JPH107632A - Production of 2-(4'-n-monosubstituted amino-2'-hydroxybenzoyl)benzoic acid - Google Patents
Production of 2-(4'-n-monosubstituted amino-2'-hydroxybenzoyl)benzoic acidInfo
- Publication number
- JPH107632A JPH107632A JP8196878A JP19687896A JPH107632A JP H107632 A JPH107632 A JP H107632A JP 8196878 A JP8196878 A JP 8196878A JP 19687896 A JP19687896 A JP 19687896A JP H107632 A JPH107632 A JP H107632A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- hydroxybenzoyl
- benzoic acid
- monosubstituted
- reaction
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は2−(4’−N−モ
ノ置換アミノ−2’−ヒドロキシベンゾイル)安息香酸
の製造方法に関するものである。 さらに詳しくは、感
圧記録紙、感熱記録紙等の記録材料用フルオラン化合物
の合成中間体として有用な一般式(2)The present invention relates to a method for producing 2- (4'-N-monosubstituted amino-2'-hydroxybenzoyl) benzoic acid. More specifically, general formula (2) useful as a synthetic intermediate of a fluoran compound for recording materials such as pressure-sensitive recording paper and heat-sensitive recording paper
【0002】[0002]
【化3】 (式中R1はアルキル基、シクロアルキル基、p−若し
くはm−位に置換基を有することもあるフェニル基を意
味し、R2は水素原子、アルキル基を意味する。)で表
される2−(4’−N−モノ置換アミノ−2’−ヒドロ
キシベンゾイル)安息香酸(以下、モノ置換ベンゾフェ
ノンカルボン酸という)の製造に関するものである。通
常のフルオラン化合物は2−(4’−N−ジ置換アミノ
−2’−ヒドロキシベンゾイル)安息香酸(以下、ジ置
換ベンゾフェノンカルボン酸という)を原料として製造
されるものが多いが、モノ置換ベンゾフェノンカルボン
酸を原料として製造されるフルオラン化合物は、前者に
くらべ特徴的な色相を持つものが多いため極めて商品価
値が高く、工業的製法の確立が待望されるものであっ
た。Embedded image (Wherein R 1 represents an alkyl group, a cycloalkyl group, or a phenyl group which may have a substituent at the p- or m-position, and R 2 represents a hydrogen atom or an alkyl group). The present invention relates to the production of (4'-N-monosubstituted amino-2'-hydroxybenzoyl) benzoic acid (hereinafter, referred to as monosubstituted benzophenonecarboxylic acid). Many ordinary fluoran compounds are produced using 2- (4'-N-disubstituted amino-2'-hydroxybenzoyl) benzoic acid (hereinafter referred to as disubstituted benzophenone carboxylic acid) as a raw material. Many fluoran compounds produced from acids have a characteristic hue compared to the former, and therefore have extremely high commercial value, and establishment of an industrial production method has been expected.
【0003】[0003]
【従来の技術】本発明の化合物に類似したジ置換ベンゾ
フェノンカルボン酸の製造法は下記の文献等に見られる
ように、一般に広く知られており、収率の良い方法とし
て常用されている。即ち、Beilstein主編第1
4巻675頁、あるいは特公昭46−4614号、特公
昭51−12626号、特開平5−213840号、特
開平6−49008号、特開平6−100512号公報
などには、3−ジ置換アミノフェノールと無水フタル酸
を無溶媒あるいは有機溶媒の存在下、70〜120℃で
数時間から数十時間反応させ目的とするジ置換ベンゾフ
ェノンカルボン酸を収率よく得る方法が開示されてい
る。これらの文献の中には、反応温度範囲の上限を12
0℃に制限していないものもある。しかし温度が高けれ
ば高いほどローダミン型色素の副生によって収率が低下
することは良く知られており、現実にこれ以上高い温度
で実施された例は聞かない。2. Description of the Related Art A process for producing a disubstituted benzophenone carboxylic acid similar to the compound of the present invention is widely known as shown in the following documents and the like, and is commonly used as a process with a high yield. That is, Beilstein main part 1
4, page 675, or JP-B-46-4614, JP-B-51-12626, JP-A-5-213840, JP-A-6-49008, JP-A-6-100512, etc. A method is disclosed in which a phenol and phthalic anhydride are reacted at 70 to 120 ° C. for several hours to several tens of hours in the absence of a solvent or in the presence of an organic solvent to obtain the desired disubstituted benzophenonecarboxylic acid in good yield. In these documents, the upper limit of the reaction temperature range is 12
Some are not limited to 0 ° C. However, it is well known that the higher the temperature is, the lower the yield is due to the by-product of the rhodamine-type dye, and there is no actual case where the temperature is higher than this.
【0004】本発明者は上記したジ置換ベンゾフェノン
カルボン酸の製法をモノ置換ベンゾフェノンカルボン酸
の製法として転用できないかどうかを試験するため、後
述の参考例に示す如く、3−ジ置換アミノフェノールに
換えて、3−モノ置換アミノフェノールを用い同様の方
法で反応を試みたが、次の一般式(3)に示す3’−ヒ
ドロキシ−2−カルボキシーベンズアニリド(以下アニ
リド体という)が主生成物となり、目的のモノ置換ベン
ゾフェノンカルボン酸を得ることはできなかった。In order to test whether the above-mentioned method for producing a disubstituted benzophenonecarboxylic acid can be diverted as a method for producing a monosubstituted benzophenonecarboxylic acid, the present inventor changed the method to 3-disubstituted aminophenol as shown in the following Reference Example. The reaction was attempted in the same manner using a 3-monosubstituted aminophenol, but the main product was 3′-hydroxy-2-carboxy-benzanilide (hereinafter referred to as anilide) represented by the following general formula (3). The desired mono-substituted benzophenonecarboxylic acid could not be obtained.
【0005】[0005]
【化4】 Embedded image
【0006】このような実験事実からもわかる通り、モ
ノ置換ベンゾフェノンカルボン酸はジ置換ベンゾフェノ
ンカルボン酸と同様な方法で簡単に得ることができず、
従来から種々の別法が検討されてきた。従来のモノ置換
ベンゾフェノンカルボン酸の製法として最も代表的な方
法は、例えば、Beilstein主編第14巻675
頁、或いは特開昭49−109119号、特開平8−1
04817号号公報に記載の方法であり、一般式(1)
のモノ置換アミノフェノール化合物とフタルイミドをほ
ぼ等モルの硼酸の存在下、150〜200℃で加熱熔融
してアミド化合物とし、次いでこのアミド化合物を更に
加水分解するという下式に示す方法である。As can be seen from these experimental facts, monosubstituted benzophenonecarboxylic acids cannot be easily obtained in the same manner as disubstituted benzophenonecarboxylic acids.
Conventionally, various alternative methods have been studied. The most typical method for producing a conventional monosubstituted benzophenone carboxylic acid is described in, for example, Beilstein's main edition, Vol. 14, 675.
Page or JP-A-49-109119, JP-A-8-1
No. 04817, a method described in the general formula (1)
Is obtained by heating and melting the monosubstituted aminophenol compound and phthalimide at 150 to 200 ° C. in the presence of substantially equimolar boric acid to form an amide compound, and then further hydrolyzing the amide compound.
【0007】[0007]
【化5】 Embedded image
【0008】しかしこの従来法は製造ルートが煩雑で多
くの装置を必要とする。また、この方法は、その採用に
より稲の育成阻害剤として知られる硼酸廃液の排出が避
けられなくなるため、硼酸廃液処理が製造面での大きな
負担となり、工業化が難しいという問題を有していた。
また別の製法として特開昭57−190049号、特開
平7−329416号、特開平8−104817号公報
には、3−モノ置換アミノフェノールをベンジル等の脱
離し易い置換基で修飾しジ置換アミノ基としたのち、前
述した一般法で無水フタル酸と反応させジ置換ベンゾフ
ェノンカルボン酸を製造し、更にこれを濃硫酸等の脱離
剤中で処理して目的とするモノ置換ベンゾフェノンカル
ボン酸を得るという方法が開示されている。しかしこの
方法も反応工程が煩雑であり、収率も十分とはいえなか
った。However, this conventional method has a complicated production route and requires many devices. In addition, this method has a problem in that the boric acid waste liquid, which is known as a rice growth inhibitor, is unavoidably discharged by the adoption of the method, so that the treatment of the boric acid waste liquid imposes a heavy burden on the production side, and industrialization is difficult.
As another production method, JP-A-57-190049, JP-A-7-329416 and JP-A-8-104817 disclose 3-disubstituted aminophenol which is modified with a readily removable substituent such as benzyl to obtain a disubstituted aminophenol. After the amino group, the di-substituted benzophenone carboxylic acid is produced by reacting with the phthalic anhydride according to the general method described above, and the resulting mono-substituted benzophenone carboxylic acid is treated with a desorbing agent such as concentrated sulfuric acid to obtain the desired mono-substituted benzophenone carboxylic acid. A method of obtaining is disclosed. However, also in this method, the reaction steps were complicated, and the yield was not sufficient.
【0009】尚、特開平8−127726号公報には、
2,6−ジ置換フェニル基でアミノ基がモノ置換された
3−モノ置換アミノフェノールに限っては、前記ジ置換
ベンゾフェノンカルボン酸の製法と同様の方法でもモノ
置換ベンゾフェノンカルボン酸を得られる旨開示されて
いる。これは限定された特定の位置に置換基を有するフ
ェニル基が、その立体的な効果により前記したアニリド
体の生成を妨げているものと考えられる。Japanese Patent Application Laid-Open No. 8-127726 discloses that
It is disclosed that mono-substituted benzophenone carboxylic acids can be obtained by the same method as the above-mentioned method for producing di-substituted benzophenone carboxylic acids only for 3-mono-substituted amino phenols in which the amino group is mono-substituted with a 2,6-di-substituted phenyl group. Have been. This is presumably because the phenyl group having a substituent at a limited specific position prevents formation of the anilide compound described above due to its steric effect.
【発明が解決しようとする課題】本発明は、従来法にお
ける以上のような状況に鑑み簡単な工程により収率よく
モノ置換ベンゾフェノンカルボン酸を製造する方法を提
供せん研究の結果到達したものである。DISCLOSURE OF THE INVENTION The present invention has been accomplished in view of the above-mentioned situation in the conventional method, and has provided a method for producing a mono-substituted benzophenonecarboxylic acid in a simple process with a high yield in a simple process. .
【0010】[0010]
【課題を解決する為の手段】即ち本発明は、一般式
(1)で表される3−モノ置換アミノフェノールと無水
フタル酸を、無溶媒あるいは有機溶媒の存在下、130
〜180℃の間で反応することを特徴とする一般式
(2)で表されるモノ置換ベンゾフェノンカルボン酸の
製造方法に係るものである。That is, the present invention relates to a method of preparing a 3-monosubstituted aminophenol represented by the general formula (1) and phthalic anhydride in the absence of a solvent or in the presence of an organic solvent.
The present invention relates to a method for producing a mono-substituted benzophenonecarboxylic acid represented by the general formula (2), wherein the reaction is carried out at a temperature of up to 180 ° C.
【0011】[0011]
【化6】 Embedded image
【0012】本発明の重要な要件の一つは反応温度であ
る。即ち、前述した様にジ置換ベンゾフェノンカルボン
酸の製法をモノ置換ベンゾフェノンカルボン酸の製法と
して単に転用したのみでは一般式(3)のアニリド体が
主生成物となり、目的とするモノ置換ベンゾフェノンカ
ルボン酸を得ることはできない。しかし、このアニリド
体を一旦単離し、無溶媒あるいは有機溶剤中で更に13
0〜180℃の高温に保持するとアニリド体は目的とす
るモノ置換ベンゾフェノンカルボン酸に転化するのであ
り、本発明はこの知見にもとづき到達したものである。
本発明を実施する当たっての反応温度はより好ましくは
135〜160℃である。One of the important requirements of the present invention is the reaction temperature. That is, as described above, if the method for producing a disubstituted benzophenonecarboxylic acid is simply diverted as a method for producing a monosubstituted benzophenonecarboxylic acid, the anilide derivative of the general formula (3) becomes a main product, and the desired monosubstituted benzophenonecarboxylic acid is converted to You can't get it. However, this anilide is isolated once, and further isolated in an organic solvent or without solvent.
The anilide is converted to the desired monosubstituted benzophenonecarboxylic acid when the temperature is maintained at a high temperature of 0 to 180 ° C., and the present invention has been achieved based on this finding.
The reaction temperature for carrying out the present invention is more preferably 135 to 160 ° C.
【0013】[0013]
【発明の実施の形態】有機溶剤中で反応をおこなう場
合、有機溶剤は3−置換アミノフェノール1重量部に対
し0.1〜20重量部が適当である。具体的にはベンゼ
ン、トルエン、エチルベンゼン、キシレン、キュメン、
プソイドキュメン、メシチレン、サイメン、クロロベン
ゼン、ジクロロベンゼン、ニトロベンゼン、クロロトル
エン、ブロモベンゼン、ヨードベンゼン、ヨードトルエ
ン、ジブロモベンゼン、ヘキサン、シクロヘキサン、メ
チルシクロヘキサン、シクロヘキサノン、テトラクロロ
エタン、テトラクロロエチレン、ビフェニール、ジフェ
ニールエーテル、オクタメチルトリシロキサン、ヘキサ
メチルジシロキサン等を単独で、或いは混合して用いる
ことができる。When the reaction is carried out in an organic solvent, the amount of the organic solvent is suitably 0.1 to 20 parts by weight per 1 part by weight of the 3-substituted aminophenol. Specifically, benzene, toluene, ethylbenzene, xylene, cumene,
Pseudocumen, mesitylene, cymen, chlorobenzene, dichlorobenzene, nitrobenzene, chlorotoluene, bromobenzene, iodobenzene, iodotoluene, dibromobenzene, hexane, cyclohexane, methylcyclohexane, cyclohexanone, tetrachloroethane, tetrachloroethylene, biphenyl, diphenyl ether, octamethyl Trisiloxane, hexamethyldisiloxane and the like can be used alone or as a mixture.
【0014】無水フタル酸は3−モノ置換アミノフェノ
ールより過剰に使用するとよい。無水フタル酸の好まし
い使用量は、3−モノ置換アミノフェノール1モルに対
し0.7〜2.0モル、更に好ましくは0.9〜1.2
モルである。無水フタル酸と3−モノ置換アミノフェノ
ールとの反応に際して、少量のピリジンを添加すると、
触媒的な効果により目的物の収率が向上する。ピリジン
は3−置換アミノフェノール1重量部に対し0.001
〜0.5重量部の範囲で添加することが好ましい。ピリ
ジンは置換基を有していてもよく、この様な例としては
α−ピコリン、β−ピコリン、γ−ピコリン、アミノピ
リジン、4−ジメチルアミノピリジンなどを例示するこ
とができる。これらピリジンは単独で、或いは混合して
用いることができる。The phthalic anhydride is preferably used in excess of the 3-monosubstituted aminophenol. The preferred amount of phthalic anhydride used is 0.7 to 2.0 mol, more preferably 0.9 to 1.2 mol per mol of 3-monosubstituted aminophenol.
Is a mole. In the reaction of phthalic anhydride with the 3-monosubstituted aminophenol, a small amount of pyridine is added,
The catalytic effect improves the yield of the desired product. Pyridine is 0.001 to 1 part by weight of 3-substituted aminophenol.
It is preferable to add in the range of 0.5 part by weight. Pyridine may have a substituent, and such examples include α-picoline, β-picoline, γ-picoline, aminopyridine, 4-dimethylaminopyridine and the like. These pyridines can be used alone or as a mixture.
【0015】特開昭62−70350号公報には、3−
ジ置換アミノフェノールと無水フタル酸の反応において
副生するローダミン型色素を水酸化アルカリで加熱し分
解反応することでジ置換ベンゾフェノンカルボン酸を得
る方法が開示されている。本発明においても3−モノ置
換アミノフェノールと無水フタル酸とを反応させた後、
モノ置換ベンゾフェノンカルボン酸を単離することな
く、出発原料として使用した3−モノ置換アミノフェノ
ール1モル当たり1〜10モル相当の水酸化アルカリを
加えて80〜140℃で熱処理し、前記3−モノ置換ア
ミノフェノールと無水フタル酸との反応で副生するロー
ダミン型色素の分解をはかり、この分解によりモノ置換
ベンゾフェノンカルボン酸をより多く得ることができ
る。JP-A-62-70350 discloses that
There is disclosed a method of obtaining a disubstituted benzophenone carboxylic acid by heating a rhodamine type dye by-produced in a reaction between a disubstituted aminophenol and phthalic anhydride with an alkali hydroxide to cause a decomposition reaction. After reacting the 3-monosubstituted aminophenol with phthalic anhydride also in the present invention,
Without isolating the monosubstituted benzophenone carboxylic acid, 1 to 10 mol of alkali hydroxide was added per 1 mol of the 3-monosubstituted aminophenol used as a starting material, and the mixture was heat-treated at 80 to 140 ° C. Decomposition of the rhodamine-type dye by-produced by the reaction between the substituted aminophenol and phthalic anhydride is measured, and this decomposition allows more monosubstituted benzophenonecarboxylic acid to be obtained.
【0016】またローダミン型色素のアルカリ分解反応
を行った後、一般式(2)で表される2−(4’−N−
モノ置換アミノ−2’−ヒドロキシベンゾイル)安息香
酸をアルカリ金属塩の結晶として析出せしめ、ろ別する
ことで精製効果を挙げることができる。またろ液に含ま
れている多量の一般式(1)で表される3−モノ置換ア
ミノフェノールは、硫酸、塩酸等で中和することにより
回収することも可能であり、経済的である。After the alkali decomposition reaction of the rhodamine type dye, 2- (4'-N-) represented by the general formula (2) is obtained.
By purifying mono-substituted amino-2'-hydroxybenzoyl) benzoic acid as crystals of an alkali metal salt and filtering off, a purification effect can be obtained. Further, a large amount of the 3-monosubstituted aminophenol represented by the general formula (1) contained in the filtrate can be recovered by neutralization with sulfuric acid, hydrochloric acid or the like, and is economical.
【0017】本発明の2−(4’−N−モノ置換アミノ
−2’−ヒドロキシベンゾイル)安息香酸としては、2
−(4’−N−メチルアミノ−2’−ヒドロキシベンゾ
イル)安息香酸、2−(4’−N−エチルアミノ−2’
−ヒドロキシベンゾイル)安息香酸、2−(4’−N−
プロピルアミノ−2’−ヒドロキシベンゾイル)安息香
酸、2−(4’−N−iso−プロピルアミノ−2’−
ヒドロキシベンゾイル)安息香酸、2−(4’−N−ブ
チルアミノ−2’−ヒドロキシベンゾイル)安息香酸、
2−(4’−N−iso−ブチルアミノ−2’−ヒドロ
キシベンゾイル)安息香酸、2−(4’−N−ペンチル
アミノ−2’−ヒドロキシベンゾイル)安息香酸、2−
(4’−N−iso−ペンチルアミノ−2’−ヒドロキ
シベンゾイル)安息香酸、2−(4’−N−ヘキシルア
ミノ−2’−ヒドロキシベンゾイル)安息香酸、2−
(4’−N−オクチルアミノ−2’−ヒドロキシベンゾ
イル)安息香酸、2−(4’−N−シクロヘキシルアミ
ノ−2’−ヒドロキシベンゾイル)安息香酸、2−
(4’−N−ベンジルアミノ−2’−ヒドロキシベンゾ
イル)安息香酸、2−(4’−N−フェニルアミノ−
2’−ヒドロキシベンゾイル)安息香酸、(4’−N−
p−トリルアミノ−2’−ヒドロキシベンゾイル)安息
香酸、(4’−N−m−トリルアミノ−2’−ヒドロキ
シベンゾイル)安息香酸、2−(4’−N−p−クロロ
フェニルアミノ−2’−ヒドロキシベンゾイル)安息香
酸、2−(5’メチル−4’−N−フェニルアミノ−
2’−ヒドロキシベンゾイル)安息香酸等を例示でき
る。The 2- (4'-N-monosubstituted amino-2'-hydroxybenzoyl) benzoic acid of the present invention is 2
-(4'-N-methylamino-2'-hydroxybenzoyl) benzoic acid, 2- (4'-N-ethylamino-2 '
-Hydroxybenzoyl) benzoic acid, 2- (4'-N-
Propylamino-2'-hydroxybenzoyl) benzoic acid, 2- (4'-N-iso-propylamino-2'-
Hydroxybenzoyl) benzoic acid, 2- (4′-N-butylamino-2′-hydroxybenzoyl) benzoic acid,
2- (4'-N-iso-butylamino-2'-hydroxybenzoyl) benzoic acid, 2- (4'-N-pentylamino-2'-hydroxybenzoyl) benzoic acid, 2-
(4′-N-iso-pentylamino-2′-hydroxybenzoyl) benzoic acid, 2- (4′-N-hexylamino-2′-hydroxybenzoyl) benzoic acid, 2-
(4′-N-octylamino-2′-hydroxybenzoyl) benzoic acid, 2- (4′-N-cyclohexylamino-2′-hydroxybenzoyl) benzoic acid, 2-
(4′-N-benzylamino-2′-hydroxybenzoyl) benzoic acid, 2- (4′-N-phenylamino-
2'-hydroxybenzoyl) benzoic acid, (4'-N-
p-tolylamino-2′-hydroxybenzoyl) benzoic acid, (4′-Nm-tolylamino-2′-hydroxybenzoyl) benzoic acid, 2- (4′-Np-chlorophenylamino-2′-hydroxybenzoyl) ) Benzoic acid, 2- (5′-methyl-4′-N-phenylamino-)
2'-hydroxybenzoyl) benzoic acid and the like.
【0018】[0018]
【実施例】次に本発明を実施例を挙げて説明する(以
下、部は重量部を表す)。 実施例1 3−iso−ペンチルアミノフェノール53.7部と無
水フタル酸66.6部をo−ジクロロベンゼン360部
と共に140℃で4時間反応を行ない濃い赤褐色の反応
液を得た。この反応液に水500部と48%水酸化ナト
リウム100部を加え、反応物を水層に溶解しo−ジク
ロロベンゼン層と分離した。反応物が溶解した水層に4
8%水酸化ナトリウム150部を加え10℃まで冷却し
て反応物をソーダ塩の結晶として析出させた後ろ別し、
得られた結晶を10%水酸化ナトリウム水溶液100部
で洗浄した。このソーダ塩を水500部に溶解し、攪拌
下に希塩酸水でpH4に調整し、淡桃色の2−(4’−
iso−ペンチルアミノ−2’−ヒドロキシベンゾイ
ル)安息香酸27.1部を得た(融点60〜80℃)。
出発原料の3−iso−ペンチルアミノフェノールに対
する目的物の収率は27.6%であった。Next, the present invention will be described with reference to examples (parts are by weight). Example 1 3-Iso-pentylaminophenol (53.7 parts) and phthalic anhydride (66.6 parts) were reacted with o-dichlorobenzene (360 parts) at 140 ° C for 4 hours to obtain a deep reddish brown reaction solution. To this reaction solution, 500 parts of water and 100 parts of 48% sodium hydroxide were added, and the reaction product was dissolved in an aqueous layer and separated from an o-dichlorobenzene layer. 4 in the aqueous layer
After adding 150 parts of 8% sodium hydroxide and cooling to 10 ° C., the reaction product was separated as crystals of soda salt, and separated.
The obtained crystals were washed with 100 parts of a 10% aqueous sodium hydroxide solution. This soda salt was dissolved in 500 parts of water, and the pH was adjusted to 4 with dilute hydrochloric acid under stirring, and pale pink 2- (4'-
27.1 parts of iso-pentylamino-2′-hydroxybenzoyl) benzoic acid were obtained (melting point 60-80 ° C.).
The yield of the target compound relative to the starting material 3-iso-pentylaminophenol was 27.6%.
【0019】実施例2 3−iso−ペンチルアミノフェノール53.7部と無
水フタル酸66.6部をo−ジクロロベンゼン360部
と共に140℃で4時間反応を行ない濃い赤褐色の反応
液を得た。次に反応液に48%水酸化ナトリウム125
部を加え、100℃で1時間ローダミン分解を行うと、
反応液は濃い赤褐色から茶色に変化した。この反応液に
水500部を加え、反応物を水層に溶解しo−ジクロロ
ベンゼン層と分離した。反応物の溶解した水層に48%
水酸化ナトリウム150部を加え10℃まで冷却して反
応物をソーダ塩の結晶として析出させた後ろ別し、得ら
れた結晶を10%水酸化ナトリウム水溶液で洗浄した。
このソーダ塩を水500部に溶解し、攪拌下に希塩酸水
でpH4に調整し、淡桃色の2−(4’−iso−ペン
チルアミノ−2’−ヒドロキシベンゾイル)安息香酸3
4.5部を得た(融点60〜80℃)。出発原料の3−
iso−ペンチルアミノフェノールに対する目的物の収
率は35.2%であった。つぎにソーダ塩のろ液にトル
エン100部を加え、攪拌下に希塩酸でpH7に調整
後、トルエン層を分取し濃縮した。その結果3−iso
−ペンチルアミノフェノール22.5部を回収すること
ができた(回収率41.9%)。Example 2 A reaction of 53.7 parts of 3-iso-pentylaminophenol and 66.6 parts of phthalic anhydride together with 360 parts of o-dichlorobenzene at 140 ° C. for 4 hours gave a dark reddish brown reaction solution. Next, 48% sodium hydroxide 125 was added to the reaction solution.
Part and add rhodamine at 100 ° C for 1 hour,
The reaction turned from dark reddish brown to brown. 500 parts of water was added to the reaction solution, and the reaction product was dissolved in the aqueous layer and separated from the o-dichlorobenzene layer. 48% in the aqueous layer containing the reactants
After adding 150 parts of sodium hydroxide and cooling to 10 ° C., the reaction product was separated out as crystals of soda salt, separated and washed with a 10% aqueous sodium hydroxide solution.
This soda salt was dissolved in 500 parts of water, and the pH was adjusted to 4 with dilute hydrochloric acid under stirring, and pale pink 2- (4′-iso-pentylamino-2′-hydroxybenzoyl) benzoic acid 3 was added.
4.5 parts were obtained (melting point 60-80 ° C.). Starting material 3-
The yield of the desired product with respect to iso-pentylaminophenol was 35.2%. Next, 100 parts of toluene was added to the soda salt filtrate, the pH was adjusted to 7 with dilute hydrochloric acid under stirring, and the toluene layer was separated and concentrated. As a result 3-iso
-22.5 parts of pentylaminophenol could be recovered (41.9% recovery).
【0020】実施例3 3−iso−ペンチルアミノフェノール53.7部と無
水フタル酸66.6部をo−ジクロロベンゼン360部
と共に反応するに際し、ピリジン5量部を用いた以外は
実施例1と同様に反応、処理して、2−(4’−iso
−ペンチルアミノ−2’−ピドロキシベンゾイル)安息
香酸45.5部を得た(融点60〜80℃)。3−is
o−ペンチルアミノフェノールに対する目的物の収率は
46.4%であった。Example 3 Example 3 was repeated except that 53.7 parts of 3-iso-pentylaminophenol and 66.6 parts of phthalic anhydride were reacted together with 360 parts of o-dichlorobenzene, using 5 parts of pyridine. Reaction and treatment are performed in the same manner to give 2- (4′-iso
45.5 parts of -pentylamino-2'-pidroxybenzoyl) benzoic acid were obtained (melting point 60-80 ° C). 3-is
The yield of the desired product relative to o-pentylaminophenol was 46.4%.
【0021】実施例4 3−シクロヘキシルアミノフェノール57部と無水フタ
ル酸46.6部をo−ジクロロベンゼン450部と共に
150℃で2時間反応を行ない濃い赤褐色の反応液を得
た。次に反応液に48%水酸化ナトリウム125部を加
え、100℃で1時間ローダミン分解を行うと反応液は
濃い赤褐色から茶色に変化した。この反応液に水500
部を加え、反応物を水層に溶解しo−ジクロロベンゼン
層と分離した。反応物の溶解した水層に48%水酸化ナ
トリウム150部を加え10℃まで冷却して反応物をソ
ーダ塩の結晶として析出させた後ろ別し、得られた結晶
を10%水酸化ナトリウム水溶液で洗浄した。このソー
ダ塩を水500部に溶解し、攪拌下に希塩酸水でpH4
に調整して、淡桃色の2−(4’−シクロヘキシルアミ
ノ−2’−ヒドロキシベンゾイル)安息香酸55.6部
を得た。(融点163〜164℃)出発原料の3−シク
ロヘキシルアミノフェノールに対する目的物の収率は5
4.8%であった。つぎにソーダ塩の濾液にトルエン1
00部を加え、攪拌下に希塩酸でpH7に調整した後、
トルエン層を分取して濃縮し3−シクロヘキシルアミノ
フェノール15.6部を回収した(回収率27.4
%)。Example 4 57 parts of 3-cyclohexylaminophenol and 46.6 parts of phthalic anhydride were reacted with 450 parts of o-dichlorobenzene at 150 ° C. for 2 hours to obtain a deep reddish brown reaction solution. Next, 125 parts of 48% sodium hydroxide was added to the reaction solution, and the reaction solution was decomposed with rhodamine at 100 ° C. for 1 hour, and the reaction solution changed from dark reddish brown to brown. 500 parts of water
The reaction product was dissolved in the aqueous layer and separated from the o-dichlorobenzene layer. To the aqueous layer in which the reaction product was dissolved, 150 parts of 48% sodium hydroxide was added, and the mixture was cooled to 10 ° C., and the reaction product was separated as soda salt crystals. The obtained crystals were separated with a 10% aqueous sodium hydroxide solution. Washed. This soda salt is dissolved in 500 parts of water and diluted with diluted hydrochloric acid to pH 4 with stirring.
To give 55.6 parts of pale pink 2- (4'-cyclohexylamino-2'-hydroxybenzoyl) benzoic acid. (Melting point: 163 to 164 ° C.) The yield of the target compound based on the starting material 3-cyclohexylaminophenol is 5
It was 4.8%. Next, toluene 1 was added to the soda salt filtrate.
After adding 00 parts and adjusting the pH to 7 with dilute hydrochloric acid under stirring,
The toluene layer was separated and concentrated to recover 15.6 parts of 3-cyclohexylaminophenol (recovery rate 27.4).
%).
【0022】実施例5 3−シクロヘキシルアミノフェノール57部と無水フタ
ル酸46.6部をo−ジクロロベンゼン450部と共に
反応するに際してピリジン5量部を用いた以外は実施例
4と同様に反応、処理して、2−(4’−シクロヘキシ
ルアミノ−2’−ヒドロキシベンゾイル)安息香酸7
1.1部を得た(融点163〜164℃)。出発原料の
3−シクロヘキシルアミノフェノールに対する目的物の
収率は69.9%であった。Example 5 The reaction and treatment were carried out in the same manner as in Example 4 except that when reacting 57 parts of 3-cyclohexylaminophenol with 46.6 parts of phthalic anhydride together with 450 parts of o-dichlorobenzene, 5 parts of pyridine was used. To give 2- (4′-cyclohexylamino-2′-hydroxybenzoyl) benzoic acid 7
1.1 parts were obtained (melting point 163-164 ° C). The yield of the desired product relative to the starting material 3-cyclohexylaminophenol was 69.9%.
【0023】実施例6 3−フェニルアミノフェノール129.5部と無水フタ
ル酸124.3部をo−ジクロロベンゼン280部と共
に反応するに際してピリジン8部を加えて150℃で5
時間反応を行ない、濃い青褐色の反応液を得た。この反
応液に水300部と48%水酸化ナトリウム250部を
加え撹拌してソーダ塩の結晶を析出させた後ろ別し、得
られた結晶をアセトン300部で洗浄した。このソーダ
塩を水1000部に溶解し、攪拌下に希塩酸水でpH4
に調整して、赤褐色結晶の2−(4’−フェニルアミノ
−2’−ヒドロキシベンゾイル)安息香酸105.2部
を得た(融点184〜186℃)。出発原料の3−フェ
ニルアミノフェノールに対する目的物の収率は45.1
%であった。Example 6 When 129.5 parts of 3-phenylaminophenol and 124.3 parts of phthalic anhydride were reacted with 280 parts of o-dichlorobenzene, 8 parts of pyridine was added, and the mixture was reacted at 150 ° C. with 5 parts.
The reaction was carried out for an hour to obtain a dark blue-brown reaction solution. To this reaction solution, 300 parts of water and 250 parts of 48% sodium hydroxide were added, and the mixture was stirred to precipitate soda salt crystals. The crystals were separated and washed with 300 parts of acetone. This soda salt is dissolved in 1000 parts of water, and diluted with diluted hydrochloric acid to pH 4 with stirring.
To give 105.2 parts of 2- (4'-phenylamino-2'-hydroxybenzoyl) benzoic acid as red-brown crystals (melting point: 184-186 ° C). The yield of the target compound with respect to the starting material 3-phenylaminophenol was 45.1.
%Met.
【0024】実施例7 3−p−トリルアミノフェノール59.7部と無水フタ
ル酸53.3部をo−ジクロロベンゼン225部と共に
150〜155℃で3.5時間反応を行ない濃い青褐色
の反応液を得た。この反応液に水300部と48%水酸
化ナトリウム250部を加え撹拌してソーダ塩の結晶を
析出させた後ろ別し、得られた結晶をアセトン300部
で洗浄した。このソーダ塩を水500部に溶解し、攪拌
下に希塩酸水でpH4に調整して、赤褐色結晶の2−
(4’−p−トリルアミノ−2’−ヒドロキシベンゾイ
ル)安息香酸34部を得た(融点189〜192℃)。
出発原料の3−p−トリルアミノフェノールに対する目
的物の収率は32.7%であった。Example 7 A reaction of 59.7 parts of 3-p-tolylaminophenol and 53.3 parts of phthalic anhydride together with 225 parts of o-dichlorobenzene at 150 to 155 ° C. for 3.5 hours to give a dark blue-brown reaction A liquid was obtained. To this reaction solution, 300 parts of water and 250 parts of 48% sodium hydroxide were added, and the mixture was stirred to precipitate soda salt crystals. The crystals were separated and washed with 300 parts of acetone. This soda salt was dissolved in 500 parts of water, and the pH was adjusted to 4 with dilute hydrochloric acid under stirring.
34 parts of (4′-p-tolylamino-2′-hydroxybenzoyl) benzoic acid were obtained (melting point: 189-192 ° C.).
The yield of the target compound relative to the starting material, 3-p-tolylaminophenol, was 32.7%.
【0025】実施例8 3−p−トリルアミノフェノール59.7部と無水フタ
ル酸53.3部をo−ジクロロベンゼン225部と共に
反応するに際してピリジン4部を加えた以外は実施例7
と同様に反応、処理して、赤褐色結晶の2−(4’−p
−トリルアミノ−2’−ヒドロキシベンゾイル)安息香
酸47.7部を得た(融点189〜192℃)。出発原
料の3−p−トリルアミノフェノールに対する目的物の
収率は45.8%であった。Example 8 Example 7 was repeated except that 49.7 parts of pyridine were added when reacting 59.7 parts of 3-p-tolylaminophenol with 53.3 parts of phthalic anhydride together with 225 parts of o-dichlorobenzene.
The reaction and treatment were carried out in the same manner as described above to give 2- (4'-p
47.7 parts of (tolylamino-2'-hydroxybenzoyl) benzoic acid were obtained (melting point 189-192 ° C). The yield of the desired product with respect to the starting material, 3-p-tolylaminophenol, was 45.8%.
【0026】参考例1 3−シクロヘキシルアミノフェノール16.4部と無水
フタル酸13.3部をトルエン120部と共に100〜
110℃で反応を行ったところ反応途中から結晶が析出
した。2時間反応後、反応液を室温まで冷却、ろ過して
無色結晶26.3部を得た(融点168〜170℃)。
出発原料の3−シクロヘキシルアミノフェノールに対す
る上記結晶の収率は90.5%であった。上記結晶化合
物は、IRおよびNMRによる構造解析の結果、N−シ
クロヘキシル−3’ヒドロキシ−2−カルボキシーベン
ズアニリドと判明した。Reference Example 1 16.4 parts of 3-cyclohexylaminophenol and 13.3 parts of phthalic anhydride were added to 100 to 100 parts of toluene together with 120 parts of toluene.
When the reaction was carried out at 110 ° C., crystals precipitated during the reaction. After reacting for 2 hours, the reaction solution was cooled to room temperature and filtered to obtain 26.3 parts of colorless crystals (melting point: 168 to 170 ° C).
The yield of the above crystals relative to the starting material 3-cyclohexylaminophenol was 90.5%. As a result of structural analysis by IR and NMR, the crystalline compound was found to be N-cyclohexyl-3′hydroxy-2-carboxy-benzanilide.
【0027】参考例2 3−p−トリルアミノフェノール19.9部と無水フタ
ル酸17.8部をo−ジクロロベンゼン120部と共に
100〜110℃で反応を行ったところ反応途中から結
晶が析出した。2時間反応後、反応液を室温まで冷却、
ろ過して無色結晶25.3部を得た(融点174〜18
3℃)。出発原料の3−p−トリルアミノフェノールに
対する上記結晶の収率は72.9%であった。上記結晶
化合物は、IRおよびNMRによる構造解析の結果、N
−p−トリル−3’ヒドロキシ−2−カルボキシ−ベン
ズアニリドと判明した。REFERENCE EXAMPLE 2 19.9 parts of 3-p-tolylaminophenol and 17.8 parts of phthalic anhydride were reacted together with 120 parts of o-dichlorobenzene at 100 to 110 ° C., and crystals were precipitated during the reaction. . After reacting for 2 hours, the reaction solution is cooled to room temperature,
Filtration gave 25.3 parts of colorless crystals (mp 174-18).
3 ° C). The yield of the above crystals relative to the starting material 3-p-tolylaminophenol was 72.9%. As a result of structural analysis by IR and NMR,
-P-tolyl-3'hydroxy-2-carboxy-benzanilide was found.
【0028】参考例3 「アニリド体のベンゾフェノンカルボン酸への転化」参
考例1で得たアニリド体20部をo−ジクロロベンゼン
100部と共に150℃で2時間反応後、実施例3と同
様に処理し、2−(4’−シクロヘキシルアミノ−2’
−ヒドロキシベンゾイル)安息香酸12.3部を得た。
アニリド体に対する収率は61.5%であった。REFERENCE EXAMPLE 3 "Conversion of anilide to benzophenonecarboxylic acid" 20 parts of the anilide obtained in Reference Example 1 were reacted with 100 parts of o-dichlorobenzene at 150 ° C. for 2 hours and treated in the same manner as in Example 3. And 2- (4'-cyclohexylamino-2 '
-Hydroxybenzoyl) benzoic acid (12.3 parts) was obtained.
The yield based on the anilide was 61.5%.
【0029】応用例1 「2−メチル−6−シクロヘキシルアミノーフルオラン
の合成」80%硫酸200部に2−(4’−シクロヘキ
シルアミノ−2’−ヒドロキシベンゾイル)安息香酸3
3.9部を20〜25℃で溶解した。次にp−クレゾー
ル14部を10℃で溶解し、さらに20℃で20時間反
応した。この反応物を氷水1000部で10℃以下を保
ちながら希釈し析出物をろ別した。ろ別した反応物をト
ルエン250部、水100部に加え、還流下に水酸化ナ
トリウムでpH10とした。次にトルエン層を分取し、
活性炭5部を加え清澄ろ過をおこなった。このトルエン
層を濃縮した残査にメタノール200部を加え、よくほ
ぐし析出した結晶をろ別し、110℃で一夜乾燥して、
淡桃色結晶37.4部を得た。融点190.2〜19
2.5℃。収率は91%であった。こうして得られた2
−メチル−6−シクロヘキシルアミノフルオランは感圧
複写システムの顕色剤として広く用いられている活性白
土上で、鮮やかな黄色に発色し、非常に実用価値の高い
ものである。Application Example 1 "Synthesis of 2-methyl-6-cyclohexylamino-fluoran" 2- (4'-cyclohexylamino-2'-hydroxybenzoyl) benzoic acid 3 in 200 parts of 80% sulfuric acid
3.9 parts were melted at 20-25 ° C. Next, 14 parts of p-cresol was dissolved at 10 ° C and further reacted at 20 ° C for 20 hours. The reaction product was diluted with 1000 parts of ice water while keeping the temperature at 10 ° C. or lower, and the precipitate was separated by filtration. The filtered reaction product was added to 250 parts of toluene and 100 parts of water, and adjusted to pH 10 with sodium hydroxide under reflux. Next, separate the toluene layer,
Activated carbon (5 parts) was added, and clarification filtration was performed. To the residue obtained by concentrating the toluene layer, 200 parts of methanol was added, and the crystals were loosened well and the precipitated crystals were separated by filtration and dried at 110 ° C. overnight.
37.4 parts of pale pink crystals were obtained. Melting point 190.2-19
2.5 ° C. The yield was 91%. 2 thus obtained
-Methyl-6-cyclohexylaminofluoran develops a vivid yellow color on activated clay widely used as a developer in a pressure-sensitive copying system, and has a very high practical value.
【0030】[0030]
【発明の効果】本発明の製造法によれば、硼酸を用いな
くても収率よく2−(4’−モノ置換アミノ−2’−ヒ
ドロキシベンゾイル)安息香酸を得ることができる。得
られたベンゾフェノンカルボン酸誘導体は情報記録用色
素として利用価値の高いフルオラン化合物の原料として
用いられる。According to the production method of the present invention, 2- (4'-monosubstituted amino-2'-hydroxybenzoyl) benzoic acid can be obtained in good yield without using boric acid. The obtained benzophenone carboxylic acid derivative is used as a raw material of a fluoran compound having high utility value as an information recording dye.
Claims (4)
くはm−位に置換基を有することもあるフェニル基を意
味し、R2は水素原子、アルキル基を意味する。)で表
される3−モノ置換アミノフェノールと無水フタル酸
を、無溶媒あるいは有機溶媒の存在下、130〜180
℃の間で反応することを特徴とする一般式(2) 【化2】 (式中R1,R2は前記に同じ)で表される2−(4’
−N−モノ置換アミノ−2’−ヒドロキシベンゾイル)
安息香酸の製造方法。1. A compound of the general formula (1) (Wherein R1 represents an alkyl group, a cycloalkyl group, or a phenyl group which may have a substituent at the p- or m-position, and R2 represents a hydrogen atom or an alkyl group). The mono-substituted aminophenol and phthalic anhydride are mixed with each other in the absence of a solvent or in the presence of an organic solvent at 130 to 180.
General formula (2) characterized in that the reaction is carried out at a temperature of ℃. (Wherein R1 and R2 are the same as described above).
-N-monosubstituted amino-2'-hydroxybenzoyl)
A method for producing benzoic acid.
シクロヘキシル基又はp−メチルフェニル基であり、R
2が水素原子である請求項1記載の2−(4’−N−モ
ノ置換アミノ−2’−ピドロキシベンゾイル)安息香酸
の製造方法。(2) R1 in the general formulas (1) and (2) is a cyclohexyl group or a p-methylphenyl group;
The method for producing 2- (4'-N-monosubstituted amino-2'-pidroxybenzoyl) benzoic acid according to claim 1, wherein 2 is a hydrogen atom.
ル酸との反応を、置換基を有することもあるピリジンの
存在下におこなうことを特徴とする請求項1又は2記載
の2−(4’−N−モノ置換アミノ−2’−ヒドロキシ
ベンゾイル)安息香酸の製造方法。3. The method according to claim 1, wherein the reaction between the 3-monosubstituted aminophenol and phthalic anhydride is carried out in the presence of pyridine which may have a substituent. A method for producing -N-monosubstituted amino-2'-hydroxybenzoyl) benzoic acid.
ル酸とを反応させた後、2−(4’−N−モノ置換アミ
ノ−2’−ヒドロキシベンゾイル)安息香酸を単離する
ことなく、出発原料として使用した3−モノ置換アミノ
フェノール1モル当たり1〜10モル相当の水酸化アル
カリを加えて80〜140℃で熱処理し、前記3−モノ
置換アミノフェノールと無水フタル酸との反応で副生す
るローダミン型色素の分解をはかることを特徴とする請
求項1又は2記載の2−(4’−N−モノ置換アミノ−
2’−ヒドロキシベンゾイル)安息香酸の製造方法。4. The reaction of 3-monosubstituted aminophenol with phthalic anhydride without isolation of 2- (4'-N-monosubstituted amino-2'-hydroxybenzoyl) benzoic acid without isolation. An alkali hydroxide equivalent to 1 to 10 moles was added to 1 mole of the 3-monosubstituted aminophenol used as a raw material and heat-treated at 80 to 140 ° C. 3. The 2- (4'-N-monosubstituted amino-) according to claim 1 or 2, wherein decomposition of the rhodamine type dye is performed.
2′-Hydroxybenzoyl) method for producing benzoic acid.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8196878A JPH107632A (en) | 1996-06-21 | 1996-06-21 | Production of 2-(4'-n-monosubstituted amino-2'-hydroxybenzoyl)benzoic acid |
GB9712844A GB2314329B (en) | 1996-06-21 | 1997-06-18 | Process for preparing 2-(4'N-monosustituted amino-2-hydroxybenzoyl)benzoic Acids |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8196878A JPH107632A (en) | 1996-06-21 | 1996-06-21 | Production of 2-(4'-n-monosubstituted amino-2'-hydroxybenzoyl)benzoic acid |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH107632A true JPH107632A (en) | 1998-01-13 |
Family
ID=16365161
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8196878A Pending JPH107632A (en) | 1996-06-21 | 1996-06-21 | Production of 2-(4'-n-monosubstituted amino-2'-hydroxybenzoyl)benzoic acid |
Country Status (2)
Country | Link |
---|---|
JP (1) | JPH107632A (en) |
GB (1) | GB2314329B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017038987A1 (en) * | 2015-09-03 | 2017-03-09 | 国立研究開発法人理化学研究所 | Rhodamine-based colorant compound and process for producing same |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4035393A (en) * | 1975-04-10 | 1977-07-12 | Ncr Corporation | Chromogenic derivatives of bis-1,1-disubstituted ethylene and a process for preparing them |
JP2764317B2 (en) * | 1989-09-25 | 1998-06-11 | 三井化学株式会社 | Benzoic acid derivative and method for producing the same |
JP3181107B2 (en) * | 1992-09-22 | 2001-07-03 | 三井化学株式会社 | Method for producing keto acid |
JP3627196B2 (en) * | 1995-01-17 | 2005-03-09 | 山田化学工業株式会社 | Fluorane compound and chromogenic recording material using the same |
-
1996
- 1996-06-21 JP JP8196878A patent/JPH107632A/en active Pending
-
1997
- 1997-06-18 GB GB9712844A patent/GB2314329B/en not_active Expired - Fee Related
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017038987A1 (en) * | 2015-09-03 | 2017-03-09 | 国立研究開発法人理化学研究所 | Rhodamine-based colorant compound and process for producing same |
JPWO2017038987A1 (en) * | 2015-09-03 | 2018-08-09 | 国立研究開発法人理化学研究所 | Rhodamine dye compound and process for producing the same |
US10435564B2 (en) | 2015-09-03 | 2019-10-08 | Riken | Rhodamine-based colorant compound and process for producing same |
Also Published As
Publication number | Publication date |
---|---|
GB9712844D0 (en) | 1997-08-20 |
GB2314329A (en) | 1997-12-24 |
GB2314329B (en) | 2000-05-31 |
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