CN104788992B - A kind of α bromos acrylamide reactive group half flower cyanines vital fluorescence dye and preparation method - Google Patents
A kind of α bromos acrylamide reactive group half flower cyanines vital fluorescence dye and preparation method Download PDFInfo
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- CN104788992B CN104788992B CN201510095919.8A CN201510095919A CN104788992B CN 104788992 B CN104788992 B CN 104788992B CN 201510095919 A CN201510095919 A CN 201510095919A CN 104788992 B CN104788992 B CN 104788992B
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Abstract
The invention discloses a kind of α bromos acrylamide reactive group half flower cyanines vital fluorescence dye and preparation method.4 picolines and the reaction of 2 chloroethylamine hydrochlorides are obtained into compound A；Compound A and benzaldehyde reaction are obtained into compound B；Compound B again with N, N diethylbenzaldehydes reaction obtain compound C；Compound C obtains compound D in aqueous hydrochloric acid solution reclaimed water solution；Compound D and 2,3 two bromo propionyl chloros react, prepare a kind of flower cyanines vital fluorescence dye of α bromos acrylamide reactive group half, it has styryl pyridine salt fluorescence chromonic structures, dye matrix is positively charged in aqueous, can with the water with isoelectric point on negatively charged protein fibre contaminated by charge attraction, without the rush dye of salt.Because containing α bromo acid/acrylic amide type reactive groups in dyestuff, can react to form covalent bond with the amino on protein fibre.It is firmly combined with wool fibre after the dyeing, color fastness is high.
Description
Technical field
The present invention relates to dyestuff and preparation method thereof, more particularly to a kind of half flower cyanines vital fluorescence dye and its preparation side
Method.
Background technology
Fluorescent dye had not only had the tinctorial property of Conventional dye but also there is waking up for transmitting fluorescence to regard characteristic.Contaminated as feature
Material, in the market is increasing to the demand of fluorescent dye in recent years.Research finds that the fluorescence suitable for textile dyeing contaminates at present
Material mainly has dispersion, acid class dyestuff, and the research on its dyed fabric performance also focuses primarily upon terylene, nylon fabric, and
Active fluorochrome kind suitable for protein fibre dyeing is but rarely reported.
Before the present invention makes, Chinese invention patent（CN 103525117 A）A kind of hemicyanine dye is disclosed to spin
The technology applied in fabric dyeing, the styryl pyridine salt Hemicyanine fluorescent dye for being provided can as Crosslinking Dyes to silk,
Wool fiber or fabric are dyeed.But crosslinking dyeing needs to use crosslinking agent to complete with dyestuff and fiber-reactive respectively,
Therefore, dyeing recipe and dyeing course are complicated.
The content of the invention
The purpose of the present invention is, in view of the shortcomings of the prior art, there is provided a kind of with reactivity higher, fluorescence effect
Really good, bright in colour, application performance is excellent, easy to use, and to there is color fastness higher after protein fibre dyeing
Half flower cyanines vital fluorescence dye and preparation method thereof.
For achieving the above object, the technical solution adopted by the present invention is：A kind of alpha-brominated acrylamide reactive group half
Flower cyanines vital fluorescence dye, its structural formula is：
。
Technical solution of the present invention also includes the flower cyanines vital fluorescence dye of alpha-brominated acrylamide reactive group as described above half
Preparation method, comprise the following steps：
（1）By 4- picolines and 2-chloroethyl amine hydrochloric acid reactant salt, the compound with following structure is obtained
；
（2）By step（1）The compound for obtaining reacts with benzaldehyde, obtains the compound with following structure：
；
（3）By step（2）Compound and N, N- diethyl amino the benzaldehyde reaction for obtaining, obtain with following structure
Compound：
；
（4）By step（3）The compound for obtaining is placed in hydrolysis in aqueous hydrochloric acid solution, obtains the change with following structure
Compound：
；
（5）By step（4）Compound and the bromo propionyl chloro of 2,3- bis- reaction for obtaining, obtain a kind of alpha-brominated acrylamide anti-
The flower cyanines vital fluorescence dye of base half, its structural formula is answered to be：
。
Specific technical scheme of the invention is：
Step（1）The synthetic method of resulting compound is, by equimolar 4- picolines and 2-chloroethyl amine hydrochloric acid
Salt is added in ethanol solution, under conditions of being 70~80 DEG C in temperature, is reacted 4~6 hours, and reaction is evaporated ethanol after stopping,
Acetone precipitation is added, compound is obtained.
Step（2）The synthetic method of compound is, by equimolar step（1）The compound for obtaining is added to benzaldehyde
In methanol solution, under conditions of being 70~80 DEG C in temperature, react 4~6 hours, reaction is evaporated methyl alcohol after stopping, adding acetone
Precipitation, obtains faint yellow compound.
Step（3）The synthetic method of compound is, by equimolar step（2）The compound and N, N- diethyl amino for obtaining
Benzaldehyde is added in ethanol solution, and catalyst drop piperidines, under conditions of being 70~80 DEG C in temperature, reaction 12~15 is added dropwise
Hour, reaction is evaporated ethanol after stopping, and with alkali alumina or neutral alumina as fixing phase, ethanol is mobile phase, carries out layer
Analysis post separation, obtains orange red component composition.
Step（4）The synthetic method of compound is, by step（3）The compound for obtaining is dissolved in water, then dense salt is added dropwise
Acid, described concentrated hydrochloric acid is the aqueous hydrochloric acid solution that concentration is 30 % by weight, and adjustment pH value is 1~2, is 60~70 in temperature
After 6~8 hours, solvent evaporated, with alkali alumina or neutral alumina as fixing phase, first uses second to acidolysis reaction under conditions of DEG C
Alcohol is mobile phase, and again with methanol is mobile phase, carries out chromatography post separation, obtains orange red compound.
Step（5）The synthetic method of compound is that the bromo propionyl chloros of 2,3- bis- are dissolved in acetone, is 0~5 in temperature
DEG C condition of ice bath under, in 1~1.5 hour, the bromo propionyl chloro acetone solns of equimolar 2,3- bis- are added drop-wise to step（4）
To compound the aqueous solution in, Na is added dropwise in course of reaction2CO3Na described in solution2CO3Solution is Na2CO3Saturated solution,
It is 6.5~7 to keep reacting liquid pH value, and after reacting 2~4 hours, it is 11~12, described NaOH to adjust pH value with NaOH solution
Solution is the NaOH aqueous solution that concentration is 30% by weight；Under conditions of being 5~10 DEG C in temperature, continue to react 2~4 hours；
After reaction stops, solvent is steamed, with alkali alumina or neutral alumina as fixing phase, ethanol is mobile phase, carries out chromatographic column
Separate, obtain orange red component composition and be the flower cyanines vital fluorescence dye of alpha-brominated acrylamide reactive group half.
Compared with prior art, the reactive dye that the present invention is produced, with styryl pyridine salt fluorescence chromonic structures, dye
Material parent is positively charged in aqueous, can with the water with isoelectric point on negatively charged protein fibre pass through electric charge
Contaminated on gravitation, without the rush dye of salt.Because in dyestuff contain alpha-brominated acid/acrylic amide type reactive group, can with protein fibre on
Amino react to form covalent bond.It is firmly combined with wool fibre after the dyeing, color fastness is high.
Specific embodiment
Technical solution of the present invention will be further described by embodiment below.
Embodiment 1：
Present embodiments provide flower cyanines vital fluorescence dye of a kind of alpha-brominated acrylamide reactive group half and preparation method thereof：
Reactive dye are formula（Ⅰ）Compound：
（Ⅰ）；
Specific preparation method is as follows：
A, compound（Ⅱ）Synthesis
（Ⅱ）；
Equimolar 4- picolines and 2-chloroethyl amine hydrochloride are added in ethanol solution, temperature is 80 DEG C, and reaction 6 is small
When, ethanol is evaporated after having reacted, acetone precipitation is added, obtain white product as compound（Ⅱ）.
B, compound（Ⅲ）Synthesis
（Ⅲ）；
Equimolar compound is added in methanol solution（Ⅱ）With benzaldehyde, temperature is 80 DEG C, is reacted 6 hours, reaction
Methyl alcohol is evaporated after complete, acetone precipitation is added, faint yellow product as compound is obtained（Ⅲ）.
C, compound（Ⅳ）Synthesis
（Ⅳ）；
Equimolar compound is added in ethanol solution（Ⅲ）With N, N- diethyl amino benzaldehydes, the drop piperidines of dropwise addition 10
As catalyst, temperature is 80 DEG C, is reacted 12 hours, and ethanol is evaporated after having reacted, and carries out chromatography post separation, uses alkali alumina
Or neutral alumina, as fixing phase, ethanol is mobile phase, orange red component as compound is obtained（Ⅳ）.
D, compound（Ⅴ）Generation
（Ⅴ）；
Compound（Ⅳ）Dissolving in aqueous, 30% concentrated hydrochloric acid is added dropwise to it, adjusts the acidolysis 6 hours of 2,60 DEG C of pH value, is steamed
Dry solvent, carries out chromatography post separation, is first mobile phase with ethanol with alkali alumina or neutral alumina as fixing phase, then
It is mobile phase with methyl alcohol, obtains orange red component as compound（Ⅴ）.
E, compound（Ⅰ）Synthesis
Compound（Ⅴ）It is dissolved in deionized water, ice bath 0 DEG C of temperature of control, the dissolving of the bromo propionyl chloros of equimolar 2,3- bis-
In acetone, it is added drop-wise in 1 hour（Ⅴ）In solution, saturation Na is added dropwise in course of reaction2CO3Solution keeps reacting liquid pH value 7, after
Continuous reaction 4 hours.Then pH value 11,10 DEG C of temperature is adjusted to continue to react 4 hours with 30%NaOH solution.After the completion of reaction, steam
Solvent, carries out chromatography post separation, is mobile phase with ethanol with alkali alumina or neutral alumina as fixing phase, obtains orange
Red component is compound（Ⅰ）：
（Ⅰ）.
In the above method：
4- picolines are following structural formula（i）Compound：
（i）；
2-chloroethyl amine hydrochloride is following structural formula（ii）Compound：
（ii）；
Benzaldehyde is following structural formula（iii）Compound：
（iii）；
N, N- diethyl amino benzaldehyde are following structural formula（iv）Compound：
（iv）；
Piperidines is following structural formula（v）Compound：
（v）；
2,3 dibromo propionyl chloride is following structural formula（vi）Compound：
（vi）.
Compound（Ⅰ）：Yield, 91%,1HNMR (DMSO-d6, 400 MHz) δ：8.71 (2H, Py-CH, d, J
= 6.8 Hz), 8.04 (2H, Py-CH, d, J=7.2 Hz), 7.93 (1H, -CH=CH-, d, J=16 Hz),
7.58 (2H, Ar-H, d, J=8.8 Hz), 7.14(1H, -CH=CH-, d, J=16 Hz), 6.76 (2H, Ar-H,
d, J=9.2 Hz), 6.67 (1H, -BrC=CH-, d, J=2.4 Hz), 6.17 (1H, -BrC=CH-, d, J=2.8
Hz), 4.55(2H, Py-CH2-, t, J =5.6 Hz), 3.70 (2H, -CH2-, q), 3.43(4H, -CH2-,
q), 1.24（1H, -NH-, s）1.13 (6H, -CH3, t, J=7.2 Hz). HRMS:It is theoretical： [M-Cl]+=
428.1332, actual measurement： [M-Cl]+= 428.1338.Maximum absorption wavelength：487nm；Maximum emission wavelength：616nm.
Embodiment 2：
Present embodiments provide by the preparation method of embodiment 1 obtain with formula（Ⅰ）The compound of structure, i.e., a kind of α-bromine
For the flower cyanines vital fluorescence dye of acrylamide reactive group half to woolen colouring method.
Specific colouring method is as follows：
Compound（Ⅰ）Consumption 1.0% (o.w.f), bath raio 1：20, Value in Dyeing Process is 7, and wool fabric and dye liquor are at 50 DEG C first
Lower stirring dyeing 10min, is then warmed up to 100 DEG C with the speed of 2 DEG C/min, is incubated 50min.Then take out wool fabric, water
Wash, soap, wash, drying, dye-uptake 93%, degree of fixation 86%.
The flower cyanines vital fluorescence dye application performance such as institute of table 1 of alpha-brominated acrylamide reactive group half prepared by the present invention
Show.
Table 1
。
Claims (8)
1. a kind of alpha-brominated acrylamide reactive group half spends the preparation method of cyanines vital fluorescence dye, it is characterised in that including as follows
Step：
（1）By 4- picolines and 2-chloroethyl amine hydrochloric acid reactant salt, the compound with following structure is obtained
；
（2）By step（1）The compound for obtaining reacts with benzaldehyde, obtains the compound with following structure：
；
（3）By step（2）Compound and N, N- diethyl amino the benzaldehyde reaction for obtaining, obtain the chemical combination with following structure
Thing：
；
（4）By step（3）The compound for obtaining is placed in hydrolysis in aqueous hydrochloric acid solution, obtains the chemical combination with following structure
Thing：
；
（5）By step（4）Compound and the bromo propionyl chloro of 2,3- bis- reaction for obtaining, after reacting 2~4 hours, are adjusted with NaOH solution
Section pH value is 11~12, under conditions of being 5~10 DEG C in temperature, continues to react 2~4 hours, obtains a kind of alpha-brominated acryloyl
The flower cyanines vital fluorescence dye of amine reactive group half, its structural formula is：
。
2. a kind of alpha-brominated acrylamide reactive group according to claim 1 half spends the preparation side of cyanines vital fluorescence dye
Method, it is characterised in that：Step（1）The synthetic method of resulting compound is, by equimolar 4- picolines and 2- chloroethenes
Amine hydrochlorate is added in ethanol solution, under conditions of being 70~80 DEG C in temperature, is reacted 4~6 hours, and reaction is evaporated after stopping
Ethanol, adds acetone precipitation, obtains compound.
3. a kind of alpha-brominated acrylamide reactive group according to claim 1 half spends the preparation side of cyanines vital fluorescence dye
Method, it is characterised in that：Step（2）The synthetic method of compound is, by equimolar step（1）The compound for obtaining and benzene first
Aldehyde is added in methanol solution, under conditions of being 70~80 DEG C in temperature, is reacted 4~6 hours, and reaction is evaporated methyl alcohol after stopping,
Acetone precipitation is added, faint yellow compound is obtained.
4. a kind of alpha-brominated acrylamide reactive group according to claim 1 half spends the preparation side of cyanines vital fluorescence dye
Method, it is characterised in that：Step（3）The synthetic method of compound is, by equimolar step（2）The compound and N, N- for obtaining
Diethyl amino benzaldehyde is added in ethanol solution, and catalyst piperidines is added dropwise, under conditions of being 70~80 DEG C in temperature, reaction
12~15 hours, reaction was evaporated ethanol after stopping, and with alkali alumina or neutral alumina as fixing phase, ethanol is mobile phase,
Chromatography post separation is carried out, orange red component composition is obtained.
5. a kind of alpha-brominated acrylamide reactive group according to claim 1 half spends the preparation side of cyanines vital fluorescence dye
Method, it is characterised in that：Step（4）The synthetic method of compound is, by step（3）The compound for obtaining is dissolved in water, then drips
Plus concentration is the aqueous hydrochloric acid solution of 30 % by weight, adjustment pH value is 1~2, acidolysis under conditions of being 60~70 DEG C in temperature
After reaction 6~8 hours, solvent evaporated, with alkali alumina or neutral alumina as fixing phase, is first mobile phase with ethanol, then
It is mobile phase with methyl alcohol, carries out chromatography post separation, obtains orange red compound.
6. a kind of alpha-brominated acrylamide reactive group according to claim 1 half spends the preparation side of cyanines vital fluorescence dye
Method, it is characterised in that：Step（5）The synthetic method of compound is the bromo propionyl chloros of 2,3- bis- to be dissolved in acetone, in temperature
Under for 0~5 DEG C of condition of ice bath, in 1~1.5 hour, the bromo propionyl chloro acetone solns of equimolar 2,3- bis- are added drop-wise to step
Suddenly（4）In the aqueous solution of the compound for obtaining, Na is added dropwise in course of reaction2CO3It is 6.5~7 that solution keeps reacting liquid pH value, instead
After answering 2~4 hours, it is 11~12 to adjust pH value with NaOH solution, under conditions of being 5~10 DEG C in temperature, continues to react 2~4
Hour；After reaction stops, solvent is steamed, with alkali alumina or neutral alumina as fixing phase, ethanol is mobile phase, carries out layer
Analysis post separation, obtains orange red component composition and is the flower cyanines vital fluorescence dye of alpha-brominated acrylamide reactive group half.
7. the preparation of the flower cyanines vital fluorescence dye method of a kind of alpha-brominated acrylamide reactive group according to claim 6 half
Method, it is characterised in that：Described Na2CO3Solution is Na2CO3Saturated solution.
8. the preparation of the flower cyanines vital fluorescence dye method of a kind of alpha-brominated acrylamide reactive group according to claim 6 half
Method, it is characterised in that：Described NaOH solution is the NaOH aqueous solution that concentration is 30% by weight.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02503005A (en) * | 1987-12-23 | 1990-09-20 | メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Amphiphilic hemicyanine compounds |
| CN101792613A (en) * | 2009-12-08 | 2010-08-04 | 湖北华丽染料工业有限公司 | Yellow reactive dye for wool and preparation method and application thereof |
| CN101965652A (en) * | 2008-03-07 | 2011-02-02 | 巴斯夫欧洲公司 | Dye sensitised solar cell |
| CN102863815A (en) * | 2012-08-06 | 2013-01-09 | 湖北华丽染料工业有限公司 | Method for preparing active dye for blue wool |
| CN103468025A (en) * | 2013-09-02 | 2013-12-25 | 朱文潮 | Bromo-acrylamide reactive dye and wool dyeing method thereof |
| CN103525117A (en) * | 2013-10-30 | 2014-01-22 | 苏州大学 | Hemicyanine fluorescent dye and preparation method and application thereof |
-
2015
- 2015-03-04 CN CN201510095919.8A patent/CN104788992B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02503005A (en) * | 1987-12-23 | 1990-09-20 | メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Amphiphilic hemicyanine compounds |
| CN101965652A (en) * | 2008-03-07 | 2011-02-02 | 巴斯夫欧洲公司 | Dye sensitised solar cell |
| CN101792613A (en) * | 2009-12-08 | 2010-08-04 | 湖北华丽染料工业有限公司 | Yellow reactive dye for wool and preparation method and application thereof |
| CN102863815A (en) * | 2012-08-06 | 2013-01-09 | 湖北华丽染料工业有限公司 | Method for preparing active dye for blue wool |
| CN103468025A (en) * | 2013-09-02 | 2013-12-25 | 朱文潮 | Bromo-acrylamide reactive dye and wool dyeing method thereof |
| CN103525117A (en) * | 2013-10-30 | 2014-01-22 | 苏州大学 | Hemicyanine fluorescent dye and preparation method and application thereof |
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