CN114853793A - Sulfuryl boron fluoride fluorescent dye and preparation method thereof - Google Patents
Sulfuryl boron fluoride fluorescent dye and preparation method thereof Download PDFInfo
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- CN114853793A CN114853793A CN202210366627.3A CN202210366627A CN114853793A CN 114853793 A CN114853793 A CN 114853793A CN 202210366627 A CN202210366627 A CN 202210366627A CN 114853793 A CN114853793 A CN 114853793A
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- C—CHEMISTRY; METALLURGY
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1055—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with other heteroatoms
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Abstract
The invention provides a sulfuryl boron fluoride fluorescent dye and a preparation method thereof, wherein the structural formula of the sulfuryl boron fluoride fluorescent dye is shown as the following formula
The invention introduces sulfonyl group into halogenated alkyl boron fluoride fluorescent molecules through substitution reaction to prepare the bright yellow sulfonyl boron fluoride fluorescent dye.
Description
Technical Field
The invention relates to synthesis of a fluorescent dye, and particularly relates to a boron sulfuryl fluoride fluorescent dye and a preparation method thereof.
Background
The labeling of dyes containing fluorescence in living bodies has been widely used and has become a research hotspot in recent years. The fluoboron fluorescence is an organic compound with high fluorescence quantum yield, the molecule has very high absorption at about 500nm of an ultraviolet spectrum, and the absorption peak of the molecule can be subjected to red shift by expanding the structure of the molecule. As the structure of the fluoboron fluorescence is continuously optimized by extensive researchers, the compound is widely applied to aspects of biological imaging, labeling and the like. However, most of the borofluoride currently has poor fluorescence solubility [ H Kim, KKim, S-H Son, J Y Choi, K-H Lee, B-T Kim, Y Byun, and Y S Choe, chem.Neurosci.2019,10,3, 1445-.
Therefore, in order to solve the above problems, the present invention is intended to provide a boron sulfofluoride fluorescent dye having good solubility and a preparation method thereof.
Disclosure of Invention
In view of this, the invention provides a boron sulfonyl fluoride fluorescent dye and a preparation method thereof, so that the boron sulfonyl fluoride fluorescent dye has good solubility.
The first purpose of the invention is to provide a bright yellow boron sulfuryl fluoride fluorescent dye, which has the following structural formula:
wherein R is one selected from aryl, substituted aryl, heterocyclic aryl and alkyl with 2-5 carbon atoms; y is selected from N, S, O, Z is selected from alkyl with 1-12 carbon atoms and alkyl with 1-12 carbon atoms containing hetero atoms; n is the number of carbon atoms on the alkane branch, and n is 3-9.
The second purpose of the invention is to provide a preparation method of the sulfuryl fluorine boron fluorescent dye, wherein the fluorine boron fluorescent molecule with the structure shown in the formula I and the thiocarboxylate with the structure shown in the formula II are mixed to perform nucleophilic substitution reaction so as to prepare the bright yellow sulfuryl fluorine boron fluorescent dye;
wherein R is one selected from aryl, substituted aryl, heterocyclic aryl and alkyl with 2-5 carbon atoms; y is one selected from N, S, O; n is the number n of carbon atoms on the alkane branched chain which is 3-9; x is halogen;
z is one selected from alkyl with 1-12 carbon atoms and alkyl with 1-12 carbon atoms containing hetero atoms; m is selected from one of sodium, potassium, magnesium and calcium.
Specifically, the feeding molar ratio of the fluorine boron fluorescent molecule to the thiocarboxylate is (0.4-0.6): 1.
Specifically, the reaction temperature of the nucleophilic substitution reaction is 60 to 100 ℃.
Specifically, the time of the nucleophilic substitution reaction is 1-3 h.
Specifically, the nucleophilic substitution reaction also comprises a solvent, wherein the solvent comprises a mixture consisting of one or more of tetrahydrofuran, dichloromethane, chloroform, acetone and DMF.
Preferably, the fluoroboron fluorescent molecule is dissolved in the solvent to obtain a first solution, and the thiocarboxylate salt is added to the first solution to perform a reaction.
Specifically, the preparation method further comprises a post-treatment process, wherein the post-treatment process is to separate by adopting column chromatography to obtain the boron sulfuryl fluoride fluorescent dye.
The invention creatively provides that compared with the prior art, the invention has the following advantages:
according to the invention, the sulfonyl group is introduced into the halogenated alkyl fluoroborate fluorescent molecule through a substitution reaction to prepare the bright yellow sulfonyl fluoroborate fluorescent dye with good solubility, so that the problem of poor solubility of the fluoroborate fluorescent dye in the prior art is solved, and the application range of the fluoroborate fluorescent dye is expanded.
Drawings
FIG. 1 shows the hydrogen spectrum of the boron sulfofluoride fluorescent dye prepared in example 1 of the present invention;
FIG. 2 is a carbon spectrum of a boron sulfofluoride fluorescent dye prepared in inventive example 1;
FIG. 3 is a mass spectrum of the boron sulfofluoride fluorescent dye prepared in inventive example 1.
Detailed Description
In order to solve the problem of poor solubility of the fluoroboric fluorescent dye in the prior art, the invention provides a sulfuryl fluoroboric fluorescent dye and a preparation method and application thereof.
The invention provides a sulfuryl fluoride boron fluorescent dye, which has a structural formula P as follows:
wherein R is one selected from aryl, substituted aryl, heterocyclic aryl and alkyl with 2-5 carbon atoms; y is selected from N, S, O, Z is selected from alkyl with 1-12 carbon atoms and alkyl with 1-12 carbon atoms containing hetero atoms; n is the number of carbon atoms on the alkane branch, and n is 3-9.
The invention also provides a preparation method of the sulfuryl fluoroboron fluorescent dye, which comprises the steps of carrying out nucleophilic substitution reaction on the fluoroboron fluorescent molecule with the structure shown in the formula I, thiocarboxylate and a solvent (a mixture consisting of one or more of tetrahydrofuran, dichloromethane, trichloromethane, acetone and DMF), wherein the reaction temperature is 60-100 ℃, and the reaction time is 1-3h, so as to prepare the sulfuryl fluoroboron fluorescent dye;
wherein R is one selected from aryl, substituted aryl, heterocyclic aryl and alkyl with 2-5 carbon atoms; y is one selected from N, S, O; n is the number n of carbon atoms on the alkane branched chain which is 3-9; x is halogen;
z is one selected from alkyl with 1-12 carbon atoms and alkyl with 1-12 carbon atoms containing hetero atoms; m is selected from one of sodium, potassium, magnesium and calcium.
The feeding molar ratio of the fluoboron fluorescent molecules to the thiocarboxylates is (0.4-0.6): 1.
In the present invention, in order to make the reaction proceed smoothly, the fluoroboric acid is dissolved in the solvent to obtain the first solution, and the thiocarboxylate is added to the first solution to perform the reaction.
The preparation method also comprises a post-treatment process, wherein the post-treatment process is to separate by adopting column chromatography to obtain the sulfuryl boron fluoride fluorescent dye.
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not mentioned are conventional conditions in the industry.
Example 1
1. This example provides a bright yellow sulfuryl boron fluoride fluorescent dye, which has the following structural formula:
2. the embodiment also provides a preparation method of the sulfuryl fluoride boron fluorescent dye, which comprises the following steps:
weighing 50mg of fluoroboric fluorescent molecule
And 2mL of tetrahydrofuran, adding 20mg of potassium thioacetate, reacting at 80 ℃ for 2 hours, and detecting the reaction progress by Thin Layer Chromatography (TLC). After the reaction is finished, purifying and separating by using a column chromatography chromatographic column, separating a product by using a eluent which is a mixed solution of petroleum ether and dichloromethane in a volume ratio of 4:1, drying after spinning to obtain a yellow solid 32.5mg, namely, a bright yellow sulfuryl boron fluoride fluorescent dye with a yield of 72%.
The boron sulfonyl fluoride fluorescent dye was characterized as follows:
1 H NMR(400MHz,CDCl 3 )δ7.16(d,J＝8Hz,2H),7.00(d,J＝8Hz,2H),5.99(s,2H),4.01(t,J＝4Hz,2H),2.92(t,J＝4Hz,2H),2.56(s,6H),2.34(s,3H),1.84(t,J＝6Hz,2H),1.64(t,J＝8Hz,2H),1.51(m,4H),1.44(s,6H)。
13 C NMR(100MHz,CDCl 3 )δ196.06,159.62,155.19,143.19,141.97,131.86,129.14,126.84,121.09,115.04,67.91,30.68,29.48,29.10,29.00,28.57,25.62,14.61。
MS: molecular formula C 27 H 33 BF 2 N 2 O 2 S, the calculated value is as follows: 498.4, test values are: 498.2316.
example 2
1. This example provides a sulfuryl fluoride boron fluorescent dye, which has the following structural formula:
2. this example also provides a preparation method of the borofluoride sulfuryl fluorescent dye, which is substantially the same as that in example 1, except that the molecular structural formula of the borofluoride fluorescent dye is as follows
The thiocarboxylate salt was sodium thioacetate with a yield of 70%.
Example 3
1. This example provides a sulfuryl fluoride boron fluorescent dye, which has the following structural formula: .
2. This example also provides a preparation method of a borofluoride sulfoamide fluorescent dye, which is substantially the same as example 1, except that the structural formula of the borofluoride fluorescent molecule is shown in the specification
The thiocarboxylate salt was potassium thioacetate with a yield of 75%.
Comparative example 1
This comparative example provides a sulfoborofluoride fluorescent dye and a preparation method thereof, which are substantially the same as example 1 except that potassium thioacetate was added in an amount of 2mg in a yield of 18%.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (7)
1. The sulfoacyl borofluoride fluorescent dye is characterized in that the structural formula of the sulfoacyl borofluoride fluorescent dye is as follows:
wherein R is one selected from aryl, substituted aryl, heterocyclic aryl and alkyl with 2-5 carbon atoms; y is selected from N, S, O, Z is selected from alkyl with 1-12 carbon atoms and alkyl with 1-12 carbon atoms containing hetero atoms; n is the number of carbon atoms on the alkane branch, and n is 3-9.
2. The preparation method of the sulfuryl boron fluoride fluorescent dye according to claim 1, characterized in that the fluoroboron fluorescent molecule with the structure shown in the formula I and the thiocarboxylate with the structure shown in the formula II are mixed for nucleophilic substitution reaction to prepare the bright yellow sulfuryl boron fluoride fluorescent dye;
wherein R is one selected from aryl, substituted aryl, heterocyclic aryl and alkyl with 2-5 carbon atoms; y is one selected from N, S, O; n is the number n of carbon atoms on the alkane branched chain which is 3-9; x is halogen;
z is one selected from alkyl with 1-12 carbon atoms and alkyl with 1-12 carbon atoms containing hetero atoms; m is selected from one of sodium, potassium, magnesium and calcium.
3. The method of claim 2, wherein: the feeding molar ratio of the fluoboron fluorescent molecules to the thiocarboxylates is (0.4-0.6): 1.
4. The method of claim 2, wherein: the reaction temperature of the nucleophilic substitution reaction is 60-100 ℃.
5. The method of claim 2, wherein: the time of the nucleophilic substitution reaction is 1-3 h.
6. The method of claim 2, wherein: the nucleophilic substitution reaction also comprises a solvent, wherein the solvent comprises a mixture composed of one or more of tetrahydrofuran, dichloromethane, trichloromethane, acetone and DMF.
7. The method of claim 2, wherein: the preparation method also comprises a post-treatment process, wherein the post-treatment process is to separate by adopting column chromatography to obtain the sulfuryl fluoride boron fluorescent dye.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002025635A (en) * | 2000-07-05 | 2002-01-25 | Japan Science & Technology Corp | Light energy-electric energy conversion system with antenna compound and charge separation type compound accumulated on electrode as mixed self-organized monomolecular film |
| CN109503640A (en) * | 2018-12-27 | 2019-03-22 | 安徽师范大学 | α-sulphur replaces fluorine boron fluorescent dye and its preparation method and application |
| CN110511236A (en) * | 2019-08-01 | 2019-11-29 | 广东工业大学 | A kind of fluorine boron pyrroles's photosensitizer and its preparation method and application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002025635A (en) * | 2000-07-05 | 2002-01-25 | Japan Science & Technology Corp | Light energy-electric energy conversion system with antenna compound and charge separation type compound accumulated on electrode as mixed self-organized monomolecular film |
| CN109503640A (en) * | 2018-12-27 | 2019-03-22 | 安徽师范大学 | α-sulphur replaces fluorine boron fluorescent dye and its preparation method and application |
| CN110511236A (en) * | 2019-08-01 | 2019-11-29 | 广东工业大学 | A kind of fluorine boron pyrroles's photosensitizer and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| HIROSHI IMAHORI等: ""Light-Harvesting and Photocurrent Generation by Gold Electrodes Modified with Mixed Self-Assembled Monolayers of Boron-Dipyrrin and Ferrocene-Porphyrin-Fullerene Triad"", 《J. AM. CHEM. SOC.》, vol. 123, pages 100 - 110 * |
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