WO2020073179A1 - 4-甲氧基苯胺基锂在催化亚胺和硼烷硼氢化反应中的应用 - Google Patents
4-甲氧基苯胺基锂在催化亚胺和硼烷硼氢化反应中的应用 Download PDFInfo
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- WO2020073179A1 WO2020073179A1 PCT/CN2018/109374 CN2018109374W WO2020073179A1 WO 2020073179 A1 WO2020073179 A1 WO 2020073179A1 CN 2018109374 W CN2018109374 W CN 2018109374W WO 2020073179 A1 WO2020073179 A1 WO 2020073179A1
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- imine
- borane
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- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 150000002466 imines Chemical class 0.000 title claims abstract description 35
- 229910000085 borane Inorganic materials 0.000 title claims abstract description 33
- 238000006197 hydroboration reaction Methods 0.000 title claims abstract description 26
- NUZZTIFRAVGNIM-UHFFFAOYSA-N COC1=CC=C(N)C=C1.[Li] Chemical compound COC1=CC=C(N)C=C1.[Li] NUZZTIFRAVGNIM-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 47
- 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 21
- -1 4-methoxyanilinium lithium Chemical compound 0.000 claims description 20
- 230000018044 dehydration Effects 0.000 claims description 17
- 238000006297 dehydration reaction Methods 0.000 claims description 17
- 238000006392 deoxygenation reaction Methods 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- MHTPKJNVDDZLQG-UHFFFAOYSA-N lithium;(4-methoxyphenyl)azanide Chemical compound [Li+].COC1=CC=C([NH-])C=C1 MHTPKJNVDDZLQG-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 230000006837 decompression Effects 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 28
- 229910052786 argon Inorganic materials 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 14
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 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 description 2
- CFBVFBIZXQEQHX-UHFFFAOYSA-N 1-(4-chlorophenyl)-n-phenylmethanimine Chemical compound C1=CC(Cl)=CC=C1C=NC1=CC=CC=C1 CFBVFBIZXQEQHX-UHFFFAOYSA-N 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 2
- MSWPGMRTURVKRJ-UHFFFAOYSA-N 1-(4-methoxyphenyl)-n-phenylmethanimine Chemical compound C1=CC(OC)=CC=C1C=NC1=CC=CC=C1 MSWPGMRTURVKRJ-UHFFFAOYSA-N 0.000 description 2
- PCICJNSIYHONRK-UHFFFAOYSA-N 1-(4-methylphenyl)-n-phenylmethanimine Chemical compound C1=CC(C)=CC=C1C=NC1=CC=CC=C1 PCICJNSIYHONRK-UHFFFAOYSA-N 0.000 description 2
- 0 C1C=CC(C=*C2=CCCC=C2)=CC1 Chemical compound C1C=CC(C=*C2=CCCC=C2)=CC1 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- UVEWQKMPXAHFST-UHFFFAOYSA-N n,1-diphenylmethanimine Chemical compound C=1C=CC=CC=1C=NC1=CC=CC=C1 UVEWQKMPXAHFST-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- 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 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000004705 aldimines Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 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
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 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
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 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
- C07F5/04—Esters of boric acids
-
- 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
- B01J31/0201—Oxygen-containing compounds
- B01J31/0204—Ethers
-
- 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
-
- 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
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
-
- 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
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
Definitions
- the invention relates to the application of 4-methoxyanilinium lithium, in particular to the high-efficiency application of 4-methoxyanilinium lithium in the catalytic hydroboration reaction of imine and borane.
- the borohydride reaction of imines has become a research hotspot in recent years.
- the reported catalysts used in the borohydride reaction of imines mainly include the catalytic systems of main group elements: magnesium, calcium, sodium, rhenium, zinc, etc. (see Manna, K .; Ji, P .; Greene, FX; Lin, WJAm. Chem. Soc. 2016, 138, 7488-7491; Lin, YC .; Hatzakis, E .; McCarthy, SM; Reichl, KD; Lai, TY. ; Yennawar, HP; Radosevich, ATJAm. Chem. Soc. 2017, 139, 6008-6016).
- the object of the invention of the present invention is to provide the application of 4-methoxyanilinyl lithium, that is, the application of 4-methoxyanilinyl lithium as a high-efficiency catalyst to catalyze the hydroboration reaction of imine and borane.
- the technical scheme adopted by the present invention is: the application of 4-methoxyanilinyl lithium in the catalytic hydroboration of imine and borane; -OCH 3 PhNHLi.
- the invention also discloses a 4-methoxyanilinyl lithium-catalyzed method for the borohydride reaction of imine and borane, which includes the following steps:
- the invention further discloses a method for preparing boric acid ester, which includes the following steps:
- the imine is selected from aldimine; the general chemical structure of the imine is as follows:
- R 1 or R 2 is one of an electron-withdrawing group or an electron-donating group, which may be selected from halogen, methyl, and methoxy; the borane is selected from pinacol borane.
- the amount of the catalyst may be 4% to 5% of the number of moles of imine, and the molar ratio of imine to pinacol borane is 1: 1 to 1: 1.2.
- the reaction temperature is room temperature
- the reaction time is 1 to 2 hours.
- the organic solvent is tetrahydrofuran.
- the present invention has the following advantages compared with the prior art:
- the present invention finds for the first time that simple 4-methoxyanilinyl lithium can efficiently catalyze the borohydride reaction between imine and borane, which is highly consistent with the economical synthesis of atoms.
- the 4-methoxyanilinyl lithium catalyst disclosed in the present invention has a high catalytic activity for the hydroboration reaction of imine and borane (4% to 5% of the moles of catalyst used), and the reaction time is short (1h to 2h).
- the reaction conditions are mild (room temperature), the reaction yield is high, the reaction is simple and controllable, the post-treatment is simple, and the reaction uses inexpensive THF as the solvent.
- the catalyst disclosed in the present invention has good universality for imines with different substitution positions and different electronic effects.
- Example 1 4-Methoxyanilinyl lithium catalyzes the hydroboration reaction of biphenylaniline with pinacol borane
- Example 2 4-Methoxyanilinyl lithium catalyzes the hydroboration reaction of benzylidene aniline with pinacol borane
- Embodiment 3 4-Methoxyanilinyl lithium catalyzes the hydroboration reaction of benzylidene and pinacol borane
- Example 4 Lithium 4-methoxyanilinyl catalyzes the hydroboration reaction of benzylidene aniline with pinacol borane
- Example 5 4-Methoxyanilinyl lithium catalyzes the hydroboration reaction of benzylidene and pinacol borane
- Example 6 Lithium 4-methoxyanilinyl catalyzes the hydroboration of N- (p-methylbenzylidene) aniline with pinacol borane
- Example 7 Lithium 4-methoxyanilinyl catalyzes the hydroboration reaction of N- (p-methoxybenzylidene) aniline with pinacol borane
- Example 8 Lithium 4-methoxyanilinyl catalyzes the hydroboration of N- (4-fluorobenzylidene) aniline with pinacol borane
- Example 9 Lithium 4-methoxyanilinate catalyzes the hydroboration of N- (4-chlorobenzylidene) aniline with pinacol borane
- Example 10 Lithium 4-methoxyanilinyl catalyzes the hydroboration of N- (4-bromobenzylidene) aniline with pinacol borane
- Example 11 4-Methoxyanilinyl lithium catalyzes the hydroboration of benzylidene-p-toluidine with pinacol borane
- Example 12 Lithium 4-methoxyanilinyl catalyzes the hydroboration of N- (benzylidene) -4-fluoroaniline with pinacol borane
- Example 13 Lithium 4-methoxyanilinyl catalyzes the hydroboration of N- (benzylidene) -4-chloroaniline with pinacol borane
- Example 14 Lithium 4-methoxyanilinyl catalyzes the hydroboration of N- (benzylidene) -4-bromoaniline with pinacol borane
- the reaction temperature of the above embodiment is room temperature; the present invention discloses for the first time that the commercial reagent 4-methoxyanilinyl lithium can catalyze the borohydride reaction of imine under mild reaction conditions, with a high yield and a wide substrate
- the scope of application, cheap catalysts and mild catalytic conditions provide possibilities for industrial applications.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
本发明涉及4-甲氧基苯胺基锂的应用,具体涉及4-甲氧基苯胺基锂在催化亚胺和硼烷的硼氢化反应中的应用。依次将催化剂、硼烷和亚胺搅拌混合均匀,反应1~2小时,暴露于空气中终止反应,反应液减压除去溶剂,得到不同取代基的硼酸酯。本发明公开的4-甲氧基苯胺基锂可以在室温条件下高活性的催化亚胺和硼烷的硼氢化反应,催化剂用量仅为亚胺摩尔量的4~5mol%,反应可达到90%以上的收率,与已有的催化体系相比,利用了简单的4-甲氧基苯胺基锂,反应条件温和,在优化条件下不同取代基的硼酸酯的产率可达99%。
Description
本发明涉及的4-甲氧基苯胺基锂的应用,具体涉及4-甲氧基苯胺基锂在催化亚胺与硼烷硼氢化反应中的高效应用。
胺类化合物及其衍生物在自然界中普遍存在,尤其广泛地存在于生物界中,具有极重要的生理作用。它们是生物,化学,医药等领域中重要的有机化合物,很多药物含有胺的官能团即氨基,例如蛋白质,核酸,抗生素和生物碱中都存在氨基。胺类化合物具有多方面使用价值,应用范围十分广泛,常常被用于合成纺织品、染料、聚合物、色素和农药等。由于羰基的硼氢化反应远比亚胺的硼氢化反应容易发生,所以开发出针对不饱和C=N键的硼氢化反应的高效催化体系,对现代工业和有机合成化学都具有重要的意义。
亚胺的硼氢化反应近几年已成为研究热点,报道的催化剂应用于亚胺的硼氢化反应主要包括,主族元素的催化体系:镁、钙、钠、铼、锌等(参见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)。但是,目前所报道的催化体系,催化剂都相对昂贵或难以制备,或者反应时间较长且要在高温下反应,有些催化体系产率很低。所以,开发温和条件下高效催化亚胺的硼氢化反应的催化体系极其重要。
本发明的发明目的是提供4-甲氧基苯胺基锂的应用,即以4-甲氧基苯胺基锂为高效催化剂催化亚胺与硼烷发生硼氢化反应的应用。
为达到上述发明目的,本发明采用的技术方案是:4-甲氧基苯胺基锂在催化亚胺与硼烷硼氢化反应中的应用;所述4-甲氧基苯胺基锂化学式为:4-OCH
3PhNHLi。
本发明还公开了4-甲氧基苯胺基锂催化亚胺与硼烷发生硼氢化反应的方法,包括以下步骤:
无水无氧环境下,惰性气体氛围下,在经过脱水脱氧处理的反应瓶中加入亚胺,加入有机溶剂,然后加入硼烷,混合均匀,再加入催化剂4-甲氧基苯胺基锂,反应1h~2h,暴露于空气中终止反应,得到产物。
本发明进一步的公开了一种硼酸酯的制备方法,包括以下步骤:
无水无氧环境下,惰性气体氛围中,在经过脱水脱氧处理的反应瓶中加入亚胺,加入有机溶剂,然后加入硼烷,混合均匀,再加入催化剂4-甲氧基苯胺基锂,反应1h~2h,暴露于空气中终止反应,得到产物。
上述技术方案中,所述亚胺选自醛亚胺;所述亚胺的化学结构通式如下:
其中R
1或R
2为吸电子基团或给电子基团中的一种,可选自卤素,甲基,甲氧基;所述硼烷选自频哪醇硼烷。
上述技术方案中,所述催化剂用量可为亚胺摩尔数的4%~5%,亚胺与频哪醇硼烷的摩尔比为1∶1~1∶1.2。
上述技术方案中,反应温度为室温,反应时间为1~2h。
上述技术方案中,有机溶剂为四氢呋喃。
上述技术方案可表示如下:
由于上述技术方案的运用,本发明与现有技术相比有如下优点:
1.本发明首次发现简单的4-甲氧基苯胺基锂能高效的催化亚胺与硼烷发生硼氢化反应,高度符合原子经济合成。
2.本发明公开的4-甲氧基苯胺基锂催化亚胺与硼烷发生硼氢化反应的催化活性高(催化剂用量摩尔数的4%~5%),反应时间短(1h~2h),反应条件温和(室温),且反应产率高,反应简单可控,后处理简单,反应采用廉价的THF为溶剂。
3.本发明公开的催化剂对于不同取代位置、不同电子效应的亚胺有着较好的普适性。
下面结合实施例对本发明做进一步描述:
实施例一:4-甲氧基苯胺基锂催化卞叉苯胺与频哪醇硼烷硼氢化反应
在经过脱水脱氧处理的反应瓶中,氩气保护下加入0.5mmol的卞叉苯胺,加入100ul THF,然后用移液枪加入0.6mmol(0.0871mL)硼烷混合均匀,最后加入69.9ul 4-甲氧基苯胺基锂的四氢呋喃溶液(0.3577M)(5mol%用量,下同),反应1h后,用滴管吸取一滴于核磁管中,加入CDCl
3配成溶液。经计算
1H谱产率为96%。产物的核磁数据:
1H NMR(CDCl
3,400MHz)δ:7.29~7.12(m,9H),6.88~6.84(t,1H),4.69(s,2H),1.29(s,12H)。
实施例二:4-甲氧基苯胺基锂催化卞叉苯胺与频哪醇硼烷硼氢化反应
在经过脱水脱氧处理的反应瓶中,氩气保护下加入0.5mmol的卞叉苯胺,加入100ul THF,然后用移液枪加入0.6mmol(0.0871mL)硼烷混合均匀,最后加入69.9ul 4-甲氧基苯胺基锂的四氢呋喃溶液(0.3577M)(5mol%用量),反应2h后,用滴管吸取一滴于核磁管中,加入CDCl
3配成溶液。经计算
1H谱产率为99%。产物的核磁数据:
1H NMR(CDCl
3,400MHz)δ:7.29~7.12(m,9H),6.88~6.84(t,1H),4.69(s,2H),1.29(s,12H)。
将4-甲氧基苯胺基锂替换为式Ⅰ的胺基锂化合物,无法得到产物。
实施例三:4-甲氧基苯胺基锂催化卞叉苯胺与频哪醇硼烷硼氢化反应
在经过脱水脱氧处理的反应瓶中,氩气保护下加入0.5mmol的卞叉苯胺,加入100ul THF,然后用移液枪加入0.6mmol(0.0871mL)硼烷混合均匀,最后加入55.9ul 4-甲氧基苯胺基锂的四氢呋喃溶液(0.3577M)(4mol%用量),反应2h后,用滴管吸取一滴于核磁管中,加入CDCl
3配成溶液。经计算
1H谱产率为96%。产物的核磁数据:
1H NMR(CDCl
3,400MHz)δ:7.29~7.12(m,9H),6.88~6.84(t,1H),4.69(s,2H),1.29(s,12H)。
实施例四:4-甲氧基苯胺基锂催化卞叉苯胺与频哪醇硼烷硼氢化反应
在经过脱水脱氧处理的反应瓶中,氩气保护下加入0.5mmol的卞叉苯胺,加入100ul THF,然后用移液枪加入0.5mmol(0.0726mL)硼烷混合均匀,最后加入69.9ul 4-甲氧基苯胺基锂的四氢呋喃溶液(0.3577M)(5mol%用量,下同),反应2h后,用滴管吸取一滴于核磁管中,加入CDCl
3配成溶液。经计算
1H谱产率为90%。产物的核磁数据:
1H NMR(CDCl
3,400MHz)δ:7.29~7.12(m,9H),6.88~6.84(t,1H),4.69(s,2H),1.29(s,12H)。
实施例五:4-甲氧基苯胺基锂催化卞叉苯胺与频哪醇硼烷硼氢化反应
在经过脱水脱氧处理的反应瓶中,氩气保护下加入0.5mmol的卞叉苯胺,加入100ul THF,然后用移液枪加入0.55mmol(0.0798mL)硼烷混合均匀,最后加入69.9ul 4-甲氧基苯胺基锂的四氢呋喃溶液(0.3577M)(5mol%用量,下同),反应2h后,用滴管吸取一滴于核磁 管中,加入CDCl
3配成溶液。经计算
1H谱产率为95%。产物的核磁数据:
1H NMR(CDCl
3,400MHz)δ:7.29~7.12(m,9H),6.88~6.84(t,1H),4.69(s,2H),1.29(s,12H)。
实施例六:4-甲氧基苯胺基锂催化N-(p-甲基苯亚甲基)苯胺与频哪醇硼烷硼氢化反应
在经过脱水脱氧处理的反应瓶中,氩气保护下加入0.5mmol的N-(p-甲基苯亚甲基)苯胺,加入100ul THF,然后用移液枪加入0.6mmol(0.0871mL)硼烷混合均匀,最后加入69.9ul 4-甲氧基苯胺基锂的四氢呋喃溶液(0.3577M)(4mol%用量,下同),反应2h后,用滴管吸取一滴于核磁管中,加入CDCl
3配成溶液。经计算
1H谱产率为99%。产物的核磁数据:
1H NMR(CDCl
3,400MHz)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)。
实施例七:4-甲氧基苯胺基锂催化N-(p-甲氧基苯亚甲基)苯胺与频哪醇硼烷硼氢化反应
在经过脱水脱氧处理的反应瓶中,氩气保护下加入0.5mmol的N-(p-甲氧基苯亚甲基)苯胺,加入100ul THF,然后用移液枪加入0.6mmol(0.0871mL)硼烷混合均匀,最后加入69.9ul 40ul 4-甲氧基苯胺基锂的四氢呋喃溶液(0.3577M)(5mol%用量,下同),反应2h后,用滴管吸取一滴于核磁管中,加入CDCl
3配成溶液。经计算
1H谱产率为99%。产物的核磁数据:
1H NMR(CDCl
3,400MHz)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)。
实施例八:4-甲氧基苯胺基锂催化N-(4-氟苯亚甲基)苯胺与频哪醇硼烷硼氢化反应
在经过脱水脱氧处理的反应瓶中,氩气保护下加入0.5mmol的N-(4-氟苯亚甲基)苯胺,加入100ul THF,然后用移液枪加入0.6mmol(0.0871mL)硼烷混合均匀,最后加入69.9ul 4-甲氧基苯胺基锂的四氢呋喃溶液(0.3577M)(5mol%用量,下同),反应2h后,用滴管吸取一滴于核磁管中,加入CDCl
3配成溶液。经计算
1H谱产率为99%。产物的核磁数据:
1H NMR(CDCl
3,400MHz)δ:7.22~7.15(d,6H),6.98~6.94(d,3H),4.66(s,2H),1.30(s,12H)。
实施例九:4-甲氧基苯胺基锂催化N-(4-氯苯亚甲基)苯胺与频哪醇硼烷硼氢化反应
在经过脱水脱氧处理的反应瓶中,氩气保护下加入0.5mmol的N-(4-氯苯亚甲基)苯胺,加入100ul THF,然后用移液枪加入0.6mmol(0.0871mL)硼烷混合均匀,最后加入69.9ul 4-甲氧基苯胺基锂的四氢呋喃溶液(0.3577M)(5mol%用量,下同),反应2h后,用滴管吸取一滴于核磁管中,加入CDCl
3配成溶液。经计算
1H谱产率为99%。产物的核磁数据:
1H NMR(CDCl
3,400MHz)δ:7.20~7.14(d,6H),6.99~6.93(d,3H),4.64(s,2H),1.30(s,12H)。
实施例十:4-甲氧基苯胺基锂催化N-(4-溴苯亚甲基)苯胺与频哪醇硼烷硼氢化反应
在经过脱水脱氧处理的反应瓶中,氩气保护下加入0.5mmol的N-(4-溴苯亚甲基)苯胺,加入100ul THF,然后用移液枪加入0.6mmol(0.0871mL)硼烷混合均匀,最后加入69.9ul 4-甲氧基苯胺基锂的四氢呋喃溶液(0.3577M)(5mol%用量,下同),反应2h后,用滴管吸取一滴于核磁管中,加入CDCl
3配成溶液。经计算
1H谱产率为99%。产物的核磁数据:
1H NMR(CDCl
3,400MHz)δ:7.24~7.16(d,6H),6.97~6.93(d,3H),4.63(s,2H),1.31(s,12H)。
实施例十一:4-甲氧基苯胺基锂催化亚苄基对甲苯胺与频哪醇硼烷硼氢化反应
在经过脱水脱氧处理的反应瓶中,氩气保护下加入0.5mmol的亚苄基对甲苯,加入100ul THF,然后用移液枪加入0.6mmol(0.0871mL)硼烷混合均匀,最后加入69.9ul 4-甲氧基苯胺基锂的四氢呋喃溶液(0.3577M)(5mol%用量,下同),反应2h后,用滴管吸取一滴于核磁管中,加入CDCl
3配成溶液。经计算
1H谱产率为99%。产物的核磁数据:
1H NMR(CDCl
3,400MHz)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)。
实施例十二:4-甲氧基苯胺基锂催化N-(苯亚甲基)-4-氟苯胺与频哪醇硼烷硼氢化反应
在经过脱水脱氧处理的反应瓶中,氩气保护下加入0.5mmol的N-(苯亚甲基)-4-氟苯胺,加入100ul THF,然后用移液枪加入0.6mmol(0.0871mL)硼烷混合均匀,最后加入69.9ul 4-甲氧基苯胺基锂的四氢呋喃溶液(0.3577M)(5mol%用量,下同),反应2h后,用滴管吸取一滴于核磁管中,加入CDCl
3配成溶液。经计算
1H谱产率为99%。产物的核磁数据:
1H NMR(CDCl
3,400MHz)δ:7.24~7.02(d,7H),6.75~6.70(d,2H),4.66(s,2H),1.32(s,12H)。
实施例十三:4-甲氧基苯胺基锂催化N-(苯亚甲基)-4-氯苯胺与频哪醇硼烷硼氢化反应
在经过脱水脱氧处理的反应瓶中,氩气保护下加入0.5mmol的N-(苯亚甲基)-4-氯苯胺,加入100ul THF,然后用移液枪加入0.6mmol(0.0871mL)硼烷混合均匀,最后加入69.9ul 4-甲氧基苯胺基锂的四氢呋喃溶液(0.3577M)(5mol%用量,下同),反应2h后,用滴管吸取一滴于核磁管中,加入CDCl
3配成溶液。经计算
1H谱产率为99%。产物的核磁数据:
1H NMR(CDCl
3,400MHz)δ:7.26~7.05(d,7H),6.74~6.69(d,2H),4.61(s,2H),1.30(s,12H)。
实施例十四:4-甲氧基苯胺基锂催化N-(苯亚甲基)-4-溴苯胺与频哪醇硼烷硼氢化反应
在经过脱水脱氧处理的反应瓶中,氩气保护下加入0.5mmol的N-(苯亚甲基)-4-溴苯胺,加入100ul THF,然后用移液枪加入0.6mmol(0.0871mL)硼烷混合均匀,最后加入69.9ul 4-甲氧基苯胺基锂的四氢呋喃溶液(0.3577M)(5mol%用量,下同),反应2h后,用滴管吸取一滴于核磁管中,加入CDCl
3配成溶液。经计算
1H谱产率为99%。产物的核磁数据:
1H NMR(CDCl
3,400MHz)δ:7.27~7.03(d,7H),6.76~6.71(d,2H),4.62(s,2H),1.30(s,12H)。
上述实施例的反应温度为室温;本发明首次公开商业化试剂4-甲氧基苯胺基锂能够在温和的反应条件催化亚胺的硼氢化反应,产率很高,具有着较广的底物适用范围,廉价的催化剂以及温和的催化条件,为工业化应用提供了可能。
Claims (10)
- 4-甲氧基苯胺基锂在催化亚胺与硼烷硼氢化反应中的应用。
- 根据权利要求1所述的应用,其特征在于,4-甲氧基苯胺基锂催化亚胺与硼烷发生硼氢化反应的方法包括以下步骤:无水无氧环境下,惰性气体氛围下,在经过脱水脱氧处理的反应瓶中加入亚胺,加入有机溶剂,然后加入硼烷,混合均匀,再加入催化剂4-甲氧基苯胺基锂,室温反应1~2h,暴露于空气中终止反应,得到产物。
- 一种亚胺与硼烷发生硼氢化反应制备硼酸酯的方法,包括以下步骤:无水无氧环境下,惰性气体氛围中,在经过脱水脱氧处理的反应瓶中加入亚胺,加入有机溶剂,然后加入硼烷,混合均匀,再加入催化剂4-甲氧基苯胺基锂,反应得到产物硼酸酯。
- 根据权利要求4所述的方法,其特征在于,所述催化剂用量为亚胺摩尔数的4%~5%,亚胺与频哪醇硼烷的摩尔比为1∶1~1∶1.2。
- 根据权利要求4所述的方法,其特征在于,所述催化剂用量为亚胺摩尔数的5%,亚胺与频哪醇硼烷的摩尔比为1∶1.2。
- 根据权利要求4所述的方法,其特征在于,反应的温度为室温,反应的时间为1~2h。
- 根据权利要求4所述的方法,其特征在于,有机溶剂为四氢呋喃。
- 4-甲氧基苯胺基锂在制备硼酸酯中的应用。
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CN107971036A (zh) * | 2017-12-04 | 2018-05-01 | 苏州大学 | 二硅胺稀土配合物在催化亚胺和硼烷的硼氢化反应中的应用 |
CN108554446A (zh) * | 2018-04-16 | 2018-09-21 | 苏州大学 | 对甲基苯胺基锂在催化醛和硼烷硼氢化反应中的应用 |
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Non-Patent Citations (3)
Title |
---|
JAMES R. LAWSON ET AL.: "Tris(2, 4, 6-trifluorophenyl)borane: An Efficient Hydroboration Catalyst", CHEMISTRY-A EUROPEAN JOURNAL, vol. 23, no. 46, 27 July 2017 (2017-07-27), pages 10997 - 11000, XP055701118, ISSN: 1521-3765 * |
MERLE ARROWSMITH ET AL.: "Magnesium Catalysis of Imine Hydroboration", CHEMISTRY-A EUROPEAN JOURNAL, vol. 19, no. 8, 18 February 2013 (2013-02-18), XP055701123, ISSN: 1521-3765 * |
YAN, DANDAN ET AL.: "Highly Efficient Hydroboration of Carbonyl Compounds Catalyzed by Tris(methylcyclopentadienyl)lanthanide Complexes", ORGANIC & BIOMOLECULAR CHEMISTRY, vol. 16, no. 15, 26 March 2018 (2018-03-26), pages 2787 - 2791, XP055701115, ISSN: 1477-0539 * |
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