JPS61137835A - Production of aromatic ketone - Google Patents

Abstract

PURPOSE:To obtain an aromatic ketone useful as an intermediate of pharmaceuticals, economicaly at a high rate of reaction, by thermally decomposing bis(hydroperoxydialkylmethyl)benzene in the presence of a catalyst, an aromatic hydrocarbon solvent, water and an anionic surfactant. CONSTITUTION:The objective compound of formula II (R is R<1> or R<2>; R<1> and R<2> are lower alkyl; X is CR<1>R2OOH, CR<1>R<2>OH or ROH) (some of which are useful as ultraviolet absorber or its intermediate, etc.) can be produced by thermally decomposing the compound of formula I in the pressure of (a) a catalyst, e.g. heavy metal salt such as inorganic or organic ferrous or ferric salt, cuprous or cupric salt, etc., (b) an aromatic hydrocarbon solvent, (c) water, and (d) an anionic surfactant, preferably at about 70-140 deg.C. The reaction time necessary in the present process is about 1/3 of that of the process devoid of the component (d). 1-2 groups of two CR<1>R<2>OOH in the compound of formula I can be converted selectively to acyl groups in relatively high yield by properly selecting the decomposition ratio of the compound of formula I.

Description

Detailed Description of the Invention [Technical Field of the Invention] The present invention produces aromatic ketones from habis(hydroperoxydialkylmethyl)benzene (DHP), more specifically, acyl-α,α-dialkylbenzyl hydroperoxides as pharmaceutical intermediates. (KPO), or α,α-dialkylacyl phenylcarbinol (KO) useful as ultraviolet absorbers or intermediates thereof, and diacylbenzene (DK).

[Conventional technology]

Examples of hydroperoxydialkylmethyl groups, tij
As a known method for converting a 2-hydroperoxy-2-propyl group into an acetyl group, for example, JP-A No. 50-255
No. 41 discloses a method for producing acetophenone by heating cumene and hydroperoxide in the presence of a copper-containing catalyst, dimethylphenylcarbinol, and water.

Furthermore, in Japanese Patent Application Laid-open No. 50-40537, Ar-C (Rt
χHz)-OOH (in the formula, Ar is an aryl group, R1 and R2
represents an alkyl group. A method is disclosed for producing aryl ketones by reacting tertiary hydroperoxides coated with ) in the presence of a copper-containing catalyst, water, and an organic solvent containing phenol.

, JP-A No. 50-40537 discloses that the hydroperoxydialkylmethyl group of dihydroperoxide of bis(hydroperoxydialkylmethyl)benzene can also be converted to an acyl group; In all of the examples given, the tertiary hydroperoxide is a monohydroperoxide of cumene hydroperoxide, and no examples are given where the tertiary hydroperoxide is a dihydroperoxide. Therefore, when the method of the publication is applied to dihydroperoxides, it is unclear how selectively only one of the two hydroperoxydialkylmethyl groups can be converted into an acyl group.

[Problems to be Solved by the Invention] The present inventors converted the hydroperoxydialkylmethyl group of DHP into an acyl group to create KP○, KO and D
A method for producing an aromatic ketone of K and accelerating the conversion reaction was investigated.

[Structure of the invention]

As a result, the inventors discovered that the above object could be achieved by employing the method described below, and completed the present invention.

That is, according to the uninvented method, bis(hydroperoxy7dialkylmethyl)benzene supported by the general formula (1) (wherein R1 and R2 represent lower alkyl groups) is catalyzed by the aromatic compound (a). (in a hydrocarbon solvent), water (C), and an anionic surfactant (general formula (n) characterized by being thermally decomposed in the presence of Φ (wherein, R is R1 in general formula (1) or R2, X 1iHOo -C(R,)(Rt)
-nohi)'o heroxydialkylmethyl group, HO-C
A method is provided for producing an aromatic ketone represented by (R,)(R,)-, which represents a hydroxy7dialkylmethyl group or RCO-, an acyl group.

Bis(hydroperoxydialkylmethyl)benzene (DHP) used in the method of the present invention has the general formula (1
) (wherein R1 and R2 represent lower alkyl groups), specifically, bis(2-hydroperoxy-2-propyl)benzene, bis(2-hydroperoxy-2-propyl), 2-butyl)benzene, bis(3-hydroperoxy-6-pentyl)benzene (
All of the above are m-integrated and p-integrated), among which m-bis(2-hydroperoxy-2
-7'bill) The use of benzene is preferred. In addition to using these DHPs in pure form in the method of the present invention,
Dialkylbenzenes corresponding to these DHPs, such as diisopropylbenzene.

An oxidized mixture of di(2-7'thyl)benzene and di(3-pentyl)benzene (all of the above m-unit and di-unit) can also be used as a raw material for the reaction. The oxidized mixture is obtained by oxidizing dialkylbenzene using a known method, for example, with a molecular enzyme in the presence of an aqueous alkaline solution. The oxidation mixture contains dialkylbenzene monohydroperoxide, dialkylbenzene monocarbinol, dialkylbenzene dicarbinol, etc. as oxidation byproducts other than DHP, but the amount of these oxidation byproducts is usually 100% by weight of DHP. Although the amount of the oxidized by-product is about 20 to 90 parts by weight, the presence of the oxidized by-product does not interfere with the reaction of the present invention. DHPJ can also be obtained by oxidizing such an oxidized mixture with an oxidizing agent such as hydrogen peroxide.
Raw materials with even higher degrees of strength may also be used.

In the present invention, the dihydroperoxide (DHP) is heated in the presence of a catalyst (gradient, aromatic hydrocarbon solvent (b), water (C), and anionic surfactant (d)) to produce the desired aromatic aroma. The family keto/ is produced.

The catalyst (a) used in the present invention includes iron compounds such as inorganic and organic ferrous salts and ferric salts such as iron sulfate, iron ammonium sulfate, iron nitrate, iron acetate, iron butyrate, and iron sulfate steel. , copper nitrate, copper perchlorate, copper chloride, copper acetate, propionate,
Examples include inorganic and organic cuprous salts such as copper butyrate, and heavy metal salts such as cupric salts. The amount of the catalyst used is usually about 1 to about 50 parts per 100 parts by weight of the DHP.
M parts, preferably from about 2 to about 20 parts by weight.

The aromatic hydrocarbon solvent (b) used in the method of the present invention is used as a solvent for DHP, and specifically includes benzene, toluene, xylene, ethylpentene, cumene, diimprobilbe/se/, trimethylbenzene, diethylbenzene, α-methyl Examples include styrene, but among these, those with relatively low boiling points such as benzene, toluene, etc. are preferred. In addition, when the above-mentioned oxidized mixture of dialkylbenzene is used as a reaction raw material, the unoxidized dialkylbenzene in the mixture serves as the aromatic hydrocarbon solvent (b). The amount of the solvent (b) used in the invention is usually about 50 parts by weight or more, preferably about 80 to 1,000 parts by weight, per 100 parts by weight of the DHP.

In the method of the present invention, the reaction is carried out in the presence of water (C) in the system, and the amount of water in this case is usually about 100 parts by weight or more, preferably about 2 parts by weight, based on 100 parts by weight of the DHP.
00 to about 2,000 parts by weight.

Specifically, the anionic surfactant used in the method of the present invention includes sodium dotecylphenyl sulfonate (
Sodium alkylphenyl sulfonate such as "trade name", ) SY-53), sodium salt of C16α-olefin sulfonic acid with an average number of carbon atoms of 16 (trade name *, ) Rivola: /1400 and DT-95), magnesium salt (D
T-95Mg) and calcium salt (Riboran 1400
(*) Lion Corporation! the law of nature. The amount of the anionic surfactant used is usually about 10 pI) m45,000 ppm% of water.
Preferably it is about 50 ppm to about 11000 ppm.

The reaction of the present invention involves the above-mentioned DHP, a catalyst (an aromatic hydrocarbon solvent, water (C), and an anionic surfactant (C)).
It is carried out by heating and stirring the mixture consisting of d). The reaction temperature in this case is usually about 60 to about 160°C, preferably about 70 to about 140°C, and the reaction time is about 200 to about 140°C.
It takes about 15 hours.

The aromatic ketone obtained by the method of the present invention has the general formula (
n) (wherein, R is either R1 or R2 in general formula (1), Xfd HOO-C(R+XRz)-(D
h)"o peroxydialkylmethyl group, HO-C(
R, XR2)-hydroxydialkylmethyl group or R
is an aromatic ketone represented by (representing an acyl group of CO-), and specifically, the ketone is acetyl-α, α-
Dimethylbenzyl hydroperoxide, acetyl-α-
KPO1α, α-dimethylacetylphenylcarbinol, α-methyl- KC such as α-ethylacetylphenylcarbinol, α-methyl-α-ethylpropionylphenylcarbinol, α,α-diethylglobionyl phenylcarbinol, and diacetylbenzene, acetylglobionylbenzene, siglobionylbenzene, etc. Among them, m-acetyl-α is an example.

Alpha-dimethylbenzyl hydroperoxide, alpha, alpha-dimethyl-m-acetylphenyl carbinol and diacetylbenzene are better. .

In the method of the present invention, when KPO is the target product of the reaction, the decomposition rate of DHP is usually about 45 to 85%, preferably about 55 to 80%, and when DK is the target product of the reaction The decomposition rate of DHP is usually in the range of 75 to 100%, preferably 85 to 100%.

In the method of the present invention, after the reaction is completed, KPO, !, is extracted from the reaction mixture using, for example, an aqueous solution of caustic soda, or distilled in a high vacuum. : DK can be separated.

〔Effect of the invention〕

By employing the method of the present invention, aromatic ketones of KPO, KG and DK can be obtained from DHP. In this case, by selecting the decomposition rate of DHP as described above, DH
KPO and DK can be obtained by converting one or two of the two hydroxydialkylmethyl groups of P into an acyl group in a relatively high yield.

In addition, since the reaction is carried out with an anionic surfactant present in the reaction system, the reaction rate can be increased, so the reaction time can be reduced to about 1/3 compared to when the surfactant is not used, so the effect is Industrially useful.

[Embodiments of the invention]

Hereinafter, the method of the present invention will be explained in more detail with reference to Examples.

Example 1 m-diisopropylbenzene dihydroperoxide (m
-DHP) 100 weight tS of liquid phase oxide of m-Si7FcxHilbenzene containing 65 wt% was dissolved in 90 parts by weight of toluene. The aqueous phase obtained by dissolving 3 parts by weight of GuS O4-5H,014,3ik in 380 parts by weight of water was charged into a flask equipped with a stirrer and a reflux condenser, and the above-mentioned DHP solution and anionic surfactant were added as " 200 ppm of "Riborane 1400 (trade name)" based on the amount of water was added, and the mixture was heated and stirred at 87° C. and reacted for 1.5 hours. As a result, K in the oil phase was 6.8 wt%ty) m-KPO1
6.8 wt% m-KC and 7. Owt% m-DK
I got it.

m-DHP conversion rate was 86 mol%, m-KPOlm-KC
and the selectivity of m-DK were 22 mol% and 28 mol%, respectively.
and 33 mol%.

Examples 2 to 6 Reactions similar to those in Example 1 were carried out by changing the type of surfactant, the amount used, the reaction temperature, and the reaction time as shown in Table 1.

The results obtained are shown in Table 1.

Comparative Example 1 Table 1 shows the results of the same procedure as in Example 6 except that no surfactant was used.

Comparative Example 2 Table 1 shows the results of the same procedure as in Comparative Example 1 except that the reaction time was 3 hours.

Comparative Examples 3 to 4 In Comparative Example 1, the reaction was carried out for 1 hour and 4 hours using 95 parts by weight of the catalyst and 1% of the nonionic surfactant (Dobanol EO). The results are shown in Table 1.

Examples 7-9 m-diisopropylbenzene dihydroperoxide (m
-D) IP) (purity 994%) 100 parts by weight was dissolved in 400 ill-1i of m-xylene. A solution prepared by dissolving 5 parts by weight of the iron sulfate catalyst shown in Table 2 in 400 parts by weight of water was charged into a flask equipped with a stirrer and a reflux condenser. Table 2 shows the results of adding 5Y-53 as an activator to water and reacting at 70°C.

Comparative Example 5 Table 2 shows the results of the same procedure as in Example 8 except that m-diisopropylbenzene dihydroperoxide (m-DHP) with a purity of 994% was used and no surfactant was added.

Claims (1)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, R^1 and R^2 represent lower alkyl groups) bis(hydroperoxydialkylmethyl)
General formula [II] characterized in that benzene is thermally decomposed in the presence of a catalyst (a), an aromatic hydrocarbon solvent (b), water (c) and an anionic surfactant (d) ▲Mathematical formula, chemical formula , tables, etc.▼[II] (In the formula, R is either R^1 or R^2 in the general formula [I], and X is HOO-C(R_1)(R_2
)- hydroperoxydialkylmethyl group, HO-C
A method for producing an aromatic ketone represented by (R_1) (R_2) - hydroxydialkylmethyl group or RCO- acyl group).