optionally water / co-additive.
  • This invention provides an improved process for the preparation of 3, 5, 5-trimethylcyclohex-2-ene-l, 4-dione (ketoisophorone, KIP) by oxidation of 3, 5, 5-trimethyl- cyclohex-3-en-l-one ( ⁇ -isophorone, ⁇ -IP) in the presence of an oxidizing agent and a catalyst system comprising a transition metal complex catalyst, an auxiliary base, possibly water, and a catalytically active co-additive chosen from the group consisting of:
  • Figure 1 depicts diagram showing the KIP yield as a function of the ⁇ -IP concentration.
  • Figure 2 depicts diagram showing the KIP yield as a function of the oxygen supplied.
  • co-additives are acetic acid, butyric acid, salicylic acid, oxalic acid, malonic acid, citric acid and further aliphatic or aromatic mono-, di- or tricarboxylic acids.
  • a ino acids such as e.g. glycine, leucine, methionine or aspartic acid, are also suitable.
  • aliphatic alcohols such as methanol, ethanol, butanol, isobutanol and tert-butanol, or phenol serve as the co-additive.
  • Co-additives which can form an enol structure such as e. g. acetoacetic esters, phenylacetone and, in particular, acetylacetone, are particularly advantageous.
  • Acetylacetone is particularly preferably employed as the co-additive, since it additionally allows higher reaction selectivities to be achieved than with other suitable co-additives .
  • a molar ratio of the co-additive to the catalyst of 1:1 to 100:1, preferably 4:1 to 40:1, based on the catalyst, can be employed.
  • Suitable carboxylic acid amides in the process according to the invention are dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide or mixtures thereof. Dimethylformamide is particularly preferred as the carboxylic acid amide.
  • the amount in which the suitable carboxylic acid amides can be used is not critical for carrying out the process according to the invention, but it is preferable to use carboxylic acid amides in amounts of 50 wt.% to 95 wt.%, preferably 65 wt.% to 85 wt.%, based on the total amount of the reaction mixture.
  • the oxygen supply in the carboxylic acid amides even had to increased up to at least about 0.8 liter of oxygen per hour and gram of ⁇ -IP. Not taking account of or not knowing these circumstances thus unavoidably leads to poor results in the reaction procedure in carboxylic acid amides, from which a supposedly lower suitability of carboxylic acid amides as the solvent for the reaction under consideration compared with the ethers and ketones described as having priority has been incorrectly assumed.
  • the catalyst system also has a significantly better stability in carboxylic acid amides than in ethers, which allows premixing of the reaction matrix in continuous operation of the process, without a drop in the selectivity of the reaction taking place over a period of time.
  • carboxylic acid amides Another great advantage of carboxylic acid amides is that the effect of the catalytically active co-additive described on the educt concentration which can be realized without a serious loss in selectivity is significantly more pronounced than, for example, in diglyme, which results in economic advantages in respect of the space/time yield of the reaction.
  • a selectivity of more than 85% is still observed, a value which can be achieved in diglyme only at educt concentrations up to a maximum of 20 wt.%.
  • the amount of auxiliary based employed can be reduced down to 10 mol%, based on the ⁇ -IP employed, without serious losses in the selectivity of the reaction which can be achieved occurring.
  • carboxylic acid amides as the solvent, in particular inexpensive dimethylformamide, offers an enormous economic advantage over the use of the very expensive ethylene glycol ethers, such as diglyme and ethylene glycol dimethyl ether, which have hitherto been described as the preferred solvents for achieving high selectivities .
  • ⁇ -IP is continuously or discontinuously brought into contact with the reaction matrix, which comprises the catalyst and the auxiliary base, as well as a catalytically active co-additive and optionally water and which is dissolved or suspended in a carboxylic acid amide as the solvent, and reacted with oxygen or an oxygen-containing gas mixture under normal pressure or increased pressure.
  • Catalysts which are used are the transition metal- containing complex catalysts mentioned in the prior art, such as manganese-salen, manganese-tetraphenylporphyrin and manganese-phthalocyanine, manganese-salen being preferred.
  • the catalyst is conventionally added in amounts of 0.001 to 3 wt.%, based on the ⁇ -IP, preferably in amounts of 0.05 to 1 wt.%.
  • the organic and inorganic bases known according to the prior art can be used as the auxiliary base, such as e.g.
  • alkylamines di- and trialkylamines , aromatic and aliphatic heterocyclic bases, sodium or potassium hydroxide solution or alcoholates, or a quaternary ammonium hydroxide, preferably trialkylamines, in particular triethylamine.
  • bases can be employed in conventional amounts, such as e.g. 5 to 60 mol%, based on the ⁇ -IP, amounts of 10 to 35 mol% being particularly preferred.
  • Carboxylic acid amides such as e.g. dimethylformamide (DMF) , diethylformamide (DEFA) and the corresponding acetamides, such as dimethylacetamide or diethylacetamide, are employed as the solvent in the process according to the invention.
  • the reaction is carried out in dimethylformamide.
  • the content of carboxylic acid amide in the reaction mixture is conventionally 50 wt.% to 95 wt.%, and amounts of 65 wt.% to 85 wt.% are preferably employed.
  • the water content in the total reaction mixture can vary between 0 and 30 wt.%. Without the addition of water, very high selectivities are achieved, but with uneconomical reaction times .
  • Water is therefore preferably employed as a reaction accelerator, in particular between 0.05 wt.% and 30 wt.%, preferably between 0.5 and 20 wt.%, particularly preferably between 0.5 wt.% and 5 wt.%, based on the total weight of the reaction mixture.
  • Oxidizing agents which can be employed in this invention are oxygen or oxygen-containing gas mixtures, such as e.g. air or oxygen diluted by addition of an inert gas, such as, for example, nitrogen.
  • the reaction can be carried out under normal pressure or increased pressure.
  • the reaction can be carried out under between 1 and 12 bar, depending on the volume content of oxygen in the oxidizing agent employed.
  • the reaction temperature can be between -30 2 C and 80 2 C, preferably between 10 2 C and 45 2 C.
  • the process according to the invention is simple to carry out and gives the reaction product in a good yield and high purity.
  • the reaction product can be isolated from the product mixture by the usual processes, in particular by vacuum distillation.
  • the yields were determined on an HP 5890 or an HP 6890 gas chromatograph using a J&W DB-5 capillary column of 30 m length, 0.32 mm internal diameter and 1 ⁇ m film thickness. Diethylacetamide was used as the internal standard. KIP, which was purified by distillation, was used as the reference substance.
  • the HPLC measurements were carried out on a system comprising a Biotronik BT 3035 UV detector, a Jasco 880 PU pump and a Spectra Physics Chrom Jet integrator.
  • the column used was an RP 18, 5 ⁇ , 250 x 4 mm internal diameter.
  • the KIP reference substance described above was used as the external standard.
  • Examples 23 to 26 illustrate the enormous influence the oxygen supply has on the ketoisophorone selectivity in the solvent DMF which can be achieved. Comparative Examples J to M demonstrate that such an effect is to be observed to only a small extent in the solvent diglyme, which is particularly preferred according to the prior art. Not knowing this sensitivity of the selectivity of the reaction in DMF to a deficient supply of oxygen thus unavoidably leads to poor results (Examples 23 to 24), from which a supposedly lower suitability of carboxylic acid amides as the solvent for the reaction under consideration compared with the ethers and ketones described as having priority in the prior art results .

Landscapes

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

Abstract

L'invention concerne un procédé amélioré de préparation de 3,5,5-triméthylcyclohex-2-ène-1,4-dione par oxydation de 3,5,5-triméthylcyclohex-3-èn-1-one en présence d'un agent d'oxydation et d'un système de catalyse comprenant un complexe de métaux de transition en tant que catalyseur, une base auxiliaire, éventuellement de l'eau et un co-additif actif du point de vue catalytique. Ce procédé est caractérisé en ce que des amides d'acide carboxylique sont employés en tant que solvant.
EP02701264A 2002-01-23 2002-01-23 Procede de preparation de 3,5,5-trimethylcyclohex-2-ene-1,4-dione Withdrawn EP1467961A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2002/000621 WO2003062184A1 (fr) 2002-01-23 2002-01-23 Procede de preparation de 3,5,5-trimethylcyclohex-2-ene-1,4-dione

Publications (1)

Publication Number Publication Date
EP1467961A1 true EP1467961A1 (fr) 2004-10-20

Family

ID=27589041

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02701264A Withdrawn EP1467961A1 (fr) 2002-01-23 2002-01-23 Procede de preparation de 3,5,5-trimethylcyclohex-2-ene-1,4-dione

Country Status (8)

Country Link
EP (1) EP1467961A1 (fr)
JP (1) JP2005526017A (fr)
KR (1) KR20040086284A (fr)
CN (1) CN1267396C (fr)
BR (1) BR0215533A (fr)
CA (1) CA2473941A1 (fr)
MX (1) MXPA04006987A (fr)
WO (1) WO2003062184A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105646196B (zh) * 2014-12-03 2018-02-23 中国科学院大连化学物理研究所 一种对甲基环己烯甲醛制备4‑甲基‑环己‑3‑烯‑1‑羧酸的方法
CN109438199B (zh) * 2018-09-20 2020-04-07 山东新和成维生素有限公司 一种连续高效氧化制备2,6,6-三甲基-2-环己烯-1,4-二酮的方法
CN117820092A (zh) * 2023-12-15 2024-04-05 万华化学集团股份有限公司 一种β-异佛尔酮制备4-氧代异佛尔酮的方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19619570A1 (de) * 1996-05-15 1997-11-20 Degussa Verfahren zur Herstellung von Ketoisophoron
DE19929362A1 (de) * 1999-06-25 2000-12-28 Basf Ag Verfahren zur Herstellung von Oxoisophoron unter Verwendung von Additiven
DE10062260A1 (de) * 2000-12-14 2002-06-20 Degussa Verfahren zur Herstellung von 3,5,5-Trimethylcyclohex-2-en-1-1,4-dion

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03062184A1 *

Also Published As

Publication number Publication date
JP2005526017A (ja) 2005-09-02
CN1267396C (zh) 2006-08-02
BR0215533A (pt) 2004-12-21
WO2003062184A1 (fr) 2003-07-31
CN1615291A (zh) 2005-05-11
CA2473941A1 (fr) 2003-07-31
MXPA04006987A (es) 2004-11-10
KR20040086284A (ko) 2004-10-08

Similar Documents

Publication Publication Date Title
Plietker et al. The acid accelerated ruthenium-catalysed dihydroxylation. Scope and limitations
US4096156A (en) Process for the catalytic manufacture of γ-butyrolactone
US3920753A (en) Method of producing glycolaldehyde
KR101736645B1 (ko) 에스테르 화합물의 제조 방법 및 그 방법에 이용하는 팔라듐 촉매
US4331608A (en) Liquid phase catalytic co-oxidation process
JP5524861B2 (ja) ケトンの製造方法
EP1467961A1 (fr) Procede de preparation de 3,5,5-trimethylcyclohex-2-ene-1,4-dione
Takai et al. Aerobic Oxygenation of Olefinic Compounds into the Corresponding. ALPHA.-Hydroxy Ketones Using the Catalyst System of OsO4 and Ni (II) Complex.
Pennequin et al. Palladium catalyzed oxidative carbonylation of alkenes by methyl formate
CN112469688A (zh) 1,3-双酰氧基-2-亚甲基丙烷的制造方法
JP3132100B2 (ja) カルボニル化合物の製造方法
KR870000767B1 (ko) 신나메이트 에스테르의 제조방법
US4739107A (en) Process for the preparation of a diester of a dicarboxylic acid
US4827023A (en) Process for the selective formation of dialkyl succinates
JP5613150B2 (ja) ケトンの製造方法
US5414137A (en) Process for preparing carbonyl compounds
JPH07149685A (ja) カルボニル化合物の製造方法
Takai et al. The Formation of 1, 4-Quinones by Oxovanadium (IV)-Complexes Catalyzed Aerobic Oxygenation of Fused Aromatic Compounds.
US5136105A (en) Oxidation of terminal olefins to aldehydes
US3502715A (en) Method for producing and stabilizing percarboxylic acid
JP2548590B2 (ja) 共役ジエンの選択的酸化カルボニル化方法
US4642371A (en) Process for the preparation of diesters of dicarboxylic acids
KR970000485B1 (ko) 2-(디알콕시메틸)카복실산 에스테르의 제조방법
US10843998B2 (en) Method for producing bis-acyloxylated exomethylene compound
JPH0648974A (ja) カルボニル化合物の製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20040618

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: DEGUSSA GMBH

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EVONIK DEGUSSA GMBH

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20070801