JPH01180863A - Production of 1-oxy-5-substituted amino-2-naphthoic acid - Google Patents
Production of 1-oxy-5-substituted amino-2-naphthoic acidInfo
- Publication number
- JPH01180863A JPH01180863A JP116488A JP116488A JPH01180863A JP H01180863 A JPH01180863 A JP H01180863A JP 116488 A JP116488 A JP 116488A JP 116488 A JP116488 A JP 116488A JP H01180863 A JPH01180863 A JP H01180863A
- Authority
- JP
- Japan
- Prior art keywords
- amino
- group
- naphthol
- oxy
- substituted amino
- 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.)
- Granted
Links
- VFFRLRQQWXGEBX-UHFFFAOYSA-N 1-aminonaphthalene-2-carboxylic acid Chemical class C1=CC=C2C(N)=C(C(O)=O)C=CC2=C1 VFFRLRQQWXGEBX-UHFFFAOYSA-N 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 30
- ZBIBQNVRTVLOHQ-UHFFFAOYSA-N 5-aminonaphthalen-1-ol Chemical compound C1=CC=C2C(N)=CC=CC2=C1O ZBIBQNVRTVLOHQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 15
- 125000001424 substituent group Chemical group 0.000 claims abstract description 7
- 125000003277 amino group Chemical group 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims abstract description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 7
- 125000001769 aryl amino group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 3
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 150000001875 compounds Chemical class 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 10
- -1 5-substituted amino-1-naphthol Chemical class 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000000049 pigment Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- BVGSTJDGMQHVGZ-UHFFFAOYSA-N n-(5-hydroxynaphthalen-1-yl)acetamide Chemical compound C1=CC=C2C(NC(=O)C)=CC=CC2=C1O BVGSTJDGMQHVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QPKNFEVLZVJGBM-UHFFFAOYSA-N 2-aminonaphthalen-1-ol Chemical class C1=CC=CC2=C(O)C(N)=CC=C21 QPKNFEVLZVJGBM-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000006664 bond formation reaction Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000021523 carboxylation Effects 0.000 description 2
- 238000006473 carboxylation reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QEBYEVQKHRUYPE-UHFFFAOYSA-N 2-(2-chlorophenyl)-5-[(1-methylpyrazol-3-yl)methyl]-4-[[methyl(pyridin-3-ylmethyl)amino]methyl]-1h-pyrazolo[4,3-c]pyridine-3,6-dione Chemical compound C1=CN(C)N=C1CN1C(=O)C=C2NN(C=3C(=CC=CC=3)Cl)C(=O)C2=C1CN(C)CC1=CC=CN=C1 QEBYEVQKHRUYPE-UHFFFAOYSA-N 0.000 description 1
- 150000005211 2-naphthoic acids Chemical class 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- FPKNJPIDCMAIDW-UHFFFAOYSA-N 5-aminonaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(N)=CC=CC2=C1C(O)=O FPKNJPIDCMAIDW-UHFFFAOYSA-N 0.000 description 1
- 241000208140 Acer Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical class OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/32—Colour coupling substances
- G03C7/34—Couplers containing phenols
- G03C7/344—Naphtholic couplers
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、カラー写真感光材料用発色剤や機能性色素等
の合成中間体として有用な１−オキシ−５−置換アミノ
−２−ナフトエ酸の改良された製造法に関し、更に詳し
くは５−アミノ−１−ナフトール〔１〕から容易に誘導
される一般式〔２〕〒表わされる５−置換アミノ−１−
ナフトールを二酸化炭素と加圧下に加熱反応させること
を特徴とする一般式〔３〕で表わされる１−オキシ−５
−置換アミノ−２−ナフトエ酸を高収率で得る製造方法
に関する。Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a 1-oxy-5-substituted amino-2-naphthoic acid useful as a color former for color photographic materials and a synthetic intermediate for functional dyes, etc. More specifically, regarding the improved method for producing 5-amino-1-naphthol [1], the 5-substituted amino-1-
1-oxy-5 represented by general formula [3] characterized by reacting naphthol with carbon dioxide under pressure and heating
The present invention relates to a method for producing -substituted amino-2-naphthoic acid in high yield.
〔１〕〔２〕〔３〕
（式中、Ｙはカルボニル基またはスルホニル基を示し、
Ｒは水素原子、アルキル基、アラル基、アリール基、ア
ルコキシ基、アリールオキシ基、アルキルアミノ基、ア
リールアミノ基を示す。）〔従来の技術〕
従来、１−オキシ−５−置換アミノ−２−ナフトエ酸類
は、その鍵中間体室ある１−オキシ−５−アミノ−２−
す７トエ酸かも誘導する方法が用いられており、例えば
特開昭６２−１２３，１５７．６２−１２３，１５８に
は、この方法による５−カルゼン酸アミド体、５−スル
ホン酸アミド体の合成例が記載されている。そして、こ
の鍵中間体である１−オキシ−５−アミノ−２−ナフト
エ酸については、５−アミノ−ナフトールをアルカリの
存在で、高圧下、炭酸ガスと高温で反応させる方法のみ
が知られている。[1] [2] [3] (wherein, Y represents a carbonyl group or a sulfonyl group,
R represents a hydrogen atom, an alkyl group, an aral group, an aryl group, an alkoxy group, an aryloxy group, an alkylamino group, or an arylamino group. ) [Prior Art] Conventionally, 1-oxy-5-substituted amino-2-naphthoic acids have been synthesized from 1-oxy-5-amino-2-
A method of inducing 5-carzene acid amide and 5-sulfonic acid amide has been used. Examples are given. Regarding this key intermediate, 1-oxy-5-amino-2-naphthoic acid, the only known method is to react 5-amino-naphthol with carbon dioxide gas in the presence of an alkali at high temperature and under high pressure. There is.
例えば、米国特許第２，４５３，１０５号（１９４Ｂ）
記載の方法は、０−−）クロロベンゼンを溶媒として温
度１７５Ｃ，圧力６０気圧の下フッ時間反応させ理論に
対して６３％の収率で目的とする１−オキシ−５−アミ
ノ−２−ナフトエ酸を得ているに過ぎない。For example, U.S. Patent No. 2,453,105 (194B)
The described method involves reaction using 0--)chlorobenzene as a solvent at a temperature of 175C and a pressure of 60 atmospheres for a period of time to obtain the desired 1-oxy-5-amino-2-naphthoic acid with a yield of 63% of theory. It's just that you're getting it.
この方法では、５−アミノ−１−ナフトール自体の融点
が高く、溶融状態で均一の反応系を保つことは困難があ
り、また有機溶媒に対する溶解度が低い為、多量の溶媒
を用いてさえ反応率が低く、長時間反応させても未反応
原料が残存し易い。In this method, 5-amino-1-naphthol itself has a high melting point, making it difficult to maintain a homogeneous reaction system in a molten state, and its solubility in organic solvents is low, so even when a large amount of solvent is used, the reaction rate is is low, and unreacted raw materials tend to remain even if the reaction is carried out for a long time.
また、１−オキシ−５−アミノ−２−ナフトエ酸を単離
する際、水蒸気蒸留などで、溶媒〒ある０−）クロロベ
ンゼンを留去する必要があり、操作が繁雑かつ低収率で
ある点で工業的に有利な方法とは言い難い。In addition, when isolating 1-oxy-5-amino-2-naphthoic acid, it is necessary to distill off the solvent (0-)chlorobenzene by steam distillation, etc., resulting in complicated operations and low yields. Therefore, it is difficult to say that it is an industrially advantageous method.
本発明者らは、このような状況に鑑み、従来法とは異な
り、５−置換アミノ−１−ナフトールを鍵中間体とする
１−オキシ−５−置換アミノ−２−ナフトエ酸類の製造
法について鋭意研究を重ねてきた結果、円滑かつ高収率
〒副生物のない高純度の１−オキシ−５−置換アミノ−
２−ナフトエ酸類が得られることを知り、本発明を完成
するに到った。In view of this situation, the present inventors have developed a method for producing 1-oxy-5-substituted amino-2-naphthoic acids that uses 5-substituted amino-1-naphthol as a key intermediate, unlike conventional methods. As a result of extensive research, we have successfully produced high-purity 1-oxy-5-substituted amino acids with no by-products.
Having learned that 2-naphthoic acids can be obtained, the present invention was completed.
本発明の目的は、工業的に有利な１−オキシ−５−置換
アミノ−２−ナフトエ酸類〔３〕の木造法を提供するこ
とにあり、その特徴とする所は、５−アミノ−１−ナフ
トール〔１〕を原料として、目的とする１−オキシ−５
−置換アミノ−２−ナフトエ酸が有するのと同一の５−
位置換基を有する鍵中間体、一般式〔２〕で表わされる
５−置換アミノ−１−ナフトール類のアルカリ塩に先づ
変換し、これを加圧容器中〒炭酸ガスと高温で反応させ
た後、酸と処理することによる１−オキシ−５−置換ア
ミノ−２−ナフトエ酸の高収率は製造方法であり、その
基本とする所は５−置換アミノ−１−ナフトールのカル
ゼキシル化反応における反応系の均一化にあり、５−ア
ミノ−１−ナフトールよりも低融点か、または使用する
溶媒に対する溶解性の改良された鍵中間体を使用するこ
とにある。The purpose of the present invention is to provide an industrially advantageous wooden method for producing 1-oxy-5-substituted amino-2-naphthoic acids [3], which is characterized by Using naphthol [1] as a raw material, the desired 1-oxy-5
-Substituted amino-2-naphthoic acid has the same 5-
A key intermediate having a positional substituent, a 5-substituted amino-1-naphthol represented by the general formula [2], was first converted into an alkali salt, and this was reacted with carbon dioxide gas at high temperature in a pressurized container. The high yield of 1-oxy-5-substituted amino-2-naphthoic acid by subsequent treatment with an acid is a manufacturing method that is based on the calzexylation reaction of 5-substituted amino-1-naphthol. The key is to homogenize the reaction system and to use an intermediate that has a lower melting point than 5-amino-1-naphthol or has improved solubility in the solvent used.
本発明の態様について、更に詳しく説明すると、５−ア
ミノ−１−ナフトールのアミノ基への置換基導入工程に
おいては、従来知られている一般法が全て利用できる。To explain the aspect of the present invention in more detail, all conventionally known general methods can be used in the step of introducing a substituent into the amino group of 5-amino-1-naphthol.
一般的な方法としては、例えばアルカリ金楓塩または有
機塩基の存在下での各種カルダン酸塩化物、スルホン酸
塩化物との反応、クロルギ酸エステル類との反応および
酸無水物との反応による酸アミドおよびウレタン結合生
成反応、またインシアナート類との反応によるウレイド
結合生成反応などが利用〒きる。反応は通常、有機溶媒
例えばトルエンの如き芳香族炭化水素、塩化メチレンな
どの塩素化炭化水素、酢酸エステル、エーテノペＮ、Ｎ
−ジメチルホルムアミド、Ｎ、Ｎ−・ジメチルアセトア
ミド、Ｎ−メチルピロリドンおよびピリジンなどを用い
て行うのが好ましい。Common methods include, for example, reactions with various cardanoic acid chlorides and sulfonic acid chlorides in the presence of alkali gold maple salts or organic bases, reactions with chloroformates, and reactions with acid anhydrides. Amide and urethane bond forming reactions, as well as ureido bond forming reactions by reaction with incyanates, etc. can be used. The reaction is usually carried out in organic solvents such as aromatic hydrocarbons such as toluene, chlorinated hydrocarbons such as methylene chloride, acetic esters, ethenope N, N
-Dimethylformamide, N,N--dimethylacetamide, N-methylpyrrolidone, pyridine, and the like are preferably used.
カルボキシル化工程では、上述の如くして誘導される５
−置換アミノ−１−ナフトールをアルカリ塩とした後、
二酸化炭素と反応させる。塩を形成させるアルカリ金属
としてはナトリウムまたはカリウムが使用できる。造塩
の方法は特に限定されないが、例えば、５−＃を換アミ
ノー１−ナフトールをアルコール中でアルカリ金属アル
コキシドまたは水酸化アルカリと処理した後、溶媒を留
去、得られた金属塩を乾固し、直ちにカルダニル化反応
に供する。In the carboxylation step, 5 is derived as described above.
- After converting the substituted amino-1-naphthol into an alkali salt,
React with carbon dioxide. Sodium or potassium can be used as the alkali metal forming the salt. The method of salt formation is not particularly limited, but for example, after treating 5-#-converted amino-1-naphthol with an alkali metal alkoxide or alkali hydroxide in alcohol, the solvent is distilled off, and the resulting metal salt is dried to dryness. and immediately subjected to cardanylation reaction.
カルダキシ化は加圧容器中、二酸化炭素加圧下に加熱反
応させる。反応温度は５０〜２５０Ｃ１特ＶＣ８０〜１
８０Ｃの範囲が好ましく、二酸化炭素の圧力はこの５〜
５ Ｑ Ｋ９Ａ２望ましくは１０〜５０に９／儂２が適
当である。カルボキシル化に要する反応時間は、対象と
する化合物の構造、二酸化炭素圧力および反応温度によ
って異なるが、通常６〜２４時間、好ましくは５〜１２
時間が適当である。反応終了後、内容物に希アルカリ水
溶液を添加し、加圧容器から取出した後、塩酸を加えて
酸性にし目的とする１−オキシ−５−置換アミノ−２−
ナフトエ酸を好収率で得ることができる。Cardaxylation is carried out by heating in a pressurized container under pressure of carbon dioxide. Reaction temperature is 50-250C1 special VC80-1
The range of 80C is preferable, and the pressure of carbon dioxide is between 5 and 80C.
5 Q K9A2 is preferably 10 to 50 to 9/2. The reaction time required for carboxylation varies depending on the structure of the target compound, carbon dioxide pressure, and reaction temperature, but is usually 6 to 24 hours, preferably 5 to 12 hours.
The time is appropriate. After the reaction is complete, a dilute aqueous alkali solution is added to the contents, and the contents are taken out from the pressurized container, and then hydrochloric acid is added to acidify the desired 1-oxy-5-substituted amino-2-
Naphthoic acid can be obtained in good yield.
従来の１−オキシ−５−置換アミノ−２−ナフトエ酸〔
６〕の製造法としては、５−アミノ−１−す７トール〔
１〕から出発して１−オキシ−５−アミノ−２−ナフト
エ酸〔２〕を経由する方法が一般的であったが、
−Ｙ−ＮＨ
〔２〕
５−アミノ−１−ナフトールの特性により、過激な反応
条件によっても反応率が低く、多量の未反応原料が残り
、単離にも繁雑な操作を喪するなど工業上多大の問題点
があった。Conventional 1-oxy-5-substituted amino-2-naphthoic acid [
6], 5-amino-1-su7toll [
The general method was to start from 1] and go through 1-oxy-5-amino-2-naphthoic acid [2], but due to the characteristics of -Y-NH [2] 5-amino-1-naphthoic acid However, even under extreme reaction conditions, the reaction rate was low, a large amount of unreacted raw materials remained, and isolation required complicated operations, resulting in many industrial problems.
これに対し、本発明は、出発原料である５−アミノ−１
−ナフトール〔１〕アミン基に先づ所望の置換基を導入
して５−置換アミノ−１−ナフトール〔２〕へ変換する
ことによって、５−アミノ−１−ナフトールに比較して
より融点を降下させるか、または反応系中で系の均一化
に寄与するような構造変換をなすことによって、引続き
行われる二酸化炭素との反応が円滑に進むので高収率↑
副生物の少すい１−オキシ−５−置換アミノ−２−ナフ
トエ酸〔６〕を得る経済性の高い画期的な製造法である
。In contrast, in the present invention, the starting material 5-amino-1
-Naphthol [1] By introducing a desired substituent into the amine group and converting it to 5-substituted amino-1-naphthol [2], the melting point is lowered more than that of 5-amino-1-naphthol. By making structural changes in the reaction system that contribute to homogenization, the subsequent reaction with carbon dioxide proceeds smoothly, resulting in a high yield↑
This is a highly economical and innovative production method that produces 1-oxy-5-substituted amino-2-naphthoic acid [6] with few by-products.
以下、本発明をさらに詳しく説明するために実施例を示
すが、これは本発明を限定するものではない。Examples are shown below to explain the present invention in more detail, but the present invention is not limited thereto.
実施例１
１−オキシ−５−アセチルアミノ−２−ナフトエ酸（化
合物〔３〕、Ｙ＝ＣＯ，Ｒ＝メチル基）の合成
（１）５−アセチルアミノ−１−ナフトール〔２〕の合
成
５−アミノ−１−ナフトール５０ ＆ （０，３１４モ
ル）をトルエン４００ｍＩｎに分散し、水冷下、無水酢
酸（０，３４２モル）を滴下して、２５Ｃで２時間攪拌
した。析出した結晶を濾過後、水で洗浄し、融点１７２
．２〜１７３．ＤＣの標記化合物５５．７１１ （収率
８６．７％）を得た。Example 1 Synthesis of 1-oxy-5-acetylamino-2-naphthoic acid (compound [3], Y=CO, R=methyl group) (1) Synthesis of 5-acetylamino-1-naphthol [2] 5 -Amino-1-naphthol 50 & (0,314 mol) was dispersed in 400 mIn of toluene, and acetic anhydride (0,342 mol) was added dropwise under water cooling, followed by stirring at 25C for 2 hours. After filtering the precipitated crystals, they were washed with water and the melting point was 172.
．． 2-173. The title compound of DC 55.711 (yield 86.7%) was obtained.
（２）１−オキシ−５−アセチルアミノ−２−ナフトエ
酸〔６〕の合成
２００ｍ１オートクレーブに上記で得た５−アセチルア
ミノ−１−ナフトール３．９ ＆ （０，０２４モル）
、２８％ナトリウムメチラート４．６９ （０，０２４
モル）を仕込み、メタノール１０ｍｌに溶解し、窒素気
流下、６０ｉＣで１時間攪拌した。さらに、１時間減圧
で濃縮乾固した後、炭酸ガスの圧力を２０ Ｋ５１／（
２２とし、外温１８０Ｃで９時間攪拌した。冷却後、５
％カセイソーダ水溶液５０ｍ１を添加し、オートクレー
ブから取りだした。さらに、濃塩酸を滴下し、ｐＨ１〜
２にし、析出した結晶を濾別して、融点２０４．４〜２
０６．５Ｕの標記化合物４．ｓｌ収率８９．６％）を得
た。(2) Synthesis of 1-oxy-5-acetylamino-2-naphthoic acid [6] 3.9 & (0,024 mol) of 5-acetylamino-1-naphthol obtained above was placed in a 200 ml autoclave.
, 28% sodium methylate 4.69 (0,024
mol), dissolved in 10 ml of methanol, and stirred at 60 iC for 1 hour under a nitrogen stream. Furthermore, after concentrating to dryness under reduced pressure for 1 hour, the pressure of carbon dioxide gas was reduced to 20 K51/(
22 and stirred for 9 hours at an external temperature of 180C. After cooling, 5
% caustic soda aqueous solution was added and the autoclave was taken out. Furthermore, add concentrated hydrochloric acid dropwise to pH 1~
2, and the precipitated crystals were filtered to obtain a melting point of 204.4-2.
06.5U of the title compound 4. sl yield of 89.6%) was obtained.
実施例２
１−オキシ−５−メトキシ力ルゼンアミドー２−ナフト
エ酸（化合物（：３）Ｙ＝ＣＯ，Ｒ＝メトキシ基）の合
成
（１） ５−メトキシカルゼンアミ）″−１−ナフト
ール〔２〕の合成
５−アミノ−１−ナフトール５０．９（０，３１４モル
）をＮ、Ｎ−、ｊメチルアセトアミｔ’３５０ｍ１、ピ
ッジン５０ｍ！の混合溶液に溶解し、水冷下、クロル炭
酸メチル６０ ｇ （０，６２ｓモル）を１時間かけて
滴下する。滴下終了後、実施例１と同様の操作で融点７
１．２〜７３．４Ｃの標記化合物６ ｙ、 ｓ ９（収
率９８，５％）を得た。Example 2 Synthesis of 1-oxy-5-methoxycarzenamide-2-naphthoic acid (compound (:3) Y=CO, R=methoxy group) (1) 5-methoxycarzenamide)''-1-naphthoic acid [2 ] Synthesis of 50.9 (0,314 mol) of 5-amino-1-naphthol was dissolved in a mixed solution of 350 ml of N,N-,j-methylacetamide and 50 ml of pidgin, and under water cooling, 60 mol of methyl chlorocarbonate was dissolved. g (0.62 s mol) was added dropwise over 1 hour. After the addition, the same procedure as in Example 1 was carried out to reduce the melting point to 7.
The title compound 6y,s9 (yield 98.5%) with 1.2-73.4C was obtained.
（２）１−オキシ−５−メトキシカルぎンアミド−２−
す７トエ酸〔３〕の合成
２００ｍ１オートクレーブに上記で得た５−メトキシカ
ルぎンアミｒ−１−ナフトール４．９（０，０１８モル
）、２８％ナトリウムメチラーシー５ｇ（０，０１８モ
ル）を仕込み、メタノール１０ｍ１Ｋ溶解し、窒素気流
下、６０Ｃで１時間攪拌した。さらに、１時間減圧で濃
縮乾固した後、炭酸ガスの圧力を２０ＫＰ／ ｍ２とし
、外温１８０Ｃで９時間攪拌した。以下、実施例１と同
様の操作で、融点２６０−５〜２３２．８Ｃの標記化合
物４．４＆（収率９３．４％）を得た。(2) 1-oxy-5-methoxycarginamide-2-
Synthesis of 7-toic acid [3] 4.9 (0,018 mol) of 5-methoxycarginami r-1-naphthol obtained above and 5 g (0,018 mol) of 28% sodium methylacyl were added to a 200 ml autoclave. The mixture was prepared, dissolved in 10 ml of methanol, and stirred at 60C for 1 hour under a nitrogen stream. Furthermore, after concentrating to dryness under reduced pressure for 1 hour, the pressure of carbon dioxide gas was set to 20 KP/m2, and the mixture was stirred at an external temperature of 180 C for 9 hours. Thereafter, the same operation as in Example 1 was performed to obtain the title compound 4.4& (yield 93.4%) having a melting point of 260-5 to 232.8C.
実施例３
１−オキシ−５−（Ｐ−トルエンスルホンアミＰ）−２
−ナフトエ酸（化合物（３） Ｙ＝８０２ 、 Ｒ＝４
−メチルフェニル基）
（１） ５− （Ｐ −トルエンスルホンアミド）−
１−ナフトール〔２〕の合成
５−アミノ−１−ナフトール５０Ｆ（０，３１４モル）
をＮ 、 Ｎ−、ジメチルアセトアミド３５０ｍ１ に
溶解シ、水冷下、Ｐ−トルエンスルホニルクロリド１２
１（０，６２９モル）を１時間かけて滴下した。滴下終
了後、実施例１と同様の操作で融点１１８．２〜１１９
．６Ｃの標記化合物８７．ｉ（収率９０．５％）を得た
。Example 3 1-oxy-5-(P-toluenesulfonamide P)-2
-naphthoic acid (compound (3) Y=802, R=4
-methylphenyl group) (1) 5- (P-toluenesulfonamide)-
Synthesis of 1-naphthol [2] 5-amino-1-naphthol 50F (0,314 mol)
was dissolved in 350 ml of N, N-, dimethylacetamide, and cooled with water to form 12 P-toluenesulfonyl chloride.
1 (0,629 mol) was added dropwise over 1 hour. After completing the dropwise addition, repeat the same procedure as in Example 1 to obtain a melting point of 118.2 to 119.
．． 6C title compound 87. i (yield 90.5%) was obtained.
（２）１−オキシ−５−（Ｐ−トルエンスルホンアミド
）−２−ナフトエ酸〔３〕の合成２００ｍｌオートクレ
ーブに上記で得た５−（Ｐ−トルエンスルホンアミド）
−１−ナフトール４ｇ（０，０１３モル）、２８％ナト
リウムメチラート（、２，５９（０，０１３モル）を仕
込み、メタノール１５ｍ１に溶解し、窒素気流下、６Ｄ
Ｃで１時間攪拌した。さらに、６０Ｃで１時間減圧で濃
縮乾固した後、炭酸ガスの圧力を１５へ／備２とし、外
温１８０Ｃで９時間攪拌した。以下、実施例１と同様の
操作で融点２０４．３〜２０５．８０の標記化合物４．
３ｇ（収率９２．５％）を得た。(2) Synthesis of 1-oxy-5-(P-toluenesulfonamide)-2-naphthoic acid [3] Place the 5-(P-toluenesulfonamide obtained above) in a 200 ml autoclave.
4 g (0,013 mol) of -1-naphthol and 28% sodium methylate (2,59 (0,013 mol)) were dissolved in 15 ml of methanol, and 6D
The mixture was stirred at C for 1 hour. Furthermore, after concentrating to dryness under reduced pressure at 60C for 1 hour, the pressure of carbon dioxide gas was increased to 15/2, and the mixture was stirred at an external temperature of 180C for 9 hours. Hereinafter, the title compound 4. having a melting point of 204.3 to 205.80 was prepared in the same manner as in Example 1.
3 g (yield 92.5%) was obtained.
実施例４
１−オキシ−５−（Ｎ’−フェニルウレイド）−２−ナ
フトエ酸（化合物（３）Ｙ＝ＣＯ，Ｒ＝フェニルアミノ
基）
（１） ５− （Ｎ’−フェニルウレイド）−１−ナ
フトール〔２〕の合成
５−アミノ−１−ナフトール５０．９（０，３１４モル
）を１，２−ジメトキシエタン５００ｍ１に溶解した後
、水冷下、フェニルインシアナート３７ｇ（０１４モル
）を１時間かけて滴下した滴下終了後、２０Ｃで３時間
攪拌した後、実施例１と同様の操作で分解点２６９２〜
２４３．０Ｃの標記化合物８［］、５．！９（収率９２
．０％）を得た。Example 4 1-oxy-5-(N'-phenylureido)-2-naphthoic acid (compound (3) Y=CO, R=phenylamino group) (1) 5-(N'-phenylureido)-1 -Synthesis of Naphthol [2] After dissolving 50.9 (0,314 mol) of 5-amino-1-naphthol in 500 ml of 1,2-dimethoxyethane, 37 g (0.14 mol) of phenyl incyanate was dissolved in 1 ml of 1,2-dimethoxyethane under cooling with water. After the completion of the dropwise addition over a period of time, after stirring at 20C for 3 hours, the decomposition point 2692 ~
243.0C title compound 8[], 5. ! 9 (yield 92
．． 0%) was obtained.
（２）１−オキシ−５−（Ｎ’−フェニルウレイＰ）−
２−ナフトエ酸〔６〕の合成
２００ｍ１オートクレーブに上記で得た５ −（Ｎ’−
フェニルウレイＦ’）−１−ナフトール４．９（０，０
１５モル）、２８係ナトリウムメチラート２．９．９（
０，０１５モル）を仕込み、メタノール１５ｍ１に溶消
し、窒素気流下、６０Ｃで１時間攪拌した。さらに、６
０Ｃ〒１時間減圧で濃縮乾固した後、炭酸ガスの圧力を
１５ＫＰ／ｃｍ２とし、外温１８０ｔ；で９時間攪拌し
た。以下、実施例１と同様の操作で融点２３０．２〜２
３２．５ｒの標記化合物３．１（収率９０．０％）を得
た。(2) 1-oxy-5-(N'-phenylurei P)-
Synthesis of 2-naphthoic acid [6] The above-obtained 5-(N'-
Phenylurei F')-1-naphthol 4.9 (0,0
15 moles), 28% sodium methylate 2.9.9 (
0,015 mol) was added, dissolved in 15 ml of methanol, and stirred at 60C for 1 hour under a nitrogen stream. Furthermore, 6
After concentrating to dryness under reduced pressure at 0C for 1 hour, the pressure of carbon dioxide gas was set to 15 KP/cm2, and the mixture was stirred at an external temperature of 180 tons for 9 hours. Hereinafter, the melting point was 230.2 to 2 by the same operation as in Example 1.
32.5r of the title compound 3.1 (yield 90.0%) was obtained.
Claims (1)
を導入し、一般式〔２〕で表わされる５−置換アミノ−
１−ナフトールを得、それを加圧下で二酸化炭素と反応
させることを特徴とする一般式〔３〕で表わされる。 １−オキシ−５−置換アミノ−２−ナフトエ酸の製造法
： ▲数式、化学式、表等があります▼〔１〕 ▲数式、化学式、表等があります▼〔２〕 ▲数式、化学式、表等があります▼〔３〕 （式中、Ｙはカルボニル基又はスルホニル基を示し、Ｒ
は水素原子、アルチル基、アラルキル基、アルコキシ基
、アリール基、アリールオキシ基、アルチルアミノ基、
アリールアミノ基を示す。）[Scope of Claims] A substituent is introduced into the amino group of 5-amino-1-naphthol [1] to obtain a 5-substituted amino-
It is represented by the general formula [3], which is characterized by obtaining 1-naphthol and reacting it with carbon dioxide under pressure. Production method of 1-oxy-5-substituted amino-2-naphthoic acid: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [1] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [2] ▲ Mathematical formulas, chemical formulas, tables, etc. ▼ [3] (In the formula, Y represents a carbonyl group or a sulfonyl group, and R
is a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryl group, an aryloxy group, an altylamino group,
Indicates an arylamino group. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP116488A JPH082853B2 (en) | 1988-01-08 | 1988-01-08 | Process for producing 1-oxy-5-substituted amino-2-naphthoic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP116488A JPH082853B2 (en) | 1988-01-08 | 1988-01-08 | Process for producing 1-oxy-5-substituted amino-2-naphthoic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01180863A true JPH01180863A (en) | 1989-07-18 |
| JPH082853B2 JPH082853B2 (en) | 1996-01-17 |
Family
ID=11493798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP116488A Expired - Fee Related JPH082853B2 (en) | 1988-01-08 | 1988-01-08 | Process for producing 1-oxy-5-substituted amino-2-naphthoic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH082853B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03218367A (en) * | 1989-10-26 | 1991-09-25 | Tanabe Seiyaku Co Ltd | Naphthyloxazolidone derivative, its production and intermediate for synthesizing the same |
-
1988
- 1988-01-08 JP JP116488A patent/JPH082853B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03218367A (en) * | 1989-10-26 | 1991-09-25 | Tanabe Seiyaku Co Ltd | Naphthyloxazolidone derivative, its production and intermediate for synthesizing the same |
| JP2601008B2 (en) * | 1989-10-26 | 1997-04-16 | 田辺製薬株式会社 | Naphthyl oxazolidone derivatives, their preparation and their synthetic intermediates |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH082853B2 (en) | 1996-01-17 |
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