CN109503640A - α-sulphur replaces fluorine boron fluorescent dye and its preparation method and application - Google Patents
α-sulphur replaces fluorine boron fluorescent dye and its preparation method and application Download PDFInfo
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- CN109503640A CN109503640A CN201811608567.1A CN201811608567A CN109503640A CN 109503640 A CN109503640 A CN 109503640A CN 201811608567 A CN201811608567 A CN 201811608567A CN 109503640 A CN109503640 A CN 109503640A
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- fluorescent dye
- fluorine boron
- phenyl
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- boron fluorescent
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 65
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical compound [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000005864 Sulphur Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 14
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 14
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 14
- 239000003550 marker Substances 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 28
- -1 2,4,6- trimethylphenyl Chemical group 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 150000002978 peroxides Chemical class 0.000 claims description 10
- 239000000975 dye Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 10
- 238000006862 quantum yield reaction Methods 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000006467 substitution reaction Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 48
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 16
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- 238000004440 column chromatography Methods 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 238000005259 measurement Methods 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000007867 post-reaction treatment Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000013558 reference substance Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WLHCBQAPPJAULW-UHFFFAOYSA-N 4-methylbenzenethiol Chemical class CC1=CC=C(S)C=C1 WLHCBQAPPJAULW-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- CMKBCTPCXZNQKX-UHFFFAOYSA-N cyclohexanethiol Chemical class SC1CCCCC1 CMKBCTPCXZNQKX-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- BFMYDTVEBKDAKJ-UHFFFAOYSA-L disodium;(2',7'-dibromo-3',6'-dioxido-3-oxospiro[2-benzofuran-1,9'-xanthene]-4'-yl)mercury;hydrate Chemical class O.[Na+].[Na+].O1C(=O)C2=CC=CC=C2C21C1=CC(Br)=C([O-])C([Hg])=C1OC1=C2C=C(Br)C([O-])=C1 BFMYDTVEBKDAKJ-UHFFFAOYSA-L 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical class CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical class CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical class OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
Abstract
The invention discloses a kind of α-sulphur to replace fluorine boron fluorescent dye and its preparation method and application, and the α-sulphur replaces the structure of fluorine boron fluorescent dye shown in formula I, wherein R1For the aliphatic group of C1-C10, the substituted fatty hydrocarbon base of C1-C10, the aryl of C6-C12 or the substituted arene base of C6-C12, R2For the aliphatic group of C1-C15, the substituted fatty hydrocarbon base of C1-C15, the aryl of C6-C12 or the substituted arene base of C6-C12.The α-sulphur replaces fluorine boron fluorescent dye to have excellent fluorescence quantum yield, dissolubility and stability, preparation method has the advantages that step is simple, raw material is easy to get simultaneously, so that the α-sulphur substitution fluorine boron fluorescent dye can be in the extensive use in fluorescent marker；
Description
Technical field
The present invention relates to fluorine boron fluorescent dyes, and in particular, to a kind of α-sulphur replaces fluorine boron fluorescent dye and its preparation side
Method.
Background technique
Two pyrroles's fluorescent dye (BODIPY) of fluorine boron is a kind of optical physics chemical property just to grow up for nearly twenties years
There is excellent luminescent dye molecule narrow absorption peak and emission peak, higher molar absorption coefficient, higher fluorescent quantum to produce
Rate, preferable photostability and chemical stability.But traditional Novel BODIPY flourescent dye above has certain defect in application,
For example their Stokes (Stokes) is displaced smaller, easy fluorescent quenching, dissolubility difference etc..
Therefore, it wants in the method for synthesizing new BODIPY fluorochrome analog or step is many and diverse in the prior art
Raw material is not easy to obtain, needs multistep synthesis and low yield.
Summary of the invention
The object of the present invention is to provide a kind of α-sulphur to replace fluorine boron fluorescent dye and its preparation method and application, which takes
There is excellent fluorescence quantum yield, dissolubility and stability for fluorine boron fluorescent dye, while the preparation method has step letter
The advantages of single, raw material is easy to get.
To achieve the goals above, the present invention provides a kind of α-sulphur to replace fluorine boron fluorescent dye, and the α-sulphur replaces fluorine boron
The structure of fluorescent dye is shown in formula I,
Wherein, R1For the aliphatic group of C1-C10, the substituted fatty hydrocarbon base of C1-C10, C6-C12 aryl or C6-C12
Substituted arene base, R2For the aliphatic group of C1-C15, the substituted fatty hydrocarbon base of C1-C15, C6-C12 aryl or C6-C12
Substituted arene base.
The present invention also provides the preparation method that a kind of above-mentioned α-sulphur replaces fluorine boron fluorescent dye, should the preparation method comprises the following steps:
Fluorine boron fluorescent dye, the mercaptan compound of the structure as shown in formula III, the peroxide of the structure as shown in Formula II contact anti-
Fluorine boron fluorescent dye should be replaced so that the α-sulphur is made,
Wherein, R1For the aliphatic group of C1-C10, the substituted fatty hydrocarbon base of C1-C10, C6-C12 aryl or C6-C12
Substituted arene base, R2For the aliphatic group of C1-C15, the substituted fatty hydrocarbon base of C1-C15, C6-C12 aryl or C6-C12
Substituted arene base.
Invention further provides a kind of above-mentioned α-sulphur to replace application of the Novel BODIPY flourescent dye in fluorescent marker.
In the above-mentioned technical solutions, α produced by the present invention-sulphur replaces the maximum emission wavelength of fluorine boron fluorescent dye to exist
Between 514-545nm, there is excellent fluorescence quantum yield, excellent dissolubility and excellent stability, on fluorescent marker
There is potential be widely applied；And synthesize α-sulphur by this method and replace Novel BODIPY flourescent dye easier, because former
Replace Novel BODIPY flourescent dye first must carry out halogenation to BODIPY to α-sulphur, is then obtained in alkaline environment by nucleophilic displacement of fluorine
It arrives.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the top view for the crystallogram that α-sulphur replaces fluorine boron fluorescent dye B1；
Fig. 2 is the front view for the crystallogram that α-sulphur replaces fluorine boron fluorescent dye B1.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of α-sulphur to replace fluorine boron fluorescent dye, and the α-sulphur replaces the structure such as formula of fluorine boron fluorescent dye
Shown in I,
Wherein, R1For the aliphatic group of C1-C10, the substituted fatty hydrocarbon base of C1-C10, C6-C12 aryl or C6-C12
Substituted arene base, R2For the aliphatic group of C1-C15, the substituted fatty hydrocarbon base of C1-C15, C6-C12 aryl or C6-C12
Substituted arene base.
In above formula, the specific type of substituent group can select in a wide range, it is contemplated that the source of raw material
It is difficult to the yield of degree and synthesis, it is preferable that R1For the straight chained alkyl of C1-C4, phenyl, C6-C10 alkyl-substituted phenyl,
The halogen substituted phenyl of the alkoxy substituted phenyl of C6-C10, C6-C10, R2For the acyclic alkyl of C1-C12, the hydroxyl of C1-C4
Replace the alkyl-substituted phenyl of alkyl, the phenyl substituted alkyl of C7-C12, the naphthenic base of C3-C6, phenyl, C7-C10；More preferably
Ground, R1For methyl, ethyl, propyl, 2,4,6- trimethylphenyl, phenyl, 2,3,4,5,6- pentafluorophenyl group, 2,6- dichlorophenyl
Or p-methoxyphenyl, R2For n-propyl, isopropyl, tert-butyl, cyclohexyl, benzyl, dodecyl, 2- hydroxyethyl,
P-methylphenyl.
On the basis of above-mentioned many embodiments, in conjunction with reality, it is preferable that the α-sulphur replaces fluorine boron fluorescent dye
Structure as shown in formula B1-B12,
The present invention also provides the preparation method that a kind of above-mentioned α-sulphur replaces fluorine boron fluorescent dye, should the preparation method comprises the following steps:
Fluorine boron fluorescent dye, the mercaptan compound of the structure as shown in formula III, the peroxide of the structure as shown in Formula II contact anti-
Fluorine boron fluorescent dye should be replaced so that the α-sulphur is made,
Wherein, R1For the aliphatic group of C1-C10, the substituted fatty hydrocarbon base of C1-C10, C6-C12 aryl or C6-C12
Substituted arene base, R2For the aliphatic group of C1-C15, the substituted fatty hydrocarbon base of C1-C15, C6-C12 aryl or C6-C12
Substituted arene base.
In above formula, the specific type of substituent group can select in a wide range, it is contemplated that the source of raw material
It is difficult to the yield of degree and synthesis, it is preferable that R1For the straight chained alkyl of C1-C4, phenyl, C6-C10 alkyl-substituted phenyl,
The halogen substituted phenyl of the alkoxy substituted phenyl of C6-C10, C6-C10, R2For the acyclic alkyl of C1-C12, the hydroxyl of C1-C4
Replace the alkyl-substituted phenyl of alkyl, the phenyl substituted alkyl of C7-C12, the naphthenic base of C3-C6, phenyl, C7-C10；More preferably
Ground, R1For methyl, ethyl, propyl, 2,4,6- trimethylphenyl, phenyl, 2,3,4,5,6- pentafluorophenyl group, 2,6- dichlorophenyl
Or p-methoxyphenyl, R2For n-propyl, isopropyl, tert-butyl, cyclohexyl, benzyl, dodecyl, 2- hydroxyethyl,
P-methylphenyl.
In the above preparation method, the dosage of each material can select in a wide range, but in order to further increase
α obtained-sulphur replaces the yield of fluorine boron fluorescent dye, it is preferable that the fluorine boron fluorescent dye of structure shown in the Formula II, peroxidating
Object, mercaptan mole ratio be 0.2:0.2-0.5:0.2-0.3；It is highly preferred that the fluorine boron fluorescence of structure shown in the Formula II contaminates
Material, peroxide, mercaptan mole ratio be 0.2:0.3-0.4:0.2-0.25.
In the above preparation method, catalytic condition can select in a wide range, but in order to further mention
α made from height-sulphur replaces the yield of fluorine boron fluorescent dye, it is preferable that the haptoreaction meets the following conditions: reaction temperature is
40-80 DEG C, reaction time 3-6h.
In the above preparation method, the type of peroxide can select in a wide range, but in order to further mention
α made from height-sulphur replaces the yield of fluorine boron fluorescent dye, it is preferable that peroxide is selected from perbenzoic acid tert-butyl, peroxide
Change at least one of hydrogen, tert-butyl hydroperoxide.
On the basis of the above embodiment, excellent in order to enable each material can be sufficiently carried out contact and react
Selection of land, the preparation method carry out in organic solvent, and the organic solvent is selected from dimethyl sulfoxide, acetonitrile, methylene chloride, first
At least one of benzene, tetrahydrofuran.Wherein, the dosage of organic solvent can also select in a wide range, but in order into
One step improves the yield that α-sulphur obtained replaces fluorine boron fluorescent dye, it is highly preferred that the fluorine boron fluorescence of structure shown in the Formula II
Dyestuff, organic solvent amount ratio be 0.2mmol:2-5mL.
Invention further provides a kind of above-mentioned α-sulphur to replace application of the Novel BODIPY flourescent dye in fluorescent marker.
The present invention will be described in detail by way of examples below.Nuclear-magnetism measurement uses the AV- of Switzerland Bruker company
500 type Nuclear Magnetic Resonance carry out；Mass spectrographic measurement is carried out using the HPLC/ESI-MS type mass spectrograph of U.S.'s Instruments Group；It is ultraviolet
The measurement of spectrum using Japanese Shimadzu Corporation UV-2450 type it is ultraviolet/visible spectrophotometer carries out, the measurement day of fluorescence spectrum
The F-4500FL sepectrophotofluorometer of this Hitachi, Ltd carries out, and the measurement of relative fluorescence quantum yield uses the survey of fluorescence spectrum
The F-4500FL sepectrophotofluorometer for determining Hitachi, Japan carries out, and the measurement of single crystal diffraction is public using Germany Bruker AXS
The II X- single crystal diffractometer of SMAR APEX of department carries out, wherein λmaxIndicate maximum absorption wavelength, εabsIndicate molar extinction coefficient,
λem maxIndicate maximum emission wavelength, ΦFIndicate that relative fluorescence quantum yield and Stokes-shift indicate Stokes displacement；
Relative fluorescence quantum yield (ΦF) measurement be with wherein relative fluorescence quantum yield ΦFMeasurement with fluorescein (Φ=0.90,
In 0.1mol/L sodium hydroxide solution) it is standard dyes, according to formula ΦF=ΦS*(IX/IS)*(AS/AX)*(nX/nS)2Meter
Gained is calculated, wherein ΦSFor the fluorescence quantum yield of reference substance CV, I is spectrogram integral area, and A is absorbance, and n is the folding of solvent
Light rate, subscript S are reference substance, and X is determinand.
Raw material used in the following embodiment: dimethyl sulfoxide is the product of Sinopharm Chemical Reagent Co., Ltd., mercaptan
It is the product of Suzhou Su Kai Lu Co., Ltd.；Fluorine boron fluorescent dye BODIPY is one in the compound of structure shown in formula A1-A5
Kind, bibliography (a) Loudet, A.；Burgess,K.Chem.Rev.2007,107,4891.(b)Ziessel,R.；
Ulrich,G.；Harriman,A.New J.Chem.2007,31,496.(c)Ulrich,G.；Ziessel,R.；Harriman,
A.Angew.Chem.,Int.Ed.2008,47,1184.(d)Lu,H.；Mack,J.；Yang,Y.；Shen,
Z.Chem.Soc.Rev.2014,43,4778.(e)Ni,Y.；Wu,J.Org.Biomol.Chem.2014,12,3774.(f)Ge,
Y.；O'Shea,D.F.Chem.Soc.Rev.2016,45,3846.
Embodiment 1
α shown in formula B1-sulphur replaces the preparation of fluorine boron fluorescent dye:
Fluorine boron fluorescent dye BODIPY A1 (0.2mmol) is added in Shrek reaction flask, 20 microlitres of rosickyite are then added
Alcohol (0.2mmol), 77 microlitres of peroxidized t-butyl perbenzoates (0.4mmol), 2mL dimethyl sulfoxides, heat in 60 DEG C of oil baths and stir
It mixes, TLC tracks contact plate, fully reacting after about 4h.Reaction solution is poured into 30mL water, methylene chloride extracts three times (3 × 30mL),
Merge organic phase, anhydrous sodium sulfate is dry, and Rotary Evaporators are spin-dried for solvent.Methylene chloride and petroleum ether make mobile phase, pass through column
Chromatography obtains red solid B1 (yield 73%).
Characterize data is as follows:1H NMR (500MHz, CDCl3) δ 7.70 (s, 1H), 6.93 (s, 2H), 6.66 (d, J=
4.5Hz, 1H), 6.45 (d, J=3.8Hz, 1H), 6.41 (d, J=4.5Hz, 1H), 6.38-6.37 (m, 1H), 3.09 (t, J=
7.3Hz, 2H), 2.35 (s, 3H), 2.09 (s, 6H), 1.89-1.82 (m, 2H), 1.11 (t, J=7.4Hz, 3H)13C NMR
(126MHz,CDCl3)δ162.01,140.81,139.66,138.48,137.18,136.68,133.97,131.08,
129.80,128.07,126.04,117.47,116.69,34.54,22.56,21.10,19.94,13.42.HRMS
calcd.for C21H23BF2N2S,[M-F]+:365.1659,found:365.1654.
Single crystal diffraction figure is as shown in Figs. 1-2, in order to more clearly from see that structure, H atom are erased.
Embodiment 2
α shown in formula B2-sulphur replaces the preparation of fluorine boron fluorescent dye:
It carries out according to the method for embodiment 1, except that 22 microlitres of isopropyl mercaptans (0.2mmol) are added.After reaction
Reason makees mobile phase with embodiment 1, methylene chloride and petroleum ether, obtains red solid B2 (yield 70%) by column chromatography for separation.
Characterize data is as follows:1H NMR(500MHz,CDCl3) δ 7.70 (s, 1H), 6.94 (s, 2H), 6.67 (d, J=
4.5Hz, 1H), 6.45 (d, J=4.3Hz, 2H), 6.38-6.36 (m, 1H), 3.71-3.62 (m, 1H), 2.35 (s, 3H), 2.10
(s, 6H), 1.52 (d, J=6.8Hz, 6H)13C NMR(126MHz,CDCl3)δ161.48,140.89,139.76,138.52,
137.01,136.74,134.03,131.15,129.88,128.11,126.07,117.95,116.71,37.71,23.59,
21.13,19.99.HRMS calcd.For C21H23BF2N2S,[M-F]+:365.1659,found:365.1651.
Embodiment 3
α shown in formula B3-sulphur replaces the preparation of fluorine boron fluorescent dye:
It carries out according to the method for embodiment 1, except that 24 microlitres of tert-butyl mercaptans (0.2mmol) are added.After reaction
Processing is with embodiment 1: methylene chloride and petroleum ether make mobile phase, obtain red solid B3 (yield by column chromatography for separation
66%).
Characterize data is as follows:1H NMR(500MHz,CDCl3) δ 7.76 (s, 1H), 6.94 (s, 2H), 6.65 (d, J=
4.4Hz, 1H), 6.61 (d, J=4.4Hz, 1H), 6.50 (d, J=3.8Hz, 1H), 6.40-6.39 (m, 1H), 2.36 (s, 3H),
2.10(s,6H),1.60(s,9H).13C NMR(126MHz,CDCl3)δ158.70,142.56,141.64,138.97,
137.04,136.78,134.77,130.75,130.23,128.49,127.45,121.83,117.73,49.34,32.00,
21.50,20.38.HRMS calcd.For C22H25BF2N2S,[M-F]+:379.1816,found:379.1818.
Embodiment 4
α shown in formula B4-sulphur replaces the preparation of fluorine boron fluorescent dye:
It carries out according to the method for embodiment 1, except that 20 microlitres of cyclohexanethiols (0.2mmol) are added.After reaction
Processing is with embodiment 1: methylene chloride and petroleum ether make mobile phase, obtain red solid B4 (yield by column chromatography for separation
68%).
Characterize data is as follows:1H NMR(500MHz,CDCl3) δ 7.69 (s, 1H), 6.93 (s, 2H), 6.65 (d, J=
4.5Hz, 1H), 6.43 (d, J=4.5Hz, 2H), 6.37-6.36 (m, 1H), 3.47-3,41 (m, 1H), 2.35 (s, 3H),
2.17–2.14(m,2H),2.09(s,6H),1.88–1.84(m,2H),1.69–1.62(m,3H),1.47–1.33(m,3H).13C
NMR(126MHz,CDCl3)δ161.69,140.52,139.46,138.47,137.05,136.73,133.92,131.11,
129.88,128.09,125.81,117.95,116.56,45.78,33.51,25.74,25.40,21.13,19.99.HRMS
calcd.For C24H27BF2N2S,[M-F]+:405.1972,found:405.1976.
Embodiment 5
α shown in formula B5-sulphur replaces the preparation of fluorine boron fluorescent dye:
It carries out according to the method for embodiment 1, except that 20 microlitres of benzyl mercaptan (0.2mmol) are added.After reaction
Reason is with embodiment 1: methylene chloride and petroleum ether make mobile phase, obtain red solid B5 (yield 66%) by column chromatography for separation.
Characterize data is as follows:1H NMR(500MHz,CDCl3)δ7.72(s,1H),7.46–7.44(m,2H),7.37–7.34
(m, 2H), 7.32-7.30 (m, 1H), 6.93 (s, 1H), 6.62 (d, J=4.5Hz, 1H), 6.48 (d, J=3.8Hz, 1H),
6.41 (d, J=4.5Hz, 1H), 6.39-6.38 (m, 1H), 4.35 (s, 2H), 2.34 (s, 3H), 2.08 (s, 6H)13C NMR
(126MHz,CDCl3)δ160.57,141.60,140.63,140.37,138.55,136.63,134.91,134.20,
130.99,129.72,128.90,128.87,128.08,127.95,126.64,117.88,117.02,37.22,21.09,
19.94.HRMS calcd.For C25H23BF2N2S,[M-F]+:413.1659,found:413.1658.
Embodiment 6
α shown in formula B6-sulphur replaces the preparation of fluorine boron fluorescent dye:
It carries out according to the method for embodiment 1, except that 47 microlitres of dodecyl mercaptan carbons (0.2mmol) are added.Reaction
Post-processing is with embodiment 1: methylene chloride and petroleum ether make mobile phase, obtain red solid B6 (yield by column chromatography for separation
65%).
Characterize data is as follows:1H NMR(500MHz,CDCl3) δ 7.70 (s, 1H), 6.93 (s, 2H), 6.66 (d, J=
4.5Hz, 1H), 6.45 (d, J=3.8Hz, 1H), 6.41 (d, J=4.5Hz, 1H), 6.38-6.36 (m, 1H), 3.10 (t, J=
7.4Hz,2H),2.35(s,3H),2.09(s,6H),1.83–1.81(m,2H),1.52–1.45(m,2H),1.37–1.26(m,
16H), 0.88 (t, J=6.9Hz, 3H)13C NMR(126MHz,CDCl3)δ162.17,140.82,139.67,138.52,
137.22,136.73,134.02,131.11,129.87,128.11,126.04,117.50,116.69,32.69,31.92,
31.45,29.71,29.63,29.56,29.44,29.34,29.11,28.84,22.69,21.12,19.97,14.11.HRMS
calcd.For C30H41BF2N2S,[M-F]+:491.3068,found:491.3068.
Embodiment 7
α shown in formula B7-sulphur replaces the preparation of fluorine boron fluorescent dye:
It carries out according to the method for embodiment 1, except that 22 microlitres of 2- hydroxyl ethyl mercaptans (0.2mmol) are added.Reaction
Post-processing is with embodiment 1: methylene chloride and petroleum ether make mobile phase, obtain red solid B7 (yield by column chromatography for separation
60%).
Characterize data is as follows:1H NMR(500MHz,CDCl3) δ 7.75 (s, 1H), 6.94 (s, 2H), 6.67 (d, J=
4.4Hz, 1H), 6.51 (d, J=3.8Hz, 1H), 6.48 (d, J=4.5Hz, 1H), 6.41-6.40 (m, 1H), 3.94 (t, J=
5.9Hz, 2H), 3.30 (t, J=6.0Hz, 2H), 2.35 (s, 3H), 2.09 (s, 6H)13C NMR(126MHz,CDCl3)δ
159.59,141.66,141.33,139.06,137.45,137.01,134.75,131.33,128.53,128.43,127.54,
118.54,117.70,61.47,36.43,21.50,20.35.HRMS calcd.For C20H21BF2N2OS,[M-2F-H]+:
347.1389,found:347.1388.
Embodiment 8
α shown in formula B8-sulphur replaces the preparation of fluorine boron fluorescent dye:
It carries out according to the method for embodiment 1, except that 24 milligrams of 4- methylbenzenethiols (0.2mmol) are added.Reaction
Post-processing is with embodiment 1: methylene chloride and petroleum ether make mobile phase, obtain red solid B8 (yield by column chromatography for separation
56%).
Characterize data is as follows:
1H NMR(500MHz,CDCl3) δ 7.74 (s, 1H), 7.58 (d, J=8.0Hz, 2H), 7.26 (d, J=8.0Hz,
2H), 6.92 (s, 2H), 6.49 (d, J=4.5Hz, 1H), 6.46 (d, J=3.9Hz, 1H), 6.39-6.38 (m, 1H), 5.79
(d, J=4.5Hz, 1H), 2.41 (s, 3H), 2.33 (s, 3H), 2.09 (s, 6H)13C NMR(126MHz,CDCl3)δ163.05,
141.35,140.70,139.65,138.48,137.53,136.64,135.38,133.99,130.60,130.54,129.75,
128.06,126.11,125.08,119.14,116.67,21.33,21.08,19.93.HRMS calcd.For
C25H23BF2N2S,[M-F]+:413.1659,found:413.1662.
Embodiment 9
α shown in formula B9-sulphur replaces the preparation of fluorine boron fluorescent dye:
It carries out according to the method for embodiment 1, except that fluorine boron fluorescent dye BODIPY A1 changes fluorine boron fluorescent dye into
BODIPY A2(0.2mmol).Post-reaction treatment is with embodiment 1: methylene chloride and petroleum ether make mobile phase, pass through column chromatography point
From obtaining red solid B9 (yield 61%).
Characterize data is as follows:1H NMR(500MHz,CDCl3)δ7.74(s,1H),7.53–7.49(m,5H),6.93(d,J
=4.4Hz, 1H), 6.71 (d, J=3.1Hz, 1H), 6.49 (d, J=4.5Hz, 1H), 6.45 (s, 1H), 3.10 (t, J=
7.3Hz, 2H), 1.89-1.82 (m, 2H), 1.11 (t, J=7.4Hz, 3H)13C NMR(126MHz,CDCl3)δ162.56,
141.49,140.06,137.26,134.37,134.22,132.91,130.79,130.51,128.73,127.81,117.99,
117.15,34.99,22.98,13.83.HRMS calcd.For C18H17BF2N2S,[M-F]+:323.1190,found:
323.1194.
Embodiment 10
α shown in formula B10-sulphur replaces the preparation of fluorine boron fluorescent dye:
It carries out according to the method for embodiment 1, except that fluorine boron fluorescent dye BODIPY A1 changes fluorine boron fluorescent dye into
BODIPY A3(0.2mmol).Post-reaction treatment is with embodiment 1: methylene chloride and petroleum ether make mobile phase, pass through column chromatography point
From obtaining red solid B10 (yield 72%).
Characterize data is as follows:1H NMR(500MHz,CDCl3) δ 7.74 (s, 1H), 6.79 (d, J=4.6Hz, 1H), 6.56
(d, J=5.2Hz, 1H), 6.54 (s, 1H), 6.46-6.45 (m, 1H), 3.13 (t, J=7.3Hz, 2H), 1.91-1.83 (m,
2H), 1.12 (t, J=7.3Hz, 3H)13C NMR(126MHz,CDCl3)δ166.38,159.25,149.80,146.12,
141.50,141.35,137.59,133.48,131.42,126.10,122.81,119.40,117.88,35.15,23.01,
13.73.HRMS calcd.For C18H12BF7N2S,[M-F]+:413.0718,found:413.0719.
Embodiment 11
α shown in formula B11-sulphur replaces the preparation of fluorine boron fluorescent dye:
It carries out according to the method for embodiment 1, except that fluorine boron fluorescent dye BODIPY A1 changes fluorine boron fluorescent dye into
BODIPY A4(0.2mmol).Post-reaction treatment is with embodiment 1: methylene chloride and petroleum ether make mobile phase, pass through column chromatography point
From obtaining red solid B11 (yield 68%).
Characterize data is as follows:1H NMR(500MHz,CDCl3)δ7.72(s,1H),7.46–7.45(m,2H),7.40–7.37
(m, 1H), 6.68 (d, J=4.6Hz, 1H), 6.47 (d, J=4.7Hz, 1H), 6.46 (s, 1H), 6.41-6.40 (m, 1H),
3.11 (t, J=7.3Hz, 2H), 1.90-1.83 (m, 2H), 1.11 (t, J=7.4Hz, 3H)13C NMR(126MHz,CDCl3)δ
164.36,140.65,137.25,135.99,134.48,133.53,131.99,131.34,131.24,128.56,125.88,
118.58,117.39,35.04,22.97,13.81.HRMS calcd.For C18H15BCl2F2N2S,[M-F]+:391.1410,
found:391.1409.
Embodiment 12
α shown in formula B12-sulphur replaces the preparation of fluorine boron fluorescent dye:
It carries out according to the method for embodiment 1, except that fluorine boron fluorescent dye BODIPY A1 changes fluorine boron fluorescent dye into
BODIPY A5(0.2mmol).Post-reaction treatment is with embodiment 1: methylene chloride and petroleum ether make mobile phase, pass through column chromatography point
From obtaining red solid B12 (yield 62%).
Characterize data is as follows:
1H NMR(500MHz,CDCl3) δ 7.72 (s, 1H), 7.47 (d, J=8.7Hz, 2H), 7.01 (d, J=8.7Hz,
2H), 6.96 (d, J=4.5Hz, 1H), 6.75 (d, J=3.7Hz, 1H), 6.48 (d, J=4.5Hz, 1H), 6.46-6.45 (m,
1H), 3.89 (s, 3H), 3.09 (t, J=7.3Hz, 2H), 189-1.81 (m, 2H), 1.11 (t, J=7.4Hz, 3H)13C NMR
(126MHz,CDCl3)δ161.85,161.66,141.65,139.68,137.18,134.23 132.71,132.46,
127.68,126.82,117.77,116.98,114.31,55.86,35.01,22.98,13.82.HRMS calcd.For
C19H19BF2N2OS,[M-F]+:353.1295,found:353.1283.
Detect example 1
The spectral property of B1-B12 in methylene chloride is detected, test result is as shown in table 1:
Table 1
In table 1: Stokes-shift=1/ λmax–1/λem max(cm-1),alogεmaxFor the log value of molar absorption coefficient；b
Φ is fluorescence quantum yield.
B1-B12 is it is found that α provided by the invention-sulphur replaces fluorine boron fluorescent dye and passes through the hair through the foregoing embodiment
α-sulphur of the method preparation of bright offer replaces fluorine boron fluorescent dye maximum emission wavelength between 540-580nm, while its
Also there is excellent fluorescence quantum yield and excellent dissolubility, before illustrating that it has good application in fluorescent marker field
Scape, while the preparation method step is simple, and raw material is easy to get.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of α-sulphur replaces fluorine boron fluorescent dye, which is characterized in that the α-sulphur replaces the structure such as Formulas I of fluorine boron fluorescent dye
It is shown,
Wherein, R1For the aliphatic group of C1-C10, the substituted fatty hydrocarbon base of C1-C10, the aryl of C6-C12 or taking for C6-C12
For aryl, R2For the aliphatic group of C1-C15, the substituted fatty hydrocarbon base of C1-C15, the aryl of C6-C12 or taking for C6-C12
For aryl.
2. α according to claim 1-sulphur replaces fluorine boron fluorescent dye, wherein R1For the straight chained alkyl of C1-C4, phenyl,
The alkyl-substituted phenyl of C6-C10, the alkoxy substituted phenyl of C6-C10, C6-C10 halogen substituted phenyl, R2For C1-C12's
Acyclic alkyl, the hydroxyl substituted alkyl group of C1-C4, the phenyl substituted alkyl of C7-C12, the naphthenic base of C3-C6, phenyl, C7-C10
Alkyl-substituted phenyl；
Preferably, R1For methyl, ethyl, propyl, 2,4,6- trimethylphenyl, phenyl, 2,3,4,5,6- pentafluorophenyl group, 2,6- bis-
Chlorphenyl or p-methoxyphenyl, R2For n-propyl, isopropyl, tert-butyl, cyclohexyl, benzyl, dodecyl, 2- hydroxyl
Ethyl, p-methylphenyl.
3. α according to claim 1-sulphur replaces fluorine boron fluorescent dye, wherein the α-sulphur replaces fluorine boron fluorescent dye
Structure as shown in formula B1-B12,
4. the preparation method that a kind of α as described in claim 1-sulphur replaces fluorine boron fluorescent dye, which is characterized in that the preparation
Method are as follows: by the fluorine boron fluorescent dye, the mercaptan compound of the structure as shown in formula III, peroxide of the structure as shown in Formula II into
Row haptoreaction replaces fluorine boron fluorescent dye so that the α-sulphur is made,
Wherein, R1For the aliphatic group of C1-C10, the substituted fatty hydrocarbon base of C1-C10, the aryl of C6-C12 or taking for C6-C12
For aryl, R2For the aliphatic group of C1-C15, the substituted fatty hydrocarbon base of C1-C15, the aryl of C6-C12 or taking for C6-C12
For aryl.
5. the preparation method according to claim 4, wherein R1Alkyl for the straight chained alkyl of C1-C4, phenyl, C6-C10 takes
For phenyl, the alkoxy substituted phenyl of C6-C10, C6-C10 halogen substituted phenyl, R2Acyclic alkyl, C1-C4 for C1-C12
Hydroxyl substituted alkyl group, the phenyl substituted alkyl of C7-C12, the naphthenic base of C3-C6, phenyl, C7-C10 alkyl-substituted phenyl；
Preferably, R1For methyl, ethyl, propyl, 2,4,6- trimethylphenyl, phenyl, 2,3,4,5,6- pentafluorophenyl group, 2,6- bis-
Chlorphenyl or p-methoxyphenyl, R2For n-propyl, isopropyl, tert-butyl, cyclohexyl, benzyl, dodecyl, 2- hydroxyl
Ethyl, p-methylphenyl.
6. preparation method according to claim 4 or 5, wherein fluorine boron fluorescent dye, the peroxide of structure shown in the Formula II
Compound, the mole ratio of mercaptan are 0.2:0.2-0.5:0.2-0.3；
Preferably, the mole ratio of the fluorine boron fluorescent dye, peroxide, mercaptan of structure shown in the Formula II is 0.2:0.3-
0.4:0.2-0.25.
7. preparation method according to claim 4 or 5, wherein the haptoreaction meets the following conditions: reaction temperature is
40-80 DEG C, reaction time 3-6h.
8. preparation method according to claim 4 or 5, wherein the peroxide be selected from perbenzoic acid tert-butyl,
At least one of hydrogen peroxide, tert-butyl hydroperoxide.
9. preparation method according to claim 4 or 5, wherein the preparation method carries out in organic solvent, described to have
Solvent is selected from least one of dimethyl sulfoxide, acetonitrile, methylene chloride, toluene, tetrahydrofuran；
Preferably, the amount ratio of the fluorine boron fluorescent dye, organic solvent of structure shown in the Formula II is 0.2mmol:2-5mL.
10. a kind of α as described in claim 1-3-sulphur replaces application of the Novel BODIPY flourescent dye in fluorescent marker.
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