CN109251217A - Application of the o-aminoanisole base lithium in catalysis imines and borine hydroboration - Google Patents
Application of the o-aminoanisole base lithium in catalysis imines and borine hydroboration Download PDFInfo
- Publication number
- CN109251217A CN109251217A CN201811134464.6A CN201811134464A CN109251217A CN 109251217 A CN109251217 A CN 109251217A CN 201811134464 A CN201811134464 A CN 201811134464A CN 109251217 A CN109251217 A CN 109251217A
- Authority
- CN
- China
- Prior art keywords
- imines
- borine
- aminoanisole
- added
- base lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000085 borane Inorganic materials 0.000 title claims abstract description 53
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 150000002466 imines Chemical class 0.000 title claims abstract description 37
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 36
- 238000006197 hydroboration reaction Methods 0.000 title claims abstract description 26
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 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 60
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 40
- 230000018044 dehydration Effects 0.000 claims description 17
- 238000006297 dehydration reaction Methods 0.000 claims description 17
- 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 16
- -1 methoxyl group Chemical group 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 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
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 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
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 26
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 26
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 22
- 238000005160 1H NMR spectroscopy Methods 0.000 description 13
- 229910052786 argon Inorganic materials 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- IFOBAKIQHNOSRE-UHFFFAOYSA-N lithium;phenylazanide Chemical compound [Li+].[NH-]C1=CC=CC=C1 IFOBAKIQHNOSRE-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000011295 pitch Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 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
- 230000005311 nuclear magnetism Effects 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
- 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
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
- B01J31/0252—Nitrogen containing compounds with a metal-nitrogen link, e.g. metal amides, metal guanidides
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 o-aminoanisole base lithium, and in particular to application of the o-aminoanisole 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.O-aminoanisole base lithium disclosed by the invention can at room temperature high activity catalysis imines and borine hydroboration, catalyst amount is only 4 ~ 5 mol% of imines mole, reaction can reach 90% or more yield, compared with existing catalyst system, simple o-aminoanisole 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 o-aminoanisole base lithium of the present invention, and in particular to sub- in catalysis to o-aminoanisole base lithium
Efficient application in amine 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-
It should mainly include the catalyst system of major element: magnesium [Manna, K.; Ji, P.; Greene, F. X.; Lin, W. J.
Am. Chem. Soc. 2016,138,7488 7491], calcium [Yadav, S.; Pahar, S.; Sen, S. S.
Chem. Commun. 2017,53 (33), 4562-4564], sodium [Wu, Y.; Shan, C.; Ying, J.; Su,
J.; Zhu, J.; Liu, L. L.; Zhao, Y. Green Chem. 2017, 19, 4169–4175]；But at present
The catalyst system reported, catalyst is all relatively expensive or is difficult to prepare or the reaction time is longer and to react at high temperature,
Some catalyst system yields are very low.So developing the catalyst system pole of the hydroboration of efficient catalytic imines under temperate condition
Its is important.
Summary of the invention
Goal of the invention of the invention is to provide the application of o-aminoanisole base lithium, i.e., is height with o-aminoanisole base lithium
It imitates catalyst imines and the application of hydroboration occurs for borine.
The first public simple o-aminoanisole base lithium of the present invention can be in the boron of mild reaction condition catalysis imines
Hydrogenation, yield is very high, has the wider substrate scope of application.Cheap catalyst and mild catalytic condition are work
Industry application provides possibility.To achieve the above object of the invention, the technical solution adopted by the present invention is that:
Application of the o-aminoanisole base lithium in catalysis imines and borine hydroboration；The o-aminoanisole base lithiumation
Formula is 2-OCH3PhNHLi。
The invention also discloses the methods that hydroboration occurs for o-aminoanisole base lithium catalysis imines and borine, including
Following steps: under anhydrous and oxygen-free environment, in atmosphere of inert gases, being added imines in the reaction flask by dehydration and deoxidation processing,
Organic solvent is added, borine is then added, is uniformly mixed, adds catalyst o-aminoanisole base lithium, reacts the h of 1h~2,
It is exposed in air and terminates reaction, obtain product.
The invention also discloses imines and borine, and the method that hydroboration prepares borate occurs, 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, is added organic molten
Then borine is added in agent, be uniformly mixed, and adds catalyst o-aminoanisole base lithium, reacts the h of 1h~2, is exposed to air
Middle termination reaction, 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 o-aminoanisole base lithium salts can efficiently be catalyzed imines and hydroboration occurs for borine
Reaction highly meets atom economy synthesis.
2. the catalytic activity that hydroboration occurs for o-aminoanisole base lithium catalysis imines disclosed by the invention and borine
High (catalyst amount can be the 4%~5% of imines molal quantity), reaction condition is mild (room temperature), and the reaction time is short (h of 1h~2),
And reaction yield is high, 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:
Embodiment one: o-aminoanisole base 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 39.2 ul O-methoxies
The tetrahydrofuran solution (0.6387M) (5 mol% dosages, similarly hereinafter) of 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 91% 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, 1H), 1.29 (s, 12H)。
Embodiment two: o-aminoanisole base 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 0.6 mmol (0.0871 mL) borine with liquid-transfering gun and is uniformly mixed, is eventually adding 39.2 ul O-methoxies
The tetrahydrofuran solution (0.6387M) (5 mol% dosages, similarly hereinafter) of anilino- lithium after reacting 1 h, draws a drop in core with dropper
In 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)。
Embodiment three: o-aminoanisole base 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 0.6 mmol (0.0871 mL) borine with liquid-transfering gun and is uniformly mixed, is eventually adding 39.2 ul O-methoxies
The tetrahydrofuran solution (0.6387M) (5 mol% dosage) of anilino- lithium after reacting 2 h, draws a drop in nuclear magnetic tube with dropper
In, 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 o-aminoanisole base lithium is replaced with to formula I, is unable to get product.
Example IV: o-aminoanisole base 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 0.6 mmol (0.0871 mL) borine with liquid-transfering gun and is uniformly mixed, is eventually adding 31.3 ul O-methoxies
The tetrahydrofuran solution (0.6387M) (4 mol% dosage) of anilino- lithium after reacting 2 h, draws a drop in nuclear magnetic tube with dropper
In, 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)。
Embodiment five: o-aminoanisole base lithium catalysis N- (pMethyl benzylidene) aniline and pinacol borine boron hydrogen
Change reaction
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 (0.6387M) (5 mol% dosages, similarly hereinafter) of 39.2 ul o-aminoanisole base lithiums after reacting 2 h, is used
Dropper draws a drop in nuclear magnetic tube, and 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: 7.23~7.08(m, 8H), 6.89~6.85 (t, 1H), 4.66 (s, 2H),
2.31 (s, 3H), 1.30 (s, 12H)。
Embodiment six: o-aminoanisole base lithium 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 (0.6387M) (5 mol% dosages, similarly hereinafter) of 39.2 ul o-aminoanisole base lithiums is added, 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: 7.22~7.13(d, 6H), 6.89~6.80 (d, 3H), 4.63 (s,
2H), 3.77 (s, 3H), 1.30 (s, 12H)。
Embodiment seven: o-aminoanisole base lithium is catalyzed N- (4- fluorobenzylidene) aniline and pinacol borine hydroboration
Reaction
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 (0.6387M) (5 mol% dosages, similarly hereinafter) of 39.2 ul o-aminoanisole base lithiums after reacting 2 h, is used
Dropper draws a drop in nuclear magnetic tube, and 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: 7.22~7.15(d, 6H), 6.98~6.94 (d, 3H), 4.66 (s, 2H),
1.30 (s, 12H)。
Embodiment eight: o-aminoanisole base lithium is catalyzed N- (4- chlorobenzene methylene) aniline and pinacol borine hydroboration
Reaction
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 (0.6387M) (5 mol% dosages, similarly hereinafter) of 39.2 ul o-aminoanisole base lithiums after reacting 2 h, is used
Dropper draws a drop in nuclear magnetic tube, and 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: 7.20~7.14(d, 6H), 6.99~6.93 (d, 3H), 4.64 (s, 2H),
1.30 (s, 12H)。
Embodiment nine: o-aminoanisole base lithium is catalyzed N- (4- bromobenzene methylene) aniline and pinacol borine hydroboration
Reaction
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 (0.6387M) (5 mol% dosages, similarly hereinafter) of 39.2 ul o-aminoanisole base lithiums after reacting 2 h, is used
Dropper draws a drop in nuclear magnetic tube, and 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: 7.24~7.16(d, 6H), 6.97~6.93 (d, 3H), 4.63 (s, 2H),
1.31 (s, 12H)。
Embodiment ten: o-aminoanisole base lithium 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 39.2 ul neighbour's methoxies
The tetrahydrofuran solution (0.6387M) (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 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 11: o-aminoanisole base lithium is catalyzed N- (benzylidene) -4- fluoroaniline and pinacol borine boron hydrogen
Change 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 39.2 ul neighbour's methoxies
The tetrahydrofuran solution (0.6387M) (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 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 12: o-aminoanisole base lithium is catalyzed N- (benzylidene) -4- chloroaniline and pinacol borine boron hydrogen
Change reaction
In the reaction flask by dehydration and deoxidation processing, the lower N-(benzylidene that 0.5 mmol is added of argon gas protection) -4- chlorobenzene
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 (0.6387M) (5 mol% dosages, similarly hereinafter) of 39.2 ul o-aminoanisole base lithiums after reacting 2 h, is used
Dropper draws a drop in nuclear magnetic tube, and 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: 7.26~7.05(d, 7H), 6.74~6.69 (d, 2H), 4.61 (s, 2H),
1.30 (s, 12H)。
Embodiment 13: o-aminoanisole base lithium is catalyzed N- (benzylidene) -4- bromaniline and pinacol borine boron hydrogen
Change reaction
In the reaction flask by dehydration and deoxidation processing, the lower N-(benzylidene that 0.5 mmol is added of argon gas protection) -4- bromobenzene
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 (0.6387M) (4 mol% dosages, similarly hereinafter) of 39.2 ul o-aminoanisole base lithiums after reacting 2 h, is used
Dropper draws a drop in nuclear magnetic tube, and 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: 7.27~7.03(d, 7H), 6.76~6.71 (d, 2H), 4.62 (s, 2H),
1.30 (s, 12H)。
Claims (10)
1. application of the o-aminoanisole base lithium in catalysis imines and borine hydroboration.
2. application according to claim 1, which is characterized in that o-aminoanisole base lithium is catalyzed imines and boron occurs for borine
The method of hydrogenation under atmosphere of inert gases, is passing through dehydration and deoxidation processing the following steps are included: under anhydrous and oxygen-free environment
Imines is added in reaction flask, organic solvent is added, borine is then added, is uniformly mixed, adds catalyst o-aminoanisole
Base 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 o-aminoanisole base lithium is the 4%~5% of imines molal quantity, and the molar ratio of imines and pinacol borine is
1: 1~1: 1.2.
4. a kind of method for preparing borate, comprising the following steps: under anhydrous and oxygen-free environment, in atmosphere of inert gases, passing through
Imines is added in the reaction flask of dehydration and deoxidation processing, organic solvent is added, borine is then added, is uniformly mixed, adds catalysis
Agent o-aminoanisole base lithium, reaction obtain 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. o-aminoanisole base lithium is preparing the application in borate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811134464.6A CN109251217B (en) | 2018-09-27 | 2018-09-27 | Application of o-methoxyanilino lithium in catalysis of imine and borane hydroboration reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811134464.6A CN109251217B (en) | 2018-09-27 | 2018-09-27 | Application of o-methoxyanilino lithium in catalysis of imine and borane hydroboration reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109251217A true CN109251217A (en) | 2019-01-22 |
| CN109251217B CN109251217B (en) | 2021-07-20 |
Family
ID=65048072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811134464.6A Active CN109251217B (en) | 2018-09-27 | 2018-09-27 | Application of o-methoxyanilino lithium in catalysis of imine and borane hydroboration reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109251217B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020073181A1 (en) * | 2018-10-08 | 2020-04-16 | 南通纺织丝绸产业技术研究院 | Application of o-methoxyaniline lithium for catalysing boron hydrogenation reaction of imine and borane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108440589A (en) * | 2018-04-16 | 2018-08-24 | 苏州大学 | The method for preparing borate based on o-methyl-benzene amido lithium |
| CN108503660A (en) * | 2018-04-16 | 2018-09-07 | 苏州大学 | Application of the anilino- lithium in catalysis aldehyde and borine hydroboration |
| CN108554446A (en) * | 2018-04-16 | 2018-09-21 | 苏州大学 | Application of the open-chain crown ether base lithium in catalysis aldehyde and borine hydroboration |
-
2018
- 2018-09-27 CN CN201811134464.6A patent/CN109251217B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108440589A (en) * | 2018-04-16 | 2018-08-24 | 苏州大学 | The method for preparing borate based on o-methyl-benzene amido lithium |
| CN108503660A (en) * | 2018-04-16 | 2018-09-07 | 苏州大学 | Application of the anilino- lithium in catalysis aldehyde and borine hydroboration |
| CN108554446A (en) * | 2018-04-16 | 2018-09-21 | 苏州大学 | Application of the open-chain crown ether base lithium in catalysis aldehyde and borine hydroboration |
Non-Patent Citations (1)
| Title |
|---|
| REBECA ARÉVALO ET AL.: "Rhenium-catalysed hydroboration of aldehydes and aldimines", 《DALTON TRANS.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020073181A1 (en) * | 2018-10-08 | 2020-04-16 | 南通纺织丝绸产业技术研究院 | Application of o-methoxyaniline lithium for catalysing boron hydrogenation reaction of imine and borane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109251217B (en) | 2021-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109331872A (en) | Application of the n-BuLi in catalysis imines and borine hydroboration | |
| CN110330535A (en) | N-heterocyclic carbine base mixed matching nickel (II) complex and its application | |
| CN107930696A (en) | Application of the front three cyclopentadienyl rare-earth complex in the hydroboration of catalysis imines and borine | |
| CN108187746A (en) | Three silicon amine rare earth metal complexs are in catalysis aldehyde and the application in pi-allyl acid reaction | |
| CN109251217A (en) | Application of the o-aminoanisole base lithium in catalysis imines and borine hydroboration | |
| CN105712899A (en) | Method for synthesizing imine at one step by means of catalyzing alcohol and amine by aid of supported cobalt compounds | |
| CN109289914A (en) | Application of the o-methyl-benzene amido lithium in catalysis imines and borine hydroboration | |
| CN109053460A (en) | A method of catalysis benzalcohol derivatives amination | |
| CN109331867A (en) | Application of the 2,6- accelerine base lithium in catalysis imines and borine hydroboration | |
| CN102755906A (en) | Application of amino aryloxy rare-earth metal-lithium amide used as catalyst | |
| CN109289913A (en) | Application of the 4- methoxybenzene amido lithium in catalysis imines and borine hydroboration | |
| CN109180714A (en) | Application of the anilino- lithium in catalysis imines and borine hydroboration | |
| CN109232622A (en) | Application of the 2,6- diisopropyl benzene amido lithium in catalysis imines and borine hydroboration | |
| US11680075B2 (en) | Application of 4-MePhNHLi in catalyzing hydroboration reaction of imine and borane | |
| CN109251216A (en) | Application of the open-chain crown ether base lithium in catalysis imines and borine hydroboration | |
| CN101314559B (en) | Preparation of aromatic chirality secondary alcohol compounds | |
| WO2008027740B1 (en) | Catalytic asymmetric synthesis of primary amines via borane reduction of oxime ethers using spiroborate esters | |
| CN110357912B (en) | Application of trisilamide rare earth complex in preparation of amine compound by catalyzing reaction of nitrile and borane | |
| CN110218227B (en) | Method for preparing aryl ketone derivative | |
| CN106478487B (en) | Pyrrolidines and its synthetic method | |
| US11845068B2 (en) | Use of n-butyllithium for catalyzing hydroboration of imine and borane | |
| WO2020073181A1 (en) | Application of o-methoxyaniline lithium for catalysing boron hydrogenation reaction of imine and borane | |
| WO2020073176A1 (en) | Applications of lithium anilide in catalyzing hydroboration reaction of imine and borane | |
| US11891408B2 (en) | Application of lithium 4-methoxyaniline in catalysis of hydroboration reaction of imine and borane | |
| WO2020073178A1 (en) | Application of lithium o-methylaniline in catalyzing hydroboration of imine with borane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |