CN108325559A - Application of the 2,6- accelerine bases lithium in catalysis aldehyde and borine hydroboration - Google Patents
Application of the 2,6- accelerine bases lithium in catalysis aldehyde and borine hydroboration Download PDFInfo
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- 229910000085 borane Inorganic materials 0.000 title claims abstract description 43
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000006197 hydroboration reaction Methods 0.000 title claims abstract description 37
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 9
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title 1
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- -1 heterocyclic aldehydes Chemical class 0.000 claims abstract description 16
- 230000018044 dehydration Effects 0.000 claims abstract description 14
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 14
- 238000012545 processing Methods 0.000 claims abstract description 14
- 150000003934 aromatic aldehydes Chemical group 0.000 claims abstract description 11
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical group CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 36
- 238000002360 preparation method Methods 0.000 claims description 6
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 3
- 238000012805 post-processing Methods 0.000 abstract description 2
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 abstract 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 36
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 36
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 34
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 18
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000005311 nuclear magnetism Effects 0.000 description 9
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- 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 4
- 230000000694 effects Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- HIKRJHFHGKZKRI-UHFFFAOYSA-N 2,4,6-trimethylbenzaldehyde Chemical class CC1=CC(C)=C(C=O)C(C)=C1 HIKRJHFHGKZKRI-UHFFFAOYSA-N 0.000 description 1
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical class ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 1
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical class O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 1
- SRWILAKSARHZPR-UHFFFAOYSA-N 3-chlorobenzaldehyde Chemical compound ClC1=CC=CC(C=O)=C1 SRWILAKSARHZPR-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application 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
- 239000012530 fluid Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The present invention relates to 2,6 accelerine base lithiums are under catalysis aldehyde and the application in borine hydroboration, 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 accelerine base lithium of catalyst is added, is uniformly mixed, add aldehyde, hydroboration is carried out, is exposed in air and terminates reaction, obtain product borate；The aldehyde is selected from aromatic aldehyde, heterocyclic aldehydes.Disclosed by the invention 2,6 accelerine base lithiums are catalyzed the catalytic activity height that hydroboration occurs with borine for aldehyde (catalyst amount is only 0.1 0.4%), reaction condition is mild (room temperature), reaction time is short (10 ~ 30 min), and reaction yield is high, reaction is simple controllable, and post-processing is simple, reaction uses solvent-free system, reduces the pollution to environment.
Description
Technical field
The application of 2,6- accelerine bases lithium of the present invention, and in particular to 2,6- accelerine base lithiums are being catalyzed
Aldehyde and the efficient application in borine hydroboration.
Technical background
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.
The product boric acid ester compound of hydroboration can not only be used as polymeric additive, gasoline additive, resistance
Agent is fired, bactericidal agent uses, it is also possible to make special surfactant, lube oil additive and motor vehicle brake fluid etc., application range ten
Divide extensive.For the hydroboration of equivalent catalysis of carbonyl class compound, obtained borate ester product is hydrolyzed, and
In contemporary Synthetic Organic Chemistry, the very effective method of synthol.Therefore, for the hydroboration research of unsaturated bond,
All have great importance for modern industry and Synthetic Organic Chemistry, is widely paid close attention to so as to cause researcher.
Various catalyst have been used for the hydroboration of aldehyde, 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 developing the catalysis of the hydroboration of efficient catalytic aldehyde under new temperate condition
System is particularly urgent.
Invention content
The goal of the invention of the present invention is to provide the application of 2,6- accelerine base lithiums, i.e., with 2,6- accelerine base lithiums
The application of aldehyde and borine generation hydroboration is catalyzed for effective catalyst；2,6- accelerine bases lithiumation of the present invention
Formula is：2,6-Me2PhNHLi, chemical structural formula are as follows：
To achieve the above object of the invention, the technical solution adopted by the present invention is：2,6- accelerine bases lithium is in catalysis aldehyde and boron
Application in alkane hydroboration；The aldehyde is selected from aromatic aldehyde, heterocyclic aldehydes.
The invention also discloses the methods of 2,6- accelerine base lithiums catalysis aldehyde and borine generation hydroboration, including
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 catalyst 2,6- accelerine base lithiums are uniformly mixed, and add aldehyde, carry out hydroboration.
The present invention further discloses a kind of preparation method of borate, 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- accelerine base lithiums are uniformly mixed, and add aldehyde, are carried out hydroboration, are exposed in air and terminate
Reaction, obtains product borate；The aldehyde is selected from aromatic aldehyde, heterocyclic aldehydes.
In above-mentioned technical proposal, the chemical structure of general formula of the aromatic aldehyde is as follows：
Wherein R is one kind in electron-withdrawing group or electron donating group, can be selected from halogen, methyl, methoxyl group；
The heterocyclic aldehydes are selected from 2 pyridine carboxaldehydes or 2 thiophene carboxaldehyde；
The borine is selected from pinacol borine.
In above-mentioned technical proposal, the catalyst amount is the 0.1-0.4% of aldehyde mole, and the molar ratio of aldehyde and borine is 1
∶1.1。
In above-mentioned technical proposal, the temperature of hydroboration is room temperature, and the reaction time is 10-30 minutes, preferably 10 minutes.
Above-mentioned technical proposal can indicate as follows：
R1Come from raw material aldehyde.
Due to the application of the above technical scheme, the present invention has the following advantages compared with prior art：
1. occurring with borine present invention firstly discovers that 2,6- accelerine bases lithium extremely can efficiently be catalyzed aromatic aldehyde/heterocyclic aldehydes
Hydroboration provides new scheme to prepare borate with borine generation hydroboration using carbonyls.
2. the catalytic activity of hydroboration occurs with borine for 2,6- accelerine bases lithium catalysis aldehyde disclosed by the invention
High (catalyst amount is only 0.1-0.4 %), reaction condition is mild (room temperature), and the reaction time is short (10 ~ 30 min), and reacts production
Rate is high, and 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 aldehyde of different the position of substitution, different electronic effects and to heterocyclic aldehydes
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- accelerine base lithiums are catalyzed benzaldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to be added 20 ul 2, the tetrahydrochysene of 6- accelerine base lithiums
Then 0.1596 mL borines are added with syringe in tetrahydrofuran solution (0.05M) (0.1 mol% dosages, similarly hereinafter), are uniformly mixed, then
0.1016 mL benzaldehydes are added with syringe, mixture is stirred at room temperature, and after reacting 10 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 C6H5CH2OB(OC(CH3)2C(CH3)2O)。1H NMR (400 MHz, CDCl3) δ 7.36-7.23 (m, 5H, Ar-H), 4.92 (s, 2H,
OCH2), 1.26 (s, 12H, CH3). 13C NMR (101 MHz, CDCl3) δ 138.76 (Ar-C), 127.81
(Ar-C), 126.89 (Ar-C), 126.24 (Ar-C), 82.48 (OC), 66.20 (OCH2), 24.15 (CH3)。
2,6- accelerine base lithiums are replaced with to the amido lithium compound of formula I, it is virtually impossible to obtain product, yield is less than
3%。
Embodiment two：2,6- accelerine base lithiums are catalyzed 4-Fluorobenzaldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to be added 40 ul 2, the tetrahydrochysene of 6- accelerine base lithiums
Tetrahydrofuran solution (0.05M) (0.2 mol% dosages), then with syringe be added 0.1596 mL borines, be uniformly mixed, then with inject
0.1072 mL 4-Fluorobenzaldehydes are added in device, and mixture is stirred at room temperature, and after reacting 10 min, nuclear-magnetism yield is 99%, later
A small amount of tetrahydrofuran and excessive borine is removed under reduced pressure to get to corresponding pinacol boratep-F-C6H4CH2OB(OC
(CH3)2C(CH3)2O)。1H NMR (400 MHz, CDCl3) δ 7.34-7.29 (m, 2H, Ar-H), 7.04-6.98
(m, 2H, Ar-H), 4.87 (s, 2H, OCH2), 1.26 (s, 12H, CH3). 13C NMR (101 MHz,
CDCl3) δ 161.71 (ds, Ar-C), 134.50 (d, J = 3.2 Hz, Ar-C), 128.14 (d, J = 8.1
Hz, Ar-C), 114.60 (ds, Ar-C), 82.54 (OC), 65.56 (OCH2), 24.11 (CH3)。
Embodiment three：2,6- accelerine base lithiums are catalyzed m chlorobenzaldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to be added 40 ul 2, the tetrahydrochysene of 6- accelerine base lithiums
Tetrahydrofuran solution (0.05M) (0.2 mol% dosages), then with syringe be added 0.1596 mL borines, be uniformly mixed, then with inject
0.0899 mL m chlorobenzaldehydes are added in device, and mixture is stirred at room temperature, and after reacting 10 min, nuclear-magnetism yield is 99%, later
A small amount of tetrahydrofuran and excessive borine is removed under reduced pressure to get to corresponding pinacol boratem-Cl-C6H4CH2OB(OC
(CH3)2C(CH3)2O)。1H NMR (400 MHz, CDCl3) δ 7.36 (s, 1H, Ar-H), 7.28-7.19 (m, 3H,
Ar-H), 4.89 (s, 2H, OCH2), 1.27 (s, 12H,CH3). 13C NMR (101 MHz, CDCl3) δ 140.75
(Ar-C), 133.75 (Ar-C), 129.08 (Ar-C), 126.99 (Ar-C), 126.30 (Ar-C), 124.17
(Ar-C), 82.61 (OC), 65.41 (OCH2), 24.05 (CH3)。
Example IV：2,6- accelerine base lithiums are catalyzed p-tolyl aldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to be added 60ul 2, the tetrahydrochysene of 6- accelerine base lithiums
Tetrahydrofuran solution (0.05M) (0.3 mol% dosages), then with syringe be added 0.1596 mL borines, be uniformly mixed, then with inject
0.1184 mL p-tolyl aldehydes are added in device, and mixture is stirred at room temperature, and after reacting 10 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 boratep-Me-C6H4CH2OB(OC
(CH3)2C(CH3)2O)。1H NMR (400 MHz, CDCl3) δ 7.24-7.22 (m, 2H,Ar-H), 7.13-7.11 (m,
2H, Ar-H), 4.87 (s, 2H, OCH2), 2.32 (s, 3H, Ar-CH3), 1.24 (s, 12H, CH3). 13C
NMR (101 MHz, CDCl3) δ 136.51 (Ar-C), 135.79 (Ar-C), 128.49 (Ar-C), 126.40
(Ar-C), 82.45 (OC), 66.13 (OCH2), 24.14 (CH3), 20.66 (CH3)。
Example IV：2,6- accelerine base lithiums are catalyzed o-tolualdehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to be added 60 ul 2, the tetrahydrochysene of 6- accelerine base lithiums
Tetrahydrofuran solution (0.05M) (0.3 mol% dosages), then with syringe be added 0.1596 mL borines, be uniformly mixed, then with inject
0.1156 mL o-tolualdehydes are added in device, 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 borateo-Me-C6H4CH2OB(OC
(CH3)2C(CH3)2O)。1H NMR (400 MHz, CDCl3) δ 7.39 (dq, J = 7.2, 3.6 Hz, 1H,Ar-H),
7.18-7.11 (m, 3H, Ar-H), 4.92 (s, 2H, OCH2), 2.30 (s, 3H, Ar-CH3), 1.26 (s,
12H, CH3). 13C NMR (101 MHz, CDCl3) δ 136.69 (Ar-C), 135.13 (Ar-C), 129.49
(Ar-C), 126.86 (d, J = 25.25, Ar-C), 125.35 (Ar-C), 82.45 (OC), 64.49 (OCH2),
24.15 (CH3), 18.18 (CH3)。
Embodiment five：2,6- accelerine base lithiums are catalyzed 2,4,6- trimethylbenzaldehydes and pinacol borine hydroboration
Reaction
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to be added 60 ul 2, the tetrahydrochysene of 6- accelerine base lithiums
Tetrahydrofuran solution (0.05M) (0.3 mol% dosages), then with syringe be added 0.1596 mL borines, be uniformly mixed, then with inject
0.1475 mL2,4,6- trimethylbenzaldehydes is added in device, 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 2,4,6-Me3-
C6H2CH2OB(OC(CH3)2C(CH3)2O)。1H NMR (400 MHz, CDCl3) δ 6.83 (s, 2H,Ar-H), 4.96
(s, 2H, OCH2), 2.38 (s, 6H, Ar-CH3), 2.25 (s, 3H, Ar-CH3), 1.26 (s, 12H, CH3).13C NMR (101 MHz, CDCl3) δ 137.25 (Ar-C), 137.08 (Ar-C), 128.67 (Ar-C), 128.41
(Ar-C), 82.28 (OC), 60.72 (OCH2), 24.15 (CH3), 20.49 (CH3), 18.95 (CH3)。
Embodiment six：2,6- accelerine base lithiums are catalyzed P-methoxybenzal-dehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to be added 40 ul 2, the tetrahydrochysene of 6- accelerine base lithiums
Tetrahydrofuran solution (0.05M) (0.4 mol% dosages), then with syringe be added 0.1596 mL borines, be uniformly mixed, then with inject
0.1214 mL P-methoxybenzal-dehyde is added in device, and mixture is stirred at room temperature, and after reacting 30 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 boratep-MeO-C6H2CH2OB
(OC(CH3)2C(CH3)2O)。1H NMR (400 MHz, CDCl3) δ 7.29-7.25 (m, 2H,Ar-H), 6.87-6.84
(m, 2H, Ar-H), 4.84 (s, 2H, OCH2), 3.78 (s, 3H, Ar-CH3), 1.21 (s, 12H, CH3).13C NMR (101 MHz, CDCl3) δ 158.56 (Ar-C), 130.98 (Ar-C), 128.03 (Ar-C), 113.19
(Ar-C), 82.38 (OC), 65.95 (OCH2), 54.74 (OCH3), 24.14 (CH3)。
Embodiment seven：2,6- accelerine base lithiums are catalyzed 2- pyridine carboxaldehydes and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to be added 40ul 2, the tetrahydrochysene of 6- accelerine base lithiums
Tetrahydrofuran solution (0.05M) (0.2 mol% dosages), then with syringe be added 0.1596 mL borines, be uniformly mixed, then with inject
0.095 mL2- pyridine carboxaldehydes are added in device, and mixture is stirred at room temperature, and after reacting 10 min, nuclear-magnetism yield is 99%, is subtracted later
Pressure removes a small amount of tetrahydrofuran and excessive borine to get to corresponding pinacol borate 2-C5H4NCOCH2OB(OC
(CH3)2C(CH3)2O)。1H NMR (400 MHz, CDCl3) δ 8.61 (d, J = 5.4 Hz, 1H, Ar-H), 7.91
(t, J = 7.7 Hz, 1H, Ar-H), 7.49-7.41 (m, 2H, Ar-H), 5.10 (s, 2H, OCH2), 1.32
(s, 12H, CH3). 13C NMR (101 MHz, CDCl3) δ 159.82 (Ar-C), 143.72 (Ar-C), 139.56
(Ar-C), 123.39 (Ar-C), 120.09 (Ar-C), 81.04 (OC), 66.47 (OCH2), 25.47 (CH3)。
Embodiment eight：2,6- accelerine base lithiums are catalyzed 2 thiophene carboxaldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to be added 40 ul 2, the tetrahydrochysene of 6- accelerine base lithiums
Tetrahydrofuran solution (0.05M) (0.2 mol% dosages), then with syringe be added 0.1596 mL borines, be uniformly mixed, then with inject
0.092 mL2- thiophenecarboxaldehydes are added in device, and mixture is stirred at room temperature, and after reacting 10 min, nuclear-magnetism yield is more than 99%, later
A small amount of tetrahydrofuran and excessive borine is removed under reduced pressure to get to corresponding pinacol borate 2-C4H3NCOCH2OB(OC
(CH3)2C(CH3)2O)。1H NMR (400 MHz, CDCl3) δ 7.25 (d, J = 4.3 Hz, 1H, Ar-H), 7.02-
6.94 (m, 2H, Ar-H), 5.04 (s, 2H, OCH2), 1.27 (s, 12H, CH3). 13C NMR (101 MHz,
CDCl3) δ 141.97 (Ar-C), 126.59 (Ar-C), 125.89 (Ar-C), 125.51 (Ar-C), 83.14
(OC), 61.63 (OCH2), 24.63 (CH3)。
Present invention firstly discovers that the hydroboration that 2,6- accelerine bases lithium can be catalyzed aldehyde with high catalytic activity is anti-
It answers, and there is very wide substrate usage range.Cheap catalyst and lower catalyst amount, mild urges
Change condition provides possibility for industrial applications.
Claims (10)
1.2,6- accelerine bases lithium is in catalysis aldehyde and the application in borine hydroboration；The aldehyde is selected from aromatic aldehyde, miscellaneous
Ring aldehyde.
2. application according to claim 1, 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 catalyst 2,6- accelerine base lithiums are uniformly mixed, and add aldehyde, carry out hydroboration.
3. application according to claim 1, which is characterized in that the chemical structure of general formula of the aromatic aldehyde is as follows：
Wherein R is one kind in electron-withdrawing group or electron donating group；
The heterocyclic aldehydes are selected from 2 pyridine carboxaldehydes or 2 thiophene carboxaldehyde；
The borine is selected from pinacol borine.
4. application according to claim 1, which is characterized in that the dosage of 2, the 6- accelerine bases lithium is aldehyde mole
The molar ratio of the 0.1-0.4% of amount, aldehyde and borine is 1: 1.1.
5. application according to claim 1, which is characterized in that the temperature of the hydroboration is room temperature, time 10-
30 minutes.
6. a kind of preparation method of borate, 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- accelerine base lithiums are uniformly mixed, and add aldehyde, are carried out hydroboration, are exposed in air and terminate
Reaction, obtains borate；The aldehyde is selected from aromatic aldehyde, heterocyclic aldehydes.
7. the preparation method of borate according to claim 6, which is characterized in that the chemical structure of general formula of the aromatic aldehyde is such as
Under：
Wherein R is one kind in electron-withdrawing group or electron donating group；
The heterocyclic aldehydes are selected from 2 pyridine carboxaldehydes or 2 thiophene carboxaldehyde；
The borine is selected from pinacol borine.
8. the preparation method of borate according to claim 6, which is characterized in that the dosage of the catalyst is aldehyde mole
0.1-0.4%.
9. the preparation method of borate according to claim 6, which is characterized in that the temperature of hydroboration is room temperature, when
Between be 10-30 minutes.
10. the preparation method of borate according to claim 6, which is characterized in that the molar ratio of aldehyde and pinacol borine is 1
∶1.1。
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109331867A (en) * | 2018-09-27 | 2019-02-15 | 苏州大学 | Application of the 2,6- accelerine base lithium in catalysis imines and borine hydroboration |
| WO2019200521A1 (en) * | 2018-04-17 | 2019-10-24 | 南通纺织丝绸产业技术研究院 | Application of anilino lithium in catalyzing hydroboration of carbonyl compound and borane |
| WO2019200524A1 (en) * | 2018-04-17 | 2019-10-24 | 南通纺织丝绸产业技术研究院 | Application of 2,6-dimethylanilino lithium in catalyzing hydroboration of carbonyl compound and borane |
| WO2020073177A1 (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-dimethylaniline 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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| CN106749372A (en) * | 2016-12-07 | 2017-05-31 | 厦门大学 | A kind of preparation method of organic boronic ester compounds |
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2018
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106749372A (en) * | 2016-12-07 | 2017-05-31 | 厦门大学 | A kind of preparation method of organic boronic ester compounds |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019200521A1 (en) * | 2018-04-17 | 2019-10-24 | 南通纺织丝绸产业技术研究院 | Application of anilino lithium in catalyzing hydroboration of carbonyl compound and borane |
| WO2019200524A1 (en) * | 2018-04-17 | 2019-10-24 | 南通纺织丝绸产业技术研究院 | Application of 2,6-dimethylanilino lithium in catalyzing hydroboration of carbonyl compound and borane |
| CN109331867A (en) * | 2018-09-27 | 2019-02-15 | 苏州大学 | Application of the 2,6- accelerine base lithium in catalysis imines and borine hydroboration |
| CN109331867B (en) * | 2018-09-27 | 2020-04-17 | 苏州大学 | Application of 2, 6-dimethylanilinium to catalysis of imine and borane hydroboration reaction |
| WO2020073177A1 (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-dimethylaniline 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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