JP5649288B2 - Method for producing phthalic dichloride compound and catalyst used in the production method - Google Patents

Description

  The present invention relates to a method for producing a phthalic acid dichloride compound useful as a raw material for agricultural chemicals, pharmaceuticals, and various polymer compounds, and a catalyst used therefor.

  As a method for producing a phthalic acid dichloride compound, there are known a method of chlorinating orthoxylene and hydrolyzing it, and a method of reacting a phthalic anhydride compound with a chlorinating agent.

  As a method using the above-mentioned ortho-xylene as a starting material, for example, 1-dichloromethyl-2-trichloromethylbenzene is obtained by photochlorination of ortho-xylene, and this is hydrolyzed to further photochlorinate via 3-chlorophthalide. Method (see Patent Document 1). However, this method requires a photochlorination facility and requires a multi-stage production process using a large amount of chlorine.

On the other hand, examples of the method using the above phthalic anhydride compound as a starting material include the following. For example, a method of reacting phthalic anhydride with phosphorus pentachloride is disclosed (see Non-Patent Document 1). However, this method generates waste containing a large amount of phosphorus.
There is also a method of reacting a phthalic anhydride compound with phosgene or thionyl chloride (see Patent Documents 2 to 5). In these methods, in order to handle toxic and dangerous phosgene, special production equipment is required, or when thionyl chloride is used, equipment for reacting it at high pressure is required.
In addition, there is a method of reacting phthalic anhydride with trichloromethylbenzene in the presence of zinc chloride (see Non-Patent Document 2, Patent Documents 6 and 7). This is a simple method that can be carried out in a normal reaction kettle, but it is necessary to use a large amount of zinc chloride depending on the reaction temperature. For example, according to Non-Patent Document 2, it is reported that the reaction proceeds at 110 to 120 ° C. when 10 mol% of zinc chloride is used with respect to phthalic anhydride, but such a large amount of catalyst used is practical. is not. On the other hand, when zinc chloride is reduced to 1 mol%, the amount is still large, but a high temperature of 200 ° C. is required to obtain a practical reaction rate. As a heat medium for realizing such a high reaction temperature, a normal aqueous medium cannot be used, a special heat medium is required, and special equipment for responding to the heat medium must be prepared.

JP 47-27949 A International Publication No. 2006-56436 Pamphlet JP 2005-330283 A US Patent Application Publication No. 2007/299282 International Publication No. 2006-58642 Pamphlet U.S. Pat. No. 1,963,748 US Pat. No. 1,963,749

Org. Synth. Coll. Vol II, page 528 J. et al. Am. Chem. Soc. 1937, p. 206

By the way, regarding the purity of the target compound in the product, in the methods of Patent Documents 2 and 4 to 7 and Non-Patent Documents 1 and 2 (specific purity is not disclosed in Patent Document 1), unreacted. Therefore, the purity of the phthalic acid dichloride compound remains at 95 to 97% at the highest. In Example 4 of Patent Document 3, an example in which phthalic acid dichloride is produced with a purity of 99% or more is described. However, in this method, it is necessary to use phosgene which lacks handleability as described above, and it is necessary to use expensive N, N-dicyclohexylformamide as a catalyst. Even if purity increases, it is not suitable for efficient and economical industrial production.
When the purity of the target compound does not increase and phthalic anhydride and diphthalic dichloride are mixed in the product, it is necessary to separate them by distillation or recrystallization. In fact, in Non-Patent Document 1, the two are separated in this way, but this separation is extremely difficult because the boiling point and melting point of both are close. Usually, even if distillation purification is performed after the reaction, a considerable amount of phthalic anhydride remains. In this regard, the reaction for generating a phthalic dichloride compound from the above phthalic anhydride compound is an equilibrium reaction, and even if the reaction rate is increased using a catalyst, the equilibrium state does not usually change, and the target phthalic dichloride does not change. Increasing purity is not easy.

  In view of the above-mentioned points, the present invention is an industrially useful high-purity phthalic acid dichloride compound, which is economical, safe, and easy to handle, with a high yield without requiring complicated processing. It is an object of the present invention to provide a method for producing a phthalic dichloride compound obtainable by the above method and a catalyst used in the method.

  As a result of intensive studies to solve the above problems, the present inventors have made a reaction between a phthalic anhydride compound and a trichloromethylbenzene compound in the presence of a catalyst containing a zirconium compound and / or a hafnium compound, thereby achieving high purity. It has been found that a phthalic dichloride compound can be obtained. And based on this knowledge, this invention of the following structures was completed.

（式中、Ｘは、ハロゲン原子、ニトロ基、メチル基、またはメトキシ基を表す。該Ｘが複数あるとき、これらは互いに同じであっても異なっていてもよい。ｎは０〜２の整数を表す。Ｒは、ハロゲン原子、クロロカルボニル基、炭素数１〜３のアルキル基、または炭素数１〜３のハロゲン置換アルキル基を表す。該Ｒが複数あるとき、これらは互いに同じであっても異なっていてもよい。ｍは０〜２の整数を表す。）
［ジルコニウム化合物：四塩化ジルコニウム、二塩化オキシジルコニウム、水酸化ジルコニウム、テトラブトキシジルコニウム、テトライソプロポキシジルコニウム、炭酸ジルコニウム、ジルコニウムカーバイド、および金属ジルコニウムから選ばれる少なくとも１種の化合物］
［ハフニウム化合物：四塩化ハフニウム、ハフニウムカーバイド、オキシ塩化ハフニウム、水酸化ハフニウム、および金属ハフニウムから選ばれる少なくとも１種の化合物］
〔２〕前記ジルコニウム化合物またはハフニウム化合物が四塩化ジルコニウムまたは四塩化ハフニウムである〔１〕に記載のフタル酸ジクロリド化合物の製造方法。
〔３〕一般式（１）で表される化合物が無水フタル酸である〔１〕または〔２〕に記載のフタル酸ジクロリド化合物の製造方法。
〔４〕一般式（１）で表される化合物が３−クロロ無水フタル酸又は４−クロロ無水フタル酸である〔１〕または〔２〕に記載のフタル酸ジクロリド化合物の製造方法。
〔５〕一般式（２）で表される化合物が４−クロロトリクロロメチルベンゼンである〔１〕〜〔４〕のいずれか１項に記載のフタル酸ジクロリド化合物の製造方法。
〔６〕前記ジルコニウム化合物および／またはハフニウム化合物を、前記一般式（１）で表される化合物に対して０．０５〜１０モル％で用いる〔１〕〜〔５〕のいずれか１項に記載のフタル酸ジクロリド化合物の製造方法。
〔７〕前記一般式（１）で表される化合物と一般式（２）で表される化合物との反応を、１４０℃〜１６０℃の範囲で行う〔１〕〜〔６〕のいずれか１項に記載のフタル酸ジクロリド化合物の製造方法。
〔８〕前記一般式（３）で表される化合物を、９８モル％以上の純度で得る〔１〕〜〔７〕のいずれか１項に記載のフタル酸ジクロリド化合物の製造方法。
〔９〕前記一般式（２）で表される化合物を、前記一般式（１）で表される化合物に対して、１〜３当量で反応させる〔１〕〜〔８〕のいずれか１項に記載のフタル酸ジクロリド化合物の製造方法。
〔１０〕前記一般式（１）で表される化合物と一般式（２）で表される化合物との反応時間が、３〜２０時間である〔１〕〜〔９〕のいずれか１項に記載のフタル酸ジクロリド化合物の製造方法。
〔１１〕下記ジルコニウム化合物および／またはハフニウム化合物からなる触媒であって、下記一般式（１）で表される化合物と一般式（２）で表される化合物とを反応させて、下記一般式（３）で表される化合物を生成させる反応に用いられることを特徴とするフタル酸ジクロリド化合物製造用触媒。

（式中、Ｘは、ハロゲン原子、ニトロ基、メチル基、またはメトキシ基を表す。該Ｘが複数あるとき、これらは互いに同じであっても異なっていてもよい。ｎは０〜２の整数を表す。Ｒは、ハロゲン原子、クロロカルボニル基、炭素数１〜３のアルキル基、または炭素数１〜３のハロゲン置換アルキル基を表す。該Ｒが複数あるとき、これらは互いに同じであっても異なっていてもよい。ｍは０〜２の整数を表す。）
［ジルコニウム化合物：四塩化ジルコニウム、二塩化オキシジルコニウム、水酸化ジルコニウム、テトラブトキシジルコニウム、テトライソプロポキシジルコニウム、炭酸ジルコニウム、ジルコニウムカーバイド、および金属ジルコニウムから選ばれる少なくとも１種の化合物］
［ハフニウム化合物：四塩化ハフニウム、ハフニウムカーバイド、オキシ塩化ハフニウム、水酸化ハフニウム、および金属ハフニウムから選ばれる少なくとも１種の化合物］
[1] In the presence of the following zirconium compound and / or hafnium compound, the compound represented by the following general formula (1) is reacted with the compound represented by the general formula (2) to give the following general formula (3) A method for producing a phthalic acid dichloride compound, characterized in that a compound represented by the formula:

(In the formula, X represents a halogen atom, a nitro group, a methyl group, or a methoxy group. When there are a plurality of Xs, these may be the same or different. N is an integer of 0-2. .R representing a is halogen atom, chloro group, alkyl group having 1 to 3 carbon atoms, or when. the R is in multiple represents a halogen location 換A alkyl group having 1 to 3 carbon atoms, which are identical to each other And m represents an integer of 0 to 2.)
[Zirconium compound: at least one compound selected from zirconium tetrachloride, oxyzirconium dichloride, zirconium hydroxide, tetrabutoxyzirconium, tetraisopropoxyzirconium, zirconium carbonate, zirconium carbide, and metallic zirconium]
[Hafnium compound: at least one compound selected from hafnium tetrachloride, hafnium carbide, hafnium oxychloride, hafnium hydroxide, and metal hafnium]
[2] The method for producing a phthalic dichloride compound according to [1], wherein the zirconium compound or hafnium compound is zirconium tetrachloride or hafnium tetrachloride.
[3] The method for producing a phthalic dichloride compound according to [1] or [2], wherein the compound represented by the general formula (1) is phthalic anhydride.
[4] The method for producing a phthalic dichloride compound according to [1] or [2], wherein the compound represented by the general formula (1) is 3-chlorophthalic anhydride or 4-chlorophthalic anhydride.
[5] The method for producing a phthalic acid dichloride compound according to any one of [1] to [4], wherein the compound represented by the general formula (2) is 4-chlorotrichloromethylbenzene.
[6] Any one of [1] to [5], wherein the zirconium compound and / or the hafnium compound is used in an amount of 0.05 to 10 mol% with respect to the compound represented by the general formula (1). Of producing a phthalic acid dichloride compound.
[7] The reaction of the compound represented by the general formula (1) and the compound represented by the general formula (2) is performed in the range of 140 ° C to 160 ° C, and any one of [1] to [6] The manufacturing method of the phthalic acid dichloride compound of claim | item.
[8] The method for producing a phthalic dichloride compound according to any one of [1] to [7], wherein the compound represented by the general formula (3) is obtained with a purity of 98 mol% or more.
[9] Any one of [1] to [8], wherein the compound represented by the general formula (2) is reacted with 1 to 3 equivalents with respect to the compound represented by the general formula (1). The manufacturing method of the phthalic-acid dichloride compound of description.
[10] The reaction time of the compound represented by the general formula (1) and the compound represented by the general formula (2) is 3 to 20 hours, according to any one of [1] to [9] A process for producing the phthalic acid dichloride compound as described.
[11] A catalyst comprising the following zirconium compound and / or hafnium compound, wherein a compound represented by the following general formula (1) and a compound represented by the general formula (2) are reacted to form the following general formula ( A catalyst for producing a phthalic dichloride compound, which is used in a reaction for producing a compound represented by 3).

(In the formula, X represents a halogen atom, a nitro group, a methyl group, or a methoxy group. When there are a plurality of Xs, these may be the same or different. N is an integer of 0-2. .R representing a is halogen atom, chloro group, alkyl group having 1 to 3 carbon atoms, or when. the R is in multiple represents a halogen location 換A alkyl group having 1 to 3 carbon atoms, which are identical to each other And m represents an integer of 0 to 2.)
[Zirconium compound: at least one compound selected from zirconium tetrachloride, oxyzirconium dichloride, zirconium hydroxide, tetrabutoxyzirconium, tetraisopropoxyzirconium, zirconium carbonate, zirconium carbide, and metallic zirconium]
[Hafnium compound: at least one compound selected from hafnium tetrachloride, hafnium carbide, hafnium oxychloride, hafnium hydroxide, and metal hafnium]

  According to the production method and catalyst of the present invention, a high-purity phthalic acid dichloride compound that is particularly required as a raw material for pharmaceuticals, agricultural chemicals, and various polymer compounds is used with a material that is excellent in handleability without toxicity and danger. It can be easily obtained in a high yield without involving complicated purification steps. In addition, according to the production method and catalyst of the present invention, it has been possible to produce a high-purity phthalic acid dichloride compound, which has been difficult in the past, with a small amount of catalyst and at a mild reaction temperature without using a special heating medium. Further, it can suitably cope with mass production on an industrial scale.

Hereinafter, the present invention will be described in detail.
In the method for producing a phthalic acid dichloride compound of the present invention, a zirconium compound that serves as a catalyst for the phthalic anhydride compound represented by the general formula (1) and the trichloromethylbenzene compound represented by the general formula (2) And / or reacting in the presence of a hafnium compound.

  In the compound represented by the general formula (1), the substitution position of the substituent X on the benzene ring is not limited, but if there is a substituent having a large steric hindrance at the ortho position, the amount of the catalyst may be increased. It is preferable to increase the reaction temperature. Specific examples of the compound represented by the general formula (1) include phthalic anhydride, 3-chlorophthalic anhydride, 4-chlorophthalic anhydride, 4,5-dichlorophthalic anhydride, 3,6-dichloro. Examples include phthalic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, 3-methoxyphthalic anhydride, 4-methylphthalic anhydride, and the like. The number n of substituents X is 0 to 2, but is preferably 0 or 1.

In the compound represented by the general formula (2), the substituent R is a halogen atom such as chlorine or bromine, a lower alkyl group such as chlorocarbonyl group, methyl group or ethyl group, trichloromethyl group, dichloromethyl group, chloro Ru halogen-substituted lower alkyl group der such as a methyl group. The lower alkyl group is, Ru alkyl der 1 to 3 carbon atoms.

  Specific examples of the compound represented by the general formula (2) include 1-chloro-4-trichloromethylbenzene, 1-chloro-2-trichloromethylbenzene, 2,4-dichloro-1-trichloromethylbenzene, 3, Examples include 4-dichloro-1-trichloromethylbenzene, 1-methyl-4-trichloromethylbenzene, 1,4-bis (trichloromethyl) benzene, 1,3-bis (trichloromethyl) benzene, and the like. Further, unsubstituted trichloromethylbenzene is also inexpensive and is preferably used in terms of economic advantages.

The amount of the compound represented by the general formula (2) is 1.0 to 3.0 equivalents relative to the compound represented by the general formula (1) to be reacted in terms of trichloromethyl group contained in the compound. It is preferable that it is 1.3 to 1.8 equivalents.
In the method for producing a phthalic dichloride compound of this embodiment, a catalyst comprising a zirconium compound and / or a hafnium compound is used. The zirconium compound, zirconium tetrachloride, dichloride oxy zirconium (zirconium oxychloride), zirconium hydroxide, tetrabutoxyzirconium, tetra-isopropoxy zirconium, zirconium carbonate is at least one selected from zirconium carbide, and metal zirconium. Hafnium compound is at least one selected from hafnium tetrachloride, Hough bromide carbide, hafnium oxychloride, hafnium hydroxide, and metal hafnium. Of these, zirconium tetrachloride and / or hafnium tetrachloride are preferable. In the present invention, the zirconium compound or the hafnium compound may include at least one of them, and both may be mixed in cases where it is unavoidably difficult to separate, and other than that, the effect of the present invention is not hindered. May further be included.
The reaction in which a phthalic anhydride compound and a trichloromethylbenzene compound are reacted to form a phthalic dichloride compound is an equilibrium reaction. When the equilibrium state is reached, the unreacted raw material is further reduced even if the reaction time is extended. As a result, the reaction yield or the purity of the target product does not increase. On the other hand, in the method for producing a phthalic dichloride compound of the present invention, the mechanism of action is not clear by using the above catalyst, but the target reaction is an equilibrium reaction as described above. The purity of the target compound can be increased.

  The amount of the catalyst comprising the zirconium compound and / or the haonium compound is preferably 0.05 to 10 mol% with respect to the compound represented by the general formula (1), preferably 0.1 to 1.0. More preferably, it is mol%. This range is suitable for industrial use, and is preferable because the reaction can be completed with good yield in a short time.

  In the method for producing a phthalic dichloride compound of the present invention, the reaction temperature when the compound represented by the general formula (1) and the compound represented by the general formula (2) are reacted is 120 to 200 ° C. Is preferable, and it is more preferable that it is 140-160 degreeC. The reaction time varies depending on conditions such as reaction scale and reaction temperature, but the reaction can be completed preferably in 3 to 20 hours, more preferably 5 to 8 hours. Moreover, by setting it as this reaction temperature range, the aqueous medium suitable for industrial production can be used as a heat medium, and is preferable. In the present invention, the above reaction is preferably performed without a solvent.

  According to the method for producing a phthalic acid dichloride compound of the present invention, the target compound represented by the general formula (3) can be obtained with high purity. For example, the target compound can be obtained with a purity of 98% or more without going through a separate purification step, and further can be increased to a purity of 99.0 to 99.5% by adjusting the reaction conditions as necessary. . By doing in this way, even if it is the use for which extremely high purity is calculated | required which was difficult with the thing of purity 95-97% obtained by the conventional manufacturing method, it is obtained with the manufacturing method of the said invention. The desired compound can be applied directly as it is. Therefore, the production method of the present invention has an advantage that it is not necessary to employ a complicated purification step for removing, for example, an unreacted phthalic anhydride compound which is difficult to separate. In the present invention, unless otherwise specified, purity means the purity of the target product after carrying out normal rectification to remove by-products and the like, and when simply expressed as “%”, it means “mol%”. is there.

  In the production method of the present invention, an unreacted compound represented by the general formula (2) that may be mixed after the completion of the reaction, a trichloromethyl group after the compound represented by the general formula (2) reacts, A catalyst comprising a compound converted to a chlorocarbonyl group and a zirconium compound and / or a hafnium compound can be easily separated, and can be easily separated from the compound represented by the general formula (3) by an ordinary distillation operation or the like. . The remaining amount of the unreacted compound represented by the general formula (1) is usually a trace amount and can be used without purification as it is. However, if necessary, it can be separated by a distillation operation or the like to further increase the purity of the target compound. Also good.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these. Hereinafter, unless otherwise specified, “%” means “mol%”.

[Example 1]
In a 2 L four-necked flask, 444 g (3.0 mol) of phthalic anhydride, 690 g (3.0 mol) of 4-chlorotrichloromethylbenzene, 0.9 g (3.8 mmol of anhydrous zirconium chloride, phthalic anhydride) 0.13%) and heated to 160 ° C. While maintaining this temperature, 345 g (1.5 mol) of 4-chlorotrichloromethylbenzene was added dropwise to the reaction mixture over 3 hours, and stirring was further continued for 3 hours.

  Gas chromatography (GC2014 [trade name] manufactured by Shimadzu Corp., column: INERT CAP5 [trade name] manufactured by GL Sciences Inc. was used for the liquid sample 1a after the above reaction. The same applies to the following examples and comparative examples.) As a result, it was found that 0.82% of phthalic anhydride remained in the liquid sample 1a. The liquid sample 1a after this reaction was distilled under reduced pressure to obtain 1456 g (yield: 98.6%) of a colorless liquid 1b. The boiling point of this colorless liquid 1b was 135 to 136 ° C./10 torr. When this colorless liquid 1b was rectified in a 23-stage distillation column, Sample 1 containing 425 g (yield 70% based on phthalic anhydride) of phthalic dichloride was obtained. The boiling point (bp) of Sample 1 was 120 to 122 ° C./4 to 5 torr (literature values of phthalic acid dichloride, bp 131 to 133 ° C./9 to 10 mmHg: see Organic Synthesis Coll. Vol II, page 528). According to the same gas chromatographic analysis as described above, the purity of phthalic dichloride in Sample 1 was 99.0%, and the residual rate of phthalic anhydride was 0.88%. Further, 487 g of 4-chlorobenzoic acid chloride having a purity of 99.7% (93% yield based on consumed 4-chlorotrichloromethylbenzene) was obtained from the liquid sample 1b by distillation.

[Example 2]
The reaction was conducted in the same manner as in Example 1 except that the amount of zirconium chloride in Example 1 was reduced from 0.13% to 0.065% using a 1 L flask. That is, a mixture of 111 g (0.75 mol) of phthalic anhydride, 258 g (1.13 mol) of 4-chlorotrichloromethylbenzene and 0.11 g of anhydrous zirconium chloride (0.065% with respect to phthalic anhydride) was added at 160 ° C. For 22 hours. The liquid sample 2a after this reaction was distilled in the same manner as in Example 1 to obtain Sample 2. Analysis of Sample 2 by gas chromatography confirmed that 0.90% of phthalic anhydride remained and phthalic acid dichloride having a purity of 98.9% was produced.

[Example 3]
Reaction was carried out in the same manner as in Example 2 except that the amount of anhydrous zirconium chloride was 0.22 g (0.13% with respect to phthalic anhydride), and the mixture was stirred at a heating temperature (reaction temperature) of 140 ° C. for 27 hours. Went. The liquid sample 3a after the reaction was distilled in the same manner as in Example 1 to obtain Sample 3. The analysis of Sample 3 by gas chromatography confirmed that 0.86% of phthalic anhydride remained and phthalic acid dichloride having a purity of 99.0% was produced.

[Example 4]
A mixture of 253 g (1.71 mol) of phthalic anhydride, 503 g (2.57 mol) of trichloromethylbenzene and 0.50 g of anhydrous zirconium chloride (0.13% with respect to phthalic anhydride) was stirred at 160 ° C. for 19 hours. did. As a result of gas chromatography analysis of the liquid sample 4a after the reaction, it was confirmed that 1.95% of phthalic anhydride remained and 95.5% (yield) of phthalic dichloride was produced. As a by-product, 1.9% of dimer of trichloromethylbenzene was produced. This was rectified to obtain 208 g of phthalic acid dichloride having a purity of 98.0% (60% yield based on phthalic anhydride).

[Example 5]
A mixture of 111 g (0.75 mol) of phthalic anhydride, 258 g (1.13 mol) of 4-chlorotrichloromethylbenzene and 0.22 g of anhydrous hafnium chloride (0.09% based on phthalic anhydride) at 160 ° C. Stir for 13 hours. Sample 5a after the reaction was distilled in the same manner as in Example 1 to obtain Sample 5. As a result of analysis of Sample 5 by gas chromatography, it was confirmed that 0.43% of phthalic anhydride remained and phthalic acid dichloride having a purity of 99.5% was produced.

[Example 6]
In a 2 L four-necked flask, 365 g (2.0 mol) of 3-chlorophthalic anhydride, 460 g (2.0 mol) of 4-chlorotrichloromethylbenzene, 1.83 g of anhydrous zirconium chloride (3-chlorophthalic anhydride) 0.39%) was added and heated to 160 ° C. While maintaining this temperature, 230 g (1.0 mol) of 4-chlorotrichloromethylbenzene was added dropwise to the reaction mixture over 3 hours, followed by further stirring for 13 hours. Analysis of the liquid sample 6a after the reaction by gas chromatography revealed that 0.65% of 3-chlorophthalic anhydride remained.
The liquid sample 6a after this reaction was distilled under reduced pressure to obtain 992 g (yield: 94.6%) of colorless liquid 6b. The boiling point (bp) of this colorless liquid 6b was 153 to 155 ° C./9 torr. This colorless liquid 6b was rectified in a 23-stage distillation column to obtain Sample 6 containing 290 g (yield 61% based on 3-chlorophthalic anhydride) of 3-chlorophthalic acid dichloride. The boiling point (bp) of Sample 6 was 134 to 138 ° C./4 to 5 torr (literature value bp 140 ° C./8 mbar: Patent Document 5). As a result of analysis by gas chromatography, the purity of 3-chlorophthalic acid dichloride in Sample 6 was 99.0%. Moreover, 332 g of 4-chlorobenzoic acid chloride having a purity of 99.7% (95% yield based on consumed 4-chlorotrichloromethylbenzene) was obtained at the same time by distillation.

[Example 7]
In a 200 mL four-necked flask, 59.3 g (0.40 mol) of phthalic anhydride, 138.0 g (0.60 mol) of 4-chlorotrichloromethylbenzene, metal zirconium (sponge form, manufactured by Kanto Chemical Co., Ltd.) 052 g (0.57 mmol, 0.14 mol% based on phthalic anhydride) was added, and stirring was continued at 155 to 156 ° C. for 18 hours. It was confirmed by GC analysis of the reaction solution that 0.97% of phthalic anhydride remained and 98.4% of phthalic dichloride was formed.

[Example 8]
A 300 mL four-necked flask was charged with 187.5 g (1.27 mol) of phthalic anhydride and 378.4 g (1.65 mol) of 4-chlorotrichloromethylbenzene, heated to 100 ° C., and then zirconium oxychloride. 1.30 g of octahydrate (4.0 mmol, 0.32% with respect to phthalic anhydride) was added and heated to 155 ° C. Further, stirring was continued for 9 hours while maintaining the temperature at 155 to 156 ° C. It was confirmed by GC analysis of the reaction solution that 0.74% of phthalic anhydride remained and 98.4% of phthalic dichloride was formed.

[Example 9]
A 300 mL four-necked flask was charged with 93.8 g (0.63 mol) of phthalic anhydride and 218.3 g (0.95 mol) of 4-chlorotrichloromethylbenzene, heated to 100 ° C., and then zirconium hydroxide. 0.32 g (2.0 mmol, 0.32% based on phthalic anhydride) was added and heated to 160 ° C. Stirring was continued for 2 hours at the same temperature, and further stirring was continued for 3 hours while maintaining the temperature at 167 to 168 ° C. It was confirmed by GC analysis of the reaction solution that 0.82% of phthalic anhydride remained and 98.6% of phthalic dichloride was produced.

[Example 10]
In a 300 mL four-necked flask, 93.8 g (0.63 mol) of phthalic anhydride, 218.3 g (0.95 mol) of 4-chlorotrichloromethylbenzene, 1.3 g (6.4 mmol, anhydrous) of phthalic acid dichloride 1 mol% with respect to phthalic acid) and heated to 110 ° C., and then added with 0.32 g of zirconium hydroxide (2.0 mmol, 0.32% with respect to phthalic anhydride) and heated to 160 ° C. did. Stirring was continued for 4 hours at the same temperature. It was confirmed by GC analysis of the reaction solution that 0.96% of phthalic anhydride remained and 98.8% of phthalic dichloride (excluding the amount of added phthalic dichloride) was formed.

[Comparative Example 1]
According to Non-Patent Document 1, 14.8 g (0.10 mol) of phthalic anhydride and 22 g (0.106 mol) of phosphorus pentachloride were reacted at 150 ° C. for 16 hours. As a result of analyzing the sample 11a after the reaction by gas chromatography, 88.8% (yield) of phthalic dichloride was formed, and 6.8% of phthalic anhydride remained. The sample 11a was distilled as it was in Example 1 to obtain 18.2 g (yield 89.7%) of a fraction of phthalic dichloride having a purity of 92.0%. Among them, 7.6% phthalic anhydride was mixed.

[Comparative Example 2]
A mixture of 222 g (1.50 mol) of phthalic anhydride, 517 g (2.25 mol) of 4-chlorotrichloromethylbenzene and 0.44 g of zinc chloride (0.22% based on phthalic anhydride) was obtained at 160 ° C. Stir for hours. The sample 22a after the reaction was distilled in the same manner as in Example 1 to obtain a sample 22. As a result of analyzing the sample 22 by gas chromatography, 4.3% of phthalic anhydride remained and phthalic acid dichloride having a purity of 95.5% was produced.

Claims (11)

In the presence of the following zirconium compound and / or hafnium compound, the compound represented by the following general formula (1) and the compound represented by the general formula (2) are reacted to represent the following general formula (3). A method for producing a phthalic acid dichloride compound, characterized in that:

(In the formula, X represents a halogen atom, a nitro group, a methyl group, or a methoxy group. When there are a plurality of Xs, these may be the same or different. N is an integer of 0-2. .R representing a is halogen atom, chloro group, alkyl group having 1 to 3 carbon atoms, or when. the R is in multiple represents a halogen location 換A alkyl group having 1 to 3 carbon atoms, which are identical to each other And m represents an integer of 0 to 2.)
[Zirconium compound: at least one compound selected from zirconium tetrachloride, oxyzirconium dichloride, zirconium hydroxide, tetrabutoxyzirconium, tetraisopropoxyzirconium, zirconium carbonate, zirconium carbide, and metallic zirconium]
[Hafnium compound: at least one compound selected from hafnium tetrachloride, hafnium carbide, hafnium oxychloride, hafnium hydroxide, and metal hafnium]   The method for producing a phthalic dichloride compound according to claim 1, wherein the zirconium compound or hafnium compound is zirconium tetrachloride or hafnium tetrachloride.   The method for producing a phthalic dichloride compound according to claim 1 or 2, wherein the compound represented by the general formula (1) is phthalic anhydride.   The method for producing a phthalic dichloride compound according to claim 1 or 2, wherein the compound represented by the general formula (1) is 3-chlorophthalic anhydride or 4-chlorophthalic anhydride.   The method for producing a phthalic dichloride compound according to any one of claims 1 to 4, wherein the compound represented by the general formula (2) is 4-chlorotrichloromethylbenzene.   The phthalic acid dichloride compound according to any one of claims 1 to 5, wherein the zirconium compound and / or the hafnium compound is used at 0.05 to 10 mol% with respect to the compound represented by the general formula (1). Manufacturing method.   The phthalate according to any one of claims 1 to 6, wherein the reaction between the compound represented by the general formula (1) and the compound represented by the general formula (2) is performed in a range of 140 ° C to 160 ° C. A method for producing an acid dichloride compound.   The method for producing a phthalic dichloride compound according to any one of claims 1 to 7, wherein the compound represented by the general formula (3) is obtained with a purity of 98 mol% or more.   The phthalic acid according to any one of claims 1 to 8, wherein the compound represented by the general formula (2) is reacted with the compound represented by the general formula (1) at 1 to 3 equivalents. A method for producing a dichloride compound.   The reaction time of the compound represented by the said General formula (1) and the compound represented by General formula (2) is 3 to 20 hours, The phthalic acid dichloride of any one of Claims 1-9 Compound production method. A catalyst comprising the following zirconium compound and / or hafnium compound, wherein a compound represented by the following general formula (1) and a compound represented by the general formula (2) are reacted to form the following general formula (3): A catalyst for producing a phthalic dichloride compound, characterized by being used in a reaction for producing a compound represented by

(In the formula, X represents a halogen atom, a nitro group, a methyl group, or a methoxy group. When there are a plurality of Xs, these may be the same or different. N is an integer of 0-2. .R representing a is halogen atom, chloro group, alkyl group having 1 to 3 carbon atoms, or when. the R is in multiple represents a halogen location 換A alkyl group having 1 to 3 carbon atoms, which are identical to each other And m represents an integer of 0 to 2.)
[Zirconium compound: at least one compound selected from zirconium tetrachloride, oxyzirconium dichloride, zirconium hydroxide, tetrabutoxyzirconium, tetraisopropoxyzirconium, zirconium carbonate, zirconium carbide, and metallic zirconium]
[Hafnium compound: at least one compound selected from hafnium tetrachloride, hafnium carbide, hafnium oxychloride, hafnium hydroxide, and metal hafnium]