CN109796480A - A kind of synthetic method of boron azepine aphthothiophenes class heteroaryl hydrocarbons and their derivates - Google Patents
A kind of synthetic method of boron azepine aphthothiophenes class heteroaryl hydrocarbons and their derivates Download PDFInfo
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Abstract
The present invention relates to a kind of synthetic methods of boron azepine aphthothiophenes class heteroaryl hydrocarbons and their derivates, and test the photophysical property and single crystal diffraction structure of these compounds, further study potential using value of such organic material in terms of organic electrochemistry, the structural formula of this compound are as follows: wherein R1, R2, R3, R4Be independent substituted or non-substituted group, including alkyl respectively, aryl (phenyl ring, thiphene ring, furan nucleus, pyrroles, pyridine, benzothiophene, benzofuran, benzopyrrole, benzo pyridine, naphthalene nucleus, anthracene nucleus, that non-alkene, aphthacene, pyrene,Linear or angled pentacene and six, indenes, fluorenes etc.).Wherein R3, R4Or single substitution halogen atom X:F, Cl, Br, I.
Description
Technical field
The present invention relates to a kind of synthetic methods of boron azepine aphthothiophenes class heteroaryl hydrocarbons and their derivates, commercially can purchase
Reagent be raw material, pass through Suzuki coupling, metal reduction, lewis base guiding the available boron nitrogen of electrophilic boron cyclization
Miscellaneous benzothiophene kind heteroaryl hydrocarbons and their derivates.This synthetic method have it is easy to operate, reaction condition is mild, the spies such as yield height
Point, such compound can be applied in organic photoelectrical material field.
Background technique
The big pi-electron system that conjugation polycyclic aromatic hydrocarbon has, thus it is often used as function photoelectric material, common application packet
It includes: field effect transistor (OFET), photovoltaic cell (OPVs), Organic Light Emitting Diode (OLED) etc..It is conjugated the π of polycyclic aromatic hydrocarbon
Electron system can adjust its conjugated structure by introducing aromatic ring and hetero atom (N, P, B etc.), to change the track of molecule
Energy level, and then change the photoelectricity physical property of compound.
In numerous heterocyclic systems, the outer layer unoccupied orbital of its boron atom of boracic aromatic ring system easily carries out coupling with supplied for electronic system
It closes, formation p- is pi-conjugated, low molecular lumo energy is dropped, to change the physicochemical properties of molecule.Organic amine is as a kind of normal
The lewis base seen, the lone pair electrons on nitrogen-atoms can form covalent bond with the outer layer unoccupied orbital of boron atom.Nitrogen boron key with
Carbon-carbon double bond isoelectronic species each other.The electronegativity difference of boron nitrogen causes boron nitrogen key to have certain polarity compared to carbon-carbon bond,
Thus boron pyridine possesses the very unique photoelectricity physical property compared with benzene, so that the thiophene system of boracic pyridine causes extensively
General concern.Between past 20 years, pi-conjugated material is contained by the trivalent boron of Willams and Kaim pionerring research and is obtained
Development by leaps and bounds, trivalent boron have empty P track, make it have unique electronics and spatial character (C.D.
Entwistle, T.B.Marder, Boron chemistry lights the way:optical properties of
Molecular and polymeric systems, Angew.Chem.Int.Ed.2002,41,2927-2931).Pi-conjugated
By the P- π effect between empty P track and π track in system, boron atom can become good electron acceptor, to adjust
The photoelectric property of conjugated polycyclic aromatic hydrocarbons.Nitrogen-atoms compared to trivalent for boron atom is the isoelectronic species of carbon atom, due to existing
The nitrogen-atoms of lone pair electrons pair, trivalent can become good electron donor.When the nitrogen-atoms of trivalent and boron atom coexist
The strong electric charge transfer of intramolecular can occur for time, adjust the photoelectricity physical property of molecule.Therefore it can apply to extensive field,
Such as nonlinear optical device, Organic Light Emitting Diode.
1958, Dewar group synthesized the naphthalene compound of boron nitrogen substitution for the first time, and nineteen sixty Dewar and White is first
It is secondary to have synthesized the 1 of monocycle ,-azepine boron derivative, 1962, the benzo thiophene that the method for Dewar et al. desulfurization replaces from boron nitrogen
Azoles has obtained more polysubstituted 1,2- azepine boron, and White in 1963 et al. has synthesized 1-H-2- phenyl -1,2- azepine boron, opens
The gate of boron nitrogen chemical (M.J.S.Dewar, V.P.Kubba, R. Pettit, 624.New heteroaromatic
Compounds.Part I.9-Aza-10-boraphenanthrene, J. Chem.Soc.1958,3073-3076).
Due to the limitation that synthetic method and people recognize such compound, to boron N doping polycyclic aromatic compound
Research it is more than 40 years or so quiet.To after 2000, the invention of simple synthesis and scientists study find boron
N doping can effectively adjust the photoelectricity physical property of aroma system, and the conjugated polycyclic aromatic hydrocarbons of boron N doping causes people again
Research interest.
The Ashe group of University of Michigan in 2000 is synthesizing monocycle 1,2- azepine boron compound aspect with mild method
It made breakthrough progress.2011, Japanese Nakamura group synthesized the virtue of boron nitrogen substitution using the method for Dewar
Fragrant hydrocarbon and developed a series of intramolecular boryls method (T. Hatakeyama, S.Hashimoto, S.Seki,
M.Nakamura, Synthesis of BN-fused polycyclic aromatics via
Tandemintramolecular electrophilic areneborylation, J.Am. Chem.Soc.2011,133,
18614-18617).2012, Nakamura et al. synthesized double benzene [6] helicenes of racemic boron nitrogen with same method
(T.Hatakeyama, S.Hashimoto, T.Oba, M. Nakamura, Azaboradibenzo [6] helicene:carrier
Inversion induced by helical homochirality, J.Am.Chem.Soc.2012,134,19600-
19603).2014, Nakamura group was using the poly-ring aromatic compounds of the boron N doping of synthesis and its derivative as phosphorescence
The material of main part layer of light emitting diode, this kind of device have the better service life.Yamaguchi group recent report is based on three alkane
Base replaces to synthesize 1, the 2- azepine boron of big π system.Kawashima is small to be combined into using Isosorbide-5-Nitrae boron nitrogen molecular as center unit
Pentacene, heptacene compound.Hatakeyama, Nakamura et al. report a series of electrophilic boryl by intramoleculars
Change to synthesize the polycyclic aromatic hydrocarbons (PAH) of double boron azo-cycle bondings.
The Molander of the later period University of Pennsylvania teaches Liu seminar, the Peking University of seminar, Boston College
Pei Jian professor seminar report the heteroaryl hydrocarbon compound isomers of boron nitrogen position substitution, subsequent scientists have synthesized boron successively
The anthracene of N doping, phenanthrene, pyrene and bigger conjugated structure boron N doping aromatic hydrocarbons.
Boron azepine benzothiophene kind heteroaryl hydrocarbon has very high researching value, Dewar as a kind of important polycyclic aromatic hydrocarbon
It has been combined into the boron azines compound of different loci with other projects, and has done optical physics test to it.((a) Bosdet,
M.J.D.；Jaska, C.A.；Piers, W.E.；Sorensen, T.S.；Parvez, M. Org.Lett.2007,9,1395. (b)
Dewar, M.J.S.；Kubba, V.P.；Pettit, R.J.Chem.Soc. 1958,3073. (c) Lu, J.-S.；Ko, S.-B.；
Walters, N.R.；Kang, Y.；Sauriol, F；Wang, S. Angew.Chem., Iht.Ed.2013,52,4544. (d)
AlbertoEt al.Org.Lett.2017,19,3458-3461)
In the past few years, it is greatly improved to the chemical research of boron N doping aromatic hydrocarbons, is closed with different methods
At the compound of the boron N doping of diversified forms.The potential application of boron N doping class compound in the electronic device is extensive
Research, but its potential application characteristic in luminescent material is widely developed not yet.
In conclusion the organic photoelectrical material that polycyclic aromatic hydrocarbon conjugated system is novel as one kind, in organic electronics field
In occupation of very important status.And there is unique photophysical property doped with different heteroatomic conjugation aromatic hydrocarbons, especially
It is the conjugation aromatic hydrocarbons of boron N doping with the characteristics of luminescence.The boron N doping of various new can be synthesized by decorating conjugated skeleton
It is conjugated aromatic hydrocarbons, is applied to field of light emitting materials.
Summary of the invention
Present invention aims at, provide a kind of Novel boron azepine aphthothiophenes and its derivative design synthetic method and its
Potential application provides more schemes to obtain more efficient organic photoelectrical material.
In order to achieve the above object, the technical solution adopted by the present invention is that:
A kind of boron azepine aphthothiophenes and its derivative, the structural formula of such compound are as follows:
Wherein R1, R2, R3, R4It is independent substituted or non-substituted group, including alkyl, aryl (phenyl ring, thiophene respectively
Ring, furan nucleus, pyrroles, pyridine, benzothiophene, benzofuran, benzopyrrole, benzo pyridine, naphthalene nucleus, anthracene nucleus, that non-alkene and four
Benzene, pyrene,, linear or angled pentacene and six, indenes, fluorenes etc.).Wherein R3, R4Or single substitution halogen original
Sub- X:F, Cl, Br, I.
The synthetic route of boron azepine aphthothiophenes compound is as follows:
Particular content is as follows:
1) precise 2,5- bis- bromo- 3,4- dinitro thiophene 1.66g, phenyl boric acid 1.48g, potassium carbonate 1.38g and four or three
Phenylphosphine palladium 0.30g is added in the round-bottomed flask of 100mL, reaction system is heated to 100 DEG C of reactions, reaction is overnight.Next day
TLC monitoring, rotary evaporation remove solvent, and methylene chloride and water extraction three times, merge organic phase, add anhydrous magnesium sulfate five points dry
Zhong Hou is filtered, and liquid phase removes solvent through Rotary Evaporators, and residue is dissolved with a small amount of toluene, using silica gel column chromatography into
Row column chromatographic runs elute phase (DCM: PE=1: 2), obtain white solid (compound 4).
2) it accurately weighs bromo- 3, the 4- diaminothiophen 326mg of 2,5- bis- and 10% palladium carbon 220.0mg is added to reaction tube
In, 5mL ethyl acetate solution, which is added, dissolves it sufficiently, after vacuumizing using vacuum water circulation pump to system, it is re-filled with hydrogen,
Repeatedly for three times.System is heated to 70 DEG C, reaction is overnight.Next day cooling reaction system, TLC monitoring, suction funnel add diatomite
It is filtered, removes palladium carbon solid, be spin-dried for solution and obtain product as light yellow solid (compound 5).
3) the precise compound 5266mg in glove box, dichlorophenyl borine 397mg and anhydrous triethylamine 304mg,
In tube sealing plus 5mL chlorobenzene dissolves.Reaction system is heated to 170 DEG C, reacts 36h.Cooling reaction system, TLC monitoring, dichloro
Methane and water extraction three times, merge organic phase, add anhydrous magnesium sulfate five minutes dry, are filtered, liquid phase is through Rotary Evaporators
Solvent is removed, residue is dissolved with a small amount of toluene, and column chromatography is carried out using silica gel column chromatography, is eluted phase (DCM: PE=1: 4),
Obtain faint yellow color solid (compound 1).
The synthetic route of boron azanaphthalene thiophthene derivative 2 is as follows:
Particular content is as follows:
1) compound 5 weighs 170.00mg, and round-bottomed flask is added in sodium carbonate 260.00mg, and reaction is stayed overnight at room temperature.TLC
Monitoring, rotary evaporation remove solvent, and methylene chloride and water extraction three times, merge organic phase, add anhydrous magnesium sulfate five minutes dry,
It is filtered, liquid phase removes solvent through Rotary Evaporators, and residue is dissolved with a small amount of toluene, carries out column layer using silica gel column chromatography
Analysis operation, elutes phase (DCM: PE=1: 2), obtains red solid (compound 6).
2) compound 6 weighs 337mg and 10% palladium carbon 258mg and is added in autoclave, and 30mL ethyl acetate is added
Solution makes it dissolve.Under conditions of 4.00MPa hydrogen, 50 DEG C are restored, and reaction is stayed overnight, to be taken out after completion of the reaction
Filter, removes remaining palladium carbon solid, and rotary evaporation removes solvent, obtains faint yellow solid product.(compound 7).
4) precise compound 10 (1.00equiv, 1.00mmol, the 266mg) in glove box, dichlorophenyl borine
(4.00equiv, 4.00mmol, 590mg) and anhydrous triethylamine (4.00equiv, 4.00mmol, 404mg), is dissolved in 5mL chlorobenzene
In tube sealing.System is heated to 170 DEG C, reacts 48h.Cooling reaction system, TLC monitoring, methylene chloride and water extract three times,
Merge organic phase, add anhydrous magnesium sulfate five minutes dry, filtered, liquid phase removes solvent through Rotary Evaporators, and residue is used
A small amount of toluene dissolution, carries out column chromatographic runs using silica gel column chromatography, elutes phase (DCM: PE=1: 2), it is solid to obtain faint yellow color
Body (compound 2).
Detailed description of the invention
Fig. 1 is the single crystal diffraction structure chart of boron azepine benzothiophene kind heteroarene derivatives,
Fig. 2 is boron azepine benzothiophene kind heteroarene derivatives Absorption and emission spectra.
Specific embodiment
Following instance helps to understand the present invention, but is not limited to the contents of the present invention.
A kind of whole synthetic method of boron azepine benzothiophene kind heteroarene derivatives of the present invention, including following synthetic route
And step:
It illustrates to above-mentioned part of compounds, particular content is as follows:
Embodiment 1: the synthesis of double miscellaneous aphthothiophenes compounds 1 of 1,2- nitrogen boron
1) synthesis of compound 4: precise 2, bromo- 3, the 4- dinitro thiophene of 5- bis- (1.00equiv, 5mmol,
1.66g), phenyl boric acid (2.10equiv, 11.5mmol, 1.48g), potassium carbonate (2.00equiv, 10.0mmol, 1.38g) and four
Triphenylphosphine palladium (0.05equiv, 0.25mmol, 0.30g) is added in the round-bottomed flask of 100mL, using vacuum oil pump to body
System is vacuumized, and is passed through high pure nitrogen using Schlenk Line, repeatedly for three times, solvents tetrahydrofurane and water (volume is added
Than 4: Isosorbide-5-Nitrae 0mL), reaction system is heated to 100 DEG C of reactions, reaction is overnight.The monitoring of next day TLC, rotary evaporation remove solvent,
Methylene chloride and water extraction three times, merge organic phase, after adding anhydrous magnesium sulfate five minutes dry, are filtered, liquid phase is through rotating
Evaporimeter removes solvent, and residue dissolve with a small amount of toluene, using silica gel column chromatography progress column chromatographic runs, elute phase (DCM:
PE=1: 2), white solid (1.47g, yield 65%) is obtained.
1H NMR (400MHz, CDCl3): δ 7.48-7.54 (m, 10H, Ar)
2) synthesis of compound 5: accurately weigh bromo- 3, the 4- diaminothiophen of 2,5- bis- (1.00equiv, 1.00 mmol,
It 326mg) is added in reaction tube with 10% palladium carbon (2.00equiv, 2.00mmol, 220.0mg), it is molten that 5mL ethyl acetate is added
Liquid dissolves it sufficiently, after vacuumizing using vacuum water circulation pump to system, is re-filled with hydrogen, repeatedly for three times.System is heated
To 70 DEG C, reaction is overnight.Next day cooling reaction system, TLC monitoring, suction funnel add diatomite to be filtered, it is solid to remove palladium carbon
Body is spin-dried for solution and obtains 7, product as light yellow solid (210mg, yield 80%).
1H NMR (400MHz, CDCl3): δ 7.51-7.56 (m, 4H, Ar), 7.44 (m, 4H, Ar), 7.27-7.32 (m, 2H,
Ar), 3.79 (br, 4H, NH2).
3) synthesis of compound 1: precise compound 5 (1.00equiv, 1.00mmol, the 266mg) in glove box,
Dichlorophenyl borine (2.50equiv, 2.50mmol, 397mg) and anhydrous triethylamine (3.00 equiv, 3.00mmol,
304mg), the dissolution of 5mL chlorobenzene is added in tube sealing.Reaction system is heated to 170 DEG C, reacts 36h.Cooling reaction system, TLC
Monitoring, methylene chloride and water extraction three times, merge organic phase, add anhydrous magnesium sulfate five minutes dry, are filtered, liquid phase is through revolving
Turn evaporimeter and remove solvent, residue is dissolved with a small amount of toluene, is carried out column chromatography using silica gel column chromatography, is eluted phase (DCM: PE
=1: 4), obtaining faint yellow color solid.(90mg, yield 20%)
1H NMR (400MHz, CDCl3): δ 8.27 (d, J=8.0Hz, 2H, Ar), 8.01 (d, J=8.0Hz, 2H, Ar),
7.97 (br, 2H, NH2), 7.84-7.82 (m, 4H, Ar), 7.74 (t, J=7.2Hz, 2H, Ar), 7.56-7.49 (m, 6H, Ar),
7.44 (t, J=72Hz, 2H, Ar)
Embodiment 2: the synthesis of double miscellaneous aphthothiophenes compound derivatives 2 of 1,2- nitrogen boron
5) it the synthesis of compound 6: weighs compound 5 (1.00equiv, 0.63mmol, 170.00mg), sodium carbonate
Round-bottomed flask is added in (4.00equiv, 2.40mmol, 260.00mg), and stirrer is added, connects spherical condensation tube, adds rubber stopper,
To system carry out vacuum pumping, be passed through high pure nitrogen using Schlenk Line, repeatedly for three times, above connect a nitrogen balloon do it is slow
Punching is slowly added to the glyoxal water solution (1.10equiv, 0.71mmol, 0.13mL) of 40wt%, and etoh solvent 10mL is added,
Reaction is stayed overnight at room temperature.TLC monitoring, rotary evaporation remove solvent, and methylene chloride and water extraction three times, merge organic phase, add
Anhydrous magnesium sulfate is five minutes dry, is filtered, and liquid phase removes solvent through Rotary Evaporators, and residue is dissolved with a small amount of toluene,
Column chromatographic runs are carried out using silica gel column chromatography, are eluted phase (DCM: PE=1: 2), red solid (0.19g, yield is obtained
92%).
1H NMR (400MHz, CDCl3): δ 8.51 (s, 2H, Ar), 8.13 (d, J=8.0Hz, 2H, Ar), 7.50 (t, J=
7.2 Hz, 2H, Ar), 7.37 (t, J=7.2Hz, 2H, CH)
6) synthesis of compound 7: compound 9 (1.00equiv, 1.00mmol, 337mg) and 10% palladium carbon
(2.00equiv, 1.00mmol, 258mg) is added in autoclave, and 30mL ethyl acetate solution is added and makes it dissolve.?
Under conditions of 4.00MPa hydrogen, 50 DEG C are restored, and reaction overnight, to be filtered after completion of the reaction, removes remaining palladium carbon
Solid, rotary evaporation remove solvent, obtain faint yellow solid product (270mg, yield 90%).
1H NMR (400MHz, CDCl3): δ 7.62 (d, J=8.0Hz, 4H, Ar), 7.46 (t, J=7.2Hz, 4H, Ar),
7.30 (t, J=7.2Hz, 2H, Ar), 4.37 (br, 2H, NH2), 3.45 (t, J=7.2Hz, 4H, CH2).
7) synthesis of compound 2: in glove box precise compound 10 (1.00equiv, 1.00mmol,
266mg), dichlorophenyl borine (4.00equiv, 4.00mmol, 590mg) and anhydrous triethylamine (4.00 equiv,
4.00mmol, 404mg), 5mL chlorobenzene is dissolved in tube sealing.System is heated to 170 DEG C, reacts 48h.Cooling reaction system,
TLC monitoring, methylene chloride and water extraction three times, merge organic phase, add anhydrous magnesium sulfate five minutes dry, are filtered, liquid phase
Solvent is removed through Rotary Evaporators, residue is dissolved with a small amount of toluene, is carried out column chromatographic runs using silica gel column chromatography, is eluted phase
(DCM: PE=1: 2) obtain faint yellow color solid (90mg, yield 20%).
1H NMR (400MHz, CDCl3): δ 7.96 (dd, J1=8.0Hz, J2=4.0Hz, 4H, Ar), 7.73-7.69 (m,
2H, Ar), 7.59 (dd, J1=6.0Hz, J2=1.6Hz, 4H, Ar), 7.51-7.43 (m, 6H, NH2), 7.37 (t, J1=
15.2Hz, J 2=7.2Hz, 2H, Ar)
In order to further study the photophysical property of such compound, we have carried out single crystal diffraction survey to such compound
Try (Fig. 1) and UV absorption and fluorescent emission (Fig. 2) test.
Claims (4)
1. a kind of boron azepine aphthothiophenes class heteroaryl hydrocarbon compound, structure are as follows:
Wherein R1, R2, R3, R4It is independent substituted or non-substituted group, including alkyl respectively, aryl, wherein R3, R4It can also be with
Individually to replace halogen atom X:F, Cl, Br, I.
2. boron azepine aphthothiophenes class heteroaryl hydrocarbon compound according to claim 1, it is characterised in that the aryl is
It is phenyl ring, thiphene ring, furan nucleus, pyrroles, pyridine, benzothiophene, benzofuran, benzopyrrole, benzo pyridine, naphthalene nucleus, anthracene nucleus, non-
That alkene, aphthacene, pyrene,Linear or angled pentacene and six, indenes or fluorenes.
3. a kind of a kind of synthetic method of boron azepine aphthothiophenes class heteroaryl hydrocarbon compound described in claim 1, it is characterized in that:
Including following synthetic route and step:
1) synthesis of compound 4: precise 2, bromo- 3, the 4- dinitro thiophene (1.00equiv, 5mmol, 1.66g) of 5- bis-, benzene
Boric acid (2.10equiv, 11.5mmol, 1.48g), potassium carbonate (2.00equiv, 10.0mmol, 1.38g) and tetra-triphenylphosphine palladium
(0.05equiv, 0.25mmol, 0.30g) is added in the round-bottomed flask of 100mL, and stirrer is added, connects spherical condensation tube,
Add rubber stopper to seal, system is vacuumized using vacuum oil pump, is passed through high pure nitrogen using Schlenk Line, repeatedly three
It is secondary, it above connects a nitrogen balloon and buffers, solvents tetrahydrofurane and water (volume ratio 4: Isosorbide-5-Nitrae 0mL) is added, reaction system is heated to
100 DEG C of reactions, reaction is overnight.The monitoring of next day TLC, rotary evaporation remove solvent, and methylene chloride and water extraction three times, merge organic
Phase is filtered, liquid phase removes solvent, a small amount of first of residue through Rotary Evaporators after adding anhydrous magnesium sulfate five minutes dry
Benzene dissolution carries out column chromatographic runs using silica gel column chromatography, elutes phase (DCM: PE=1: 2), obtain white solid
2) synthesis of compound 5: bromo- 3, the 4- diaminothiophen (1.00equiv, 1.00mmol, 326mg) of 2,5- bis- is accurately weighed
It is added in reaction tube with 10% palladium carbon (2.00equiv, 2.00mmol, 220.0mg), 5mL ethyl acetate solution, which is added, makes it
Sufficiently dissolution is re-filled with hydrogen, repeatedly for three times after vacuumizing using vacuum water circulation pump to system.System is heated to 70 DEG C,
Reaction is overnight.Next day cooling reaction system, TLC monitoring, suction funnel add diatomite to be filtered, remove palladium carbon solid, be spin-dried for
Solution obtains product as light yellow solid
3) synthesis of compound 1: precise compound 5 (1.00equiv, 1.00mmol, 266mg), dichloro in glove box
Phenylborinane (2.50equiv, 2.50mmol, 397mg) and anhydrous triethylamine (3.00equiv, 3.00mmol, 304mg), are being sealed
The dissolution of Guan Zhongjia 5mL chlorobenzene.Reaction system is heated to 170 DEG C, reacts 36h.Cooling reaction system, TLC monitoring, methylene chloride
Three times with water extraction, merge organic phase, add anhydrous magnesium sulfate five minutes dry, filtered, liquid phase is removed through Rotary Evaporators
Solvent, residue are dissolved with a small amount of toluene, are carried out column chromatography using silica gel column chromatography, are eluted phase (DCM: PE=1: 4), obtain light
Yellow color solid.
4. a kind of synthetic method of boron azepine aphthothiophenes class heteroarene derivatives described in claim 1, it is characterized in that: including
Following synthetic route and step
5) it the synthesis of compound 6: weighs compound 5 (1.00equiv, 0.63mmol, 170.00mg), sodium carbonate
Round-bottomed flask is added in (4.00equiv, 2.40mmol, 260.00mg), and stirrer is added, connects spherical condensation tube, adds rubber stopper,
To system carry out vacuum pumping, be passed through high pure nitrogen using Schlenk Line, repeatedly for three times, above connect a nitrogen balloon do it is slow
Punching is slowly added to 8 aqueous solution of glyoxal (1.10equiv, 0.71mmol, 0.13mL) of 40wt%, and etoh solvent 10mL is added,
Reaction is stayed overnight at room temperature.TLC monitoring, rotary evaporation remove solvent, and methylene chloride and water extraction three times, merge organic phase, add
Anhydrous magnesium sulfate is five minutes dry, is filtered, and liquid phase removes solvent through Rotary Evaporators, and residue is dissolved with a small amount of toluene,
Column chromatographic runs are carried out using silica gel column chromatography, are eluted phase (DCM: PE=1: 2), red solid is obtained
6) synthesis of compound 7: compound 7 (1.00equiv, 1.00mmol, 337mg) and 10% palladium carbon (2.00equiv,
1.00mmol, 258mg) it is added in autoclave, 30mL ethyl acetate solution is added and makes it dissolve.In 4.00MPa hydrogen
Under conditions of, 50 DEG C are restored, and reaction overnight, to be filtered after completion of the reaction, removes remaining palladium carbon solid, rotation is steamed
Hair removes solvent, obtains faint yellow solid product.
7) synthesis of compound 2: precise compound 10 (1.00equiv, 1.00mmol, 266mg), dichloro in glove box
Phenylborinane (4.00equiv, 4.00mmol, 590mg) and anhydrous triethylamine (4.00equiv, 4.00mmol, 404mg), are dissolved in
5mL chlorobenzene is in tube sealing.System is heated to 170 DEG C, reacts 48h.Cooling reaction system, TLC monitoring, methylene chloride and water extraction
It takes three times, merges organic phase, add anhydrous magnesium sulfate five minutes dry, filtered, liquid phase removes solvent through Rotary Evaporators, remains
Excess is dissolved with a small amount of toluene, is carried out column chromatographic runs using silica gel column chromatography, is eluted phase (DCM: PE=1: 2), obtain yellowish
Color color solid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113058646A (en) * | 2021-03-26 | 2021-07-02 | 南京林业大学 | Heterogeneous hindered Lewis acid-base pair catalyst and preparation method and application thereof |
| CN114106029A (en) * | 2021-12-20 | 2022-03-01 | 中国科学院长春应用化学研究所 | Organic molecule containing boron-nitrogen coordination bond and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113058646A (en) * | 2021-03-26 | 2021-07-02 | 南京林业大学 | Heterogeneous hindered Lewis acid-base pair catalyst and preparation method and application thereof |
| CN114106029A (en) * | 2021-12-20 | 2022-03-01 | 中国科学院长春应用化学研究所 | Organic molecule containing boron-nitrogen coordination bond and preparation method thereof |
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