CN109331867B - Application of 2, 6-dimethylanilinium to catalysis of imine and borane hydroboration reaction - Google Patents
Application of 2, 6-dimethylanilinium to catalysis of imine and borane hydroboration reaction Download PDFInfo
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- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims abstract description 62
- UFFBMTHBGFGIHF-UHFFFAOYSA-O (2,6-dimethylphenyl)azanium Chemical compound CC1=CC=CC(C)=C1[NH3+] UFFBMTHBGFGIHF-UHFFFAOYSA-O 0.000 title claims abstract description 33
- 229910000085 borane Inorganic materials 0.000 title claims abstract description 31
- 238000006197 hydroboration reaction Methods 0.000 title claims abstract description 31
- 150000002466 imines Chemical class 0.000 title claims abstract description 27
- 238000006555 catalytic reaction Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- -1 borate ester Chemical class 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 49
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 24
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical group CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 claims description 18
- 230000018044 dehydration Effects 0.000 claims description 16
- 238000006297 dehydration reaction Methods 0.000 claims description 16
- UVEWQKMPXAHFST-UHFFFAOYSA-N n,1-diphenylmethanimine Chemical group C=1C=CC=CC=1C=NC1=CC=CC=C1 UVEWQKMPXAHFST-UHFFFAOYSA-N 0.000 claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- CFBVFBIZXQEQHX-UHFFFAOYSA-N 1-(4-chlorophenyl)-n-phenylmethanimine Chemical compound C1=CC(Cl)=CC=C1C=NC1=CC=CC=C1 CFBVFBIZXQEQHX-UHFFFAOYSA-N 0.000 claims description 3
- MPRONVWLCPZXOB-UHFFFAOYSA-N 1-(4-fluorophenyl)-n-phenylmethanimine Chemical compound C1=CC(F)=CC=C1C=NC1=CC=CC=C1 MPRONVWLCPZXOB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- DJGDQBWKJYPZEF-UHFFFAOYSA-N n-(4-bromophenyl)-1-phenylmethanimine Chemical compound C1=CC(Br)=CC=C1N=CC1=CC=CC=C1 DJGDQBWKJYPZEF-UHFFFAOYSA-N 0.000 claims description 3
- NWCAQYVAHZWHIO-UHFFFAOYSA-N n-(4-chlorophenyl)-1-phenylmethanimine Chemical compound C1=CC(Cl)=CC=C1N=CC1=CC=CC=C1 NWCAQYVAHZWHIO-UHFFFAOYSA-N 0.000 claims description 3
- OEJZOCTWYUFFNN-UHFFFAOYSA-N n-(4-fluorophenyl)-1-phenylmethanimine Chemical compound C1=CC(F)=CC=C1N=CC1=CC=CC=C1 OEJZOCTWYUFFNN-UHFFFAOYSA-N 0.000 claims description 3
- MJSLSMOBYCYMIM-UHFFFAOYSA-N 1-(4-bromophenyl)-n-phenylmethanimine Chemical compound C1=CC(Br)=CC=C1C=NC1=CC=CC=C1 MJSLSMOBYCYMIM-UHFFFAOYSA-N 0.000 claims description 2
- KHXTYWYNOORAKD-UHFFFAOYSA-N [Li+].Cc1cccc(C)c1N Chemical compound [Li+].Cc1cccc(C)c1N KHXTYWYNOORAKD-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 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
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 26
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 7
- NEKQDXLRUORFPU-UHFFFAOYSA-N lithium;(2,6-dimethylphenyl)azanide Chemical compound [Li+].CC1=CC=CC(C)=C1[NH-] NEKQDXLRUORFPU-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BOAKUGQLOZCFCZ-UHFFFAOYSA-N 2-(4-bromophenyl)-N-phenylethanimine Chemical compound C1=CC(Br)=CC=C1CC=NC1=CC=CC=C1 BOAKUGQLOZCFCZ-UHFFFAOYSA-N 0.000 description 1
- 241001289435 Astragalus brachycalyx Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000002917 Fraxinus ornus Nutrition 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 group 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004327 boric acid Substances 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
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KDKHRAVKGIIQHF-UHFFFAOYSA-N methyl n-phenylbenzenecarboximidate Chemical compound C=1C=CC=CC=1C(OC)=NC1=CC=CC=C1 KDKHRAVKGIIQHF-UHFFFAOYSA-N 0.000 description 1
- CBXWICRJSHEQJT-UHFFFAOYSA-N n,1-diphenylethanimine Chemical compound C=1C=CC=CC=1C(C)=NC1=CC=CC=C1 CBXWICRJSHEQJT-UHFFFAOYSA-N 0.000 description 1
- MSFVFFZPHJPOHP-UHFFFAOYSA-N n-(4-methylphenyl)-1-phenylmethanimine Chemical compound C1=CC(C)=CC=C1N=CC1=CC=CC=C1 MSFVFFZPHJPOHP-UHFFFAOYSA-N 0.000 description 1
- ILCQYORZHHFLNL-UHFFFAOYSA-N n-bromoaniline Chemical compound BrNC1=CC=CC=C1 ILCQYORZHHFLNL-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
- 230000001766 physiological effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 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
- 230000002194 synthesizing effect Effects 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention relates to application of 2, 6-dimethylanilinium, in particular to application of 2, 6-dimethylanilinium in catalyzing hydroboration reaction of imine and borane. And stirring and mixing the catalyst, borane and imine uniformly in sequence, reacting for 1-2 hours, exposing the mixture to air to terminate the reaction, and decompressing the reaction solution to remove the solvent to obtain the borate with different substituent groups. The 2, 6-dimethylanilinium disclosed by the invention can catalyze the hydroboration reaction of imine and borane with high activity at room temperature, the dosage of the catalyst is only 4-5 mol% of the molar weight of imine, the reaction yield can reach more than 90%, compared with the existing catalytic system, the simple 2, 6-dimethylanilinium is utilized, the reaction condition is mild, and the yield of borate ester with different substituents can reach 99% under the optimized condition.
Description
Technical Field
The invention relates to application of 2, 6-dimethylanilinium, in particular to efficient application of 2, 6-dimethylanilinium in catalyzing hydroboration reaction of imine and borane.
Technical Field
The amine compounds and derivatives thereof are ubiquitous in nature, especially widely exist in the biological world, and have extremely important physiological effects. They are important organic compounds in the fields of biology, chemistry, medicine, etc., and many drugs contain amine functional groups, i.e., amino groups, such as those found in proteins, nucleic acids, antibiotics, and alkaloids. The amine compound has various use values and wide application range, and is often used for synthesizing textiles, dyes, polymers, pigments, pesticides and the like. Since the hydroboration reaction of carbonyl is far easier to occur than that of imine, a high-efficiency catalytic system for the hydroboration reaction of unsaturated C = N bond is developed, and the method has important significance for modern industry and organic synthetic chemistry.
Hydroboration of iminesIn recent years, the application of the reported catalyst to the hydroboration reaction of imine mainly comprises a catalytic system of main group elements: magnesium, calcium, sodium, rhenium, zinc, etc. (see 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, 6008-6016). However, the catalyst systems reported at present are relatively expensive or difficult to prepare, or have long reaction time and are required to react at high temperature, and some catalytic systems have low yield. Therefore, it is very important to develop a catalytic system for efficiently catalyzing the hydroboration reaction of imine under mild conditions.
Disclosure of Invention
The invention aims to provide application of 2, 6-dimethylanilinium, namely application of 2, 6-dimethylanilinium serving as a high-efficiency catalyst for catalyzing imine and borane to undergo hydroboration reaction.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: the application of 2, 6-dimethylanilinium in catalyzing hydroboration reaction of aldehyde and borane; the chemical formula of the 2, 6-dimethylanilinium is as follows: 2,6-Me2PhNHLi。
The invention also discloses a method for catalyzing imine and borane to perform hydroboration reaction by using 2, 6-dimethylanilinium, which comprises the following steps:
under the anhydrous and oxygen-free environment and the inert gas atmosphere, adding imine into a reaction bottle subjected to dehydration and deoxidation treatment, adding an organic solvent, then adding borane, uniformly mixing, adding a catalyst 2, 6-dimethylanilinium, reacting for 1-2 h, and exposing in the air to terminate the reaction to obtain a product.
The invention further discloses a preparation method of the boric acid ester, which comprises the following steps:
under the anhydrous and oxygen-free environment and in the inert gas atmosphere, adding imine into a reaction bottle subjected to dehydration and deoxidation treatment, adding an organic solvent, then adding borane, uniformly mixing, adding a catalyst 2, 6-dimethylanilinium, reacting for 1-2 h, and exposing in the air to terminate the reaction to obtain a product.
In the above technical scheme, the imine is selected from aldimine; the chemical structural general formula of the imine is as follows:
wherein R is1Or R2Is one of electron withdrawing group or electron donating group, and can be selected from halogen, methyl and methoxy; the borane is selected from pinacol borane.
In the technical scheme, the using amount of the catalyst can be 4-5% of the mole number of the imine, and the mole ratio of the imine to the pinacol borane is 1: 1-1: 1.2.
In the technical scheme, the reaction temperature is room temperature, and the reaction time is 1-2 h.
In the above technical scheme, the organic solvent is tetrahydrofuran.
The above technical solution can be expressed as follows:
due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the invention discovers for the first time that simple 2, 6-dimethylanilinium can efficiently catalyze imine and borane to carry out hydroboration reaction, and is highly in line with atom economic synthesis.
2. The 2, 6-dimethylanilinium disclosed by the invention has the advantages of high catalytic activity (4-5% of the mole number of the catalyst), mild reaction conditions (room temperature), short reaction time (1-2 h), high reaction yield, simple and controllable reaction, simple post-treatment and low-cost THF (tetrahydrofuran) adopted as a solvent in the reaction.
3. The catalyst disclosed by the invention has better universality for imines with different substitution positions and different electronic effects.
Detailed Description
The invention is further described below with reference to examples:
the first embodiment is as follows: lithium 2, 6-dimethylanilino for catalyzing the hydroboration reaction of benzylidene aniline and pinacol borane
Adding 0.5 mmol of benzylidene aniline into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100ul of THF, adding 0.5 mmol (0.0726 mL) of borane into a liquid transfer gun, uniformly mixing, finally adding 42.2 ul of 2, 6-dimethylanilinium tetrahydrofuran solution (0.5926M) (5 mol% dosage, the same below) into the reaction bottle, reacting for 2 hours, absorbing one drop by a dropper into a nuclear magnetic tube, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 90%. Nuclear magnetic data of the 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 two: lithium 2, 6-dimethylanilino for catalyzing the hydroboration reaction of benzylidene aniline and pinacol borane
Adding 0.5 mmol of benzylidene aniline into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100ul of THF, adding 0.55 mmol (0.0798 mL) of borane into a liquid-transferring gun, uniformly mixing, finally adding 42.2 ul of 2, 6-dimethylanilinium tetrahydrofuran solution (0.5926M) (5 mol% dosage, the same below) into the reaction bottle, reacting for 2 hours, sucking one drop by a dropper into a nuclear magnetic tube, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 96%. Nuclear magnetic data of the 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 three: lithium 2, 6-dimethylanilino for catalyzing the hydroboration reaction of benzylidene aniline and pinacol borane
Adding 0.5 mmol of benzylidene aniline into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100ul of THF, adding 0.6 mmol (0.0871 mL) of borane into a liquid-transferring gun, uniformly mixing, finally adding 42.2 ul of 2, 6-dimethylanilinium tetrahydrofuran solution (0.5926M) (5 mol% dosage), reacting for 2h, sucking one drop by a dropper into a nuclear magnetic tube, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the 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 product cannot be obtained by replacing 2, 6-dimethylanilinium with an aminolithium compound of formula i.
EXAMPLE four lithium 2, 6-dimethylanilino catalyzed hydroboration of benzylidene aniline with pinacol borane
In a reaction bottle subjected to dehydration and deoxidation treatment, 0.5 mmol of benzylidene aniline is added under the protection of argon, 100ul of THF is added, then 0.6 mmol (0.0871 mL) of borane is added by a liquid-transferring gun and mixed uniformly, finally 42.2 ul of 2, 6-dimethylanilinium tetrahydrofuran solution (0.5926M) (5 mol% dosage, the same below) is added, after 1h of reaction, the solution is absorbed into a nuclear magnetic tube by a dropper in a drop manner, and CDCl3 is added to prepare the solution. Is calculated by1The yield of the H spectrum is 96%. Nuclear magnetic data of the 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 five: lithium 2, 6-dimethylanilino for catalyzing the hydroboration reaction of benzylidene aniline and pinacol borane
Adding 0.5 mmol of benzylidene aniline into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100ul of THF, adding 0.6 mmol (0.0871 mL) of borane into a liquid-transferring gun, uniformly mixing, finally adding 33.8 ul of 2, 6-dimethylanilinium tetrahydrofuran solution (0.5926M) (4 mol% dosage), reacting for 2h, sucking one drop by a dropper into a nuclear magnetic tube, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 96%. Nuclear magnetic data of the 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 six: 2, 6-dimethylanilinium catalyzed N-, (pHydroboration of (methylbenzylidene) aniline with pinacol borane
Adding 0.5 mmol of the mixture into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argonN-(p-methylbenzylidene) aniline, 100ul THF, 0.6 mmol (0.0871 mL) borane by means of a pipette, mixing homogeneously, finally 42.2 ul of a solution of lithium 2, 6-dimethylanilino in tetrahydrofuran (0.5926M) (5 mol% amount, the same applies hereinafter) are added, after 2h of reaction, one drop is pipetted into a nuclear magnetic tube, CDCl is added3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the 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)。
example seven: 2, 6-dimethylanilinium catalyzed N-, (pHydroboration of (methoxy benzylidene) aniline with pinacol borane
Adding 0.5 mmol of N-, (N) into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argonp-methoxybenzylidene) aniline, 100ul THF, 0.6 mmol (0.0871 mL) borane by pipette, mixing well, finally 42.2 ul2, 6-dimethylanilinium in tetrahydrofuran (0.5926M) (5 mol% amount, the same below) are added, after 2h reaction, one drop is pipetted into a nuclear magnetic tube, CDCl is added3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the 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)。
example eight: 2, 6-dimethylanilinium catalyzed hydroboration reaction of N- (4-fluorobenzylidene) aniline and pinacol borane
Adding 0.5 mmol of N- (4-fluorobenzylidene) aniline into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100ul of THF, then adding 0.6 mmol (0.0871 mL) of borane into a liquid-transferring gun, uniformly mixing, finally adding 42.2 ul of a tetrahydrofuran solution (0.5926M) of 2, 6-dimethylanilinium (5 mol% of the amount, the same below) into the reaction bottle, absorbing one drop by a dropper into a nuclear magnetic tube after reacting for 2 hours, and adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the product:1HNMR (CDCl3, 400 MHz)δ: 7.22~7.15(d, 6H), 6.98~6.94 (d, 3H), 4.66 (s, 2H),1.30 (s, 12H)。
example nine: 2, 6-dimethylanilino lithium catalyst N- (4-chlorobenzylidene) aniline and pinacol borane hydroboration reaction
Adding 0.5 mmol of N- (4-chlorobenzylidene) aniline into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100ul of THF, then adding 0.6 mmol (0.0871 mL) of borane into a liquid-transferring gun, uniformly mixing, finally adding 42.2 ul of a tetrahydrofuran solution (0.5926M) of 2, 6-dimethylanilinium (5 mol% of the amount, the same below) into the reaction bottle, absorbing one drop into a nuclear magnetic tube by using a dropper after reacting for 2 hours, and adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the product:1HNMR (CDCl3, 400 MHz)δ: 7.20~7.14(d, 6H), 6.99~6.93 (d, 3H), 4.64 (s, 2H),1.30 (s, 12H)。
example ten: 2, 6-dimethylanilinium catalyzed hydroboration reaction of N- (4-bromobenzyl methylene) aniline and pinacol borane
Adding 0.5 mmol of N- (4-bromobenzylidene) aniline into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100ul of THF, then adding 0.6 mmol (0.0871 mL) of borane into a liquid-transferring gun, uniformly mixing, finally adding 42.2 ul of a tetrahydrofuran solution (0.5926M) of 2, 6-dimethylanilinium (5 mol percent of the amount, the same below) into the reaction bottle, absorbing one drop by a dropper into a nuclear magnetic tube after reacting for 2 hours, and adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the product:1HNMR (CDCl3, 400 MHz)δ: 7.24~7.16(d, 6H), 6.97~6.93 (d, 3H), 4.63 (s, 2H),1.31 (s, 12H)。
example eleven: 2, 6-dimethylanilinium catalyzed hydroboration reaction of benzylidene p-toluidine and pinacol borane
Adding 0.5 mmol of benzylidene p-toluene into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100ul of THF, then adding 0.6 mmol (0.0871 mL) of borane into a liquid-transferring gun, uniformly mixing, finally adding 42.2 ul of 2, 6-dimethylanilinium tetrahydrofuran solution (0.5926M) (5 mol% dosage, the same below) into the reaction bottle, reacting for 2 hours, sucking one drop into a nuclear magnetic tube by a dropper, adding CDCl3Preparing a solution. Warp gaugeCalculating out1The yield of the H spectrum is 99%. Nuclear magnetic data of the 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)。
example twelve: 2, 6-dimethylanilinium catalyzed hydroboration reaction of N- (benzylidene) -4-fluoroaniline and pinacol borane
Adding 0.5 mmol of N- (benzylidene) -4-fluoroaniline into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100ul of THF, then adding 0.6 mmol (0.0871 mL) of borane into a pipette gun, uniformly mixing, finally adding 42.2 ul of a tetrahydrofuran solution (0.5926M) of 2, 6-dimethylanilinium (5 mol% of the amount, the same below), reacting for 2 hours, sucking one drop by a dropper into a nuclear magnetic tube, and adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the 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)。
example thirteen: 2, 6-dimethylanilino lithium for catalyzing hydroboration reaction of N- (benzylidene) -4-chloroaniline and pinacol borane
Adding 0.5 mmol of N- (benzylidene) -4-chloroaniline into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100ul of THF, then adding 0.6 mmol (0.0871 mL) of borane into a pipette gun, uniformly mixing, finally adding 42.2 ul of a tetrahydrofuran solution (0.5926M) of 2, 6-dimethylanilinium (5 mol% of the amount, the same below), reacting for 2 hours, sucking one drop by a dropper into a nuclear magnetic tube, and adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the 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)。
example fourteen: 2, 6-dimethylanilino lithium catalyzed hydroboration reaction of N- (benzylidene) -4-bromoaniline and pinacol borane
In a reaction bottle which is dehydrated and deoxidized, 0.5 mmol of N- (benzylidene) -4-bromoaniline is added under the protection of argon, 100ul of THF is added, and then 0.6 mmol of (N, N-bromoaniline) is added by a liquid-transferring gun0.0871 mL) borane, and finally 42.2 ul of a tetrahydrofuran solution of lithium 2, 6-dimethylanilino (0.5926M) (5 mol% dosage, the same below) were added, and after 2 hours of reaction, one drop was pipetted into a nuclear magnetic tube, and CDCl was added3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the 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 in the above examples was room temperature; the invention discovers for the first time that simple 2, 6-dimethylanilinium can catalyze the hydroboration reaction of imine under mild reaction conditions, has high yield and wide substrate application range. Cheap catalyst and mild catalytic condition, and provides possibility for industrial application.
Claims (1)
- The application of 2, 6-dimethylanilinium in catalyzing imine and borane hydroboration reaction is characterized in that the method for catalyzing imine and borane hydroboration reaction by using 2, 6-dimethylanilinium comprises the following steps: under the anhydrous and oxygen-free environment and the inert gas atmosphere, adding imine into a reaction bottle subjected to dehydration and deoxidation treatment, adding an organic solvent, then adding borane, uniformly mixing, adding a catalyst 2, 6-dimethylanilinium lithium, reacting at room temperature for 1-2 h, and exposing the mixture in the air to terminate the reaction to obtain a product; the imine is benzylidene aniline and N- (N-)p-methylbenzylidene) aniline, N- (4-fluorobenzylidene) aniline, N- (4-chlorobenzylidene) aniline, N- (4-bromobenzylidene) aniline, N- (benzylidene) -4-fluoroaniline, N- (benzylidene) -4-chloroaniline, or N- (benzylidene) -4-bromoaniline; the borane is selected from pinacol borane; the organic solvent is tetrahydrofuran; the dosage of the 2, 6-dimethylanilinium is 4 to 5 percent of the mole number of the imine, and the mole ratio of the imine to the pinacol borane is 1: 1 to 1: 1.2.
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