CN101693717B - Preparation method of temperature-sensitive paper additives - Google Patents
Preparation method of temperature-sensitive paper additives Download PDFInfo
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- CN101693717B CN101693717B CN2009100192034A CN200910019203A CN101693717B CN 101693717 B CN101693717 B CN 101693717B CN 2009100192034 A CN2009100192034 A CN 2009100192034A CN 200910019203 A CN200910019203 A CN 200910019203A CN 101693717 B CN101693717 B CN 101693717B
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Abstract
The invention relates to a preparation method of temperature-sensitive paper additives. Raw materials comprise N-formyl radical-4-methoxy-2-methylaniline and 4-(N-ethyl-N-isoamyl) aminoketones acid. The mole ratio is 0.8 to 1.2 :1, the preparation method comprises condensation reaction and cyclization hydrolyzation, when N-formyl radical-4-methoxy-2-methylaniline and 4-(N-ethyl-N-isoamyl) aminoketones acid conduct the condensation reaction under the existance of concentrated sulfuric acid, the formyl radical group plays a role in protecting amido, which reduces the generation of sulfonation materials through a series of side effects with concentrated sulfuric acid and also reduces the treatment process of sulfonation materials. The preparation method has the advantages of providing simple production process, increasing selectivity and yield coefficients of reaction and lowering production cost.
Description
Technical field
The present invention relates to a kind of preparation method of temperature-sensitive paper additives, relate in particular to the preparation method of a kind of high melting compound 3-(N-ethyl-N-isopentyl) amino-6-methyl-7-anilino fluorane.
Background technology
Compound 3-(N-ethyl-N-isopentyl)-6-methyl-7-anilino fluorane is a kind of novel temperature-sensitive paper additives, mainly as coupler.In this compound, introduce different substituting groups, the monochrome that can not only obtain various tones is black in to adapt to different needs, and can improve performances such as the sun-proof of coupler, water-fast, fast light, organic solvent-resistant, sensitivity, color development degree, with this material writing that develops the color, the shelf time is long.3-(N-ethyl-N-isopentyl)-6-methyl-7-anilino fluorane has two kinds of different crystal formations, a kind of high-melting-point crystallization, and its melting range is at 163-168 ℃; A kind of low melting point crystallization, 145-156 ℃ of its melting range; In the crystal formation of above different melting points, when its during as temperature-sensitive or pressure sensitive recording material, high-melting-point crystalline compound has fast, the not easy to fade advantage of color development speed, particularly the effect aspect color darkness and background dyeing is more outstanding.
At Japanese Patent JP2002173607-A, JP 3903269 B2 disclose the preparation method of temperature-sensitive paper additives 3-(N-ethyl-N-isopentyl)-6-methyl-7-anilino fluorane among USP4444591 and the Chinese patent CN101058583.Traditional preparation method is that the compound 4-methoxyl group-2-methyldiphenylamine with 4-(N-ethyl-N-isopentyl) amino ketone acid or 4-(N-ethyl-N-isopentyl) keto-amine hydrochlorate and chemical formula V is dissolved in 98% vitriol oil, low temperature (0-15 ℃) reaction 10-48hrs, after the reaction, again reaction mixture is poured in a large amount of frozen water and formed throw out, throw out is collected through filtering, washing obtains filter cake, this filter cake joins in the mixed solution of toluene and water, add the neutralization of NaOH solution, 80 ℃ of insulation 1.0h, toluene layer is told in extraction, cooling, it is 145-156 ℃ pale yellow crystals that centrifugal oven dry obtains fusing point, can be converted into dystectic 3-(N-ethyl-N-isopentyl)-6-methyl-7-anilino fluorane after then pale yellow crystals being heated in the chlorobenzene equal solvent.
There is following problem in above traditional preparation method:
(1) because traditional preparation method's operation steps is various, long reaction time, and it is poor as the 4-methoxyl group-2-methyldiphenylamine stability of raw material, oxidized easily, the easy and vitriol oil generation side reaction generation sulfonated bodies of 4-methoxyl group-2-methyldiphenylamine in the reaction process, causing yield is about 80%, about content 98%, still need solubilizing agent refining, complex process, production cost is higher.
(2) reaction mixture need add in a large amount of frozen water, form throw out, throw out will produce the dilute sulphuric acid waste water that a large amount of concentration are 5%-25% through filtering, washing again, easily environment is polluted, processing costs is very high, increased production cost, and being in great demand of reaction process water, the waste great amount of water resources.
(3) filter cake adds in the mixed solution of toluene and water, adds the neutralization of NaOH solution, can produce after the extracting and demixing to contain salinity and the higher alkaline waste water of organic impurity in a large number, easily environment is polluted, and processing costs is very high, has increased production cost.
Summary of the invention
The technical problem to be solved in the present invention is the deficiency at technique scheme, and a kind of preparation method of temperature-sensitive paper additives is provided.Utilize this method to prepare 3-(N-ethyl-N-isopentyl) amino-6-methyl-7-anilino fluorane, production technique is simple, environmental pollution is little, production cost is low.
For solving above technical problem, the technical solution adopted in the present invention is: a kind of preparation method of temperature-sensitive paper additives is characterized in that: the starting material of described additive comprise:
The compound of Formula I, name is called N-formyl radical-4-methoxyl group-2-methyldiphenylamine;
The compound of Formulae II, name is called the amino ketone acid of 4-(N-ethyl-N-isopentyl);
More than two kinds of compounds that raw-material mol ratio is a Formula I: the compound of Formulae II=0.8～1.2: 1;
Described preparation method comprises the steps:
1) condensation reaction: get above two kinds of starting material according to mol ratio, in the container that fills the vitriol oil, add the compound of Formulae II lentamente, when adding, stir, after having added the compound of Formulae II, slowly add the compound of Formula I again, after having added the compound of Formula I, continue at room temperature to react 2-8h, obtain comprising the reaction solution of compound shown in the Formulae II I;
2) extracting and demixing: the reaction solution that obtains is splashed in the mixing solutions of organic solvent and 30% alkaline solution and carry out the extracting and demixing first time, isolate upper strata organism and lower floor's inorganics;
3) cyclization hydrolysis: the alkaline aqueous solution of 10%-30% is joined for the first time after the extracting and demixing in the organism of isolated upper strata, regulate pH value 〉=10, through being heated to 80-100 ℃ of backflow, extracting and demixing for the second time, upper strata organism after the second time extracting and demixing is cooled to 0-15 ℃, filter, washing obtains compound 3-shown in the Formula I V (N-ethyl-N-isopentyl) amino-6-methyl-7-anilino fluorane.
The further optimization of technique scheme, in the step (2), after the extracting and demixing, isolated lower floor inorganics obtains 60～65% sulphuric acid soln after filtering for the first time.
The further optimization of 30% alkaline solution, in the step (2), used alkali is NaOH, KOH, Na in described 30% alkaline solution
2CO
3With K
2CO
3In at least a.
The further optimization of 30% alkaline solution, the mol ratio of the compound amount of the consumption of alkali and Formulae II is 20～25: 1 in described 30% alkaline solution.
A kind of concrete prioritization scheme of 30% alkaline solution, the used preferred NaOH of alkali in described 30% alkaline solution.
The further optimization of 10%-30% alkaline aqueous solution, in the step (2), used alkali is NaOH, KOH, Na in the described 10%-30% alkaline aqueous solution
2CO
3With K
2CO
3In at least a.
The further optimization of 10%-30% alkaline aqueous solution, the mol ratio of the compound amount of the consumption of alkali and Formulae II is 3～15: 1 in the described 10%-30% alkaline aqueous solution.
A kind of concrete prioritization scheme of 10%-30% alkaline aqueous solution, the used preferred NaOH of alkali in the described 10%-30% alkaline aqueous solution.
The further optimization of organic solvent, in the step (2), described organic solvent is any in toluene, dimethylbenzene, ethylbenzene, isopropyl benzene, chlorobenzene, dichlorobenzene and the bromobenzene.
The further optimization of organic solvent, the volume ratio of the consumption of described organic solvent and the compound amount of Formulae II is 5～15: 1.
The present invention takes above technical scheme, compared with prior art, has the following advantages:
1) compound of the compound of Formula I used in the present invention chemical formula V of the prior art relatively;
1. the compound of Formula I is compared with the compound of chemical formula V; be that N-formyl radical-4-methoxyl group-2-methyldiphenylamine is easier to be more synthetic than 4-methoxyl group-2-methyldiphenylamine, reactions steps is few, the low and energy stable existence of production cost; be difficult for oxidizedly, be convenient to long-term deposit.
When 2. the compound of the compound of Formula I and Formulae II reacts, be that N-formyl radical-4-methoxyl group-2-methyldiphenylamine and 4-(N-ethyl-N-isopentyl) are when amino ketone acid carries out condensation reaction in the presence of the vitriol oil, because the amido protecting effect is played in the existence of formyl group in the compound of Formula I, having reduced the compound of compound, Formulae II of Formula I and the vitriol oil a series of side reactions takes place generates sulfonated bodiess, reduced the treatment process of sulfonated bodies, production technique is simple, improve the selectivity and the reaction yield of reaction, reduced production cost; The yield of product is up to 88.3%, and content need not made with extra care purification can surpass 99.5%.
3. the formyl radical in the compound of Formula I can carry out taking off voluntarily in the process when the cyclization hydrolysis at the cyclization hydrolysis reaction, does not need to utilize independent technology that formyl radical is taken off, and has reduced production cost.
2) among the temperature-sensitive paper additives preparation method of the present invention, reacted reaction solution is directly splashed in the mixing solutions of organic solvent and 30% alkaline solution rather than and add in a large amount of frozen water reaction mixture, therefore after first time extracting and demixing, obtain the sulphuric acid soln of 60-65% behind lower floor's filtration desalination, can utilize again, do not have waste acid water to produce, reduced pollution, and saved water resources environment.
3) alkaline aqueous solution of 10%-30% is joined for the first time after the extracting and demixing in the organism of isolated upper strata, regulate pH value 〉=10, then through reflux, for the second time after the extracting and demixing, contained the very low alkaline waste water of salinity on a small quantity, reduced pollution, be easy to carry out processing up to standard after entering the sewage disposal workshop environment, processing costs is low, has reduced production cost.
The invention will be further described below in conjunction with embodiment.
Embodiment
Embodiment 1; adding concentration is 98% vitriol oil 100ml in the there-necked flask of 250ml; get the compound N-formyl radical-4-methoxyl group-2-methyldiphenylamine 24.1g (0.1mol) of Formula I and compound 4-(N-ethyl-N-isopentyl) the amino ketone acid 35.5g (0.1mol) of Formulae II; the compound that in flask, adds Formulae II at first lentamente; when adding, stir; the temperature of the liquid that reacts is remained between room temperature 20-25 ℃; after having added the compound of Formulae II; the compound that slowly adds Formula I again; added the compound of Formula I; continue at room temperature to keep reaction 2.0h, obtain comprising the reaction solution of compound shown in the Formulae II I.
The NaOH solution 300g that in the reaction flask of 1000ml, adds toluene 200ml and 30%, obtain mixing solutions, slowly splash into the above-mentioned reaction solution that comprises compound shown in the Formulae II I in the reaction flask then, stir while splashing into, carry out the extracting and demixing first time, isolate upper strata organism and lower floor's inorganics.
10%NaOH solution is joined in the organism of the isolated upper strata of the extracting and demixing first time, regulate pH value 〉=10, be heated to 80-100 ℃ of backflow 1.0h, extracting and demixing for the second time, isolate upper strata organism and lower floor's inorganics, the isolated upper strata of extracting and demixing second time organism is got compound 3-(N-ethyl-N-isopentyl) amino-6-methyl-7-anilino fluorane 44.7g shown in the Formula I V after washing, be cooled to 10-15 ℃, filter, wash and drying, yield is 86.3%, through HPLC check product content is 99.8%, fusing point 166.7-167.0 ℃.
After first time extracting and demixing, isolated lower floor inorganics obtains 60～65% sulphuric acid soln after filtering, further can utilize again after the filtration treatment again.
The process of above chemical reaction is as follows:
Below for prepare the data contrast table of 1 ton of 3-(N-ethyl-N-isopentyl) amino-6-methyl-7-anilino fluorane respectively according to above method and traditional method preparation:
As can be seen from the above table, 3-(N-ethyl-N-isopentyl) amino-6-methyl-7-anilino fluorane that uses preparation method of the present invention to produce, its purity, fusing point index surpass the product index of produced in conventional processes after measured, compare with traditional method, production process of the present invention produces more a spot of sulfonated bodies, acid waste water and alkaline waste water, reduced the pollution to environment, environment is more friendly; Save the treatment process of sulfonated bodies, acid waste water and alkaline waste water, production technique is simple, has reduced production cost; In the production process, do not need to add a large amount of frozen water, saved water resources; Reaction times is shorter, has improved production efficiency, and the concentration that produces in the production process is the sulphuric acid soln of 60-65%, further can utilize again after the filtration treatment again, and production cost is low.
Embodiment 2; adding concentration is 99% vitriol oil 100ml in the there-necked flask of 250ml; get the compound N-formyl radical-4-methoxyl group-2-methyldiphenylamine 28.9g (0.12mol) of Formula I and compound 4-(N-ethyl-N-isopentyl) the amino ketone acid 35.5g (0.1mol) of Formulae II; the compound that in flask, adds Formulae II at first lentamente; when adding, stir; the temperature of the liquid that reacts is remained between room temperature 20-25 ℃; after having added the compound of Formulae II; the compound that slowly adds Formula I again; added the compound of Formula I; continue at room temperature to keep reaction 4.0h, obtain comprising the reaction solution of compound shown in the Formulae II I.
The NaOH solution 300g that in the reaction flask of 1000ml, adds dimethylbenzene 200ml and 30%, obtain mixing solutions, slowly splash into the above-mentioned reaction solution that comprises compound shown in the Formulae II I in the reaction flask then, stir while splashing into, carry out the extracting and demixing first time, isolate upper strata organism and lower floor's inorganics.
20%NaOH solution is joined in the organism of the isolated upper strata of the extracting and demixing first time, regulate pH value 〉=10, be heated to 80-100 ℃ of backflow 0.5h, extracting and demixing for the second time, isolate upper strata organism and lower floor's inorganics, the isolated upper strata of extracting and demixing second time organism is got compound 3-(N-ethyl-N-isopentyl) amino-6-methyl-7-anilino fluorane 45.1g shown in the Formula I V after washing, be cooled to 5-10 ℃, filter, wash and drying, yield is 87.1%, through HPLC check product content is 99.64%, fusing point 167.1-167.2 ℃.
After first time extracting and demixing, isolated lower floor inorganics obtains 60～65% sulphuric acid soln after filtering, further can utilize again after the filtration treatment again.
The process of above chemical reaction is as follows:
Below for prepare the data contrast table of 1 ton of 3-(N-ethyl-N-isopentyl) amino-6-methyl-7-anilino fluorane respectively according to above method and traditional method preparation:
As can be seen from the above table, 3-(N-ethyl-N-isopentyl) amino-6-methyl-7-anilino fluorane that uses preparation method of the present invention to produce, its purity, fusing point index are all above the product index of produced in conventional processes after measured, compare with traditional method, production process of the present invention produces more a spot of sulfonated bodies, acid waste water and alkaline waste water, reduced the pollution to environment, environment is more friendly; Save the treatment process of sulfonated bodies, acid waste water and alkaline waste water, production technique is simple, has reduced production cost; In the production process, do not need to add a large amount of frozen water, saved water resources; Reaction times is shorter, has improved production efficiency, and the concentration that produces in the production process is the sulphuric acid soln of 60-65%, can utilize after treatment again, and production cost is low.
Embodiment 3; adding concentration is 99.5% vitriol oil 100ml in the there-necked flask of 250ml; get the compound N-formyl radical-4-methoxyl group-2-methyldiphenylamine 19.28g (0.08mol) of Formula I and compound 4-(N-ethyl-N-isopentyl) the amino ketone acid 35.5g (0.1mol) of Formulae II; the compound that in flask, adds Formulae II at first lentamente; when adding, stir; the temperature of the liquid that reacts is remained between room temperature 20-25 ℃; after having added the compound of Formulae II; the compound that slowly adds Formula I again; added the compound of Formula I; continue at room temperature to keep reaction 8.0h, obtain comprising the reaction solution of compound shown in the Formulae II I.
The KOH solution 420g that in the reaction flask of 1000ml, adds chlorobenzene 200ml and 30%, obtain mixing solutions, slowly splash into the above-mentioned reaction solution that comprises compound shown in the Formulae II I in the reaction flask then, stir while splashing into, carry out the extracting and demixing first time, isolate upper strata organism and lower floor's inorganics.
30%KaOH solution is joined in the organism of the isolated upper strata of the extracting and demixing first time, regulate pH value 〉=10, be heated to 80-100 ℃ of backflow 1.0h, extracting and demixing for the second time, isolate upper strata organism and lower floor's inorganics, the isolated upper strata of extracting and demixing second time organism is got compound 3-(N-ethyl-N-isopentyl) amino-6-methyl-7-anilino fluorane 36.76g shown in the Formula I V after washing, be cooled to 0-5 ℃, filter, wash and drying, yield is 88.7%, through HPLC check product content is 99.82%, fusing point 166.8-167.0 ℃.
After first time extracting and demixing, isolated lower floor inorganics obtains 60～65% sulphuric acid soln after filtering, further can utilize again after the filtration treatment again.
The process of above chemical reaction is as follows:
Below for prepare the data contrast table of 1 ton of 3-(N-ethyl-N-isopentyl) amino-6-methyl-7-anilino fluorane respectively according to above method and traditional method preparation:
As can be seen from the above table, 3-(N-ethyl-N-isopentyl) amino-6-methyl-7-anilino fluorane that uses preparation method of the present invention to produce, its purity, fusing point index are all above the product index of produced in conventional processes after measured, compare with traditional method, production process of the present invention produces more a spot of sulfonated bodies, acid waste water and alkaline waste water, reduced the pollution to environment, environment is more friendly; Save the treatment process of sulfonated bodies, acid waste water and alkaline waste water, production technique is simple, has reduced production cost; In the production process, do not need to add a large amount of frozen water, saved water resources; Reaction times is shorter, has improved production efficiency, and the concentration that produces in the production process is the sulphuric acid soln of 60-65%, can utilize after treatment again, and production cost is low.
Among the above embodiment, alkali used in 30% alkaline solution and the alkaline aqueous solution can also be NaOH, KOH, Na
2CO
3With K
2CO
3In several combinations.
Organic solvent can also be in dimethylbenzene, ethylbenzene, isopropyl benzene, chlorobenzene, dichlorobenzene and the bromobenzene any.
Claims (5)
1. the preparation method of a temperature-sensitive paper additives, it is characterized in that: the starting material of described additive comprise:
The compound of Formula I, name is called N-formyl radical-4-methoxyl group-2-methyldiphenylamine;
The compound of Formulae II, name is called the amino ketone acid of 4-(N-ethyl-N-isopentyl);
More than two kinds of compounds that raw-material mol ratio is a Formula I: the compound of Formulae II=0.8～1.2: 1;
Described preparation method comprises the steps:
(1) condensation reaction: get above two kinds of starting material according to mol ratio, in the container that fills the vitriol oil, add the compound of Formulae II lentamente, when adding, stir, after having added the compound of Formulae II, slowly add the compound of Formula I again, after having added the compound of Formula I, continue at room temperature to react 2-8h, obtain comprising the reaction solution of compound shown in the Formulae II I;
(2) extracting and demixing: the reaction solution that obtains is splashed in the mixing solutions of organic solvent and 30% alkaline solution and carry out the extracting and demixing first time, isolate upper strata organism and lower floor's inorganics, the volume ratio of the consumption of organic solvent and the compound amount of Formulae II is that the mol ratio of the compound amount of the consumption of alkali in 5～15: 1,30% alkaline solution and Formulae II is 20～25: 1; Used alkali is NaOH, KOH, Na in described 30% alkaline solution
2CO
3With K
2CO
3In at least a;
(3) cyclization hydrolysis: the alkaline aqueous solution of 10%-30% is joined for the first time after the extracting and demixing in the organism of isolated upper strata, regulate pH value 〉=10, through being heated to 80-100 ℃ of backflow, extracting and demixing for the second time, upper strata organism after the second time extracting and demixing is cooled to 0-15 ℃, filter, washing obtains compound 3-shown in the Formula I V (N-ethyl-N-isopentyl) amino-6-methyl-7-anilino fluorane, the mol ratio of the compound amount of the consumption of alkali and Formulae II is 3～15: 1 in the 10%-30% alkaline aqueous solution, and used alkali is NaOH in the described 10%-30% alkaline aqueous solution, KOH, Na
2CO
3With K
2CO
3In at least a.
2. the preparation method of a kind of temperature-sensitive paper additives as claimed in claim 1 is characterized in that: in the step (2), after the extracting and demixing, isolated lower floor inorganics obtains 60～65% sulphuric acid soln after filtering for the first time.
3. the preparation method of a kind of temperature-sensitive paper additives as claimed in claim 1 is characterized in that: in the step (2), and the used preferred NaOH of alkali in described 30% alkaline solution.
4. the preparation method of a kind of temperature-sensitive paper additives as claimed in claim 1 is characterized in that: in the step (3), and the used preferred NaOH of alkali in the described 10%-30% alkaline aqueous solution.
5. the preparation method of a kind of temperature-sensitive paper additives as claimed in claim 1, it is characterized in that: in the step (2), described organic solvent is any in toluene, dimethylbenzene, ethylbenzene, isopropyl benzene, chlorobenzene, dichlorobenzene and the bromobenzene.
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| CN2009100192034A CN101693717B (en) | 2009-10-09 | 2009-10-09 | Preparation method of temperature-sensitive paper additives |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4444591A (en) * | 1977-08-02 | 1984-04-24 | Yamada Chemical Co., Ltd. | Chromogenic compounds and the use thereof as color former in copying or recording materials |
| GB2171111A (en) * | 1985-02-16 | 1986-08-20 | Ciba Geigy Ag | Novel synthesis of 2,6-diamino fluorans |
| CN1854201A (en) * | 2005-04-19 | 2006-11-01 | 寿光富康制药有限公司 | Production of thermosensitive dye |
| CN101058583A (en) * | 2006-04-17 | 2007-10-24 | 蓬莱市维迅精细化工研究所 | Method of preparing high melting point 3-(N-ethyl-N-isoamyl) amino-6-methyl-7-anilinofluorane |
-
2009
- 2009-10-09 CN CN2009100192034A patent/CN101693717B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4444591A (en) * | 1977-08-02 | 1984-04-24 | Yamada Chemical Co., Ltd. | Chromogenic compounds and the use thereof as color former in copying or recording materials |
| GB2171111A (en) * | 1985-02-16 | 1986-08-20 | Ciba Geigy Ag | Novel synthesis of 2,6-diamino fluorans |
| CN1854201A (en) * | 2005-04-19 | 2006-11-01 | 寿光富康制药有限公司 | Production of thermosensitive dye |
| CN101058583A (en) * | 2006-04-17 | 2007-10-24 | 蓬莱市维迅精细化工研究所 | Method of preparing high melting point 3-(N-ethyl-N-isoamyl) amino-6-methyl-7-anilinofluorane |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2002-173607A 2002.06.21 |
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Inventor after: Yuan Jinting Inventor after: Yang Lei Inventor after: Lin Liming Inventor after: Fang Yuxiang Inventor before: Li Zhengyuan Inventor before: Chen Jianping Inventor before: Fang Yuxiang Inventor before: Song Benxi Inventor before: Lin Liming |
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Effective date of registration: 20180411 Address after: 262700 5, East Street, Shouguang college, Shandong Patentee after: Shandong Rui Kang refined Co., Ltd. Address before: 262700 East Street, 5 St. Cheng Street College, Shouguang City, Shandong Patentee before: Shouguang Fukang Pharmaceutical Co., Ltd. |