JP5236274B2 - Method for producing 6-hydroxy-2-naphthoic acid regenerated product - Google Patents
Method for producing 6-hydroxy-2-naphthoic acid regenerated product Download PDFInfo
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- JP5236274B2 JP5236274B2 JP2007332484A JP2007332484A JP5236274B2 JP 5236274 B2 JP5236274 B2 JP 5236274B2 JP 2007332484 A JP2007332484 A JP 2007332484A JP 2007332484 A JP2007332484 A JP 2007332484A JP 5236274 B2 JP5236274 B2 JP 5236274B2
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- naphthoic acid
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- hydroxyethoxy
- naphthoic
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- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 title claims description 93
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- GTBGNVGUBBOCEQ-UHFFFAOYSA-N 6-(2-hydroxyethoxy)naphthalene-2-carboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(OCCO)=CC=C21 GTBGNVGUBBOCEQ-UHFFFAOYSA-N 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 42
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 40
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 claims description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 23
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- -1 alkali metal salt Chemical class 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- IUJMPBDJRAXYCK-UHFFFAOYSA-N 6-[2-(6-carboxynaphthalen-2-yl)oxyethoxy]naphthalene-2-carboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(OCCOC3=CC4=CC=C(C=C4C=C3)C(=O)O)=CC=C21 IUJMPBDJRAXYCK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims description 15
- 150000007513 acids Chemical class 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 11
- 239000012452 mother liquor Substances 0.000 claims description 11
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 10
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 description 29
- AEMBWNDIEFEPTH-UHFFFAOYSA-N n-tert-butyl-n-ethylnitrous amide Chemical compound CCN(N=O)C(C)(C)C AEMBWNDIEFEPTH-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 2
- VIRWKAJWTKAIMA-UHFFFAOYSA-N 2-chloroethyl acetate Chemical compound CC(=O)OCCCl VIRWKAJWTKAIMA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KQQUNPUXYGSGJN-UHFFFAOYSA-N OCCC=1C=C2C=CC(=CC2=CC=1)C(=O)O Chemical compound OCCC=1C=C2C=CC(=CC2=CC=1)C(=O)O KQQUNPUXYGSGJN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- KHKOANDBAAGYCX-UHFFFAOYSA-N methyl 6-(2-hydroxyethoxy)naphthalene-2-carboxylate Chemical compound C1=C(OCCO)C=CC2=CC(C(=O)OC)=CC=C21 KHKOANDBAAGYCX-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- SJJCQDRGABAVBB-UHFFFAOYSA-N 1-hydroxy-2-naphthoic acid Chemical compound C1=CC=CC2=C(O)C(C(=O)O)=CC=C21 SJJCQDRGABAVBB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- LTPOSIZJPSDSIL-UHFFFAOYSA-N 5,6-diphenylmorpholin-2-one Chemical compound O1C(=O)CNC(C=2C=CC=CC=2)C1C1=CC=CC=C1 LTPOSIZJPSDSIL-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XYDJVDKROADETA-UHFFFAOYSA-L [K+].[K+].OC=1C=C2C=CC(=CC2=CC1)C(=O)[O-].OC=1C=C2C=CC(=CC2=CC1)C(=O)[O-] Chemical compound [K+].[K+].OC=1C=C2C=CC(=CC2=CC1)C(=O)[O-].OC=1C=C2C=CC(=CC2=CC1)C(=O)[O-] XYDJVDKROADETA-UHFFFAOYSA-L 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- RJJQNHWDBCGYCD-UHFFFAOYSA-N naphthalen-2-ol;potassium Chemical compound [K].C1=CC=CC2=CC(O)=CC=C21 RJJQNHWDBCGYCD-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000005489 p-toluenesulfonic acid group Chemical class 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- OBNIFGYZZBTPPR-UHFFFAOYSA-M potassium;6-hydroxynaphthalene-2-carboxylate Chemical compound [K+].C1=C(C([O-])=O)C=CC2=CC(O)=CC=C21 OBNIFGYZZBTPPR-UHFFFAOYSA-M 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
本発明は、６−（２-ヒドロキシエトキシ）−２−ナフトエ酸からの６−ヒドロキシ−２−ナフトエ酸再生品の製造方法に関する。 The present invention relates to a method for producing a 6-hydroxy-2-naphthoic acid regenerated product from 6- (2-hydroxyethoxy) -2-naphthoic acid.
６，６’−（エチレンジオキシ）ビス−２−ナフトエ酸（以下ＥＢＮＡとも称する）は、高性能ポリエステルの製造原料として重要な化合物である（特許文献１および２を参照）。 6,6 '-(Ethylenedioxy) bis-2-naphthoic acid (hereinafter also referred to as EBNA) is an important compound as a raw material for producing high-performance polyester (see Patent Documents 1 and 2).
ＥＢＮＡの製造方法としては、６−ヒドロキシ−２−ナフトエ酸のジアルカリ金属塩と１，２−ジハロゲン化エタンを反応させＥＢＮＡのアルカリ金属塩を製造し、次いで、水やエチレングリコールなどの溶媒中でＥＢＮＡのアルカリ金属塩を、ほぼ当量の酸と反応させる方法（特許文献３）が知られている。 As a method for producing EBNA, a dialkali metal salt of 6-hydroxy-2-naphthoic acid and 1,2-dihalogenated ethane are reacted to produce an alkali metal salt of EBNA, and then in a solvent such as water or ethylene glycol. A method of reacting an alkali metal salt of EBNA with an approximately equivalent amount of acid (Patent Document 3) is known.
しかし、特許文献３に記載されるＥＢＮＡの製造方法においては、未反応の２−ヒドロキシ−６−ナフトエ酸のアルカリ金属塩とともに、副生物である６−（２−ヒドロキシエトキシ）−２−ナフトエ酸のアルカリ金属塩が多量に生成する。したがって、反応後の母液から６−ヒドロキシ−２−ナフトエ酸を回収しようとしても、回収物は６−ヒドロキシ−２−ナフトエ酸と６−（２−ヒドロキシエトキシ）−２−ナフトエ酸の混合物となる問題がある。 However, in the method for producing EBNA described in Patent Document 3, 6- (2-hydroxyethoxy) -2-naphthoic acid, which is a by-product, together with an unreacted alkali metal salt of 2-hydroxy-6-naphthoic acid. A large amount of the alkali metal salt is formed. Accordingly, even if 6-hydroxy-2-naphthoic acid is to be recovered from the mother liquor after the reaction, the recovered product is a mixture of 6-hydroxy-2-naphthoic acid and 6- (2-hydroxyethoxy) -2-naphthoic acid. There's a problem.
このため、回収された６−ヒドロキシ−２−ナフトエ酸と６−（２−ヒドロキシエトキシ）−２−ナフトエ酸の混合物から、クロマト分離などの高コストの方法で６−ヒドロキシ−２−ナフトエ酸を回収する必要があり、また、残りは廃棄物として処理されるほかなく、ＥＢＮＡの製造コストは非常に高いものとなっている。 For this reason, 6-hydroxy-2-naphthoic acid is converted from a mixture of recovered 6-hydroxy-2-naphthoic acid and 6- (2-hydroxyethoxy) -2-naphthoic acid by a high-cost method such as chromatographic separation. It is necessary to collect it, and the rest is treated as waste, and the production cost of EBNA is very high.
これらの問題から、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸から６−ヒドロキシ−２−ナフトエ酸を製造し、ＥＢＮＡの製造原料として再利用可能とする方法の開発が望まれている。
本発明の目的は、６−(２-ヒドロキシエトキシ)−２−ナフトエ酸から６−ヒドロキシ−２−ナフトエ酸再生品を製造する方法を提供することにある。さらに、本発明の目的は、６−ヒドロキシ−２−ナフトエ酸再生品を用いる６，６’−（エチレンジオキシ）ビス−２−ナフトエ酸の製造方法を提供することにある。 An object of the present invention is to provide a method for producing a 6-hydroxy-2-naphthoic acid regenerated product from 6- (2-hydroxyethoxy) -2-naphthoic acid. Another object of the present invention is to provide a method for producing 6,6 '-(ethylenedioxy) bis-2-naphthoic acid using a 6-hydroxy-2-naphthoic acid regenerated product.
本発明は、６−（２-ヒドロキシエトキシ）−２−ナフトエ酸を、硫酸、塩酸およびｐ−トルエンスルホン酸からなる群より選択される１種以上の酸と、水中にて１５０〜２５０℃において反応させることを含む、６−ヒドロキシ−２−ナフトエ酸再生品の製造方法を提供する。 The present invention relates to 6- (2-hydroxyethoxy) -2-naphthoic acid, one or more acids selected from the group consisting of sulfuric acid, hydrochloric acid and p-toluenesulfonic acid at 150 to 250 ° C. in water. Provided is a method for producing a 6-hydroxy-2-naphthoic acid regenerated product, which comprises reacting.
さらに、本発明は、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸および６−ヒドロキシ−２−ナフトエ酸を含むナフトエ酸組成物を、硫酸、塩酸およびｐ−トルエンスルホン酸からなる群より選択される１種以上の酸と、水中にて１５０〜２５０℃において反応させることを含む、６−ヒドロキシ−２−ナフトエ酸再生品の製造方法を提供する。 Further, in the present invention, the naphthoic acid composition containing 6- (2-hydroxyethoxy) -2-naphthoic acid and 6-hydroxy-2-naphthoic acid is selected from the group consisting of sulfuric acid, hydrochloric acid and p-toluenesulfonic acid. There is provided a method for producing a 6-hydroxy-2-naphthoic acid regenerated product, which comprises reacting with one or more kinds of acids in water at 150 to 250 ° C.
本明細書および特許請求の範囲において、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸、または、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸および６−ヒドロキシ−２−ナフトエ酸を含むナフトエ酸組成物を、硫酸、塩酸およびｐ−トルエンスルホン酸からなる群より選択される１種以上の酸と、水中にて１５０〜２５０℃において反応させることにより製造された、６−ヒドロキシ−２−ナフトエ酸を主成分とする製品を「６−ヒドロキシ−２−ナフトエ酸再生品」と表す。
「６−ヒドロキシ−２−ナフトエ酸を主成分とする」とは、製品中に、製品の乾燥重量に対して６−ヒドロキシ−２−ナフトエ酸を５０重量％以上含むことをいう。
In the present specification and claims, 6- (2-hydroxyethoxy) -2-naphthoic acid or 6- (2-hydroxyethoxy) -2-naphthoic acid and 6-hydroxy-2-naphthoic acid are included. 6-hydroxy-2 produced by reacting a naphthoic acid composition with one or more acids selected from the group consisting of sulfuric acid, hydrochloric acid and p-toluenesulfonic acid in water at 150 to 250 ° C. -A product mainly composed of naphthoic acid is referred to as "6-hydroxy-2-naphthoic acid recycled product".
“Mainly containing 6-hydroxy-2-naphthoic acid” means that the product contains 50% by weight or more of 6-hydroxy-2-naphthoic acid based on the dry weight of the product.
本発明において用いる、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸の製造方法は特に制限されないが、例えば、６−ヒドロキシ−２−ナフトエ酸のエステル誘導体（例えば、メチルエステル、エチルエステル）を、エチレンオキシドなどと反応させ、ヒドロキシエチル化を行い、次いでエステル基を加水分解することにより製造することができる。また６−ヒドロキシ−２−ナフトエ酸を、塩基性条件にて、酢酸２−クロロエチルと反応させエーテル化を行った後に、脱アセチル化することによっても製造することができる。 The method for producing 6- (2-hydroxyethoxy) -2-naphthoic acid used in the present invention is not particularly limited. For example, ester derivatives of 6-hydroxy-2-naphthoic acid (for example, methyl ester, ethyl ester) are used. It can be produced by reacting with ethylene oxide, etc., performing hydroxyethylation, and then hydrolyzing the ester group. Alternatively, it can also be produced by reacting 6-hydroxy-2-naphthoic acid with 2-chloroethyl acetate under basic conditions and etherifying, followed by deacetylation.
本発明において、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸は、単一の化合物として使用してもよいし、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸および６−ヒドロキシ−２−ナフトエ酸を含むナフトエ酸組成物に含まれる形態で用いてもよい。 In the present invention, 6- (2-hydroxyethoxy) -2-naphthoic acid may be used as a single compound, or 6- (2-hydroxyethoxy) -2-naphthoic acid and 6-hydroxy-2. -You may use in the form contained in the naphthoic acid composition containing a naphthoic acid.
本明細書および特許請求の範囲において、ナフトエ酸組成物とは、その乾燥重量中、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸および６−ヒドロキシ−２−ナフトエ酸を合計量で、３０重量％以上、より好ましくは５０重量％以上、特に好ましくは７０重量％以上含むものである。 In the present specification and claims, the naphthoic acid composition is a total amount of 6- (2-hydroxyethoxy) -2-naphthoic acid and 6-hydroxy-2-naphthoic acid in the dry weight of 30. It contains at least 50% by weight, more preferably at least 50% by weight, particularly preferably at least 70% by weight.
ナフトエ酸組成物中の６−ヒドロキシ−２−ナフトエ酸および６−（２−ヒドロキシエトキシ）−２−ナフトエ酸の含有量は、高速液体クロマトグラフなどの常法によって確認することができる。 The contents of 6-hydroxy-2-naphthoic acid and 6- (2-hydroxyethoxy) -2-naphthoic acid in the naphthoic acid composition can be confirmed by a conventional method such as high performance liquid chromatography.
本発明において使用するナフトエ酸組成物としては、以下の（１）〜（５）の工程により得られたものを用いるのが好ましい。
（１）６−ヒドロキシ−２−ナフトエ酸と塩基性アルカリ金属化合物を反応させて６−ヒドロキシ−２−ナフトエ酸のジアルカリ金属塩の水溶液を調製する工程、
（２）６−ヒドロキシ−２−ナフトエ酸のジアルカリ金属塩と、１，２−ジハロゲン化エタンを反応させ、６，６’−（エチレンジオキシ）ビス−２−ナフトエ酸のアルカリ金属塩を調製する工程、
（３）工程（２）で得られた反応液を、６，６’−（エチレンジオキシ）ビス−２−ナフトエ酸のアルカリ金属塩と母液とに分離する工程、
（４）工程（３）で得られた母液を酸性化し、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸および６−ヒドロキシ−２−ナフトエ酸を含むナフトエ酸組成物を析出させる工程、および、
（５）工程（４）にて析出したナフトエ酸組成物を回収する工程。
As the naphthoic acid composition used in the present invention, those obtained by the following steps (1) to (5) are preferably used.
(1) reacting 6-hydroxy-2-naphthoic acid with a basic alkali metal compound to prepare an aqueous solution of a dialkali metal salt of 6-hydroxy-2-naphthoic acid,
(2) A dialkali metal salt of 6-hydroxy-2-naphthoic acid and 1,2-dihalogenated ethane are reacted to prepare an alkali metal salt of 6,6 ′-(ethylenedioxy) bis-2-naphthoic acid The process of
(3) A step of separating the reaction solution obtained in step (2) into an alkali metal salt of 6,6 ′-(ethylenedioxy) bis-2-naphthoic acid and a mother liquor,
(4) acidifying the mother liquor obtained in step (3) to precipitate a naphthoic acid composition containing 6- (2-hydroxyethoxy) -2-naphthoic acid and 6-hydroxy-2-naphthoic acid, and ,
(5) A step of recovering the naphthoic acid composition precipitated in step (4).
以下に、上記の工程（１）〜（５）について説明する。
まず、工程（１）について説明する。
工程（１）において用いる塩基性アルカリ金属化合物の好適な例としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、ナトリウムメトキシド、カリウムメトキシドなどが挙げられる。これらの中では入手が容易で取り扱いやすいことなどから、水酸化ナトリウムおよび／または水酸化カリウムを用いるのがより好ましく、水酸化カリウムを単独で用いるのが特に好ましい。
Below, said process (1)-(5) is demonstrated.
First, step (1) will be described.
Preferable examples of the basic alkali metal compound used in step (1) include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide and the like. Among these, sodium hydroxide and / or potassium hydroxide is more preferable because it is easily available and easy to handle, and it is particularly preferable to use potassium hydroxide alone.
６−ヒドロキシ−２−ナフトエ酸のジアルカリ金属塩の水溶液は、６−ヒドロキシ−２−ナフトエ酸と塩基性アルカリ金属化合物を、水を溶媒に用いて反応させることにより調製することができる。 An aqueous solution of a dialkali metal salt of 6-hydroxy-2-naphthoic acid can be prepared by reacting 6-hydroxy-2-naphthoic acid with a basic alkali metal compound using water as a solvent.
６−ヒドロキシ−２−ナフトエ酸は工業的に入手可能なものを用いればよいが、一般的には以下に記載する方法などにより製造することが出来る。
６−ヒドロキシ−２−ナフトエ酸は、特開昭５７−０９５９３９号公報や、特開昭５８−０９９４３６号公報に記載される方法などを参照し、β−ナフトールカリウムと二酸化炭素とを高温、高圧で反応させるコルベ・シュミット法により６−ヒドロキシ−２−ナフトエ酸のカリウム塩を生成させた後に、６−ヒドロキシ−２−ナフトエ酸のカリウム塩の水溶液を調製し、得られた水溶液を酸析し、析出する６−ヒドロキシ−２−ナフトエ酸を分離回収することにより製造することが出来る。
６−ヒドロキシ−２−ナフトエ酸は、所望により、水、メタノール、エタノール、メタノール水溶液、エタノール水溶液などの溶媒を用いて再結晶を行う方法などによって精製した後に使用してもよい。
6-Hydroxy-2-naphthoic acid may be an industrially available one, but can generally be produced by the method described below.
6-Hydroxy-2-naphthoic acid is obtained by referring to the method described in JP-A-57-095939 and JP-A-58-099436, and the like, by adding β-naphthol potassium and carbon dioxide at high temperature and high pressure. After producing a potassium salt of 6-hydroxy-2-naphthoic acid by the Kolbe-Schmidt method to be reacted in Step 1, an aqueous solution of 6-hydroxy-2-naphthoic acid potassium salt is prepared, and the obtained aqueous solution is acidified. It can be produced by separating and recovering the precipitated 6-hydroxy-2-naphthoic acid.
If desired, 6-hydroxy-2-naphthoic acid may be used after purification by a method of recrystallization using a solvent such as water, methanol, ethanol, aqueous methanol solution, aqueous ethanol solution or the like.
６−ヒドロキシ−２−ナフトエ酸と塩基性アルカリ金属化合物を反応させる温度は特に制限されないが、１０〜１００℃が好ましく、５０〜１００℃がより好ましい。 The temperature at which 6-hydroxy-2-naphthoic acid is reacted with the basic alkali metal compound is not particularly limited, but is preferably 10 to 100 ° C, more preferably 50 to 100 ° C.
６−ヒドロキシ−２−ナフトエ酸と塩基性アルカリ金属化合物の反応は、空気中で行ってもよいが、窒素、ヘリウム、アルゴンなどの不活性ガス雰囲気下で行うのがより好ましい。 The reaction of 6-hydroxy-2-naphthoic acid and a basic alkali metal compound may be performed in air, but is more preferably performed in an inert gas atmosphere such as nitrogen, helium, or argon.
６−ヒドロキシ−２−ナフトエ酸ジアルカリ金属塩を調製する際の、６−ヒドロキシ−２−ナフトエ酸に対する塩基性アルカリ金属化合物の使用量は、アルカリ金属として６−ヒドロキシ−２−ナフトエ酸１モルに対して１．８〜２．２モルであるのが好ましく、１．９〜２．１モルであるのがより好ましい。 When preparing a 6-hydroxy-2-naphthoic acid dialkali metal salt, the amount of the basic alkali metal compound used for 6-hydroxy-2-naphthoic acid is 1 mol of 6-hydroxy-2-naphthoic acid as an alkali metal. The amount is preferably 1.8 to 2.2 mol, more preferably 1.9 to 2.1 mol.
６−ヒドロキシ−２−ナフトエ酸と塩基性アルカリ金属化合物を反応させる圧力は特に制限されず、大気圧下、減圧下、加圧下の何れの条件でもよい。 The pressure at which 6-hydroxy-2-naphthoic acid is reacted with the basic alkali metal compound is not particularly limited, and may be any condition under atmospheric pressure, reduced pressure, or increased pressure.
次いで、工程（２）について説明する。
工程（２）において用いられる１，２−ジハロゲン化エタンとして好適なものとしては、１，２−ジクロロエタン、１，２−ジブロモエタン、またはこれらの混合物が挙げられ、これらの中では１，２−ジクロロエタンを単独で用いるのがより好ましい。
１，２−ジクロロエタン、１，２−ジブロモエタンなどの１，２−ジハロゲン化エタンは、工業的に入手可能なものを用いればよい。
Next, step (2) will be described.
Suitable examples of the 1,2-dihalogenated ethane used in step (2) include 1,2-dichloroethane, 1,2-dibromoethane, or a mixture thereof. More preferably, dichloroethane is used alone.
As the 1,2-dihalogenated ethane such as 1,2-dichloroethane and 1,2-dibromoethane, those commercially available may be used.
１，２−ジハロゲン化エタンの使用量は、６−ヒドロキシ−２−ナフトエ酸ジアルカリ金属塩１モルに対して、０．３〜０．６モル用いるのが好ましく、０．４〜０．５８モル用いるのがより好ましく、０．４５〜０．５５モル用いるのが特に好ましい。 The amount of 1,2-dihalogenated ethane used is preferably 0.3 to 0.6 mol, preferably 0.4 to 0.58 mol, per mol of 6-hydroxy-2-naphthoic acid dialkali metal salt. It is more preferable to use it, and it is especially preferable to use 0.45-0.55 mol.
工程（２）において、６−ヒドロキシ−２−ナフトエ酸ジアルカリ金属塩と１，２−ジハロゲン化エタンを反応させる温度としては５０〜２５０℃が好ましく、６０〜２２０℃がより好ましく、８０〜２００℃が特に好ましい。 In the step (2), the temperature at which 6-hydroxy-2-naphthoic acid dialkali metal salt and 1,2-dihalogenated ethane are reacted is preferably 50 to 250 ° C, more preferably 60 to 220 ° C, and 80 to 200 ° C. Is particularly preferred.
６−ヒドロキシ−２−ナフトエ酸ジアルカリ金属塩と１，２−ジハロゲン化エタンの反応温度が反応液の沸点を超える場合は、耐圧反応装置を用いて反応を行えばよい。 When the reaction temperature of 6-hydroxy-2-naphthoic acid dialkali metal salt and 1,2-dihalogenated ethane exceeds the boiling point of the reaction solution, the reaction may be carried out using a pressure resistant reactor.
６−ヒドロキシ−２−ナフトエ酸ジアルカリ金属塩と１，２−ジハロゲン化エタンを反応させる時間は、反応が良好に進行する限り特に制限されないが、典型的には０．５〜５０時間、より好ましくは１〜１０時間で行われる。 The time for reacting the dialkali metal salt of 6-hydroxy-2-naphthoic acid and 1,2-dihalogenated ethane is not particularly limited as long as the reaction proceeds well, but typically 0.5 to 50 hours, more preferably Is performed in 1 to 10 hours.
次に、工程（３）について説明する。
工程（２）によって、６，６’−（エチレンジオキシ）ビス−２−ナフトエ酸のアルカリ金属塩（モノアルカリ金属塩とジアルカリ金属塩の混合物）が析出した懸濁液が得られる。該懸濁液を、遠心分離、フィルタープレスなどの常法を用いて、６，６’−（エチレンジオキシ）ビス−２−ナフトエ酸のアルカリ金属塩と母液とに分離すればよい。
Next, process (3) is demonstrated.
By the step (2), a suspension in which an alkali metal salt of 6,6 ′-(ethylenedioxy) bis-2-naphthoic acid (a mixture of a monoalkali metal salt and a dialkali metal salt) is obtained. The suspension may be separated into an alkali metal salt of 6,6 ′-(ethylenedioxy) bis-2-naphthoic acid and a mother liquor using conventional methods such as centrifugation and filter press.
次に工程（４）について説明する。
工程（４）において、工程（３）で得られた母液の酸性化に用いる酸は、硫酸、塩酸、硝酸などの無機酸や、酢酸、蟻酸、プロピオン酸、安息香酸などの有機酸を用いればよい。母液を酸性化する際のｐＨは１〜５が好ましく、1〜４がより好ましい。
Next, process (4) is demonstrated.
In step (4), the acid used for acidification of the mother liquor obtained in step (3) may be an inorganic acid such as sulfuric acid, hydrochloric acid or nitric acid, or an organic acid such as acetic acid, formic acid, propionic acid or benzoic acid. Good. 1-5 are preferable and, as for pH at the time of acidifying a mother liquid, 1-4 are more preferable.
母液の酸性化を行う際の雰囲気や温度は、６−ヒドロキシ−２−ナフトエ酸および６−（２−ヒドロキシエトキシ）−２−ナフトエ酸を含むナフトエ酸組成物を回収可能であれば特に制限されず、雰囲気としては窒素、ヘリウム、アルゴンなどの不活性ガス雰囲気で行うのがよく、温度としては０〜１００℃で行うのが好ましく、１０〜９０℃で行うのがより好ましく、２０〜８０℃で行うのが特に好ましい。 The atmosphere and temperature for acidifying the mother liquor are particularly limited as long as a naphthoic acid composition containing 6-hydroxy-2-naphthoic acid and 6- (2-hydroxyethoxy) -2-naphthoic acid can be recovered. However, the atmosphere is preferably an inert gas atmosphere such as nitrogen, helium, and argon, and the temperature is preferably 0 to 100 ° C, more preferably 10 to 90 ° C, and more preferably 20 to 80 ° C. It is particularly preferable to carry out at
次に工程（５）について説明する。
工程（５）において、工程（４）で析出させたナフトエ酸組成物を回収する方法は特に制限されないが、遠心分離やフィルタープレスなどの常法により行えばよい。
Next, process (5) is demonstrated.
In the step (5), the method for recovering the naphthoic acid composition precipitated in the step (4) is not particularly limited, but may be performed by a conventional method such as centrifugation or filter press.
このようにして、工程（１）〜（５）を経て得られた、６−ヒドロキシ−２−ナフトエ酸および６−（２−ヒドロキシエトキシ）−２−ナフトエ酸を含むナフトエ酸組成物は、所望により乾燥した後に、酸との反応工程に用いればよい。 Thus, the naphthoic acid composition containing 6-hydroxy-2-naphthoic acid and 6- (2-hydroxyethoxy) -2-naphthoic acid obtained through steps (1) to (5) is desired. After drying by the above method, it may be used in a reaction step with an acid.
本発明において、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸、または、６−ヒドロキシ−２−ナフトエ酸および６−（２−ヒドロキシエトキシ）−２−ナフトエ酸を含むナフトエ酸組成物との反応に使用する酸としては、硫酸、塩酸およびｐ−トルエンスルホン酸からなる群より選択される１種以上の酸を用いる。 In the present invention, 6- (2-hydroxyethoxy) -2-naphthoic acid or a naphthoic acid composition containing 6-hydroxy-2-naphthoic acid and 6- (2-hydroxyethoxy) -2-naphthoic acid As the acid used for the reaction, one or more acids selected from the group consisting of sulfuric acid, hydrochloric acid and p-toluenesulfonic acid are used.
これらの酸のなかでは、安価であり、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸との反応の際に副反応が起こりにくいことなどから、硫酸を単独で使用するのがより好ましい。 Among these acids, it is more preferable to use sulfuric acid alone because it is inexpensive and hardly causes side reactions during the reaction with 6- (2-hydroxyethoxy) -2-naphthoic acid.
酸の使用量としては、反応が良好に進行するかぎり特に制限されないが、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸のモル数に対して、０．５〜１０倍モルが好ましく、１．０〜３．０倍モルがより好ましい。 The amount of acid used is not particularly limited as long as the reaction proceeds satisfactorily, but is preferably 0.5 to 10-fold moles relative to the number of moles of 6- (2-hydroxyethoxy) -2-naphthoic acid. 0.0-3.0 times mole is more preferable.
ナフトエ酸組成物を用いる場合には、ナフトエ酸組成物中の６−（２−ヒドロキシエトキシ）−２−ナフトエ酸含有量を勘案して、酸の使用量を定めればよい。 When the naphthoic acid composition is used, the amount of acid used may be determined in consideration of the 6- (2-hydroxyethoxy) -2-naphthoic acid content in the naphthoic acid composition.
本発明において、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸、または、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸および６−ヒドロキシ−２−ナフトエ酸を含むナフトエ酸組成物と、硫酸、塩酸およびｐ−トルエンスルホン酸からなる群より選択される１種以上の酸との反応に用いる溶媒は水である。溶媒に用いる水は、本発明の目的を損なわない範囲で、トルエン、キシレンなどの６−（２−ヒドロキシエトキシ）−２−ナフトエ酸と硫酸、塩酸およびｐ−トルエンスルホン酸からなる群より選択される１種以上の酸との反応に不活性な有機溶媒を含んでいてもよい。 In the present invention, 6- (2-hydroxyethoxy) -2-naphthoic acid or a naphthoic acid composition containing 6- (2-hydroxyethoxy) -2-naphthoic acid and 6-hydroxy-2-naphthoic acid, The solvent used for the reaction with one or more acids selected from the group consisting of sulfuric acid, hydrochloric acid and p-toluenesulfonic acid is water. Water used for the solvent is selected from the group consisting of 6- (2-hydroxyethoxy) -2-naphthoic acid such as toluene and xylene, sulfuric acid, hydrochloric acid, and p-toluenesulfonic acid, as long as the object of the present invention is not impaired. An organic solvent inert to the reaction with one or more acids may be included.
溶媒である水が有機溶媒を含む場合の有機溶媒の含有量は、水と有機溶媒の合計重量に対して３０重量％以下が好ましく、２０重量％以下がより好ましく、１０重量％以下が特に好ましい。 When the solvent water contains an organic solvent, the content of the organic solvent is preferably 30% by weight or less, more preferably 20% by weight or less, and particularly preferably 10% by weight or less based on the total weight of water and the organic solvent. .
溶媒である水の使用量は、反応が良好に進行する限り特に制限されないが、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸、または、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸および６−ヒドロキシ−２−ナフトエ酸を含むナフトエ酸組成物の乾燥重量に対して、０．５〜１００重量倍用いるのが好ましく、１〜５０重量倍用いるのがより好ましく、２〜３０重量倍用いるのが特に好ましい。 The amount of water used as a solvent is not particularly limited as long as the reaction proceeds well, but 6- (2-hydroxyethoxy) -2-naphthoic acid or 6- (2-hydroxyethoxy) -2-naphthoic acid And 0.5 to 100 times by weight, more preferably 1 to 50 times by weight, more preferably 2 to 30 times by weight based on the dry weight of the naphthoic acid composition containing 6-hydroxy-2-naphthoic acid It is particularly preferable to use it.
本発明において、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸、または、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸および６−ヒドロキシ−２−ナフトエ酸を含むナフトエ酸組成物と、硫酸、塩酸およびｐ−トルエンスルホン酸からなる群より選択される１種以上の酸との反応は、１５０〜２５０℃、より好ましくは１５０〜２００℃で行う。 In the present invention, 6- (2-hydroxyethoxy) -2-naphthoic acid or a naphthoic acid composition containing 6- (2-hydroxyethoxy) -2-naphthoic acid and 6-hydroxy-2-naphthoic acid, The reaction with one or more acids selected from the group consisting of sulfuric acid, hydrochloric acid and p-toluenesulfonic acid is carried out at 150 to 250 ° C, more preferably 150 to 200 ° C.
反応温度が１５０℃より低ければ、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸から６−ヒドロキシ−２−ナフトエ酸への変換が効率よく行われにくく、２５０℃より高ければ、生成した６−ヒドロキシ−２−ナフトエ酸が脱炭酸などの副反応により分解しやすい傾向がある。 If the reaction temperature is lower than 150 ° C., the conversion of 6- (2-hydroxyethoxy) -2-naphthoic acid to 6-hydroxy-2-naphthoic acid is difficult to be carried out efficiently. -Hydroxy-2-naphthoic acid tends to be easily decomposed by side reactions such as decarboxylation.
本発明においては、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸、または、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸および６−ヒドロキシ−２−ナフトエ酸を含むナフトエ酸組成物と、硫酸、塩酸およびｐ−トルエンスルホン酸からなる群より選択される１種以上の酸との反応温度が、溶媒に用いる水の沸点より高いため、反応装置には、耐圧反応装置（オートクレーブ）を用いる。 In the present invention, 6- (2-hydroxyethoxy) -2-naphthoic acid, or a naphthoic acid composition containing 6- (2-hydroxyethoxy) -2-naphthoic acid and 6-hydroxy-2-naphthoic acid, Since the reaction temperature with one or more acids selected from the group consisting of sulfuric acid, hydrochloric acid and p-toluenesulfonic acid is higher than the boiling point of water used for the solvent, the reactor is equipped with a pressure-resistant reactor (autoclave). Use.
６−（２−ヒドロキシエトキシ）−２−ナフトエ酸、または、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸および６−ヒドロキシ−２−ナフトエ酸を含むナフトエ酸組成物と、硫酸、塩酸およびｐ−トルエンスルホン酸からなる群より選択される１種以上の酸との反応を行う反応装置内の雰囲気は特に制限されないが、窒素、ヘリウム、アルゴンなどの不活性ガス雰囲気が好ましい。 6- (2-hydroxyethoxy) -2-naphthoic acid or a naphthoic acid composition comprising 6- (2-hydroxyethoxy) -2-naphthoic acid and 6-hydroxy-2-naphthoic acid, sulfuric acid, hydrochloric acid and The atmosphere in the reaction apparatus for performing the reaction with one or more acids selected from the group consisting of p-toluenesulfonic acid is not particularly limited, but an inert gas atmosphere such as nitrogen, helium, or argon is preferable.
６−（２−ヒドロキシエトキシ）−２−ナフトエ酸、または、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸および６−ヒドロキシ−２−ナフトエ酸を含むナフトエ酸組成物と、硫酸、塩酸およびｐ−トルエンスルホン酸からなる群より選択される１種以上の酸との反応時間は特に制限されないが、通常、１〜２０時間、より好ましくは６〜１０時間で行われる。 6- (2-hydroxyethoxy) -2-naphthoic acid or a naphthoic acid composition comprising 6- (2-hydroxyethoxy) -2-naphthoic acid and 6-hydroxy-2-naphthoic acid, sulfuric acid, hydrochloric acid and The reaction time with one or more acids selected from the group consisting of p-toluenesulfonic acids is not particularly limited, but is usually 1 to 20 hours, more preferably 6 to 10 hours.
反応の完了は、反応液の試料を一部採取し、高速液体クロマトグラフなどの常法により分析し、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸の含有量を測定することによって確認することが出来る。 Completion of the reaction is confirmed by taking a sample of the reaction solution, analyzing it by a conventional method such as high performance liquid chromatography, and measuring the content of 6- (2-hydroxyethoxy) -2-naphthoic acid. I can do it.
以上説明した反応を終了した後に、反応液を０〜８０℃程度に冷却し、反応液中に析出している６−ヒドロキシ−２−ナフトエ酸の再生品を、遠心分離やフィルタープレスなどの常法により回収すればよい。 After the reaction described above is completed, the reaction solution is cooled to about 0 to 80 ° C., and the regenerated product of 6-hydroxy-2-naphthoic acid precipitated in the reaction solution is usually centrifuged or filtered. It may be recovered by the law.
このようにして得られる、６−ヒドロキシ−２−ナフトエ酸の再生品は、６−ヒドロキシ−２−ナフトエ酸の含有量と６−（２−ヒドロキシエチル）−２−ナフトエ酸の含有量の合計に対する、６−（２−ヒドロキシエチル）−２−ナフトエ酸の含有量の比率が１０重量％以下であるのが好ましく、５重量％以下であるのがより好ましい。 The regenerated product of 6-hydroxy-2-naphthoic acid thus obtained is the sum of the content of 6-hydroxy-2-naphthoic acid and the content of 6- (2-hydroxyethyl) -2-naphthoic acid. The ratio of the content of 6- (2-hydroxyethyl) -2-naphthoic acid relative to is preferably 10% by weight or less, and more preferably 5% by weight or less.
以上のように、本発明の方法によって、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸、または、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸および６−ヒドロキシ−２−ナフトエ酸を含むナフトエ酸組成物から、安価に６−ヒドロキシ−２−ナフトエ酸再生品を製造することが可能となり、さらに本発明の６−ヒドロキシ−２−ナフトエ酸再生品を、ＥＢＮＡ製造原料である６−ヒドロキシ−２−ナフトエ酸の一部または全部に用いることによってＥＢＮＡを安価に製造することが可能になるものである。 As described above, according to the method of the present invention, 6- (2-hydroxyethoxy) -2-naphthoic acid, or 6- (2-hydroxyethoxy) -2-naphthoic acid and 6-hydroxy-2-naphthoic acid are converted. The 6-hydroxy-2-naphthoic acid regenerated product can be produced at low cost from the naphthoic acid composition containing the 6-hydroxy-2-naphthoic acid regenerated product of the present invention. EBNA can be produced at low cost by using a part or all of hydroxy-2-naphthoic acid.
６−ヒドロキシ−２−ナフトエ酸再生品を原料の一部または全部に用いるＥＢＮＡの製造方法としては、以下の（Ａ）〜（Ｃ）の工程を含むＥＢＮＡの製造方法が好適である。
（Ａ）６−ヒドロキシ−２−ナフトエ酸と塩基性アルカリ金属化合物を反応させて６−ヒドロキシ−２−ナフトエ酸のジアルカリ金属塩の水溶液を調製する工程、
（Ｂ）６−ヒドロキシ−２−ナフトエ酸のジアルカリ金属塩を１，２−ジハロゲン化エタンと反応させ、６，６’−（エチレンジオキシ）ビス−２−ナフトエ酸のアルカリ金属塩を調製する工程、および、
（Ｃ）６，６’−（エチレンジオキシ）ビス−２−ナフトエ酸のアルカリ金属塩を酸と反応させ、６，６’−（エチレンジオキシ）ビス−２−ナフトエ酸とする工程。
As a method for producing EBNA using 6-hydroxy-2-naphthoic acid regenerated product as a part or all of the raw material, a method for producing EBNA including the following steps (A) to (C) is suitable.
(A) a step of reacting 6-hydroxy-2-naphthoic acid with a basic alkali metal compound to prepare an aqueous solution of a dialkali metal salt of 6-hydroxy-2-naphthoic acid,
(B) A dialkali metal salt of 6-hydroxy-2-naphthoic acid is reacted with 1,2-dihalogenated ethane to prepare an alkali metal salt of 6,6 ′-(ethylenedioxy) bis-2-naphthoic acid. Process, and
(C) A step of reacting an alkali metal salt of 6,6 ′-(ethylenedioxy) bis-2-naphthoic acid with an acid to obtain 6,6 ′-(ethylenedioxy) bis-2-naphthoic acid.
以下、実施例により本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail by way of examples.
〔参考例１：６−（２−ヒドロキシエトキシ）−２−ナフトエ酸の調製〕
６−ヒドロキシ−２−ナフトエ酸メチル３４．４ｇ、炭酸カリウム２６．０ｇ、ポリエチレングリコール０．３ｇ、およびＮ，Ｎ−ジメチルホルムアミド１８３ｇを攪拌装置、温度計、およびジムロート冷却器を備える容量３００ｍｌの四つ口フラスコに仕込み、窒素雰囲気下に８０℃まで昇温した後、酢酸２−クロロエチル２５．２ｇを２０分かけて滴下した。
[Reference Example 1: Preparation of 6- (2-hydroxyethoxy) -2-naphthoic acid]
Methyl 6-hydroxy-2-naphthoate (34.4 g), potassium carbonate (26.0 g), polyethylene glycol (0.3 g), and N, N-dimethylformamide (183 g) were mixed with a stirrer, thermometer, and Dimroth condenser. After charging into a necked flask and raising the temperature to 80 ° C. in a nitrogen atmosphere, 25.2 g of 2-chloroethyl acetate was added dropwise over 20 minutes.
次いで、８０〜９０℃で２４時間攪拌した後に、水１２８ｇおよびメタノール６４ｇを加え、更に６５〜７５℃にて８時間攪拌し反応を行った。 Subsequently, after stirring at 80-90 degreeC for 24 hours, 128 g of water and 64 g of methanol were added, and also it stirred at 65-75 degreeC for 8 hours, and reacted.
反応終了後に、反応液より析出物をろ過により回収し、乾燥することで６−（２−ヒドロキシエトキシ）−２−ナフトエ酸メチルを３２．３ｇ得た。 After completion of the reaction, the precipitate was collected from the reaction solution by filtration and dried to obtain 32.3 g of methyl 6- (2-hydroxyethoxy) -2-naphthoate.
得られた６−（２−ヒドロキシエトキシ）−２−ナフトエ酸メチル３１．６ｇ、４８％水酸化ナトリウム水溶液１０．３ｇ、および５０％メタノール水溶液３５０ｇを温度計、およびジムロート冷却器を備える容量５００ｍｌの四つ口フラスコに仕込み、窒素雰囲気下にて、２時間還流させた。この反応液に７０％硫酸水溶液１８．５ｇを１時間かけて滴下し、析出物をろ過により回収し、乾燥することで６−（２−ヒドロキシエトキシ）−２−ナフトエ酸２９．８ｇを得た。 The obtained methyl 6- (2-hydroxyethoxy) -2-naphthoate (31.6 g), 48% aqueous sodium hydroxide solution (10.3 g), and 50% aqueous methanol solution (350 g) were thermometerd and a 500 ml capacity equipped with a Dimroth condenser A four-necked flask was charged and refluxed for 2 hours under a nitrogen atmosphere. To this reaction solution, 18.5 g of 70% aqueous sulfuric acid was added dropwise over 1 hour, and the precipitate was collected by filtration and dried to obtain 29.8 g of 6- (2-hydroxyethoxy) -2-naphthoic acid. .
〔参考例２：６−ヒドロキシ−２−ナフトエ酸および６-(２-ヒドロキシエトキシ)−２−ナフトエ酸を含むナフトエ酸組成物の調製〕
○ＥＢＮＡカリウム塩の製造
６−ヒドロキシ−２−ナフトエ酸ジカリウム塩１５０モルを含む水溶液１４０ｋｇとジクロロエタン７．４ｋｇ（７５モル）を、容量１９０Ｌの攪拌機を備えた耐圧容器に仕込んだ。耐圧容器を密閉した後、攪拌下に反応液を１４０〜１５０℃に昇温し、同温度にて１時間反応した。
反応終了後、反応液を３０℃まで冷却した後、遠心分離機により、析出したＥＢＮＡのカリウム塩を母液と分離し、分離されたＥＢＮＡのカリウム塩を遠心分離機上で水４０Ｋｇにより洗浄した。得られた母液（洗浄水を含む）の重量は１６０Ｋｇであった。
[Reference Example 2: Preparation of naphthoic acid composition containing 6-hydroxy-2-naphthoic acid and 6- (2-hydroxyethoxy) -2-naphthoic acid]
Production of EBNA potassium salt 140 kg of an aqueous solution containing 150 mol of 6-hydroxy-2-naphthoic acid dipotassium salt and 7.4 kg (75 mol) of dichloroethane were charged into a pressure vessel equipped with a stirrer having a capacity of 190 L. After sealing the pressure vessel, the reaction solution was heated to 140-150 ° C. with stirring and reacted at the same temperature for 1 hour.
After completion of the reaction, the reaction solution was cooled to 30 ° C., and then the precipitated potassium salt of EBNA was separated from the mother liquor with a centrifuge, and the separated potassium salt of EBNA was washed with 40 kg of water on the centrifuge. The weight of the mother liquor obtained (including washing water) was 160 kg.
○ナフトエ酸組成物の回収
ＥＢＮＡのカリウム塩の製造工程により得られた母液１６０Ｋｇを、容量３００Ｌの攪拌機を備えた容器に仕込み、９５℃に昇温した後に、７０％硫酸水溶液を用いて１時間かけてｐＨ３に調整した。次いで、析出物を遠心分離機により回収した後に乾燥し、６−ヒドロキシ−２−ナフトエ酸および６−（２−ヒドロキシエトキシ）−２−ナフトエ酸を含むナフトエ酸組成物２０Ｋｇを得た。
Recovery of naphthoic acid composition 160 Kg of mother liquor obtained by the process of producing EBNA potassium salt was charged into a vessel equipped with a 300 L capacity stirrer, heated to 95 ° C, and then 1 hour using 70% aqueous sulfuric acid. To adjust the pH to 3. Next, the precipitate was collected by a centrifuge and then dried to obtain 20 kg of a naphthoic acid composition containing 6-hydroxy-2-naphthoic acid and 6- (2-hydroxyethoxy) -2-naphthoic acid.
得られたナフトエ酸組成物は、６−ヒドロキシ−２−ナフトエ酸を５７重量％、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸を１５．１重量％含むものであった。 The obtained naphthoic acid composition contained 57% by weight of 6-hydroxy-2-naphthoic acid and 15.1% by weight of 6- (2-hydroxyethoxy) -2-naphthoic acid.
〔実施例１〕
参考例１の方法に従い調製した６−（２−ヒドロキシエトキシ）−２−ナフトエ酸３１．８ｇ(０．１４ｍｏｌ)、７０ｗｔ％硫酸水溶液１９．２ｇ(０．２８ｍｏｌ)、および水４５０ｇを容量１Ｌのオートクレーブに仕込み、窒素置換した後１８０℃にて６時間反応を行った。
[Example 1]
6- (2-hydroxyethoxy) -2-naphthoic acid 31.8 g (0.14 mol) prepared according to the method of Reference Example 1, 19.2 g (0.28 mol) of 70 wt% sulfuric acid aqueous solution, and 450 g of water having a capacity of 1 L The mixture was charged into an autoclave and purged with nitrogen, and then reacted at 180 ° C. for 6 hours.
反応終了後、反応液を室温まで冷却した後、析出物をろ過により回収し、乾燥することにより６−ヒドロキシ−２−ナフトエ酸再生品２４．２ｇを得た。 After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitate was collected by filtration and dried to obtain 24.2 g of a 6-hydroxy-2-naphthoic acid regenerated product.
得られた６−ヒドロキシ−２−ナフトエ酸再生品の組成を表１に記す。 The composition of the obtained 6-hydroxy-2-naphthoic acid regenerated product is shown in Table 1.
〔実施例２〕
７０ｗｔ％硫酸水溶液の使用量を９．６ｇ（０．１４ｍｏｌ）に変えることの他は、実施例１と同様にして、６−ヒドロキシ−２−ナフトエ酸再生品２４．５ｇを得た。
[Example 2]
24.5 g of a 6-hydroxy-2-naphthoic acid regenerated product was obtained in the same manner as in Example 1 except that the amount of the 70 wt% sulfuric acid aqueous solution was changed to 9.6 g (0.14 mol).
得られた６−ヒドロキシ−２−ナフトエ酸再生品の組成を表１に示す。 The composition of the obtained 6-hydroxy-2-naphthoic acid regenerated product is shown in Table 1.
〔実施例３〕
６−（２−ヒドロキシエトキシ）−２−ナフトエ酸１０．０ｇ（４３ｍｍｏｌ）、３５ｗｔ％塩酸水溶液４．９ｇ（４７ｍｍｏｌ）、および水４８５ｇを容量１Ｌのオートクレーブに仕込み、窒素置換した後１８０℃にて６時間反応を行った。
Example 3
An autoclave having a capacity of 1 L was charged with 10.0 g (43 mmol) of 6- (2-hydroxyethoxy) -2-naphthoic acid, 4.9 g (47 mmol) of 35 wt% hydrochloric acid aqueous solution, and 485 g of water. The reaction was performed for 6 hours.
反応終了後、反応液を室温まで冷却した後、析出物をろ過により回収し、乾燥することにより６−ヒドロキシ−２−ナフトエ酸再生品７．５ｇを得た。 After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitate was collected by filtration and dried to obtain 7.5 g of a 6-hydroxy-2-naphthoic acid regenerated product.
得られた６−ヒドロキシ−２−ナフトエ酸再生品の組成を表１に記す。 The composition of the obtained 6-hydroxy-2-naphthoic acid regenerated product is shown in Table 1.
〔実施例４〕
６−（２−ヒドロキシエトキシ）−２−ナフトエ酸１０．０（４３ｍｍｏｌ）ｇ、ｐ−トルエンスルホン酸一水和物（ＰＴＳ）９．０ｇ（４７ｍｍｏｌ）、および水４８１ｇを容量１Ｌのオートクレーブに仕込み、窒素置換した後に、１８０℃にて６時間反応を行った。
Example 4
An autoclave having a capacity of 1 L was charged with 10.0 (43 mmol) g of 6- (2-hydroxyethoxy) -2-naphthoic acid, 9.0 g (47 mmol) of p-toluenesulfonic acid monohydrate (PTS), and 481 g of water. After purging with nitrogen, the reaction was carried out at 180 ° C. for 6 hours.
反応終了後、反応液を室温まで冷却した後、析出物をろ過により回収し、乾燥することにより６−ヒドロキシ−２−ナフトエ酸の再生品７．７ｇを得た。 After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitate was collected by filtration and dried to obtain 7.7 g of a regenerated product of 6-hydroxy-2-naphthoic acid.
得られた６−ヒドロキシ−２−ナフトエ酸再生品の組成を表１に記す。 The composition of the obtained 6-hydroxy-2-naphthoic acid regenerated product is shown in Table 1.
表１：６−ヒドロキシ−２−ナフトエ酸再生品の組成
〔実施例５〕
６−ヒドロキシ−２−ナフトエ酸２８．５ｇ（１５１ｍｍｏｌ）、および６−（２−ヒドロキシエトキシ）−２−ナフトエ酸７．６ｇ（３３ｍｍｏｌ）を含む、参考例２で得られたナフトエ酸組成物５０ｇと、７０ｗｔ％硫酸水溶液３５．７ｇ（２５５ｍｍｏｌ）、および水５００を容量１Ｌのオートクレーブに仕込み、窒素置換した後に、１８０℃にて６時間反応を行った。
Example 5
50 g of the naphthoic acid composition obtained in Reference Example 2 containing 28.5 g (151 mmol) of 6-hydroxy-2-naphthoic acid and 7.6 g (33 mmol) of 6- (2-hydroxyethoxy) -2-naphthoic acid Then, 35.7 g (255 mmol) of 70 wt% sulfuric acid aqueous solution and water 500 were charged into an autoclave having a capacity of 1 L, purged with nitrogen, and then reacted at 180 ° C. for 6 hours.
反応終了後、反応液を室温まで冷却した後、析出物をろ過により回収し、乾燥することにより６−ヒドロキシ−２−ナフトエ酸の再生品４７．８ｇを得た。 After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitate was collected by filtration and dried to obtain 47.8 g of a regenerated product of 6-hydroxy-2-naphthoic acid.
得られた６−ヒドロキシ−２−ナフトエ酸再生品の組成を表２に記す。 The composition of the obtained 6-hydroxy-2-naphthoic acid regenerated product is shown in Table 2.
〔実施例６〜８、比較例１〕
硫酸の使用量を表２に記載する量に変えることの他は、実施例５と同様にして、６−ヒドロキシ−２−ナフトエ酸再生品を得た。
[Examples 6 to 8, Comparative Example 1]
A 6-hydroxy-2-naphthoic acid regenerated product was obtained in the same manner as in Example 5 except that the amount of sulfuric acid used was changed to the amount shown in Table 2.
得られた６−ヒドロキシ−２−ナフトエ酸再生品の組成を表２に記す。 The composition of the obtained 6-hydroxy-2-naphthoic acid regenerated product is shown in Table 2.
表２：６−ヒドロキシ−２−ナフトエ酸再生品の組成
＊２：検出されず。
Table 2: Composition of 6-hydroxy-2-naphthoic acid recycled products
* 2: Not detected.
Claims (4)
（１）６−ヒドロキシ−２−ナフトエ酸と塩基性アルカリ金属化合物を反応させて６−ヒドロキシ−２−ナフトエ酸のジアルカリ金属塩の水溶液を調製する工程、
（２）６−ヒドロキシ−２−ナフトエ酸のジアルカリ金属塩と、１，２−ジハロゲン化エタンを反応させ、６，６’−（エチレンジオキシ）ビス−２−ナフトエ酸のアルカリ金属塩を調製する工程、
（３）工程（２）で得られた反応液を、６，６’−（エチレンジオキシ）ビス−２−ナフトエ酸のアルカリ金属塩と母液とに分離する工程、
（４）工程（３）で得られた母液を酸性化し、６−（２−ヒドロキシエトキシ）−２−ナフトエ酸および６−ヒドロキシ−２−ナフトエ酸を含むナフトエ酸組成物を析出させる工程、および、
（５）工程（４）にて析出したナフトエ酸組成物を回収する工程。 The method for producing a 6-hydroxy-2-naphthoic acid recycled product according to claim 2, wherein the naphthoic acid composition is obtained by the following steps (1) to (5):
(1) reacting 6-hydroxy-2-naphthoic acid with a basic alkali metal compound to prepare an aqueous solution of a dialkali metal salt of 6-hydroxy-2-naphthoic acid,
(2) A dialkali metal salt of 6-hydroxy-2-naphthoic acid and 1,2-dihalogenated ethane are reacted to prepare an alkali metal salt of 6,6 ′-(ethylenedioxy) bis-2-naphthoic acid The process of
(3) A step of separating the reaction solution obtained in step (2) into an alkali metal salt of 6,6 ′-(ethylenedioxy) bis-2-naphthoic acid and a mother liquor,
(4) acidifying the mother liquor obtained in step (3) to precipitate a naphthoic acid composition containing 6- (2-hydroxyethoxy) -2-naphthoic acid and 6-hydroxy-2-naphthoic acid, and ,
(5) A step of recovering the naphthoic acid composition precipitated in step (4).
（Ａ）６−ヒドロキシ−２−ナフトエ酸と塩基性アルカリ金属化合物を反応させて６−ヒドロキシ−２−ナフトエ酸のジアルカリ金属塩の水溶液を調製する工程、
（Ｂ）６−ヒドロキシ−２−ナフトエ酸のジアルカリ金属塩を１，２−ジハロゲン化エタンと反応させ、６，６’−（エチレンジオキシ）ビス−２−ナフトエ酸のアルカリ金属塩を調製する工程、および、
（Ｃ）６，６’−（エチレンジオキシ）ビス−２−ナフトエ酸のアルカリ金属塩を酸と反応させ、６，６’−（エチレンジオキシ）ビス−２−ナフトエ酸とする工程。 6. A method for producing 6,6 ′-(ethylenedioxy) bis-2-naphthoic acid, including the following steps (A) to (C), which is used in step (A): 6-hydroxy-2- A part or all of naphthoic acid is a 6-hydroxy-2-naphthoic acid regenerated product obtained by the method according to any one of claims 1 to 3, wherein 6,6 '-(ethylenedioxy) bis- Method for producing 2-naphthoic acid:
(A) a step of reacting 6-hydroxy-2-naphthoic acid with a basic alkali metal compound to prepare an aqueous solution of a dialkali metal salt of 6-hydroxy-2-naphthoic acid,
(B) A dialkali metal salt of 6-hydroxy-2-naphthoic acid is reacted with 1,2-dihalogenated ethane to prepare an alkali metal salt of 6,6 ′-(ethylenedioxy) bis-2-naphthoic acid. Process, and
(C) A step of reacting an alkali metal salt of 6,6 ′-(ethylenedioxy) bis-2-naphthoic acid with an acid to obtain 6,6 ′-(ethylenedioxy) bis-2-naphthoic acid.
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