CN109232622A - Application of the 2,6- diisopropyl benzene amido lithium in catalysis imines and borine hydroboration - Google Patents
Application of the 2,6- diisopropyl benzene amido lithium in catalysis imines and borine hydroboration Download PDFInfo
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- imines
- borine
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- 229910000085 borane Inorganic materials 0.000 title claims abstract description 54
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 39
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 150000002466 imines Chemical class 0.000 title claims abstract description 35
- 238000006197 hydroboration reaction Methods 0.000 title claims abstract description 29
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 10
- 125000003368 amide group Chemical group 0.000 title abstract description 21
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 title abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 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 6
- 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 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 17
- -1 amido lithium Chemical compound 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- OEUOYRGMNTTYGG-UHFFFAOYSA-N [Li+].CCC[N-]C1=CC=CC=C1 Chemical compound [Li+].CCC[N-]C1=CC=CC=C1 OEUOYRGMNTTYGG-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 125000001424 substituent group Chemical group 0.000 abstract 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 28
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-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 12
- 150000001412 amines Chemical class 0.000 description 9
- 229910052796 boron Inorganic materials 0.000 description 7
- 230000005311 nuclear magnetism Effects 0.000 description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- 239000011295 pitch Substances 0.000 description 5
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- 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
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 150000001335 aliphatic alkanes 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
- 230000015572 biosynthetic process 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IFOBAKIQHNOSRE-UHFFFAOYSA-N lithium;phenylazanide Chemical compound [Li+].[NH-]C1=CC=CC=C1 IFOBAKIQHNOSRE-UHFFFAOYSA-N 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
- 238000002360 preparation method 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
- 238000003786 synthesis reaction Methods 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
- B01J31/0238—Amines with a primary amino group
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
- B01J2231/344—Boronation, e.g. by adding R-B(OR)2
Landscapes
- 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 2,6-DIPA base lithium, and in particular to application of the 2,6-DIPA base lithium 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.Disclosed by the invention 2,6- diisopropyl benzene amido lithium 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, simple 2,6-DIPA base lithium is utilized, reaction condition is mild, and the yield of the borate of different substituents is up to 99% with optimal conditions.
Description
Technical field
The application of 2,6-DIPA base lithium of the present invention, and in particular to 2,6-DIPA base lithium exists
The efficient application being catalyzed in imines and borine hydroboration.
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..By
It is easy to happen in the hydroboration of carbonyl more than the hydroboration of imines, so developing the boron for unsaturation C=N key
The efficient catalytic system of hydrogenation, all has 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 2,6-DIPA base lithium, i.e., with 2,6-DIPA
Base lithium is the application that effective catalyst is catalyzed imines and hydroboration occurs for borine.
To achieve the above object of the invention, the technical solution adopted by the present invention is that: 2,6-DIPA base lithium is being catalyzed
Application in aldehyde and borine hydroboration；The 2,6- diisopropyl benzene amido lithiumation formula are as follows: 2,6-iPr2PhNHLi。
Imines is catalyzed the invention also discloses 2,6-DIPA base lithium and the method for hydroboration occurs for borine,
The following steps are included: under atmosphere of inert gases, being added in the reaction flask by dehydration and deoxidation processing sub- under anhydrous and oxygen-free environment
Amine is added organic solvent, borine is then added, and is uniformly mixed, and adds catalyst 2,6-DIPA base lithium, reacts 1h
~2 h are exposed in air and terminate reaction, obtain product.
The present invention further discloses a kind of preparation method of borate, comprising the following steps: under anhydrous and oxygen-free environment,
In atmosphere of inert gases, imines is added in the reaction flask by dehydration and deoxidation processing, organic solvent is added, boron is then added
Alkane is uniformly mixed, and adds catalyst 2,6-DIPA base lithium, reacts the h of 1h~2, is exposed in air and is terminated instead
It answers, obtains product.
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 simple 2,6- diisopropyl benzene amido lithium can efficiently be catalyzed imines and boron hydrogen occurs for borine
Change reaction, highly meets atom economy synthesis.
2. the catalysis that hydroboration occurs for 2,6- diisopropyl benzene amido lithium catalysis imines disclosed by the invention and borine
Active height (the 4%~5% of catalyst amount molal quantity), reaction condition is mild (room temperature), and the reaction time is short (h of 1h~2), and anti-
Product yield is high, and reaction is simple controllable, and 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 pervasive
Property.
Specific embodiment
The present invention is described further below with reference to embodiment:
One: 2,6- diisopropyl benzene amido lithium of embodiment 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 40.9 ul 2,6- bis- is different
The tetrahydrofuran solution (0.6115M) (5 mol% dosages, similarly hereinafter) of propyl anilino- lithium after reacting 1 h, draws a drop with dropper
In nuclear magnetic tube, CDCl is added3Wiring 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)。
Two: 2,6- diisopropyl benzene amido lithium of embodiment 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 40.9 ul 2,6- bis- is different
The tetrahydrofuran solution (0.6115M) (5 mol% dosage) of propyl anilino- lithium 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: 7.29~7.12(m, 9H), 6.88~6.84 (t, 1H), 4.69 (s, 2H), 1.29 (s, 12H)。
The amido lithium compound that 2,6-DIPA base lithium is replaced with to formula I, is unable to get product.
Three: 2,6- diisopropyl benzene amido lithium of embodiment 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 32.7 ul 2,6- bis- is different
The tetrahydrofuran solution (0.6115M) (4 mol% dosage) of propyl anilino- lithium after reacting 2 h, draws a drop in core with dropper
In magnetic tube, CDCl is added3Wiring solution-forming.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)。
Example IV: 2,6- diisopropyl benzene amido lithium 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 40.9 ul 2,6- diformazan
The tetrahydrofuran solution (0.6115M) (5 mol% dosages, similarly hereinafter) of base anilino- lithium, react 2 h after, with dropper draw one drop in
In nuclear magnetic tube, CDCl is added3Wiring 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)。
Five: 2,6- diisopropyl benzene amido lithium of embodiment 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 40.9 ul 2,6- bis-
The tetrahydrofuran solution (0.6115M) (5 mol% dosages, similarly hereinafter) of cumene amido lithium after reacting 2 h, draws one with dropper
It drips in nuclear magnetic tube, CDCl is added3Wiring 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)。
Six: 2,6- diisopropyl benzene amido lithium of embodiment 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
The tetrahydrofuran solution (0.6115M) (5 mol% dosages, similarly hereinafter) of 40.9 ul 2,6-DIPA base lithiums reacts 2 h
Afterwards, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1It is 99% that H, which composes yield,.The nuclear-magnetism number of product
According to: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)。
Seven: 2,6- diisopropyl benzene amido lithium of embodiment catalysis N- (pMethoxyl group base 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 (pMethoxyl group base benzene methylene
Base) aniline, 100 ul THF are added, 0.6 mmol (0.0871 mL) borine then is added with liquid-transfering gun and is uniformly mixed, finally
The tetrahydrofuran solution (0.6115M) (5 mol% dosages, similarly hereinafter) of 40.9 ul 2,6-DIPA base lithiums is added, reacts
After 2 h, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1It is 99% that H, which composes yield,.The core of product
Magnetic data: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)。
Eight: 2,6- diisopropyl benzene amido lithium of embodiment is catalyzed N- (4- fluorobenzylidene) aniline and pinacol borine boron
Hydrogenation
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
The tetrahydrofuran solution (0.6115M) (5 mol% dosages, similarly hereinafter) of 40.9 ul 2,6-DIPA base lithiums reacts 2 h
Afterwards, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1It is 99% that H, which composes yield,.The nuclear-magnetism number of product
According to: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)。
Nine: 2,6- diisopropyl benzene amido lithium of embodiment is catalyzed N- (4- chlorobenzene methylene) aniline and pinacol borine boron
Hydrogenation
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
The tetrahydrofuran solution (0.6115M) (5 mol% dosages, similarly hereinafter) of 40.9 ul 2,6-DIPA base lithiums reacts 2 h
Afterwards, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1It is 99% that H, which composes yield,.The nuclear-magnetism number of product
According to: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)。
Ten: 2,6- diisopropyl benzene amido lithium of embodiment is catalyzed N- (4- bromobenzene methylene) aniline and pinacol borine boron
Hydrogenation
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
The tetrahydrofuran solution (0.6115M) (5 mol% dosages, similarly hereinafter) of 40.9 ul 2,6-DIPA base lithiums reacts 2 h
Afterwards, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1It is 99% that H, which composes yield,.The nuclear-magnetism number of product
According to: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)。
11: 2,6- diisopropyl benzene amido lithium of embodiment is catalyzed benzal para-totuidine and pinacol borine hydroboration
Reaction
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 40.9 ul 2,6-
The tetrahydrofuran solution (0.6115M) (5 mol% dosages, similarly hereinafter) of diisopropyl benzene amido lithium is drawn after reacting 2 h with dropper
CDCl is added in nuclear magnetic tube in one drop3Wiring 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)。
12: 2,6- diisopropyl benzene amido lithium of embodiment 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
The tetrahydrofuran solution (0.6115M) (5 mol% dosages, similarly hereinafter) of 40.9 ul 2,6-DIPA base lithiums reacts 2 h
Afterwards, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1It is 99% that H, which composes yield,.The nuclear-magnetism number of product
According to: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)。
13: 2,6- diisopropyl benzene amido lithium of embodiment 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
The tetrahydrofuran solution (0.6115M) (5 mol% dosages, similarly hereinafter) of 40.9 ul 2,6-DIPA base lithiums reacts 2 h
Afterwards, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1It is 99% that H, which composes yield,.The nuclear-magnetism number of product
According to: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)。
14: 2,6- diisopropyl benzene amido lithium of embodiment 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
The tetrahydrofuran solution (0.6115M) (5 mol% dosages, similarly hereinafter) of 40.9 ul 2,6-DIPA base lithiums reacts 2 h
Afterwards, a drop is drawn in nuclear magnetic tube with dropper, CDCl is added3Wiring solution-forming.It is computed1It is 99% that H, which composes yield,.The nuclear-magnetism number of product
According to: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；The first public commercialization reagent 2,6- diisopropyl benzene amido of the present invention
Lithium can be in the hydroboration of mild reaction condition catalysis imines, and yield is very high, has the wider substrate scope of application,
Cheap catalyst and mild catalytic condition provide possibility for industrial applications.
Claims (10)
- Application of the 1.2,6- diisopropyl benzene amido lithium in catalysis imines and borine hydroboration.
- 2. application according to claim 1, which is characterized in that 2,6-DIPA base lithium is catalyzed imines and borine is sent out The method of raw hydroboration under atmosphere of inert gases, is being passed through at dehydration and deoxidation the following steps are included: under anhydrous and oxygen-free environment Imines is added in the reaction flask of reason, organic solvent is added, borine is then added, is uniformly mixed, adds catalyst 2,6- bis- is different Propyl anilino- lithium reacts at room temperature 1~2 h, is exposed in air and terminates reaction, obtains 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 2,6-DIPA base lithium is the 4%~5% of imines molal quantity, mole of imines and pinacol borine Than being 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 2,6-DIPA base lithium, 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 h it is characterized in that, the temperature of reaction is room temperature.
- 9. according to the method described in claim 4, it is characterized in that, organic solvent is tetrahydrofuran.
- 10.2,6- diisopropyl benzene amido lithium is preparing the application in borate.
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| CN108383863A (en) * | 2018-04-16 | 2018-08-10 | 苏州大学 | Application of the 2,6- diisopropyl benzene amido lithiums in preparing borate |
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| CN108503659A (en) * | 2018-04-16 | 2018-09-07 | 苏州大学 | The method for preparing borate using 2,6- diisopropyl benzene amido lithiums |
| CN108558925A (en) * | 2018-04-16 | 2018-09-21 | 南通纺织丝绸产业技术研究院 | Application of the 2,6- diisopropyl benzene amido lithiums in catalysis ketone and borine hydroboration |
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| CN108383863A (en) * | 2018-04-16 | 2018-08-10 | 苏州大学 | Application of the 2,6- diisopropyl benzene amido lithiums in preparing borate |
| CN108395447A (en) * | 2018-04-16 | 2018-08-14 | 苏州大学张家港工业技术研究院 | The method for preparing borate based on 2,6- diisopropyl benzene amido lithiums catalysis aldehyde reaction |
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