EP2188232A2 - Procédé de production de composés carbonyle aromatiques - Google Patents

Procédé de production de composés carbonyle aromatiques

Info

Publication number
EP2188232A2
EP2188232A2 EP08785792A EP08785792A EP2188232A2 EP 2188232 A2 EP2188232 A2 EP 2188232A2 EP 08785792 A EP08785792 A EP 08785792A EP 08785792 A EP08785792 A EP 08785792A EP 2188232 A2 EP2188232 A2 EP 2188232A2
Authority
EP
European Patent Office
Prior art keywords
sulfoxide
aromatic
mmol
alkyl
methyl
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Withdrawn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
EP08785792A
Other languages
German (de)
English (en)
Inventor
Klaus Forstinger
Thomas Sommer
Daniel Decker
Andreas Martin
Angela KÖCKRITZ
Michael Kant
Alexander Hofmann
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.)
Weylchem Frankfurt GmbH
Original Assignee
Weylchem Frankfurt 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 Weylchem Frankfurt GmbH filed Critical Weylchem Frankfurt GmbH
Publication of EP2188232A2 publication Critical patent/EP2188232A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
    • 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

Definitions

  • the present invention relates to a process for preparing an aromatic carbonyl compound by oxidation of a methyl or methylene group bonded to the aromatic, in which the aromatic is reacted in the presence of an oxidizing agent and a sulfoxide.
  • Aromatic carbonyl compounds are important intermediates or target products in the intermediate and fine chemicals industry.
  • environmentally friendly methods of direct oxidation of alkyl aromatics with atmospheric oxygen are used industrially.
  • liquid phase processes for example for the production of benzaldehyde
  • gas phase processes for example for the synthesis of methoxybenzaldehyde or para-chlorobenzaldehyde (see US Pat. No. 4,054,607, EP 0 723 949).
  • these methods are not generally applicable and suffer in part from low activities, low selectivities and the formation of by-products.
  • the risk of formation of by-products is high.
  • the oxidation is carried out in the presence of an oxidizing agent and a sulfoxide or sulfide added in catalytic amounts.
  • the sulfoxides or sulfides act as oxygen carriers in an oxidative environment.
  • dialkyl, alkylaryl and Diarylsulfoxide and their mixtures or corresponding sulfides There are no details in terms of conversion, selectivity and space-time yield with respect to combinations of certain alkyl compounds with certain sulfoxides or sulfides.
  • ionization potentials of substituted alkylaromatic compounds differ significantly from the unsubstituted toluene and thus has Type and location of the substitution Influence on the oxidation rate or the selectivity of the reaction.
  • the ionization potential of aromatics is crucial for the formation of radical cations RH + * , the first activation step in oxidation reactions of this type. Since only a few simple alkyl aromatics or corresponding oxidation products have tabulated ionization potentials, quantum chemical calculations were carried out for other compounds.
  • ionization potentials of solvents for example dimethyl sulfoxide (DMSO). It was surprisingly found that in DMSO sometimes high selectivities for the desired oxidation products occurred. Furthermore, it has been found that methyl aromatics, which can be oxidized in good yields into the aldehydes, have ionization potentials lower than that of DMSO. On the other hand, methyl aromatics with higher oxidation potentials than DMSO can not be oxidized or only poorly oxidized.
  • solvents for example dimethyl sulfoxide (DMSO)
  • the object of the present invention is to further improve yields and selectivities in the described catalytic oxidation of alkylaromatics to aromatic aldehydes with respect to an industrial application.
  • the invention is based on a process for the preparation of an aromatic carbonyl compound by oxidation of an aromatic bonded methyl or methylene group in which the aromatic is reacted in the presence of an oxidizing agent.
  • the invention is based on the finding that, surprisingly, the yield of aldehydes and the selectivity of the oxidation process can be increased if, in addition, a sulfoxide is present, wherein the ionization potentials of the aromatics to be oxidized and the sulfoxide are aligned with each other. If a maximum deviation of the ionization potentials of ⁇ 0.25 eV is maintained, the yield and selectivity with respect to the aldehydes are considerably increased. Selectivity increases of 50-100% are possible in comparison to combinations with higher deviations of the ionization potentials. The closer the ionization potentials of sulfoxide and aromatic are matched to each other, the higher the yield and selectivity with respect to the aldehydes. Without wishing to be bound by theory, it can be assumed that the formation of radical cations plays a decisive role in the first activation step of the oxidation reaction.
  • the invention thus achieves the above object by a process for the oxidation of alkylaromatics with an oxidizing agent in the presence of a sulfoxide, wherein a sulfoxide is selected for the oxidation of a specific aromatics, the ionization potential of the height of the ionization potential of the aromatic to be oxidized by a maximum ⁇ 0.25 eV, preferably by a maximum of ⁇ 0.2 eV, in particular by a maximum of ⁇ 0.1. eV deviates.
  • the alkylaromatic compound is a compound of formula (I)
  • A is a mononuclear or polynuclear aromatic ring system which may also contain heteroatoms, and
  • R 1 is C 1 -C 15 -alkyl, halogen, haloalkyl, alkoxy, carboxy, alkoxycarbonyl, cyano, amino, amido, sulfonyl, unsubstituted or substituted phenyl and unsubstituted or substituted phenoxy.
  • substituents R1 may be the same or different, i. be chosen independently.
  • A is an aromatic group of the formula (II)
  • the sulfoxide is a compound of formula (III),
  • R 2 - SO - R 3 (III) where R 2 and R 3 independently of one another represent substituted or unsubstituted radicals selected from among alkyl, aryl, naphthyl and biphenyl.
  • R2 or R3 carry one or more substituents selected from the group alkyl, halogen, haloalkyl, methoxy, carboxy, alkoxycarbonyl, cyano, amino, amido, sulfonyl, phenyl and phenoxy.
  • Particularly preferred compounds of the formula I are p, p'-dimethylbiphenyl, p, p'-dimethyl-biphenyl ether, p-methoxytoluene, 4-methyl-2'-cyano-biphenyl, p-xylene, p-bromotoluene , p-chlorotoluene, terephthalaldehyde and p-cyanotoluene.
  • Particularly preferred compounds of formula III are 1, 1'-dinaphthylsulfoxide, di-tert-butyl-sulfoxide, phenyl-benzylsulfoxide, naphthyl-methyl-sulfoxide, Diisopropyl sulfoxide, diphenyl sulfoxide, bis (p-chlorophenyl) sulfoxide, phenyl-methyl sulfoxide, diethyl sulfoxide, dimethyl sulfoxide, trifluoromethyl-phenyl-sulfoxide, bis (monofluoromethyl) sulfoxide, trifluoromethyl-methyl-sulfoxide and
  • peroxo compounds such as peroxodisulfate, oxone, hydrogen peroxide, alkyl peroxides, peracids, as well as molecular oxygen can be used. Preference is given to peroxodisulfate.
  • the ionization potentials of the sulfoxides and of the aromatics to be oxidized are determined by the B3LYP (Becke-3-Parameter-Lee-Yang-Parr) method.
  • LCAO linear combination of atomic orbital
  • the goal of quantum chemical molecular orbital methods is always to determine the energy of molecules. These are regarded as an ensemble of atomic nuclei and surrounding electrons in space. The electrons are described in quantum mechanical approximation by wave functions. These wave functions are approximated by basis sets (eg 3-21 G, 6-31 G * ), the larger the base set, the more accurate the calculation.
  • B3LYP / 6-31G * specifies the method and basis set with which the calculation should be performed.
  • the B3LYP (Becke-3-parameter Lee-Yang-Parr) method is a hybrid density functional theo (DFT) method that gives very good results for small molecules.
  • ionization potentials for the preferred aromatics and sulfoxides are summarized, which were determined by the B3LYP method with the basis set 6-31 G * . It should be noted that the values for ionization potentials stored in the NIST database were not determined according to standardized procedures and may therefore be subject to errors. Moreover, they are not completely available. ionization potential according to
  • the reaction is otherwise carried out in the manner known to those skilled in the art. Temperature, solvents, etc. are adapted to the aromatics to be oxidized. The reaction is generally conducted at temperatures of 40- 100 0 C, molar ratios aromatic: sulfoxide of from 25: 1 to 1: 1, preferably 10: 1 to 1, 1: 1, especially 5: 1 to 1, 2: 1 aromatic: Oxidizer from 1:50 to 1: 1 and carried out in a period of 1 to 10 hours.
  • the solvents used are strongly polar solvents such as water, acetonitrile, nitromethane, acetic acid, DMF and mixtures thereof, preferably water and acetonitrile.
  • Example 1 Preparation of p-chlorobenzaldehyde from p-chlorotoluene a) System p-chlorotoluene / dimethyl sulfoxide (not according to the invention)
  • the combined organic phases are collected and dried over Na 2 SO 4 .
  • the product composition is determined by GC or HPLC.
  • the yield of p-chlorobenzaldehyde is 38%.
  • the difference in the ionization potentials is 0.3 eV.
  • the yield of p-chlorobenzaldehyde is 50%. Compared to the reaction with DMSO as sulfoxide, the yield is thus higher by a factor of 1.32.
  • the difference in the ionization potentials here is 0.2 eV.
  • the yield of p-chlorobenzaldehyde is 14%. Compared to the reaction with DMSO as sulfoxide, the yield is only at a factor of 0.37. The difference in ionization potentials here is 0.6 eV.
  • the yield of p-bromobenzaldehyde is 34%.
  • the difference in ionization potentials is 0.4 eV.
  • the yield of p-bromobenzaldehyde is 66%. Compared to the reaction with DMSO as sulfoxide, the yield is thus higher by a factor of 1.94.
  • the difference in the ionization potentials here is 0.2 eV.

Landscapes

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

Abstract

L'invention concerne un procédé de production d'un composé carbonyle aromatique par oxydation d'un groupe méthyle ou méthylène lié à des composés aromatiques, procédé caractérisé en ce que le composé aromatique est mis à réagir en présence d'un agent d'oxydation et d'un sulfoxyde, et en ce qu'on sélectionne un sulfoxyde pour l'oxydation d'un composé aromatique spécifique, dont le potentiel d'ionisation s'écarte au maximum de ± 0,25 eV du potentiel d'ionisation du composé aromatique à oxyder.
EP08785792A 2007-09-07 2008-09-02 Procédé de production de composés carbonyle aromatiques Withdrawn EP2188232A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007042544 2007-09-07
PCT/EP2008/007147 WO2009033586A2 (fr) 2007-09-07 2008-09-02 Procédé de production de composés carbonyle aromatiques

Publications (1)

Publication Number Publication Date
EP2188232A2 true EP2188232A2 (fr) 2010-05-26

Family

ID=40219456

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08785792A Withdrawn EP2188232A2 (fr) 2007-09-07 2008-09-02 Procédé de production de composés carbonyle aromatiques

Country Status (3)

Country Link
US (1) US8338649B2 (fr)
EP (1) EP2188232A2 (fr)
WO (1) WO2009033586A2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116623198A (zh) * 2023-04-10 2023-08-22 南开大学 电化学氧化反应制备芳香羰基化合物的方法及芳香羰基化合物

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS584012B2 (ja) * 1975-07-21 1983-01-24 田辺製薬株式会社 アニスアルデヒドノセイホウ
DE19502805C2 (de) * 1995-01-30 2000-05-11 Hoechst Ag Verfahren zur Herstellung von Halogenbenzaldehyden
CH696355A5 (de) 2002-11-14 2007-05-15 Clariant Speciality Fine Chemi Katalytisches Verfahren zur Herstellung von Carbonyl-Verbindungen.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009033586A2 *

Also Published As

Publication number Publication date
WO2009033586A3 (fr) 2009-07-09
WO2009033586A2 (fr) 2009-03-19
US20100312017A1 (en) 2010-12-09
US8338649B2 (en) 2012-12-25

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