CN100532384C - Beta-enol imine structure boron fluoride complex and method of synthesizing the same - Google Patents
Beta-enol imine structure boron fluoride complex and method of synthesizing the same Download PDFInfo
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- CN100532384C CN100532384C CNB2007100707135A CN200710070713A CN100532384C CN 100532384 C CN100532384 C CN 100532384C CN B2007100707135 A CNB2007100707135 A CN B2007100707135A CN 200710070713 A CN200710070713 A CN 200710070713A CN 100532384 C CN100532384 C CN 100532384C
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Abstract
The invention discloses a boron triflouride composition of Beta-enol imine structure and the synthetic method. The method is that the 3-(2-oxo-2-aromatic ethyl benzyliden)-3, 4- dihydroquinoxaline-2-ketone or 3-(2-oxo-2-aromatic ethyl benzyliden)-3, 4- dihydro benzoxazine-2-ketone is adopted as ligand and refluxes and reacts with the boron trifluoride aster with 5 times to 10 times overdose in the acetic acid/toluene mixed liquor with volume rate of 1 : 1 for 5min and then cooled and crystallized. The boron triflouride composition of Beta-enol imine is a novel compound, which can produce strong green fluorescence in the visible region and has easily gained raw materials of the ligand, easy preparation, high synthetic yield of the composition and strong heat stability. The compound is suitable for the development and preparation of the photoluminescence materials, fluorescent probe, fluorescent tracer and photosensitizer in the cancer treatment of the photodynamics.
Description
Technical field
The present invention relates to fluorescence luminescent material, especially relate to a kind of beta-enol imine structure boron fluoride title complex and synthetic method thereof.
Background technology
Organic boron difluoride title complex is important fluorescence luminescent material, wherein common pyrroles's methine type that is mainly (be N, N-bitooth ligand type is shown in structural formula 1) and β-enol ketone type (be O, O-bitooth ligand type is shown in structural formula 2).The scientific worker of countries in the world is the two research and development very abundant and deep (J.Am.Chem.Soc.2007,129,1842～1843 to this; J.Am.Chem.Soc.2005,127,12162～12163; J.Org.Chem.2006,71,1718～1721; Langmuir 2006,22, and 4750～4757; J.Phys.Chem.B 2004,108, and 8641～8651; Chem.Phys.2005,313,151～157 and institute draw pertinent literature), yet up to now, contain N, the report of organic boron difluoride title complex of O-bitooth ligand is but very rare.β-enamine ketone is to have N, the part of O-double coordination base, be that a class is uncommon but part that coordination ability is powerful, its tautomer β-enol imines can form with the boron trifluoride diethyl etherate effect and contain N, the organic boron difluoride title complex of the β of O-bitooth ligand-enol imines type (shown in structural formula 3).(Aust.J.Chem.2003,56,1209～1214 in for the few known β-enol imines type boron difluoride title complex of number; New J.Chem.2002,26,1070～1075), because of the short and small fluorescent emission that causes of the conjugated system in its structure at ultraviolet region, be unfavorable for the direct observation of human eye.
Structural formula 1 structural formula 2 structural formulas 3
Summary of the invention
The object of the invention is to provide a kind of beta-enol imine structure boron fluoride title complex and synthetic method thereof.β-enamine ketone structure is assigned in 3-(2-oxo-2-virtue ethidine)-3,4-dihydrobenzo oxazines-2-ketone or 3-(2-oxo-2-virtue ethidine)-3, in 4-dihydro-quinoxaline-2-ketone, itself and boron trifluoride diethyl etherate are reacted, obtain β-enol imines type boron difluoride title complex.
The technical scheme that the present invention solves its technical problem employing is as follows:
One, beta-enol imine structure boron fluoride title complex, the general structure of this title complex is as follows:
Wherein: during X=O, part is 3-(2-oxo-2-virtue ethidine)-3,4-dihydrobenzo oxazines-2-ketone, and during X=NH, part is 3-(2-oxo-2-virtue ethidine)-3,4-dihydro-quinoxaline-2-ketone; R is H, OCH
3, Cl or NO
2Group.
Two, the synthetic method of beta-enol imine structure boron fluoride title complex:
Excessive 5-10 boron trifluoride diethyl etherate is doubly used in part and boron trifluoride diethyl etherate reaction in the reaction; Be reflected in acetate/toluene mixture liquid that volume ratio is 1:1 and refluxed 5 minutes, slowly be cooled to crystallization after the room temperature.
Described part is wherein: during X=O, part is 3-(2-oxo-2-virtue ethidine)-3,4-dihydrobenzo oxazines-2-ketone, and during X=NH, part is 3-(2-oxo-2-virtue ethidine)-3,4-dihydro-quinoxaline-2-ketone; R is H, OCH
3, Cl or NO
2Group; Its chemical equation is as follows:
Title complex 1:X=NH, R=H; Orange-yellow powder, fusing point: 313～314 ℃;
Title complex 2:X=NH, R=CH
3O; Deep red needle crystal, fusing point: 283～285 ℃;
Title complex 3:X=NH, R=Cl; The carmetta powder, fusing point: 297～298 ℃;
Title complex 4:X=NH, R=NO
2Brick-red plate crystal, fusing point: 324～326 ℃;
Title complex 5:X=O, R=H; The soil Red powder, fusing point: 256～257 ℃;
Title complex 6:X=O, R=CH
3O; Rose needle crystal, fusing point: 236～238 ℃;
Title complex 7:X=O, R=Cl; The large red powder, fusing point: 243～245 ℃;
Title complex 8:X=O, R=NO
2Orange red plate crystal, fusing point: 257～259 ℃.
Because reactant has tautomeric character, part takes β-enol imine structure with N in the boron difluoride title complex of generation, the O double coordination, and the title complex of generation has very high thermostability and reaction yield, and general yield is all more than 90%.Through slowly cooling to room temperature after the reaction, title complex is separated out with crystallization or pulverulent solids form, and purity is generally more than 98%.Do not reach 98% title complex for minority purity, can be in acetate/toluene (1:1 volume ratio) mixed solution recrystallization and purifying.
Title complex is dissolved in and forms bright yellow-green fluorescence solution in the organic solvent, and the spectral quality of its solution 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 tetrahydrofuran solution;
Annotate 2: fluorescence quantum yield is an object of reference with tetracene (Φ=0.6), adopts the dilute solution relative method to measure.
By table 1 as seen, the maximum emission wavelength of this two classes boron difluoride title complex (is seen attached Fig. 1 and 2) near 520nm, belongs to yellow-green light wave band in the visible region (seeing accompanying drawing 3).The character of substituent R to the influence of the molar absorptivity of title complex significantly and be rule and change, promptly substituting group is when scolding electronic property to become electrophilic character, molar absorptivity correspondingly from large to small; In addition, also be the clear regularity variation between their molar absorptivity of title complex of two kinds of part generations, be 3-(2-oxo-2-virtue ethidine)-3,4-dihydrobenzo oxazines-2-ketone is that the molar absorptivity of the boron difluoride that generates of part is than corresponding 3-(2-oxo-2-virtue ethidine)-3,4-dihydro-quinoxaline-2-ketone is that the molar absorptivity of the title complex that part generated is little, and this explanation nitrogen-atoms is eager to excel than the degree that Sauerstoffatom participates in the title complex conjugated system.Yet, there is not clear and definite regularity relation between the fluorescence quantum yield of title complex and the complex structure, R is that its fluorescence intensity ratio of title complex R of electron withdrawing group scolds the title complex of electronics base to want weak a lot, can observe this phenomenon significantly by simple range estimation but in general.
In addition, the kind of organic solvent is less to the wavelength affects of title complex ultraviolet absorption peak and fluorescence emission peak, but very remarkable to the influence of its fluorescence intensity, is example with title complex 1, and solvent sees Table 2 to its influence:
Table 2 organic solvent is to the influence of title complex 1
Annotate 1: all mensuration are all at room temperature carried out;
Annotate 2: strength of solution is 2.057 * 10
-8M;
Annotate 3: fluorescence intensity level is corresponding with the maximum emission wavelength in the fluorescence emission spectrum.
The beneficial effect that the present invention has is:
β-enamine ketone structure is assigned in 3-(2-oxo-2-virtue ethidine)-3,4-dihydrobenzo oxazines-2-ketone or 3-(2-oxo-2-virtue ethidine)-3, in 4-dihydro-quinoxaline-2-ketone, itself and boron trifluoride diethyl etherate are reacted, the β of gained-enol imines type boron difluoride title complex is a new compound, they not only produce the intensive yellow-green fluorescence at visible region, and the raw material of part be easy to get, prepare easy, the synthesis yield height of title complex.Title complex presents bright yellow-green fluorescence in organic solvent, fluorescence exciting wavelength is about 445nm, and emission wavelength is about 520nm, and fluorescence quantum yield is in 0.593～0.869 scope, and has very strong thermostability.Because human eye is the highest to the susceptibility of yellow-green light, resolving power is the strongest, therefore institute of the present invention synthetic fluorescent chemicals is specially adapted to the preparation of embedded photoluminescent material, fluorescent probe and fluorescent tracer, have higher fluorescence quantum yield owing to it simultaneously, thereby be applicable to that also exploitation becomes the photosensitizers in the photodynamics cancer therapy.
Description of drawings
Fluorescent exciting spectral curve and the fluorescence emission spectral curve of Fig. 1 title complex 1 in tetrahydrofuran solution.
Fluorescent exciting spectral curve and the fluorescence emission spectral curve of Fig. 2 title complex 5 in tetrahydrofuran solution.
The title complex 2 under Fig. 3 ultra violet lamp and the tetrahydrofuran solution of title complex 6 (being the tetrahydrofuran solution of title complex 2 in the cuvette of left side, is the tetrahydrofuran solution of title complex 6 in the cuvette of right side).
The proton nmr spectra of Fig. 4 title complex 5 (400M hertz, deuterated dimethyl sulfoxide are solvent, and tetramethylsilane is interior mark).
The carbon-13 nmr spectra of Fig. 5 title complex 5 (100M hertz, deuterated dimethyl sulfoxide are solvent, and tetramethylsilane is interior mark).
Embodiment
Embodiment 1:
At room temperature, with 3.11g (10mmol) 3-(2-oxo-2-benzene ethidine)-3,4-dihydro-quinoxaline-2-ketone places the mixed solution of 30mL acetate and toluene (1:1 volume ratio), on heating jacket, this mixed solution is heated to little boiling, drip boron trifluoride ether solution 5mL (53mmol) with the dropper middling speed, finish the back brown-red solution and continue boiling reflux 5min, remove heating jacket question response liquid and slowly be cooled to room temperature, have a large amount of pulverulent solids to separate out.Suction filtration, solid dry with room temperature after ethanol and the ether washing for several times successively, and the orange-yellow pulverulent solids of gained is title complex 1, productive rate 96%.
Embodiment 2:
At room temperature, with 3.41g (10mmol) 3-[2-oxo-2-(4-p-methoxy-phenyl) ethidine]-3,4-dihydro-quinoxaline-2-ketone places the mixed solution of 30mL acetate and toluene (1:1 volume ratio), on heating jacket, this mixed solution is heated to little boiling, drip boron trifluoride ether solution 8mL (66mmol) with the dropper middling speed, finish the back brown-red solution and continue boiling reflux 5min, remove heating jacket question response liquid and slowly be cooled to room temperature, have a large amount of pulverulent solids to separate out.Suction filtration, solid dry with room temperature after ethanol and the ether washing for several times successively, and gained is title complex 2, productive rate 99%.
Embodiment 3:
At room temperature, with 3.45g (10mmol) 3-[2-oxo-2-(4-chloro-phenyl-) ethidine]-3,4-dihydro-quinoxaline-2-ketone places the mixed solution of 30mL acetate and toluene (1:1 volume ratio), on heating jacket, this mixed solution is heated to little boiling, drip boron trifluoride ether solution 9mL (75mmol) with the dropper middling speed, finish the back brown-red solution and continue boiling reflux 5min, remove heating jacket question response liquid and slowly be cooled to room temperature, have a large amount of pulverulent solids to separate out.Suction filtration, solid dry with room temperature after ethanol and the ether washing for several times successively, and gained carmetta powder is title complex 3, productive rate 93%.
Embodiment 4:
At room temperature, with 3.56g (10mmol) 3-[2-oxo-2-(4-nitrophenyl) ethidine]-3,4-dihydro-quinoxaline-2-ketone places the mixed solution of 60mL acetate and toluene (1:1 volume ratio), on heating jacket, this mixed solution is heated to little boiling, drip boron trifluoride ether solution 10mL (100mmol) with the dropper middling speed, finish the back brown-red solution and continue boiling reflux 5min, remove heating jacket question response liquid and slowly be cooled to room temperature, have a large amount of chip solids to separate out.Suction filtration, solid dry with room temperature after ethanol and the ether washing for several times successively, use the mixed solution of small amount of acetic acid and toluene (1:1 volume ratio) to carry out recrystallization again, and the brick-red plate crystal of gained is title complex 4, productive rate 90%.
Embodiment 5:
At room temperature, with 3.12g (10mmol) 3-(2-oxo-2-benzene ethidine)-3,4-dihydrobenzo oxazines-2-ketone places the mixed solution of 30mL acetate and toluene (1:1 volume ratio), on heating jacket, this mixed solution is heated to little boiling, drip boron trifluoride ether solution 5mL (53mmol) with the dropper middling speed, finish the back brown-red solution and continue boiling reflux 5min, remove heating jacket question response liquid and slowly be cooled to room temperature, have a large amount of pulverulent solids to separate out.Suction filtration, solid dry with room temperature after ethanol and the ether washing for several times successively, and gained soil Red powder is title complex 5, productive rate 99% (structural characterization is seen accompanying drawing 4 and accompanying drawing 5).
Embodiment 6:
At room temperature, with 3.42g (10mmol) 3-[2-oxo-2-(4-p-methoxy-phenyl) ethidine]-3,4-dihydrobenzo oxazines-2-ketone places the mixed solution of 30mL acetate and toluene (1:1 volume ratio), on heating jacket, this mixed solution is heated to little boiling, drip boron trifluoride ether solution 8mL (66mmol) with the dropper middling speed, finish the back brown-red solution and continue boiling reflux 5min, remove heating jacket question response liquid and slowly be cooled to room temperature, have needle-like solid to separate out.Suction filtration, solid dry with room temperature after ethanol and the ether washing for several times successively, and gained rose needle crystal is title complex 6, productive rate 99%.
Embodiment 7:
At room temperature, with 3.46g (10mmol) 3-[2-oxo-2-(4-chloro-phenyl-) ethidine]-3,4-dihydrobenzo oxazines-2-ketone places the mixed solution of 30mL acetate and toluene (1:1 volume ratio), on heating jacket, this mixed solution is heated to little boiling, drip boron trifluoride ether solution 9mL (75mmol) with the dropper middling speed, finish the back brown-red solution and continue boiling reflux 5min, remove heating jacket question response liquid and slowly be cooled to room temperature, have body of powder to separate out.Suction filtration, solid dry with room temperature after ethanol and the ether washing for several times successively, and gained large red powder is title complex 7, productive rate 95%.
Embodiment 8:
At room temperature, with 3.57g (10mmol) 3-[2-oxo-2-(4-nitrophenyl) ethidine]-3,4-dihydrobenzo oxazines-2-ketone places the mixed solution of 30mL acetate and toluene (1:1 volume ratio), on heating jacket, this mixed solution is heated to little boiling, drip boron trifluoride ether solution 10mL (100mmol) with the dropper middling speed, finish the back brown-red solution and continue boiling reflux 5min, remove heating jacket question response liquid and slowly be cooled to room temperature, have needle-like solid to separate out.Suction filtration, solid dry with room temperature after ethanol and the ether washing for several times successively, use the mixed solution of small amount of acetic acid and toluene (1:1 volume ratio) to carry out recrystallization again, and the orange red plate crystal of gained is title complex 8, productive rate 92%.
Above-mentioned embodiment is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (3)
1, a kind of beta-enol imine structure boron fluoride title complex, it is characterized in that: the general structure of this title complex is as follows:
X=NH or O,
Wherein: X=O, part are 3-(2-oxo-2-virtue ethidine)-3,4-Er hydrogen benzoxazine-2-ketone; X=NH, part are 3-(2-oxo-2-virtue ethidine)-3,4-dihydro-quinoxaline-2-ketone; R is H, OCH
3, Cl or NO
2Group.
2, a kind of synthetic method of beta-enol imine structure boron fluoride title complex is characterized in that the step of this method is as follows: part and boron trifluoride diethyl etherate reaction, use excessive 5～10 times boron trifluoride diethyl etherate in the reaction; Be reflected in acetate/toluene mixture liquid that volume ratio is 1:1 and refluxed 5 minutes, slowly be cooled to crystallization after the room temperature;
The general structure of this title complex is as follows:
X=NH or O,
Wherein: X=O, part are 3-(2-oxo-2-virtue ethidine)-3,4-Er hydrogen benzoxazine-2-ketone; X=NH, part are 3-(2-oxo-2-virtue ethidine)-3,4-dihydro-quinoxaline-2-ketone; R is H, OCH
3, Cl or NO
2Group.
3, the synthetic method of beta-enol imine structure boron fluoride title complex according to claim 2 is characterized in that: X=NH or O, and wherein: X=O, part are 3-(2-oxo-2-virtue ethidine)-3,4-Er hydrogen benzoxazine-2-ketone; X=NH, part are 3-(2-oxo-2-virtue ethidine)-3,4-dihydro-quinoxaline-2-ketone; R is H, OCH
3, Cl or NO
2Group, its chemical equation is as follows:
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| CN102040617B (en) * | 2010-11-24 | 2012-06-27 | 浙江理工大学 | Organic boron difluoride complex and preparation method thereof |
| RU2469295C1 (en) * | 2011-08-01 | 2012-12-10 | Учреждение Российской академии наук Центр фотохимии РАН | Method of detecting benzene, toluene and xylene in air |
| CN103664919B (en) * | 2012-09-26 | 2016-02-10 | 李超 | A kind ofly can be used for the compound preparing chemotherapeutics |
| CN102993223A (en) * | 2012-09-28 | 2013-03-27 | 浙江理工大学 | Organic boron difluoride complex containing N,O-bidentate ligand |
| CN102993224A (en) * | 2012-09-28 | 2013-03-27 | 浙江理工大学 | Organic boron difluoride complex |
| RU2499249C1 (en) * | 2012-11-19 | 2013-11-20 | Федеральное государственное бюджетное учреждение науки Центр фотохимии Российской академии наук (ЦФ РАН) | Method of detecting pyridine in air |
| CN104262373B (en) * | 2014-08-20 | 2016-08-17 | 北京理工大学 | A kind of targeting detection the fluorescence probe of inhibition cancer cell, preparation method and application |
| CN110467578A (en) * | 2018-05-11 | 2019-11-19 | 南京大学 | A kind of human cysteine fluorescence probe and its preparation method and purposes |
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