CN102321063B - Method for preparing unsymmetrical rhodamine - Google Patents
Method for preparing unsymmetrical rhodamine Download PDFInfo
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- CN102321063B CN102321063B CN201110201694.1A CN201110201694A CN102321063B CN 102321063 B CN102321063 B CN 102321063B CN 201110201694 A CN201110201694 A CN 201110201694A CN 102321063 B CN102321063 B CN 102321063B
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- rhodamine
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- esterification
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- asymmetric rhodamine
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- 0 CCN(CC)C(CC=C1C(c2ccccc2C(O)=O)=C2c3c4cccc3)C=C1OC2=C(*)C4=O Chemical compound CCN(CC)C(CC=C1C(c2ccccc2C(O)=O)=C2c3c4cccc3)C=C1OC2=C(*)C4=O 0.000 description 3
- FQNKTJPBXAZUGC-UHFFFAOYSA-N CCN(CC)c1ccc(C(c(cccc2)c2C(O)=O)=O)c(O)c1 Chemical compound CCN(CC)c1ccc(C(c(cccc2)c2C(O)=O)=O)c(O)c1 FQNKTJPBXAZUGC-UHFFFAOYSA-N 0.000 description 2
- OMEIGPOGTGJBBQ-UHFFFAOYSA-N CCN(CC)c(cc1O2)ccc1C(c(cccc1)c1C(OCC)=O)=C(c1c3cccc1)C2=CC3=O Chemical compound CCN(CC)c(cc1O2)ccc1C(c(cccc1)c1C(OCC)=O)=C(c1c3cccc1)C2=CC3=O OMEIGPOGTGJBBQ-UHFFFAOYSA-N 0.000 description 1
- RLFMUDMGOHOFIE-UHFFFAOYSA-N CCN(CC)c(cc1O2)ccc1C(c1ccccc1C(OCC)=O)=C(c1c3cccc1)C2=C(C(OCC)=O)C3=O Chemical compound CCN(CC)c(cc1O2)ccc1C(c1ccccc1C(OCC)=O)=C(c1c3cccc1)C2=C(C(OCC)=O)C3=O RLFMUDMGOHOFIE-UHFFFAOYSA-N 0.000 description 1
- WAVOOWVINKGEHS-UHFFFAOYSA-N CCN(CC)c1cccc(O)c1 Chemical compound CCN(CC)c1cccc(O)c1 WAVOOWVINKGEHS-UHFFFAOYSA-N 0.000 description 1
- JNVQTZHEEIATCI-UHFFFAOYSA-N CCOC(c(c(O)cc1ccccc11)c1O)=O Chemical compound CCOC(c(c(O)cc1ccccc11)c1O)=O JNVQTZHEEIATCI-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N O=C(c1ccccc11)OC1=O Chemical compound O=C(c1ccccc11)OC1=O LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention relates to a method for preparing unsymmetrical rhodamine. The method comprises the following steps of: reacting N,N-diethyl m-aminophenol with phthalic anhydride to prepare an intermediate ketonic acid; reacting the ketonic acid with the corresponding binaphthol structure under the action of a catalyst to generate the unsymmetrical rhodamine; directly performing ethyl esterification on the crude products and performing column chromatography; and recrystallizing to obtain unsymmetrical rhodamine dye which meets the requirements and has different structures. Compared with the prior art, the method has the advantages of low requirement on equipment, low production cost and high production efficiency and is easy to operate. The obtained novel rhodamine has good fluorescence property and high stability and can be widely applied.
Description
Technical field
The present invention relates to the preparation method of a kind of organic fluorescence (laser) dyestuff, especially relate to a kind of preparation method of asymmetric rhodamine.
Background technology
Rhodamine compound take xanthene as the alkaline xanthene dye of parent, due to special structure and corresponding fluorescent characteristic, makes rhodamine fluorescence dye be widely used in information science, fluorescent mark, the aspects such as laser dyes.Compared with other conventional fluorescence dye, dye stuff of rhodamine kinds has good light stability, fluorescence quantum yield advantages of higher.
The synthetic method of rhodamine compound is a lot, divide from synthesis step and can be divided into the large class of direct condensing method, stepwise condensation method two, and divide to be divided into from structural modification and female ring is modified, base ring is modified and the synthesis of how chromophoric rhodamine fluorescence dye.Owing to containing conjugation II key and more active auxochrome group in molecular structure, modifying by introducing the structure of different functional groups to rhodamine, many rhodamine derivatives (comprising asymmetric rhodamine) can be gone out by design and synthesis.These modifications can be carried out after condensation reaction, also can modify aromatic ring or hetero-aromatic ring before synthesis.Rhodamine through modifying compensate for the shortcomings such as lipotropy difference, specific selectivity is bad, quantum yield is lower, emission wavelength is lower well and asymmetric rhodamine can increase its stoke shift effectively, is conducive to improving its resolving power.
Direct condensing method is generally used for synthesizing the rhodamine fluorescence dye of substituting group symmetry.The classics synthesis of rhodamine fluorescence dye is exactly belong to this class methods, by suitable amino phenol and various phenylformic acid, phthalic acid, phthalic anhydride, sulfosalicylic acid and anhydride reaction thereof, with the vitriol oil, Zinc Chloride Anhydrous and other Lewis acid as catalyst condensation.
Stepwise condensation method can be used for synthesizing the rhodamine fluorescence dye of substituting group symmetry, also can be used for the asymmetric rhodamine fluorescence dye of synthesis substituting group.Stepwise condensation method on the whole reaction conditions is gentleer, and by product is less, has an obvious advantage compared with direct condensing method, can be used for synthesizing the asymmetric rhodamine fluorescence dye of substituting group, and this has enriched rhodamine fluorescence dye kind greatly.Regional choice synthesis method is also referred to as just based on this stepwise condensation method.
At present about the research report of rhodamine ester class chemical combination has had a lot, but also do not find that the research about the asymmetric rhodamine of naphthalenediol structure is reported, the synthesis of this structure is easy, and there is certain stoke shift and higher fluorescence intensity, light stability is good, as a kind of novel rhodamine fluorescence dye, can be widely used in laser dyes, fluorescent probe, the aspects such as fluorescent mark.
The purification of current dye stuff of rhodamine kinds mainly adopts the rhodamine ester of silica gel column chromatography to preparation to purify, and eluent used comprises chloroform, methylene dichloride, methyl alcohol etc.For the asymmetric rhodamine of naphthalenediol structure, after column chromatography, again by recrystallization, significantly improve the purity of product, effectively ensure and improve its fluorescence intensity.
At present, due to the widespread use of dye stuff of rhodamine kinds, the particular demands of the rhodamine of each wave band is also increased gradually, the asymmetric rhodamine of naphthalenediol structure, because of its easy synthetic method and stronger fluorescence intensity, the application on its specific wavelength has possessed its unrivaled advantage, and the dye stuff of rhodamine kinds therefore studying various novel specific wavelength has very large using value and economic worth.
Summary of the invention
Object of the present invention is exactly provide the method for the asymmetric rhodamine of preparation that a kind of purity is high, fluorescence intensity is high, have good stability to overcome defect that above-mentioned prior art exists.
Object of the present invention can be achieved through the following technical solutions:
Prepare a method for asymmetric rhodamine, it is characterized in that, the method comprises the following steps:
(1) preparation of intermediate ketone acid: get N, the Tetra hydro Phthalic anhydride of N-diethyl Metha Amino Phenon and its 1-2 times of molar weight, as raw material, utilizes the toluene of 10-50 times of quality to dissolve, stirs under nitrogen protection condition, reflux 5-10 hour, after cooling, suction filtration obtains intermediate ketone acid;
(2) preparation of asymmetric rhodamine: get the intermediate ketone acid that step (1) prepares, naphthalenediol ethyl formate and catalyzer, the add-on of naphthalenediol ethyl formate is 1-3 times of molar weight of intermediate ketone acid, be heated to 100-160 DEG C of reaction 2-10 hour, the mixture obtained is dropped in the water of 40-80 times of quality and separates out precipitation, suction filtration, obtains crude product after drying;
(3) esterification of asymmetric rhodamine crude product: by the dissolving crude product of asymmetric rhodamine that obtains in the ethanolic soln of 20-50 times of weight, add catalyzer, back flow reaction 10-30 hour, rotary evaporation removes solvent, use methylene dichloride dissolved product, with a large amount of water washings removing catalyzer, after concentrated methylene chloride solution, obtain the asymmetric rhodamine crude product of esterification;
(4) purifying of asymmetric rhodamine: asymmetric rhodamine crude product recrystallization after column chromatography of the esterification obtained is obtained the asymmetric rhodamine of sterling.
Catalyzer described in step (2) is selected from zinc chloride, sulfuric acid, phosphoric acid, phosphorus oxychloride or methanesulfonic, and the weight ratio of catalyzer and intermediate ketone acid is 1 ~ 2: 3 ~ 4.
Catalyzer described in step (3) is selected from the vitriol oil, sulfur oxychloride or hydrogen chloride gas, and the volume ratio of catalyzer and ethanolic soln is 1: 10 ~ 20.
The solvent that recrystallization described in step (4) adopts is one or both in methyl alcohol, ethanol, propyl alcohol or ethyl acetate.
The structural formula of the asymmetric rhodamine of sterling described in step (4) is:
The asymmetric rhodamine of above-mentioned different structure can be obtained with the synthesis of different catalyst rhodamines.
Synthetic route is as follows:
Wherein, R is-H ,-COOCH
3cH
2group, corresponds to the asymmetric rhodamine of above-mentioned two kinds of structures respectively.
Compared with prior art, the present invention can obtain the asymmetric rhodamine fluorescent dyes of a class, and its purity can reach detection and application requiring, have certain stoke shift, fluorescence intensity is high, has good stability, and produce the solvent low price used, required equipment is simple.
Accompanying drawing explanation
Fig. 1 is uv-absorbing and the fluorogram of the asymmetric rhodamine that enforcement 1 prepares.
Fig. 2 is uv-absorbing and the fluorogram of the asymmetric rhodamine that enforcement 2 prepares.
Fig. 3 is process route chart of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
The preparation of asymmetric rhodamine I and purifying:
In the 250ml there-necked flask that magnetic agitation is housed, add N, N-diethyl Metha Amino Phenon 9.9g, Tetra hydro Phthalic anhydride 9.0g, dissolve with 150ml toluene, N
2protection, stir, reflux is stopped reaction after 8 hours, and be cooled to suction filtration after room temperature, filter cake water recrystallization, obtains faint yellow styloid, i.e. ketone acid 11.7g, yield 62.5%.
Ketone acid 3.1g is added, naphthalenediol ethyl formate 4.6g, zinc chloride 1.3g in the 100mL round-bottomed flask that magnetic agitation is housed.120 DEG C of heated and stirred reaction 6h.Dropped in 200ml water by the mixture obtained and separate out precipitation, suction filtration, obtains crude product after filtration cakes torrefaction.
Get dissolving crude product that 3g obtains in the dehydrated alcohol of 100ml, under ice-water bath, instill the vitriol oil of 5ml.Then reflux 24 hours.Rotary evaporation goes out desolventizing, uses methylene dichloride dissolved product, removes catalyzer with a large amount of water washings.The crude product of asymmetric rhodamine I is obtained after concentrated methylene chloride solution.
Take dichloromethane/ethyl acetate as eluent, silica gel is that weighting material separation obtains asymmetric rhodamine I, and be sterling rhodamine I with obtaining yellow rhabdolith after ethyl alcohol recrystallization, its structural formula is:
its uv-absorbing and fluorogram are as shown in Figure 1.
1H NMR(500MHz，CDCl
3)：δ0.87(t，3H)，1.23(t，6H)，3.41-3.46(q，4H)，3.99-4.01(m，2H)，6.43(dd，1H)，6.58(t，3H)，6.88(d，1H)，7.06-7.10(t，1H)，7.35(t，1H)，7.68-7.71(m，2H)，8.30(m，1H)，8.45(d，1H)。
Embodiment 2
The preparation of asymmetric rhodamine II and purifying:
In the 250ml there-necked flask that magnetic agitation is housed, add N, N-diethyl Metha Amino Phenon 9.9g, Tetra hydro Phthalic anhydride 9.0g, dissolve with 150ml toluene, N
2protection, stir, reflux is stopped reaction after 8 hours, and be cooled to suction filtration after room temperature, filter cake water recrystallization, obtains faint yellow styloid, i.e. ketone acid 11.7g, yield 62.5%.
Ketone acid 3.1g is added, naphthalenediol ethyl formate 4.6g, methanesulfonic 10ml in the 100mL round-bottomed flask that magnetic agitation is housed.100 DEG C of heated and stirred reaction 10h.Dropped in 200ml water by the mixture obtained and separate out precipitation, suction filtration, obtains crude product after filtration cakes torrefaction.
Get dissolving crude product that 3g obtains in the dehydrated alcohol of 100ml, under ice-water bath, instill the vitriol oil of 5ml.Then reflux 24 hours.Rotary evaporation goes out desolventizing, uses methylene dichloride dissolved product, removes catalyzer with a large amount of water washings.The crude product of asymmetric rhodamine II is obtained after concentrated methylene chloride solution.
Take dichloromethane/ethyl acetate as eluent, silica gel is that weighting material separation obtains asymmetric rhodamine II, is sterling rhodamine II with obtaining yellow rhabdolith after ethyl alcohol recrystallization.Its structural formula is:
its uv-absorbing and fluorogram are as shown in Figure 2.
1H NMR(500MHz，CDCl
3)：δ0.90(t，3H)，1.21(t，6H)，1.47-1.51(t，3H)，3.40-3.46(q，4H)，3.95-4.10(m，2H)，4.54-4.56(m，2H)，6.45-6.48(dd，1H)，6.54(d，1H)，6.63(d，1H)，6.67(d，1H)，7.07-7.10(m，1H)，7.16-7.18(m，1H)，7.33-7.37(t，1H)，7.67-7.70(m，1H)，8.28-8.32(m，1H)，8.45-8.47(dd，1H)。
Embodiment 3
Prepare a method for asymmetric rhodamine, as shown in Figure 3, the method comprises the following steps in its technical process:
(1) preparation of intermediate ketone acid: get N, the Tetra hydro Phthalic anhydride of N-diethyl Metha Amino Phenon and its equimolar amount, as raw material, utilizes the toluene of 10 times of quality to dissolve, stirs under nitrogen protection condition, reflux 5 hours, after cooling, suction filtration obtains intermediate ketone acid;
(2) preparation of asymmetric rhodamine: get the intermediate ketone acid that step (1) prepares, the naphthalenediol ethyl formate of equimultiple molar weight and catalyzer zinc chloride, the weight ratio of zinc chloride and intermediate ketone acid is 1: 4, be heated to 100 DEG C of reactions 10 hours, the mixture obtained is dropped in the water of 40-80 times of quality and separates out precipitation, suction filtration, obtains crude product after drying;
(3) esterification of asymmetric rhodamine crude product: by the asymmetric rhodamine dissolving crude product that obtains in the ethanolic soln of 20 times of weight, add the catalyzer vitriol oil, the volume ratio of the vitriol oil and ethanolic soln is 1: 10, back flow reaction 10 hours, rotary evaporation removes solvent, use methylene dichloride dissolved product, with a large amount of water washings removing catalyzer, after concentrated methylene chloride solution, obtain the asymmetric rhodamine crude product of esterification.
(4) purifying of asymmetric rhodamine: will obtain asymmetric rhodamine crude product recrystallization after column chromatography of esterification, the solvent of recrystallization is methyl alcohol, obtains the asymmetric rhodamine of sterling.
Embodiment 4
Prepare a method for asymmetric rhodamine, comprise the following steps:
(1) preparation of intermediate ketone acid: get N, the Tetra hydro Phthalic anhydride of N-diethyl Metha Amino Phenon and its 2 times of molar weights, as raw material, utilizes the toluene of 50 times of quality to dissolve, stirs under nitrogen protection condition, reflux 10 hours, after cooling, suction filtration obtains intermediate ketone acid;
(2) preparation of asymmetric rhodamine: get the intermediate ketone acid that step (1) prepares, the naphthalenediol ethyl formate of 3 times of molar weights and catalyzer phosphoric acid, the weight ratio of phosphoric acid and intermediate ketone acid is 2: 3, be heated to 160 DEG C of reactions 2 hours, the mixture obtained is dropped in the water of 80 times of quality and separate out precipitation, suction filtration, obtains crude product after drying;
(3) esterification of asymmetric rhodamine crude product: by the asymmetric rhodamine dissolving crude product that obtains in the ethanolic soln of 50 times of weight, add catalyzer sulfur oxychloride, the volume ratio of sulfur oxychloride and ethanolic soln is 1: 15, back flow reaction 30 hours, rotary evaporation removes solvent, use methylene dichloride dissolved product, with a large amount of water washings removing catalyzer, after concentrated methylene chloride solution, obtain the asymmetric rhodamine crude product of esterification.
(4) purifying of asymmetric rhodamine: will obtain asymmetric rhodamine crude product recrystallization after column chromatography of esterification, the solvent of recrystallization is the mixed solvent of methyl alcohol and propyl alcohol, obtains the asymmetric rhodamine of sterling.
Claims (1)
1. prepare a method for the asymmetric rhodamine of esterification, it is characterized in that, the method comprises the following steps:
(1) preparation of intermediate ketone acid: get N, the Tetra hydro Phthalic anhydride of N-diethyl Metha Amino Phenon and its 1-2 times of molar weight, as raw material, utilizes the toluene of 10-50 times of quality to dissolve, stirs under nitrogen protection condition, reflux 5-10 hour, after cooling, suction filtration obtains intermediate ketone acid;
(2) preparation of asymmetric rhodamine: get the intermediate ketone acid that step (1) prepares, naphthalenediol ethyl formate and catalyzer, the add-on of naphthalenediol ethyl formate is 1-3 times of molar weight of intermediate ketone acid, be heated to 100-160 DEG C of reaction 2-10 hour, the mixture obtained is dropped in the water of 40-80 times of quality and separates out precipitation, suction filtration, obtains crude product after drying;
(3) esterification of asymmetric rhodamine crude product: by the dissolving crude product of asymmetric rhodamine that obtains in the ethanolic soln of 20-50 times of weight, add catalyzer, back flow reaction 10-30 hour, rotary evaporation removes solvent, use methylene dichloride dissolved product, with a large amount of water washings removing catalyzer, after concentrated methylene chloride solution, obtain the asymmetric rhodamine crude product of esterification;
(4) purifying of the asymmetric rhodamine of esterification: the asymmetric rhodamine asymmetric rhodamine crude product recrystallization after column chromatography of the esterification obtained being obtained the esterification of purifying;
Catalyzer described in step (2) is selected from zinc chloride, sulfuric acid, phosphoric acid, phosphorus oxychloride or methanesulfonic, and the weight ratio of catalyzer and intermediate ketone acid is 1 ~ 2 ︰ 3 ~ 4;
Catalyzer described in step (3) is selected from the vitriol oil, sulfur oxychloride or hydrogen chloride gas, and the volume ratio of catalyzer and ethanolic soln is 1 ︰ 10 ~ 20;
The solvent that recrystallization described in step (4) adopts is one or both in methyl alcohol, ethanol, propyl alcohol or ethyl acetate; The structural formula of the asymmetric rhodamine of the esterification of described purifying is:
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| CN109609998B (en) * | 2019-01-22 | 2020-09-22 | 中国药科大学 | Room temperature growth method of rhodamine B lactone single crystal |
| CN113072561A (en) * | 2021-03-29 | 2021-07-06 | 华东理工大学 | Synthesis method of long-wavelength asymmetric rhodamine dye |
| CN113549050B (en) * | 2021-07-13 | 2022-07-05 | 江苏耐雀生物工程技术有限公司 | Small-molecule fluorescent probe and preparation method and application thereof |
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