JPH072865A - Fluoran compound - Google Patents

Fluoran compound

Info

Publication number
JPH072865A
JPH072865A JP3246160A JP24616091A JPH072865A JP H072865 A JPH072865 A JP H072865A JP 3246160 A JP3246160 A JP 3246160A JP 24616091 A JP24616091 A JP 24616091A JP H072865 A JPH072865 A JP H072865A
Authority
JP
Japan
Prior art keywords
compound
alkyl
anilino
formula
methylfluorane
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
Application number
JP3246160A
Other languages
Japanese (ja)
Inventor
Tsuneto Eda
恒人 江田
Yasuhisa Iwasaki
泰久 岩崎
Ikuzo Nishiguchi
郁三 西口
Yoshio Ishino
義夫 石野
Tsunesuke Hirashima
恒亮 平嶋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yamamoto Chemicals Inc
Osaka City
Original Assignee
Yamamoto Chemicals Inc
Osaka City
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Yamamoto Chemicals Inc, Osaka City filed Critical Yamamoto Chemicals Inc
Priority to JP3246160A priority Critical patent/JPH072865A/en
Publication of JPH072865A publication Critical patent/JPH072865A/en
Pending legal-status Critical Current

Links

Landscapes

  • Heat Sensitive Colour Forming Recording (AREA)
  • Color Printing (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

PURPOSE:To obtain a new fluoran compound, useful as a color former used in pressure-sensitive and heat-sensitive recording materials, thermal color changing materials, etc., by substituting NH group in a 2-anilino-6-dialkylamino-3- methylfluoran. CONSTITUTION:A 2-anilino-6-dialkylamino-3-methylfluoran expressed by formula I (R1 and R2 are 3-4C alkyl) is used and hydrogen atom bound to nitrogen atom of anilino group in this compound is reacted with a compound such as ethyl orthoformate, a benzoyl halide, an alkyl halogenated carbonate, a benzyl halide, an allyl halide or a dialkyl sulfate to afford the objective fluoran compound expressed by formula II [R<3> is COR4 (R4 is H, 1-4C alkyl, phenyl which may have a substituent group), COOR5 (R5 is 1-4C alkyl), CH2R6 (R6 is phenyl which may have a substituent group), CH2CH=CH2 or 1-4C alkyl].

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明はフルオラン化合物に関す
る。詳細には、感圧記録材料、感熱記録材料等の発色性
記録材料や熱変色材料に用いる発色剤として有用な新規
のフルオラン化合物に関する。
FIELD OF THE INVENTION The present invention relates to fluoran compounds. More specifically, the present invention relates to a novel fluoran compound useful as a color former for color-forming recording materials such as pressure-sensitive recording materials and heat-sensitive recording materials and thermochromic materials.

【0002】[0002]

【従来の技術及び発明が解決しようとする課題】近年、
電子供与性発色剤(以下発色剤という)と電子受容性顕
色剤(以下顕色剤という)との発色反応を利用した感圧
記録材料、感熱記録材料等の発色性記録材料が、情報産
業の発達、事務処理の合理化に伴い、その需要が飛躍的
に増大している。また最近では、発色剤、顕色剤および
発色制御剤とから成る熱変色材料が、可逆的熱変色性を
利用したサーモクロミズム的使用、例えば衣料、玩具、
文具、ディスプレーパネル等の分野での使用が増大して
いる。これらの発色性記録材料および熱変色材料用の赤
色発色系発色剤としては、従来、2−クロロ−6−ジエ
チルアミノ−3−メチルフルオラン、3−ジエチルアミ
ノ−7,8−ベンゾフルオラン、3,3−ビス(1−ブ
チル−2−メチルインドール−3−イル)フタリド等が
実用に供されている。しかしながら、これらの発色剤は
発色前の地肌白色度、発色色相、発色像の堅牢性等にお
いて未だ十分なものではなく、更に優れた発色剤が望ま
れている。本発明の目的は、赤発色系発色剤として有用
な新規なフルオラン化合物を提供することにある。また
本発明の他の目的は、現在大量に生産されている黒発色
系のフルオランを原料として、効率的に製造できる赤発
色系フルオラン化合物を提供することにある。
2. Description of the Related Art In recent years,
Color-forming recording materials, such as pressure-sensitive recording materials and heat-sensitive recording materials, which utilize the color-forming reaction between an electron-donating color developing agent (hereinafter referred to as color developing agent) and an electron-accepting color developing agent (hereinafter referred to as color developing agent) With the development of and the rationalization of paperwork, the demand for them has increased dramatically. Also, recently, a thermochromic material consisting of a color former, a color developer and a color control agent is used for thermochromic use utilizing reversible thermochromism, such as clothing, toys,
The use in the field of stationery and display panels is increasing. As the red color-developing color formers for these color-forming recording materials and thermochromic materials, 2-chloro-6-diethylamino-3-methylfluorane, 3-diethylamino-7,8-benzofluorane, 3, 3-bis (1-butyl-2-methylindol-3-yl) phthalide and the like are put to practical use. However, these color formers are not yet sufficient in terms of background whiteness before color formation, color hue, fastness of color image, and the like, and further excellent color formers are desired. An object of the present invention is to provide a novel fluorane compound which is useful as a red color-forming color developing agent. Another object of the present invention is to provide a red-coloring fluoran compound that can be efficiently produced using black-coloring fluoran, which is currently mass-produced, as a raw material.

【0003】[0003]

【課題を解決するための手段】本発明の目的は、一般式
(I)で表される新規なフルオラン化合物により達成さ
れた。
The object of the present invention has been achieved by the novel fluorane compound represented by the general formula (I).

【化2】 (式中、R1およびR2は炭素数3〜4個のアルキル基を
示し、R3は−COR4、−COOR5、−CH26、−
CH2CH=CH2又は炭素数1〜4個のアルキル基を示
し、R4は水素原子、炭素数1〜4個のアルキル基又は
置換基を有しても良いフェニル基を示し、R5は炭素数
1〜4個のアルキル基を示し、R6は置換基を有しても
良いフェニル基を示す。) 一般式(I)で表されるフルオラン化合物において、R
1およびR2がブチル基であるものが、記録材料に用いた
場合の地肌白色度が高いことや、原料となる黒色系フル
オランが大量に製造されていること等から特に好まし
い。R4は好ましくは水素原子、メチル基、エチル基、
プロピル基又はフェニル基である。R5は好ましくはプ
ロピル基又はブチル基である。R6は好ましくはフェニ
ル基である。
[Chemical 2] (In the formula, R 1 and R 2 represent an alkyl group having 3 to 4 carbon atoms, and R 3 represents —COR 4 , —COOR 5 , —CH 2 R 6 , and —
CH 2 CH═CH 2 or an alkyl group having 1 to 4 carbon atoms, R 4 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group which may have a substituent, R 5 Represents an alkyl group having 1 to 4 carbon atoms, and R 6 represents a phenyl group which may have a substituent. ) In the fluorane compound represented by the general formula (I), R
It is particularly preferable that 1 and R 2 are butyl groups because of their high background whiteness when used as a recording material and because black fluoran as a raw material is produced in large quantities. R 4 is preferably a hydrogen atom, a methyl group, an ethyl group,
A propyl group or a phenyl group. R 5 is preferably a propyl group or a butyl group. R 6 is preferably a phenyl group.

【0004】一般式(I)で表されるフルオラン化合物
は、公知のフルオラン化合物の製法に従って、下記式
(II)で示されるベンゾフェノン化合物と下記式(II
I)で示されるジフェニルアミン化合物とを、濃硫酸の
ような縮合剤を用いて反応させることによっても製造で
きる。
The fluoran compound represented by the general formula (I) is a benzophenone compound represented by the following formula (II) and the following formula (II) according to a known method for producing a fluoran compound.
It can also be produced by reacting the diphenylamine compound represented by I) with a condensing agent such as concentrated sulfuric acid.

【化3】 [Chemical 3]

【化4】 (式(II)、式(III)において、Rは水素原子又は低級
アルキル基を示し、R1、R2およびR3は前記と同じも
のを示す。)
[Chemical 4] (In the formulas (II) and (III), R represents a hydrogen atom or a lower alkyl group, and R 1 , R 2 and R 3 represent the same as above.)

【0005】しかしながら、原料として現在大量に生産
されている式(IV)で示される2−アニリノ−6−ジア
ルキルアミノ−3−メチルフルオランを用い、アニリノ
基の窒素原子に結合している水素原子を置換することに
よって製造する方法によるのが、生産効率上有利であ
る。
However, a 2-anilino-6-dialkylamino-3-methylfluorane represented by the formula (IV), which is currently produced in a large amount, is used as a raw material, and a hydrogen atom bonded to the nitrogen atom of the anilino group is used. It is advantageous in terms of production efficiency that it is produced by substituting

【化5】 (式中、R1およびR2は前記と同じものを示す。) 後者の製造法において、式(IV)で表される原料フルオ
ラン化合物のアニリノ基の窒素原子上の水素原子を置換
する方法としては公知の種々の方法が適用できるが、製
造される式(I)で表されるフルオラン化合物の置換基
3の種類により、例えば下記の方法が用いられる。
[Chemical 5] (In the formula, R 1 and R 2 are the same as above.) In the latter production method, a method for substituting the hydrogen atom on the nitrogen atom of the anilino group of the starting fluorane compound represented by the formula (IV) Although various known methods can be applied, for example, the following method is used depending on the kind of the substituent R 3 of the fluorane compound represented by the formula (I) to be produced.

【0006】(1)R3が−COR4でR4が水素原子で
あるもの:式(IV)フルオランをオルトギ酸エチルとと
もに、触媒量の硫酸の存在下還流する。 (2)R3が−COR4でR4が炭素数1〜4個のアルキ
ル基であるもの:式(IV)フルオランを脂肪族酸無水物
と還流する。 (3)R3が−COR4でR4がフェニル基であるもの:
式(IV)フルオランをハロゲン化ベンゾイルと還流す
る。 (4)R3が−COOR5でR5が炭素数1〜4個のアル
キル基であるもの:式(IV)フルオランをハロゲン化炭
酸アルキルと還流する。 (5)R3が−CH26でR6がフェニル基であるもの:
式(IV)フルオランとハロゲン化ベンジルを、極性溶媒
中塩基の存在下に130℃付近で反応する。 (6)R3が−CH2CH=CH2であるもの:式(IV)
フルオランとハロゲン化アリルを、極性溶媒中塩基の存
在下に130℃付近で反応する。 (7)R3が炭素数1〜4個のアルキル基であるもの:
式(IV)フルオランをジアルキル硫酸のようなアルキル
化剤と反応させる。
(1) R 3 is —COR 4 and R 4 is a hydrogen atom: Fluorane of the formula (IV) is refluxed with ethyl orthoformate in the presence of a catalytic amount of sulfuric acid. (2) R 3 is —COR 4 and R 4 is an alkyl group having 1 to 4 carbon atoms: Fluorane of the formula (IV) is refluxed with an aliphatic acid anhydride. (3) R 3 is —COR 4 and R 4 is a phenyl group:
The formula (IV) fluorane is refluxed with a benzoyl halide. (4) R 3 is —COOR 5 and R 5 is an alkyl group having 1 to 4 carbon atoms: Formula (IV) fluorane is refluxed with an alkyl halide carbonate. (5) R 3 is —CH 2 R 6 and R 6 is a phenyl group:
The formula (IV) fluorane and benzyl halide are reacted in the presence of a base in a polar solvent at around 130 ° C. (6) R 3 is -CH 2 CH = CH 2: Formula (IV)
Fluorane and allyl halide are reacted in the presence of a base in a polar solvent at around 130 ° C. (7) R 3 is an alkyl group having 1 to 4 carbon atoms:
The formula (IV) fluorane is reacted with an alkylating agent such as a dialkyl sulfuric acid.

【0007】一般式(IV)で表されるフルオラン化合物
は、例えば特開平3−195775号公報に記載の公知
の方法により容易に製造できる。
The fluoran compound represented by the general formula (IV) can be easily produced by a known method described in, for example, JP-A-3-195775.

【実施例】以下に実施例を示すが、本発明はこの実施例
に限定されるものではない。
EXAMPLES Examples will be shown below, but the present invention is not limited to these examples.

【0008】(実施例1) 2−(N−アセチルアニリノ)−6−ジ−n−ブチルア
ミノ−3−メチルフルオラン(化合物)の合成 2−アニリノ−6−ジ−n−ブチルアミノ−3−メチル
フルオラン5.32g(10mmol)を無水酢酸50
ml中、139℃で5時間撹拌還流した。反応液を10
%苛性ソーダ水溶液200mlに排出し、分離した油状
物をトルエン200mlで抽出した。トルエン抽出液を
中性になるまで水洗後分液し、減圧下に溶媒を留去し
た。残留物にメタノール20mlを添加し、室温で15
時間撹拌した。析出した沈澱を濾取、乾燥し目的物5.
35g(収率93%)をやや茶色味を帯びた白色の粉末
(m.p.174〜175℃)として得た。下記の分析
結果より目的の化合物であることを確認した。 MS(m/z):574(M+) IR(KBr):1750cm-1(ラクトンのC=O) 1670cm-1(アセチルのC=O)1 H−NMR(270MHz、CDCl3):δ8.03-6.40(p
pm)(m;14H),3.27(t;4H),2.17(s;3H),1.93(s;3H),1.60-
1.33(m;8H),0.93(t;6H) 元素分析値: C H N 実測値 77.48% 6.70% 4.81% 理論値(C373824) 77.31% 6.68% 4.87% 95%酢酸中における特性吸収波長およびTLC(シリ
カゲル)上での発色色相を表1に示す。
(Example 1) Synthesis of 2- (N-acetylanilino) -6-di-n-butylamino-3-methylfluorane (compound) 2-anilino-6-di-n-butylamino- 5.32 g (10 mmol) of 3-methylfluorane was added to 50 ml of acetic anhydride.
The mixture was refluxed with stirring in ml at 139 ° C. for 5 hours. 10 reaction liquids
The mixture was discharged into 200 ml of an aqueous solution of caustic soda, and the separated oily substance was extracted with 200 ml of toluene. The toluene extract was washed with water until neutral and then separated, and the solvent was distilled off under reduced pressure. 20 ml of methanol was added to the residue and the mixture was stirred at room temperature for 15 minutes.
Stir for hours. The deposited precipitate is filtered and dried to obtain the desired product 5.
35 g (yield 93%) was obtained as a slightly brownish white powder (mp 174 to 175 ° C.). It was confirmed from the following analysis results that the target compound was obtained. MS (m / z): 574 (M +) IR (KBr): 1750cm -1 1670cm -1 (C = O lactone) (acetyl C = O) 1 H-NMR (270MHz, CDCl 3): δ8. 03-6.40 (p
pm) (m; 14H), 3.27 (t; 4H), 2.17 (s; 3H), 1.93 (s; 3H), 1.60-
1.33 (m; 8H), 0.93 (t; 6H) Elemental analysis value: C H N measured value 77.48% 6.70% 4.81% Theoretical value (C 37 H 38 N 2 O 4 ) 77.31% Table 1 shows characteristic absorption wavelengths in 6.68% 4.87% 95% acetic acid and the coloring hue on TLC (silica gel).

【0009】(実施例2) 6−ジ−n−ブチルアミノ−3−メチル−2−(N−プ
ロピオニルアニリノ)フルオラン(化合物)の合成 2−アニリノ−6−ジ−n−ブチルアミノ−3−メチル
フルオラン5.32g(10mmol)を無水プロピオ
ン酸50ml中、167℃で1時間撹拌還流した。実施
例1と同様の後処理を行い、目的物5.05g(収率8
6%)をやや茶色味を帯びた白色の粉末(m.p.17
5〜176℃)として得た。下記の分析結果より目的の
化合物であることを確認した。 MS(m/z):588(M+) IR(KBr):1750cm-1(ラクトンのC=O) 1670cm-1(プロピオニルのC=O)1 H−NMR(270MHz、CDCl3):δ8.03-6.37
(m;14H),3.30(t;4H),2.20(s;3H),1.63(s;3H),1.60-1.37
(m;8H),0.90(t;6H) 元素分析値: C H N 実測値 77.64% 7.05% 4.73% 理論値(C384024)77.51% 6.86% 4.76% 95%酢酸中における特性吸収波長およびTLC(シリ
カゲル)上での発色色相を表1に示す。
(Example 2) Synthesis of 6-di-n-butylamino-3-methyl-2- (N-propionylanilino) fluorane (compound) 2-anilino-6-di-n-butylamino-3 -Methylfluorane (5.32 g, 10 mmol) was stirred and refluxed for 1 hour at 167 ° C in 50 ml of propionic anhydride. The same post-treatment as in Example 1 was carried out to obtain 5.05 g of the desired product (yield 8
6%) as a slightly brownish white powder (mp. 17)
5 to 176 ° C.). It was confirmed from the following analysis results that the target compound was obtained. MS (m / z): 588 (M +) IR (KBr): 1750cm -1 1670cm -1 (C = O lactone) (propionyl C = O) 1 H-NMR (270MHz, CDCl 3): δ8. 03-6.37
(m; 14H), 3.30 (t; 4H), 2.20 (s; 3H), 1.63 (s; 3H), 1.60-1.37
(m; 8H), 0.90 (t; 6H) Elemental analysis value: C H N measured value 77.64% 7.05% 4.73% theoretical value (C 38 H 40 N 2 O 4 ) 77.51% 6 Table 1 shows characteristic absorption wavelengths in 0.86% 4.76% 95% acetic acid and coloring hues on TLC (silica gel).

【0010】(実施例3) 2−(N−ベンゾイルアニリノ)−6−ジ−n−ブチル
アミノ−3−メチルフルオラン(化合物)の合成 2−アニリノ−6−ジ−n−ブチルアミノ−3−メチル
フルオラン5.32g(10mmol)をトルエン20
mlに80℃で撹拌溶解後、塩化ベンゾイル4.22g
(30mmol)を5分間で滴下し、110℃で1.5
時間撹拌還流した。反応液を10%苛性ソーダ水溶液2
00mlに排出し、分離した油状物をトルエン200m
lで抽出した。トルエン抽出液を中性になるまで水洗後
分液し、減圧下に溶媒を留去し、残留物をシリカゲルの
カラムクロマトグラフィーを用いて精製し、目的物4.
81g(収率76%)をやや茶色味を帯びた白色の粉末
(m.p.266〜267℃)として得た。下記の分析
結果より目的の化合物であることを確認した。 MS(m/z):637(M++1) IR(KBr):1760cm-1(ラクトンのC=O) 1660cm-1(ベンゾイルのC=O)1 H−NMR(270MHz、CDCl3):δ7.97-6.4
3(ppm)(m;19H),3.27(t;4H)2.20(s;3H),1.57-1.33(m;8
H),0.93:(t;6H) 元素分析値: C H N 実測値 79.68% 6.40% 4.45% 理論値(C424024) 79.21% 6.34% 4.40% 95%酢酸中における特性吸収波長およびTLC(シリ
カゲル)上での発色色相を表1に示す。
(Example 3) Synthesis of 2- (N-benzoylanilino) -6-di-n-butylamino-3-methylfluorane (compound) 2-anilino-6-di-n-butylamino- 5.32 g (10 mmol) of 3-methylfluorane was added to toluene 20.
After stirring and dissolving in 80 ml at 80 ° C, 4.22 g of benzoyl chloride
(30 mmol) was added dropwise over 5 minutes, and at 110 ° C, 1.5
The mixture was stirred and refluxed for hours. The reaction solution is a 10% aqueous sodium hydroxide solution 2
It was discharged to 00 ml, and the separated oily substance was added to 200 m of toluene.
It was extracted with 1. The toluene extract is washed with water until it becomes neutral, then separated, the solvent is distilled off under reduced pressure, and the residue is purified by silica gel column chromatography to obtain the desired product 4.
81 g (yield 76%) was obtained as a slightly brownish white powder (mp 266 to 267 ° C.). It was confirmed from the following analysis results that the target compound was obtained. MS (m / z): 637 (M + +1) IR (KBr): 1760 cm -1 (C = O of lactone) 1660 cm -1 (C = O of benzoyl) 1 H-NMR (270 MHz, CDCl 3 ): δ7 .97-6.4
3 (ppm) (m; 19H), 3.27 (t; 4H) 2.20 (s; 3H), 1.57-1.33 (m; 8
H), 0.93: (t; 6H) Elemental analysis: C H N Found 79.68% 6.40% 4.45% theory (C 42 H 40 N 2 O 4) 79.21% 6.34 Table 1 shows characteristic absorption wavelengths in% 4.40% 95% acetic acid and coloring hues on TLC (silica gel).

【0011】(実施例4) 2−(N−カルボブトキシアニリノ)−6−ジ−n−ブ
チルアミノ−3−メチルフルオラン(化合物)の合成 2−アニリノ−6−ジ−n−ブチルアミノ−3−メチル
フルオラン5.32g(10mmol)をクロロ炭酸ブ
チル13.7g(100mmol)とともに、95〜9
7℃で18時間撹拌還流した。実施例3と同様の後処理
を行い、目的物2.3g(収率36%)をやや茶色味を
帯びた白色の粉末(m.p.117〜118℃)として
得た。下記の分析結果より目的の化合物であることを確
認した。 MS(m/z):633(M++1) IR(KBr):1760cm-1(ラクトンのC=O) 1710cm-1(カルボブトキシのC=O)1 H−NMR(270MHz、CDCl3):δ8.03-6.3
7(ppm)(m;14H),4.03(m;2H)3.30(t;4H),2.17(s;3H),1.60
-1.37(m;8H),0.87:(t;6H),0.83(m;3H) 元素分析値: C H N 実測値 76.13% 7.04% 4.49% 理論値(C404425) 75.91% 7.02% 4.43% 95%酢酸中における特性吸収波長はTLC(シリカゲ
ル)上での発色色相を表1に示す。
(Example 4) Synthesis of 2- (N-carbobutoxyanilino) -6-di-n-butylamino-3-methylfluorane (compound) 2-anilino-6-di-n-butylamino 95-3-9 with 5.32 g (10 mmol) of -3-methylfluorane together with 13.7 g (100 mmol) of butyl chlorocarbonate.
The mixture was stirred and refluxed at 7 ° C for 18 hours. The same post-treatment as in Example 3 was performed to obtain 2.3 g (yield 36%) of the target product as a slightly brownish white powder (mp 117 to 118 ° C.). It was confirmed from the following analysis results that the target compound was obtained. MS (m / z): 633 (M + +1) IR (KBr): 1760cm -1 (C = O of Karubobutokishi) 1710cm -1 (C = O lactone) 1 H-NMR (270MHz, CDCl 3): δ8.03-6.3
7 (ppm) (m; 14H), 4.03 (m; 2H) 3.30 (t; 4H), 2.17 (s; 3H), 1.60
-1.37 (m; 8H), 0.87: (t; 6H), 0.83 (m; 3H) Elemental analysis value: C H N measured value 76.13% 7.04% 4.49% theoretical value (C 40 H 44 N 2 O 5 ) 75.91% 7.02% 4.43% 95% The characteristic absorption wavelength in acetic acid is shown in Table 1 as the coloring hue on TLC (silica gel).

【0012】(実施例5) 6−ジ−n−ブチルアミノ−2−(N−ホルミルアニリ
ノ)−3−メチルフルオラン(化合物)の合成 2−アニリノ−6−ジ−n−ブチルアミノ−3−メチル
フルオラン5.32g(10mmol)をオルトギ酸エ
チル50ml及び濃硫酸2滴とともに140〜143℃
で3時間撹拌還流した。実施例3と同様の後処理を行
い、目的物3.5g(収率62%)をやや茶色味を帯び
た白色の粉末(m.p.191〜192℃)として得
た。下記の分析結果より目的の化合物であることを確認
した。 MS(m/z):561(M++1) IR(KBr):1760cm-1(ラクトンのC=O) 1690cm-1(ホルミルのC=O)1 H−NMR(270MHz、CDCl3):δ8.70(pp
m)(s;1H),8.27(s;1H),8.00-6.40(m;14H),3.27(t;4H),2.
10(s;3H),1.57-1.33(m;8H),0.97:(t;6H) 元素分析値: C H N 実測値 77.09% 6.45% 4.89% 理論値(C363624) 77.11% 6.48% 5.00% 95%酢酸中における特性吸収波長およびTLC(シリ
カゲル)上での発色色相を表1に示す。
(Example 5) Synthesis of 6-di-n-butylamino-2- (N-formylanilino) -3-methylfluorane (compound) 2-anilino-6-di-n-butylamino-3- Methylfluorane 5.32 g (10 mmol) was added together with 50 ml of ethyl orthoformate and 2 drops of concentrated sulfuric acid at 140 to 143 ° C.
It was stirred and refluxed for 3 hours. The same post-treatment as in Example 3 was carried out to obtain 3.5 g of the desired product (yield 62%) as a slightly brownish white powder (mp 191 to 192 ° C). It was confirmed from the following analysis results that the target compound was obtained. MS (m / z): 561 (M + +1) IR (KBr): 1760 cm -1 (C = O of lactone) 1690 cm -1 (C = O of formyl) 1 H-NMR (270 MHz, CDCl 3 ): δ8 .70 (pp
m) (s; 1H), 8.27 (s; 1H), 8.00-6.40 (m; 14H), 3.27 (t; 4H), 2.
10 (s; 3H), 1.57-1.33 (m; 8H), 0.97: (t; 6H) Elemental analysis value: C H N measured value 77.09% 6.45% 4.89% theoretical value (C 36 H 36 N 2 O 4 ) 77.11% 6.48% 5.00% 95% The characteristic absorption wavelength in acetic acid and the coloring hue on TLC (silica gel) are shown in Table 1.

【0013】(実施例6) 2−(N−ベンジルアニリノ)−6−ジ−n−ブチルア
ミノ−3−メチルフルオラン(化合物)の合成 水酸化カリウム1g(15mmol)とDMSO50m
lを95℃加熱撹拌し、この中に2−アニリノ−6−ジ
−n−ブチルアミノ−3−メチルフルオラン5.32g
(10mmol)を添加、30分間撹拌して溶解した。
次いでこれに塩化ベンジル3.8g(30mmol)を
10分間で滴下後130℃で15時間撹拌した。実施例
3と同様の後処理を行い、目的物2.1g(収率34
%)をやや茶色味を帯びた白色の粉末(m.p.188
〜190℃)として得た。下記の分析結果より目的の化
合物であることを確認した。 MS(m/z):623(M++1) , IR(KBr):1760cm-1(ラクトンのC=O)1 H−NMR(270MHz、CDCl3):δ7.90-6.2
6(ppm)(m;19H),4.63(d;2H),3.27(t;4H),2.30(s;3H),1.5
7-1.30,(m;8H)0.93(t;6H) 元素分析値: C H N 実測値 80.90% 6.80% 4.45% 理論値(C424223) 80.98% 6.81% 4.50% 95%酢酸中における特性吸収波長およびTLC(シリ
カゲル)上での発色色相を表1に示す。
(Example 6) Synthesis of 2- (N-benzylanilino) -6-di-n-butylamino-3-methylfluorane (compound) 1 g (15 mmol) of potassium hydroxide and 50 m of DMSO
1 was heated and stirred at 95 ° C., and 5.32 g of 2-anilino-6-di-n-butylamino-3-methylfluorane was added thereto.
(10 mmol) was added and dissolved by stirring for 30 minutes.
Next, 3.8 g (30 mmol) of benzyl chloride was added dropwise over 10 minutes, and the mixture was stirred at 130 ° C. for 15 hours. The same post-treatment as in Example 3 was carried out to obtain 2.1 g of the desired product (yield 34
%) As a slightly brownish white powder (mp 188)
˜190 ° C.). It was confirmed from the following analysis results that the target compound was obtained. MS (m / z): 623 (M + +1), IR (KBr): 1760 cm -1 (C = O of lactone) 1 H-NMR (270 MHz, CDCl 3 ): δ 7.90-6.2.
6 (ppm) (m; 19H), 4.63 (d; 2H), 3.27 (t; 4H), 2.30 (s; 3H), 1.5
7-1.30, (m; 8H) 0.93 (t; 6H) Elemental analysis: C H N Found 80.90% 6.80% 4.45% theory (C 42 H 42 N 2 O 3) 80. Table 1 shows characteristic absorption wavelengths in 98% 6.81% 4.50% 95% acetic acid and the coloring hue on TLC (silica gel).

【0014】(実施例7) 2−(N−アリルアニリノ)−6−ジ−n−ブチルアミ
ノ−3−メチルフルオラン(化合物)の合成 水酸化カリウム1g(15mmol)とDMF50mlを
90〜100℃で加熱撹拌し、この中に2−アニリノ−
6−ジ−n−ブチルアミノ−3−メチルフルオラン5.
32g(10mmol)を添加、30分間撹拌して溶解
した。次いでこれに臭化アリル6.05g(50mmo
l)を10分間で滴下後129〜132℃で15時間撹
拌した。実施例3と同様の後処理を行い、目的物2.3
g(収率40%)をやや茶色味を帯びた白色の粉末(m.
p.134〜135℃)として得た。下記の分析結果よ
り目的の化合物であることを確認した。 MS(m/z):573(M++1) IR(KBr):1750cm-1(ラクトンのC=O)1 H−NMR(270MHz、CDCl3):δ7.97-6.4
0(ppm)(m;14H),5.80(m;1H),5.23(m;2H),4.00(m;2H),3.3
0(t;4H),2.13(s;3H),1.60-1.33(m;8H),0.97(t;6H) 元素分析値: C H N 実測値 79.93% 6.98% 4.89% 理論値(C384023) 79.68% 7.05% 4.89% 95%酢酸中における特性吸収波長およびTLC(シリ
カゲル)上での発色色相を表1に示す。
(Example 7) Synthesis of 2- (N-allylanilino) -6-di-n-butylamino-3-methylfluorane (compound) 1 g (15 mmol) of potassium hydroxide and 50 ml of DMF at 90-100 ° C. Heat and stir, and then add 2-anilino-
6-di-n-butylamino-3-methylfluorane 5.
32 g (10 mmol) was added and dissolved by stirring for 30 minutes. Then to this was added 6.05 g of allyl bromide (50 mmo
l) was added dropwise over 10 minutes, and the mixture was stirred at 129 to 132 ° C. for 15 hours. The same post-treatment as in Example 3 was carried out to obtain the target compound 2.3.
g (yield 40%) as a slightly brownish white powder (m.
p.134-135 ° C). It was confirmed from the following analysis results that the target compound was obtained. MS (m / z): 573 (M + +1) IR (KBr): 1750 cm -1 (C = O of lactone) 1 H-NMR (270 MHz, CDCl 3 ): δ7.97-6.4.
0 (ppm) (m; 14H), 5.80 (m; 1H), 5.23 (m; 2H), 4.00 (m; 2H), 3.3
0 (t; 4H), 2.13 (s; 3H), 1.60-1.33 (m; 8H), 0.97 (t; 6H) Elemental analysis value: C H N measured value 79.93% 6.98% 4.89% Theoretical value (C 38 H 40 N 2 O 3 ) 79.68% 7.05% 4.89% 95% The characteristic absorption wavelength in acetic acid and the coloring hue on TLC (silica gel) are shown in Table 1.

【0015】(実施例8) 6−ジ−n−ブチルアミノ−2−(N−メチルアニリ
ノ)−3−メチルフルオラン(化合物)の合成 2−アニリノ−6−ジ−n−ブチルアミノ−3−メチル
フルオラン5.32g(10mmol)をジメチル硫酸
6.5g(158mmol)とを、130〜132℃で
1.5時間撹拌した。実施例3と同様の後処理を行い、
目的物3.7g(収率68%)を帯桃白色の粉末(m.
p.196〜197℃)として得た。下記の分析結果よ
り目的の化合物であることを確認した。 MS(m/z):547(M++1) IR(KBr):1760cm-1(ラクトンのC=O)1 H−NMR(270MHz、CDCl3):δ7.97-6.4
0(ppm)(m;14H),3.30(t;4H),3.13(s;3H),2.10(s;3H),1.6
0-1.37(m;8H),0.97(t;6H) 元素分析値: C H N 実測値 79.03% 7.01% 5.08% 理論値(C363823) 79.08% 7.02% 5.12% 95%酢酸中における特性吸収波長およびTLC(シリ
カゲル)上での発色色相を表1に示す。
(Example 8) Synthesis of 6-di-n-butylamino-2- (N-methylanilino) -3-methylfluorane (compound) 2-anilino-6-di-n-butylamino-3- Methylfluorane (5.32 g, 10 mmol) and dimethyl sulfate (6.5 g, 158 mmol) were stirred at 130 to 132 ° C. for 1.5 hours. After the same post-treatment as in Example 3,
3.7 g (yield 68%) of the desired product was obtained as a pinkish white powder (m.p.
p. 196-197 ° C). It was confirmed from the following analysis results that the target compound was obtained. MS (m / z): 547 (M + +1) IR (KBr): 1760 cm -1 (C = O of lactone) 1 H-NMR (270 MHz, CDCl 3 ): δ7.97-6.4.
0 (ppm) (m; 14H), 3.30 (t; 4H), 3.13 (s; 3H), 2.10 (s; 3H), 1.6
0-1.37 (m; 8H), 0.97 (t; 6H) Elemental analysis value: C H N measured value 79.03% 7.01% 5.08% theoretical value (C 36 H 38 N 2 O 3 ) 79. Table 1 shows the characteristic absorption wavelength in 08% 7.02% 5.12% 95% acetic acid and the coloring hue on TLC (silica gel).

【0016】95%酢酸中における特性吸収波長および
TLC上での発色色相
Characteristic absorption wavelength and color hue on TLC in 95% acetic acid

【表1】 [Table 1]

【0017】[0017]

【発明の効果】本発明の前記一般式(I)で表される新
規なフルオラン化合物は、感圧記録材料、感熱記録材料
等の発色性記録材料や熱変色材料に用いられる発色剤と
して有用な物質である。
INDUSTRIAL APPLICABILITY The novel fluoran compound represented by the above general formula (I) of the present invention is useful as a color former used in color-forming recording materials such as pressure-sensitive recording materials and heat-sensitive recording materials and thermochromic materials. It is a substance.

─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───

【手続補正書】[Procedure amendment]

【提出日】平成3年12月9日[Submission date] December 9, 1991

【手続補正1】[Procedure Amendment 1]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0010[Correction target item name] 0010

【補正方法】変更[Correction method] Change

【補正内容】[Correction content]

【0010】(実施例3) 2−(N−ベンゾイルアニリノ)−6−ジ−n−ブチル
アミノ−3−メチルフルオラン(化合物)の合成 2−アニリノ−6−ジ−n−ブチルアミノ−3−メチル
フルオラン5.32g(10mmol)をトルエン20
mlに80℃で撹拌溶解後、塩化ベンゾイル4.22g
(30mmol)を5分間で滴下し、110℃で1.5
時間撹拌還流した。反応液を10%苛性ソーダ水溶液2
00mlに排出し、分離した油状物をトルエン200m
lで抽出した。トルエン抽出液を中性になるまで水洗後
分液し、減圧下に溶媒を留去し、残留物をシリカゲルの
カラムクロマトグラフィーを用いて精製し、目的物4.
81g(収率76%)をやや茶色味を帯びた白色の粉末
(m.p.266〜267℃)として得た。下記の分析
結果より目的の化合物であることを確認した。 MS(m/z):637(M++1) IR(KBr):1760cm-1(ラクトンのC=O) 1660cm-1(ベンゾイルのC=O)1 H−NMR(270MHz、CDCl3):δ7.97
−6.43(ppm)(m;19H),3.27(t;
4H)2.20(s;3H),1.57−1 .33
(m;8H),0.93(t;6H) 元素分析値: C H N 実測値 79.68% 6.40% 4.45% 理論値(C424024) 79.21% 6.34% 4.40% 95%酢酸中における特性吸収波長およびTLC(シリ
カゲル)上での発色色相を表1に示す。
(Example 3) Synthesis of 2- (N-benzoylanilino) -6-di-n-butylamino-3-methylfluorane (compound) 2-anilino-6-di-n-butylamino- 5.32 g (10 mmol) of 3-methylfluorane was added to toluene 20.
After stirring and dissolving in 80 ml at 80 ° C, 4.22 g of benzoyl chloride
(30 mmol) was added dropwise over 5 minutes, and at 110 ° C, 1.5
The mixture was stirred and refluxed for hours. The reaction solution is a 10% aqueous sodium hydroxide solution 2
It was discharged to 00 ml, and the separated oily substance was added to 200 m of toluene.
It was extracted with 1. The toluene extract is washed with water until it becomes neutral, then separated, the solvent is distilled off under reduced pressure, and the residue is purified by silica gel column chromatography to obtain the desired product 4.
81 g (yield 76%) was obtained as a slightly brownish white powder (mp 266 to 267 ° C.). It was confirmed from the following analysis results that the target compound was obtained. MS (m / z): 637 (M + +1) IR (KBr): 1760 cm -1 (C = O of lactone) 1660 cm -1 (C = O of benzoyl) 1 H-NMR (270 MHz, CDCl 3 ): δ7 .97
-6.43 (ppm) (m; 19H), 3.27 (t;
4H) , 2.20 (s; 3H), 1.57-1. 33
(M; 8H), 0.9 3 (t; 6H) Elemental analysis: C H N Found 79.68% 6.40% 4.45% theory (C 42 H 40 N 2 O 4) 79. Table 1 shows the characteristic absorption wavelengths in 21% 6.34% 4.40% 95% acetic acid and the coloring hue on TLC (silica gel).

【手続補正2】[Procedure Amendment 2]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0011[Correction target item name] 0011

【補正方法】変更[Correction method] Change

【補正内容】[Correction content]

【0011】(実施例4) 2−(N−カルボブトキシアニリノ)−6−ジ−n−ブ
チルアミノ−3−メチルフルオラン(化合物)の合成 2−アニリノ−6−ジ−n−ブチルアミノ−3−メチル
フルオラン5.32g(10mmol)をクロロ炭酸ブ
チル13.7g(100mmol)とともに、95〜9
7℃で18時間撹拌還流した。実施例3と同様の後処理
を行い、目的物2.3g(収率36%)をやや茶色味を
帯びた白色の粉末(m.p.117〜118℃)として
得た。下記の分析結果より目的の化合物であることを確
認した。 MS(m/z):633(M++1) IR(KBr):1760cm-1(ラクトンのC=O) 1710cm-1(カルボブトキシのC=O)1 H−NMR(270MHz、CDCl3):δ8.03
−6.37(ppm)(m;14H),4.03(m;
2H)3.30(t;4H),2.17(s;3
H),1.60−1.37(m;8H),0.8
t;6H),0.83(m;3H) 元素分析値: C H N 実測値 76.13% 7.04% 4.49% 理論値(C404425) 75.91% 7.02% 4.43% 95%酢酸中における特性吸収波長およびTLC(シリ
カゲル)上での発色色相を表1に示す。
(Example 4) Synthesis of 2- (N-carbobutoxyanilino) -6-di-n-butylamino-3-methylfluorane (compound) 2-anilino-6-di-n-butylamino 95-3-9 with 5.32 g (10 mmol) of -3-methylfluorane together with 13.7 g (100 mmol) of butyl chlorocarbonate.
The mixture was stirred and refluxed at 7 ° C for 18 hours. The same post-treatment as in Example 3 was performed to obtain 2.3 g (yield 36%) of the target product as a slightly brownish white powder (mp 117 to 118 ° C.). It was confirmed from the following analysis results that the target compound was obtained. MS (m / z): 633 (M + +1) IR (KBr): 1760cm -1 (C = O of Karubobutokishi) 1710cm -1 (C = O lactone) 1 H-NMR (270MHz, CDCl 3): δ 8.03
-6.37 (ppm) (m; 14H), 4.03 (m;
2H) , 3.30 (t; 4H), 2.17 (s; 3
H), 1.60-1.37 (m; 8H ), 0.8 7
(T; 6H), 0.83 ( m; 3H) Elemental analysis: C H N Found 76.13% 7.04% 4.49% theory (C 40 H 44 N 2 O 5) 75.91 Table 1 shows characteristic absorption wavelengths in 7.02% 4.43% 95% acetic acid and coloring hues on TLC (silica gel).

【手続補正3】[Procedure 3]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0012[Correction target item name] 0012

【補正方法】変更[Correction method] Change

【補正内容】[Correction content]

【0012】(実施例5) 6−ジ−n−ブチルアミノ−2−(N−ホルミルアニリ
ノ)−3−メチルフルオラン(化合物)の合成 2−アニリノ−6−ジ−n−ブチルアミノ−3−メチル
フルオラン5.32g(10mmol)をオルトギ酸エ
チル50ml及び濃硫酸2滴とともに140〜143℃
で3時間撹拌還流した。実施例3と同様の後処理を行
い、目的物3.5g(収率62%)をやや茶色味を帯び
た白色の粉末(m.p.191〜192℃)として得
た。下記の分析結果より目的の化合物であることを確認
した。 MS(m/z):561(M++1) IR(KBr):1760cm-1(ラクトンのC=O) 1690cm-1(ホルミルのC=O)1 H−NMR(270MHz、CDCl3):δ8.70
(ppm)(s;1H),8.27(s;1H),8.
00−6.40(m;14H),3.27(t;4
H),2.10(s;3H),1.57−1.33
(m;8H),0.97(t;6H) 元素分析値: C H N 実測値 77.09% 6.45% 4.89% 理論値(C363624) 77.11% 6.48% 5.00% 95%酢酸中における特性吸収波長およびTLC(シリ
カゲル)上での発色色相を表1に示す。
(Example 5) Synthesis of 6-di-n-butylamino-2- (N-formylanilino) -3-methylfluorane (compound) 2-anilino-6-di-n-butylamino-3- Methylfluorane 5.32 g (10 mmol) was added together with 50 ml of ethyl orthoformate and 2 drops of concentrated sulfuric acid at 140 to 143 ° C.
It was stirred and refluxed for 3 hours. The same post-treatment as in Example 3 was carried out to obtain 3.5 g of the desired product (yield 62%) as a slightly brownish white powder (mp 191 to 192 ° C). It was confirmed from the following analysis results that the target compound was obtained. MS (m / z): 561 (M + +1) IR (KBr): 1760 cm -1 (C = O of lactone) 1690 cm -1 (C = O of formyl) 1 H-NMR (270 MHz, CDCl 3 ): δ8 .70
(Ppm) (s; 1H), 8.27 (s; 1H), 8.
00-6.40 (m; 14H), 3.27 (t; 4
H), 2.10 (s; 3H), 1.57-1.33
(M; 8H), 0.9 7 (t; 6H) Elemental analysis: C H N Found 77.09% 6.45% 4.89% theory (C 36 H 36 N 2 O 4) 77. Table 1 shows characteristic absorption wavelengths in 11% 6.48% 5.00% 95% acetic acid and the coloring hue on TLC (silica gel).

【手続補正4】[Procedure amendment 4]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0013[Correction target item name] 0013

【補正方法】変更[Correction method] Change

【補正内容】[Correction content]

【0013】(実施例6) 2−(N−ベンジルアニリノ)−6−ジ−n−ブチルア
ミノ−3−メチルフルオラン(化合物)の合成 水酸化カリウム1g(15mmol)とDMSO50m
lを95℃加熱撹拌し、この中に2−アニリノ−6−
ジ−n−ブチルアミノ−3−メチルフルオラン5.32
g(10mmol)を添加、30分間撹拌して溶解し
た。次いでこれに塩化ベンジル3.8g(30mmo
l)を10分間で滴下後130℃で15時間撹拌した。
実施例3と同様の後処理を行い、目的物2.1g(収率
34%)をやや茶色味を帯びた白色の粉末(m.p.1
88〜190℃)として得た。下記の分析結果より目的
の化合物であることを確認した。 MS(m/z):623(M++1) IR(KBr):1760cm-1(ラクトンのC=O)1 H−NMR(270MHz、CDCl3):δ7.90
−6.26(ppm)(m;19H),4.63(d;
2H),3.27(t;4H),2.30(s;3
H),1.57−1.30(m;8H)0.93
(t;6H) 元素分析値: C H N 実測値 80.90% 6.80% 4.45% 理論値(C424223) 80.98% 6.81% 4.50% 95%酢酸中における特性吸収波長およびTLC(シリ
カゲル)上での発色色相を表1に示す。
(Example 6) Synthesis of 2- (N-benzylanilino) -6-di-n-butylamino-3-methylfluorane (compound) 1 g (15 mmol) of potassium hydroxide and 50 m of DMSO
1 was heated and stirred at 95 ° C. , and 2-anilino-6-
Di-n-butylamino-3-methylfluorane 5.32
g (10 mmol) was added and dissolved by stirring for 30 minutes. Next, 3.8 g of benzyl chloride (30 mmo
l) was added dropwise over 10 minutes and then stirred at 130 ° C. for 15 hours.
The same post-treatment as in Example 3 was carried out, and 2.1 g (yield 34%) of the desired product was obtained as a slightly brownish white powder (mp. 1).
88-190 ° C). It was confirmed from the following analysis results that the target compound was obtained. MS (m / z): 623 (M + +1) IR (KBr): 1760 cm -1 (C = O of lactone) 1 H-NMR (270 MHz, CDCl 3 ): δ 7.90
-6.26 (ppm) (m; 19H), 4.63 (d;
2H), 3.27 (t; 4H), 2.30 (s; 3
H), 1.57-1.30 (m; 8H) , 0.93
(T; 6H) Elemental analysis: C H N Found 80.90% 6.80% 4.45% theory (C 42 H 42 N 2 O 3) 80.98% 6.81% 4.50% Table 1 shows characteristic absorption wavelengths in 95% acetic acid and coloring hues on TLC (silica gel).

フロントページの続き (72)発明者 西口 郁三 大阪府枚方市楠葉丘2丁目7−2 (72)発明者 石野 義夫 京都府京都市上京区塔之段藪之下町428番 地 (72)発明者 平嶋 恒亮 大阪府堺市新金岡町1丁7番6−104Front page continuation (72) Inventor Ikuzo Nishiguchi 2-7-2 Kusuhaoka, Hirakata City, Osaka Prefecture (72) Inventor Yoshio Ishino, 428, Tonodan Yabinoshita Town, Kamigyo-ku, Kyoto City, Kyoto Prefecture (72) Tsune Hirashima, Inventor Ryo 1-7-6-104 Shin-Kanaoka-cho, Sakai City, Osaka Prefecture

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】 一般式(I)で表されるフルオラン化合
物。 【化1】 (式中、R1およびR2は炭素数3〜4個のアルキル基を
示し、R3は−COR4、−COOR5、−CH26、−
CH2CH=CH2又は炭素数1〜4個のアルキル基を示
し、R4は水素原子、炭素数1〜4個のアルキル基又は
置換基を有しても良いフェニル基を示し、R5は炭素数
1〜4個のアルキル基を示し、R6は置換基を有しても
良いフェニル基を示す。)
1. A fluoran compound represented by the general formula (I). [Chemical 1] (In the formula, R 1 and R 2 represent an alkyl group having 3 to 4 carbon atoms, and R 3 represents —COR 4 , —COOR 5 , —CH 2 R 6 , and —
CH 2 CH═CH 2 or an alkyl group having 1 to 4 carbon atoms, R 4 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group which may have a substituent, R 5 Represents an alkyl group having 1 to 4 carbon atoms, and R 6 represents a phenyl group which may have a substituent. )
JP3246160A 1991-09-25 1991-09-25 Fluoran compound Pending JPH072865A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP3246160A JPH072865A (en) 1991-09-25 1991-09-25 Fluoran compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP3246160A JPH072865A (en) 1991-09-25 1991-09-25 Fluoran compound

Publications (1)

Publication Number Publication Date
JPH072865A true JPH072865A (en) 1995-01-06

Family

ID=17144397

Family Applications (1)

Application Number Title Priority Date Filing Date
JP3246160A Pending JPH072865A (en) 1991-09-25 1991-09-25 Fluoran compound

Country Status (1)

Country Link
JP (1) JPH072865A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6140513A (en) * 1996-09-27 2000-10-31 Mitsubishi Paper Mills Limited Color forming dye precursor, composition containing the same and color forming heat-sensitive recording material
CN102775810A (en) * 2012-07-23 2012-11-14 烟台大学 Fluorane color former and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6140513A (en) * 1996-09-27 2000-10-31 Mitsubishi Paper Mills Limited Color forming dye precursor, composition containing the same and color forming heat-sensitive recording material
DE19742593B4 (en) * 1996-09-27 2004-06-17 Mitsubishi Paper Mills Limited New color-forming dye precursor, composition containing the same and color-forming heat-sensitive recording material
CN102775810A (en) * 2012-07-23 2012-11-14 烟台大学 Fluorane color former and preparation method thereof

Similar Documents

Publication Publication Date Title
US4775754A (en) Preparation of leuco dyes
JPH072865A (en) Fluoran compound
JP2806714B2 (en) Fluoran compound and method for producing the same
JPH0725881A (en) Fluoran compound
SU1313856A1 (en) Method for producing derivatives of cis- or trans-diaminodibenzoyl-dibenzo-18-crown-6
US4431840A (en) Process for preparing 2-benzoylbenzoic acids
JPH04323267A (en) Production of trimethine dye
JPS6051157A (en) 4-alkoxy-2-methylbenzylidene derivative
JPS5865755A (en) 3-(substituted amino)-9-(2&#34;-phenylanilino)-benzo(d)fluoran
JPH041160A (en) 3-aminophenol derivative and production thereof
JPS6116966A (en) Phthalide, its production, and heat-sensitive recording paper containing the same as an electrodonative color developer
JPS62273264A (en) Production of fluoran compound
JPH05163275A (en) New fluoran compound
JP2815970B2 (en) 3-Aminophenol derivative and method for producing the same
JPS6363648A (en) Diphenylethylene derivative and production thereof
JP2997724B2 (en) Method for producing phthalide compound
Lácová Reaction of 2-benzothiazolylthioethanoic acid with phthalic anhydride under conditions of Gabriel modification of Perkin synthesis
JPS59142254A (en) Novel fluoran derivative and thermal recording material using the same
JPH06108044A (en) Phthalide compound
HU201728B (en) Process for producing 3-(2-halogenethylamino)-3-pentenedicarboxylic acid-dialkyl esters
JPH03240761A (en) Benzoic acid derivative and production thereof
JPS6283180A (en) Recording material
JPS6040165A (en) Production of fluoran compound
JPH0219856B2 (en)
JPS62121769A (en) Fluoran derivative, production thereof and recording material containing the same