CN101831288B - Amide derivative of rhodamine B and preparation method thereof - Google Patents
Amide derivative of rhodamine B and preparation method thereof Download PDFInfo
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- CN101831288B CN101831288B CN 201010157452 CN201010157452A CN101831288B CN 101831288 B CN101831288 B CN 101831288B CN 201010157452 CN201010157452 CN 201010157452 CN 201010157452 A CN201010157452 A CN 201010157452A CN 101831288 B CN101831288 B CN 101831288B
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- rhodamine
- acid
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- amine
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Abstract
The invention provides an amide derivative of rhodamine B and a preparation method thereof. In the method, rhodamine B dye with carboxyl on 1-site is used as a matrix and reacts with amine to generate the rhodamine B amide derivative. The method comprises the following steps of: dissolving the rhodamine B with carboxyl on the 1-site into a dry organic solvent, adding alkyl amine into the organic solvent, reacting the mixture under the protection of inert gas, and removing the solvent by reduced pressure distillation; and purifying the obtained substrate by using eluent through a chromatographic column, acidifying the purified substrate, drying the acidified product under vacuum, and removing the solvent to obtain a target product of the rhodamine B amide derivative. The amide derivative of the rhodamine B provided by the invention has the following structure.
Description
Technical field
The present invention relates to a kind of fluorescence dye---amide derivatives of rhodamine B and preparation method thereof.
Background technology
Dye stuff of rhodamine kinds is the important member of xanthene dyestuff family, absorbs emission and all is in the longer wavelength place, and fluorescence quantum yield is high, and optical extinction coefficient is large, and to the stability of light, people have carried out long research to them.Due to its good optical property, its fluorescent probe as the metal ion that detects trace of report is arranged, as the bioprobe of monitoring bio reaction, and as the laser dyes of luminescent material.With the rhodamine of benzene carboxyl, due to an active carbonyl being arranged on its structure, in ethanol methyl alcohol isopolarity solution, there is the benzene carboxyl to participate in typical acid base equilibrium, affect the stability of its optical property.Also just because of the stronger carbonyl of this polarity, make the lipophilicity of rhodamine more weak, limited its application.Therefore, improve have favorable optical performance with the lipophilicity of the rhodamine of benzene carboxyl and to the stability of pH value, important using value is arranged.
Summary of the invention
The present invention seeks to make have good optical property with the lipophilicity of benzene carboxyl rhodamine B and the pH value stabilization is improved.
For achieving the above object, basic ideas of the present invention are: will affect bright rhodamine B lipophilicity and to the benzene Carboxylamide of pH value stabilization.Amide group can not be hydrolyzed under acid-base condition and seem stable.The alkyl chain of introducing, be conducive to the optical plastics microcosmic on realize that molecular entanglement is to reach uniform mixing, as luminescent material.
A kind of rhodamine B amide derivatives that the benzene invention provides, its structure is as shown below:
Wherein, R
BBe rhodamine B; R is the alkyl with 2～14 carbon atoms.
The present invention also provides a kind of preparation method of rhodamine B amide derivatives, there is the rhodamine B of carboxyl to be dissolved in dry organic solvent the 1-bit strip, the concentration 0.05～0.2 (mmol/ml) of rhodamine B in organic solvent, add alkylamine, rhodamine B and alkylamine mol ratio are 30～50: 50～70.Mixture is at rare gas element N
2Under protection, the temperature stirring reaction at 0 ℃ between the organic solvent boiling point 6～20 hours, underpressure distillation desolventizing.After the substrate that obtains is purified through chromatographic column (100 order silica gel particles are filled) with eluent, with the sour acidifying of volume fraction 1%～6%.Solution obtains target product through the vacuum-drying desolventizing.
Above-mentioned dry organic solvent used is a kind of of toluene, acetonitrile, methyl-sulphoxide, chloroform, methylene dichloride, tetracol phenixin.
Above-mentioned alkylamine used is a kind of in ethamine, propylamine, butylamine, amylamine, hexylamine, heptyl amice, octylame, nonyl amine, decyl amine, undecylamine, amino dodecane, tridecyl amine, tetradecy lamine.
A kind of in the mixing solutions that above-mentioned eluent used is ethanol or methyl alcohol with methylene dichloride, chloroform or toluene mix, its volume ratio is 1: 1.
The acid that above-mentioned acidifying is used is a kind of in tartrate, succsinic acid, lactic acid, toxilic acid, oxalic acid, hydrochloric acid, sulfuric acid.
Above-mentioned chromatographic column selects 100 order silica gel particles to fill.
Beneficial effect of the present invention:
Laser dyes rhodamine B acid amides of the present invention has following characteristics: 1) because lipophilicity is stronger, this dyestuff is faster with respect to the dissolution rate of unmodified rhodamine in chloroform; 2) take chloroform as dispersion agent and during the blend of optical plastics polymethylmethacrylate, this dyestuff can Uniform Dispersion; 3) this dyestuff is to the pH value stabilization; 4) in the mode of doping, dyestuff is distributed in the middle of optical plastics, than with polymerization methods, dyestuff being introduced optical plastics, has the advantages such as flexible operation is easy; 5) the rhodamine acid amides is more stable in acid alkaline environment than rhodamine ester class.
Embodiment
Embodiment one
Have the rhodamine B of carboxyl to be dissolved in dry organic solvent acetonitrile the 1-bit strip, the concentration 0.05mmol/ml of rhodamine B in acetonitrile adds amino dodecane, and rhodamine B and amino dodecane mol ratio are 30: 70.Mixture is at rare gas element N
2Under protection, the temperature stirring reaction at 0 ℃ between the organic solvent boiling point 10 hours, underpressure distillation desolventizing.After the substrate that obtains is purified through chromatographic column (100 order silica gel particles are filled) with eluent (methanol/toluene, its volume ratio are 1: 1), with the hcl acidifying of volume fraction 6%.Solution obtains the garnet solid through the vacuum-drying desolventizing, is the hydrochloride form of rhodamine B lauramide.Yield 83%.
Nuclear magnetic resonance measuring: 1H NMR (CDCl
3) δ (ppm): 7.90 (Ar) h, 7.88 (Ar) j, 7.47 (Ar) i, 7.44 (Ar) l, 7.11 (CONHCH
2CH
2(CH
2) 9CH
3)) e, 6.92 (Ar) o, 6.72 (Ar) (h, n), 3.42 (N (CH
2CH
3)
2) r, 3.02 (CONHCH
2CH
2(CH
2) 9CH
3) d, 2.10 (N+ (CH
2CH
3)
2) g, 1.2 ((N+ (CH
2CH
3)
2, N (CH
2CH
3)
2) f, 1.17 (CONHCH
2CH
2(CH
2) 9CH
3) b, 0.96 (CONHCH
2CH
2(CH
2) 9CH
3)) c, 0.80 (CONHCH
2CH
2(CH
2) 9CH3) a.
Embodiment two
Have the rhodamine B of carboxyl to be dissolved in dry organic solvent acetonitrile the 1-bit strip, the concentration 0.2mmol/ml of rhodamine B in acetonitrile adds tetradecy lamine, and rhodamine B and tetradecy lamine mol ratio are 30: 70.Mixture is at rare gas element N
2Under protection, the temperature stirring reaction at 0 ℃ between the organic solvent boiling point 20 hours, underpressure distillation desolventizing.After the substrate that obtains is purified through chromatographic column (100 order silica gel particles are filled) with eluent (ethanol/toluene, its volume ratio are 1: 1), with the hcl acidifying of volume fraction 6%.Solution obtains the garnet solid through the vacuum-drying desolventizing, is the hydrochloride form of rhodamine B myristamide.Yield 78%.
Embodiment three
Have the rhodamine B of carboxyl to be dissolved in dry organic solvent methyl-sulphoxide the 1-bit strip, the concentration 0.1mmol/ml of rhodamine B in methyl-sulphoxide adds decyl amine, and rhodamine B and decyl amine mol ratio are 40: 60.Mixture is at rare gas element N
2Under protection, the temperature stirring reaction at 0 ℃ between the organic solvent boiling point 15 hours, underpressure distillation desolventizing.After the substrate that obtains is purified through chromatographic column (100 order silica gel particles are filled) with eluent (ethanol/dichloromethane, its volume ratio are 1: 1), with the sulfuric acid acidation of volume fraction 3%.Solution obtains the garnet solid through the vacuum-drying desolventizing, is the sulphate form of rhodamine B decyl amide.Yield 77%.
Embodiment four
Have the rhodamine B of carboxyl to be dissolved in dry organic solvents, chloroform the 1-bit strip, the concentration 0.2mmol/ml of rhodamine B in chloroform adds heptyl amice, and rhodamine B and heptyl amice mol ratio are 30: 70.Mixture is at rare gas element N
2Under protection, the temperature stirring reaction at 0 ℃ between the organic solvent boiling point 12 hours, underpressure distillation desolventizing.After the substrate that obtains is purified through chromatographic column (100 order silica gel particles are filled) with eluent (methyl alcohol/chloroform, its volume ratio are 1: 1), with the oxalic acid acidifying of volume fraction 6%.Solution obtains red solid through the vacuum-drying desolventizing, is the oxalate form of rhodamine B heptamide.Yield 86%.
Embodiment five
Have the rhodamine B of carboxyl to be dissolved in dry organic solvent toluene the 1-bit strip, the concentration 0.1mmol/ml of rhodamine B in toluene adds amino dodecane, and rhodamine B and amino dodecane mol ratio are 50: 50.Mixture is at rare gas element N
2Under protection, the temperature stirring reaction at 0 ℃ between the organic solvent boiling point 15 hours, underpressure distillation desolventizing.After the substrate that obtains is purified through chromatographic column (100 order silica gel particles are filled) with eluent (ethanol/dichloromethane, its volume ratio are 1: 1), with the hcl acidifying of volume fraction 6%.Solution obtains the garnet solid through the vacuum-drying desolventizing, is the hydrochloride form of rhodamine B lauramide.Yield 71%.
Embodiment six
Have the rhodamine B of carboxyl to be dissolved in dry organic solvents, chloroform the 1-bit strip, the concentration 0.5mmol/ml of rhodamine B in chloroform adds ethamine, and rhodamine B and ethamine mol ratio are 30: 70.Mixture is at rare gas element N
2Under protection, the temperature stirring reaction at 0 ℃ between the organic solvent boiling point 8 hours, underpressure distillation desolventizing.After the substrate that obtains is purified through chromatographic column (100 order silica gel particles are filled) with eluent (ethanol/methylene, its volume ratio are 1: 1), with the tartrate acidifying of volume fraction 1%.Solution obtains the incarnadine solid through the vacuum-drying desolventizing, is the hydrochloride form of rhodamine B ethanamide.Yield 73%.
Embodiment seven
Have the rhodamine B of carboxyl to be dissolved in dry organic solvent carbon tetrachloride the 1-bit strip, the concentration 0.2mmol/ml of rhodamine B in tetracol phenixin adds butylamine, and rhodamine B and butylamine mol ratio are 40: 60.Mixture is at rare gas element N
2Under protection, the temperature stirring reaction at 0 ℃ between the organic solvent boiling point 10 hours, underpressure distillation desolventizing.After the substrate that obtains is purified through chromatographic column (100 order silica gel particles are filled) with eluent (ethanol/methyl-sulphoxide, its volume ratio are 1: 1), with the succsinic acid acidifying of volume fraction 2%.Solution obtains the incarnadine solid through the vacuum-drying desolventizing, is the hydrochloride form of rhodamine B butyramide.Yield 76%.
Claims (5)
1. the amide derivatives of a rhodamine B, its structure is as shown below:
Wherein, R
BBe rhodamine B; R is the alkyl with 2～14 carbon atoms;
2. the preparation method of the amide derivatives of the described rhodamine B of claim 1, it is characterized in that: have the rhodamine B of carboxyl to be dissolved in dry organic solvent the 1-bit strip, the concentration of rhodamine B in organic solvent is 0.05～0.2mmol/ml, add alkylamine, rhodamine B and alkylamine mol ratio are 30～50: 50～70; Mixture under rare gas element N2 protection, at 0 ℃ to the temperature stirring reaction between the organic solvent boiling point 6～20 hours, underpressure distillation desolventizing; After the substrate that obtains is purified through chromatographic column with eluent, with the sour acidifying of volume fraction 1%～6%; Solution obtains target product through the vacuum-drying desolventizing;
Abovementioned alkyl amine is a kind of in ethamine, propylamine, butylamine, amylamine, hexylamine, heptyl amice, octylame, nonyl amine, decyl amine, undecylamine, amino dodecane, tridecyl amine, tetradecy lamine;
The acid that above-mentioned acidifying is used is a kind of in tartrate, succsinic acid, lactic acid, toxilic acid, oxalic acid, hydrochloric acid, sulfuric acid.
3. preparation method according to claim 2 is characterized in that: the organic solvent of above-mentioned drying is a kind of in toluene, acetonitrile, methyl-sulphoxide, chloroform, methylene dichloride, tetracol phenixin.
4. preparation method according to claim 2 is characterized in that: a kind of in the mixing solutions that above-mentioned eluent is ethanol or methyl alcohol with methylene dichloride, chloroform or toluene mix, its volume ratio is 1: 1.
5. rhodamine acid amides preparation method according to claim 2 is characterized in that: above-mentioned chromatographic column selects 100 order silica gel particles to fill.
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| CN102212605A (en) * | 2011-04-08 | 2011-10-12 | 厦门大学 | Application of rhodamine B derivatives |
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