JP2002037759A - Method for producing acrylic acid ester or methacrylic acid ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To a (meth)acrylic acid ester of a hydroxyalkyl group-containing benzoic acid derivative or cinnamic acid derivative, not using a large excess amount of (meth)acrylic acid, preventing the occurrence of a white insoluble matter in a treatment (distillation of acrylic acid used in an excess amount) after the reaction while reducing a by-product. SOLUTION: In this method for producing an acrylic acid ester or a methacrylic acid ester from acrylic acid or methacrylic acid and a corresponding hydroxyalkyl group-containing benzoic acid derivative or cinnamic acid derivative, acrylic acid or methacrylic acid is converted into a corresponding acid halide, the acid halide is not isolated and is reacted with the benzoic acid derivative or the cinnamic acid derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a (meth) acrylate containing an aromatic ring, which is a raw material for a functional polymer such as a liquid crystal polymer.

[0002]

2. Description of the Related Art A process for producing a (meth) acrylate (acrylate or methacrylate) containing no benzoic acid or cinnamic acid in the molecule has been known for a long time. JP-A-42777 describes a method for producing a (meth) acrylate using (meth) acrylic acid and an alcohol in the presence of an acid catalyst. This method is also applied to a method for producing a corresponding (meth) acrylate from a benzoic acid derivative and a cinnamic acid derivative having a hydroxyalkyl group. Research report by Portugall et al. [Makromol. Chem. 183, 2311
(1982)] and a research report by Ahlheim Markus et al. [Makromol. Chem. 193 volumes,
779 (1992)]. It can be produced by a method using an excess of (meth) acrylic acid in the presence of chloroform, which is an azeotropic solvent with water. However, chloroform used in this method is known to be highly toxic. Benzene, which is generally used as an azeotropic solvent with water at 100 ° C. or lower, is also highly toxic. A method in which acrylic acid or methacrylic acid is used as a solvent in place of these highly toxic solvents is disclosed in JP-A-8-310996. However, when acrylic acid or methacrylic acid used in an excessive amount is removed by distillation under reduced pressure, there is a problem that a white insoluble material, which is considered to be a polymer of acrylic acid or methacrylic acid, adheres to the distillation apparatus.

[0003] As another method, for example, D.I. J. B
Roer et al. [Makromol. Chem.
190, 2255 (1989)] and Koch T
Omas et al. [Makromol. Chem.
190, p. 1369 (1989)], and a method using (meth) acrylic acid chloride is known. Since the reaction proceeds rapidly without using a large excess of (meth) acrylic acid chloride, there is an advantage that an insoluble polymer is not generated by an operation after the reaction. However, in this method, (meth) acrylic acid chloride has a strong tearing property, and its handling requires careful attention. Further, (meth) acrylic acid chloride can be obtained as a reagent, but it is difficult to obtain it in large quantities, which has been an obstacle in producing the corresponding acrylate. Furthermore, when (meth) acrylic acid chloride is used when producing (meth) acrylic acid ester from a benzoic acid derivative having a hydroxyalkyl group, there is a problem in that by-products are generated. We analyzed the main by-products and found that hydrogen halide generated during the reaction was a by-product added to the acrylic acid site.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to use a large excess of (meth) acrylic acid when producing a (meth) acrylic ester of a benzoic acid derivative or a cinnamic acid derivative having a hydroxyalkyl group. An object of the present invention is to provide a production method which does not produce white insolubles during the post-reaction treatment (distillation of acrylic acid used in a large excess) without producing by-products.

[0005]

The object of the present invention has been achieved by the following production method. (1) In a method for producing a corresponding acrylic acid or methacrylic acid ester from a benzoic acid derivative or a cinnamic acid derivative having acrylic acid or methacrylic acid and a hydroxyalkyl group, acrylic acid or methacrylic acid is converted to a corresponding acid halide. And reacting the benzoic acid derivative or the cinnamic acid derivative without isolating the acid halide. (2) In a method for producing a corresponding acrylic acid or methacrylic acid ester from an acid halide of acrylic acid or methacrylic acid and a benzoic acid derivative or a cinnamic acid derivative having a hydroxyalkyl group, a conjugate acid is added to the reaction product after completion of the reaction. A method for producing an acrylic ester or a methacrylic ester, wherein a base having a pKa of 6 or more is added and stirred. (3) In a method for producing a corresponding acrylic acid or methacrylic acid ester from an acid halide of acrylic acid or methacrylic acid and a benzoic acid derivative or a cinnamic acid derivative having a hydroxyalkyl group, a conjugate acid is added to the reaction product after completion of the reaction. The method according to (1), wherein a base having a pKa of 6 or more is added and stirred. (4) A synthesis method according to (1), wherein the benzoic acid derivative and the cinnamic acid derivative having a hydroxyalkyl group are represented by the following formula (I): Formula (I)

[0006]

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[In the formula (I), R represents an alkylene group, X represents an oxygen atom or a sulfur atom, and n represents 0 or 1
Represents an integer of. (5) The synthesis method according to (2), wherein the benzoic acid derivative and the cinnamic acid derivative having a hydroxyalkyl group are represented by the above formula (I). (6) The synthesis method according to (3), wherein the benzoic acid derivative and the cinnamic acid derivative having a hydroxyalkyl group are represented by the above formula (I).

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The manufacturing method has at least three steps. That is, (1) a step of producing a corresponding acid halide from (meth) acrylic acid, and then (2) reacting the acid halide with a benzoic acid or cinnamic acid derivative having a hydroxyalkyl group to form a corresponding (meth) acrylic acid. (3) a step of treating the reaction product with a base to reduce impurities.

In the step (1) of producing a corresponding acid halide from (meth) acrylic acid, the amount of (meth) acrylic acid used is based on the molar amount of benzoic acid or cinnamic acid derivative having hydroxyalkyl group charged. 0.8 times to 10
The molar ratio is preferably 0.8 to 5 times, and more preferably 0.9 to 3 times. The reaction solvent is preferably an aprotic solvent. Examples of aprotic solvents include tetrahydrofuran, 1,4-dioxolane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, tetramethylurea, acetonitrile, ethyl acetate, butyl acetate, acetone, Includes dichloromethane, chloroform and hexane.

Regarding the reagent for generating an acid halide,
New Experimental Chemistry, Vol. 14, Synthesis and Reaction of Organic Compounds II,
It is described on pages 1106-1112. Examples of such reagents include thionyl chloride, oxalic acid dichloride, phosphorus oxychloride (phosphoryl chloride), phosphorus trichloride, phosphorus pentachloride, phosgene (and equivalents thereof). Thionyl chloride and oxalic acid dichloride are preferred. The amount of the reagent for generating an acid halide is 0.1 to the charged mole of acrylic acid.
It is preferably from 8 to 3 times, more preferably from 0.9 to 2.5 times, most preferably from 0.9 to 2 times. A catalyst may be used to generate an acid halide. Such catalysts are described in New Experimental Chemistry Course, Vol. 14, Synthesis and Reaction II of Organic Compounds, pp. 1106-1112. Examples of catalysts include zinc chloride, pyridine, triethylamine, iodine and N, N-dimethylformamide. N, N-dimethylformamide is preferred.

In the step (2) of reacting an acid halide with a benzoic acid or cinnamic acid derivative having a hydroxyalkyl group to produce a corresponding (meth) acrylic acid ester, the solution containing an acid halide has a hydroxyalkyl group. A solution containing a benzoic acid or a cinnamic acid derivative may be added, and conversely, a solution containing an acid halide may be added to a solution containing a benzoic acid or a cinnamic acid derivative having a hydroxyalkyl group. In the reaction with an acid halide, a base may be used. However, if the basicity of the base used is strong, benzoic acid (or cinnamic acid) is dissociated to generate a by-product. As the basicity of the base used, the logarithmic value of the acid dissociation constant of the corresponding conjugate acid (pK
Those having a) of 6 or less are preferred. Examples of bases are N, N-
Includes dimethylaniline, pyridine and 2,6-lutidine. N, N-dimethylaniline is preferred.

Finally, in step (3), the reaction product is treated with a base to reduce impurities. When an acid halide is reacted with a benzoic acid or a cinnamic acid derivative having a hydroxyalkyl group, when a base is not used or when a weak base is used, the concentration of hydrogen halide generated increases as the reaction proceeds. As a result, it was found that a compound in which hydrogen halide was newly added to the acrylic acid site of the target product was by-produced. This by-product was difficult to separate from the target substance, and could not be easily removed even when recrystallization was repeated.

As a result of the study by the present inventors, the reaction solution after the reaction or the crude crystals obtained by the treatment after the reaction is stirred is stirred in the presence of a base, and the by-product to which hydrogen halide is added is dehalogenated. It turned out that a hydrogen reaction occurred and it was converted to the target product. The base used at this time preferably has a sufficient basicity to promote the dehydrohalogenation reaction, and a base having a pKa of the conjugate acid of the base of more than 6 is preferable. Examples of the base include triethylamine, isopropyldiethylamine and N-methylpiperidine.

The compounds used in the present invention are preferably those represented by the formula (I). Formula (I)

[0015]

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In the formula, R represents an alkylene group, X represents an oxygen atom or a sulfur atom, and n represents an integer of 0 or 1.
Hereinafter, the formula (I) will be described in more detail. The alkylene group represented by R may be unsubstituted or substituted, and has 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms.
For example, an unsubstituted alkylene group (eg, ethylene, trimethylene, butylene, pentylene, hexylene, 2-ethylbutylene, 3-ethylbutylene), a substituted alkylene (for example, an acylamino group, an alkoxy group, a vinyl Groups, a phenyl group, an acyloxy group, an alkylthio group, an alkoxycarbonyl group, an acyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom), and a cyano group, among which an acylamino group, an alkoxy group, an acyloxy group, The alkoxycarbonyl group and the acyl group preferably have 1 to 20 carbon atoms, and more preferably 1 to 10. Specific examples include 3-methoxybutylene, 2-acetoxypropylene, 2-methylthiobutylene, and 4-methoxycarbonyl. Xylene,
3-acetylbutylene, 5-chlorohexylene). Further, the carbon atom of the alkylene group may be replaced by another atom, for example, an oxygen atom and a sulfur atom, specifically, 2-ethyleneoxyethylene and 2-ethylenethioethylene. X represents an oxygen atom or a sulfur atom, but may be substituted at any position of the aromatic ring, and the aromatic ring may be substituted with a substituent other than X, and the substituent may be a halogen atom, an acetyl group, Examples include a formyl group, a cyano group, a trifluoromethyl group, a difluoromethyl group, a methyl group, and an ethyl group.

Hereinafter, the (meth) produced according to the present invention will be described.
Specific examples of the acrylate and the alcohol derivative used as a raw material are shown.

[0018]

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Ｎ n X Q: hydrogen atom Q: acryloyl Q: Methacryloyl # 2 O 101 201 301 3 O 102 202 302 4 O 103 203 3036 O 104 204 304 8 O 105 205 305 10 O 106 206 306 2 S 107 207 307 3 S 108 208 308 4 S 109 209 309 6 S 110 210 310 8 S 111 211 311 10 S 112 112 212 312 ─────────────────────────────────

[0020]

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Ｎ n X Q: hydrogen atom Q: acryloyl Q: Methacryloyl ０ 0 O 113 213 313 1 O 114 214 214 314 2 O 115 215 315 0 O 116 216 316

[0022]

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──────────────────────────────────── n X Q: hydrogen atom Q: acryloyl Q: Methacryloyl ──────────────────────────────────── 2 O 117 217 317 3 O 118 218 318 4 O 119 219 319 5 O 120 220 320 6 O 121 221 321 7 O 122 222 322 8 O 123 223 323 9 O 124 224 324 10 O 125 225 325 2 S 126 226 326 3 S 127 227 327 428 29 128 228 229 329 8 S 130 230 330 10 10 S 131 231 331

[0024]

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──────────────────────────────────── n X Q: hydrogen atom Q: acryloyl Q: Methacryloyl ──────────────────────────────────── 2 O 132 232 332 4 O 133 233 333 336 O 134 234 334 8 O 135 235 335 4 S 136 236 336 6S 137 237 337 ───

[0026]

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──────────────────────────────────── n X Q: hydrogen atom Q: acryloyl Q: Methacryloyl # 0 O 138 238 338 1 O 139 239 339 2 O 140 240 340 0 S 141 241 341 ────────────────────────────────────

[0028]

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Ｎ n X Q: hydrogen atom Q: acryloyl Q: Methacryloyl ──────────────────────────────────── 0 O 142 242 342 1 O 143 243 343 343 2 O 144 244 344 0 S 145 245 345

[0030]

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──────────────────────────────────── Z Q: hydrogen atom Q: acryloyl Q: methacryloyl ──────────────────────────────────── -CH ₃ 146 246 346 -C ₂ H ₅ 147 247 347 -OCH ₃ 148 248 348 -OC ₂ H ₅ 149 249 349 -CO ₂ CH ₃ 150 250 350 -COCH ₃ 151 251 351 -CF ₃ 152 252 352 -F 153 253 353 -Cl 154 254 354 -Br 155 255 355 I 156 256 356 ────────────────────────────────────

[0032]

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──────────────────────────────────── Z Q: hydrogen atom Q: acryloyl Q: methacryloyl ────────────────────────────────────-OCH ₃ 157 257 357 -OC ₂ H ₅ 158 258 358 -OCOCH ₃ 159 259 359 -CH = CH ₂ 160 260 360 Phenyl 161 261 361 -CO-CH ₃ 162 262 362 362 -SCH ₃ 163 263 363 -CO ₂ CH ₃ 164 264 364 -NHCOCH ₃ 165 265 365 -Br 166 66 366 ────────────────────────────────────

[0034]

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──────────────────────────────────── Q: hydrogen atom Q: acryloyl Q: methacryloyl ─ ─────────────────────────────────── 167 267 367 ──────────── ────────────────────────

[0036]

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──────────────────────────────────── Q: hydrogen atom Q: acryloyl Q: methacryloyl ─ ─────────────────────────────────── 168 268 368 ──────────── ────────────────────────

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──────────────────────────────────── Q: hydrogen atom Q: acryloyl Q: methacryloyl ─ １６ 169 269 369 ──────────── ────────────────────────

[0039]

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──────────────────────────────────── Q: hydrogen atom Q: acryloyl Q: methacryloyl ─ ─────────────────────────────────── 170 270 370 ──────────── ────────────────────────

[0041]

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──────────────────────────────────── Q: hydrogen atom Q: acryloyl Q: methacryloyl ─────────────────────────────────── 171 271 371 ──────────── ────────────────────────

[0043]

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──────────────────────────────────── Q: hydrogen atom Q: acryloyl Q: methacryloyl １７ 172 272 372 ──────────── ────────────────────────

[0045]

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──────────────────────────────────── Q: hydrogen atom Q: acryloyl Q: methacryloyl ─────────────────────────────────── 173 273 373 ──────────── ────────────────────────

[0047]

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──────────────────────────────────── Q: hydrogen atom Q: acryloyl Q: methacryloyl ─ １７ 174 274 374 ──────────── ────────────────────────

[0049]

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Ｎ n X Q: hydrogen atom Q: acryloyl Q: Methacryloyl ──────────────────────────────────── 2 O 401 501 601 3 O 402 502 602 4 O 403 503 603 5 O 404 504 604 6 O 405 505 605 607 7 O 406 506 606 8 O 407 507 607 9 O 408 508 608 10 O 409 509 609 2 S 410 510 610 410 S 411 511 611 511 ────────────────────────────

[0051]

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Ｎn X Q: hydrogen atom Q: acryloyl Q: Methacryloyl ０ 0 O 412 512 612 1 O 413 513 613 613 2 O 414 514 614 0 S 415 515 615 ────────────────────────────────────

[0053]

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Ｎ n X Q: hydrogen atom Q: acryloyl Q: Methacryloyl ──────────────────────────────────── 2 O 416 516 616 3 O 417 517 617 417 O 418 518 618 6 O 419 519 519 8 O 420 520 620 10 O 421 521 621 2S 422 522 622 4 S 423 523 623 ─────────────

[0055]

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Ｎ n X Q: hydrogen atom Q: acryloyl Q: Methacryloyl ──────────────────────────────────── 2 O 424 524 624 3 O 425 525 625 4 O 426 526 626 6 O 427 527 627 8 O 428 528 628 2 S 429 529 629 3 S 430 530 630 4 4 S 431 531 631 ─────────────

[0057]

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──────────────────────────────────── Z Q: hydrogen atom Q: acryloyl Q: methacryloyl ────────────────────────────────────—CH ₃ 432 532 632 -C ₂ H ₅ 433 533 633 —OCH ₃ 434 534 634 —OC ₂ H ₅ 435 535 635 —CO ₂ CH ₃ 436 536 636 —COCH ₃ 437 537 637 —CF ₃ 438 538 638 —F 439 539 639 —Cl 440 540 640 −Br 441 441 441 I 442 542 642 ────────────────────────────────────

[0059]

Example 1 (Synthesis of 503) In a 300 ml three-necked flask, 80 ml of tetrahydrofuran (hereinafter referred to as THF), 8 ml (0.116 mol) of acrylic acid, and N, N-dimethylformamide (hereinafter referred to as DMF). ) Add 0.4 ml and stir. There oxalic acid dichloride 10 ml (0.116 mol)
, And the mixture is heated and stirred at 40 ° C. for 1 hour. Next, a solution of 403 (23 g, 0.1 mol) and N, N-dimethylacetamide (hereinafter referred to as DMAc) is added dropwise. After the addition, the mixture is heated and stirred at 60 ° C. for 1.5 hours.
Next, the reaction solution is cooled and 100 ml of water is added to the reaction solution. The obtained solution is added to 700 ml of water containing 32 ml of concentrated hydrochloric acid and stirred. The resulting solid was filtered by vacuum filtration and dried to obtain 26 g of crude crystals. As a result of analysis by high performance liquid chromatography (hereinafter referred to as HPLC), 32% of hydrogen chloride adduct was contained in addition to the target substance, but no other by-product was contained in 1% or more.

Example 2 (Base treatment of crude crystals of 503) 25 g of crude crystals obtained in Example 1 were dissolved in 130 ml of DMAc, 10 ml of triethylamine was added, and the mixture was stirred at 60 ° C. for 1 hour. The reaction solution is added to 700 ml containing 32 ml of concentrated hydrochloric acid and stirred. The resulting solid was filtered under reduced pressure and dried to obtain 22 g of crude crystals. As a result of analysis by HPLC, no hydrogen chloride adduct was detected, and it was found that the target product 503 contained 99.5%. The target compound was identified by 1H-NMR and elemental analysis.

Example 3 (Method of Base Treatment of Reaction Solution) In a 300 ml three-necked flask, 80 ml of THF, 8 ml (0.116 mol) of acrylic acid, and 0.4 ml of DMF were added and stirred. Thereto, 10 ml (0.116 mol) of oxalic acid dichloride was added dropwise, and after the addition, the mixture was heated and stirred at 40 ° C. for 1 hour. Next 40
A solution of 3 (23 g, 0.1 mol) and DMAc is added dropwise. After the addition, the mixture is heated and stirred at 60 ° C. for 1.5 hours. Next, 40 ml (0.29 mol) of triethylamine was added to the reaction solution, and the mixture was heated and stirred at 60 ° C. for 1.5 hours. After the reaction, the reaction solution was cooled and 100 ml of water was added to the reaction solution. The obtained solution was added to 700 ml of water containing 32 ml of concentrated hydrochloric acid and stirred, and the resulting solid was filtered by filtration under reduced pressure and dried to obtain crude crystals.
g (85%). As a result of analysis by HPLC, no hydrogen chloride adduct was detected, and it was found that the target product 503 contained 99.5%.

Example 4 (Synthesis Example of Benzoic Acid Derivative) The same reaction was carried out using 103 instead of 403 used in Example 3. As a result, 24 g (87%) of 203 was obtained. The structure of the product is 1
It was determined by H-NMR and elemental analysis.

[Example 5] (Synthesis example using thionyl chloride)
The same reaction was carried out using DMAc instead of HF and using thionyl chloride instead of oxalic acid dichloride. As a result, 27 g (93%) of 503 was obtained.

Example 6 (Synthesis of 205) The reaction was carried out in the same manner as in Example 3 except that 105 was used instead of 403. As a result, 27 g (96%) of the target product 205 was obtained.

Example 7 (Synthesis of 254) A reaction was carried out in the same manner as in Example 5 except that 154 was used instead of 403. As a result, 31 g of target product 254 was obtained.

Example 8 (Synthesis of 603) The reaction was carried out in the same manner as in Example 5, except that methacrylic acid was used instead of acrylic acid. As a result, 26 g of target product 603 was obtained.

Comparative Example 1 (Method Using Excess Acrylic Acid) JP-A-8-3109
According to the method described in Example 2 of 96, acrylic acid was reacted with the compound 103 described in the present invention. After the reaction,
When excess acrylic acid was removed under reduced pressure at 70 ° C,
A white insoluble matter adhered to the upper part of the reaction vessel. It could not be removed with an organic solvent such as acetone. Note that the object 20
3 was obtained in an amount of 25 g (95%).

Claims (6)

[Claims] 1. A method for producing a corresponding acrylic acid or methacrylic acid ester from a benzoic acid derivative or a cinnamic acid derivative having acrylic acid or methacrylic acid and a hydroxyalkyl group, wherein acrylic acid or methacrylic acid is converted to a corresponding acid halide. Converting a benzoic acid derivative or a cinnamic acid derivative without isolating the acid halide, and producing the acrylate or methacrylate. 2. A method for producing a corresponding acrylic acid or methacrylic acid ester from an acid halide of acrylic acid or methacrylic acid and a benzoic acid derivative or a cinnamic acid derivative having a hydroxyalkyl group, the reaction product comprising: A method for producing an acrylate or methacrylate, comprising adding a base having a pKa of a conjugate acid of 6 or more and stirring the mixture. 3. A method for producing a corresponding acrylic acid or methacrylic acid ester from an acid halide of acrylic acid or methacrylic acid and a benzoic acid derivative or a cinnamic acid derivative having a hydroxyalkyl group, the method comprising the steps of: The method for producing an acrylate or methacrylate according to claim 1, wherein a base having a pKa of the conjugate acid of 6 or more is added and stirred. 4. The method according to claim 1, wherein the benzoic acid derivative or cinnamic acid derivative having a hydroxyalkyl group is represented by the following formula (I): [In the formula (I), R represents an alkylene group, X represents an oxygen atom or a sulfur atom, and n represents an integer of 0 or 1.] 5. The method according to claim 2, wherein the benzoic acid derivative or cinnamic acid derivative having a hydroxyalkyl group is represented by the following formula (I): [In the formula (I), R represents an alkylene group, X represents an oxygen atom or a sulfur atom, and n represents an integer of 0 or 1.] 6. The method according to claim 3, wherein the benzoic acid derivative and the cinnamic acid derivative having a hydroxyalkyl group are represented by the following formula (I): [In the formula (I), R represents an alkylene group, X represents an oxygen atom or a sulfur atom, and n represents an integer of 0 or 1.]