CN113683633B - Preparation method of alkyl borate - Google Patents
Preparation method of alkyl borate Download PDFInfo
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- CN113683633B CN113683633B CN202111012419.5A CN202111012419A CN113683633B CN 113683633 B CN113683633 B CN 113683633B CN 202111012419 A CN202111012419 A CN 202111012419A CN 113683633 B CN113683633 B CN 113683633B
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- -1 alkyl borate Chemical compound 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical compound CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001336 alkenes Chemical class 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical group [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 claims abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 11
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 28
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 18
- 239000000047 product Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000036541 health Effects 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 239000013067 intermediate product Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 238000010327 methods by industry Methods 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 7
- 150000003624 transition metals Chemical class 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 238000002955 isolation Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000006197 hydroboration reaction Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 229910000103 lithium hydride Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- CORMBJOFDGICKF-UHFFFAOYSA-N 1,3,5-trimethoxy 2-vinyl benzene Natural products COC1=CC(OC)=C(C=C)C(OC)=C1 CORMBJOFDGICKF-UHFFFAOYSA-N 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 description 1
- PDELBHCVXBSVPJ-UHFFFAOYSA-N 2-ethenyl-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=C(C=C)C(C)=C1 PDELBHCVXBSVPJ-UHFFFAOYSA-N 0.000 description 1
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical compound C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 description 1
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 238000005885 boration reaction Methods 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 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 System
- C07F5/02—Boron compounds
Abstract
The invention discloses a preparation method of alkyl borate, which comprises the steps of adding olefin substances, pinacol borane and a lithium amide catalyst into a reaction vessel filled with an organic solvent under the atmosphere of nitrogen, stirring and mixing, reacting at 80-120 ℃ for 20-30h after uniform mixing, and filtering and purifying after the reaction is finished to obtain the alkyl borate; the lithium amide catalyst is lithium bis (trimethylsilyl) amide; the invention has mild reaction conditions, easy achievement and safety; the method can directly synthesize the target product without separating intermediate products, the highest yield can reach 99 percent, greatly simplifies the process engineering, reduces the energy consumption and has the advantage of high yield; in addition, the waste solution is less in the reaction process, and other polluted gas and liquid are not discharged, so that the invention reduces the discharge of the waste solution and has the advantages of protecting the environment and guaranteeing the health of operators; the toxicity of the substances used in the invention is lower, thus ensuring the health of operators.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a preparation method of alkyl borate.
Background
Organoboron chemistry has been an extremely important part of the chemical field from none to the last. The discovery of the suzuki coupling reaction (Suzuki coupling reaction) enables the organic borate compounds to be effectively applied to the construction of carbon-carbon bonds, not only can be widely touted in the field of organic synthesis, but also can be widely applied in the fields of material chemistry and pharmaceutical chemistry. Therefore, efficient and convenient synthesis of organic borate raw materials is particularly important.
The recent development of transition metal catalyzed cross-coupling reactions has led to the start of more and more metal catalysts to be applied in the field of organoboronates synthesis. There are several methods in common: the first uses borane as raw material, alkene or alkyne as substrate, and carries out the hydroboration reaction catalyzed by transition metal (J.Am.chem.Soc.1992, 114, 6671.), so as to realize the synthesis of alkyl borate or alkenyl borate; the second uses biboronate as raw material, alkene or alkyne as substrate, and carries out transition metal catalyzed boration reaction (J.Am.chem.Soc.2010, 132, 2548), and corresponding mono-or di-substituted alkyl or alkenyl borate can be obtained; thirdly, activating C-H bond by noble metal or catalyzing C-H bond activation reaction by using guided palladium (chem. Rev.2010,110, 890.) to synthesize organic borate by taking biboronate and arene or alkane as raw materials; the fourth is a coupling reaction of the type of palace (Miyaura) carried out under transition metal catalysis using alkyl electrophiles (angel. Chem. Int. Ed.2012,51,528.) starting from alkyl halides and bisborates, the corresponding alkyl borates can be obtained.
Transition metal catalysis revolutionized the chemistry of synthesis. However, as the demand for sustainable chemical processes increases, efforts have been made to replace transition metals with earth-rich, non-toxic and harmless environmental alternatives; the main group elements provide many of these properties and are increasingly useful catalysts for synthetic transformations. In particular, reductive functionalization of unsaturated polar bonds (e.g., c=o, c=nr) with silicon and boron reagents has been extensively studied; although lithium compounds have been found to be useful as lewis acid base catalysts and stoichiometric hydride reagents, there is a lack of broader catalytic applications and lithium compounds cannot be further generalized on a large scale.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a preparation method of alkyl borate, which takes lithium amide as a catalyst, has easily obtained reactant raw materials, simple reaction process, safety and high yield.
In order to achieve the above purpose, the present invention provides the following technical solutions: a preparation method of alkyl borate is characterized in that: under the nitrogen atmosphere, adding olefin substances, pinacol borane (HBpin) and an aminolithium catalyst into a reaction vessel filled with an organic solvent, stirring and mixing, reacting at 80-120 ℃ for 20-30h after uniform mixing, and filtering and purifying after the reaction is finished to obtain the alkyl borate.
As a further improvement of the invention, the lithium amide catalyst is lithium bis (trimethylsilyl) amide (LiN (TMS) 2 )。
As a further improvement of the invention, the structural formula of the olefin substance isWherein R1 is any one of phenyl, alkyl, 4-chlorophenyl, 4-methylphenyl, 2-naphthyl, 2,4, 6-trimethylphenyl, 2, 4-dimethylphenyl and 2-chlorophenyl.
As a further improvement of the invention, the molar ratio of the olefin substance to the pinacol borane is 1:1.5-2.5.
As a further improvement of the invention, the molar ratio of the olefin substance to the lithium amide catalyst is 1:0.05-0.15.
As a further improvement of the present invention, the organic solvent is toluene.
The reaction formula of the invention is as follows:
the reaction mechanism of the invention is that
Firstly, reacting pinacol borane with lithium silamide to obtain a lithium hydride intermediate A, inserting carbon-carbon double bonds into the lithium hydride intermediate A to obtain an alkyl lithium intermediate B, and reacting the alkyl lithium intermediate B with the pinacol borane to obtain products of alkyl boron and the lithium hydride intermediate, so as to complete catalytic cycle.
The inventor discovers that under the catalysis system of lithium silamine, the alkene hydroboration reaction is catalyzed to realize the synthesis of alkyl borate with diversified structures, and the method has high atom economy, high bond forming efficiency and mild reaction conditions; compared with the prior method, the reaction condition and the substrate universality are obviously improved, and the non-transition metal catalyst is used, which is difficult to realize by other methods; the organic boron reagent prepared by the method has high quality, high yield, good reaction universality, high economy of reaction atoms and convenient post-treatment; realizes the construction of organoboron compounds by olefin hydroboration without metal catalysis, and provides an important reference for the construction of organoboron reagents.
The invention has the beneficial effects that:
(1) The reaction universality is good, the yield is high, most of the reaction yield is over 90 percent, and the atom economy is high;
(2) The method is an important supplement to olefin hydroboration, and provides an important thought for constructing an organoboron-containing compound;
(3) The reaction conditions are mild and do not require large/cumbersome additives;
(4) The lithium silicate catalyst has simple structure, low price and no metal catalyst.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
Preparation of 4, 5-tetramethyl-2-phenethyl-1, 3, 2-dioxaborane, the structural formula is as follows:
the preparation method comprises the following steps: under the protection of nitrogen, raw material styrene (0.5 mmol), pinacol borane (1.0 mmol) and catalyst LHMDS (10 mol%) are added into a reaction vessel, stirred and mixed, and an organic solvent toluene (0.5 mL) is reacted for 24 hours at 100 ℃ after uniform mixing, so that a product is prepared, and the separation yield of the product is 99%.
1 H NMR(500MHz,CDCl 3 ):δ7.26–7.20(m,4H),7.15(m,1H),2.74(t,J＝8.0Hz,2H),1.21(s,12H),1.14(t,J＝8.0Hz,2H). 13 C NMR(125MHz,CDCl 3 ):δ144.6,128.3,128.1,125.6,83.2,30.1,24.9,13.1(br,C-B).
Example 2
Preparation of 2- (4-chlorophenyl ethyl) -4, 5-tetramethyl-1, 3,2 dioxaborane, the structural formula is as follows:
the preparation method comprises the following steps: under the protection of nitrogen, 4-chlorostyrene (0.5 mmol), pinacol borane (1.0 mmol) and catalyst LHMDS (10 mol%), toluene (0.5 mL) are added into a reaction vessel, and the reaction is carried out at 100 ℃ for 24 hours, and the product isolation yield is 96%.
1 H NMR(500MHz,CDCl 3 )δ7.21(d,J＝8Hz,2H),7.13(d,J＝8Hz,2H),2.71(t,J＝8Hz,2H),1.21(s,12H),1.11(t,J＝8Hz,2H). 13 C NMR(125Mz,CDCl 3 )δ142.9,131.3,129.5,128.3,83.3,29.4,24.9,15.4(br,C-B).
Example 3
Preparation of 4, 5-tetramethyl-2- (3-phenylpropyl) -1,3, 2-dioxaborane, the structural formula is as follows:
the preparation method comprises the following steps: under the protection of nitrogen, allylbenzene (0.5 mmol), pinacol borane (1.0 mmol) catalyst LHMDS (10 mol%), toluene (0.5 mL) and the product isolation yield 94% were added to a reaction vessel and reacted at 100℃for 24 h.
1 H NMR(500MHz,CDCl 3 ):δ7.26–7.23(m,2H),7.17-7.13(m,3H),2.60(t,J＝8.0Hz,2H),1.73(m,2H)，1.23(s,12H),0.82(t,J＝8.0Hz,2H). 13 C NMR(125MHz,CDCl 3 ):δ142.8,128.6,128.3,125.7,83.0,38.7,26.2,24.9,11.1(br,C-B).
Example 4
Preparation of 4, 5-tetramethyl-2- (4-methylphenylethyl) -1,3, 2-dioxaborane, the structural formula is as follows:
the preparation method comprises the following steps: under the protection of nitrogen, 4-methyl styrene (0.5 mmol), pinacol borane (1.0 mmol) and catalyst LHMDS (10 mol%), toluene (0.5 mL) are added into a reaction vessel, and the reaction is carried out at 100 ℃ for 24 hours, and the product isolation yield is 96%.
1 H NMR(500MHz,CDCl 3 )δ7.11-7.05(m,4H),2.70(t,J＝8.0Hz,2H),2.29(s,3H),1.22(s,12H),1.12(t,J＝8.0Hz,2H)； 13 C NMR(125MHz,CDCl 3 )δ141.5,134.9,129.0,128.0,83.2,29.6,24.9,21.1.
Example 5
Preparation of 4, 5-tetramethyl-2- (naphthyl) -1,3, 2-dioxaborane, the structural formula is as follows:
the preparation method comprises the following steps: under the protection of nitrogen, raw material 2-vinylnaphthalene (0.5 mmol), pinacol borane (1.0 mmol) and catalyst LHMDS (10 mol%), toluene (0.5 mL) are added into a reaction vessel, and the reaction is carried out at 100 ℃ for 24h, and the product isolation yield is 88%.
1 H NMR(500MHz,CDCl 3 )δ7.84-7.79(m,3H),7.70(s,1H),7.49-7.41(m,3H),2.98(t,J＝8.0Hz,2H),1.30(t,J＝8.0Hz,2H),1.26(s,12H)； 13 CNMR(125MHz,CDCl 3 )δ142.0,133.7,132.0,127.7,127.6,127.5,127.3,125.8,125.7,125.0,83.2,30.2,24.9.
Example 6
Preparation of 4, 5-tetramethyl-2- (2, 4, 6-trimethylphenethyl) -1,3, 2-dioxaborane, the structural formula is as follows:
the preparation method comprises the following steps: under the protection of nitrogen, raw material 2,4, 6-trimethylstyrene (0.5 mmol), pinacol borane (1.0 mmol) and catalyst LHMDS (10 mol%), toluene (0.5 mL) are added into a reaction vessel to react for 24h at 100 ℃, and the product separation yield is 86%.
1 H NMR(500MHz,CDCl 3 )6.86(s,2H),2.71(t,J＝8.3Hz,2H),2.34(s,6H),2.28(s,3H),1.31(s,12H),1.02(t,J＝8.3Hz,2H). 13 C NMR(125MHz,CDCl 3 )δ138.5,135.6,134.6,128.8,83.1,24.9,23.3,20.8,19.7.
Example 7
Preparation of 2- (2, 4-dimethylbenzene ethyl) -4, 5-tetramethyl-1, 3, 2-dioxaborane, the structural formula is as follows:
the preparation method comprises the following steps: the raw material 2, 4-dimethylstyrene (0.5 mmol), pinacolborane (1.0 mmol) and catalyst LHMDS (10 mol%), toluene (0.5 mL) were charged into a reaction vessel under nitrogen protection, and reacted at 100℃for 24 hours, and the product was isolated in 83%.
1 H NMR(500MHz,CDCl 3 )δ7.09(m,1H),6.95(m,2H),2.70–2.66(t,J＝8.3Hz,2H),2.29(s,6H),1.26(s,12H),1.10(t,J＝8.3Hz,2H). 13 C NMR(125MHz,CDCl 3 )δ139.5,135.6,134.9,130.8,128.0,126.5,83.1,26.8,24.9,20.9,19.2.
Example 8
Preparation of 4, 5-tetramethyl-2- (2-chlorophenyl) -1,3, 2-dioxaborane, the structural formula is as follows:
the preparation method comprises the following steps: under the protection of nitrogen, raw material 2-chlorostyrene (0.5 mmol), pinacol borane (1.0 mmol) and catalyst LHMDS (10 mol%), toluene (0.5 mL) are added into a reaction vessel, and the reaction is carried out at 100 ℃ for 24 hours, and the product isolation yield is 80%.
1 H NMR(500MHz,CDCl 3 )δ7.25–7.32(m,2H),7.08–7.18(m,2H),2.84(t,J＝8.0Hz,2H),1.24(s,12H),1.15(t,J＝8.0Hz,2H)； 13 C NMR(125MHz,CDCl 3 )δ141.9,133.9,129.8,129.4,127.1,126.7,83.2,27.9,24.9.
The method can directly synthesize the target product without separating intermediate products, and only needs stirring reaction under normal pressure to obtain the target product, wherein the highest yield can reach 99%, thus greatly simplifying process engineering, reducing energy consumption and having the advantage of high yield; in addition, the waste solution is less in the reaction process, and other polluted gases and liquid are not discharged, so that the invention reduces the discharge of the waste solution and has the advantages of protecting the environment and guaranteeing the health of operators; the toxicity of the substances used in the invention is lower, thus ensuring the health of operators; in addition, a series of alkyl borate substances can be prepared, and the method has strong substrate universality and provides better guarantee for developing the alkyl borate substances.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above examples, and all technical solutions belonging to the concept of the present invention belong to the protection scope of the present invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.
Claims (4)
1. A preparation method of alkyl borate is characterized in that: adding olefin substances, pinacol borane and a lithium amide catalyst into a reaction vessel filled with an organic solvent under the nitrogen atmosphere, stirring and mixing, reacting at 80-120 ℃ for 20-30h after uniform mixing, and filtering and purifying after the reaction is finished to obtain alkyl borate;
the lithium amide catalyst is lithium bis (trimethylsilyl) amide;
the structural formula of the olefin substance isWherein R is 1 Is any one of phenyl, alkyl, 4-chlorophenyl, 4-methylphenyl, 2-naphthyl, 2,4, 6-trimethylphenyl, 2, 4-dimethylphenyl and 2-chlorophenyl.
2. The method for producing an alkyl borate as claimed in claim 1, wherein: the molar ratio of the olefin substances to the pinacol borane is 1:1.5-2.5.
3. The method for producing an alkyl borate as claimed in claim 1, wherein: the molar ratio of the olefin substance to the lithium amide catalyst is 1:0.05-0.15.
4. The method for producing an alkyl borate as claimed in claim 1, wherein: the organic solvent is toluene.
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