EP2188232A2

EP2188232A2 - Method for producing aromatic carbonyl compounds

Info

Publication number: EP2188232A2
Application number: EP08785792A
Authority: EP
Inventors: Klaus Forstinger; Thomas Sommer; Daniel Decker; Andreas Martin; Angela KÖCKRITZ; Michael Kant; Alexander Hofmann
Original assignee: Weylchem Frankfurt GmbH
Current assignee: Weylchem Frankfurt GmbH
Priority date: 2007-09-07
Filing date: 2008-09-02
Publication date: 2010-05-26
Also published as: US8338649B2; WO2009033586A3; US20100312017A1; WO2009033586A2

Abstract

The invention relates to a method for producing aromatic carbonyl compounds by oxidation of a methyl or methylene group bound to the aromatic compound. According to said method, the aromatic compound is reacted in the presence of an oxidant and a sulfoxide, a sulfoxide being selected for oxidizing a specific aromatic compound, which sulfoxide has an ionization potential that deviates from the ionization potential of the aromatic compound to be oxidized by not more than ± 0.25 eV.

Description

Process for the preparation of aromatic carbonyl compounds

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.

Technological background and state of the art

Aromatic carbonyl compounds (aldehydes, ketones) are important intermediates or target products in the intermediate and fine chemicals industry. In addition to classical synthesis methods, for example using benzene chlorides, environmentally friendly methods of direct oxidation of alkyl aromatics with atmospheric oxygen are used industrially. There are known liquid phase processes, for example for the production of benzaldehyde, as well as gas phase processes, for example for the synthesis of methoxybenzaldehyde or para-chlorobenzaldehyde (see US Pat. No. 4,054,607, EP 0 723 949). However, these methods are not generally applicable and suffer in part from low activities, low selectivities and the formation of by-products. In particular, when there are further substituents on the aromatic ring system, the risk of formation of by-products is high.

WO 2004/043891 discloses a catalytic oxidation process for preparing aliphatic and aromatic carbonyl compounds from starting materials which contain at least one aliphatic and / or aromatically bound functional group of the formula - [- CH (R) -X] _n where R = H, alkyl or aryl and X = H have. 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. There are mentioned 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.

Furthermore, it is known from the thesis of F. Antognoli (ETH Zurich, 2003) that the ionization potential can be used to assess the reactivity of various substituted aromatics, 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.

Furthermore, ionization potentials of solvents, for example dimethyl sulfoxide (DMSO), are also indicated in the above-mentioned work. 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.

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.

Preferably, the alkylaromatic compound is a compound of formula (I)

where a = 1 - 3 and b = 0 - 4, 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.

If more than one substituent R1 is present, ie b = 2, 3 or 4, the substituents R1 may be the same or different, i. be chosen independently.

Preferably A is an aromatic group of the formula (II)

C (6 + 4m) -nN _n H (6 + 2m) -xyn (H) where m = 0 - 2. and n = 0 - 2., and x = 1-3 and y = 1-4, wherein (x + y ) <((6 + 4m) -n).

Furthermore, it is preferred if 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.

Particularly preferred 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

Bis (trifluoromethyl) sulfoxide.

As the oxidizing agent, peroxo compounds such as peroxodisulfate, oxone, hydrogen peroxide, alkyl peroxides, peracids, as well as molecular oxygen can be used. Preference is given to peroxodisulfate.

Finally, it is preferred if 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.

Molecular orbital calculations are based on the LCAO (linear combination of atomic orbital) method. 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.

In the following Tables 1 and 2 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

Aromat B3LYP / 6-31G * p, p'-dimethyl-biphenyl 7.5 p, p'-dimethyl-biphenyl ether 7.5 p-methoxytoluene 7.8

4-methyl-2'-cyano-biphenyl 8.1 p-xylene 8.3 p-bromotoluene 8.4 p-chlorotoluene 8.5

Terephthalaldehyde 9.5 p-cyanotoluene 9.7

Table 1

ionization potential according to

Sulfoxide (SO) B3LYP / 6-31G *

1, 1'-dinaphthyl-SO 7,5

Di-tert-butyl-SO 7,9

Phenyl benzyl-SO 7,9

Naphthyl-methyl-SO 7,9

Diisopropyl-SO 8,2

Diphenyl-SO 8,2

Bis (p-chlorophenyl) -SO 8,3

Phenyl-methyl-SO 8,4

Diethyl-SO 8,5

Dimethyl-SO 8,8

Trifluoromethyl-phenyl-SO 9,1

Bis (monofluoromethyl) -SO 9.5

Trifluoromethyl-methyl-SO 9,8 Bis (trifluoromethyl) -SO 10,6

Table 2

From these data calculated with the B3LYP method pairs can be formed consisting of aromatic and sulfoxide, in which the ionization potential by a maximum of ± 0.25 eV, preferably by ± 0.2 eV, in particular by ± 0.1. eV differs. Table 3 names some preferred combinations according to the invention.

Aromatic sulfoxide (s) p, p'-dimethyl-biphenyl 1, 1'-dinaphthyl-SO p, p'-dimethyl-biphenyl ether 1, 1'-dinaphthyl-SO p-methoxytoluene di-tert-butyl, phenyl-benzyl - and naphthyl-methyl-SO

4-methyl-2'-cyano-biphenyl diisopropyl, diphenyl and bis (p-chlorophenyl) -SO p-xylene diisopropyl, diphenyl, bis (p-chlorophenyl) -,

Phenyl-methyl- and diethyl-SO p-bromotoluene diisopropyl-, diphenyl-, bis (p-chlorophenyl) -,

Phenyl-methyl- and diethyl-SO p-chlorotoluene bis (p-chlorophenyl) -, phenyl-methyl- and diethyl-SO

Terephthalaldehyde bis (monofluoromethyl) -SO p -cyanotoluene trifluoromethyl-methyl-SO

Table 3

It has surprisingly been found that the oxidation process can be carried out with high yields and good selectivity, if reference is made to the pairs of aromatic educt and sulfoxide mentioned in Table 3.

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.

The following examples are intended to illustrate the invention in more detail, without, however, restricting it to the specific embodiments described.

Example 1: Preparation of p-chlorobenzaldehyde from p-chlorotoluene a) System p-chlorotoluene / dimethyl sulfoxide (not according to the invention)

In a purged with argon, at reaction temperature (70 ⁰ C) preheated 500 ml of 3-necked flask 5.06 g (40 mmol) of 4-chlorotoluene, 90 ml of acetonitrile and 2 ml (28.2 mmol) of dimethyl sulfoxide with stirring (DMSO). To this is added 187.3 mg (0.75 mmol) of CuSO ₄ .5H ₂ O and 81.8 mg (0.30 mmol) of FeSO ₄ .7H ₂ O dissolved in 15 ml of water. The solution is 10 min. strongly stirred. Then, with further vigorous stirring within 60 min. a solution of 22 g of Na ₂ S ₂ O ₈ (92.4 mmol) in 60 ml of water was added by means of a syringe pump. The reaction solution is then stirred at 70 ^° C. for a further 3 hours. After completion of the reaction and cooling to room temperature, ethyl acetate is added, the biphasic mixture is separated and the aqueous phase exhaustively extracted with more ethyl acetate.

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.

b) System p-chlorotoluene / (methylphenyl) sulfoxide (according to the invention)

In a purged with argon, at reaction temperature (70 ⁰ C) preheated 500 ml of 3-necked flask 5.06 g (40 mmol) of 4-chlorotoluene, 90 ml of acetonitrile and 3.96 g (28.2 mmol ) (Methylphenyl) sulfoxide. To this is added 187.3 mg (0.75 mmol) of CuSO ₄ .5H ₂ O and 81.8 mg (0.30 mmol) of FeSO ₄ .7H ₂ O dissolved in 15 ml of water. The solution is 10 min. strongly stirred. Then, with further vigorous stirring within 60 min. a solution of 22 g of Na ₂ S ₂ O ₈ (92.4 mmol) in 60 ml of water was added by means of a syringe pump. The reaction solution is then stirred at 70 ^° C. for a further 3 hours.

After the reaction is complete and cooled to room temperature, ethyl acetate is added, the biphasic mixture is separated and the aqueous phase exhaustively extracted with more ethyl acetate.

The yield of p-chlorobenzaldehyde is 58%. Compared with the reaction with DMSO as sulfoxide, the yield is thus higher by a factor of 1.53. The difference in the ionization potentials here is only 0.1 eV. c) system p-chlorotoluene / bis (p-chlorophenyl) sulfoxide (according to the invention)

In a purged with argon, at reaction temperature (70 ⁰ C) preheated 500 ml of 3-necked flask 5.06 g (40 mmol) of p-chlorotoluene, 90 ml of acetonitrile and 7.64 g (28.2 mmol ) Added bis (p-chlorophenyl) sulfoxide. To this is added 187.3 mg (0.75 mmol) of CuSO ₄ .5H ₂ O and 81.8 mg (0.30 mmol) of FeSO ₄ .7H ₂ O dissolved in 15 ml of water. The solution is 10 min. strongly stirred. Then, with further vigorous stirring within 60 min. a solution of 22 g of Na ₂ S ₂ Os (92.4 mmol) in 60 ml of water was added by means of a syringe pump. The reaction solution is then stirred at 70 ^° C. for a further 3 hours.

After completion of the reaction and cooling to room temperature, ethyl acetate is added, the biphasic mixture is separated and the aqueous phase exhaustively extracted with more ethyl acetate.

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.

d) System p-Chiortoluol / (trifluoromethyl-phenyl) sulfoxide (comparative)

In a purged with argon, at reaction temperature (70 ⁰ C) preheated 500 ml of 3-necked flask 5.06 g (40 mmol) of 4-chlorotoluene, 90 ml of acetonitrile and 5.48 g (28.2 mmol ) (Trifluoromethyl-phenyl) sulfoxide. To this is added 164.8 mg (0.66 mmol) of CuSO ₄ .5H ₂ O and 60 mg of FeSO ₄ .7H ₂ O (0.22 mmol) dissolved in 15 ml of water. The solution is 10 min. strongly stirred. Then, with further vigorous stirring within 60 min. a solution of 22 g of Na ₂ S ₂ O ₈ (92.4 mmol) in 60 ml of water was added by means of a syringe pump. The reaction solution is then stirred for a further 3 h at 70 ° C. After completion of the reaction and cooling to room temperature, ethyl acetate is added, the biphasic mixture is separated and the aqueous phase extracted exhaustively with more ethyl acetate.

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.

Example 2 Preparation of p-bromobenzaldehyde from p-bromotoluene a) System p-bromotoluene / dimethyl sulfoxide (not according to the invention)

In a purged with argon, at reaction temperature (7O ⁰ C) preheated 500 ml of 3-necked flask with stirring 6.84 g (40 mmol) of 4-bromotoluene, 80 ml of acetonitrile and 1, 8 ml (25.4 mmol ) Dimethyl sulfoxide (DMSO). To this is added 149.8 (0.60 mmol) CuSO ₄ .5H ₂ O and 95.5 mg (0.35 mmol) FeSO ₄ .7H ₂ O dissolved in 15 ml water. The solution is 10 min. strongly stirred. Then, with further vigorous stirring within 60 min. a solution of 21 g of Na ₂ S ₂ Os (88.2 mmol) in 70 ml of water was added by means of a syringe pump. The reaction solution is then stirred for a further hour at 70.degree.

After the reaction and cooling to room temperature, methylene chloride is added, the two-phase mixture is separated and the aqueous phase extracted exhaustively with more methylene chloride.

The yield of p-bromobenzaldehyde is 34%. The difference in ionization potentials is 0.4 eV.

b) System p-bromotoluene / diphenylsulfoxide (according to the invention)

In a purged with argon, at reaction temperature (70 ° C) preheated 500 ml 3-necked flask with stirring 6.84 g (40 mmol) 4 Bromotoluene, 80 ml of acetonitrile and 5.14 g (25.4 mmol) of diphenylsulfoxide (IP = 8.2 / 8.6). To this is added 149.8 (0.60 mmol) CuSO ₄ .5H ₂ O and 95.5 mg (0.35 mmol) FeSO ₄ .7H ₂ O dissolved in 15 ml water. The solution is 10 min. strongly stirred. Then, with further vigorous stirring within 60 min. a solution of 21 g of Na ₂ S ₂ Os (88.2 mmol) in 70 ml of water was added by means of a syringe pump. The reaction solution is then stirred for a further hour at 70.degree.

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.

c) System p-bromotoluene / di (tert-butyl) sulfoxide (comparative)

In a purged with argon, at reaction temperature (70 ⁰ C) preheated 500 ml of 3-necked flask with stirring 6.84 g (40 mmol) of 4-bromotoluene, 80 ml of acetonitrile and 4.12 g (25.4 mmol ) Di (tert-butyl) sulfoxide (IP = 7.9 / 8.2). To this is added 149.8 (0.60 mmol) CuSO ₄ .5H ₂ O and 95.5 mg (0.35 mmol) FeSO ₄ .7H ₂ O dissolved in 15 ml water. The solution is 10 min. strongly stirred. Then, with further vigorous stirring within 60 min. a solution of 21 g of Na ₂ S ₂ O ₈ (88.2 mmol) in 70 ml of water was added by means of a syringe pump. The reaction solution is then stirred for a further hour at 70 ^° C.

After the reaction and cooling to room temperature, methylene chloride is added, the two-phase mixture is separated and the aqueous phase exhaustively extracted with more methylene chloride. The yield of p-bromobenzaldehyde is 15%. Compared to the reaction with DMSO as sulfoxide, the yield is only at a factor of 0.44. The difference in the ionization potentials here is 0.5 eV.

Claims

claims

1. A process for the preparation of an aromatic carbonyl compound by oxidation of a bound to the aromatic methyl or methylene group in which the aromatic is reacted in the presence of an oxidizing agent and a sulfoxide, characterized in that a combination of sulfoxide and aromatic is selected whose ionization potentials, calculated according to Becke-3 parameters-Lee-Yang-Parr method, not more than ± 0.25 eV differ from each other.

2. The method of claim 1, wherein the aromatic compound of the formula (I)

where a = 1 - 3 and b = 0 - 4;

A is a mononuclear or polynuclear aromatic ring system which may also contain heteroatoms and

R 1 represents C 1 -C ₅ -alkyl, halogen, haloalkyl, alkoxy, carboxy, alkoxycarbonyl, cyano, amino, amido, sulfonyl, unsubstituted or substituted phenyl and unsubstituted or substituted phenoxy.

3. The method of claim 2, wherein A is an aromatic group of the formula (II)

4. The method according to any one of the preceding claims, wherein the sulfoxide is a compound of formula (III)

R 2 - SO - R 3 (III) wherein R 2 and R 3 independently of one another represent substituted or unsubstituted radicals selected from the group consisting of alkyl, aryl, naphthyl and biphenyl.

5. The method of claim 4, wherein 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.

6. The method according to any one of the preceding claims, wherein a sulfoxide is selected, the ionization potential of the height of the ionization potential of the aromatic to be oxidized by not more than ± 0.2 eV, in particular by not more than ± 0.1. eV deviates.