JPH0830039B2 - Method for producing aromatic carbonate compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an aromatic carbonate compound, and more particularly to a phenol compound and a di-aliphatic carbonate or an aliphatic aromatic carbonate. The present invention relates to a method for producing an aromatic carbonate in a high yield, which is easy to purify, by reacting the above in the presence of a specific catalyst.

(Prior Art and Its Problems) A phenolic compound is reacted with a dialiphatic carbonate or an aliphatic aromatic carbonate to produce an aromatic carbonate compound composed of an aliphatic aromatic carbonate, a diaromatic carbonate or a mixture thereof. It is well known that this reaction is represented by the following formula:

Or 2ROCO ₂ ArArOCO ₂ Ar + ROCO ₂ R (3) However, among the above reactions, the reactions of (1) and (2) are
Since the equilibrium constants K ₁ and K ₂ shown below are low and the equilibrium is biased toward the raw material system and the reaction rate is slow, ROCO ₂ Ar and ArOCO
_It has the drawback that the yield of ₂ Ar is very low.

Therefore, many attempts have been made to find a suitable catalyst for improving the yield in this reaction system.

For example, JP-A-51-105032 describes a Lewis acid and a metal compound and a transition metal compound capable of forming a Lewis acid. Preferred examples include AlX ₃ , TiX ₃ ,
TiX ₄ , UX ₄ , VOX ₃ , VX ₅ , ZnX ₂ and FeX ₃ (X is halogen, acetoxy, alkoxy, aryloxy) are exemplified.

However, since Lewis acid is a compound having a corrosive property, it is not preferable for a reaction apparatus and the like, and the method of using the compound as a catalyst also has a low yield of a target product and is industrially excellent. Is hard to say.

The object of the present invention is to find a catalyst having sufficient activity from compounds that have not been known as conventional catalysts, and to use it to eliminate the above-mentioned drawbacks, and to obtain aromatic compounds in high yield in a short time. It is to provide a method for producing carbonate.

(Means for Solving Problems) The present invention has been made in order to achieve the above-mentioned object, and the reaction of a phenol compound with a di-aliphatic carbonate or an aliphatic aromatic carbonate of a specific catalyst is performed. It is characterized by being performed in the presence.

That is, according to the present invention, a phenol compound is reacted with a dialiphatic carbonate or an aliphatic aromatic carbonate to give an aromatic carbonate compound selected from an aliphatic aromatic carbonate, a diaromatic carbonate and a mixture thereof. A method for producing, characterized in that one or more compounds selected from the group consisting of Sc, Cr, Mo, W, Mn, Au, Ga, In, Bi, Te and lanthanoids are used as a catalyst. A method is provided.

Further, according to the present invention, the aliphatic aromatic carbonate produced by the above method, or a mixture of the aliphatic aromatic carbonate and the diaromatic carbonate is further heated in the presence of a catalyst to give the diaromatic carbonate. A method of manufacturing is provided.

(Function) The present invention finds a novel compound having excellent catalytic activity, which has not been known as a catalyst, when reacting a phenol compound with a dialiphatic carbonate or an aliphatic aromatic carbonate, and uses this as a catalyst. This is based on the new finding that an aromatic carbonate compound can be produced with a high yield, and that according to this method, product separation and catalyst recovery can be easily performed. .

(Explanation of Preferred Embodiments) Phenol Compound The phenol compound in the present invention is represented by the general formula [I] ArOH ... [I], wherein Ar represents an aromatic residue, and a substituted or unsubstituted benzene ring, It represents a naphthalene ring, an anthracene ring, a tetralin ring or the like.

Specifically, phenol, o, m, p-cresol, o, m, p
-Chlorophenol, o, m, p-Ethylphenol, o, m, p
-(Iso) propylphenol, o, m, p-phenoxyphenol, o, m, p-phenylphenol, o, m, p-methoxyphenol, o, m, p-nitrophenol, 2,6-dimethylphenol, 2,4-dimethylphenol, and
3,4-dimethylphenol, 2,6-dibutylphenol,
Examples thereof include α-naphthol, β-naphthol and β-anthrol, and of these, phenol is most preferably used.

Dialiphatic Carbonate The aliphatic carbonate in the invention has the general formula [II] (In the formula, R ′ is a monovalent aliphatic hydrocarbon group), more specifically, R ′ is preferably an alkyl group or a cycloalkyl group, and two R ′ May be linked to each other, and the alkyl group is a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples thereof include a butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, and an octyl group.The cycloalkyl group has 4 to 7 ring carbon atoms, for example,
Examples thereof include a cyclobutyl group, a cyclopentyl group, a methylcyclohexyl group, a cyclohexyl group, and a cycloheptyl group. Further, an ethylene group is exemplified as one in which two R's are linked.

Specifically as the compound represented by the above formula [II],
Examples thereof include dimethyl carbonate, diethyl carbonate, di-normal butyl carbonate, dicyclohexyl carbonate, dibenzyl carbonate, di-normal octyl carbonate, diisopropyl carbonate, ethylene carbonate, etc. Among them, dimethyl carbonate is preferably used.

Aliphatic Aromatic Carbonate The aliphatic aromatic carbonate in the present invention has the general formula [III] Wherein Ar is the same as the above formula [I] and R ′ is the same as the above formula [II]. Specifically, phenylmethyl carbonate, phenylethyl carbonate, phenylcyclohexyl carbonate, tolylmethyl carbonate, etc. Is mentioned.

Aromatic Carbonate Compound The aromatic carbonate compound which is a product in the present invention is an aliphatic aromatic carbonate, a diaromatic carbonate or a mixture thereof is selected, and among these, the diaromatic carbonate has the formula: (Ar is the same as the above formula [I]), and specifically,
Examples include diphenyl carbonate, di (methylphenyl) carbonate, di (dimethylphenyl) carbonate, and dinaphthyl carbonate.

Catalyst The catalyst in the present invention is Sc, Cr, Mo, W, Mn, Au, Ga, In, Bi,
It refers to one or more compounds selected from the group consisting of Te and lanthanoids. Among them, compounds of Sc, Mo, Mn, Au, Bi, and lanthanoids have high catalytic activity and can obtain products in high yield. be able to.

As these compounds, these halogen compounds,
Examples thereof include oxides, hydrides, carboxylic acid compounds, nitric acid compounds, alkoxy compounds, acetylacetonate compounds, sulfuric acid compounds, cyclopentadienyl compounds, carbonyl compounds, phosphine complexes and amine complexes.

Sc ₂ O ₃ , ScC ₂ , Sc (OH) ₃ , ScCl ₃ , ScF ₃ ; Mo (CH ₃ COCHCOCH ₃ ) ₃ , Mo (CO) ₆ , Mo ₂ O ₃ , Mo (OH) ₃ , MoO ₂ ,
_{C 5 H 5 MoC 6 H 6} ; Mn 2 (CO) 10, Mn (CH 3 COCHCOCH 3) 3, MnO 2, KMnO 4, Mn 2 O 7,
MnCl ₂ ; NaAuCl ₂ · 2H ₂ O, AuCl ₃ , AuF ₃ ; Bi (OCOCH ₃ ), BiH ₃ , Mg ₃ Bi ₂ ; La (OCOCH ₃ ) ₂ , La (OH) ₃ , Ce (OH) ₃ , Pr (OH) ₃ , Nd (OH) ₃ , P
m (OH) ₃ , Sm (OH) ₃ , Eu (OH) ₃ , Gd (OH) ₃ , Lu (OH) ₃ , LuCl ₃
・ 6H ₂ O, La (NO) ₃ ) ₃ , La ₂ O ₃ ; Cr (CH ₃ COCHCOCH ₃ ) ₃ , Cr (CO) ₆ , Cr ₂ O ₃ , Cr (OH) ₃ , K ₂ Cr ₂ O
₇ , (NH ₄ ) ₂ Cr ₂ O ₇ , [Cr (H ₂ O) ₆ ] Cl ₃ , CrO ₃ ; W (CO) ₆ , WO ₂ , WO ₃ , WF ₆ , WCl ₆ , WBr ₆ ; Ga ( _{NO 3) 3, GaCl 2,} GaCl 3; In 2 O 3, (InH 3) n, InCl 2; TeCl 4, TeH 2, TeF 6, TeO 2, TeCl 4, H 2 TeCl 6, TeO; etc. include However, among them, Sc ₂ O ₃ , Mo (CH ₃ COCHCOCH ₃ ) ₃ , Mo (CO) ₆ , Mn ₂ (CO) ₁₀ , Mn (C
H ₃ COCHCOCH ₃ ) ₃ , NaAuCl ₂ · 2H ₂ O, Bi (OCOCH ₃ ), La (OCOCH
₃ ) ₂ , LuCl ₃ .6H ₂ O are preferably used.

These catalysts exhibit sufficiently excellent catalytic action even when used alone, but two or more catalysts may be used in combination.

The amount of catalyst used is generally called the amount of catalyst,
An amount effective for catalyzing the ester conversion reaction between the phenol compound and the aliphatic aromatic carbonate, and is 10 to 10 ^-4 mol%, preferably
It is used in an amount of 0.2 to 10 ^-3 mol%.

The reaction temperature can be a wide range of 30 to 370 ° C., and particularly in the range of 150 to 320 ° C., the target product can be obtained in high yield and short reaction time.

The reaction time varies depending on the type of catalyst, the amount used, the reaction temperature, etc., but is 2 minutes to 40 hours, preferably 10 minutes to 3 hours, and especially when the reaction temperature is set to a high temperature of 230 ° C. or higher, the reaction The equilibrium constants K ₁ and K ₂ become large, and it becomes possible to react in a short time of 10 minutes to 1 hour. In this case, in addition to the advantage of being economically superior There is a feature that it can be obtained.

In the present invention, the reaction of the phenol compound and the di-aliphatic carbonate or the aliphatic aromatic carbonate is carried out at a molar ratio of 5: 1 to 1: 5, but a reaction in the vicinity of an equimolar ratio is preferably carried out, It is possible to obtain an aromatic carbonate having a high selectivity of the target product and a high production rate (STY) per reactor volume.

In order to improve the yield of aromatic carbonate, the conventional method of shifting the equilibrium to the product system by carrying out the reaction while removing the generated ROH out of the reaction system is applicable to the method of the present invention. You can Furthermore, when removing ROH, as in the prior art, by adding an azeotropic agent such as benzene or heptane to the reaction system and removing it as an azeotrope with ROH, more efficient ROH can be obtained. It can be removed.

In the present invention, the aliphatic aromatic carbonate produced by the method described in the item 1 or the mixture of the aliphatic aromatic carbonate and the diaromatic carbonate is further heated in the presence of a catalyst to give the diaromatic. Carbonates can be produced.

In this case, the same catalyst as that used in the preceding reaction may be used, but a different catalyst may be used as long as it is within the range of the above-described catalyst.

This reaction is represented by the aforementioned reaction formula (3), and the reaction temperature is 50 to 370 ° C, preferably 150 to 320 ° C.
The temperature is 0 ° C., and the pressure can be increased, normal pressure, or reduced pressure, but it is preferable to perform the reaction under reduced pressure while removing the produced dialiphatic carbonate outside the reaction system.

(Effect of the invention) According to the present invention, the reaction of a phenol compound and a di-aliphatic carbonate or an aliphatic aromatic carbonate,
Aromas can be obtained at high yields in the presence of a catalyst composed of one or more compounds selected from the group consisting of Sc, Cr, Mo, W, Mn, Au, Ga, In, Bi, Te and lanthanoids. Along with being able to produce a group carbonate compound, this method has the effect that the separation of the product and the recovery of the catalyst can be performed easily, and this effect is Sc, Mo, Mn, Au, as a catalyst.
It becomes more remarkable when one or more compounds selected from the group consisting of Bi and lanthanoids are used.

(Examples) Hereinafter, the present invention will be described in detail based on Examples.

Example 1 0.11 mol of phenol, 0.11 mol of dimethyl carbonate and 0.01 g of Mn ₂ (CO) ₁₀ were placed in a 50 ml autoclave, and 250
Heated at 0 ° C for 30 minutes. As a result of analyzing the reaction solution by gas chromatography, the conversion rate of phenol was 15.17%, and on the basis of phenol, anisole was 1.78%, phenylmethyl carbonate (PMC) was 12.50%, and diphenyl carbonate (DPC) was 0.89%. Was generated at a rate. PMC and DP
The overall selectivity of C was 88.3%.

Examples 2 to 12 The procedure of Example 1 was repeated, except that the catalysts listed in Table 1 were used. The results are shown in Table 1.

Example 13 7 mmol phenylmethyl carbonate, Mn ₂ (CO)
₁₀ 0.01 g was heated at 200 ° C. for 1 hour in an autoclave.
As a result of analyzing the reaction solution by gas chromatography, 1.7 mmol of diphenyl carbonate and 1.7 mmol of dimethyl carbonate were produced.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location B01J 27/22 X 27/25 X 31/04 X 31/20 X 31/22 X C07B 61/00 300

Claims (8)

[Claims] 1. A method for producing an aromatic carbonate compound selected from an aliphatic aromatic carbonate, a diaromatic carbonate and a mixture thereof by reacting a phenol compound with a dialiphatic carbonate or an aliphatic aromatic carbonate. At, as catalysts, Sc, Cr, Mo, W, M
A method comprising using one or more compounds selected from the group consisting of n, Au, Ga, In, Bi, Te and lanthanoids. 2. The method according to claim 1, wherein one or more compounds selected from the group consisting of Sc, Mo, Mn, Au, Bi and lanthanoids are used as the catalyst. 3. The method according to claim 1, wherein the reaction is carried out under a temperature condition of 150 to 320 ° C. 4. The method according to claim 1, wherein the molar ratio of the phenol compound to the di-aliphatic carbonate or the aliphatic-aromatic carbonate is 5: 1 to 1: 5. 5. The catalyst concentration is 0.
The method according to claim 1, wherein the amount is from 2 mol% to 10 ^-3 mol%. 6. The method according to claim 1, wherein the phenol compound is phenol. 7. The method according to claim 1, wherein the dialiphatic carbonate is dimethyl carbonate. 8. An aliphatic aromatic carbonate produced by the method according to claim 1 or a mixture of an aliphatic aromatic carbonate and a diaromatic carbonate is further heated in the presence of a catalyst. A method for producing a diaromatic carbonate.