JP7715550B2 - Method for producing itaconic acid chloride - Google Patents

Description

The present invention relates to a method for producing itaconic acid chloride.

Itaconic acid is expected to be used as a plant-derived polymer monomer. However, under the polymerization conditions for polycondensation polymers that utilize the carboxyl group of itaconic acid, it is difficult to produce high-molecular-weight polymers while retaining the internal olefins of itaconic acid. On the other hand, itaconic acid chloride is more reactive than itaconic acid, so it is expected that polymerization conditions can be relaxed to obtain polycondensation polymers containing internal olefins.

For example, as methods for synthesizing itaconic acid chloride from itaconic acid as a raw material, Patent Documents 1 and 2 describe a method using thionyl chloride as a chlorinating agent, and Non-Patent Document 1 describes a method using phosphorus pentachloride as a chlorinating agent. Also known is a document that describes synthesizing itaconic acid chloride by reacting itaconic anhydride as a raw material with phosphorus pentachloride (Non-Patent Document 2). However, other than these methods, almost no other methods for producing itaconic acid chloride are known.

Chinese Patent Application Publication No. 102731440 Chinese Patent Application Publication No. 104030916

H. Feuer, S. M. Pier, Org. Synth. 1953, Vol. 33, p. 41. W. Petri, Chem. Ber. 1881, Vol. 14, pp. 1634-1637.

However, as a result of investigations by the present inventors, it has been found that itaconic acid chloride cannot be obtained in a high yield by the methods described in Patent Documents 1 and 2 (see Comparative Examples 2 and 3 in the present specification). Moreover, even if itaconic acid chloride can be obtained in a high yield by detailed investigation of the conditions, special equipment is required to treat the by-produced sulfur dioxide, making the method unsuitable for industrial implementation. Phosphorus pentachloride used in the methods described in Non-Patent Documents 1 and 2 is designated as a toxic substance, and handling large amounts is difficult, making the method unsuitable for industrial implementation.
Conventional methods for producing itaconic acid chloride have the above problems, and from the viewpoint of industrial implementation, a new method for producing itaconic acid chloride is desired.

The present invention aims to provide a method for producing itaconic acid chloride that can produce itaconic acid chloride in good yield without handling hazardous reagents or waste materials.

In view of the above problems, the present inventors have investigated the chlorination reaction of itaconic acid to obtain itaconic acid chloride from the viewpoints of chlorinating agents and catalysts. As a result, they have found that high-purity itaconic acid chloride can be obtained in high yield by reacting dichloromethyl alkyl ether with itaconic acid in the presence of a Lewis acid catalyst such as a zinc catalyst. They have also found that the above-mentioned method discovered by the present inventors can also be used to obtain high-purity itaconic acid chloride in high yield when itaconic anhydride is used as a raw material.
The present invention has been completed based on these findings.

That is, the above problems were solved by the following means.
[1]
A method for producing itaconic acid chloride, comprising reacting itaconic acid or itaconic anhydride with a dichloromethyl alkyl ether represented by the following general formula (1) in the presence of a Lewis acid catalyst:
In the above formula, R represents an alkyl group having 1 to 4 carbon atoms.
[2]
The method for producing itaconic acid chloride according to [1], wherein the Lewis acid catalyst is zinc chloride or zinc oxide.
[3]
The method for producing itaconic acid chloride according to [1] or [2], wherein the dichloromethyl alkyl ether represented by the general formula (1) is dichloromethyl propyl ether or dichloromethyl butyl ether.

In this invention, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as the lower and upper limits.

According to the method for producing itaconic acid chloride of the present invention, itaconic acid chloride can be obtained in good yield without handling hazardous reagents or waste materials.
Furthermore, according to the method for producing itaconic acid chloride of the present invention, the by-produced alkyl formate can be recovered and reused as a raw material for dichloromethyl alkyl ether.

<Method for producing itaconic acid chloride>
In the method for producing itaconic acid chloride of the present invention (hereinafter also referred to as "the production method of the present invention"), as described above, itaconic acid chloride (ClC(=O)C(=CH 2 )CH ₂ C(=O)Cl) is produced in good yield by a chlorination reaction in which itaconic acid or itaconic anhydride is reacted with a dichloromethyl alkyl ether represented by the following general formula (1) in the presence of a Lewis acid catalyst _.
By the above chlorination reaction, itaconic acid chloride is usually obtained as a mixture of itaconic acid chloride, a formic acid ester, and itaconic anhydride (hereinafter also referred to as a "reaction mixture"). High-purity itaconic acid chloride can be obtained in high yield by a simple purification treatment of the reaction mixture of this chlorination reaction by distillation.
The dichloromethyl alkyl ether represented by general formula (1) (hereinafter, also simply referred to as "dichloromethyl alkyl ether") and Lewis acid catalyst used in the production method of the present invention, the solvent that may be used in the chlorination reaction, the reaction conditions in the chlorination reaction, and the distillation treatment will be described below.

(Dichloromethyl alkyl ether represented by general formula (1))

In the above formula, R represents an alkyl group having 1 to 4 carbon atoms.
The alkyl group having 1 to 4 carbon atoms that can be taken as the above R is preferably a primary alkyl group. Specific examples of the alkyl group having 1 to 4 carbon atoms that can be taken as R include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an isobutyl group.

As a result of the above chlorination reaction, alkyl formate corresponding to the dichloromethyl alkyl ether used is produced as a by-product together with the target product, itaconic acid chloride.
Dichloromethyl methyl ether has been widely used as a chlorinating agent or formylating agent, during which dichloromethyl methyl ether is converted to methyl formate. Methyl formate is a special flammable substance with a boiling point of 31°C and a flash point of -20°C, and is not preferred for handling in industrial practice from a safety standpoint. From the viewpoint of being able to increase the flash point of the by-produced alkyl formate and enabling safer handling in industrial practice, it is preferable to use dichloromethyl propyl ether or dichloromethyl butyl ether.

However, not all dichloromethyl alkyl ethers with similar structures necessarily exhibit the same reactivity. In fact, in a study of the formylation of benzene using dichloromethyl alkyl ethers, the present inventors reported that the yield of benzaldehyde decreased as the alkyl group became longer, and that benzaldehyde was obtained only in very low yields with dichloromethyl propyl ether or dichloromethyl butyl ether (Warashina, T. et al., Tetrahedron, 2019, Vol. 75, pp. 608-616).
That is, the fact that dichloromethyl propyl ether or dichloromethyl butyl ether is an effective chlorinating agent in the production method of the present invention cannot be easily inferred from the existence of a similar reaction using dichloromethyl methyl ether. However, when a dichloromethyl alkyl ether in which R is a long-chain alkyl group having 5 or more carbon atoms in the above general formula (1) is used, the reactivity is extremely reduced, as shown in Comparative Examples 4 and 5 described below. For this reason, in the production method of the present invention, the upper limit of R in the above general formula (1) is 4 or less.

In the chlorination reaction using itaconic acid as a raw material, the amount of dichloromethyl alkyl ether used is preferably 2.0 to 3.0 equivalents, more preferably 2.3 to 2.8 equivalents, per equivalent of itaconic acid.
On the other hand, in the chlorination reaction using itaconic anhydride as the raw material, the amount of dichloromethyl alkyl ether used per equivalent of itaconic anhydride is preferably 1.0 to 2.0 equivalents, more preferably 1.2 to 1.4 equivalents.

The above dichloromethyl alkyl ether can be produced in high yield and with high purity by the method described in JP 2015-231961 A.

(Lewis acid catalyst)
In the production method of the present invention, as will be described later, itaconic acid chloride can be obtained by carrying out a chlorination reaction using the above-mentioned dichloromethyl alkyl ether as a chlorinating agent in the presence of a Lewis acid catalyst.
The Lewis acid used as the Lewis acid catalyst is a commonly known Lewis acid and is not particularly limited as long as it can produce itaconic acid chloride by the production method of the present invention. Examples include zinc chloride, zinc oxide, titanium chloride, zirconium chloride, etc. That is, in the production method of the present invention, Lewis acids such as zinc chloride, titanium chloride, and zirconium chloride function as Lewis acid catalysts in the chlorination reaction using a dichloromethyl alkyl ether as a chlorinating agent. Furthermore, as described below, Lewis acids such as zinc oxide themselves are converted into other Lewis acids by reaction with dichloromethyl alkyl ether, and the obtained Lewis acid functions as a Lewis acid catalyst in the chlorination reaction using a dichloromethyl alkyl ether as a chlorinating agent.
Among these, zinc chloride or zinc oxide is preferred from the viewpoint of catalytic activity, and zinc oxide is more preferred from the viewpoint of industrialization.
Zinc chloride is generally produced by reacting zinc oxide with hydrogen chloride. Zinc chloride is highly deliquescent and hygroscopic, so it reacts easily with moisture in the air, is prone to blocking, and has a pungent odor when handled in large quantities. In contrast, zinc oxide is a powder that is easy to handle and inexpensive because it is less reactive with moisture in the air and is stable.
The present inventors compared the catalytic ability of zinc chloride and zinc oxide and found that the reaction was smoother when zinc oxide, which is a fine powder, was used.
Furthermore, supporting evidence that zinc oxide reacts rapidly with dichloromethyl alkyl ether to form zinc chloride was clarified in Reference Example 1 described below. The experimental results are also supported by the fact that the surface of the zinc chloride catalyst produced in the reaction system is not in contact with the atmosphere containing moisture, and therefore has high catalytic surface activity. This is something that has not been described in any prior art documents.
The amount of the Lewis acid catalyst used is selected from the range of 0.01 to 10 mol % relative to 100 mol % of itaconic acid or itaconic anhydride, and usually 1 to 2 mol % is sufficient.

(solvent)
The production method of the present invention may be carried out in the absence of a solvent or in the presence of a solvent.
When a solvent is used, any solvent can be used without particular limitation as long as it is stable under the reaction conditions of the present invention (a solvent that does not substantially react with the reaction reagent, itaconic acid chloride), and examples thereof include chlorinated hydrocarbon solvents (dichloromethane, trichloromethane, 1,2-dichloroethane, 1,2-dichloropropane, etc.).
These may be used alone or in combination of two or more. When a solvent is used, the amount of the solvent used per mole of itaconic acid or itaconic anhydride as the raw material is preferably 100 ml or more, more preferably 200 to 2000 ml.
From an industrial perspective, not using a solvent is preferable because it improves reactor efficiency, simplifies post-treatment, and is environmentally friendly.

(Reaction conditions for chlorination reaction)
In the chlorination reaction in which itaconic acid or itaconic anhydride is reacted with the dichloromethyl alkyl ether in the presence of a Lewis acid catalyst, a mixture of these raw materials and the catalyst is initially stirred in the form of a slurry (suspension), but gradually becomes a homogeneous solution.
The reaction temperature in the chlorination reaction is usually 5 to 30° C., preferably around room temperature (25° C.). Depending on the type of formate ester produced as a by-product, the reaction may be slightly heated up to the boiling point thereof (boiling point of butyl formate: about 107° C., boiling point of propyl formate: about 81° C.), for example, up to 40 to 60° C.
The reaction time for the chlorination reaction varies depending on the reaction scale, the Lewis acid catalyst used, the type of dichloromethyl alkyl ether, the reaction temperature, etc., but is usually 1 to 30 hours.

(Distillation process)
The distillation method is not particularly limited, and a conventional method can be employed. For example, alkyl formate and itaconic acid chloride can be easily separated by simple distillation, but itaconic anhydride and itaconic acid chloride can be separated from the reaction mixture by distillation under reduced pressure using equipment equipped with a rectification column, if necessary.
In the production method of the present invention, it is also possible to adjust the reaction conditions so that less than 4% of itaconic anhydride remains at the end of the reaction (the pure content of itaconic acid chloride in the reaction mixture is 96% or more). In this case, itaconic acid chloride with a purity of 98% or more, which is practically required, can be obtained by simple distillation.

The following describes in more detail two embodiments: one using itaconic acid as a raw material (Embodiment 1) and one using itaconic anhydride as a raw material (Embodiment 2).

[Embodiment 1]

In the first embodiment of the present invention, as shown in the above reaction scheme, itaconic acid can be produced by stirring itaconic acid and two or more equivalents of the above dichloromethyl alkyl ether in the presence of a catalytic amount of a Lewis acid catalyst.
The reaction mixture (reaction liquid) of the chlorination reaction contains, in addition to the target product, itaconic acid chloride, a by-product, alkyl formate, and a reaction intermediate, itaconic anhydride. By distilling this reaction mixture, the target product, itaconic acid chloride, can be easily separated and obtained in high yield. Furthermore, the alkyl formate separated by distillation can be reused as a raw material for synthesizing the dichloromethyl alkyl ether, as described in JP 2015-231961 A.

A method for converting a monocarboxylic acid into the corresponding carboxylic acid chloride using dichloromethyl methyl ether as a chlorinating agent, which is a dichloromethyl alkyl ether, is known. For example, Organic Syntheses, Coll., 1990, Vol. 7, p. 467, describes a useful method for preparing α-ketocarboxylic acid chloride, in which pyruvic acid is reacted with dichloromethyl methyl ether without using a catalyst to convert it into pyruvic acid chloride. It also describes that pyruvic acid chloride can be obtained only in very low yields when common chlorinating agents such as thionyl chloride and phosphorus trichloride are used.
However, even when the above-mentioned method for obtaining pyruvic acid chloride, i.e., the method of reacting itaconic acid with dichloromethyl methyl ether without a catalyst, was applied to the method for producing itaconic acid chloride of the present invention using itaconic acid, which is not a monocarboxylic acid, as a starting material, no itaconic acid chloride was obtained at all, and only itaconic anhydride was obtained in quantitative yield (see Comparative Example 1 described later). Itaconic acid tends to form a cyclic acid anhydride structure within the molecule, and it has become clear that the conversion of such a dicarboxylic acid to an acid chloride does not work well simply by applying known methods.
Furthermore, even when itaconic acid was reacted with thionyl chloride and dimethylformamide (DMF) in accordance with the disclosures of Patent Documents 1 and 2, only a small amount of itaconic acid chloride was produced (see Comparative Example 2 described below). Furthermore, even when zinc chloride or zinc oxide was further added to this, almost no itaconic acid chloride was obtained. This was also the case when itaconic anhydride was reacted with oxalyl chloride, DMF, and zinc oxide, and only 3% of itaconic acid chloride was produced (see Comparative Example 3 described below).

[Embodiment 2]

As described in the first embodiment, itaconic acid can be easily converted to itaconic anhydride by dichloromethyl alkyl ether. It is presumed from the examples and comparative examples that the reaction of this itaconic anhydride with dichloromethyl alkyl ether in the presence of a Lewis acid catalyst results in ring-opening and the production of itaconic acid chloride. Therefore, a method for producing itaconic acid chloride using itaconic anhydride as a raw material is expected to reduce the amount of expensive dichloromethyl alkyl ether used.
Therefore, in the second embodiment of the present invention, itaconic acid chloride can be produced by stirring itaconic anhydride and one equivalent of the dichloromethyl alkyl ether in the presence of a catalytic amount of a Lewis acid catalyst, as shown in the above reaction scheme. As in the first embodiment, the reaction mixture of the chlorination reaction (a mixture of itaconic acid chloride, alkyl formate, and itaconic anhydride) is distilled, whereby the target itaconic acid chloride can be easily separated and obtained in high yield.
In the above-mentioned embodiment 1, an equivalent amount of hydrogen chloride is generated when itaconic anhydride is formed, whereas the reaction in embodiment 2 is preferable in that no hydrogen chloride is generated.

When two carboxy groups are present in close proximity, acid anhydrides tend to be generated, and attempts to convert cyclic acid anhydrides into dicarboxylic acid chlorides have been studied by predecessors. For example, F. M. Menge et al., Angew. Chem. Int. Ed. 2002, Vol. 41, pp. 2581-2584, describes a method in which all three carboxy groups in 1,3,5-ciscyclohexanetricarboxylic acid are converted into acid chlorides and used as a raw material for the target compound. In this method, 1,3,5-ciscyclohexanetricarboxylic acid is first reacted with thionyl chloride to obtain a compound having one acid chloride and an acid anhydride structure per molecule. This compound is then reacted with dichloromethyl methyl ether in the presence of zinc chloride to obtain 1,3,5-ciscyclohexanetricarboxylic acid chloride having three acid chlorides per molecule. Also, F. Johnson et al., J. Am. Chem. Soc., 1982, Vol. 104, pp. 2190-2198, reported that the corresponding acid chloride was obtained in 80% yield by refluxing acetyl malate anhydride with dichloromethyl methyl ether in the presence of zinc chloride.
The present inventors have found a reaction route for efficiently producing itaconic acid chloride from itaconic anhydride, a synthesis method for which was previously unknown, by applying the above-mentioned reaction conditions to itaconic anhydride. Furthermore, while prior art documents mention that dicarboxylic acids can be synthesized by ring-opening an acid anhydride using zinc chloride and dichloromethyl methyl ether, the present invention has clarified that from an industrial viewpoint, this method can be changed to zinc oxide and dichloromethyl propyl ether or dichloromethyl butyl ether.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. Room temperature means 25°C.
The itaconic acid chloride isolated in the examples of the present invention, except for Example 3, had a purity of 98% or more.
The measurements were carried out according to the following method.
- Measurement of the composition ratio of the solution after the reaction is completed -
Measurement equipment: Gas chromatography with mass spectrometry (GCMS) (detector: TCD)
Conversion rate and GC yield (%) = {(peak area of itaconic acid chloride) / (peak area of itaconic acid chloride + peak area of itaconic anhydride)} × 100

Example 1
6.50 g (50 mmol) of itaconic acid was suspended in 15 mL of dichloromethane, and 134 mg (0.98 mmol) of zinc chloride and 18.3 g (159 mmol) of dichloromethyl methyl ether were added, followed by stirring at room temperature (rt) for 3 hours. During stirring, the solution gradually became homogeneous. After the reaction was completed, the solution was distilled under reduced pressure to obtain 7.2 g of itaconic acid chloride (yield 86%).
(Identification of Itaconic Acid Chloride)
bp: 74 to 75°C/2 torr (reference value described in Non-Patent Document 1: bp: 71 to 72°C/2 torr)
GCMS: m/z=131 (M ⁺ -Cl), 103 (base peak, M ⁺ -COCl).
300MHz ¹ H-NMR (CDCl ₃ ): δ = 3.93 (J = 0.9Hz, 2H), 6.32 (J = 0.9Hz, 1H), 6.85 (J = 0.3Hz, 1H)
75MHz ^13C -NMR ( _CDCl3 ): δ=48.67, 136.43, 138.10, 167.70, 170.15.
IR (neat): 1794cm ^-1 , 1734cm ^-1

Methanol and one drop of pyridine were added to a portion of the obtained itaconic acid chloride, and the mixture was stirred for 0.5 hours, and the production of itaconic acid dimethyl ester was confirmed by GCMS.
GCMS: m/z=158 (M ⁺ ), 143 (M ⁺ -CH ₃ ), 127 (M ⁺ -OCH ₃ ), 99 (base peak, M ⁺ -COOCH ₃ ).

Example 2
5.6 g (50 mmol) of itaconic anhydride, 135 mg (1.0 mmol) of zinc chloride, 7.27 g (71.5 mmol) of dichloromethyl methyl ether, and 20 mL of dichloromethane were placed in a 100 mL flask and stirred at room temperature (rt) for 0.5 hours, followed by stirring at 40°C for 2 hours. The conversion rate of the solution after the reaction was 96.0%. The solution after the reaction was distilled to obtain 6.5 g of itaconic acid chloride (yield 78%).

<Examples 3 to 8, Comparative Example 4>
In accordance with Example 1, 1.95 g (15 mmol) of itaconic acid (ITA) was used and reacted under the conditions shown in Table 1 below, followed by Kugelrohr distillation (95 to 100°C/2 torr). The results are shown in Table 1.

<Examples 9 to 15, Comparative Example 5>
In accordance with Example 2, 3.36 g (30 mmol) of itaconic anhydride (ITAH) was used and reacted under the conditions shown in Table 2 below, followed by Kugelrohr distillation (95-100°C/2 torr). The results are shown in Table 2.

(Table notes)
In the examples where a solvent was used, the solvent was used so that the ratio of raw material ITA or ITAH (mol)/solvent (L) was 3M or 2.5M.
"-" in the GC or isolation column for ITOC yield means that confirmation by the method described in the corresponding column was not performed.
The value in the column for ITOC isolation yield means the yield (%) of ITOC obtained by distillation.

The following can be seen from the results in Tables 1 and 2 above and the results of Example 16 and Comparative Examples 1 to 3 described below.
As shown in Comparative Example 1 described later, the reaction with dichloromethyl alkyl ether in the absence of a catalyst did not produce itaconic acid chloride at all, but only itaconic anhydride in quantitative yield. Furthermore, even when itaconic acid was reacted with thionyl chloride and dimethylformamide (DMF) according to the methods described in Patent Documents 1 and 2, only a small amount of itaconic acid chloride was produced (Comparative Example 2), and even when itaconic anhydride was reacted with oxalyl chloride, DMF, and zinc oxide, only 3% of itaconic acid chloride was produced (Comparative Example 3).
Furthermore, as shown in the above Comparative Examples 4 and 5, when dichloromethyl hexyl ether was used, the reactivity was extremely reduced, and only trace amounts were observed by GC analysis.
In contrast to these, it was confirmed that in Examples 1 to 16 according to the production method of the present invention, the target product, itaconic acid chloride, was obtained in a good yield of 42% or more.

Example 16: Large-scale synthesis
Itaconic anhydride (40 g, 0.36 mol), dichloromethyl n-butyl ether (72.3 g, 0.46 mol, 1.27 eq), and zinc oxide (0.58 g, 0.007 mol, 0.02 eq) were placed in a 200 mL flask and stirred at room temperature for 16 hours. GC analysis showed that the conversion rate was 97.8%. After the reaction was completed, the solution was distilled under reduced pressure (boiling point 73-74°C/4-5 torr) to obtain 72.8 g of itaconic acid chloride (yield 79%). The purity of the isolated itaconic acid chloride as determined by GC was 99.3%.

Comparative Example 1: Reaction without catalyst
1.34 g (10.3 mmol) of itaconic acid was suspended in 3 mL of dichloromethane, and 3.48 g (30.3 mmol) of dichloromethyl methyl ether was added without adding a catalyst. The mixture was stirred at room temperature for 2 hours, and then further stirred at 40°C for 1 hour and 15 minutes. GCMS detected only itaconic anhydride. Distillation of the solvent yielded 1.12 g of white crystals, and itaconic anhydride with a melting point of 64-68°C was obtained in quantitative yield.
GCMS: m/z=112 (M ⁺ , relative intensity 0.12%), 68 (M ⁺ -CO ₂ , relative intensity 68%), 40 (basepeak).

Comparative Example 2: Use of thionyl chloride and DMF
3.2 g (24.6 mmol) of itaconic acid was suspended in 6 mL of dichloromethane, and one drop of DMF was added. 7.18 g (60.3 mmol) of thionyl chloride was added at room temperature, and the mixture was stirred for 5 hours in a 50°C oil bath (slight reflux). GCMS analysis of the reaction mixture revealed that a large amount of itaconic anhydride was detected, and only a trace amount of itaconic acid chloride was observed.

Comparative Example 3: Use of oxalyl chloride, DMF, and zinc oxide
3.36 g (30.0 mmol) of itaconic anhydride, 15 mg of zinc oxide, 5.0 g (40.0 mmol) of oxalyl chloride, and one drop of DMF were added in that order, and the mixture was stirred for 3 hours at 50° C. GC analysis of the brown reaction mixture revealed that a large amount of itaconic anhydride remained, and only 3% of itaconic acid chloride was produced.

<Reference example: Conversion of zinc oxide to zinc chloride in a reaction system>
162.7 mg (1.02 mmol) of dichloromethyl butyl ether was dissolved in 0.5 mL of anhydrous dichloromethane. 35 mg (0.43 mmol) of zinc oxide was added to this solution and stirred at room temperature for 10 minutes. Analysis of the reaction solution by GC revealed that butyl formate was produced in a total area of 55%.
From these results, it can be inferred that zinc oxide was rapidly converted to zinc chloride, and that this was a quantitative conversion.

As described above, the chlorination reaction of itaconic acid or itaconic anhydride is carried out in the presence of a Lewis acid catalyst using a dichloromethyl alkyl ether represented by general formula (1) defined in the present invention as a chlorinating agent, thereby producing the target product, itaconic acid chloride, in high yield. Itaconic acid chloride can also be obtained in high yield by subjecting the solution after the reaction to a simple distillation treatment.

Claims (3)

A method for producing itaconic acid chloride, comprising reacting itaconic acid or itaconic anhydride with a dichloromethyl alkyl ether represented by the following general formula (1) in the presence of a Lewis acid catalyst:
In the above formula, R represents an alkyl group having 1 to 4 carbon atoms. The method for producing itaconic acid chloride according to claim 1, wherein the Lewis acid catalyst is zinc chloride or zinc oxide. The method for producing itaconic acid chloride according to claim 1 or 2, wherein the dichloromethyl alkyl ether represented by general formula (1) is dichloromethyl propyl ether or dichloromethyl butyl ether.