CN106946918A - Asymmetric pyrroles's fluorescent dye of naphthalene nucleus fusion fluorine boron two and preparation method thereof - Google Patents
Asymmetric pyrroles's fluorescent dye of naphthalene nucleus fusion fluorine boron two and preparation method thereof Download PDFInfo
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- CN106946918A CN106946918A CN201710173298.XA CN201710173298A CN106946918A CN 106946918 A CN106946918 A CN 106946918A CN 201710173298 A CN201710173298 A CN 201710173298A CN 106946918 A CN106946918 A CN 106946918A
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- pyrroles
- fluorine boron
- fluorescent dye
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- naphthalene nucleus
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- 150000003233 pyrroles Chemical class 0.000 title claims abstract description 39
- 230000004927 fusion Effects 0.000 title claims abstract description 33
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 29
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical compound [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 150000002790 naphthalenes Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 150000002240 furans Chemical class 0.000 claims abstract description 7
- 229930192474 thiophene Natural products 0.000 claims abstract description 7
- -1 substituted-phenyl Chemical group 0.000 claims abstract description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 239000011737 fluorine Substances 0.000 claims abstract description 3
- 239000003068 molecular probe Substances 0.000 claims abstract description 3
- 150000003577 thiophenes Chemical class 0.000 claims abstract description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- PORCGGHTMISDCW-UHFFFAOYSA-N [B].IF Chemical compound [B].IF PORCGGHTMISDCW-UHFFFAOYSA-N 0.000 claims description 9
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 8
- 235000010338 boric acid Nutrition 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003444 phase transfer catalyst Substances 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- DGUWACLYDSWXRZ-UHFFFAOYSA-N (2-formylphenyl)boronic acid Chemical class OB(O)C1=CC=CC=C1C=O DGUWACLYDSWXRZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005619 boric acid group Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000005580 one pot reaction Methods 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- GVHWLCYABLWGIR-UHFFFAOYSA-N (3-fluoro-2-formylphenyl)boronic acid Chemical class OB(O)C1=CC=CC(F)=C1C=O GVHWLCYABLWGIR-UHFFFAOYSA-N 0.000 claims 1
- 238000004440 column chromatography Methods 0.000 claims 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000008033 biological extinction Effects 0.000 abstract description 4
- 230000003595 spectral effect Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 125000002346 iodo group Chemical group I* 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 238000000799 fluorescence microscopy Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- KYMASEFRCQGTMK-UHFFFAOYSA-N Bc1ccccc1C Chemical compound Bc1ccccc1C KYMASEFRCQGTMK-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000006000 Knoevenagel condensation reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 description 1
- 150000001454 anthracenes Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 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 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 210000003463 organelle Anatomy 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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 Table
- 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
-
- 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
- C09K2211/1003—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
- 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
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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
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
This hair belongs to fine chemistry industry, technical field of organic synthesis, and in particular to a kind of asymmetric pyrroles's fluorescent dye of naphthalene nucleus fusion fluorine boron two and preparation method thereof.The asymmetric pyrroles's fluorescent dye of naphthalene nucleus fusion fluorine boron two has the structural formula as shown in (I)：
Description
Technical field
The present invention relates to fine chemistry industry, technical field of organic synthesis, and in particular to a kind of asymmetric naphthalene nucleus fusion fluorine boron two
Pyrroles's fluorescent dye and preparation method thereof.
Background technology
The pyrroles of fluorine boron two (BODIPY) dyestuff is a nearly twenties years class light just grow up and in widespread attention
Physical and chemical performance very excellent fluorescent chemicals.Shown in its mother nucleus structure and numbering system such as following formula (A), two pyrrole rings
Between be fixed on by boron bridged bond and methine bridged bond with a rigid plane.This dye has photo and thermal stability
Good, molar extinction coefficient is big (to be typically larger than 80000cm-1M-1), modifiability is strong, spectrum half-peak width, fluorescence quantum yield
High, insensitive to environment pH the features such as, it is widely used in the fields such as biological label, organelle fluorescence imaging, up-conversion.
The UV absorption and fluorescent emission maximum wavelength of traditional BODIPY dyestuffs are general between 470-530nm, serious system
About its application in the cell imaging.The near-infrared fluorescent BODIPY dyestuffs for absorbing and launching with long wavelength are opened as people
The center of gravity of hair, the absorption of this kind of dyestuff and transmitting maximum wavelength are more than 650nm, and penetration power is strong, can be prevented effectively from water, protein etc.
The interference of background.
Aromatic ring fusion BODIPY refer to aromatic rings such as phenyl ring, anthracene nucleus, naphthalene nucleus, phenanthrene ring, thiophene, furans by chemical modification or
On the heterocyclic fused precursor structure to BODIPY, using the effect of extended conjugation system, the HOMO-LUMO energy of fluorescent dye is reduced
It is differential, make Absorption and emission spectra red shift.The method of synthesis near-infrared fluorescent BODIPY dyestuffs mainly has two major classes at present：(1)
The pyrroles of aromatic ring fusion is synthesized, then with aldehyde reaction and aoxidizing coordination fluorine boron (Eur.J.Org.Chem., 2016,2016,4429-
4435.；RSC Advances,2016,6,52180-52188.)；(2) simple BODIPY is synthesized, by 2,6- halos, and with
Aromatic yl acid reaction, carries out internal oxidation fusion and obtains (J.Org.Chem., 2016,81,229-237. afterwards；
Org.Lett.,2014,16,6080-6083.).Synthetic method (1) step is more, and the pyrroles of aromatic ring fusion is easily oxidized, increase
Synthesis difficulty.And this method can only obtain the BODIPYs of symmetrical structure.Synthetic method (2) will BODIPY dyestuffs base
Pass through two-step reaction on plinth, final product yield is relatively low.These factors affects combined coefficient of near-infrared BODIPY dyestuffs
And extensive use.
The content of the invention
The purpose of the present invention is：The fusion BODIPY synthetic methods reported at present for solution are relatively complicated, products obtained therefrom
The problem of using symmetrical structure to be main, a kind of asymmetric pyrroles's fluorescent dye of naphthalene nucleus fusion fluorine boron two and preparation method thereof is proposed, is made
Its synthetic method is simple, convenient separation, yield are higher；And with for example high molar extinction coefficient of excellent spectral quality, stronger
Fluorescent emission, make its photostability high, can further be modified into molecular probe.
The present invention is achieved by the following technical solutions：A kind of asymmetric pyrroles's fluorescent dye tool of naphthalene nucleus fusion fluorine boron two
Just like the structural formula shown in (I)：
In formula, the one kind of Ar in phenyl, substituted-phenyl, thiophene, substituted thiophene, furans, substituted furan.R is selected from first
One kind in base, methoxyl group, fluorine.
The preparation method of the pyrroles's fluorescent dye of asymmetric naphthalene nucleus fusion fluorine boron two of the present invention is：In inert gas shielding
Under, using the pyrroles of iodo fluorine boron two and substitution phenyl boric acid as raw material, in the basic conditions, 1 equivalent phase transfer catalyst is added,
80 DEG C of palladium chtalyst one pot reaction 4~14 hours in solvent, then the pyrrole of fluorine boron two that naphthalene nucleus fusion is made is separated through silica gel column chromatography
Cough up fluorescent dye.
The pyrroles of iodo fluorine boron two is preferably 2 single pyrroles of iodo fluorine boron two, and 2, the 4- bit substituents of wherein pyrroles are
Methyl.
The substitution phenyl boric acid is selected from 2- formylphenylboronic acids, 2- formoxyl -5- fluorobenzoic boric acids, the fluoro- 2- formoxyls benzene of 3-
One kind in boric acid, the pyrroles of iodo fluorine boron two is 1 with the mol ratio of substitution phenyl boric acid:1.5.
The one kind of the solvent in toluene, tetrahydrofuran, the usage amount of solvent is the amount for dissolving solute.
The phase transfer catalyst is selected from 18 hats 6, TBAB (TBAB), tetrabutylammonium chloride, dodecyl three
One kind in ammonio methacrylate；Preferably, using TBAB；The mol ratio of phase transfer catalyst and iodo BODIPY
For 1-2：1.
The asymmetric pyrroles's fluorescent dye of naphthalene nucleus fusion fluorine boron two is in near-infrared ion detection, fluorescence imaging functional material
In application.
Advantages of the present invention is embodied in, and naphthalene nucleus fusion can effectively extend BODIPY π tracks, be conducive to electron delocalization, from
And realize the near infrared absorption and fluorescent emission of molecule.Compared to [a]-fusion (1,2/6,7), [b]-condense (2,3/
5,6) low molecular HOMO-LUMO energy levels can further drop, so as to there is the spectrum of more red shift than the former；Described is asymmetric
5 of naphthalene nucleus fusion BODIPY dyestuffs can further be modified, and ion identification group, design are introduced by Knoevenagel reactions
Synthesizing new near infrared fluorescent probe；The described pyrroles's fluorescent dye of asymmetric naphthalene nucleus fusion fluorine boron two has synthesis and separation letter
Single, yield is higher, and for example high molar extinction coefficient of excellent spectral quality, light are stable to be greatly improved, and is a kind of preferable near-infrared
Optical function material.
Compared with prior art, beneficial effects of the present invention are also embodied in：
(1) preparation method is simple, and yield is higher, and separation is simple, it is easy to industrialized production.
(2) synthetic method is wide using scope, and the raw material containing electron and electron-withdrawing substituent all can be used.
(3) have a wide range of application, dissymmetrical structure can be modified further for designing new construction fluorescence probe.
Embodiment
The present invention is described in further detail below by embodiment, it is raw materials used commercially available in embodiment.
Embodiment 1
In a 50ml Schlenk reaction bulb, list iodo BODIPY (50mg, 0.11mmol), 2- formoxyl benzene are added
Boric acid (25mg, 0.165mmol), tetra-triphenylphosphine palladium (13mg, 0.011mmol), 20ml tetrahydrofurans, TBAB (35mg,
0.11mmol),3mL 2M Na2CO3The aqueous solution.Logical nitrogen 20 minutes, 80 DEG C of stirring reactions 6 hours.With chromatographic column (DCM：PE=
35:65) separation can obtain atropurpureus solid product 17.7mg, and yield is 39%.Product of the structural formula as shown in (I-1) is not
The symmetrical pyrroles's fluorescent dye of naphthalene nucleus fusion fluorine boron two.1H NMR(400MHz,CDCl3) δ=8.22 (d, 1H), 7.88 (d, 1H),
7.80(d,1H),7.69(d,1H),7.57–7.56(m,3H),7.48(t,1H),7.41–7.37(m,3H),6.16(s,1H),
2.69(s,3H),2.01(s,3H),1.45(s,3H)ppm.MALDI-TOF-MS:calcd for[C26H21BF2N2]+:
410.18；found:410.57[M]+,391.52[M-F]+.
Synthetic reaction equation is as follows：
Embodiment 2
In a 50ml Schlenk reaction bulb, list iodo BODIPY (50mg, 0.11mmol), the fluoro- 2- first of 5- are added
Acyl group phenyl boric acid (28mg, 0.165mmol), tetra-triphenylphosphine palladium (13mg, 0.011mmol), 20ml tetrahydrofurans, TBAB
(35mg, 0.11mmol), 3mL 2M Na2CO3The aqueous solution.Logical nitrogen 20 minutes, 80 DEG C of stirring reactions 6 hours.Use chromatographic column
(DCM：PE=35:65) separation can obtain atropurpureus solid product 21mg, yield 45%.Production of the structural formula as shown in (I-2)
The asymmetric pyrroles's fluorescent dye of naphthalene nucleus fusion fluorine boron two of thing.
1H NMR(400MHz,CDCl3) δ=7.88-7.77 (m, 3H), 7.67 (d, 1H), 7.59-7.56 (m, 3H),
7.41-7.38(m,2H),7.16-7.11(m,1H),6.18(s,1H),2.70(s,3H),1.97(s,3H),1.46(s,3H)
ppm.
MALDI-TOF-MS:calcd for[C26H20BF3N2]+:428.17；found:428.47[M]+,409.58[M-F
]+.
Synthetic reaction equation is as follows：
Embodiment 3
In a 50ml Schlenk reaction bulb, list iodo BODIPY (50mg, 0.11mmol), the fluoro- 2- first of 3- are added
Acyl group phenyl boric acid (28mg, 0.165mmol), tetra-triphenylphosphine palladium (13mg, 0.011mmol), 20ml tetrahydrofurans, TBAB
(35mg, 0.11mmol), 3mL 2M Na2CO3The aqueous solution.Logical nitrogen 20 minutes, 80 DEG C of stirring reactions 6 hours.Use chromatographic column
(DCM：PE=35:65) separation can obtain atropurpureus solid product 10mg, yield 21%.Production of the structural formula as shown in (I-3)
The asymmetric pyrroles's fluorescent dye of naphthalene nucleus fusion fluorine boron two of thing.
1H NMR(400MHz,CDCl3) δ=8.03-8.01 (m, 3H), 7.95 (d, 1H), 7.72-7.67 (m, 1H), 7.58
(t,3H),7.42-7.37(m,2H),7.08(t,1H),6.19(s,1H),2.71(s,3H),1.99(s,3H),1.46(s,3H)
ppm.
MALDI-TOF-MS:calcd for[C26H20BF3N2]+:428.17；found:428.34[M]+,409.25[M-F
]+.
Synthetic reaction equation is as follows：
Embodiment 4
In a 50ml Schlenk reaction bulb, list iodo BODIPY (30mg, 0.06mmol), 2- formoxyl benzene are added
Boric acid (14mg, 0.09mmol), tetra-triphenylphosphine palladium (7mg, 0.006mmol), 20ml tetrahydrofurans, TBAB (19mg,
0.06mmol),3mL 2M Na2CO3The aqueous solution.Logical nitrogen 20 minutes, 80 DEG C of stirring reactions 12 hours.With chromatographic column (DCM：PE
=35:65) separation can obtain gold solid product 16mg, and yield is 58%.Product of the structural formula as shown in (I-4) is asymmetric
The pyrroles's fluorescent dye of naphthalene nucleus fusion fluorine boron two.
1H NMR(400MHz,CDCl3) δ=8.25 (d, 1H), 7.89 (d, 1H), 7.81 (d, 1H), 7.70 (d, 1H),
7.58(d,2H),7.47(t,1H),7.39(t,1H),7.30(d,2H),6.16(s,1H),2.69(s,3H),2.01(s,3H),
1.54(s,3H),1.46(s,3H),1.41(s,6H)ppm.
MALDI-TOF-MS:calcd for[C30H29BF2N2]+:466.24；found:466.36[M]+,447.44[M-F
]+.
Synthetic reaction equation is as follows：
Embodiment 5
In a 50ml Schlenk reaction bulb, list iodo BODIPY (30mg, 0.06mmol), 2- formoxyl benzene are added
Boric acid (14mg, 0.09mmol), tetra-triphenylphosphine palladium (7mg, 0.006mmol), 20ml tetrahydrofurans, TBAB (19mg,
0.06mmol),3mL 2M Na2CO3The aqueous solution.Logical nitrogen 20 minutes, 80 DEG C of stirring reactions 14 hours.With chromatographic column (DCM：PE
=35:65) separation can obtain dark red solid product 17mg, and yield is 61%.Product of the structural formula as shown in (I-5) be not right
Claim the pyrroles's fluorescent dye of naphthalene nucleus fusion fluorine boron two.
1H NMR(400MHz,CDCl3) δ=8.27 (d, 1H), 7.80 (d, 2H), 7.81 (d, 2H), 7.72 (d, 2H),
7.52-7.44(m,2H),7.40(t,1H),6.15(s,1H),2.69(s,3H),2.40(s,3H),2.14(s,6H),2.09
(s,3H),1.44(s,3H)ppm.
MALDI-TOF-MS:calcd for[C29H27BF2N2]+:452.22；found:452.47[M]+,433.56[M-F
]+.
Synthetic reaction equation is as follows：
Embodiment 6
In a 50ml Schlenk reaction bulb, list iodo BODIPY (50mg, 0.13mmol), 2- formoxyl benzene are added
Boric acid (30mg, 0.2mmol), tetra-triphenylphosphine palladium (15.4mg, 0.013mmol), 20ml tetrahydrofurans, TBAB (43mg,
0.13mmol),3mL 2M Na2CO3The aqueous solution.Logical nitrogen 20 minutes, 80 DEG C of stirring reactions 3 hours.With chromatographic column (DCM：PE=
1:1) separation can obtain black solid product 15.8mg, and yield is 27%.The asymmetric naphthalene of product of the structural formula as shown in (I-6)
The pyrroles's fluorescent dye of ring fusion fluorine boron two.
1H NMR(400MHz,CDCl3) δ=8.20 (d, 1H), 7.90 (d, 2H), 7.86 (d, 1H), 7.82 (d, 1H),
7.72(d,1H),7.60(d,2H),7.51(t,1H),7.42(t,1H),6.20(s,1H),2.70(s,3H),1.99(s,3H),
1.44(s,3H)ppm.
MALDI-TOF-MS:calcd for[C27H20BF2N3]+:435.17；found:435.26[M]+,416.28[M-F
]+.
Synthetic reaction equation is as follows：
Claims (7)
1. a kind of asymmetric pyrroles's fluorescent dye of naphthalene nucleus fusion fluorine boron two, it is characterised in that described fluorescent dye has such as (I)
Shown structural formula：
In formula, the one kind of Ar in phenyl, substituted-phenyl, thiophene, substituted thiophene, furans, substituted furan.R is selected from methyl, first
One kind in epoxide, fluorine.
2. a kind of preparation method of the pyrroles's fluorescent dye of naphthalene nucleus fusion fluorine boron two asymmetric as claimed in claim 1, its feature exists
In described preparation method is：Under inert gas shielding, using the pyrroles of iodo fluorine boron two and substitution phenyl boric acid as raw material,
Under alkalescence condition, 1 equivalent phase transfer catalyst, in a solvent 80 DEG C of palladium chtalyst one pot reaction 4~14 hours, then through silicon are added
The pyrroles's fluorescent dye of fluorine boron two of asymmetric naphthalene nucleus fusion is made in plastic column chromatography separation.
3. the preparation method of the asymmetric pyrroles's fluorescent dye of naphthalene nucleus fusion fluorine boron two according to claim 2, its feature exists
In the pyrroles of iodo fluorine boron two is 2 single pyrroles of iodo fluorine boron two, and wherein 2, the 4- positions of pyrroles are methyl.
4. the preparation method of the pyrroles's fluorescent dye of asymmetric naphthalene nucleus fusion fluorine boron two according to Claims 2 or 3, its feature
It is that the substitution phenyl boric acid is selected from 2- formylphenylboronic acids, 2- formoxyl -5- fluorobenzoic boric acids, the fluoro- 2- formylphenylboronic acids of 3-
In one kind, the pyrroles of iodo fluorine boron two with substitution phenyl boric acid mol ratio be 1:1.5.
5. the preparation method of the asymmetric pyrroles's fluorescent dye of naphthalene nucleus fusion fluorine boron two according to claim 2, its feature exists
In the one kind of solvent in toluene, tetrahydrofuran.
6. the preparation method of the asymmetric pyrroles's fluorescent dye of naphthalene nucleus fusion fluorine boron two according to claim 2, its feature exists
In phase transfer catalyst is selected from 18 hats 6, TBAB (TBAB), tetrabutylammonium chloride, DTAC
In one kind, the mol ratio of phase transfer catalyst and the pyrroles of iodo fluorine boron two are 1-2:1.
7. the asymmetric pyrroles's fluorescent dye of naphthalene nucleus fusion fluorine boron two as claimed in claim 1 is in near-infrared fluorescent molecular probe material
Application in material.
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