CN102775810B - Fluorane color former and preparation method thereof - Google Patents
Fluorane color former and preparation method thereof Download PDFInfo
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- CN102775810B CN102775810B CN201210255320.2A CN201210255320A CN102775810B CN 102775810 B CN102775810 B CN 102775810B CN 201210255320 A CN201210255320 A CN 201210255320A CN 102775810 B CN102775810 B CN 102775810B
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- 0 *c(cccc1)c1C(c(ccc([N+]N)c1)c1N=O)=O Chemical compound *c(cccc1)c1C(c(ccc([N+]N)c1)c1N=O)=O 0.000 description 2
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 temperature-sensitive coupler as a kind of functional dye, be widely used in facsimile transmission paper, press the aspects such as electrothermal sensitive recording paper, 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 Material of Fluoran functional pigment is the main flow of temperature-sensitive coupler, there is Stability Analysis of Structures, highly sensitive and the good feature of quality picture storage stability of quality, on the amino of fluorane, introduce different substituted radicals and can obtain respectively color and the different fluorane of performance, chromatogram series can be from yellow to red-purple, especially black kind form and aspect are pure, almost complete monopoly all black coupler kinds, common Material of Fluoran black coupler is shown below.
ODB-1 is industrial applications black coupler early, and quality picture is dark, and storage stability is good.Compound structure is simple in addition, and low price can be applicable in the various heat/pressure sensitive recording papers such as fax, label.ODB-2 is the electrothermal sensitive recording paper coupler being most widely used in the world at present, and except having the performance of ODB-1, during for electrothermal sensitive recording paper, whiteness is high, becomes chromatic sensitivity good, both can use separately, also can be used from high-speed facsimile paper with S205 mono-.
The coupler consumptions such as electrothermal sensitive recording paper uses coupler except aobvious black at present, red, green, yellow are also very large, and conventional redness, green, yellow thermo sensitive color 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 poor, production cost is higher.
Summary of the invention
The object of this invention is to provide that a kind of developing sensitivity is high, weathering resistance and compatibleness new Material of Fluoran coupler preferably.
Another object of the present invention is to provide the preparation method of this Material of Fluoran coupler.
The technical scheme that the present invention takes:
A 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 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 of preparing Material of Fluoran coupler of the present invention; it is that to take N-formyl radical-2-methyl-4-methoxy diphenylamine be raw material; with diphenyl-keto-acid derivative condensation under sulfuric acid catalysis condition; again under organic solvent exists; under alkaline condition, closed loop is prepared from; the structure of described diphenyl-keto-acid derivative is as shown in formula II, and its operational path is as follows:
Wherein said sulfuric acid is the vitriol oil or the oleum of mass concentration 93-105%.
Described alkali is sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus or ammoniacal liquor.
The temperature of described condensation reaction is 0-30 ℃.
Described 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 as follows:
Described sulfuric acid is dropped in reaction flask, be cooled to 0-8 ℃, under agitation condition, slowly add diphenyl-keto-acid derivative, then slowly add N-formyl radical-2-methyl-4-methoxy diphenylamine; At 0-30 ℃, react 20h; The mol ratio of described diphenyl-keto-acid derivative and N-formyl radical-2-methyl-4-methoxy diphenylamine is 1:0.8-1.2; After reaction finishes, under agitation condition, reaction solution is slowly poured in frozen water, separated out solid, filter, washing, obtains filter cake.
Measure 100-200 mL organic solvent, 50-100 mL water, 20-80 mL 30% alkaline solution and join in reaction flask, under agitation condition, the above-mentioned filter cake of 80-120 g is joined in reaction flask, be warming up to backflow, insulation reaction 2h, separatory, hot wash organic phase, activated carbon decolorizing, heat filtering, cooling, crystallization, filter, be dried to obtain product.
The present invention has that cost of material is cheap, easy and simple to handle, product purity is high, be easy to industrialized feature.The red coupler of synthetic novel Material of Fluoran is compared with conventional at present red coupler Red-DCF, Red-520, has that developing sensitivity is high, good weatherability, both can use separately also can with the composite use of black coupler such as ODB-1, ODB-2, S205.
Accompanying drawing explanation
Fig. 1 is the mass spectrum of compound 3-(N-ethyl-N-isopentyl) amino-6-methyl-7-(formanilide) base fluorane;
Fig. 2 is the mass spectrum of compound 3-dibutylamino-6-methyl-7-(formanilide) base fluorane;
Fig. 3 is compound 3-(N-ethyl-N-isopentyl) amino-6-methyl-7-(formanilide) base fluorane
1hNMR figure;
Fig. 4 is compound 3-dibutylamino-6-methyl-7-(formanilide) base fluorane
1hNMR figure.
Embodiment
embodiment 1
Synthesizing of 3-(N-ethyl-N-isopentyl) amino-6-methyl-7-(formanilide) base fluorane
Take 108g 98% sulfuric acid and drop in reaction flask, ice-water bath cooling (temperature control is at 5-8 ℃), under 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 agitation condition, reaction solution is slowly poured in 200g frozen water, separated out a large amount of solids, filter, washing, obtains 86 grams of pink filter cakes.
Measure 110ml toluene, 50ml water, 30ml 30% aqueous sodium hydroxide solution and join in reaction flask, under agitation condition, slowly above-mentioned filter cake is joined in 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, filter, dry to obtain white or off-white color solid 18g, yield 80%, its mass spectrum and
1hNMR distinguishes as shown in figures 1 and 3, HPLC:>=99.0%, M.P. 164-166 ℃.
embodiment 2
Synthesizing of 3-(N-ethyl-N-isopentyl) amino-6-methyl-7-(formanilide) base fluorane
Take the oleum of 108g105% and drop in reaction flask, ice-water bath cooling (temperature control is at 5-8 ℃), under 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 agitation condition, reaction solution is slowly poured in 200g frozen water, separated out a large amount of solids, filter, washing, obtains 92 grams of pink filter cakes.
Measure 110ml chlorobenzene, 60ml water, 30ml 30% aqueous sodium hydroxide solution and join in reaction flask, under agitation condition, slowly above-mentioned filter cake is joined in 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, filter, be dried to obtain white or off-white color solid 17.5g, yield 78%, HPLC: >=99.0%, M.P.164-166 ℃.
embodiment 3
Synthesizing of 3-dibutylamino-6-methyl-7-(formanilide) base fluorane
Take 136g 98% sulfuric acid and drop in reaction flask, ice-water bath cooling (temperature control is at 5-8 ℃), under 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 agitation condition, reaction solution is slowly poured in 400g frozen water, separated out a large amount of solids, filter, washing, obtains 118 grams of pink filter cakes.
Measure 180ml toluene, 75ml water, 52ml 30% aqueous sodium hydroxide solution and join in reaction flask, under agitation condition, slowly above-mentioned filter cake is joined in 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, filter, dry to obtain white or off-white color solid 30g, yield 85%, its mass spectrum and
1hNMR distinguishes as shown in Figure 2 and Figure 4, HPLC:>=99.0%, M.P. 189-191 ℃.
embodiment 4
Synthesizing of 3-dibutylamino-6-methyl-7-(formanilide) base fluorane
Take 136g 93% sulfuric acid and drop in reaction flask, ice-water bath cooling (temperature control is at 5-8 ℃), under 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 agitation condition, reaction solution is slowly poured in 400g frozen water, separated out a large amount of solids, filter, washing, obtains 115 grams of filter cakes.
Measure 180ml chlorobenzene, 80ml water, 50ml 30% aqueous sodium hydroxide solution and join in reaction flask, under agitation condition, slowly above-mentioned filter cake is joined in 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, filter, be dried to obtain white or off-white color solid 29g, yield 82%, HPLC: >=99.0%, M.P.189-191 ℃.
Claims (3)
1. a method of preparing the Material of Fluoran coupler shown in formula I, it is characterized in that: sulfuric acid is dropped in reaction flask, be cooled to 0-8 ℃, under agitation condition, slowly add diphenyl-keto-acid derivative, then slowly add N-formyl radical-2-methyl-4-methoxy diphenylamine; At 0-30 ℃, react 20h; The mol ratio of described diphenyl-keto-acid derivative and N-formyl radical-2-methyl-4-methoxy diphenylamine is 1:0.8-1.2; After reaction finishes, under agitation condition, reaction solution is slowly poured in frozen water, separated out solid, filter, washing, obtains filter cake;
Measure 100-200 mL organic solvent, 50-100 mL water, 20-80 mL 30% alkaline solution and join in reaction flask, under agitation condition, the above-mentioned filter cake of 80-120 g is joined in reaction flask, be warming up to backflow, insulation reaction 2h, separatory, hot wash organic phase, activated carbon decolorizing, heat filtering, cooling, crystallization, filter, be dried to obtain product;
Wherein: described alkali is sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus or ammoniacal liquor; Described organic solvent is toluene, m-xylene, p-Xylol, sym-trimethylbenzene, unsym-trimethyl benzene, chlorobenzene, orthodichlorobenzene or bromobenzene;
As shown in the formula (III), its operational path is as follows for the structure of described diphenyl-keto-acid derivative:
；
Wherein, R
1: C
1-C
5alkane or H;
R
2: C
1-C
5alkane, H or aromatic hydrocarbons.
2. the method for preparing the Material of Fluoran coupler shown in formula I 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 according to claim 1 and 2, is characterized in that described sulfuric acid is sulfuric acid or the oleum of mass concentration 93-105%.
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| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH072865A (en) * | 1991-09-25 | 1995-01-06 | Yamamoto Chem Inc | Fluoran compound |
| US7807607B2 (en) * | 2006-05-12 | 2010-10-05 | Zink Imaging, Inc. | Color-forming compounds and use thereof in imaging members and methods |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
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