JPH02235844A - Production of hydroxynaphthalenecarboxylic acid - Google Patents
Production of hydroxynaphthalenecarboxylic acidInfo
- Publication number
- JPH02235844A JPH02235844A JP1055142A JP5514289A JPH02235844A JP H02235844 A JPH02235844 A JP H02235844A JP 1055142 A JP1055142 A JP 1055142A JP 5514289 A JP5514289 A JP 5514289A JP H02235844 A JPH02235844 A JP H02235844A
- Authority
- JP
- Japan
- Prior art keywords
- alkali metal
- hydroxynaphthalene
- acid
- reaction
- ability
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 15
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000008096 xylene Substances 0.000 claims abstract description 4
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 3
- 229920000570 polyether Polymers 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 44
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000012453 solvate Substances 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 36
- 239000001569 carbon dioxide Substances 0.000 abstract description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 18
- -1 alkali metal salt Chemical class 0.000 abstract description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract description 13
- 239000000975 dye Substances 0.000 abstract description 6
- 238000002955 isolation Methods 0.000 abstract description 5
- 230000000269 nucleophilic effect Effects 0.000 abstract description 2
- 238000007614 solvation Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 239000008346 aqueous phase Substances 0.000 description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 8
- 239000007810 chemical reaction solvent Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- 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 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001535 HNCA Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 150000001339 alkali metal compounds Chemical class 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 241001494479 Pecora Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 1
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 1
- VWVRASTUFJRTHW-UHFFFAOYSA-N 2-[3-(azetidin-3-yloxy)-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound O=C(CN1C=C(C(OC2CNC2)=N1)C1=CN=C(NC2CC3=C(C2)C=CC=C3)N=C1)N1CCC2=C(C1)N=NN2 VWVRASTUFJRTHW-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101000654316 Centruroides limpidus Beta-toxin Cll2 Proteins 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021395 porridge Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はα−ナフトール、β−ナ７トール等のヒドロキ
シナフタリンのアルカリ金属塩と二酸化炭素との反応に
よるヒドロキシナフタリンカルがン酸の製法に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for producing hydroxynaphthalene carboxylic acid by reacting an alkali metal salt of hydroxynaphthalene such as α-naphthol or β-na7tol with carbon dioxide. .
更Ｋ詳しくは、該反応を芳香族炭化水素類を溶媒として
用い、アルカリ金属イオンと求核的溶媒和する能力を有
する非プロトン性溶媒および／又はアルカリ金属イオン
と配位する能力ｔ−１する化合物の存在下、常圧または
加圧下で行う事によク１−ヒドロキシナフタリンー２−
カルゲン酸、２−ヒドロキシナフタリン−１−カルゲン
酸等のヒドロキシナフタリンカルゲン酸を極めて高い収
率で得る方法に関するものである。More specifically, the reaction is carried out using aromatic hydrocarbons as a solvent, and an aprotic solvent having the ability to nucleophilically solvate an alkali metal ion and/or the ability to coordinate with an alkali metal ion (t-1). In the presence of a compound, 1-hydroxynaphthalene-2-
The present invention relates to a method for obtaining hydroxynaphthalenecargenic acid such as cargenic acid and 2-hydroxynaphthalene-1-cargeneic acid in an extremely high yield.
（従来の技術）
１−ヒドロキシナフタリン−２−カル〆ン酸（以下、１
− ＨＮＣＡと略記する。）あるいは２−ヒドロキシ
ナフタリン−１−カル〆ンａ！（以下、２ − ＨＮＣ
Ａと略記する）は、染料、感熱染料、写真材料等の中間
体として利用され、工業的に有用な化合物である。従来
よシα−ナフトールあるいはβ−ナフトールのカリウム
塩あるいはナトリウム塩を、ノオキサンあるいはピリジ
ン等の極性溶剤中で二酸化炭素と反応させる事Ｋより、
１−ＨＮＣＡあるいは２ − ＨＮＣＡを得る方法は知
られている。例えば、Ｊ．ｐｒ拳Ｃｈ＠ｍ．，（ＩＶ）
２．５３（１９５５ ）にはβ−ナフトールのカリウ
ム塩を二酸化炭素とソオキサン中で５５℃で３時間反応
させる事により８２重量襲の収率で２ − ｝ｎＩＪｃ
Ａを得ている事が報告されている。またＰｏｌｔｓｈ．
１００ ， ９５４にはα−ナフトールのナトリウム
塩と二酸化炭素をピリジンとヅオキサンの混合溶媒中で
反応温度７０℃で３時間反応させる事により１ − Ｈ
ＮＣＡが４４重量％の収率で得られる事が報告されてい
る。(Prior art) 1-Hydroxynaphthalene-2-carboxylic acid (hereinafter referred to as 1
- Abbreviated as HNCA. ) or 2-hydroxynaphthalene-1-carline a! (Hereinafter, 2-HNC
A) is used as an intermediate for dyes, heat-sensitive dyes, photographic materials, etc., and is an industrially useful compound. Conventionally, potassium salt or sodium salt of α-naphthol or β-naphthol is reacted with carbon dioxide in a polar solvent such as nooxane or pyridine.
Methods for obtaining 1-HNCA or 2-HNCA are known. For example, J. pr fist Ch@m. ,(IV)
2.53 (1955), the potassium salt of β-naphthol was reacted with carbon dioxide in sooxane at 55°C for 3 hours to produce 2-}nIJc in a yield of 82% by weight.
It has been reported that he received an A. Also Poltsh.
100, 954, 1-H was obtained by reacting the sodium salt of α-naphthol with carbon dioxide in a mixed solvent of pyridine and duoxane at a reaction temperature of 70°C for 3 hours.
It has been reported that NCA can be obtained in a yield of 44% by weight.
（発明が解決しようとする課題）
しかし、これらの方法は必ずしも収率が高いとは言えず
、また、生成した１ − ｝［ＮＣＡあるいは２−ΔＣ
Ａを反応系より単離する事が容易でないという問題があ
る。すなわち、α−あるいはβ−ナフトールのカリウム
塩あるいはナトリウム塩と二酸化炭素の反応では、最初
Ｋ１−あるいは２−ヒドロキシナフタリンカルボ／酸の
カリウムあるいはナ｝ ＩＪウム塩が生成するが、これ
らを有離酸である１ − ＨＮＣＡあるいは２ − Ｈ
ＮＣＡとして単離するには、反応後、反応溶液中に水を
添加して、それらの塩を水Ｋ抽出し、その後得られた水
相を鉱酸で醸性にして酸析する方法が一般的である。し
かし、ジオキサン等の水溶性の極性溶剤を用いている場
合Ｋ反応溶液Ｋ水を添加すると、水相が反応溶媒である
ジオキサンと均一になり、生成物の１−オるいは２−ヒ
ドロキナフタリンカルゲン酸のカリウムあるいはナ｝
ＩＪウム塩が反応溶媒から分離できない事Ｋなる。一方
、生成物の単離を容易Ｋする為、水に不溶解な溶媒、す
なわちトルエン等の芳香族炭化水素系の溶媒を反応溶媒
として用いた場合には反応収率が極めて低いと言う問題
がある。(Problems to be Solved by the Invention) However, these methods cannot necessarily be said to have high yields, and the produced 1-}[NCA or 2-ΔC
There is a problem that it is not easy to isolate A from the reaction system. That is, in the reaction of potassium salt or sodium salt of α- or β-naphthol with carbon dioxide, potassium or sodium salt of K1- or 2-hydroxynaphthalene carbo/acid is first produced, but these are converted into free acid. 1-HNCA or 2-H
To isolate NCA, the general method is to add water to the reaction solution after the reaction, extract the salts with water, and then acidify the resulting aqueous phase with mineral acid. It is true. However, when a water-soluble polar solvent such as dioxane is used, adding K water to the K reaction solution will make the aqueous phase homogeneous with the reaction solvent dioxane, and the product 1- or 2-hydroquinaphthalene cargen. acid potassium or sodium
This means that the IJ salt cannot be separated from the reaction solvent. On the other hand, when a water-insoluble solvent, that is, an aromatic hydrocarbon solvent such as toluene, is used as a reaction solvent to facilitate isolation of the product, there is a problem that the reaction yield is extremely low. be.
（ｖＩＡ題を解決するための手段）
本発明者らは、上述した問題のないヒドロキシナフタリ
ンカルボン酸の製法を鋭意研究した結果、ヒドロキシナ
フタリンのアルカリ金属塩と二駿化炭素との反応を、溶
媒として芳香族炭化水素類を用い、アルカリ金属イオン
と求核的溶媒和する能力を有する非プロトン性溶媒およ
び／又はアルカリ金属イオンと配位する能力を有する化
合物の存在下、常圧または加圧下で行うと、好収率でヒ
ドロキシナフタリンカルゲン酸が得られ、また生成物の
反応系からの単離が容易であることを見い出し、本発明
を完成するに至った。(Means for Solving the vIA Problem) As a result of intensive research into a method for producing hydroxynaphthalene carboxylic acid free from the above-mentioned problems, the present inventors discovered that the reaction between an alkali metal salt of hydroxynaphthalene and carbon disuride was Using aromatic hydrocarbons as a solvent, in the presence of an aprotic solvent having the ability to nucleophilically solvate with alkali metal ions and/or a compound having the ability to coordinate with alkali metal ions, under normal pressure or increased pressure. When carried out, hydroxynaphthalene cargenic acid was obtained in good yield and the product was found to be easily isolated from the reaction system, leading to the completion of the present invention.
すなわち本発明は、ヒドロキシナフタリンのアルカリ金
属塩と二酸化炭素とを、芳香族炭化水素類を溶媒とし、
アルカリ金属イオンと求核的溶媒和する能力を有する非
プロトン性溶媒および／又はアルカリ金属イオンと配位
する能力を有する化合物の存在下に反応させることを特
徴とするヒドロキシナ７タリンカルゲン酸の製法を提供
するものである。That is, the present invention uses an alkali metal salt of hydroxynaphthalene and carbon dioxide, an aromatic hydrocarbon as a solvent,
A method for producing hydroxyna-7-talincargenic acid, characterized by reacting it in the presence of an aprotic solvent having the ability to nucleophilically solvate with an alkali metal ion and/or a compound having the ability to coordinate with an alkali metal ion. It provides:
本発明で用いるヒドロキシナフタリンのアルカリ金属塩
としては、例えばα−あるいはβ−ナ７トールのナトリ
ウム塩あるいはカリウム塩が好ましい。これらは充分脱
水されていることが必要であり、常法によりα−あるい
はβ−ナフトールと水酸化ナトリウム、水酸化カリウム
、炭酸ナトリウム、炭酸カリウム等のアルカリ金属化合
物とから作ることができる。例えば、α−あるいはβ一
ナフトールに対し０．９７〜１．０３当量比でアルカリ
金属化合物を反応させ、その後窒素等の不活性ガスの気
流下、常圧あるいは減圧下で１００〜３００℃Ｋ加熱し
、脱水することにょシ作ることができる。あるいは本発
明で用いる反応溶媒中でα一あるいはβ−ナフトールを
アルカリ金属化合物と反応させ、その後共沸脱水するこ
とＫよシ作ることもでき、この場合はそのまま反応に使
用できるので特に有利である。As the alkali metal salt of hydroxynaphthalene used in the present invention, for example, sodium salt or potassium salt of α- or β-natol is preferable. These need to be sufficiently dehydrated and can be prepared from α- or β-naphthol and an alkali metal compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. by a conventional method. For example, an alkali metal compound is reacted with α- or β-naphthol at an equivalent ratio of 0.97 to 1.03, and then heated at 100 to 300°C under a stream of inert gas such as nitrogen at normal pressure or reduced pressure. It can also help with dehydration. Alternatively, it can be prepared by reacting α- or β-naphthol with an alkali metal compound in the reaction solvent used in the present invention and then azeotropically dehydrating it. In this case, it is particularly advantageous because it can be used as is in the reaction. .
本発明で反応溶媒として使用する芳香族炭化水素類とし
ては、例えばベンゼン、トルエン、キシレン、エチルベ
ンゼン、イソプロビルベンゼン、メシチレン、グノイド
キエメン、エチルトルエン等を挙げる事ができ、それぞ
れ単独あるいは二種以上混合して使用する。Examples of the aromatic hydrocarbons used as a reaction solvent in the present invention include benzene, toluene, xylene, ethylbenzene, isopropylbenzene, mesitylene, gnoid oxide, and ethyltoluene, each of which may be used alone or in combination of two or more. and use it.
使用される芳香族炭化水素類は、原料であるヒドロキシ
ナフタリンのアルカリ金属塩の使用量に対して０． １
〜２０の重量倍の量が通常使用されるが、ナフトールの
塩が容易に溶解し、かつ反応後のヒドロキシナフタリン
カルゲン酸を単離する操作が容易な点から１〜５重量倍
の範囲で使用すると好ましい●
一方、芳香族炭化水素溶媒と同時Ｋ用いられるアルカリ
金属イオンと求核的溶媒和する能力を有する非グロト／
性溶媒としては、例えばアセトン、メチルエチルケトン
、メチルイソプチルケトン、シクロヘキサノン等のケト
ン類；テトラヒドロフラン、ジオキサン、１，２−ノメ
トキシエタン、ジフヱニルエーテル、ジエチルエーテル
、ジイソグロビルエーテル等のエーテル類；ジメチルホ
ルムアミド、ジメチルアセトアミド、Ｎ−メテルピロリ
ド／等のアミド類；アセトニトリル、グロビオニトリル
、ペンゾニトリル等ノ二｝ ＩＪ ル類； ｘチレンカ
ー〆＄−｝、：７’ロピレンカー〆ネート、シメチルカ
ーゲネート、ノフェニルカーボネート等のカー〆ネート
類；ニトロベンゼン、二トロトルエン、ニトロアニソー
ル等の二トロ化合物；ゾメチルスルホキシド、テトラメ
チレンスルホラン、ノメチルスルホラン等の有機イオウ
酸化物などを挙げる事ができ、なかでもジメチルスルホ
キシド、ゾオキサ／、二トロベンゼンが特に好ましい。The aromatic hydrocarbons used are 0.0% relative to the amount of the alkali metal salt of hydroxynaphthalene used as the raw material. 1
The amount is usually used in an amount of ~20 times the weight, but it is used in a range of 1 to 5 times the weight because the naphthol salt is easily dissolved and the operation for isolating the hydroxynaphthalene cargenic acid after the reaction is easy. It is preferable that ● On the other hand, non-glotto/
Examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as tetrahydrofuran, dioxane, 1,2-nomethoxyethane, diphenyl ether, diethyl ether, and diisoglobyl ether. Amides such as dimethylformamide, dimethylacetamide, N-metherpyrrolide/etc.; Acetonitrile, globionitrile, penzonitrile, etc.; IJ groups; , carbonate such as nophenyl carbonate; nitro compounds such as nitrobenzene, nitrotoluene, and nitroanisole; and organic sulfur oxides such as zomethyl sulfoxide, tetramethylene sulfolane, and nomethyl sulfolane. However, dimethyl sulfoxide, zoxachloride, and nitrobenzene are particularly preferred.
アルカリ金属イオンと求核的溶媒和する能力を有する非
プロトン性溶媒の使用量は、溶媒よシ少なければよく，
特に限定されないが、通常触媒量で十分である。具体的
Ｋは原料であるヒドロキシナフタリンのアルカリ金属塩
の使用量に対し、通常０．０００１〜１．０モル倍、な
かでも収率の点、かつ反応後のとドロキシナフタリンカ
ルデン酸を単離する操作が容易な点から０．０１〜０．
１０モル倍の範囲が好ましい。The amount of aprotic solvent that has the ability to nucleophilically solvate alkali metal ions may be smaller than that of the solvent.
Although not particularly limited, a catalytic amount is usually sufficient. The specific K is usually 0.0001 to 1.0 times the amount of the alkali metal salt of hydroxynaphthalene used as a raw material, especially from the viewpoint of yield and the amount of hydroxynaphthalene caldenic acid used after the reaction. 0.01 to 0.0 from the viewpoint of easy release operation.
A range of 10 moles is preferred.
さらに、芳香族炭化水素溶媒と同時に用いられるアルカ
リ金属イオンと配位する能力を有する化合物としては、
例えば環状ポリエーテル等が挙げられ、なかでもクラウ
ンエーテルが好ましい。クラウ／エーテルとしては、例
えば１２−クラウン−４−エーテル、１５−クラウン−
５−エーテル、１８−クラウン−６−エーテル、ジペ／
ゾ−１８−クラウン−６−エーテル等を挙げる事ができ
、なかでも１８−クラウン−６−エーテルが特に好まし
い。アルカリ金属イオンと配位する能力を有する化合物
の使用量は溶媒よシ少なければよく、特Ｋ限定されない
が、通常触媒量で十分である。具体的には原科であるヒ
ドロキシナフタリンのアルカリ金属塩の使用量Ｋ対し、
通常０．０００１〜１．０モル倍、なかでも収率の点、
かつ反応後のヒドロキシナフタリンカルゲン酸を単離す
る操作が容易な点から０．０００１〜０．１０モル倍の
範囲が好ましい。Furthermore, compounds that have the ability to coordinate with alkali metal ions that are used simultaneously with aromatic hydrocarbon solvents include:
Examples include cyclic polyethers, among which crown ethers are preferred. Examples of crown/ether include 12-crown-4-ether, 15-crown-
5-ether, 18-crown-6-ether, zype/
Examples include zo-18-crown-6-ether, among which 18-crown-6-ether is particularly preferred. The amount of the compound having the ability to coordinate with an alkali metal ion may be smaller than that of the solvent, and is not particularly limited, but a catalytic amount is usually sufficient. Specifically, for the usage amount K of the alkali metal salt of hydroxynaphthalene, which is the raw material,
Usually 0.0001 to 1.0 times the mole, especially in terms of yield,
In addition, from the viewpoint of easy operation for isolating hydroxynaphthalene cargenic acid after the reaction, the amount is preferably in the range of 0.0001 to 0.10 times by mole.
反応は、例えばヒドロキシナフタリンの金属塩全反応溶
媒中Ｋ分散し、その後アルカリ金属イオンと求核的溶媒
和を有する非プロトン性溶媒および／又はアルカリ金属
イオンと配位する能力を有する化合物を反応系に添加し
、次に二酸化炭素を反応系に導入する事によシ通常行わ
れる。この場合使用される二酸化炭素の量はぶ料のヒド
ロキ７ナフタリンのアルカリ金属塩Ｋ対して当量比で通
常０． ８〜３の範囲であるが、なかでも反応を充分進
行させると共に二酸化炭素を有効Ｋ利用する意味から０
．９５〜１．１の範囲が好ましい。反応の温度は、通常
２０〜１５０℃の範囲で行われるが、温度が低いと反応
は進行せず、また高いと副反応が多く起るので、５０〜
１２０Ｃの範囲が好ましい。反応の圧力は常圧でも充分
であるが、なかでも０． ５〜２０Ｋ４／ａｍ（グージ
圧）の範囲で加圧すると収率が高くなるので好ましい。In the reaction, for example, a metal salt of hydroxynaphthalene is dispersed in a total reaction solvent, and then an aprotic solvent having nucleophilic solvation with an alkali metal ion and/or a compound having the ability to coordinate with an alkali metal ion is added to the reaction system. This is usually done by adding carbon dioxide to the reaction system. In this case, the amount of carbon dioxide used is usually 0.00% in equivalent ratio to the alkali metal salt K of hydroxynaphthalene as the raw material. The range is from 8 to 3, but from the standpoint of allowing the reaction to proceed sufficiently and utilizing carbon dioxide effectively, 0 is the most important.
．． The range of 95 to 1.1 is preferred. The reaction temperature is usually in the range of 20 to 150°C, but if the temperature is low, the reaction will not proceed, and if it is high, many side reactions will occur.
A range of 120C is preferred. Normal pressure is sufficient for the reaction, but especially 0. It is preferable to pressurize in the range of 5 to 20 K4/am (Gouge pressure) because the yield increases.
カくシて得られたヒドロキシナフタリンヵルゲン酸のア
ルカリ金属塩は、反応溶液中に水を加える事Ｋよシ水相
として抽出される。水相は靜置することにより反応溶媒
のニトロベンゼン類から分離される。分離された水相Ｋ
塩酸あるいは鉱酸を加えることにより、まず、水相の一
を７にして未反応のヒドロキシナフタリンが水相よク析
出させる。これをν過Ｋより除き、Ｆ液にさらＫ塩酸あ
るいは鉱酸を加え、声を２とすると、白色結晶が析出す
る。これをテ過あるいは遠心分離により水相と分離し、
水洗、乾燥することにより７０〜８５重量襲の高収率で
高純度のヒドロキシナフタリンカルがン酸が得られる。The alkali metal salt of hydroxynaphthalene cargenic acid obtained by oxidation is extracted as an aqueous phase by adding water to the reaction solution. The aqueous phase is separated from the reaction solvent nitrobenzene by standing still. Separated aqueous phase K
By adding hydrochloric acid or mineral acid, the aqueous phase is first reduced to 7 to cause unreacted hydroxynaphthalene to precipitate out from the aqueous phase. This is removed by ν over K, further K hydrochloric acid or mineral acid is added to the F solution, and when the temperature is set to 2, white crystals are precipitated. This is separated from the aqueous phase by filtration or centrifugation,
By washing with water and drying, hydroxynaphthalene calcaric acid with a high yield and purity of 70 to 85% by weight can be obtained.
本発明の製法で作られるヒドロキシナフタリンカルポン
酸は、そのまま、染料、感熱染料の中間体として利用す
る拳ができるが、場合Ｋよっては、水等の溶媒を用いて
再結晶によυさらに精製して利用することもできる。Hydroxynaphthalenecarboxylic acid produced by the production method of the present invention can be used as is as an intermediate for dyes and heat-sensitive dyes, but in some cases, it may be further purified by recrystallization using a solvent such as water. It can also be used as
（実施例）
以下に実施例および比較例を示して本発明を具体的Ｋ説
明する。尚、例中の襲はすべて重量％である。(Example) The present invention will be specifically explained below with reference to Examples and Comparative Examples. In addition, all values in the examples are weight %.
実施例１
１４４ｐ（１．０モル）のα−ナフトールを２００１ｊ
の水一エタノール（ ５０ ： ５０重量比と溶解した
後、５６Ｐ（１モル）の水酸化カリウムを加え、混合し
た。その後、加熱し、エタノールと水を蒸発させた。得
られた固９のα−ナフトールのカリウム塩を粉砕し、さ
らＫ３０ｓｏｌＨｇの減圧下、１２０℃で１２時間乾燥
して粉末のα−ナ７トールのカリウム塩１８２？を得た
。得られたα−ナフ｝ 一ルのカリウム塩１ ８．２
％（ ０． １モル）とノメチルスルホキシド０．３
９ ｐ（ ０．０ ０ ５モル）ｆ．モレキュラーシー
プで乾燥したペンゼン８０ｆ中忙加え、６０℃に加温し
、溶解分散させた。次いで攪拌しながら４．４Ｐ（０．
１モル）の二酸化炭酸を８時間かけて反応系内に導入し
ながら１．ＯＫ＃／ｃｍ２（ダージ圧）で反応させた。Example 1 144p (1.0 mol) of α-naphthol was added to 2001j
After dissolving water and ethanol (50:50 weight ratio), 56P (1 mol) of potassium hydroxide was added and mixed. Then, the ethanol and water were evaporated by heating. The α of the obtained solid 9 - The potassium salt of naphthol was ground and further dried at 120°C for 12 hours under a reduced pressure of 30 solHg to obtain a powder of potassium salt of α-naphthol of 182 cm. salt 1 8.2
% (0.1 mol) and nomethyl sulfoxide 0.3
9 p (0.005 mol) f. Penzene, which had been dried with a molecular sheep, was added to a medium of 80°C and heated to 60°C to dissolve and disperse. Then, while stirring, 4.4P (0.
1 mol) of carbon dioxide was introduced into the reaction system over 8 hours. The reaction was carried out at OK#/cm2 (dirge pressure).
反応後、１００−の水を加え、良く混合し、その後靜置
すると２相に分離した。分液Ｋよシ得た水相にｌＯ％硫
酸を加え、声を７にして少量の未反応のα−ナフトール
を水相よシ析出させ、これを炉過によシ除き、Ｆ？’ｌ
ＥＫさらＫＩＯ一硫酸を加え、一を２にして大量の結晶
を析出させた。これを炉過し、５０＋ｊの水で洗浄し九
後、１００℃で３（ｌｌＨｆの減圧下、１２時間乾燥し
てｌ−ヒドロキシナフタリン−２−カルゲン酸１３．５
？（収率７２％）を得た。このものの融点は１８７〜１
８９℃でおった。また高速液体クロマトグラフの分析Ｋ
よる純度は９８．０％であった。After the reaction, 100 ml of water was added, mixed well, and then allowed to stand, resulting in separation into two phases. Add 10% sulfuric acid to the aqueous phase obtained from separation K, adjust the volume to 7, precipitate a small amount of unreacted α-naphthol from the aqueous phase, remove it by filtration, and remove it by filtration. 'l
EK and KIO monosulfuric acid were added and the mixture was mixed to precipitate a large amount of crystals. This was filtered in an oven, washed with 50+j of water, and then dried at 100°C for 12 hours under a reduced pressure of 3 (11 Hf) to give 13.5 l-hydroxynaphthalene-2-cargenic acid.
? (yield 72%). The melting point of this thing is 187-1
It was kept at 89°C. Also, high-performance liquid chromatography analysis K
The purity was 98.0%.
実施例２
ジメチルスルホキシト９の代ＤＥＣジメテルホルムアミ
ド０．７３ＳＬ（ ０．０ １モル）を用い、常圧で反
応させた以外は実施例１と同様にして１−ヒドロキシナ
フタリン−２−カル〆ン酸 １２．２Ｐ（収率６５％）
を得た。Example 2 1-Hydroxynaphthalene-2-cal was prepared in the same manner as in Example 1 except that 0.73 SL (0.01 mol) of DEC dimethylformamide was used instead of dimethyl sulfoxide 9 and the reaction was carried out at normal pressure. phosphoric acid 12.2P (yield 65%)
I got it.
実施例３
１ ４．４ ｆ （ ０．１ モル）のα−ナフトール
を７ｏ？の｝Ａｊｌンｌ／（溶解し、これＶＣ ５．
６ ｆ （ ０．１ モル）の固形水酸化カリウムを加
えた後、加熱し、共沸脱水によシ水を除いた。その後、
７０℃Ｋ冷却し、ジオキサ／ｏ．４４ｆ（ ０．０ ０
５モル）１ｋ加え、次に攪拌しながら４．４｝（０．
１モル）の二酸化炭素を６時間かけて反応系Ｋ導入しな
がら２．０Ｋｆ／ｃｌＬ２（デーノ圧）で反応させた。Example 3 1 4.4 f (0.1 mol) of α-naphthol was mixed with 7o? }Ajlnl/(dissolve, this VC 5.
After adding 6 f (0.1 mol) of solid potassium hydroxide, the mixture was heated and water was removed by azeotropic dehydration. after that,
Cool to 70°C and add dioxa/o. 44f( 0.0 0
5 mol) 1k, then 4.4}(0.5 mol) was added while stirring.
The reaction was carried out at 2.0 Kf/clL2 (Deno pressure) while introducing 1 mol of carbon dioxide into the reaction system K over 6 hours.
反応後、ｌＯＯ１１ｌの水を加え、生成した１−ヒドロ
キシナフタリン−２−カル？ン酸のカリウム塩を水相へ
抽出した。靜置分液して得られた水相に１０％硫酸を加
え、声を７にして少量の未反応のα−ナフトールを析出
させた。これｔ−Ｆ過Ｋより除き、Ｆ液にさらに１０％
硫酸を加え、声を２にして白色結晶を析出させた。After the reaction, 11 liters of water was added to produce 1-hydroxynaphthalene-2-cal? The potassium salt of acid was extracted into the aqueous phase. 10% sulfuric acid was added to the aqueous phase obtained by standing still, and the volume was adjusted to 7 to precipitate a small amount of unreacted α-naphthol. Remove this from t-F perk and add 10% to F solution.
Sulfuric acid was added and the volume was turned down to 2 to precipitate white crystals.
これを戸過し、５０１Ｌｌの水で水洗した後、ｌ ＯＯ
Ｃで３０１１１１Ｈ［の減圧下、１２時間乾燥して１−
ヒドロキシナフタリン−２−カルゲン酸１４．７Ｐ（収
率７８嘩）を得た。After passing this through the door and washing it with 501L of water, lOO
Dry for 12 hours under reduced pressure of 301111H at
14.7 P of hydroxynaphthalene-2-cargenic acid (yield: 78 grams) was obtained.
実施例４
ジオキサンの代，９Ｋエチレンヵーポネート０．６１Ｆ
（０．００７モル）を使用し、常圧で反応させた以外は
実施例３と同様にしてｌ−ヒドロキシナフタリン−２−
カルゴン酸１２．２Ｐ（収率６５％）を得た。Example 4 Dioxane substitute, 9K ethylene carbonate 0.61F
l-Hydroxynaphthalene-2-
Cargonic acid 12.2P (yield 65%) was obtained.
実施例５
ゾオキサンの代りＫ １，２−ジメトキシエタン０．６
３ ？（ ０．０ ０ ７モル）を使用し、常圧で反
応させた以外は実施例３と同様にして１−ヒドロキ７ナ
フタリン−２−カルゲン酸８．５５４（収率４５％）を
得た。Example 5 Substitute for Zoxane K 1,2-dimethoxyethane 0.6
3? (0.007 mol) was used, and 8.554 (yield: 45%) of 1-hydroxy-7naphthalene-2-cargenic acid was obtained in the same manner as in Example 3, except that the reaction was carried out at normal pressure.
実施例６
ジオキサンの代シにニトロベンゼン０．６２Ｌ？（ ０
．０ ０ ５モル）を使用した以外は実施例３と同様に
して１−ヒドロキシナフタリン−２−カルゴン酸１４．
５１％（収率７７％）を得た。Example 6 0.62L of nitrobenzene instead of dioxane? (0
．． 1-Hydroxynaphthalene-2-cargonic acid 14.
51% (yield 77%) was obtained.
実施例７
ジオキサンの代シにア七トニトリル０．２１％（ ０．
０ ０ ５モル〕を使用し、常圧で反応させた以外は実
施例３と同様Ｋしてｌ−ヒドロキシナ７タリ／−２−カ
ル？冫１１１０．３ｐ（収率５５％）を得た。Example 7 0.21% acetonitrile (0.21%) in place of dioxane.
0 0 5 mol] was used and the reaction was carried out at normal pressure. 1110.3p (yield 55%) was obtained.
実施例８
ジオキサンの代，９Ｋ１８−クラウン−６−エーテル０
．５ ３ ＰＣ ０．０ ０ ２モル）ｔ−使用した以
外は実施例３と同様にして１−ヒドロキシナフタリン−
２一カル？ン酸１４．ＩＰ（収率７５％）を得た。Example 8 Dioxane, 9K18-crown-6-ether 0
．． 5 3 PC 0.0 0 2 mol) 1-Hydroxynaphthalene-
21 Cal? acid14. IP (yield 75%) was obtained.
実施例９
固形水酸化カリウム５．６９（０．１モル）の代りに固
形水酸化ナトリウム４．０，ｌｉ’（０．１モル）を使
用した以外は実施例３と同様Ｋしてｌ−ヒドロキシナフ
タリン−２−カルポン酸１３．７Ｐ（収率７３％）ｔ得
た。Example 9 K and l- 13.7P (yield 73%) of hydroxynaphthalene-2-carboxylic acid was obtained.
比較例１
実施例ｌと同様Ｋして製造したα−ナ７トールのカリウ
ム塩１８．２ｐ（０．１モル）ｔ−モレキ纂ラーシープ
で脱水した８０？のジオキサンに溶解させた。加温して
８０℃にし、攪拌しながら４．４１（０．１モル）の二
酸化炭素を１時間かけて常圧で反応系に導入し、反応を
行い、１−とドロキシナフタリン−２−カル〆ン酸のカ
リウム塩のノオキサン溶液１０２．６Ｐを得た。次いで
、この溶液に１００−の水を加えたが、実施例１の様に
水相と溶媒相には分離せず、均一相Ｋなり、このままで
は１−ヒドロキシナフタリン−２一カル？／酸の単離は
困難であった。そこで、上記と同様にして得た１−ヒド
ロキシナフタリン−２−カルゴ／酸のカリウム塩のジオ
キサン浴液１０２．１を加熱し、ジオキサンを蒸留し、
固体の１−ヒドロキシナフタリン−２−カルゲン酸のカ
リウム塩と未反応のα−ナ７トールのカリウム塩の混合
物２４．３９−を得た。この場合、蒸留途中に固形物が
析出し、攪拌が不可能となった。その為伝熱が不良とな
り、ゾオキサンを完全Ｋ除くのに長時間を要した。また
伝熱が均一でない為、部分的に局部加熱されたことによ
る変色が見られた。得られた１−ヒドロキシナフタリン
−２−カル〆ン酸のカリウム塩と未反応のα−ナフトー
ルのカリウム塩の混合物に１００ｄの水を加えて溶解し
、その後１０％硫ｒ１ｌ．ｔ−加え、ｐｌ−１ｆ：７に
して、析出した少董の未反応のα−ナ７トールをＦ過Ｋ
よ９除いた。このｐ液Ｋさらに１０％硫酸を加え、一を
２にして灰色結晶を析出させた。これを炉遇し、水洗し
、その後、１００℃で３０ｆｉＩ｛ｇの減圧下、１２時
間乾燥して１一ヒドロキシナフタリン−２−カルビン酸
１５．７５’（収率８４％）ｔｌ−得た。Comparative Example 1 18.2 p (0.1 mol) of a potassium salt of α-Na7tol prepared in the same manner as in Example 1 was dehydrated using a t-moller sheep. of dioxane. The temperature was heated to 80°C, and while stirring, 4.41 (0.1 mol) of carbon dioxide was introduced into the reaction system at normal pressure over 1 hour to carry out the reaction, and 1- and droxynaphthalene-2- 102.6 P of a nooxane solution of potassium salt of carboxylic acid was obtained. Next, 100-water was added to this solution, but it did not separate into an aqueous phase and a solvent phase as in Example 1, but a homogeneous phase K formed. /Isolation of the acid was difficult. Therefore, dioxane bath solution 102.1 of potassium salt of 1-hydroxynaphthalene-2-cargo/acid obtained in the same manner as above was heated to distill dioxane,
A mixture of solid potassium salt of 1-hydroxynaphthalene-2-cargenic acid and unreacted potassium salt of α-na7tol was obtained, 24.39-. In this case, solid matter precipitated during the distillation, making stirring impossible. As a result, heat transfer was poor, and it took a long time to completely remove K from the zooxane. Also, because the heat transfer was not uniform, discoloration was observed due to localized heating. A mixture of the obtained potassium salt of 1-hydroxynaphthalene-2-carboxylic acid and the unreacted potassium salt of α-naphthol was dissolved in 100 d of water, and then 1 liter of 10% sulfur was added. t-added, pl-1f: 7, precipitated unreacted α-natol was filtered through F-K.
I removed 9. Further, 10% sulfuric acid was added to this p-liquid K to precipitate gray crystals. This was heated in an oven, washed with water, and then dried at 100° C. under a reduced pressure of 30 fiI{g for 12 hours to obtain 15.75' (yield: 84%) of 1-hydroxynaphthalene-2-carbic acid.
比較例２
実施例１と同様にして得たα−ナ７トールのカリウム塩
１８．２ｐ（０．１モル）ｆｔモレキ瓢ラーシープで脱
水した８０ｙ−のトルエンに加え、攪拌し、分散させた
。加温して８０℃にし、攪拌しながら４．４Ｐ（０．１
モル）の二酸化炭素ｆ．１時間かけて常圧で反応系に導
入し、反応を行った。反応後、１００−の水を添加し、
生成し九１−ヒドロキシナフタリン−２−カルボン酸の
カリウム塩を水相に抽出した。靜置後分液し、トルエン
相から水相を分離した。次いで水相１ｃＩＯ％硫酸を加
え、ｐＨを７１ＣＬて未反応のα−ナフトールを析出さ
せた。Comparative Example 2 18.2 p (0.1 mol) of the potassium salt of α-Na7tol obtained in the same manner as in Example 1 was added to 80 y of toluene dehydrated with a ft. moleki porridge, and the mixture was stirred and dispersed. Heat to 80℃ and add 4.4P (0.1
moles) of carbon dioxide f. The mixture was introduced into the reaction system at normal pressure over a period of 1 hour, and the reaction was carried out. After the reaction, add 100 - of water,
The resulting potassium salt of 91-hydroxynaphthalene-2-carboxylic acid was extracted into the aqueous phase. After standing still, the mixture was separated to separate the aqueous phase from the toluene phase. Next, 1 cIO% sulfuric acid was added to the aqueous phase to adjust the pH to 71 CL to precipitate unreacted α-naphthol.
これを戸過により除いた後、Ｆ液にさらＫＩＯ％硫酸を
加え、ＰＨを２にして白色結晶を析出させた。After removing this by filtration, KIO% sulfuric acid was further added to the F solution to adjust the pH to 2 and precipitate white crystals.
これを炉過し、水洗後、１００℃で３０ＷＨｇの減圧下
、乾燥して１−とドロキシナフタリン−２−カルゲ／酸
３．ｚ？（収率１７％）を得た。This was filtered through an oven, washed with water, and dried at 100°C under a reduced pressure of 30 WHg to obtain 1- and droxynaphthalene-2-calge/acid 3. Z? (yield: 17%).
比較例３〜６
溶媒としてジオキサンの代シに各々ジメチルスルホキシ
ド（比１［３）、ジメチルホルムアミド（比ＩＨＭＡ）
、エチレンカーボネート（比較例５）、１，２−ジメト
キシエタン（比較例６）を用いた以外は比較例１と同様
にして得た結果を表−１にまとめて示す。いずれの場合
も、生成物の単離はゾオキサ／を用いた場合と同様に困
難であった。Comparative Examples 3 to 6 Dimethyl sulfoxide (ratio 1 [3) and dimethyl formamide (ratio IHMA) were used as solvents in place of dioxane, respectively.
Table 1 summarizes the results obtained in the same manner as in Comparative Example 1 except that , ethylene carbonate (Comparative Example 5), and 1,2-dimethoxyethane (Comparative Example 6) were used. In both cases, isolation of the product was as difficult as with Zoxa/.
実施例１０
２ ８．８ ｐ（ ０． ２モル）のβ−ナフトールを
１２０１のキシレンに溶解し、これに１ １．２ Ｐ（
０． ２モル）の固形水酸化カリウムを加えた後、加
熱し、共沸脱水Ｋよク水を除いた。その後７０℃に冷却
し、ソメチルスルホキシドＯ、７８Ｆ（０．０１モル）
を加エ、その後、攪拌しながら８．８｝（０．２モル）
の二酸化炭素を６時間かけて反応系に導入しながら５Ｋ
ｔ／１２（ｒ−ジ圧）の加圧下で反応させた。反応後、
２５０−の水を加え、生成した２−ヒドロキシナフタリ
ン−１−カルポ／酸のカリウム塩を水相Ｋ抽出した。靜
置後、分液し、得られた水相ＶＣ１０２硫酸を加え、一
を７にして少量の未反応のβ−ナフトールを析出させた
。これを炉過によシ除い友後、Ｆ液にさらに１０％硫酸
を加え、一を２＆Ｃして白色結晶を析出させた。このも
のを戸過し、１５０１ｊの水で水洗後、８０℃で３０Ｗ
Ｈｇの減圧下、１２時間乾燥して２−ヒドロキシナフタ
リン−１一カルポ７＠２９．３ｆ（収率７８％）を得た
。Example 10 2 8.8 p (0.2 mol) of β-naphthol was dissolved in 1201 xylene, and 1 1.2 p (
0. After adding 2 moles of solid potassium hydroxide, the mixture was heated to remove the water from the azeotropic dehydration. After that, it was cooled to 70°C, and somethylsulfoxide O, 78F (0.01 mol) was added.
8.8} (0.2 mol) while stirring.
5K while introducing carbon dioxide into the reaction system over 6 hours.
The reaction was carried out under a pressure of t/12 (r-dipressure). After the reaction,
250-ml of water was added, and the resulting potassium salt of 2-hydroxynaphthalene-1-carpo/acid was extracted with the aqueous phase K. After the mixture was allowed to stand still, the liquid was separated, and the obtained aqueous phase VC102 sulfuric acid was added to the mixture, and a small amount of unreacted β-naphthol was precipitated. After filtering and removing the mixture in an oven, 10% sulfuric acid was further added to the F solution, and the mixture was heated for 2 hours to precipitate white crystals. Pass this item through the door, wash it with 1501J water, and then heat it at 80℃ for 30W.
It was dried under reduced pressure of Hg for 12 hours to obtain 2-hydroxynaphthalene-1-carpo [email protected] (yield 78%).
このものの高速液体クロマトグラフィの分析では純度が
９８．０％であった。Analysis of this product by high performance liquid chromatography showed that the purity was 98.0%.
実施例１１
ノメチルスルホキシドの代シにゾオキサン０．８８ｐ（
０．０１モル）を用い、常圧で反応させた以外は実施例
５と同様にして２−ヒドロキシナフタリン−１−カルゲ
ン酸ｚ４．４Ｐ（収率６５％）を得た。Example 11 Zoxane 0.88p (in place of methyl sulfoxide)
2-hydroxynaphthalene-1-cargenic acid z4.4P (yield: 65%) was obtained in the same manner as in Example 5, except that the reaction was carried out at normal pressure.
冥施例１２
固形水酸化カリウム１ １．２ ５４（ ０． ２モル
）の代りＫ１６．０５１−の５０％水酸化ナ｝ ＩＪウ
ム水溶ｇを用いた以外は実施例１０と同様にして２−ヒ
ドロキシナフタリン−１−カルゲン酸２４．４５’（収
率６ｓ聳）を得た。Example 12 2- was prepared in the same manner as in Example 10 except that 50% sodium hydroxide of K16.051 was used instead of solid potassium hydroxide 11.2 54 (0.2 mol). 24.45' of hydroxynaphthalene-1-cargenic acid (yield: 6 seconds) was obtained.
比較例７
２ ８．８ ｝（ ０． ２モル〕のβ−ナフトールを
２２０？のジメチルスルホキシドに溶解した後、１１．
２５’１００？留去させて反応系を脱水し九。その後７
０１Ｋ冷却し、攪拌しながら８．８｝（０．２モル）の
二酸化炭素を２時間かけて常圧で反応系Ｋ導入した。反
応後、２５０′ＩＬｔの水を加えたが、水相は分離せず
、２−ヒドロキシナフタリン−１−カル〆ン酸の単離は
困難であった。Comparative Example 7 After dissolving 28.8} (0.2 mol) of β-naphthol in 220? of dimethyl sulfoxide, 11.
25'100? 9. Dehydrate the reaction system by distilling it off. then 7
After cooling to 0.01 K, 8.8} (0.2 mol) of carbon dioxide was introduced into the reaction system K at normal pressure over 2 hours while stirring. After the reaction, 250'ILt of water was added, but the aqueous phase did not separate, making it difficult to isolate 2-hydroxynaphthalene-1-carboxylic acid.
−１−カルポン酸のカリウム塩と未反応のβ−ナ７トー
ルのカリウム塩の混合物４ ７． ５ ｆを得た。-Mixture of potassium salt of 1-carboxylic acid and unreacted potassium salt of β-natol 7. 5 f was obtained.
この場合、蒸留途中Ｋ固彫物が析出し、攪拌が不均一で
ない為、部分的に局部加熱されたことＫよる変色か見ら
れ九。得られた２−ヒドロキシナフタリン−１一カルゲ
ン酸のカリウム塩と未反応のβ−ナ７トールのカリウム
塩の混合物に２００１１７の水を加えて溶解し、その後
１０％硫酸を加え、声を７にして析出した少量の未反応
のβ−ナフトールｔ−ヂ過により除いた。この炉液Ｋさ
らに１０囁硫酸を加え、声を２にして灰色結晶を析出さ
せた。これを戸過し、水洗後、１００℃で３０１１１Ｈ
ｇの減圧下、１２時間乾燥して２−ヒドロキ７ナ７タリ
／−１−カルゲン酸３０、８？（収率８２％）を得た。In this case, solid K particles precipitated during the distillation, and discoloration was observed due to localized heating due to uneven stirring.9. 200117 water was added to the mixture of the obtained potassium salt of 2-hydroxynaphthalene-1 monocargenic acid and the unreacted potassium salt of β-na7tol to dissolve it, and then 10% sulfuric acid was added to make the voice 7. A small amount of unreacted β-naphthol precipitated was removed by t-difiltration. This furnace liquid K was further added with 10 sulfuric acid, and the volume was adjusted to 2 to precipitate gray crystals. Pass this through the door, wash it with water, and heat it to 30111H at 100℃.
It was dried for 12 hours under reduced pressure of 2-hydroxy-7-tal/-1-cargenic acid 30,8?g. (yield 82%).
比較例８
ジメチルスルホキシドを用いない以外は実施例１０と同
様にして２−ヒドロキシナフタリン−ｌ一カルボン酸５
．６ｐ（収″４１５％）を得た。Comparative Example 8 2-Hydroxynaphthalene-l monocarboxylic acid 5 was prepared in the same manner as in Example 10 except that dimethyl sulfoxide was not used.
．． 6p (yield: 415%) was obtained.
実施例１〜１２および比較例１〜８の結果をまとめ表−
ＩＫ示す。A table summarizing the results of Examples 1 to 12 and Comparative Examples 1 to 8.
Show IK.
Ｉ
／
／
／
（発明の効果）
以上述べ丸ようにヒドロキシナフタリンのアルカリ金属
塩と二酸化炭素とを芳香族炭化水素類を溶媒として用い
、アルカリ金属イオンと求核的溶媒和する能力を有する
非プロトン性溶媒および／又はアルカリ金属イオンと配
位する能力を有する化合物の存在下Ｋ反応させることよ
シヒドロキシナフタリンカル？ン酸を製造するという本
発明の製法は、高収率でかつ生成物の単離が容易なこと
から工業的に極めて優れた方法である。I / / / (Effect of the invention) As stated above, an aprotic compound having the ability to nucleophilically solvate an alkali metal ion with an alkali metal salt of hydroxynaphthalene and carbon dioxide using an aromatic hydrocarbon as a solvent. Is it possible to react hydroxynaphthalene in the presence of a neutral solvent and/or a compound capable of coordinating with an alkali metal ion? The method of the present invention for producing phosphoric acid is an extremely excellent method industrially because of its high yield and easy isolation of the product.
代理人 弁理士 高 橋 勝 利Agent Patent Attorney Katsutoshi Takahashi
Claims (1)
素とを、芳香族炭化水素類を溶媒とし、アルカリ金属イ
オンと求核的溶媒和する能力を有する非プロトン性溶媒
および／又はアルカリ金属イオンと配位する能力を有す
る化合物の存在下に反応させることを特徴とするヒドロ
キシナフタリンカルボン酸の製法。 ２、アルカリ金属イオンと求核的溶媒和する能力を有す
る非プロトン性溶媒および／又はアルカリ金属イオンと
配位する能力を有する化合物の使用量が、ヒドロキシナ
フタリンのアルカリ金属の使用量の０．０００１〜１．
０モル倍である請求項１記載の製法。 ３、ヒドロキシナフタリンがα−ナフトールおよび／又
はβ−ナフトールである請求項１記載の製法。 ４、アルカリ金属がナトリウムおよび／又はカリウムで
ある請求項１記載の製法。 ５、アルカリ金属イオンと配位する能力を有する化合物
が環状ポリエーテル類である請求項１記載の製法。 ６、芳香族炭化水素類がベンゼン、トルエンおよびキシ
レンから選ばれる１種以上の化合物である請求項１記載
の製法。 ７、反応を加圧下、温度５０〜９０℃の範囲で行う請求
項１記載の製法。[Scope of Claims] 1. An aprotic solvent and/or alkali having the ability to nucleophilically solvate an alkali metal ion and an alkali metal ion using an aromatic hydrocarbon as a solvent. 1. A method for producing hydroxynaphthalene carboxylic acid, which comprises reacting in the presence of a compound capable of coordinating with metal ions. 2. The amount of the aprotic solvent that has the ability to nucleophilically solvate with alkali metal ions and/or the compound that has the ability to coordinate with alkali metal ions is 0.0001 of the amount of alkali metal used in hydroxynaphthalene. ~1.
The method according to claim 1, wherein the amount is 0 mole. 3. The method according to claim 1, wherein the hydroxynaphthalene is α-naphthol and/or β-naphthol. 4. The method according to claim 1, wherein the alkali metal is sodium and/or potassium. 5. The method according to claim 1, wherein the compound having the ability to coordinate with an alkali metal ion is a cyclic polyether. 6. The method according to claim 1, wherein the aromatic hydrocarbon is one or more compounds selected from benzene, toluene and xylene. 7. The method according to claim 1, wherein the reaction is carried out under pressure at a temperature in the range of 50 to 90°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1055142A JPH02235844A (en) | 1989-03-09 | 1989-03-09 | Production of hydroxynaphthalenecarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1055142A JPH02235844A (en) | 1989-03-09 | 1989-03-09 | Production of hydroxynaphthalenecarboxylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02235844A true JPH02235844A (en) | 1990-09-18 |
Family
ID=12990523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1055142A Pending JPH02235844A (en) | 1989-03-09 | 1989-03-09 | Production of hydroxynaphthalenecarboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02235844A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006160624A (en) * | 2004-12-03 | 2006-06-22 | Chiba Inst Of Technology | Method for producing aromatic hydroxy carboxylic acid |
| JP2012246261A (en) * | 2011-05-30 | 2012-12-13 | Ueno Fine Chem Ind Ltd | Method for producing aromatic hydroxycarboxylic acid |
-
1989
- 1989-03-09 JP JP1055142A patent/JPH02235844A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006160624A (en) * | 2004-12-03 | 2006-06-22 | Chiba Inst Of Technology | Method for producing aromatic hydroxy carboxylic acid |
| JP2012246261A (en) * | 2011-05-30 | 2012-12-13 | Ueno Fine Chem Ind Ltd | Method for producing aromatic hydroxycarboxylic acid |
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