CN104177392B - A kind of benzo B-N with fluorescent functional mixes pentalene and preparation method thereof - Google Patents
A kind of benzo B-N with fluorescent functional mixes pentalene and preparation method thereof Download PDFInfo
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- CN104177392B CN104177392B CN201410349074.6A CN201410349074A CN104177392B CN 104177392 B CN104177392 B CN 104177392B CN 201410349074 A CN201410349074 A CN 201410349074A CN 104177392 B CN104177392 B CN 104177392B
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- triethylamine
- pentalene
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- 0 *C(B1c2ccccc2)=C(*)N(B2c3ccccc3)N1c1c2cc(*)cc1 Chemical compound *C(B1c2ccccc2)=C(*)N(B2c3ccccc3)N1c1c2cc(*)cc1 0.000 description 3
Abstract
The benzo B-N with fluorescent functional mixes a preparation method for pentalene, using triethylamine as promotor, reaction raw materials hydrazone, phenyl dibrominated boron triethylamine, triethylamine is mixed, adds toluene, be heated to 110
oc, reaction 8h, after react, filter drain with hexane extraction or direct in toluene condensing crystal, benzo B-N can be obtained and to mix pentalene.Advantage of the present invention and beneficial effect are: use hydrazone as constructing skeleton, cheaper starting materials and easily preparing; Use triethylamine as promotor, reaction conditions is gentle, and aftertreatment is easy, environmental friendliness; The fluorescence benzo B-N obtained pentalene of mixing has strong liquid and solid fluorescence; Avoid and use metal catalyst or excessive Lewis acid as catalyzer, condition is violent and aftertreatment is loaded down with trivial details.
Description
Technical field
The present invention relates to the mix new synthesis technology, particularly a kind of benzo B-N with fluorescent functional of pentalene of B-N to mix pentalene and preparation method thereof.
Background technology
Boron nitrogen heterocyclic is the very important functional molecular of a class, has very significance, had and apply very widely in photoelectric material in the theoretical investigation in aromaticity and antiaromaticity field.In pi-conjugated system, introduce boron nitrogen key can the photoelectric property of significant change system, can strengthen intermolecular dipole-dipole interaction simultaneously.In the last few years, the research of the p-type π-electron material of the boron participation of electron deficiency was increasing.Much boron π-electron system of mixing is synthesized out, and is widely used in a lot of field, such as: device for non-linear optical, and two-photon absorption and emissive material and Organic Light Emitting Diode (OLED).Traditional method of constructing boron nitrogen heterocyclic has: 1) class Friedel-Crafts reaction, see Org.Lett.2007, and 9,1395-1398, this kind of reaction generally needs a large amount of Lewis acids as catalyzer, and reaction conditions is very harsh, the waste that simultaneous is a large amount of and pollution, aftertreatment is loaded down with trivial details; 2) metal catalytic, see J.Am.Chem.Soc.2010,132,16340-16342, this kind of reaction itself needs special metal catalyst, and each catalyzer does not have versatility to different reactions, the synthesis of raw material is also very difficult, and this makes this kind of method of constructing boron nitrogen heterocyclic become complicated.The defect of these methods itself is that reaction is complicated, processes loaded down with trivial details.The report simultaneously constructing two boron nitrogen heterocyclics only has a few example: wherein an example class Friedel-Crafts reaction constructs the boron nitrogen heterocyclic of two benzos simultaneously, see J.Am.Chem.Soc.2011,133,18614 – 18617, in synthesis with excessive aluminum chloride as catalyzer.Another example constructs the report of two boron nitrogen heterocyclics simultaneously, and see Angew.Chem.Int.Ed.2013,52,3117-3120, in synthesis, only the synthesis of raw material just relates to multistep and catalyzes and synthesizes, and route is tediously long, and operation inconvenience, the condition of last Cheng Huan is too harsh.Construct the report of two boron nitrogen heterocyclics, the acquisition of raw material is inconvenient simultaneously, and the reaction response condition of constructing boron nitrogen heterocyclic is harsh.
Summary of the invention
The object of the invention is the defect overcoming conventional synthesis process, a kind of benzo B-N with fluorescent functional is provided to mix pentalene and preparation method thereof, this preparation method does not use Lewis acid or any metal and other metal auxiliary reagent, but the hydrazone " one kettle way " adopting triethylamine to promote is constructed benzo B-N and to be mixed pentalene, unique by product of this reaction is quaternary ammonium salt, and can to mix pentalene by the synthesis of the high yield benzo B-N with strong liquid and solid fluorescence; This preparation method is easy to operate, reaction conditions is gentle and pollution-free.
Technical scheme of the present invention:
The benzo B-N with fluorescent functional mixes a pentalene, and its chemical structure of general formula is
In formula: Het is 2-thiophene or phenyl, R is H or phenyl, and X is Cl, Br, Me.
The benzo B-N with fluorescent functional mixes a preparation method for pentalene, and adopt hydrazone part as constructing skeleton, using triethylamine as promotor, utilize hydrazone " one kettle way " to synthesize, step is as follows:
1) hydrazone part, phenyl dibrominated boron triethylamine and triethylamine are mixed, then add toluene, obtain mixed solution;
2) above-mentioned mixed solution is reacted 8h at 110 DEG C of temperature, after filtration and drain solvent with vacuum pump;
3) by above-mentioned solvent hexane extraction, with hexanes wash after crystallization, the benzo B-N with fluorescent functional can be obtained and to mix pentalene.
Described hydrazone part is methyl phenyl ketone phenylhydrazone, thiophene ethyl ketone phenylhydrazone, phenylbenzyl ketone phenylhydrazone, phenylbenzyl ketone-4-methyl phenylhydrazone, phenylbenzyl ketone-4-chlorobenzene hydrazone, phenylbenzyl ketone-4-bromobenzene hydrazone, the mol ratio of hydrazone part, phenyl dibrominated boron triethylamine and triethylamine is 1:2:2,, the amount ratio of hydrazone part and toluene is 1mmol:10mL.
Advantage of the present invention and beneficial effect are: this preparation method adopts hydrazone part as constructing skeleton, cheaper starting materials and be easy to preparation; Use triethylamine as promotor, reaction conditions is gentle, and aftertreatment is easily easy, environmental friendliness; Obtained benzo B-N pentalene of mixing has strong liquid and solid fluorescence.
Embodiment
Embodiment given below is in order to the present invention is described, instead of limits the invention.
Reaction and separation processes in embodiment carries out under all using Schlenk instrument to protect under high-purity argon gas.
Embodiment 1:
The benzo B-N with fluorescent functional mixes a pentalene, and its chemical structural formula is
，
Its preparation method is, adopt hydrazone part as constructing skeleton, using triethylamine as promotor, utilize hydrazone " one kettle way " to synthesize, reaction process is as follows:
，
Step is as follows:
1) 0.21g methyl phenyl ketone phenylhydrazone, 0.698g phenyl dibrominated boron triethylamine and 0.202g triethylamine are joined in reaction tubes mix, then add 10mL toluene, obtain mixed solution;
2) above-mentioned mixed solution is reacted 8h at 110 DEG C of temperature, after filtration and drain solvent with vacuum pump;
3) by above-mentioned solvent hexane extraction, with hexanes wash after crystallization, product 0.16g is obtained, productive rate 42%.MS（M
+）=382。Make solvent with methylene dichloride, there is no characteristic fluorescence excitation wavelength, selective exitation wavelength: 315nm, fluorescence emission wavelengths 376nm, quantum yield: 15%.
Embodiment 2:
The benzo B-N with fluorescent functional mixes a pentalene, and its chemical structural formula is
，
Its preparation method is, adopt hydrazone part as constructing skeleton, using triethylamine as promotor, utilize hydrazone " one kettle way " to synthesize, reaction process is as follows:
，
Step is as follows:
1) 0.216g thiophene ethyl ketone phenylhydrazone, 0.698g phenyl dibrominated boron triethylamine and 0.202g triethylamine are joined in reaction tubes mix, then add 10mL toluene, obtain mixed solution;
2) above-mentioned mixed solution is reacted 8h at 110 DEG C of temperature, after filtration and drain solvent with vacuum pump;
3) by above-mentioned solvent hexane extraction, with hexanes wash after crystallization, product 0.28g is obtained, productive rate 75%.MS（M
+）=388。Make solvent with methylene dichloride, there is no characteristic fluorescence excitation wavelength, selective exitation wavelength: 315nm, fluorescence emission wavelengths 375nm, quantum yield: 21%.
Embodiment 3:
The benzo B-N with fluorescent functional mixes a pentalene, and its chemical structural formula is
，
Its preparation method is, adopt hydrazone part as constructing skeleton, using triethylamine as promotor, utilize hydrazone " one kettle way " to synthesize, reaction process is as follows:
，
Step is as follows:
1) 0.286g phenylbenzyl ketone phenylhydrazone, 0.698g phenyl dibrominated boron triethylamine and 0.202g triethylamine are joined in reaction tubes mix, then add 10mL toluene, obtain mixed solution;
2) above-mentioned mixed solution is reacted 8h at 110 DEG C of temperature, after filtration and drain solvent with vacuum pump;
3) by above-mentioned solvent hexane extraction, with hexanes wash after crystallization, product 0.32g is obtained, productive rate 70%.MS（M
+）=458。Make solvent with methylene dichloride, there is no characteristic fluorescence excitation wavelength, selective exitation wavelength: 315nm, fluorescence emission wavelengths 376nm, quantum yield: 22%.
Embodiment 4:
The benzo B-N with fluorescent functional mixes a pentalene, and its chemical structural formula is
，
Its preparation method is, adopt hydrazone part as constructing skeleton, using triethylamine as promotor, utilize hydrazone " one kettle way " to synthesize, reaction process is as follows:
，
Step is as follows:
1) the bromo-phenylhydrazone of 0.364g phenylbenzyl ketone-4-, 0.698g phenyl dibrominated boron triethylamine and 0.202g triethylamine are joined in reaction tubes mix, then add 10mL toluene, obtain mixed solution;
2) above-mentioned mixed solution is reacted 8h at 110 DEG C of temperature, after filtration and drain solvent with vacuum pump;
3) by above-mentioned solvent hexane extraction, with hexanes wash after crystallization, product 0.38g is obtained, productive rate 73%.MS（M
+）=536。Make solvent with methylene dichloride, there is no characteristic fluorescence excitation wavelength, selective exitation wavelength: 315nm, fluorescence emission wavelengths 375nm, quantum yield: 17%.
Claims (2)
1. the benzo B-N with fluorescent functional mixes a preparation method for pentalene, and the mix chemical structure of general formula of pentalene of described benzo B-N is
In formula: Het is 2-thiophene or phenyl, R is H or phenyl, and X is Cl, Br, Me; Or be selected from the compound of following structure:
It is characterized in that: adopt hydrazone part as constructing skeleton, using triethylamine as promotor, utilize hydrazone " one kettle way " to synthesize, step is as follows:
1) hydrazone part, phenyl dibrominated boron triethylamine and triethylamine are mixed, then add toluene, obtain mixed solution;
2) above-mentioned mixed solution is reacted 8h at 110 DEG C of temperature, after filtration and drain solvent with vacuum pump;
3) by above-mentioned solvent hexane extraction, with hexanes wash after crystallization, the benzo B-N with fluorescent functional can be obtained and to mix pentalene.
2. the benzo B-N according to claim 1 with fluorescent functional mixes the preparation method of pentalene, it is characterized in that: described hydrazone part is methyl phenyl ketone phenylhydrazone, thiophene ethyl ketone phenylhydrazone, phenylbenzyl ketone phenylhydrazone, phenylbenzyl ketone-4-methyl phenylhydrazone, phenylbenzyl ketone-4-chlorobenzene hydrazone, phenylbenzyl ketone-4-bromobenzene hydrazone, the mol ratio of hydrazone part, phenyl dibrominated boron triethylamine and triethylamine is 1:2:2, and the amount ratio of hydrazone part and toluene is 1mmol:10mL.
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Non-Patent Citations (2)
| Title |
|---|
| Pentalenes—From Highly Reactive Antiaromatics to Substrates for Material Science;Henning Hopf et al.;《Angew. Chem. Int. Ed.》;20131011;第52卷;第12226页左栏最后一段，Scheme 7及右栏第一段 * |
| Recent Advances in Azaborine Chemistry;Patrick G. Campbell et al.;《Angew. Chem. Int. Ed.》;20120529;第51卷;第6084页左栏最后一段及Scheme 27 * |
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