JPH082853B2 - Process for producing 1-oxy-5-substituted amino-2-naphthoic acid - Google Patents
Process for producing 1-oxy-5-substituted amino-2-naphthoic acidInfo
- Publication number
- JPH082853B2 JPH082853B2 JP116488A JP116488A JPH082853B2 JP H082853 B2 JPH082853 B2 JP H082853B2 JP 116488 A JP116488 A JP 116488A JP 116488 A JP116488 A JP 116488A JP H082853 B2 JPH082853 B2 JP H082853B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- oxy
- naphthol
- amino
- 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.)
- Expired - Fee Related
Links
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)
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〕で表わされる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。The present invention relates to 1-oxy-5-substituted amino-2-naphthoic acid useful as a synthetic intermediate for color formers for color photographic light-sensitive materials and functional dyes. In more detail, the 5-substituted amino-1 represented by the general formula [2] easily derived from 5-amino-1-naphthol [1].
-1-naphtho represented by the general formula [3], characterized in that naphthol is heated and reacted with carbon dioxide under pressure.
The present invention relates to a method for producing 5-substituted amino-2-naphthoic acid in high yield.
（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、その鍵中間体である１−オキシ−５−アミノ−２
−ナフトエ酸から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−カルボン酸アミド体、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。 (In the formula, 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 are 1-oxy-5-amino-2, which is a key intermediate thereof.
-A method of deriving from naphthoic acid has been used. For example, JP-A-62-123,157, 62-123,158 describes synthetic examples of 5-carboxylic acid amides and 5-sulfonic acid amides by this method. There is. And regarding 1-oxy-5-amino-2-naphthoic acid, which is this key intermediate,
5-amino-naphthol in the presence of alkali under high pressure,
Only the method of reacting with carbon dioxide at high temperature is known.
例えば、米国特許第2,453,105号（1948）記載の方法
は、０−ジクロロベンゼンを溶媒として温度175℃、圧
力60気圧の下で７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, the method described in U.S. Pat. No. 2,453,105 (1948) was carried out by using 0-dichlorobenzene as a solvent at a temperature of 175 ° C. and a pressure of 60 atm for 7 hours to obtain a yield of 63% with respect to the theory. Only -oxy-5-amino-2-naphthoic acid is obtained.
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。According to this method, the melting point of 5-amino-1-naphthol itself is high, it is difficult to maintain a homogeneous reaction system in a molten state, and the solubility in organic solvents is low. Is low, and unreacted raw materials are likely to remain even after reaction 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、溶媒である０−ジクロロ
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 0-dichlorobenzene as a solvent by steam distillation or the like, and the operation is complicated and the yield is low. It is hard to say that this 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
率で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
成するに到つた。In view of such a situation, the present inventors, unlike the conventional method, about a method for producing 1-oxy-5-substituted amino-2-naphthoic acids using 5-substituted amino-1-naphthol as a key intermediate. As a result of earnest studies, they have found that smooth, high-yield, high-purity 1-oxy-5-substituted amino-2-naphthoic acids with no by-products can be obtained, and have completed the present invention.
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〕の製造法を提供する
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、これを加圧容器中で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
ルボ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。An object of the present invention is to provide an industrially advantageous method for producing 1-oxy-5-substituted amino-2-naphthoic acids [3], which is characterized by 5-amino-1- Using naphthol [1] as a raw material, the desired 1-oxy-
The same 5 that a 5-substituted amino-2-naphthoic acid has
It is first converted into a key intermediate having a -position substituent, an alkali salt of 5-substituted amino-1-naphthol represented by the general formula [2], and this is reacted with carbon dioxide gas at a high temperature in a pressure vessel. After that, the high yield of 1-oxy-5-substituted amino-2-naphthoic acid by treating with acid is a production method, and the basis is the carboxylation reaction of 5-substituted amino-1-naphthol. The homogenization of the reaction system in
It consists in using a key intermediate having a lower melting point than amino-1-naphthol or an 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。一般的な方法としては、例えばアルカリ金属塩また
は有機塩基の存在下での各種カルボン酸塩化物、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、またはイソ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できる。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、エーテル、
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。The aspect of the present invention will be described in more detail.
In the step of introducing a substituent into the amino group of amino-1-naphthol, all the conventionally known general methods can be used. As a general method, for example, acid amides by reaction with various carboxylic acid chlorides in the presence of alkali metal salts or organic bases, reaction with sulfonic acid chlorides, reaction with chloroformic acid esters, and reaction with acid anhydrides. And urethane bond formation reaction, or ureido bond formation reaction by reaction with isocyanates, etc. can be used. The reaction is usually an organic solvent such as an aromatic hydrocarbon such as toluene, a chlorinated hydrocarbon such as methylene chloride, an acetic ester, an ether,
It is preferable to use N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and pyridine.
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−置換ア
ミノ−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、直ちにカルボニル化反
応に供する。In the carboxylation step, the 5-substituted amino-1-naphthol derived as described above is converted to an alkali salt and then reacted with carbon dioxide. As the alkali metal forming a salt, sodium or potassium can be used.
The method of salt formation is not particularly limited, but for example, 5-substituted amino-1-naphthol is treated with an alkali metal alkoxide or an alkali hydroxide in alcohol, the solvent is distilled off, and the obtained metal salt is dried to dryness. Immediately use for carbonylation reaction.
カルボ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50〜250℃、特に80〜180℃の範
囲が好ましく、二酸化炭素の圧力はこの５〜50Kg/cm2望
ましくは10〜30Kg/cm2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つて異なるが、通常３〜24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。Carboxylation is carried out by heating under pressure of carbon dioxide in a pressure vessel. The reaction temperature is preferably 50 to 250 ° C., particularly 80 to 180 ° C., and the carbon dioxide pressure is 5 to 50 kg / cm 2, preferably 10 to 30 kg / cm 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 3 to 24 hours, preferably 5 to 12 hours. After the reaction,
After adding a dilute alkaline aqueous solution to the contents and taking out from the pressure vessel, hydrochloric acid is added to acidify the desired 1-oxy-
The 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
〔３〕の製造法としては、５−アミノ−１−ナフトール
〔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つたが、 ５−アミノ−１−ナフトールの特性により、過激な反
応条件によつても反応率が低く、多量の未反応原料が残
り、単離にも繁雑な操作を要するなど工業上多大の問題
点があつた。As a conventional method for producing 1-oxy-5-substituted amino-2-naphthoic acid [3], 1-oxy-5-amino-2-naphthoic acid starting from 5-amino-1-naphthol [1] is used. Although the method of passing through [2] was common, Due to the characteristics of 5-amino-1-naphthol, the reaction rate is low even under extreme reaction conditions, a large amount of unreacted raw material remains, and a complicated operation is required for isolation. It was
これに対し、本発明は、出願原料である５−アミノ−
１−ナフトール〔１〕アミノ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
ることによつて、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つて、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
で副生物の少ない１−オキシ−５−置換アミノ−２−ナ
フトエ酸〔３〕を得る経済性の高い画期的な製造法であ
る。On the other hand, the present invention relates to 5-amino-
By introducing desired substituents into 1-naphthol [1] amino group first and converting it to 5-substituted amino-1-naphthol [2], the By lowering the melting point or by performing a structural transformation that contributes to homogenization of the system in the reaction system, the subsequent reaction with carbon dioxide proceeds smoothly, resulting in high yield and low by-products. This is a highly economical and epoch-making production method for obtaining 1-oxy-5-substituted amino-2-naphthoic acid [3].
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 will be shown below for illustrating the present invention further in detail, but this does not limit the present invention.
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50g（0.314モル）をトル
エン400mlnに分散し、水冷下、無水酢酸（0.342モル）
を滴下して、25℃で２時間撹拌した。析出した結晶を濾
過後、水で洗浄し、融点172.2〜173.0℃の標記化合物5
5.7g（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 50 g (0.314 mol) of -amino-1-naphthol was dispersed in 400 ml of toluene, and acetic anhydride (0.342 mol) was added under water cooling.
Was added dropwise, and the mixture was stirred at 25 ° C for 2 hours. The precipitated crystals were filtered and washed with water to give the title compound 5 having a melting point of 172.2 to 173.0 ° C.
5.7 g (yield 86.7%) was obtained.
（２） １−オキシ−５−アセチルアミノ−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−アセチルアミ
ノ−１−ナフトール3.9g（0.024モル）、28％ナトリウ
ムメチラート4.6g（0.024モル）を仕込み、メタノール1
0mlに溶解し、窒素気流下、60℃で１時間撹拌した。さ
らに、１時間減圧で濃縮乾固した後、炭酸ガスの圧力を
20Kg/cm2とし、外温180℃で９時間撹拌した。冷却後、
５％カセイソーダ水溶液50ml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204.4〜206.5℃の標
記化合物4.3g（収率89.6％）を得た。(2) Synthesis of 1-oxy-5-acetylamino-2-naphthoic acid [3] In a 200 ml autoclave, 3.9 g (0.024 mol) of 5-acetylamino-1-naphthol obtained above and 4.6 g of 28% sodium methylate. Charge (0.024 mol), methanol 1
It was dissolved in 0 ml and stirred under a nitrogen stream at 60 ° C. for 1 hour. Furthermore, after concentrating to dryness under reduced pressure for 1 hour, the pressure of carbon dioxide gas was increased.
The mixture was adjusted to 20 kg / cm 2 and stirred at an external temperature of 180 ° C. for 9 hours. After cooling
50 ml of 5% caustic soda aqueous solution was added and taken out from the autoclave. Further, concentrated hydrochloric acid was added dropwise to adjust the pH to 1-2, and the precipitated crystals were filtered off to obtain 4.3 g (yield 89.6%) of the title compound having a melting point of 204.4-206.5 ° C.
実施例２ １−オキシ−５−メトキシカルボンアミド−２−ナフト
エ酸（化合物〔３〕Ｙ＝CO、Ｒ＝メトキシ基）の合成 （１） ５−メトキシカルボンアミド−１−ナフトール
〔２〕の合成 ５−アミノ−１−ナフトール50g（0.314モル）をN,N
−ジメチルアセトアミド350ml、ピリジン50mlの混合溶
液に溶解し、水冷下、クロル炭酸メチル60g（0.628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71.2〜73.4℃の標記化合物67.5g（収
率98.5％）を得た。Example 2 Synthesis of 1-oxy-5-methoxycarboxamide-2-naphthoic acid (Compound [3] Y = CO, R = methoxy group) (1) Synthesis of 5-methoxycarboxamide-1-naphthol [2] 50 g (0.314 mol) of 5-amino-1-naphthol was added to N, N
-Dissolve in a mixed solution of 350 ml of dimethylacetamide and 50 ml of pyridine, and add 60 g (0.628 mol) of methyl chlorocarbonate dropwise over 1 hour while cooling with water. After the dropwise addition, the same procedure as in Example 1 was carried out to obtain 67.5 g (yield 98.5%) of the title compound having a melting point of 71.2 to 73.4 ° C.
（２） １−オキシ−５−メトキシカルボンアミド−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−メトキシカル
ボンアミド−１−ナフトール4g（0.018モル）、28％ナ
トリウムメチラート3.5g（0.018モル）を仕込み、メタ
ノール10mlに溶解し、窒素気流下、60℃で１時間撹拌し
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20Kg/cm2とし、外温180℃で９時間撹拌した。以
下、実施例１と同様の操作で、融点230.5〜232.8℃の標
記化合物4.4g（収率93.4％）を得た。(2) 1-oxy-5-methoxycarbonamide-2
-Synthesis of naphthoic acid [3] Into a 200 ml autoclave was charged 4 g (0.018 mol) of 5-methoxycarbonamide-1-naphthol obtained above and 3.5 g (0.018 mol) of 28% sodium methylate and dissolved in 10 ml of methanol. The mixture was stirred at 60 ° C for 1 hour under a nitrogen stream. After further concentrating to dryness under reduced pressure for 1 hour, the pressure of carbon dioxide was adjusted to 20 kg / cm 2 and the mixture was stirred at an external temperature of 180 ° C. for 9 hours. Thereafter, by the same operation as in Example 1, 4.4 g (yield 93.4%) of the title compound having a melting point of 230.5 to 232.8 ° C was obtained.
実施例３ １−オキシ−５−（Ｐ−トルエンスルホンアミド）−２
−ナフトエ酸（化合物〔３〕Ｙ＝SO2,R＝４−メチルフ
エニル基） （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50g（0.314モル）をN,N
−ジメチルアセトアミド350mlに溶解し、水冷下、Ｐ−
トルエンスルホニルクロリド120g（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118.2〜119.6℃の標記化合物87.9g（収率90.5
％）を得た。Example 3 1-oxy-5- (P-toluenesulfonamide) -2
- naphthoic acid (compound [3] Y = SO 2, R = 4- methylphenyl group) (1) 5- (P- toluenesulfonamido) -1-naphthol (2) 5-amino-1-naphthol 50 g ( 0.314 mol) to N, N
-Dissolve in 350 ml of dimethylacetamide, and under water cooling, P-
120 g (0.629 mol) of toluenesulfonyl chloride was added dropwise over 1 hour. After the dropwise addition, the same procedure as in Example 1 was repeated to obtain 87.9 g of the title compound having a melting point of 118.2 to 119.6 ° C (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（2.5g（0.013モル）を仕込
み、メタノール15mlに溶解し、窒素気流下、60℃で１時
間撹拌した。さらに、60℃で１時間減圧で濃縮乾固した
後、炭酸ガスの圧力を15Kg/cm2とし、外温180℃で９時
間撹拌した。以下、実施例１と同様の操作で融点204.3
〜205.8℃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] 4 g (0.013 mol) of 5- (P-toluenesulfonamide) -1-naphthol obtained above in a 200 ml autoclave. ),
28% Sodium methylate (2.5 g (0.013 mol) was charged, dissolved in 15 ml of methanol, and stirred under a nitrogen stream for 1 hour at 60 ° C. Further, the mixture was concentrated to dryness under reduced pressure at 60 ° C. for 1 hour and then carbon dioxide gas was added. The pressure was 15 Kg / cm 2 and the mixture was stirred for 9 hours at an external temperature of 180 ° C. Then, the same operation as in Example 1 was followed to give a melting point of 204.3
4.3 g (92.5% yield) of the title compound was obtained at ˜205.8 ° C.
実施例４ １−オキシ−５−（Ｎ′−フエニルウレイド）−２−ナ
フトエ酸（化合物〔３〕Ｙ＝CO,R＝フエニルアミノ基） （１） ５−（Ｎ′−フエニルウレイド）−１−ナフト
ール〔２〕の合成 ５−アミノ−１−ナフトール50g（0.314モル）を1,2
−ジメトキシエタン500mlに溶解した後、水冷下、フエ
ニルイソシアナート37g（0.314モル）を１時間かけて滴
下した滴下終了後、20℃で３時間撹拌した後、実施例１
と同様の操作で分解点239.2〜243.0℃の標記化合物80.5
g（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-naphthol [ 2] Synthesis of 5-amino-1-naphthol 50 g (0.314 mol) 1,2
-After dissolving in 500 ml of dimethoxyethane, 37 g (0.314 mol) of phenyl isocyanate was added dropwise over 1 hour under cooling with water, and after the dropping was completed, the mixture was stirred at 20 ° C for 3 hours, and then Example 1
Following the same procedure as for Degradation point 239.2-243.0 ℃, the title compound 80.5
g (yield 92.0%) was obtained.
（２） １−オキシ−５−（Ｎ′−フエニルウレイド）
−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−（Ｎ′−フエ
ニルウレイド）−１−ナフトール4g（0.015モル）,28％
ナトリウムメチラート2.9g（0.015モル）を仕込み、メ
タノール15mlに溶解し、窒素気流下、60℃で１時間撹拌
した。さらに、60℃で１時間減圧で濃縮乾固した後、炭
酸ガスの圧力を15Kg/cm2とし、外温180℃で９時間撹拌
した。以下、実施例１と同様の操作で融点230.2〜232.5
℃の標記化合物3.5g（収率90.0％）を得た。(2) 1-oxy-5- (N'-phenylureido)
Synthesis of 2-naphthoic acid [3] 4- (N'-phenylureido) -1-naphthol obtained above in a 200 ml autoclave 4 g (0.015 mol), 28%
2.9 g (0.015 mol) of sodium methylate was charged, dissolved in 15 ml of methanol, and stirred at 60 ° C. for 1 hour under a nitrogen stream. After further concentrating to dryness at 60 ° C. for 1 hour under reduced pressure, the pressure of carbon dioxide gas was adjusted to 15 kg / cm 2, and the mixture was stirred at an external temperature of 180 ° C. for 9 hours. Thereafter, the same operation as in Example 1 was carried out to give a melting point of 230.2 to 232.5.
3.5 g (yield 90.0%) of the title compound at ℃ was obtained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 271/30 275/42 303/38 303/40 307/02 307/10 311/08 311/21 Ｇ０３Ｃ 7/34 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location C07C 271/30 275/42 303/38 303/40 307/02 307/10 311/08 311/21 G03C 7/34
Claims (1)
ノ基に置換基を導入し、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： （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。）1. A 5-amino-1-naphthol [1] represented by the general formula [2], wherein a substituent is introduced into the amino group.
It is represented by the general formula [3] which is characterized in that a substituted amino-1-naphthol is obtained and reacted with carbon dioxide under pressure. Method for producing 1-oxy-5-substituted amino-2-naphthoic acid: (In the formula, Y represents a carbonyl group or a sulfonyl group, and R
Represents a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylamino group and 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 JPH01180863A (en) | 1989-07-18 |
| JPH082853B2 true 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) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5182296A (en) * | 1989-10-26 | 1993-01-26 | Tanabe Seiyaky Co., Ltd. | Naphthyloxazolidone derivatives |
-
1988
- 1988-01-08 JP JP116488A patent/JPH082853B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01180863A (en) | 1989-07-18 |
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