CN102040617B - Organic boron difluoride complex and preparation method thereof - Google Patents
Organic boron difluoride complex and preparation method thereof Download PDFInfo
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- OKZIUSOJQLYFSE-UHFFFAOYSA-N difluoroboron Chemical compound F[B]F OKZIUSOJQLYFSE-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000010668 complexation reaction Methods 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 55
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- 230000003252 repetitive effect Effects 0.000 claims description 11
- 238000005201 scrubbing Methods 0.000 claims description 11
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 34
- 239000003446 ligand Substances 0.000 abstract description 6
- 238000006862 quantum yield reaction Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 150000007530 organic bases Chemical class 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 abstract 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract 2
- 238000010992 reflux Methods 0.000 abstract 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 16
- 239000000843 powder Substances 0.000 description 12
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 11
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 9
- 229910015900 BF3 Inorganic materials 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 4
- JUMVYDGWHJBSIT-UHFFFAOYSA-N 2-quinolin-2-ylphenol Chemical compound OC1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 JUMVYDGWHJBSIT-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 3
- 229940094989 trimethylsilane Drugs 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 0 *c(c(*)c1)cc(-c(cc2)nc(cc3*)c2cc3I)c1O Chemical compound *c(c(*)c1)cc(-c(cc2)nc(cc3*)c2cc3I)c1O 0.000 description 1
- RMWXATYACOMBSI-UHFFFAOYSA-N 2-(6-chloroquinolin-2-yl)phenol Chemical compound Oc1ccccc1-c1ccc2cc(Cl)ccc2n1 RMWXATYACOMBSI-UHFFFAOYSA-N 0.000 description 1
- GBCMPZGNRZXZDO-UHFFFAOYSA-N 4-bromo-2-quinolin-2-ylphenol Chemical compound Oc1ccc(Br)cc1-c1ccc2ccccc2n1 GBCMPZGNRZXZDO-UHFFFAOYSA-N 0.000 description 1
- WNOFNXWMXFGZAJ-UHFFFAOYSA-N 4-methyl-2-quinolin-2-ylphenol Chemical compound Cc1ccc(O)c(c1)-c1ccc2ccccc2n1 WNOFNXWMXFGZAJ-UHFFFAOYSA-N 0.000 description 1
- LSJWPUVTKADCJU-UHFFFAOYSA-N 4-nitro-2-quinolin-2-ylphenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1C1=CC=C(C=CC=C2)C2=N1 LSJWPUVTKADCJU-UHFFFAOYSA-N 0.000 description 1
- DIPGJEFIWRWOAG-UHFFFAOYSA-N 5-methyl-2-quinolin-2-ylphenol Chemical compound CC=1C=CC(=C(C1)O)C1=NC2=CC=CC=C2C=C1 DIPGJEFIWRWOAG-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 239000000990 laser dye Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000011275 oncology therapy Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- ZHNFLHYOFXQIOW-LPYZJUEESA-N quinine sulfate dihydrate Chemical compound [H+].[H+].O.O.[O-]S([O-])(=O)=O.C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21.C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 ZHNFLHYOFXQIOW-LPYZJUEESA-N 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
The invention discloses an organic boron difluoride complex which is a compound the structural formula I of which is shown in the specification, wherein R1 and R2 are OCH3, H or Cl independently respectively; R3 and R4 are H, NO2, Br, CH3 or OCH3 independently respectively; the complex has stable chemical properties, strong thermal stability, high fluorescence quantum yield and large molar absorption coefficient; furthermore, the complex not only has strong solution fluorescence, but also has significant solid fluorescence. The invention further discloses a preparation method of the organic boron difluoride complex, and the organic boron difluoride complex is prepared by carrying out room temperature or reflux reaction on a ligand and boron trifluoride diethyl etherate in an anhydrous organic solvent in the presence of organic base; and the method has the advantages of mild reaction conditions, short reaction time, high product yield and fastness and simpleness in separation and purification.
Description
Technical field
The present invention relates to the organic synthesis field, be specifically related to a kind of organic boron difluoride title complex and preparation method thereof.
Background technology
Organic boron difluoride title complex is important fluorescence luminescent material, with regard to the coordination mode of boron atom, wherein most importantly is the N of representative with pyrroles's methine; N-bitooth ligand type and be the O of representative with β-enol ketone; Two types on O-bitooth ligand type, the research of its performance and application quite go deep into and abundant (Chem.Rev., 2007; 107,4891; Angew.Chem.Int.Ed., 2008,47,1184; New J.Chem., 2007,31,496; J.Phys.Org.Chem.1996,9,7; J.Am.Chem.Soc., 2007,129,8942; Tetrahedron, 2007,63,9354).
Yet as the N that contains of above-mentioned both isosteres, the research of organic boron difluoride title complex of O-bitooth ligand is but less relatively, and is wherein very few especially relevant for the report with luminescent properties kind.Can learn from the preliminary relation of structure and luminescent properties; It is the luminous necessary structural condition of title complex that the N tooth has nonrotational property σ key; Two types of N with β-enol imine structure are disclosed among the Chinese invention patent ZL 200710070713.5 on this basis; The boron difluoride title complex of O-bidentate aglucon, these two types of title complexs have all demonstrated the intensive green fluorescence in organic solution.Only several examples are about luminous N in the document, and the structure of the organic boron difluoride title complex of O-bitooth ligand has also possessed this key element of the nonrotational property of N tooth σ key (Org.Lett., 2008,10,633; Org.Lett., 2008,10,4437; Inorg.Chem., 2009,48,7230; Luminescence, 2007,126,447).
Summary of the invention
The invention provides a kind of organic boron difluoride title complex that has HS solid and fluorescent liquid at visible region.
The present invention also provides a kind of preparation method of organic boron difluoride title complex, and this method mild condition, the reaction times is short, yield is high, and the product separation and purification is easy.
A kind of organic boron difluoride title complex is the compound shown in the following structural formula I:
Among the structural formula I, R
1Be OCH
3, H or Cl; R
2Be OCH
3, H or Cl; R
3Be H, NO
2, Br, CH
3Or OCH
3R
4Be H, NO
2, Br, CH
3Or OCH
3
A kind of preparation method of organic boron difluoride title complex comprises step: with part and BFEE reaction, make the compound shown in the structural formula I:
Among the structural formula I, R
1Be OCH
3, H or Cl; R
2Be OCH
3, H or Cl; R
3Be H, NO
2, Br, CH
3Or OCH
3R
4Be H, NO
2, Br, CH
3Or OCH
3
Described part is the compound shown in the following structural formula II:
R in the structural formula II
1, R
2, R
3, R
4Respectively with structural formula I in R
1, R
2, R
3, R
4Has identical implication.
Described BFEE is preferably excessive in reaction, and the mol ratio of preferred part and BFEE is 1: 3-5.
In order to reach better invention effect, preferably:
Described reaction conditions is: 20 ℃-30 ℃ stir down 30min-50min or behind 55 ℃-65 ℃ heating 15min-25min natural crystallization, the gained crystal is used the anhydrous diethyl ether repetitive scrubbing, makes organic boron difluoride title complex.
Add acid binding agent (being organic bases) in the described reaction so that alkaline environment to be provided, described acid binding agent is triethylamine, N, N-diisopropylethylamine or diethylamine.
The mol ratio of described acid binding agent and part is 2～3: 1.
Described being reflected in the anhydrous organic solvent carried out, and described anhydrous organic solvent is one or more in ether, methylene dichloride, chloroform, benzene, toluene, THF, acetone, the ETHYLE ACETATE.
The organic boron difluoride title complex of the present invention is by heterocycle property N, and biological under alkaline anhydrous solvent condition, the reaction with BFEE of the 2-of O-bitooth ligand (2-quinolyl) phenol derivmives blend obtains, with room temperature or to be heated to be routine its reaction formula following:
Because described part has the structure of phenolic hydroxyl group, is converted into the coordination ability that corresponding phenol negative oxygen ion form can strengthen part with alkali, suitable organic bases is triethylamine, N, N-diisopropylethylamine or diethylamine; Be reflected in the anhydrous organic solvent and stir 30min-50min down or heat 15min-25min in 55 ℃-65 ℃ in 20 ℃-30 ℃; Separate out pulverulent solids; Filter the back for several times with the anhydrous diethyl ether repetitive scrubbing; Naturally promptly get the target title complex after drying, productive rate is general all more than 70%, and the available organic solvent has one or more in ether, methylene dichloride, chloroform, benzene, toluene, THF, acetone, the ETHYLE ACETATE etc.
Compared with prior art, the present invention has following advantage:
It is that part, chemical property are stablized, thermostability is strong, fluorescence quantum yield is high, molar absorptivity is big and have solid-state light and the novel cpd of fluorescent liquid with 2-(2-quinolyl) phenol derivmives blend biology that the organic boron difluoride title complex of the present invention is one type, and the preparation that this title complex can be luminescent material, fluorescent probe, fluorescent tracer, information storage medium, laser dyes and photodynamics cancer therapy photosensitizers etc. provides brand-new alternative materials with exploitation.
Preparing method's mild condition, the reaction times of the organic boron difluoride title complex of the present invention is short, yield is high, and the product separation and purification is easy.
Description of drawings
Fig. 1 be uv absorption spectrum curve (a) in dichloromethane solution of the title complex 8 of embodiment 8 preparation, fluorescence emission spectral curve (b) with and solid fluorescence launching curve (c); Wherein, X-coordinate is wavelength (Wavelength/nm), and ordinate zou is respectively ultraviolet absorptivity value (Absorption Value) or fluorescence intensity (Fluorescence Intensity);
Fig. 2 is the fluorescence property performance of dichloromethane solution under UV-irradiation of the title complex 8 of embodiment 8 preparations;
Fig. 3 is the fluorescence property performance of solid under UV-irradiation of the title complex 8 of embodiment 8 preparations;
Fig. 4 is the infrared spectrogram that the title complex 6 of embodiment 6 preparations adopts the KBr pressed disc method; Wherein, X-coordinate is wave number (Wavenumbers/cm
-1);
Fig. 5 is the proton nmr spectra of the title complex 6 of embodiment 6 preparations, and the condition of proton nmr spectra is: 400M hertz, DMSO-d
6Be solvent, trimethyl silane (TMS) is interior mark;
Fig. 6 is the carbon-13 nmr spectra of the title complex 6 of embodiment 6 preparations, and the condition of carbon-13 nmr spectra is: 100M hertz, DMSO-d
6Be solvent, TMS is interior mark.
Embodiment
At room temperature; With 2.81g (10mmol) 2-(6; 7-dimethoxy-2-quinolyl) phenol places the 15mL toluene solution, stirs down and drips triethylamine 4.2mL (30mmol), drips boron trifluoride ether solution 2.8mL (30mmol) after 15 minutes; Finish continued and stir 45min, have solid precipitation to separate out gradually.Solid collected by filtration is used the anhydrous diethyl ether repetitive scrubbing with solid, obtains pale yellow powder shape title complex 1 after drying naturally, yield 81%.
The infrared spectrogram of above-mentioned title complex 1, proton nmr spectra and carbon-13 nmr spectra are following:
IR(KBr)：υ＝1603，1516，1250，1083，849cm
-1。
1H?NMR(DMSO-d
6)：δ＝4.02(s，3H)，4.15(s，3H)，7.02(t，J＝8.0Hz，1H)，7.07(s，1H)，7.19(d，J＝8.4Hz，1H)，7.48(t，J＝8.0Hz，1H)，7.83(d，J＝8.0Hz，1H)，7.94(d，J＝8.8Hz，1H)，8.29(m，2H)。
13C?NMR(DMSO-d
6)：δ＝56.20，56.62，104.45，105.70，114.90，116.38，120.04，120.29，124.06，126.12，134.48，137.67，140.46，149.81，150.44，154.55，155.41。
At room temperature; 2.56g (10mmol) 2-(6-chloro-2-quinolyl) phenol is placed the 15mL benzole soln, stir down and drip triethylamine 3.7mL (27mmol), drip boron trifluoride ether solution 4.2mL (45mmol) after 15 minutes; Finish continued and stir 45min, have solid precipitation to separate out gradually.Solid collected by filtration is used the anhydrous diethyl ether repetitive scrubbing with solid, obtains yellow powder shape title complex 2 after drying naturally, yield 76%.
The infrared spectrogram of above-mentioned title complex 2, proton nmr spectra and carbon-13 nmr spectra are following:
IR(KBr)：υ＝1614，1517，1358，1265，1165，1099，930，847，754cm
-1。
1H?NMR(DMSO-d
6)：δ＝7.07(t，J＝7.6Hz，1H)，7.20(d，J＝8.4Hz，1H)，7.56(t，J＝7.6Hz，1H)，7.63(d，J＝8.4Hz，1H)，7.84(d，J＝8.8Hz，1H)，7.90(d，J＝8.4Hz，1H)，8.15(d，J＝8.8Hz，1H)，8.47(d，J＝8.8Hz，1H)，8.96(s，1H)。
13C?NMR(DMSO-d
6)：δ＝117.31，120.43，120.67，124.18，124.28，124.38，125.97，126.87，129.24，129.47，136.12，139.66，142.43，153.57，156.44。
At room temperature; 2.21g (10mmol) 2-(2-quinolyl) phenol is placed the 10mL ethyl acetate solution, stir down and drip triethylamine 2.9mL (21mmol), drip boron trifluoride ether solution 2.8mL (30mmol) after 15 minutes; Finish continued and stir 45min, have solid precipitation to separate out gradually.Solid collected by filtration is used the anhydrous diethyl ether repetitive scrubbing with solid, obtains yellow powder shape title complex 3 after drying naturally, yield 86%.
The infrared spectrogram of above-mentioned title complex 3, proton nmr spectra and carbon-13 nmr spectra are following:
IR(KBr)：υ＝1609，1560，1523，1481，1265，1085，922，760cm
-1。
1H?NMR(DMSO-d
6)：δ＝7.06(t，J＝7.6Hz，1H)，7.21(d，J＝8.4Hz，1H)，7.54(t，J＝8.0Hz，1H)，7.69(t，J＝7.6Hz，1H)，7.91(m，3H)，8.18(d，J＝8.8Hz，1H)，8.52(d，J＝8.8Hz，1H)，8.96(d，J＝8.8Hz，1H)。
13C?NMR(DMSO-d
6)：δ＝117.08，120.34，120.47，124.84，124.92，126.74，127.64，128.06，128.41，132.98，135.64，140.36，142.81，152.83，156.39。
At room temperature; 2.66g (10mmol) 4-nitro-2-(2-quinolyl) phenol is placed the 10mL acetone soln; Stir and drip triethylamine 4.2mL (30mmol) down; Drip boron trifluoride ether solution 4.8mL (50mmol) after 15 minutes in heating under 60 ℃, finish continued insulated and stirred 20min, have solid precipitation to separate out gradually.Solid collected by filtration is used the anhydrous diethyl ether repetitive scrubbing with solid, obtains colour of loess toner after drying naturally, powder title complex 4, yield 71%.
The infrared spectrogram of above-mentioned title complex 4, proton nmr spectra and carbon-13 nmr spectra are following:
IR(KBr)：υ＝1615，1513，1329，1074，929，846cm
-1。
1H?NMR(DMSO-d
6)：δ＝7.35(d，J＝8.8Hz，1H)，7.91(t，J＝7.6Hz，1H)，8.11(t，J＝7.6Hz，1H)，8.39(d，J＝8.4Hz，1H)，8.47(d，J＝9.2Hz，1H)，8.71(d，J＝8.4Hz，1H)，8.96(d，J＝8.4Hz，1H)，9.14(d，J＝9.2Hz，1H)，9.26(s，1H)。
13C?NMR(DMSO-d
6)：δ＝118.48，118.78，118.95，124.31，126.88，126.94，127.27，128.06，131.29，139.07，139.42，143.56，155.56，155.43，165.96。
At room temperature; 3.0g (10mmol) 4-bromo-2-(2-quinolyl) phenol is placed the 10mL chloroformic solution; Stir and drip triethylamine 4.2mL (30mmol) down; Drip boron trifluoride ether solution 4.8mL (50mmol) after 15 minutes in heating under 60 ℃, finish continued insulated and stirred 20min, have solid precipitation to separate out gradually.Solid collected by filtration is used the anhydrous diethyl ether repetitive scrubbing with solid, obtains the Powdered title complex 5 of khaki color after drying naturally, yield 77%.
The infrared spectrogram of above-mentioned title complex 5, proton nmr spectra and carbon-13 nmr spectra are following:
IR(KBr)：υ＝1607，1555，1523，1479，1348，1089，927，828cm
-1。
1H?NMR(DMSO-d
6)：δ＝6.99(d，J＝8.8Hz，1H)，7.54(d，J＝8.8Hz，1H)，7.70(t，J＝7.2Hz，1H)，7.87(t，J＝8.4Hz，1H)，8.10(t，J＝8.4Hz，2H)，8.37(s，1H)，8.45(d，J＝8.8Hz，1H)，8.63(d，J＝8.8Hz，1H)。
13C?NMR(DMSO-d
6)：δ＝110.11，118.58，120.17，120.92，126.65，126.90，127.36，127.99，130.18，131.12，134.52，138.77，143.81，156.07，159.02。
At room temperature; 2.34g (10mmol) 4-methyl-2-(2-quinolyl) phenol is placed the 15mL dichloromethane solution; Stir down and drip N, N-diisopropylethylamine 3.5mL (20mmol) drips boron trifluoride ether solution 2.8mL (30mmol) after 15 minutes; Finish continued and stir 45min, have solid precipitation to separate out gradually.Solid collected by filtration is used the anhydrous diethyl ether repetitive scrubbing with solid, obtains the Powdered title complex 6 of yellow-green colour after drying naturally, yield 91%.
The infrared spectrogram of above-mentioned title complex 6, proton nmr spectra and carbon-13 nmr spectra are following:
IR(KBr)：υ＝1620，1560，1524，1496，1384，1325，1265，1100，1077，920，831.755cm
-1。
1H?NMR(DMSO-d
6)：δ＝2.39(s，3H)，7.11(d，J＝8.4Hz，1H)，7.35(d，J＝8.8Hz，1H)，7.67(m，2H)，7.89(m，2H)，8.16(d，J＝8.8Hz，1H)，8.49(d，J＝8.8Hz，1H)，8.95(d，J＝9.6Hz，1H)。
13C?NMR(DMSO-d
6)：δ＝20.84，117.11，120.07，124.71，124.80，124.89，126.45，127.56，127.93，128.37，129.63，132.89，136.84，142.64，152.88，154.33.
At room temperature; 2.34g (10mmol) 5-methyl-2-(2-quinolyl) phenol is placed the 15mL tetrahydrofuran solution; Stir and drip diethylamine 2.1mL (20mmol) down; Drip boron trifluoride ether solution 2.8mL (30mmol) after 15 minutes, finish continued and stir 45min, have solid precipitation to separate out gradually.Solid collected by filtration is used the anhydrous diethyl ether repetitive scrubbing with solid, obtains the Powdered title complex 7 of yellow-green colour after drying naturally, yield 94%.
The infrared spectrogram of above-mentioned title complex 7, proton nmr spectra and carbon-13 nmr spectra are following:
IR(KBr)：υ＝1616，1553，1526，1262，1086，090cm
-1。
1H?NMR(DMSO-d
6)：δ＝2.40(s，3H)，6.84(d，J＝8.0Hz，1H)，7.00(s，1H)，7.64(t，J＝7.6Hz，1H)，7.76(d，J＝8.4Hz，1H)，7.87(t，J＝7.6Hz，2H)，8.08(d，J＝8.8Hz，1H)，8.43(d，J＝8.8Hz，1H)，9.92(d，J＝8.8Hz，1H)。
13C?NMR(DMSO-d
6)：δ＝21.25，118.04，118.17，119.03，121.91，123.15，127.44，127.90，128.03，129.27，132.05，139.01，143.96，146.95，152.32，155.31。
At room temperature; 2.51g (10mmol) 5-methoxyl group-2-(2-quinolyl) phenol is placed the 15mL toluene solution; Stir down and drip N, N-diisopropylethylamine 3.5mL (20mmol) drips boron trifluoride ether solution 2.8mL (30mmol) after 15 minutes; Finish continued and stir 45min, have solid precipitation to separate out gradually.Solid collected by filtration is used the anhydrous diethyl ether repetitive scrubbing with solid, obtains the Powdered title complex 8 of yellow-green colour after drying naturally, yield 83%.
The infrared spectrogram of above-mentioned title complex 8, proton nmr spectra and carbon-13 nmr spectra are following:
IR(KBr)：υ＝1617，1557，1380，1263，1224，1080，910，833cm
-1。
1H?NMR(DMSO-d
6)：δ＝3.88(s，3H)，6.62(m，2H)，7.61(t，J＝7.6Hz，1H)，7.84(m，3H)，8.00(d，J＝9.2Hz，1H)，8.37(d，J＝9.2Hz，1H)，8.87(d，J＝8.8Hz，1H)。
13C?NMR(DMSO-d
6)：δ＝55.69，102.51，110.03，116.69，124.29，124.38，124.47，126.98，127.43，128.08，128.35，132.73，142.19，152.65，158.73，166.06。
Detect through infrared spectrogram, proton nmr spectra and carbon-13 nmr spectra, show that the title complex 1-8 of embodiment 1-8 preparation has following structure:
Title complex 1:R
1=OCH
3, R
2=OCH
3, R
3=R
4=H; Pale yellow powder, fusing point: 272-273 ℃;
Title complex 2:R
1=Cl, R
2=R
3=R
4=H; Yellow powder, fusing point: 262-264 ℃;
Title complex 3:R
1=R
2=R
3=R
4=H; Yellow powder, fusing point: 264-265 ℃;
Title complex 4:R
1=R
2=R
4=H, R
3=NO
2The khaki color powder, fusing point:＞300 ℃;
Title complex 5:R
1=R
2=R
4=H, R
3=Br; The khaki color powder, fusing point: 294-295 ℃;
Title complex 6:R
1=R
2=R
4=H, R
3=CH
3The yellow-green colour powder, fusing point: 264-265 ℃;
Title complex 7:R
1=R
2=R
3=H; R
4=CH
3The yellow-green colour powder, fusing point: 257-259 ℃;
Title complex 8:R
1=R
2=R
3=H; R
4=OCH
3The yellow-green colour powder, fusing point: 243-244 ℃.
Under UV-irradiation, the solid and the organic solution of the organic boron difluoride title complex of the present invention present bright fluorescence, and the color of solid fluorescence is generally yellow-green colour (removing indivedual cyans that are), and the color of its solution fluorescence is by the transition gradually of blueness, cyan, blue-greenish colour.With title complex 1-8 is example, and spectral quality can see the following form 1:
The spectral quality of table 1 title complex
Annotate 1: spectral quality is all measured at room temperature the dichloromethane solution;
Annotate 2: fluorescence quantum yield Φ is an object of reference with Quinine Sulphate Di HC (Φ=0.55,0.5mM aqueous sulfuric acid), adopts the dilute solution relative method to measure.
Visible by data in the table 1, above-mentioned title complex contains on the phenol ring the title complex of electron-withdrawing substituent, and remaining title complex its organic solution and solid under UV-irradiation demonstrate intensive fluorescence.The uv-absorbing wavelength is in the 363nm-394nm scope, and the fluorescent emission wavelength is in the 441nm-502nm scope, and fluorescence quantum yield is in the 0.13-0.96 scope.
When being connected with electron-withdrawing substituent on the phenol ring; The fluorescence of title complex weakens very significantly, and this can obtain from the quantum yield data of corresponding title complex embodying, and then makes its solid fluorescence to measure; Even when substituting group was nitro, title complex had not had fluorescence property fully.Although caused the reduction of title complex quantum yield when introducing electron withdrawing group on the quinoline ring, effect does not have on the phenol ring so strong yet.No matter at the quinoline ring still on the phenol ring, introduce the enhancing of scolding the electronics base all to help the complex fluorescent performance, but as if the electronics base of scolding on the phenol ring has bigger enhancement effect of fluorescence, especially when scold the electronics base be in the phenol Sauerstoffatom between during the position.This shows that the electrical variation of phenol substitution in ring base is more remarkable to title complex integral fluorescence Effect on Performance.Because on phenol ring or quinoline ring, introducing substituting group has increased sterically hindered; Make and intermolecularly can't produce dense packing; Reduced to attract the equimolecular interphase interaction such as π-π; Add significantly Stock ' s displacement and eliminated the self-quenching effect, therefore cause title complex to produce the emission of intensive solid fluorescence.
Claims (7)
1. an organic boron difluoride title complex is characterized in that, is the compound shown in the following structural formula I:
Among the structural formula I, R
1Be OCH
3, H or Cl; R
2Be OCH
3, H or Cl; R
3Be H, NO
2, Br, CH
3Or OCH
3R
4Be H, NO
2, Br, CH
3Or OCH
3
2. the preparation method of an organic boron difluoride title complex comprises step: with part and BFEE reaction, make the compound shown in the structural formula I:
Among the structural formula I, R
1Be OCH
3, H or Cl; R
2Be OCH
3, H or Cl; R
3Be H, NO
2, Br, CH
3Or OCH
3R
4Be H, NO
2, Br, CH
3Or OCH
3
Described part is the compound shown in the following structural formula II:
R in the structural formula II
1, R
2, R
3, R
4Respectively with structural formula I in R
1, R
2, R
3, R
4Has identical implication.
3. the preparation method of organic boron difluoride title complex according to claim 2 is characterized in that, the mol ratio of described part and BFEE is 1: 3-5.
4. the preparation method of organic boron difluoride title complex according to claim 2; It is characterized in that; Described reaction conditions is: stir 30min-50min down or natural crystallization behind 55 ℃-65 ℃ heating 15min-25min at 20 ℃-30 ℃; The gained crystal is used the anhydrous diethyl ether repetitive scrubbing, makes organic boron difluoride title complex.
5. according to the preparation method of claim 2 or 4 described organic boron difluoride title complexs, it is characterized in that, add acid binding agent in the described reaction, described acid binding agent is triethylamine, N, N-diisopropylethylamine or diethylamine.
6. the preparation method of organic boron difluoride title complex according to claim 5 is characterized in that, the mol ratio of described acid binding agent and part is 2～3: 1.
7. according to the preparation method of claim 2 or 4 described organic boron difluoride title complexs; It is characterized in that; Described being reflected in the anhydrous organic solvent carried out, and described anhydrous organic solvent is one or more in ether, methylene dichloride, chloroform, benzene, toluene, THF, acetone, the ETHYLE ACETATE.
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