WO2010038737A1 - Procédé de production d'un composé diester d'acide 6,6'-(alkylènedioxy)di-2-naphthoïque - Google Patents

Procédé de production d'un composé diester d'acide 6,6'-(alkylènedioxy)di-2-naphthoïque Download PDF

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WO2010038737A1
WO2010038737A1 PCT/JP2009/066949 JP2009066949W WO2010038737A1 WO 2010038737 A1 WO2010038737 A1 WO 2010038737A1 JP 2009066949 W JP2009066949 W JP 2009066949W WO 2010038737 A1 WO2010038737 A1 WO 2010038737A1
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formula
naphthoic acid
alkylenedioxy
acid diester
producing
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PCT/JP2009/066949
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English (en)
Japanese (ja)
Inventor
章博 田中
秀樹 武蔵
暢之 垣内
大悟 齊藤
武明 庄子
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日産化学工業株式会社
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Publication of WO2010038737A1 publication Critical patent/WO2010038737A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form

Definitions

  • the present invention relates to a method for producing a 6,6 ′-(alkylenedioxy) di-2-naphthoic acid diester compound.
  • aromatic dicarboxylic acid derivatives have been widely used as raw materials for polyesters and polyimides.
  • terephthalic acid is used as a raw material for polyethylene terephthalate, polybutylene terephthalate and polyparaphenylene terephthalamide
  • naphthalenedicarboxylic acid is used as a raw material for polyethylene naphthalate.
  • Polyethylene naphthalate is known to have higher mechanical and thermal performance than polyethylene terephthalate obtained from terephthalic acid as one raw material. For example, it has been reported that a polyester obtained by polymerizing 6,6 ′-(ethylenedioxy) di-2-naphthoic acid has physical properties superior to those of conventional polyesters (Patent Document 1).
  • Non-Patent Document 4 a reaction in which 6-hydroxy-2-naphthoic acid ester is reacted with alkyl halide and alkyl sulfonate to synthesize 6-alkoxy-2-naphthoic acid ester. This reaction is not satisfactory because the yield is as low as about 60%.
  • JP-A-60-135428 Japanese Patent Laid-Open No. 61-1646 JP 61-161245 A JP-A-9-52863
  • the present invention has been made in view of such circumstances, and is a practical use of 6,6 ′-(alkylenedioxy) di-2-naphthoic acid ester compounds that do not generate harmful by-products such as vinyl chloride.
  • An object of the present invention is to provide a simple manufacturing method.
  • the present inventor has reacted 2-hydroxy-6-naphthoic acid ester compound and alkylene disulfonic acid ester compound in an organic solvent in the presence of a base.
  • the present invention was completed by finding that the desired product was obtained in high yield.
  • R 1 represents an alkyl group having 1 to 20 carbon atoms which may include an ether bond or an ester bond, or a hydroxyalkyl group having 1 to 20 carbon atoms which may include an ether bond or an ester bond.
  • R 1 is represented by formula (6), (In the formula, R 4 represents a hydrogen atom or a methyl group, and l represents an integer of 1 to 4.) 5).
  • R 2 and R 3 are represented by formula (7), (Wherein p represents an integer of 0 to 5) 6).
  • R 2 and R 3 are represented by formula (8): (In the formula, q represents an integer of 0 to 5.) 7).
  • R 2 and R 3 are represented by the formula (9): (Wherein R 5 to R 9 each independently represents a hydrogen atom or a methyl group.) 8).
  • X is represented by the formula (10): (Wherein r represents an integer of 1 to 6) 9.
  • the base is at least one selected from alkali metal inorganic acid salts, alkali metal hydroxides, alkali metal alkoxides and alicyclic amines; 11.
  • the base is selected from sodium carbonate, potassium carbonate, potassium phosphate, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium t-butoxy, and 1,8-diazabicyclo [5.4.0] -7-undecene 10 manufacturing methods which are at least one kind of 12 11.
  • the manufacturing method of 14 whose said organic solvent is cyclohexanone is provided.
  • a 6,6 ′-(alkylenedioxy) di-2-naphthoic acid ester compound can be obtained in high yield.
  • the production method of the present invention is a practical method that can be used as an industrial production method because no harmful by-products such as vinyl chloride are generated.
  • n is normal, “i” is iso, “s” is secondary, “t” is tertiary, “c” is cyclo, “o” is ortho, “M” means meta, and “p” means para.
  • R 1 is an alkyl group having 1 to 20 carbon atoms which may contain an ether bond or an ester bond, or a hydroxy group having 1 to 20 carbon atoms which may contain an ether bond or an ester bond.
  • the alkyl group having 1 to 20 carbon atoms which may contain an ether bond or an ester bond may be linear, branched or cyclic.
  • Examples of the hydroxyalkyl group having 1 to 20 carbon atoms which may contain an ether bond or an ester bond include groups in which at least one hydrogen atom of the alkyl group having 1 to 20 carbon atoms is substituted with a hydroxyl group. . Specifically, hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 1,2-dihydroxyethyl, 2,3-dihydroxy And propyl, 2- (2-hydroxyethoxy) ethyl, 2- (2- (2-hydroxyethoxy) ethoxy) ethyl and the like.
  • R 1 it is particularly preferable to use groups represented by the following formulas (4) to (6) as R 1 .
  • n an integer of 0 to 5.
  • n an integer of 1 to 6.
  • R 4 represents a hydrogen atom or a methyl group, and l represents an integer of 1 to 4.
  • R 2 and R 3 each independently represents an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or 1 to 6 represents an aryl group which may be substituted with 6 alkyl groups.
  • the alkyl group having 1 to 6 carbon atoms may be linear, branched or cyclic, and is methyl, ethyl, n-propyl, i-propyl, c-propyl, n-butyl, i-butyl, s -Butyl, t-butyl, c-butyl, 1-methyl-c-propyl, 2-methyl-c-propyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl -N-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, c-pentyl, 1-methyl -C-butyl, 2-methyl-c-butyl, 3-methyl-c-butyl, 1,2-dimethyl-c-propyl, 2,3-dimethyl-c-
  • haloalkyl group having 1 to 6 carbon atoms examples include groups in which at least one hydrogen atom of the alkyl group having 1 to 6 carbon atoms is substituted with a halogen atom.
  • the halogen atom may be any of chlorine, bromine, iodine and fluorine atoms. Specific examples include trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2,2-pentafluoroethyl, 2,2,3,3,3-pentafluoropropyl, and the like. .
  • hydroxyalkyl group having 1 to 6 carbon atoms examples include groups in which at least one hydrogen atom of the alkyl group having 1 to 6 carbon atoms is substituted with a hydroxyl group. Specific examples include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 1,2-dihydroxyethyl and the like.
  • Examples of the aryl group that may be substituted with an alkyl group having 1 to 6 carbon atoms include a phenyl group, a naphthyl group, and a biphenylyl group that may be substituted with an alkyl group having 1 to 6 carbon atoms.
  • Specific examples of the phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms include phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, p-ethylphenyl and pi-propyl.
  • Examples include phenyl, pt-butylphenyl, 3,5-dimethylphenyl, 3,5-diethylphenyl, 3,5-di-i-propylphenyl, 2,4,6-trimethylphenyl and the like.
  • Specific examples of the naphthyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms include 1-naphthyl, 2-naphthyl, 2-butyl-1-naphthyl, 3-butyl-1-naphthyl and 4-butyl.
  • R 5 to R 9 each independently represents a hydrogen atom or a methyl group.
  • X represents an alkylene group having 1 to 20 carbon atoms which may contain an ether bond or an ester bond.
  • the alkylene group may be linear, branched or cyclic, for example, methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, etc., as an alkylene group containing an ether bond or an ester bond, Examples include the structures shown in the following (a) to (k).
  • the base used in the reaction of the 2-hydroxy-6-naphthoic acid ester compound represented by the above formula (1) and the alkylene disulfonic acid ester compound represented by the above formula (2) is particularly limited.
  • alkali metal inorganic acid salts such as sodium carbonate, potassium carbonate, potassium phosphate, and sodium phosphate
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
  • sodium methoxide, t-butoxy potassium Alkali metal alkoxides such as triethylamine, tri-n-butylamine and other alicyclic amines
  • 1,8-diazabicyclo [5.4.0] -7-undecene hereinafter referred to as DBU), 1,5-diazabicyclo [4] .3.0]
  • Cycloaliphatic amines such as nonene
  • Aromatic amines such as pyridine and 2-methyl-5-ethylpyridine
  • emissions and the like.
  • sodium carbonate, potassium carbonate, potassium phosphate, sodium hydroxide, potassium hydroxide, sodium methoxide, t-butoxy Potassium and DBU are preferable, and potassium carbonate is more preferable.
  • the amount of the base used is not particularly limited and is usually about 1 to 10 equivalents relative to the compound of formula (1), preferably 1 to 5 equivalents, and more preferably 1 to 3 equivalents.
  • the organic solvent used in the reaction is not particularly limited, and any solvent that does not affect the reaction can be appropriately selected and used from various solvents used in general organic synthesis.
  • Specific examples thereof include amide compounds such as N-methyl-2-pyrrolidone (hereinafter referred to as NMP), N, N-dimethylformamide (hereinafter referred to as DMF), N, N-dimethylacetamide; acetonitrile, propionitrile, Nitrile compounds such as butyronitrile; ester compounds such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate; ketone compounds such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone and cyclohexanone; pentane, hexane, cyclohexane, octane and decane Aliphatic hydrocarbon compounds such as decalin and petroleum ether; aromatic hydro
  • At least one selected from NMP, DMF, acetonitrile, butyl acetate, 4-methyl-2-pentanone, and cyclohexanone are preferred, and cyclohexanone is particularly preferred.
  • the reaction temperature is arbitrary as long as it is not higher than the boiling point of the solvent. However, in consideration of obtaining the desired product in a short time and with good yield, it is preferably 20 to 150 ° C, more preferably 50 to 130 ° C, and 70 to 120 ° C. Is even more preferable.
  • the reaction time varies depending on the reaction temperature, the base used, the organic solvent species, and the like, and thus cannot be defined unconditionally, but is usually about 1 to 48 hours. After completion of the reaction, the reaction solution is cooled, and the precipitated crude crystals can be purified by a known method such as recrystallization to obtain a pure target product.
  • Methyl 6-hydroxy-2-naphthoate Tokyo Chemical Industry Co., Ltd. 6-Hydroxy-2-naphthoic acid: Tokyo Chemical Industry Co., Ltd.
  • Ethanol Kanto Chemical Co., Ltd. (special grade) n-Butanol: Pure Chemical Co., Ltd. (1st grade) 2- (2-methoxyethoxy) ethanol: Pure Chemical Co., Ltd. (special grade) 1,2-bis (tosyloxy) ethane: Tokyo Chemical Industry Co., Ltd.
  • Ethylene glycol Kanto Chemical Co., Ltd. (first grade) 1,6-Hexanediol: Pure Chemical Co., Ltd. (1st grade) Diethylene glycol: Kanto Chemical Co., Ltd.
  • the conversion of the 6,6 ′-(alkylenedioxy) di-2-naphthoic acid diester compound represented by the formula (3) was obtained by reverse phase high performance liquid chromatography (manufactured by Agilent, 1100 series). Using the percentage area of the peak in the obtained chart, it was determined by the following calculation formula.
  • the intermediate in the formula means a compound obtained by reacting a 6-hydroxy-2-naphthoic acid ester compound and an alkylene disulfonic acid ester compound on a one-to-one basis.
  • Example 1 Synthesis of methyl 6,6 '-(ethylenedioxy) di-2-naphthoate 0.5 g (2.5 mmol) of methyl 6-hydroxy-2-naphthoate in a 10 ml test tube 1,2-bis (mesyloxy) ethane 0.3 g (1.4 mmol) obtained in Step 1, 0.4 g (2.9 mmol) of potassium carbonate as a base, and 3.0 g of NMP as an organic solvent were added. When the mixture was stirred at 0 ° C. for 2 hours, the conversion was 80%.
  • Example 2 Synthesis of methyl 6,6 '-(ethylenedioxy) di-2-naphthoate
  • a 200 ml four-necked flask 10.1 g (50 mmol) of methyl 6-hydroxy-2-naphthoate, 1, 9.5 g (26 mmol) of 2-bis (tosyloxy) ethane, 5.5 g (40 mmol) of potassium carbonate as a base, and 60.0 g of cyclohexanone as an organic solvent were added and stirred at 115 ° C. for 5 hours. Was 99%. Then, it cooled and filtered and the white crude crystal was obtained. The crude crystals were washed with water and recrystallized with 19 mass times NMP to obtain 9.6 g (yield 89%) of methyl 6,6 ′-(ethylenedioxy) di-2-naphthoate as white crystals.
  • Example 3 to 13 Synthesis of methyl 6,6 '-(ethylenedioxy) di-2-naphthoate Using the same raw materials as in Example 2, the solvent, base, reaction temperature and reaction time are as shown in Table 1. To produce methyl 6,6 ′-(ethylenedioxy) di-2-naphthoate. The conversion rates are also shown in Table 1.
  • Synthesis Example 6 Synthesis of 1,6-bis (tosyloxy) hexane
  • 2.0 g (17 mmol) of 1,6-hexanediol, 6.9 g (68 mmol) of triethylamine, triethylamine hydrochloride 0 .40 g (2.9 mmol) and 13.6 g of acetonitrile were added and stirred, and cooled to 0 ° C. in an ice bath.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un composé diester d'acide 6,6'-(alkylènedioxy)di-2-naphthoïque représenté par la formule (3) qui est produit par réaction d'un composé ester d'acide 2-hydroxy-6-naphthoïque représenté par la formule (1) (dans laquelle R1 représente un groupe alkyle contenant 1 à 20 atomes de carbone qui peut contenir une liaison éther ou une liaison ester, ou une liaison similaire) avec un composé ester d'acide alkylènedisulfonique représenté par la formule (2) (dans laquelle R2 et R3 représentent indépendamment un groupe alkyle contenant 1 à 6 atomes de carbone, ou un groupe similaire, et X représente un groupe alkylène contenant 1 à 20 atomes de carbone qui peut contenir une liaison éther ou une liaison ester) dans un solvant organique en présence d'une base. Ce procédé ne produit pas de sous-produits dangereux comme le chlorure de vinyle et est pratique pour la production d'un composé diester d'acide 6,6'-(alkylènedioxy)di-2-naphthoïque.
PCT/JP2009/066949 2008-10-02 2009-09-29 Procédé de production d'un composé diester d'acide 6,6'-(alkylènedioxy)di-2-naphthoïque WO2010038737A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108558613A (zh) * 2018-06-05 2018-09-21 西安近代化学研究所 一种1，2-二（2-（2,6-二甲基苯氧基）乙氧基）乙烷的制备方法

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CN104768914A (zh) * 2012-11-15 2015-07-08 帝人株式会社 6,6’-(亚乙基二氧基)二-2-萘甲酸二酯的制造方法

Citations (2)

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JPS60215648A (ja) * 1984-04-12 1985-10-29 Teijin Ltd ６，６′−（エチレンジオキシ）−ジ−２−ナフト工酸，その誘導体及びそれらの製造法
JPS61152641A (ja) * 1984-12-27 1986-07-11 Teijin Ltd ビス（β−ヒドロキシエチル）６，６′−（エチレンジオキシ）ジ−２−ナフトエ−ト及びその製造法

Patent Citations (2)

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JPS60215648A (ja) * 1984-04-12 1985-10-29 Teijin Ltd ６，６′−（エチレンジオキシ）−ジ−２−ナフト工酸，その誘導体及びそれらの製造法
JPS61152641A (ja) * 1984-12-27 1986-07-11 Teijin Ltd ビス（β−ヒドロキシエチル）６，６′−（エチレンジオキシ）ジ−２−ナフトエ−ト及びその製造法

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Title
RIEDEL, PAUL J. ET AL.: "Naphthoic acid derivatives as hydrogen bond donors in supramolecular materials", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 102, no. 6, 2006, pages 5890 - 5894 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108558613A (zh) * 2018-06-05 2018-09-21 西安近代化学研究所 一种1，2-二（2-（2,6-二甲基苯氧基）乙氧基）乙烷的制备方法

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