CN108503659A - The method for preparing borate using 2,6- diisopropyl benzene amido lithiums - Google Patents
The method for preparing borate using 2,6- diisopropyl benzene amido lithiums Download PDFInfo
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- CN108503659A CN108503659A CN201810336700.6A CN201810336700A CN108503659A CN 108503659 A CN108503659 A CN 108503659A CN 201810336700 A CN201810336700 A CN 201810336700A CN 108503659 A CN108503659 A CN 108503659A
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- ketone
- borine
- hydroboration
- borate
- base lithium
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- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 11
- 229910000085 borane Inorganic materials 0.000 claims abstract description 34
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006197 hydroboration reaction Methods 0.000 claims abstract description 28
- 150000002576 ketones Chemical class 0.000 claims abstract description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- -1 heterocyclic ketone Chemical class 0.000 claims abstract description 14
- 150000008365 aromatic ketones Chemical group 0.000 claims abstract description 12
- 230000018044 dehydration Effects 0.000 claims abstract description 11
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 11
- 238000012545 processing Methods 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 18
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- WYJOVVXUZNRJQY-UHFFFAOYSA-N 2-Acetylthiophene Chemical group CC(=O)C1=CC=CS1 WYJOVVXUZNRJQY-UHFFFAOYSA-N 0.000 claims description 4
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 6
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 abstract description 4
- 125000003368 amide group Chemical group 0.000 abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000005311 nuclear magnetism Effects 0.000 description 6
- YOMBUJAFGMOIGS-UHFFFAOYSA-N 2-fluoro-1-phenylethanone Chemical compound FCC(=O)C1=CC=CC=C1 YOMBUJAFGMOIGS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate 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
-
- 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 discloses utilize 2, the method that 6 diisopropyl benzene amido lithiums prepare borate, under anhydrous and oxygen-free environment, in atmosphere of inert gases, borine is added in the reaction bulb by dehydration and deoxidation processing, then 2,6 diisopropyl benzene amido lithium of catalyst is added, is uniformly mixed, add ketone, hydroboration occurs, is exposed in air and terminates reaction, obtain borate；The ketone is aromatic ketone or heterocyclic ketone.Present invention firstly discovers that 2,6 diisopropyl benzene amido lithiums extremely can efficiently be catalyzed aromatic ketone or heterocyclic ketone occurs hydroboration with borine, new scheme is provided to prepare borate with borine generation hydroboration using carbonyls.
Description
Technical field
The application of 2,6-DIPA base lithium of the present invention, and in particular to utilize 2,6-DIPA base
The method that lithium prepares borate.
Technical background
Hydroboration research for unsaturated bond all has important meaning for modern industry and Synthetic Organic Chemistry
Justice is widely paid close attention to so as to cause researcher.
Various catalyst have been used for the hydroboration of ketone, especially in recent years, about this kind of reaction
It reports many.Since under no catalysts conditions, the hydroboration of carbonyls is difficult to occur.So for this one kind
The research emphasis of reaction exactly develops efficient catalyst system and catalyzing.But the catalyst system and catalyzing reported at present, catalyst are all opposite
Costliness or reaction condition are more harsh.
So the catalyst system and catalyzing for developing the hydroboration of efficient catalytic ketone under new temperate condition is particularly urgent.
Invention content
The goal of the invention of the present invention is to provide the application of 2,6-DIPA base lithium, i.e., with 2,6-DIPA
Base lithium is that effective catalyst is catalyzed ketone and borine occurs hydroboration and prepares borate；The 2,6- diisopropyl benzenes amido lithium
Chemical formula is：2,6-iPr2- PhNHLi, chemical structural formula are as follows：
To achieve the above object of the invention, the technical solution adopted by the present invention is：
A method of borate being prepared using 2,6-DIPA base lithium, is included the following steps：
Under anhydrous and oxygen-free environment, in atmosphere of inert gases, borine is added in the reaction bulb by dehydration and deoxidation processing, then adds
Enter catalyst 2,6-DIPA base lithium, be uniformly mixed, add ketone, hydroboration occurs, is exposed in air eventually
It only reacts, obtains borate；The ketone is aromatic ketone or heterocyclic ketone.
The present invention further discloses 2,6- diisopropyl benzene amido lithiums in catalysis ketone and borine hydroboration
Using；The ketone is aromatic ketone or heterocyclic ketone.
The invention also discloses the method for 2,6-DIPA base lithium catalysis ketone and borine generation hydroboration, packets
Include following steps：
Under anhydrous and oxygen-free environment, under atmosphere of inert gases, borine is added in the reaction bulb by dehydration and deoxidation processing, then adds
Enter 2,6-DIPA base lithium, be uniformly mixed, add ketone, hydroboration occurs.
In above-mentioned technical proposal, the chemical structure of general formula of the aromatic ketone is as follows：
Wherein R is one kind in electron-withdrawing group or electron donating group, can be selected from halogen, methyl；
The heterocyclic ketone is selected from 2- acetyl thiophenes；
The borine is selected from pinacol borine；
The dosage of the catalyst is the 0.3-0.4% of ketone mole, and the molar ratio of ketone and borine is 1: 1.1；
The temperature of hydroboration is room temperature, and the reaction time is 20 minutes.
Above-mentioned technical proposal can indicate as follows：
R1, R2Come from raw ketone.
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 2,6- diisopropyl benzene amidos lithium extremely can efficiently be catalyzed aromatic ketone or heterocyclic ketone and boron
Hydroboration occurs for alkane, and new side is provided to prepare borate with borine generation hydroboration using carbonyls
Case.
2. the catalysis that hydroboration occurs with borine for 2,6- diisopropyl benzenes amido lithium catalysis ketone disclosed by the invention is lived
Property high (catalyst amount is only 0.3-0.4 %), reaction condition is mild (room temperature), and the reaction time is short (20min), and reaction yield
Height, reaction is simple controllable, and post-processing is simple, and reaction uses solvent-free system, reduces the pollution to environment.
3. catalyst disclosed by the invention is for the aromatic ketone of different the position of substitution, different electronic effects and to heterocyclic ketone
There is preferable universality, the boric acid ester compound to obtain different substituents structure provides more selections.
Specific implementation mode
The present invention is described further with reference to embodiment：
Embodiment one：2,6- diisopropyl benzene amido lithiums are catalyzed acetophenone and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to be added the four of 60 ul 2,6-DIPA base lithiums
Hydrogen tetrahydrofuran solution (0.05M) (0.3 mol% dosages), then with syringe be added 0.1596 mL borines, be uniformly mixed, then with note
0.117 mL acetophenones are added in emitter, and mixture is stirred at room temperature, and after reacting 20 min, nuclear-magnetism yield is 99%, is depressurized later
A small amount of tetrahydrofuran and excessive borine are removed to get to corresponding pinacol borate.C6H5CH(CH3)OB(OC(CH3)2C
(CH3)2O)。1H NMR (400 MHz, CDCl3) δ 7.38-7.21 (m, 5H, Ar-H), 5.24 (q, J = 6.5
Hz, 1H, OCH), 1.49 (d, J = 6.5 Hz, 3H, CH3), 1.22 (d, J = 11.9 Hz, 12H, CH3).13C NMR (101 MHz, CDCl3) δ 144.09 (Ar-C), 127.71 (Ar-C), 126.62 (Ar-C), 124.86
(Ar-C), 82.26 (OC), 72.10 (OCH), 24.98 (CH3), 24.07 (d, J = 4.5 Hz, CH3)。
Embodiment two：2,6- diisopropyl benzene amido lithiums are catalyzed to fluoro acetophenone and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to be added the four of 80 ul 2,6-DIPA base lithiums
Hydrogen tetrahydrofuran solution (0.05M) (0.4 mol% dosages), then with syringe be added 0.1596 mL borines, be uniformly mixed, then with note
0.1208 mL is added to fluoro acetophenone in emitter, and mixture is stirred at room temperature, and after reacting 20 min, nuclear-magnetism yield is 99%, it
A small amount of tetrahydrofuran and excessive borine are removed under reduced pressure afterwards to get to corresponding pinacol borate.1H NMR (400
MHz, CDCl3) δ 7.35-7.30 (m, 2H, Ar-H), 7.02-6.96 (m, 2H, Ar-H), 5.22 (q, J =
6.4 Hz, 1H, OCH), 1.47 (d, J = 6.5 Hz, 3H, CH3), 1.22 (d, J = 11.6 Hz, 12H,
CH3). 13C NMR (101 MHz, CDCl3) δ 161.94 (ds, Ar-C), 140.34 (d, J = 3.1 Hz, Ar-
C), 127.02 (d, J = 8.0 Hz, Ar-C), 114.93 (ds, Ar-C), 82.80 (OC), 72.00 (OCH),
25.40 (CH3), 24.52 (d, J = 6.1 Hz, CH3)。
Embodiment three：Fluoro acetophenone and pinacol borine hydroboration between the catalysis of 2,6- diisopropyl benzene amido lithiums
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to be added the four of 80 ul 2,6-DIPA base lithiums
Hydrogen tetrahydrofuran solution (0.05M) (0.4 mol% dosages), then with syringe be added 0.1596 mL borines, be uniformly mixed, then with note
Fluoro acetophenone between 0.1226 mL is added in emitter, and mixture is stirred at room temperature, and after reacting 20 min, nuclear-magnetism yield is 99%, it
A small amount of tetrahydrofuran and excessive borine are removed under reduced pressure afterwards to get to corresponding pinacol borate.1H NMR (400
MHz, CDCl3) δ 7.29-7.24 (m, 1H, Ar-H), 7.12-7.08 (m, 2H, Ar-H), 6.94-6.89 (m,
1H, Ar-H), 5.23 (q, J = 6.4 Hz, 1H, OCH), 1.48 (d, J = 6.5 Hz, 3H, CH3), 1.23
(d, J = 11.4 Hz, 12H, CH3).13C NMR (101 MHz, CDCl3) δ 162.85 (ds, Ar-C),
147.26 (d, J = 6.9 Hz, Ar-C), 129.67 (d, J = 8.2 Hz, Ar-C), 120.88 (d, J =
2.8 Hz, Ar-C), 113.87 (ds, Ar-C), 112.33 (ds, Ar-C), 82.87 (OC), 71.95 (d, J
= 1.8 Hz, OCH), 25.30 (CH3), 24.52 (d, J = 4.2 Hz, CH3)。
Example IV：2,6- diisopropyl benzene amido lithiums are catalyzed parachloroacetophenone and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to be added the four of 80 ul 2,6-DIPA base lithiums
Hydrogen tetrahydrofuran solution (0.05M) (0.4 mol% dosages), then with syringe be added 0.1596 mL borines, be uniformly mixed, then with note
0.1297 mL parachloroacetophenones are added in emitter, and mixture is stirred at room temperature, and after reacting 20 min, nuclear-magnetism yield is 99%, it
A small amount of tetrahydrofuran and excessive borine are removed under reduced pressure afterwards to get to corresponding pinacol borate.1H NMR (400
MHz, CDCl3) δ 7.31-7.26 (m, 4H, Ar-H), 5.21 (q, J = 6.4 Hz, 1H, OCH), 1.46
(d, J = 6.5 Hz, 3H, CH3), 1.22 (d, J = 11.4 Hz, 12H, CH3). 13C NMR (101 MHz,
CDCl3) δ 142.62 (Ar-C), 132.26 (Ar-C), 127.83 (Ar-C), 126.29 (Ar-C), 82.35
(OC), 71.45 (OCH), 24.87 (CH3), 24.04 (d, J = 4.7 Hz, CH3)。
Embodiment five：2,6- diisopropyl benzene amido lithiums are catalyzed melilotal and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to be added the four of 80 ul 2,6-DIPA base lithiums
Hydrogen tetrahydrofuran solution (0.05M) (0.4 mol% dosages), then with syringe be added 0.1596 mL borines, be uniformly mixed, then with note
0.1335 mL melilotal is added in emitter, and mixture is stirred at room temperature, and after reacting 20 min, nuclear-magnetism yield is 99%,
A small amount of tetrahydrofuran and excessive borine are removed under reduced pressure later to get to corresponding pinacol borate.1H NMR (400
MHz, CDCl3) δ 7.26-7.24 (m, 2H, Ar-H), 7.11-7.13 (m, 2H, Ar-H), 5.21 (q, J =
6.4 Hz, 1H, OCH), 2.32 (s, 3H, Ar-CH3), 1.47 (d, J = 6.5 Hz, 3H, CH3), 1.22
(d, J = 10.4 Hz, 12H, CH3). 13C NMR (101 MHz, CDCl3) δ 141.17 (Ar-C), 136.17
(Ar-C), 128.38 (Ar-C), 124.82 (Ar-C), 82.21 (OC), 71.96 (OCH), 24.99 (CH3),
24.08 (d, J = 3.7 Hz, CH3), 20.61 (s, Ar-CH3)。
Embodiment six：2,6- diisopropyl benzene amido lithiums are catalyzed to 2- acetyl thiophenes and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to be added the four of 80 ul 2,6-DIPA base lithiums
Hydrogen tetrahydrofuran solution (0.05M) (0.4 mol% dosages), then with syringe be added 0.1596 mL borines, be uniformly mixed, then with note
0.1097 mL2- acetyl thiophenes are added in emitter, and mixture is stirred at room temperature, and after reacting 20 min, nuclear-magnetism yield is 99%, it
A small amount of tetrahydrofuran and excessive borine are removed under reduced pressure afterwards to get to corresponding pinacol borate.1H NMR (400
MHz, CDCl3) δ 7.20-7.18 (m, 1H, Ar-H), 6.97-6.91 (m, 2H, Ar-H), 5.48 (q, J =
6.4 Hz, 1H, OCH), 1.60 (d, J = 6.4 Hz, 3H, CH3), 1.24 (d, J = 4.9 Hz, 12H,
CH3). 13C NMR (101 MHz, CDCl3) δ 147.72 (Ar-C), 125.90 (Ar-C), 123.63 (Ar-C),
122.79 (Ar-C), 82.44 (OC), 68.15 (OCH), 24.58 (CH3), 24.09 (d, J = 9.8 Hz,
CH3)。
2,6-DIPA base lithium is replaced with to the amido lithium compound of formula I, it is virtually impossible to obtain product, yield is small
In 6%.
Although belonging to carbonyls, ketone and aldehyde have different reaction properties, this is common sense, and the prior art exists simultaneously
Using keto-aldehyde as raw material, but only there is a situation where a kind of raw materials to react；Electron donating group can weaken the electropositive of carbonyl carbon, to cut
The nucleophilic addition activity of weak carbonyl, aromatic aldehyde is since conjugation reduces carbonyl activity, to different the position of substitution, different electronic effects
Aromatic compound and fatty compound have and larger react difference.
Present invention firstly discovers that 2,6-DIPA base lithium can be catalyzed aromatic ketone, heterocycle with high catalytic activity
The hydroboration of ketone, and there is very wide substrate usage range.Cheap catalyst and lower catalyst are used
Amount, mild catalytic condition provide possibility for industrial applications.
Claims (10)
1. the method for preparing borate using 2,6-DIPA base lithium, includes the following steps：
Under anhydrous and oxygen-free environment, in atmosphere of inert gases, borine is added in the reaction bulb by dehydration and deoxidation processing, then adds
Enter catalyst 2,6-DIPA base lithium, be uniformly mixed, add ketone, hydroboration occurs, is exposed in air eventually
It only reacts, obtains borate；The ketone is aromatic ketone or heterocyclic ketone.
2. the method for preparing borate using 2,6-DIPA base lithium according to claim 1, which is characterized in that institute
The chemical structure of general formula for stating aromatic ketone is as follows：
Wherein R is one kind in electron-withdrawing group or electron donating group；
The heterocyclic ketone is selected from 2- acetyl thiophenes.
3. the method for preparing borate using 2,6-DIPA base lithium according to claim 1, which is characterized in that institute
It states borine and is selected from pinacol borine.
4. the method for preparing borate using 2,6-DIPA base lithium according to claim 1, which is characterized in that institute
The dosage for stating catalyst is the 0.3-0.4% of ketone mole, and the molar ratio of ketone and borine is 1: 1.1.
5. the method for preparing borate using 2,6-DIPA base lithium according to claim 1, which is characterized in that boron
The temperature of hydrogenation is room temperature, and the time is 20 minutes.
6.2,6- diisopropyl benzene amido lithiums are in catalysis ketone and the application in borine hydroboration；The ketone be aromatic ketone or
Heterocyclic ketone.
7. application according to claim 6, which is characterized in that the hydroboration includes the following steps：
Under anhydrous and oxygen-free environment, under atmosphere of inert gases, borine is added in the reaction bulb by dehydration and deoxidation processing, then adds
Enter 2,6-DIPA base lithium, be uniformly mixed, add ketone, hydroboration occurs.
8. application according to claim 6, which is characterized in that the chemical structure of general formula of the aromatic ketone is as follows：
Wherein R is one kind in electron-withdrawing group or electron donating group；
The heterocyclic ketone is selected from 2- acetyl thiophenes；
The borine is selected from pinacol borine.
9. application according to claim 6, which is characterized in that the dosage of the 2,6-DIPA base lithium is rubbed for ketone
The molar ratio of the 0.3-0.4% of your amount, ketone and borine is 1: 1.1.
10. application according to claim 6, which is characterized in that the temperature of hydroboration is room temperature, and the time is 20 points
Clock.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232622A (en) * | 2018-09-27 | 2019-01-18 | 南通纺织丝绸产业技术研究院 | Application of the 2,6- diisopropyl benzene amido lithium in catalysis imines and borine hydroboration |
| WO2019200525A1 (en) * | 2018-04-17 | 2019-10-24 | 南通纺织丝绸产业技术研究院 | Application of 2,6-diisopropylanilino lithium in catalyzing hydroboration of carbonyl compound and borane |
| WO2020073180A1 (en) * | 2018-10-08 | 2020-04-16 | 南通纺织丝绸产业技术研究院 | Application of lithium 2,6-diisopropylaniline in catalyzing hydroboration of imine with borane |
| CN111747972A (en) * | 2020-06-16 | 2020-10-09 | 苏州大学 | Deprotonated beta-ketimine lithium compound and preparation method thereof |
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| WO2019200525A1 (en) * | 2018-04-17 | 2019-10-24 | 南通纺织丝绸产业技术研究院 | Application of 2,6-diisopropylanilino lithium in catalyzing hydroboration of carbonyl compound and borane |
| CN109232622A (en) * | 2018-09-27 | 2019-01-18 | 南通纺织丝绸产业技术研究院 | Application of the 2,6- diisopropyl benzene amido lithium in catalysis imines and borine hydroboration |
| CN109232622B (en) * | 2018-09-27 | 2021-07-20 | 南通纺织丝绸产业技术研究院 | Application of 2, 6-diisopropylaniline lithium in catalyzing imine and borane hydroboration reaction |
| WO2020073180A1 (en) * | 2018-10-08 | 2020-04-16 | 南通纺织丝绸产业技术研究院 | Application of lithium 2,6-diisopropylaniline in catalyzing hydroboration of imine with borane |
| CN111747972A (en) * | 2020-06-16 | 2020-10-09 | 苏州大学 | Deprotonated beta-ketimine lithium compound and preparation method thereof |
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