CN109331872A - Application of the n-BuLi in catalysis imines and borine hydroboration - Google Patents
Application of the n-BuLi in catalysis imines and borine hydroboration Download PDFInfo
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- CN109331872A CN109331872A CN201811133200.9A CN201811133200A CN109331872A CN 109331872 A CN109331872 A CN 109331872A CN 201811133200 A CN201811133200 A CN 201811133200A CN 109331872 A CN109331872 A CN 109331872A
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- imines
- borine
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- 229910000085 borane Inorganic materials 0.000 title claims abstract description 56
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 title claims abstract description 47
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 150000002466 imines Chemical class 0.000 title claims abstract description 38
- 238000006197 hydroboration reaction Methods 0.000 title claims abstract description 35
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 64
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 42
- 230000018044 dehydration Effects 0.000 claims description 18
- 238000006297 dehydration reaction Methods 0.000 claims description 18
- 238000012545 processing Methods 0.000 claims description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 17
- -1 methoxyl group Chemical group 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 28
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 26
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 8
- 230000005311 nuclear magnetism Effects 0.000 description 7
- 239000011295 pitch Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MPRONVWLCPZXOB-UHFFFAOYSA-N 1-(4-fluorophenyl)-n-phenylmethanimine Chemical compound C1=CC(F)=CC=C1C=NC1=CC=CC=C1 MPRONVWLCPZXOB-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000004705 aldimines Chemical class 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- DJGDQBWKJYPZEF-UHFFFAOYSA-N n-(4-bromophenyl)-1-phenylmethanimine Chemical compound C1=CC(Br)=CC=C1N=CC1=CC=CC=C1 DJGDQBWKJYPZEF-UHFFFAOYSA-N 0.000 description 1
- NWCAQYVAHZWHIO-UHFFFAOYSA-N n-(4-chlorophenyl)-1-phenylmethanimine Chemical compound C1=CC(Cl)=CC=C1N=CC1=CC=CC=C1 NWCAQYVAHZWHIO-UHFFFAOYSA-N 0.000 description 1
- OEJZOCTWYUFFNN-UHFFFAOYSA-N n-(4-fluorophenyl)-1-phenylmethanimine Chemical compound C1=CC(F)=CC=C1N=CC1=CC=CC=C1 OEJZOCTWYUFFNN-UHFFFAOYSA-N 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/122—Metal aryl or alkyl compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The present invention relates to the applications of n-BuLi, and in particular to application of the n-BuLi in the hydroboration of catalysis imines and borine.Successively catalyst, borine and imines are uniformly mixed, reacted 1~2 hour, is exposed in air and terminates reaction, reaction solution is removed under reduced pressure solvent, obtains the borate of different substituents.N-BuLi disclosed by the invention can at room temperature high activity catalysis imines and borine hydroboration, catalyst amount is only 4 ~ 5mol% of imines mole, reaction can reach 90% or more yield, compared with existing catalyst system, commercialization reagent n-BuLi is utilized, reaction condition is mild, and the yield of the borate of different substituents is up to 99% in limited conditions.
Description
Technical field
The application of commercialization reagent n-BuLi of the present invention, and in particular to n-BuLi is catalyzed imines and borine
Synthesis application.
Technical background
Aminated compounds and its derivative are generally existing in nature, especially universally present in living nature, have
Epochmaking physiological action.They are biologies, chemical, and important organic compound, many drugs contain amine in medicine and other fields
Functional group, that is, amino, such as protein, all there is amino in antibiotic and alkaloid in nucleic acid.Aminated compounds has multi-party
Face use value, application range is very extensive, is typically used to synthesize textile, dyestuff, polymer, pigment and pesticide etc..It is existing
Hydroboration with the presence of technology about C=O key, since the hydroboration of carbonyl is easy more than the hydroboration of imines
Occur, therefore the prior art is very harsh about the condition of C=N key hydroboration, so developing for unsaturation C=N key
Hydroboration efficient catalytic system, all have great importance to modern industry and Synthetic Organic Chemistry.
The hydroboration of imines has become research hotspot in recent years, and the hydroboration that the catalyst of report is applied to imines is anti-
Should mainly include the catalyst system of major element: magnesium, calcium, sodium, rhenium, zinc etc. be (referring to Manna, K.; Ji, P.; Greene,
F. X.; Lin, W. J. Am. Chem. Soc.2016, 138, 7488−7491；Lin, Y-C.; Hatzakis, E.;
McCarthy, S. M.; Reichl, K. D.; Lai, T-Y.; Yennawar, H. P.; Radosevich, A. T.J. Am. Chem. Soc.2017, 139, 6,008 6016).But the catalyst system reported at present, catalyst are all opposite
Expensive or be difficult to prepare or the reaction time is longer and to react at high temperature, some catalyst system yields are very low.So opening
The catalyst system for sending out the hydroboration of efficient catalytic imines under temperate condition is of crucial importance.
Summary of the invention
Goal of the invention of the invention is to provide the application of n-BuLi, i.e., is catalyzed imines by effective catalyst of n-BuLi
The application of hydroboration occurs with borine.
To achieve the above object of the invention, the technical solution adopted by the present invention is that: n-BuLi is in catalysis imines and borine boron
Application in hydrogenation；The n-BuLi is commercialized reagent n-butyllithium.
The invention also discloses the methods that hydroboration occurs for n-BuLi catalysis imines and borine, including following step
It is rapid: under anhydrous and oxygen-free environment, under atmosphere of inert gases, imines to be added in the reaction flask by dehydration and deoxidation processing, addition has
Then borine is added in solvent, be uniformly mixed, and adds catalyst n-BuLi, reacts 1~2 h, is exposed in air and terminates
Reaction, obtains product.
The present invention further discloses a kind of methods that imines and borine generation hydroboration prepare borate, including with
Lower step: under anhydrous and oxygen-free environment, in atmosphere of inert gases, imines is added in the reaction flask by dehydration and deoxidation processing, adds
Enter organic solvent, borine is then added, be uniformly mixed, add catalyst n-BuLi, reacts 1~2 h, be exposed in air
Reaction is terminated, product borate is obtained.
In above-mentioned technical proposal, the imines is selected from aldimine；The general formula of the chemical structure of the imines is as follows:
Wherein R1Or R2For one of electron-withdrawing group or electron donating group, halogen, methyl, methoxyl group can be selected from；The boron
Alkane is selected from pinacol borine.
In above-mentioned technical proposal, the catalyst amount can be the 4%~5% of imines molal quantity, imines and pinacol borine
Molar ratio be 1: 1~1: 1.2.
In above-mentioned technical proposal, reaction temperature is room temperature, and the reaction time is 1~2 h.
In above-mentioned technical proposal, organic solvent is tetrahydrofuran.
Above-mentioned technical proposal can be expressed as follows:
Due to the application of the above technical scheme, the present invention has the following advantages compared with prior art:
1. present invention firstly discovers that commercialized n-BuLi can efficiently be catalyzed imines and hydroboration, height occur for borine
Meet atom economy synthesis.
2. high (the catalyst of catalytic activity that hydroboration occurs for n-BuLi catalysis imines disclosed by the invention and borine
The 4%~5% of dosage molal quantity), reaction condition is mild (room temperature), and the reaction time is short (1~2h), and reaction yield is high, reaction letter
Single controllable, post-processing is simple, and reaction uses cheap THF for solvent.
3. catalyst disclosed by the invention has the imines of different the position of substitution, different electronic effects preferable general
It is suitable.
Specific embodiment
The present invention is described further below with reference to embodiment:
Embodiment one: n-BuLi is catalyzed Bian fork aniline and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, the lower Bian that 0.5 mmol is added of argon gas protection pitches aniline, and 100 ul are added
Then THF is added 0.5 mmol (0.0726 mL) borine with liquid-transfering gun and is uniformly mixed, is eventually adding 25 ul n-BuLis
Tetrahydrofuran solution (1M) (5 mol% dosages, similarly hereinafter) after reacting 2 h, is drawn a drop in nuclear magnetic tube with dropper, is added
CDCl3Wiring solution-forming.It is computed1It is 90% that H, which composes yield,.The nuclear magnetic data of product:1H NMR (CDCl3, 400 MHz) δ:
7.29~7.12(m, 9H), 6.88~6.84 (t, 1H), 4.69 (s, 2H), 1.29 (s, 12H)。
Embodiment two: n-BuLi is catalyzed Bian fork aniline and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, the lower Bian that 0.5 mmol is added of argon gas protection pitches aniline, and 100 ul are added
Then THF is added 0.55 mmol (0.0798 mL) borine with liquid-transfering gun and is uniformly mixed, is eventually adding 25 ul n-BuLis
Tetrahydrofuran solution (1M) (5 mol% dosages, similarly hereinafter) after reacting 2 h, is drawn a drop in nuclear magnetic tube with dropper, is added
CDCl3Wiring solution-forming.It is computed1It is 95% that H, which composes yield,.The nuclear magnetic data of product:1H NMR (CDCl3, 400 MHz) δ:
7.29~7.12(m, 9H), 6.88~6.84 (t, 1H), 4.69 (s, 2H), 1.29 (s, 12H)。
Embodiment three: n-BuLi is catalyzed Bian fork aniline and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, the lower Bian that 0.5 mmol is added of argon gas protection pitches aniline, and 100 ul are added
Then THF is added 0.6 mmol (0.0871 mL) borine with liquid-transfering gun and is uniformly mixed, is eventually adding 25 ul n-BuLis
Tetrahydrofuran solution (1M) (5 mol% dosages, similarly hereinafter) after reacting 1 h, is drawn a drop in nuclear magnetic tube with dropper, is added
CDCl3Wiring solution-forming.It is computed1It is 96% that H, which composes yield,.The nuclear magnetic data of product:1H NMR (CDCl3, 400 MHz) δ:
7.29~7.12(m, 9H), 6.88~6.84 (t, 1H), 4.69 (s, 2H), 1.29 (s, 12H)。
Example IV: n-BuLi is catalyzed Bian fork aniline and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, the lower Bian that 0.5 mmol is added of argon gas protection pitches aniline, and 100 ul are added
Then THF is added 0.6 mmol (0.0871 mL) borine with liquid-transfering gun and is uniformly mixed, is eventually adding 20 ul n-BuLis
Tetrahydrofuran solution (1M) (4 mol% dosage) after reacting 2 h, draws a drop in nuclear magnetic tube with dropper, CDCl is added3Match
At solution.It is computed1It is 97% that H, which composes yield,.The nuclear magnetic data of product:1H NMR (CDCl3, 400 MHz) δ: 7.29~7.12
(m, 9H), 6.88~6.84 (t, 1H), 4.69 (s, 2H), 1.29 (s, 12H)。
Embodiment five: n-BuLi is catalyzed Bian fork aniline and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, the lower Bian that 0.5 mmol is added of argon gas protection pitches aniline, and 100 ul are added
Then THF is added 0.6 mmol (0.0871 mL) borine with liquid-transfering gun and is uniformly mixed, is eventually adding 25 ul n-BuLis
Tetrahydrofuran solution (1M) (5 mol% dosage) after reacting 2 h, draws a drop in nuclear magnetic tube with dropper, CDCl is added3It is made into
Solution.It is computed1It is 99% that H, which composes yield,.The nuclear magnetic data of product:1H NMR (CDCl3, 400 MHz) δ: 7.29~7.12
(m, 9H), 6.88~6.84 (t, 1H), 4.69 (s, 2H), 1.29 (s, 12H)。
The amido lithium compound that n-BuLi is replaced with to formula I, is unable to get product.
Embodiment six: n-BuLi catalysis N- (pMethyl benzylidene) aniline and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, N- that argon gas protection is lower to be added 0.5 mmol (pMethyl benzylidene) benzene
100 ul THF are added in amine, and 0.6 mmol (0.0871 mL) borine then is added with liquid-transfering gun and is uniformly mixed, is eventually adding 25
The tetrahydrofuran solution (1M) (5 mol% dosages, similarly hereinafter) of ul n-BuLi after reacting 2 h, draws a drop in nuclear-magnetism with dropper
CDCl is added in Guan Zhong3Wiring solution-forming.It is computed1It is 99% that H, which composes yield,.The nuclear magnetic data of product:1H NMR (CDCl3, 400
MHz) δ: 7.23~7.08(m, 8H), 6.89~6.85 (t, 1H), 4.66 (s, 2H), 2.31 (s, 3H), 1.30
(s, 12H)。
Embodiment seven: n-BuLi catalysis N- (pMethoxybenzylidene) aniline and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, N- that argon gas protection is lower to be added 0.5 mmol (pMethoxybenzylidene)
100 ul THF are added in aniline, and 0.6 mmol (0.0871 mL) borine then is added with liquid-transfering gun and is uniformly mixed, is eventually adding
The tetrahydrofuran solution (1M) (4 mol% dosages, similarly hereinafter) of 20ul n-BuLi after reacting 2 h, draws a drop in core with dropper
In magnetic tube, CDCl is added3Wiring solution-forming.It is computed1It is 99% that H, which composes yield,.The nuclear magnetic data of product:1H NMR (CDCl3, 400
MHz) δ: 7.22~7.13(d, 6H), 6.89~6.80 (d, 3H), 4.63 (s, 2H), 3.77 (s, 3H), 1.30
(s, 12H)。
Embodiment eight: n-BuLi is catalyzed N- (4- fluorobenzylidene) aniline and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, lower N- (4- fluorobenzylidene) benzene that 0.5 mmol is added of argon gas protection
100 ul THF are added in amine, and 0.6 mmol (0.0871 mL) borine then is added with liquid-transfering gun and is uniformly mixed, is eventually adding 25
The tetrahydrofuran solution (1M) (5 mol% dosages, similarly hereinafter) of ul n-BuLi after reacting 2 h, draws a drop in nuclear-magnetism with dropper
CDCl is added in Guan Zhong3Wiring solution-forming.It is computed1It is 99% that H, which composes yield,.The nuclear magnetic data of product:1H NMR (CDCl3, 400
MHz) δ: 7.22~7.15(d, 6H), 6.98~6.94 (d, 3H), 4.66 (s, 2H), 1.30 (s, 12H)。
Embodiment nine: n-BuLi is catalyzed N- (4- chlorobenzene methylene) aniline and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, lower N- (the 4- chlorobenzene methylene) benzene that 0.5 mmol is added of argon gas protection
100 ul THF are added in amine, and 0.6 mmol (0.0871 mL) borine then is added with liquid-transfering gun and is uniformly mixed, is eventually adding 25
The tetrahydrofuran solution (1M) (5 mol% dosages, similarly hereinafter) of ul n-BuLi after reacting 2 h, draws a drop in nuclear-magnetism with dropper
CDCl is added in Guan Zhong3Wiring solution-forming.It is computed1It is 99% that H, which composes yield,.The nuclear magnetic data of product:1H NMR (CDCl3, 400
MHz) δ: 7.20~7.14(d, 6H), 6.99~6.93 (d, 3H), 4.64 (s, 2H), 1.30 (s, 12H)。
Embodiment ten: n-BuLi is catalyzed N- (4- bromobenzene methylene) aniline and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, lower N- (the 4- bromobenzene methylene) benzene that 0.5 mmol is added of argon gas protection
100 ul THF are added in amine, and 0.6 mmol (0.0871 mL) borine then is added with liquid-transfering gun and is uniformly mixed, is eventually adding 25
The tetrahydrofuran solution (1M) (5 mol% dosages, similarly hereinafter) of ul n-BuLi after reacting 2 h, draws a drop in nuclear-magnetism with dropper
CDCl is added in Guan Zhong3Wiring solution-forming.It is computed1It is 99% that H, which composes yield,.The nuclear magnetic data of product:1H NMR (CDCl3, 400
MHz) δ: 7.24~7.16(d, 6H), 6.97~6.93 (d, 3H), 4.63 (s, 2H), 1.31 (s, 12H)。
Embodiment 11: n-BuLi is catalyzed benzal para-totuidine and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, the lower benzal that 0.5 mmol is added of argon gas protection is added 100 to toluene
Then ul THF is added 0.6 mmol (0.0871 mL) borine with liquid-transfering gun and is uniformly mixed, is eventually adding 25 ul n-BuLis
Tetrahydrofuran solution (1M) (5 mol% dosages, similarly hereinafter), react 2 h after, with dropper draw one drop in nuclear magnetic tube, be added
CDCl3Wiring solution-forming.It is computed1It is 99% that H, which composes yield,.The nuclear magnetic data of product:1H NMR (CDCl3, 400 MHz) δ:
7.32~7.28(d, 5H), 7.10~7.08 (d, 2H), 6.64~6.60 (d, 2H), 4.62 (s, 2H), 1.31
(s, 12H)。
Embodiment 12: n-BuLi is catalyzed N- (benzylidene) -4- fluoroaniline and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, lower N- (the benzylidene) -4- fluorobenzene that 0.5 mmol is added of argon gas protection
100 ul THF are added in amine, and 0.6 mmol (0.0871 mL) borine then is added with liquid-transfering gun and is uniformly mixed, is eventually adding 25
The tetrahydrofuran solution (1M) (5 mol% dosages, similarly hereinafter) of ul n-BuLi after reacting 2 h, draws a drop in nuclear-magnetism with dropper
CDCl is added in Guan Zhong3Wiring solution-forming.It is computed1It is 99% that H, which composes yield,.The nuclear magnetic data of product:1H NMR (CDCl3, 400
MHz) δ: 7.24~7.02(d, 7H), 6.75~6.70 (d, 2H), 4.66 (s, 2H), 1.32 (s, 12H)。
Embodiment 13: n-BuLi is catalyzed N- (benzylidene) -4- chloroaniline and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, lower N- (the benzylidene) -4- chlorobenzene that 0.5 mmol is added of argon gas protection
100 ul THF are added in amine, and 0.6 mmol (0.0871 mL) borine then is added with liquid-transfering gun and is uniformly mixed, is eventually adding 25
The tetrahydrofuran solution (1M) (5 mol% dosages, similarly hereinafter) of ul n-BuLi after reacting 2 h, draws a drop in nuclear-magnetism with dropper
CDCl is added in Guan Zhong3Wiring solution-forming.It is computed1It is 99% that H, which composes yield,.The nuclear magnetic data of product:1H NMR (CDCl3, 400
MHz) δ: 7.26~7.05(d, 7H), 6.74~6.69 (d, 2H), 4.61 (s, 2H), 1.30 (s, 12H)。
Embodiment 14: n-BuLi is catalyzed N- (benzylidene) -4- bromaniline and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, lower N- (the benzylidene) -4- bromobenzene that 0.5 mmol is added of argon gas protection
100 ul THF are added in amine, and 0.6 mmol (0.0871 mL) borine then is added with liquid-transfering gun and is uniformly mixed, is eventually adding 25
The tetrahydrofuran solution (1M) (5 mol% dosages, similarly hereinafter) of ul n-BuLi after reacting 2 h, draws a drop in nuclear-magnetism with dropper
CDCl is added in Guan Zhong3Wiring solution-forming.It is computed1It is 99% that H, which composes yield,.The nuclear magnetic data of product:1H NMR (CDCl3, 400
MHz) δ: 7.27~7.03(d, 7H), 6.76~6.71 (d, 2H), 4.62 (s, 2H), 1.30 (s, 12H)。
The reaction temperature of above-described embodiment is room temperature；Present invention firstly discovers that commercialization reagent n-BuLi can be mild
Reaction condition catalysis imines hydroboration, yield is very high, has the wider substrate scope of application, cheap catalyst
And mild catalytic condition, possibility is provided for industrial applications.
Claims (10)
1. application of the n-BuLi in catalysis imines and borine hydroboration.
2. application according to claim 1, which is characterized in that n-BuLi is catalyzed imines and borine generation hydroboration is anti-
The method answered is the following steps are included: under anhydrous and oxygen-free environment, under atmosphere of inert gases, in the reaction flask by dehydration and deoxidation processing
Middle addition imines is added organic solvent, borine is then added, and is uniformly mixed, and adds catalyst n-BuLi, room temperature reaction 1
~2 h are exposed in air and terminate reaction, obtain product.
3. application according to claim 2, which is characterized in that the general formula of the chemical structure of the imines is as follows:
Wherein R1Or R2For one of electron-withdrawing group or electron donating group, it is selected from halogen, methyl, methoxyl group；The borine choosing
From pinacol borine；The organic solvent is tetrahydrofuran；
The dosage of the n-BuLi is the 4%~5% of imines molal quantity, and the molar ratio of imines and pinacol borine is 1: 1~1:
1.2。
4. the method that hydroboration prepares borate occurs for a kind of imines and borine, comprising the following steps: anhydrous and oxygen-free environment
Under, in atmosphere of inert gases, imines is added in the reaction flask by dehydration and deoxidation processing, organic solvent is added, is then added
Borine is uniformly mixed, and adds catalyst n-BuLi, and reaction obtains product borate.
5. according to the method described in claim 4, it is characterized in that, the general formula of the chemical structure of the imines is as follows:
Wherein R1Or R2For one of electron-withdrawing group or electron donating group, it is selected from halogen, methyl, methoxyl group；The borine choosing
From pinacol borine.
6. according to the method described in claim 4, it is characterized in that, the catalyst amount be imines molal quantity 4%~5%,
The molar ratio of imines and pinacol borine is 1: 1~1: 1.2.
7. according to the method described in claim 4, it is characterized in that, the catalyst amount is the 5% of imines molal quantity, imines
Molar ratio with pinacol borine is 1: 1.2.
8. according to the method described in claim 4, the time of reaction is 1~2 it is characterized in that, the temperature of reaction is room temperature
h。
9. according to the method described in claim 4, it is characterized in that, organic solvent is tetrahydrofuran.
10. the borate of preparation according to the method for claim 4.
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| WO2020073175A1 (en) * | 2018-10-08 | 2020-04-16 | 苏州大学张家港工业技术研究院 | Use of n-butyllithium for catalyzing hydroboration of imine and borane |
| CN111303201A (en) * | 2020-03-13 | 2020-06-19 | 苏州大学 | Application of n-butyl lithium in catalysis of cyanogen silicification reaction of ketone and silane |
| CN111763226A (en) * | 2020-06-16 | 2020-10-13 | 苏州大学 | Hydroboration reaction method of carbonic ester |
| WO2021253847A1 (en) * | 2020-06-16 | 2021-12-23 | 苏州大学 | Use of deprotonated phenyl bridged β-ketimine lithium compound in hydroboration reaction |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020073175A1 (en) * | 2018-10-08 | 2020-04-16 | 苏州大学张家港工业技术研究院 | Use of n-butyllithium for catalyzing hydroboration of imine and borane |
| US11845068B2 (en) | 2018-10-08 | 2023-12-19 | Soochow University | Use of n-butyllithium for catalyzing hydroboration of imine and borane |
| CN111303201A (en) * | 2020-03-13 | 2020-06-19 | 苏州大学 | Application of n-butyl lithium in catalysis of cyanogen silicification reaction of ketone and silane |
| CN111763226A (en) * | 2020-06-16 | 2020-10-13 | 苏州大学 | Hydroboration reaction method of carbonic ester |
| WO2021253847A1 (en) * | 2020-06-16 | 2021-12-23 | 苏州大学 | Use of deprotonated phenyl bridged β-ketimine lithium compound in hydroboration reaction |
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