JP2764317B2 - Benzoic acid derivative and method for producing the same - Google Patents
Benzoic acid derivative and method for producing the sameInfo
- Publication number
- JP2764317B2 JP2764317B2 JP24643689A JP24643689A JP2764317B2 JP 2764317 B2 JP2764317 B2 JP 2764317B2 JP 24643689 A JP24643689 A JP 24643689A JP 24643689 A JP24643689 A JP 24643689A JP 2764317 B2 JP2764317 B2 JP 2764317B2
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- JP
- Japan
- Prior art keywords
- compound
- benzoic acid
- producing
- isobutyl
- general formula
- 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.)
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- 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、新規な安息香酸誘導体およびその製造法に
関する。Description: TECHNICAL FIELD The present invention relates to a novel benzoic acid derivative and a method for producing the same.
さらに詳しくは、記録材料として有用なフルオラン化
合物の重要な製造原料となる安息香酸誘導体およびその
製造法に関する。More specifically, the present invention relates to a benzoic acid derivative which is an important raw material for producing a fluoran compound useful as a recording material and a method for producing the same.
従来、無色ないし淡色の電子供与性化合物（発色性化
合物）と有機もしくは無機の電子受容性物質（顕色剤）
との呈色反応を利用し、圧力、熱または電気などの外部
エネルギーの媒介により伝達される情報を記録する方式
として、感圧記録、感熱記録および通電感熱記録などが
ある。Conventionally, a colorless or light-colored electron-donating compound (color-forming compound) and an organic or inorganic electron-accepting substance (color developer)
As a method for recording information transmitted by mediation of external energy such as pressure, heat or electricity by utilizing a color reaction with a pressure-sensitive recording, a heat-sensitive recording, and a heat-sensitive recording.
これらの記録方式には、発色性化合物としてフルオラ
ン化合物が広く用いられている。In these recording methods, a fluoran compound is widely used as a coloring compound.
フルオラン化合物の原料となる安息香酸誘導体として
は、従来、例えば、式（IIIa）および式（IIIb）が知ら
れている。As the benzoic acid derivative used as a raw material of the fluoran compound, for example, formula (IIIa) and formula (IIIb) are known.
これらの安息香酸誘導体を原料として、それぞれ式
（IVa）および（IVb）のフルオラン化合物が製造されて
いる。 Fluorane compounds of formulas (IVa) and (IVb) have been produced using these benzoic acid derivatives as raw materials.
しかし（IVa）の化合物は、感圧記録材料として用い
るには、カプセルオイルに対する溶解度が極めて低いと
いう欠点があり、また感熱記録材料として用いるには、
例えば、ビスフェノールＡ等の顕色剤と混合すると、そ
れ自体灰色ないし黒灰色に発色し、これを紙に塗布する
と、灰色ないし黒灰色に着色（地汚れ）した紙しか得ら
れないという欠点があった。 However, the compound of (IVa) has a drawback that its solubility in capsule oil is extremely low when used as a pressure-sensitive recording material.
For example, when it is mixed with a developer such as bisphenol A, it develops a gray or black-gray color by itself, and when it is applied to paper, there is a drawback that only paper colored (ground stain) with a gray or black-gray color can be obtained. Was.
また（IVb）の化合物は、感熱記録材料として用いる
には、発色する温度が高すぎるため、現在、より高速か
つ高密度に記録しょうとする要望に適合した充分な性能
と言えず、より低温ですみやかに発色する発色性化合
物、およびこのような化合物を製造するための原料化合
物が強く望まれている。In addition, the compound (IVb) has too high a color developing temperature to be used as a heat-sensitive recording material, and therefore cannot be said to have sufficient performance to meet the demand for recording at higher speed and higher density at present. There is a strong demand for a color-forming compound that rapidly develops color, and a starting compound for producing such a compound.
本発明の課題は、上記の欠点を解消した感圧および感
熱等の記録材料に適したフルオラン化合物の原料とし
て、有用な安息香酸誘導体およびその製造方法を提供す
ることである。An object of the present invention is to provide a benzoic acid derivative useful as a raw material of a fluoran compound suitable for a recording material such as pressure-sensitive and heat-sensitive which has solved the above-mentioned disadvantages, and a method for producing the same.
本発明者らは、上述の課題を解決するために種々の化
合物を探索し、本発明に到達した。The present inventors have searched for various compounds in order to solve the above-mentioned problems, and have reached the present invention.
すなわち、本発明は一般式（Ｉ） （式中、Ｒ1は炭素数１〜４のアルキル基を示す）で表
される安息香酸誘導体、およびこの誘導体を一般式（I
I） （式中、Ｒ2には炭素数１〜４のアルキル基を示す）で
表される３−アミノフェノール誘導体と無水フタル酸と
を反応させて製造する方法である。That is, the present invention provides a compound represented by the general formula (I) Wherein R 1 represents an alkyl group having 1 to 4 carbon atoms, and a benzoic acid derivative represented by the general formula (I
I) (Wherein, R 2 represents an alkyl group having 1 to 4 carbon atoms), and is produced by reacting a 3-aminophenol derivative represented by the following formula with phthalic anhydride.
本発明の化合物は、前記の一般式（Ｉ）で表される安
息香酸誘導体であり、一般式（Ｉ）において、Ｒ1はメ
チル基、エチル基、ｎ−プロピル基、イソプロピル基、
ｎ−ブチル基、イソブチル基、sec−ブチル基等の炭素
数１〜４のアルキル基が例示される。The compound of the present invention is a benzoic acid derivative represented by the above general formula (I), wherein R 1 is a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
Examples thereof include an alkyl group having 1 to 4 carbon atoms, such as an n-butyl group, an isobutyl group, and a sec-butyl group.
本発明の化合物は、代表的には一般式（II）の３−ア
ミノフェノール誘導体と無水フタル酸とを無溶媒、ある
いはベンゼン、トルエン、キシレンまたはテトラクロロ
エチレン等の溶媒中で反応させることにより製造するこ
とができる。The compound of the present invention is typically produced by reacting a 3-aminophenol derivative of the general formula (II) with phthalic anhydride without solvent or in a solvent such as benzene, toluene, xylene or tetrachloroethylene. Can be.
反応温度は、60〜140℃の範囲で行うことが好まし
く、反応時間は反応温度により異なるが、数時間から数
十時間の間が好ましい。The reaction temperature is preferably in the range of 60 to 140 ° C., and the reaction time varies depending on the reaction temperature, but is preferably between several hours and several tens of hours.
また、この反応の際、例えば、塩化亜鉛のごときルイ
ス酸を添加してもよい。At the time of this reaction, for example, a Lewis acid such as zinc chloride may be added.
本発明の方法で用いる３−アミノフェノール誘導体
は、一般式（II）において、Ｒ2がメチル基、エチル
基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、
イソブチル基、sec−ブチル基等の炭素数１〜４のアル
キル基である化合物が例示される。In the 3-aminophenol derivative used in the method of the present invention, in the general formula (II), R 2 represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Examples of the compound include an alkyl group having 1 to 4 carbon atoms such as an isobutyl group and a sec-butyl group.
これらの化合物は、例えば、一般式（II）においてＲ
2がメチル基の化合物は、例えば、レゾルシンとイソブ
チルアミンとより得られる３−Ｎ−イソブチルアミノフ
ェノールを、２−メトキシエチルブロマイド、または２
−メトキシエチルトシレートのような２−メトキシエチ
ル化剤で２−メトキシエチル化を行なうことにより製造
できる。また、例えば、レゾルシンと２−メトキシエチ
ルアミンとより製造される３−Ｎ−２′−メトキシエチ
ルアミノフェノールを、イソブチルクロライド、イソブ
チルブロマイド、またはイソブチルトシレートのような
イソブチル化剤によりイソブチル化を行なうことによっ
ても好適に製造することができる。These compounds are, for example, those represented by R in general formula (II)
The compound in which 2 is a methyl group is, for example, 3-N-isobutylaminophenol obtained from resorcinol and isobutylamine, 2-methoxyethyl bromide, or 2
Can be produced by performing 2-methoxyethylation with a 2-methoxyethylating agent such as -methoxyethyl tosylate. Further, for example, isobutylation of 3-N-2′-methoxyethylaminophenol produced from resorcinol and 2-methoxyethylamine with an isobutylating agent such as isobutyl chloride, isobutyl bromide, or isobutyl tosylate. Can also be suitably manufactured.
本発明の一般式（Ｉ）で表わされる化合物はフルオラ
ン化合物の製造における原料として非常に有用である。The compound represented by the general formula (I) of the present invention is very useful as a raw material in producing a fluoran compound.
本発明の一般式（Ｉ）で表わされる化合物を用いて製
造されるフルオラン化合物、例えば、式（Ｖ）の化合物
は、 感圧複写シートに使用する際、カプセルオイルに対する
溶解度が極めて高く、かつ感熱記録材料に使用すると地
汚れのない、白色度の高い紙が得られ式（IVa）や式（I
Vb）の化合物に比較して、より低温ですみやかに黒色に
発色するというすぐれた特徴を有している。The fluoran compound produced using the compound represented by the general formula (I) of the present invention, for example, the compound of the formula (V) is When used in a pressure-sensitive copying sheet, a paper having extremely high solubility in capsule oil and using the heat-sensitive recording material, which is free from background smear and has high whiteness, can be obtained using the formulas (IVa) and (I).
Compared to the compound of Vb), it has an excellent feature that it rapidly develops a black color at lower temperatures.
以下、実施例により、本発明を更に具体的に説明する
が、本発明は、これらの実施例に限定されるものではな
い。Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.
実施例１ 〔一般式（Ｉ）においてＲ1がメチル基の化合物の製
造〕 ３−Ｎ−イソブチルアミノフェノールと２−メトキシ
エチルトシレートより製造した３−Ｎ−イソブチル−Ｎ
−２′−メトキシエチルアミノフェノール94gを無水フ
タル酸93gを250mlのトルエン中、110℃で10時間攪拌し
た。30mlの水を加えた後、60℃で30分間攪拌後、トルエ
ン層を分離後、さらに温水（300ml）で２回洗浄した。
トルエン層を分離し、トルエンを減圧下留去した後、残
渣にイソプロパノール500ml及び50％NaOH水150mlを加
え、析出したナトリウム塩を濾過し、イソプロパノール
50mlで洗浄した。このナトリウム塩を水500mlに分散
後、濃塩酸でpH5〜６とした後、10℃にて24時間放置
後、析出した結晶を濾過、水洗、乾燥し、33gのクリー
ム色の結晶として２−（２′−ヒドロキシ−４′−Ｎ−
イソブチル−Ｎ−２″−メトキシエチルアミノベンゾイ
ル）安息香酸を得た。Example 1 [Production of compound in which R 1 is a methyl group in general formula (I)] 3-N-isobutyl-N produced from 3-N-isobutylaminophenol and 2-methoxyethyl tosylate
94 g of -2'-methoxyethylaminophenol and 93 g of phthalic anhydride were stirred in 250 ml of toluene at 110 ° C for 10 hours. After adding 30 ml of water, the mixture was stirred at 60 ° C. for 30 minutes, and the toluene layer was separated and further washed twice with warm water (300 ml).
After the toluene layer was separated and toluene was distilled off under reduced pressure, 500 ml of isopropanol and 150 ml of 50% NaOH water were added to the residue, and the precipitated sodium salt was filtered.
Washed with 50 ml. This sodium salt was dispersed in 500 ml of water, adjusted to pH 5 to 6 with concentrated hydrochloric acid, left at 10 ° C. for 24 hours, and the precipitated crystals were filtered, washed with water and dried to give 33 g of creamy crystals as 2- ( 2'-hydroxy-4'-N-
Isobutyl-N-2 "-methoxyethylaminobenzoyl) benzoic acid was obtained.
収率21％融点、149〜150℃ 実施例２ 〔一般式（Ｉ）においてＲ1がエチル基の化合物の製
造〕 実施例１において３−Ｎ−イソブチル−Ｎ−２′−メ
トキシエチルアミノフェノールの代りに３−Ｎ−イソブ
チル−Ｎ−２′−エトキシエチルアミノフェノールを使
用した他は実施例１に記載した方法と同様の方法により
２−（２′−ヒドロキシ−４′−Ｎ−イソブチル−Ｎ−
２″−エトキシエチルアミノベンゾイル）安息香酸を収
率38％で得た。融点134〜136℃ 実施例３ 〔一般式（Ｉ）においてＲ1がイソプロピル基の化合物
の製造〕 実施例１において３−Ｎ−イソブチル−Ｎ−２′−メ
トキシエチルアミノフェノールの代りに３−Ｎ−イソブ
チル−Ｎ−２−イソプポキシエチルアミノフェノールを
使用した他は、実施例１に記載した方法と同様の方法に
より２−（２′−ヒドロキシ−４′−Ｎ−イソブチル−
Ｎ−２″−イソプロポキシエチルアミノベンゾイル）安
息香酸を収率40％で融点62-65℃の結晶として得た。Yield: 21%, melting point: 149-150 ° C. Example 2 [Production of a compound in which R 1 is an ethyl group in the general formula (I)] In Example 1, 3-N-isobutyl-N-2′-methoxyethylaminophenol 2- (2'-Hydroxy-4'-N-isobutyl-N) was prepared in the same manner as described in Example 1 except that 3-N-isobutyl-N-2'-ethoxyethylaminophenol was used instead. −
2 ″ -ethoxyethylaminobenzoyl) benzoic acid was obtained in a yield of 38%. Melting point: 134 to 136 ° C. Example 3 [Production of a compound of the general formula (I) in which R 1 is an isopropyl group] The procedure of Example 1 was repeated, except that 3-N-isobutyl-N-2-isopropoxyethylaminophenol was used instead of N-isobutyl-N-2'-methoxyethylaminophenol. -(2'-hydroxy-4'-N-isobutyl-
N-2 "-isopropoxyethylaminobenzoyl) benzoic acid was obtained as crystals with a yield of 40% and a melting point of 62-65 ° C.
実施例４ 〔一般式（Ｉ）においてＲ1がｎ−ブチル基の化合物の
製造〕 実施例１において３−Ｎ−イソブチル−Ｎ−２′−メ
トキシエチルアミノフェノールの代りに３−Ｎ−イソブ
チル−Ｎ−２′−ｎ−ブトキシエチルアミノフェノール
を使用した他は実施例１に記載した方法と同様の方法に
より２−（２′−ヒドロキシ−４′−Ｎ−イソブチル−
Ｎ−２″−ｎ−ブトキシエチルアミノベンゾイル）安息
香酸を42％の収率で粘い油状物として得た。Example 4 [Production of a compound of the formula (I) wherein R 1 is an n-butyl group] In Example 1, 3-N-isobutyl- is used instead of 3-N-isobutyl-N-2'-methoxyethylaminophenol. Except that N-2'-n-butoxyethylaminophenol was used, 2- (2'-hydroxy-4'-N-isobutyl-) was prepared in the same manner as described in Example 1.
N-2 "-n-butoxyethylaminobenzoyl) benzoic acid was obtained as a viscous oil in 42% yield.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭61−229591（ＪＰ，Ａ) 特開 昭61−91259（ＪＰ，Ａ) 欧州公開176161（ＥＰ，Ａ１) (58)調査した分野(Int.Cl.6，ＤＢ名) C07C 229/00 C07C 227/00 ＣＡ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-61-229591 (JP, A) JP-A-61-91259 (JP, A) European publication 176161 (EP, A1) (58) Fields investigated (Int .Cl. 6 , DB name) C07C 229/00 C07C 227/00 CA (STN)
Claims (2)
される安息香酸誘導体。1. The compound of the general formula (I) (Wherein, R 1 represents an alkyl group having 1 to 4 carbon atoms).
される３−アミノフェノール誘導体と無水フタル酸とを
反応させることを特徴とする請求項１記載の一般式
（Ｉ）で表される安息香酸誘導体の製造法。2. A compound of the general formula (II) 3. The general formula (I) according to claim 1, wherein a 3-aminophenol derivative represented by the formula (1) wherein R2 represents an alkyl group having 1 to 4 carbon atoms is reacted with phthalic anhydride. A method for producing a benzoic acid derivative represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24643689A JP2764317B2 (en) | 1989-09-25 | 1989-09-25 | Benzoic acid derivative and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24643689A JP2764317B2 (en) | 1989-09-25 | 1989-09-25 | Benzoic acid derivative and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03109364A JPH03109364A (en) | 1991-05-09 |
| JP2764317B2 true JP2764317B2 (en) | 1998-06-11 |
Family
ID=17148447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24643689A Expired - Fee Related JP2764317B2 (en) | 1989-09-25 | 1989-09-25 | Benzoic acid derivative and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2764317B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH107632A (en) * | 1996-06-21 | 1998-01-13 | Yamada Chem Co Ltd | Production of 2-(4'-n-monosubstituted amino-2'-hydroxybenzoyl)benzoic acid |
| GB9700376D0 (en) * | 1997-01-09 | 1997-02-26 | Ciba Geigy Ag | Production of keto acids |
-
1989
- 1989-09-25 JP JP24643689A patent/JP2764317B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03109364A (en) | 1991-05-09 |
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