CN102775810A - Fluorane color former and preparation method thereof - Google Patents
Fluorane color former and preparation method thereof Download PDFInfo
- Publication number
- CN102775810A CN102775810A CN2012102553202A CN201210255320A CN102775810A CN 102775810 A CN102775810 A CN 102775810A CN 2012102553202 A CN2012102553202 A CN 2012102553202A CN 201210255320 A CN201210255320 A CN 201210255320A CN 102775810 A CN102775810 A CN 102775810A
- Authority
- CN
- China
- Prior art keywords
- fluoran
- coupler
- sulfuric acid
- fluorane
- color former
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses fluorane color former and a preparation method thereof. The fluorane color former is shown in a formula (I). R1 is alkanes from C1 to C5 or H. R2 is alkanes from C1 to C5, H or aromatics. The preparation method of the fluorane color former includes using N-formyl-2-methyl-4-methoxydiphenylamine as material, performing condensation with benzophenone acid derivatives under the condition of sulfuric acid catalysis, and preparing in closed loop under the alkaline condition in the presence of organic solvent. The fluorane color former is low in material price, simple to prepare, high in product purity and easy to industrialize.
Description
Technical field
The present invention relates to a kind of Material of Fluoran coupler and preparation method thereof.
Background technology
Press the temperature-sensitive coupler as a kind of functional dye; Aspects such as facsimile transmission paper, pressure electrothermal sensitive recording paper have been widely used in; Its main chemical structure has phthalein ketone (comprising azepine phthalein ketone and triarylmethane compound), Material of Fluoran, fluorenes class, phenothiazines 、 phenoxazine class and cluck ton class etc.; Wherein the Material of Fluoran functional pigment is the main flow of temperature-sensitive coupler, has Stability Analysis of Structures, quality is highly sensitive and the good characteristics of quality picture storage stability, on the amino of fluorane, introduces different substituted radicals and can obtain color and the different fluorane of performance respectively; Chromatogram series can be from the yellow to the red-purple; Especially black kind form and aspect are pure, almost completely monopolized all black coupler kinds, and common Material of Fluoran black coupler is shown below.
ODB-1 is an industrial applications black coupler early, and the quality picture is dark, and storage stability is good.Compound structure is simple in addition, and low price can be applicable in various heat/pressure sensitive recording papers such as fax, label.ODB-2 uses the most widely electrothermal sensitive recording paper to use coupler at present in the world, and except that the performance with ODB-1, whiteness is high when being used for electrothermal sensitive recording paper, becomes chromatic sensitivity good, both can use separately, also can be used for speed-fax paper with S205.
Except showing black, coupler consumptions such as redness, green, yellow are also very big with coupler for electrothermal sensitive recording paper at present, and redness, green, yellow thermo sensitive color commonly used are shown below.
Wherein Red-DCF, Red-520 are the red coupler of Material of Fluoran, and this coupler developing sensitivity is lower, weathering resistance and compatibleness is relatively poor, production cost is higher.
Summary of the invention
The purpose of this invention is to provide a kind of developing sensitivity height, weathering resistance and the new preferably Material of Fluoran coupler of compatibleness.
Another object of the present invention provides the preparation method of this Material of Fluoran coupler.
The technical scheme that the present invention takes:
A kind of Material of Fluoran coupler, its general formula is:
Ⅰ
Wherein, R
1: C
1-C
5Alkane or H;
R
2: C
1-C
5Alkane, H or aromatic hydrocarbons.
R in the Material of Fluoran coupler of the present invention
1Preferably-C
2H
5,-C
4H
9Or-CH
3, R
2Preferably-C
5H
11,-C
2H
5,-C
4H
9,-C
6H
11Or-C
7H
7
A kind of method for preparing Material of Fluoran coupler of the present invention; It is to be raw material with N-formyl radical-2-methyl-4-methoxy diphenylamine; With diphenyl-keto-acid derivative condensation under the sulfuric acid catalysis condition, in the presence of organic solvent, closed loop is prepared under the alkaline condition again; The structure of said diphenyl-keto-acid derivative is shown in formula II, and its operational path is following:
Wherein said sulfuric acid is the vitriol oil or the oleum of mass concentration 93-105%.
Said alkali is sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood, sodium hydrogencarbonate, saleratus or ammoniacal liquor.
The temperature of said condensation reaction is 0-30 ℃.
Said organic solvent is toluene, m-xylene, p-Xylol, sym-trimethylbenzene, unsym-trimethyl benzene, chlorobenzene, orthodichlorobenzene or bromobenzene.
The detailed process of the inventive method is following:
Said sulfuric acid is dropped in the reaction flask, be cooled to 0-8 ℃, under the agitation condition, slowly add diphenyl-keto-acid derivative, slowly add N-formyl radical-2-methyl-4-methoxy diphenylamine then; 0-30 ℃ is reacted 20h down; The mol ratio of said diphenyl-keto-acid derivative and N-formyl radical-2-methyl-4-methoxy diphenylamine is 1:0.8-1.2; Reaction under the agitation condition, is slowly poured reaction solution in the frozen water after finishing, and separates out solid, filters, and washing gets filter cake.
Measure 100-200 mL organic solvent, 50-100 mL water, 20-80 mL 30% alkaline solution and join in the reaction flask, under the agitation condition, the above-mentioned filter cake of 80-120 g is joined in the reaction flask, be warming up to backflow; Insulation reaction 2h, separatory, hot wash organic phase; Activated carbon decolorizing, heat filtering, cooling; Crystallization filters, the dry product that gets.
The present invention has that cost of material is cheap, easy and simple to handle, product purity is high, be easy to industrialized characteristics.The red coupler of the novel Material of Fluoran of synthetic is compared with red coupler Red-DCF, Red-520 commonly used at present, has developing sensitivity height, good weatherability, both can use separately also can with the composite uses of black coupler such as ODB-1, ODB-2, S205.
Description of drawings
Fig. 1 is the mass spectrum of compound 3-(N-ethyl-N-isopentyl) amino-basic fluorane of 6-methyl-7-(formanilide);
Fig. 2 is the mass spectrum of compound 3-dibutylamino-basic fluorane of 6-methyl-7-(formanilide);
Fig. 3 is compound 3-(N-ethyl-N-isopentyl) amino-basic fluorane of 6-methyl-7-(formanilide)
1HNMR figure;
Fig. 4 is compound 3-dibutylamino-basic fluorane of 6-methyl-7-(formanilide)
1HNMR figure.
Embodiment
Synthesizing of 3-(N-ethyl-N-isopentyl) amino-basic fluorane of 6-methyl-7-(formanilide)
Take by weighing 108g 98% sulfuric acid and drop in the reaction flask, ice-water bath cooling (temperature control is at 5-8 ℃) under the agitation condition, slowly adds raw material 2-hydroxyl-4-(N-ethyl-N-isopentyl) amino-2-carboxyl-benzophenone 14.6g, and about 4h adds; Slowly add N-formyl radical-2-methyl-4-methoxy diphenylamine 9.4g, about 4h adds; 5 ℃ of insulation reaction 20h; Under the agitation condition, reaction solution is slowly poured in the 200g frozen water, separated out a large amount of solids, filter, washing gets pink filter cake 86 grams.
Measure 110ml toluene, 50ml water, 30ml 30% aqueous sodium hydroxide solution and join in the reaction flask, under the agitation condition, slowly above-mentioned filter cake is joined in the reaction flask, slowly be warming up to back flow reaction 2h; Separatory, 100ml hot wash organic phase, 0.5g activated carbon decolorizing, heat filtering; Cooling, crystallization filters; Dry white or off-white color solid 18g, yield 80%, its mass spectrum with
1HNMR is as shown in figures 1 and 3 respectively, HPLC:>=99.0%, and M.P. 164-166 ℃.
Embodiment 2
Synthesizing of 3-(N-ethyl-N-isopentyl) amino-basic fluorane of 6-methyl-7-(formanilide)
Take by weighing the oleum of 108g105% and drop in the reaction flask, ice-water bath cooling (temperature control is at 5-8 ℃) under the agitation condition, slowly adds raw material 2-hydroxyl-4-(N-ethyl-N-isopentyl) amino-2-carboxyl-benzophenone 14.6g, and about 4h adds; Slowly add N-formyl radical-2-methyl-4-methoxy diphenylamine 7.9g, about 4h adds; 10 ℃ of insulation reaction 20h; Under the agitation condition, reaction solution is slowly poured in the 200g frozen water, separated out a large amount of solids, filter, washing gets pink filter cake 92 grams.
Measure 110ml chlorobenzene, 60ml water, 30ml 30% aqueous sodium hydroxide solution and join in the reaction flask, under the agitation condition, slowly above-mentioned filter cake is joined in the reaction flask, slowly be warming up to back flow reaction 2h; Separatory, 100ml hot wash organic phase, 0.5g activated carbon decolorizing, heat filtering; Cooling, crystallization filters, dry white or off-white color solid 17.5g; Yield 78%, HPLC: >=99.0%, M.P.164-166 ℃.
Embodiment 3
Synthesizing of 3-dibutylamino-basic fluorane of 6-methyl-7-(formanilide)
Take by weighing 136g 98% sulfuric acid and drop in the reaction flask, ice-water bath cooling (temperature control is at 5-8 ℃) under the agitation condition, slowly adds raw material 2-hydroxyl-4-dibutylamino-2-carboxyl-benzophenone 23.4g, and about 4h adds; Slowly add N-formyl radical-2-methyl-4-methoxy diphenylamine 14.6g, about 4h adds; 0 ℃ of insulation reaction 20h; Under the agitation condition, reaction solution is slowly poured in the 400g frozen water, separated out a large amount of solids, filter, washing gets pink filter cake 118 grams.
Measure 180ml toluene, 75ml water, 52ml 30% aqueous sodium hydroxide solution and join in the reaction flask, under the agitation condition, slowly above-mentioned filter cake is joined in the reaction flask, slowly be warming up to back flow reaction 2h; Separatory, 150ml hot wash organic phase, 1g activated carbon decolorizing, heat filtering; Cooling, crystallization filters; Dry white or off-white color solid 30g, yield 85%, its mass spectrum with
1HNMR is respectively like Fig. 2 and shown in Figure 4, HPLC:>=99.0%, and M.P. 189-191 ℃.
Embodiment 4
Synthesizing of 3-dibutylamino-basic fluorane of 6-methyl-7-(formanilide)
Take by weighing 136g 93% sulfuric acid and drop in the reaction flask, ice-water bath cooling (temperature control is at 5-8 ℃) under the agitation condition, slowly adds raw material 2-hydroxyl-4-dibutylamino-2-carboxyl-benzophenone 23.4g, and about 4h adds; Slowly add N-formyl radical-2-methyl-4-methoxy diphenylamine 18.2g, about 4h adds; 20 ℃ of insulation reaction 20h; Under the agitation condition, reaction solution is slowly poured in the 400g frozen water, separated out a large amount of solids, filter, washing gets filter cake 115 grams.
Measure 180ml chlorobenzene, 80ml water, 50ml 30% aqueous sodium hydroxide solution and join in the reaction flask, under the agitation condition, slowly above-mentioned filter cake is joined in the reaction flask, slowly be warming up to back flow reaction 2h; Separatory, 150ml hot wash organic phase, 1g activated carbon decolorizing, heat filtering; Cooling, crystallization filters, dry white or off-white color solid 29g; Yield 82%, HPLC: >=99.0%, M.P.189-191 ℃.
Claims (7)
1. Material of Fluoran coupler is characterized in that its general formula is shown in formula I:
Wherein, R
1: C
1-C
5Alkane or H;
R
2: C
1-C
5Alkane, H or aromatic hydrocarbons.
2. Material of Fluoran coupler according to claim 1 is characterized in that: R
1For-C
2H
5,-C
4H
9Or-CH
3, R
2For-C
5H
11,-C
2H
5,-C
4H
9,-C
6H
11Or-C
7H
7
3. method for preparing claim 1 or 2 described Material of Fluoran couplers; It is characterized in that with N-formyl radical-2-methyl-4-methoxy diphenylamine be raw material; With diphenyl-keto-acid derivative condensation under the sulfuric acid catalysis condition, in the presence of organic solvent, closed loop is prepared under the alkaline condition again; The structure of said diphenyl-keto-acid derivative is shown in formula II, and its operational path is following:
4. method according to claim 3 is characterized in that said sulfuric acid is sulfuric acid or the oleum of mass concentration 93-105%.
5. method according to claim 4 is characterized in that said alkali is sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood, sodium hydrogencarbonate, saleratus or ammoniacal liquor.
6. method according to claim 5, the temperature that it is characterized in that said condensation reaction is 0-30 ℃.
7. method according to claim 6 is characterized in that said organic solvent is toluene, m-xylene, p-Xylol, sym-trimethylbenzene, unsym-trimethyl benzene, chlorobenzene, orthodichlorobenzene or bromobenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210255320.2A CN102775810B (en) | 2012-07-23 | 2012-07-23 | Fluorane color former and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210255320.2A CN102775810B (en) | 2012-07-23 | 2012-07-23 | Fluorane color former and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102775810A true CN102775810A (en) | 2012-11-14 |
| CN102775810B CN102775810B (en) | 2014-12-03 |
Family
ID=47120927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210255320.2A Active CN102775810B (en) | 2012-07-23 | 2012-07-23 | Fluorane color former and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102775810B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108191883A (en) * | 2017-11-21 | 2018-06-22 | 衢州学院 | A kind of preparation method of Fluorane color former |
| CN112014500A (en) * | 2020-08-24 | 2020-12-01 | 河北建新化工股份有限公司 | Method for measuring content of N-formanilino fluorane |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH072865A (en) * | 1991-09-25 | 1995-01-06 | Yamamoto Chem Inc | Fluoran compound |
| CN1496346A (en) * | 2000-03-02 | 2004-05-12 | 旭化成株式会社 | Novel colour former and recording material |
| EP1655638A1 (en) * | 2004-11-08 | 2006-05-10 | Kabushiki Kaisha Toshiba | Erasable image forming material |
| CN1854201A (en) * | 2005-04-19 | 2006-11-01 | 寿光富康制药有限公司 | Production of thermosensitive dye |
| US20090137389A1 (en) * | 2006-05-12 | 2009-05-28 | Zink Imaging, Inc. | Novel color-forming compounds and use thereof in imaging members and methods |
| CN101693717A (en) * | 2009-10-09 | 2010-04-14 | 寿光富康制药有限公司 | Preparation method of temperature-sensitive paper additives |
-
2012
- 2012-07-23 CN CN201210255320.2A patent/CN102775810B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH072865A (en) * | 1991-09-25 | 1995-01-06 | Yamamoto Chem Inc | Fluoran compound |
| CN1496346A (en) * | 2000-03-02 | 2004-05-12 | 旭化成株式会社 | Novel colour former and recording material |
| EP1655638A1 (en) * | 2004-11-08 | 2006-05-10 | Kabushiki Kaisha Toshiba | Erasable image forming material |
| CN1854201A (en) * | 2005-04-19 | 2006-11-01 | 寿光富康制药有限公司 | Production of thermosensitive dye |
| US20090137389A1 (en) * | 2006-05-12 | 2009-05-28 | Zink Imaging, Inc. | Novel color-forming compounds and use thereof in imaging members and methods |
| CN101693717A (en) * | 2009-10-09 | 2010-04-14 | 寿光富康制药有限公司 | Preparation method of temperature-sensitive paper additives |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108191883A (en) * | 2017-11-21 | 2018-06-22 | 衢州学院 | A kind of preparation method of Fluorane color former |
| CN108191883B (en) * | 2017-11-21 | 2020-06-23 | 衢州学院 | Preparation method of fluorane color coupler |
| CN112014500A (en) * | 2020-08-24 | 2020-12-01 | 河北建新化工股份有限公司 | Method for measuring content of N-formanilino fluorane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102775810B (en) | 2014-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102329277B (en) | Method for preparing Parecoxib | |
| CN104710815B (en) | Novel rhodafluor fluorescent dye with characteristics of large stokes shift and near-infrared fluorescence emitting, and synthesis method thereof | |
| CN106675080B (en) | A kind of synthetic method of solvent green 3 | |
| JP5813561B2 (en) | Color material and method for producing the same | |
| CN102775810B (en) | Fluorane color former and preparation method thereof | |
| CN107474053B (en) | The preparation method of Yi Zhong piceneketone type solvent dye | |
| CN108047753A (en) | The synthetic method of red naphthalene nucleus ketone dyes | |
| CN107089982B (en) | 4,5- bis- substitute -1- hydrogen-pyrroles (2,3-f) quinoline -2,7,9- tricarboxylic esters compound and application | |
| CN104845404B (en) | A kind of method of synthesis Material of Fluoran black fever pressure-sensitive color coupler | |
| CN114163450B (en) | Thermochromic material with single rhodamine structure, developing composition, preparation method and application thereof | |
| CN109608429A (en) | A kind of synthesis technology of sulfonic group rhodamine compound | |
| CN101323619A (en) | Manufacturing method of fluorane compounds | |
| CN106661339B (en) | Azopigment composition and its manufacturing method | |
| WO2014061143A1 (en) | Coloring material and method for producing same | |
| CN111518409B (en) | Synthetic method of solvent red 169 | |
| CN105859559A (en) | Production method of 3-ethoxy-4-nitrophenol | |
| CN105838105A (en) | Method for preparing black fluorane thermal-pressure sensitive dye by virtue of one-step method | |
| US4062877A (en) | Process for the preparation of violet dyestuffs of the triphenylmethane series | |
| CN108191883A (en) | A kind of preparation method of Fluorane color former | |
| CN114163431B (en) | Thermochromic material with double-crystal violet lactone structure, color developing composition, preparation method and application of color developing composition | |
| CN109942525A (en) | A method of preparing heat sensitive dye intermediate PHT | |
| CN116621804B (en) | Chemical kinetics resolution method of 5-and 6-carboxyfluorescein compound isomer | |
| Fort et al. | The chemistry of dyestuffs: a manual for students of chemistry and dyeing | |
| CN106632386A (en) | 3'-(2,4-difluoro) anilino-6'-piperidyl fluorine and preparation method thereof | |
| CN106117239B (en) | The synthetic method and its catalyst of a kind of fluorane compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |