CN113563372A - Synthesis method of alkenyl borate - Google Patents
Synthesis method of alkenyl borate Download PDFInfo
- Publication number
- CN113563372A CN113563372A CN202111012403.4A CN202111012403A CN113563372A CN 113563372 A CN113563372 A CN 113563372A CN 202111012403 A CN202111012403 A CN 202111012403A CN 113563372 A CN113563372 A CN 113563372A
- Authority
- CN
- China
- Prior art keywords
- phenylacetylene
- alkyne
- catalyst
- synthesizing
- alkenyl borate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 alkenyl borate Chemical compound 0.000 title claims abstract description 31
- 238000001308 synthesis method Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000000034 method Methods 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 18
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 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 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 10
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims abstract description 9
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims abstract description 8
- KSZVOXHGCKKOLL-UHFFFAOYSA-N 4-Ethynyltoluene Chemical group CC1=CC=C(C#C)C=C1 KSZVOXHGCKKOLL-UHFFFAOYSA-N 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 34
- ZNTJVJSUNSUMPP-UHFFFAOYSA-N 1-ethyl-4-ethynylbenzene Chemical group CCC1=CC=C(C#C)C=C1 ZNTJVJSUNSUMPP-UHFFFAOYSA-N 0.000 claims description 3
- KBIAVTUACPKPFJ-UHFFFAOYSA-N 1-ethynyl-4-methoxybenzene Chemical group COC1=CC=C(C#C)C=C1 KBIAVTUACPKPFJ-UHFFFAOYSA-N 0.000 claims description 3
- BPBNKCIVWFCMJY-UHFFFAOYSA-N 1-ethynyl-4-phenylbenzene Chemical group C1=CC(C#C)=CC=C1C1=CC=CC=C1 BPBNKCIVWFCMJY-UHFFFAOYSA-N 0.000 claims description 3
- DKFHWNGVMWFBJE-UHFFFAOYSA-N 1-ethynylcyclohexene Chemical group C#CC1=CCCCC1 DKFHWNGVMWFBJE-UHFFFAOYSA-N 0.000 claims description 3
- ZSYQVVKVKBVHIL-UHFFFAOYSA-N 1-tert-butyl-4-ethynylbenzene Chemical group CC(C)(C)C1=CC=C(C#C)C=C1 ZSYQVVKVKBVHIL-UHFFFAOYSA-N 0.000 claims description 3
- PPWNCLVNXGCGAF-UHFFFAOYSA-N 3,3-dimethylbut-1-yne Chemical group CC(C)(C)C#C PPWNCLVNXGCGAF-UHFFFAOYSA-N 0.000 claims description 3
- CRFJRGSTIQFTQW-UHFFFAOYSA-N acetylene fluorobenzene Chemical group C#C.FC1=CC=CC=C1 CRFJRGSTIQFTQW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 22
- 239000002994 raw material Substances 0.000 abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000036541 health Effects 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000013067 intermediate product Substances 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 40
- 238000002360 preparation method Methods 0.000 description 21
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 238000002955 isolation Methods 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 238000006197 hydroboration reaction Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 229910000103 lithium hydride Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- IPLBOIYJNOXPAD-WXUKJITCSA-N 4,4,5,5-tetramethyl-2-[(e)-2-[4-[(e)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethenyl]phenyl]ethenyl]-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1\C=C\C(C=C1)=CC=C1\C=C\B1OC(C)(C)C(C)(C)O1 IPLBOIYJNOXPAD-WXUKJITCSA-N 0.000 description 1
- AXWMVUQAGIGMNZ-UHFFFAOYSA-N N[Li].[Si] Chemical compound N[Li].[Si] AXWMVUQAGIGMNZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- C07F5/025—Boronic and borinic acid compounds
Abstract
The invention discloses a method for synthesizing alkenyl borate, which comprises the steps of adding alkyne substances, pinacol borane and lithium amide catalysts into a reaction vessel filled with an organic solvent under the atmosphere of nitrogen, stirring and mixing, reacting at the temperature of 70-110 ℃ after uniform mixing for 18-28h, and filtering and purifying after the reaction is finished to obtain a product; the lithium amide catalyst is lithium bis (trimethylsilyl) amide; the alkyne substance is any one of phenylacetylene, 4-methyl phenylacetylene and the like; the invention has mild reaction conditions, is easy to achieve and is safe; the method can directly synthesize the target product without separating intermediate products, and the yield can reach 98 percent to the maximum; the catalyst is easy to prepare, and reactant raw materials are easy to obtain; the method has the advantages of reducing the discharge of waste solution, protecting the environment and ensuring the health of operators.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a method for synthesizing alkenyl borate.
Background
Organoboron chemistry has been developed to date and is an extremely important part of the chemical field. The discovery of Suzuki coupling reaction (Suzuki coupling reaction) enables the organic borate compound to be effectively applied to the construction of carbon-carbon bonds, and the compound can be widely applied to the fields of organic synthesis and material chemistry and pharmaceutical chemistry. Therefore, it is very important to synthesize the organoboronate starting material efficiently and conveniently.
In recent years, the synthesis of organic carbon compounds is an important task because carbon-boron bonds are easily converted into various carbon-carbon and carbon-heteroatom bonds; in particular, transition metal catalysis has become an important synthetic strategy for the boronation of alkynes to alkenyl boronates. In the existing technology for preparing alkenyl borate, transition metals such as Rh, Ru, Ir, Fe and the like are always relied on, and the reports of cheap and easily obtained alkali metal catalysis polysubstituted alkyne hydroboration are few. The literature (org. chem. front.,2019,6, 2949-2953) reports that an n-butyllithium promotes borohydrido, but the reaction conditions are severe and the functional group tolerance is poor. The literature (Angew. chem. int. Ed.2016,55, 15356-15359) reports aluminium-catalyzed borohydrido of alkynes, but the yields are generally low and the catalyst preparation is cumbersome and has certain limitations, which also limit the alkenyl boronate formation
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the method for synthesizing the alkenyl borate, the method takes the lithium amide as the catalyst, the catalyst is easy to prepare, the reactant raw materials are easy to obtain, the reaction process is simple and safe, and the yield is high.
In order to achieve the purpose, the invention provides the following technical scheme: a method for synthesizing alkenyl borate comprises the steps of adding alkyne substances, pinacol borane (HBpin) and lithium amide catalyst into a reaction vessel filled with an organic solvent under the nitrogen atmosphere, stirring and mixing, reacting at the temperature of 70-110 ℃ for 18-28h after uniform mixing, and filtering and purifying after the reaction is finished to obtain the alkenyl borate.
As a further improvement of the invention, the lithium amide catalyst is lithium bis (trimethylsilyl) amide (LiN (TMS)2) LHMDS for short.
As a further improvement of the invention, the alkyne substance is any one of phenylacetylene, 4-methyl phenylacetylene, 4-ethyl phenylacetylene, 4-tert-butyl phenylacetylene, 4-phenyl phenylacetylene, 4-fluorobenzene acetylene, 1, 4-phenylacetylene, 4-methoxy phenylacetylene, tert-butyl acetylene and cyclohexenyl acetylene.
As a further improvement of the invention, the ratio of the added molar parts of the alkyne substance and the pinacolborane is 1: 1.1-1.5.
As a further improvement of the invention, the molar ratio of the added alkyne substance to the lithium amide catalyst is 1: 0.04-0.10.
As a further improvement of the invention, the organic solvent is toluene.
The reaction formula of the invention is as follows:
mechanism of reaction of the present invention
Firstly, pinacol borane reacts with silicon amido lithium to obtain a lithium hydride intermediate, a lithium hydride intermediate A is inserted into a carbon-carbon triple bond to obtain an alkenyl lithium intermediate B, and the alkenyl lithium intermediate B reacts with pinacol borane to obtain products of alkenyl boron and the lithium hydride intermediate to complete catalytic cycle.
Through intensive research, the inventor discovers that the synthesis of alkenyl borate with diversified structures is realized by catalyzing alkyne hydroboration reaction under a silicon amido lithium catalytic system, and the method has the advantages of high atom economy, high bonding efficiency and mild reaction conditions. Compared with the prior method, the method has the advantages that the reaction conditions and the substrate universality are obviously improved, which is difficult to realize by other methods. The organic boron reagent prepared by the method has the advantages of high quality, high yield, good reaction universality, high reaction atom economy and convenient post-treatment; the method realizes the construction of the organoboron compound by catalyzing the hydroboration of the alkyne with the alkali and provides important reference for the construction of the organoboron reagent.
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 alkyne hydroboration and provides an important idea for constructing the organic boron-containing compound;
(3) the reaction conditions are mild and no large amount of/fussy additives are needed;
(4) the silicon amino lithium catalyst has simple structure and low price, can be purchased commercially, and does not use metal catalyst in the reaction.
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
(E) Preparation of 4,4,5, 5-tetramethyl-2-styryl-1, 3, 2-dioxaborane, structural formula:
the preparation method comprises the following steps: under the protection of nitrogen, adding raw materials of phenylacetylene (0.5mmol), pinacol borane (0.6mmol), a catalyst LHMDS (7 mol%) and an organic solvent toluene (0.5mL) into a reaction vessel, stirring and mixing, reacting at 80 ℃ for 24h after uniform mixing, filtering and purifying to obtain a product; the product isolation yield was 98%.
1H NMR(500MHz,CDCl3):δ7.50–7.48(m,2H),7.40(d,J＝18.5Hz,1H),7.35–7.26(m,3H),6.17(d,J＝18.5Hz,1H),1.31(s,12H).13C NMR(125MHz,CDCl3):δ149.7,137.6,129.0,128.7,127.2,83.5,24.9.
Example 2
(E) Preparation of-4, 4,5, 5-tetramethyl-2- (4-methylstyryl) -1,3, 2-dioxaborane, structural formula:
the preparation method comprises the following steps: under the protection of nitrogen, adding raw materials of 4-methyl phenylacetylene (0.5mmol), pinacol borane (0.6mmol), a catalyst LHMDS (7 mol%) and an organic solvent of toluene (0.5mL) into a reaction vessel, stirring and mixing, reacting at 80 ℃ for 24 hours after uniform mixing, filtering and purifying to obtain a product; the product isolation yield was 89%.
1H NMR(500MHz,CDCl3)δ7.40-7.36(m,3H),7.12-7.10(m,2H),6.11(d,J＝18.5Hz,1H),2.31(s,3H),1.29(s,12H).13C NMR(125MHz,CDCl3)δ149.5,138.9,134.8,129.3,127.0,83.2,24.8,21.3.
Example 3
(E) Preparation of (E) -2- (4-ethylstyryl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane, structural formula:
the preparation method comprises the following steps: under the protection of nitrogen, adding raw materials of 4-ethyl phenylacetylene (0.5mmol), pinacol borane (0.6mmol), a catalyst LHMDS (7 mol%) and an organic solvent of toluene (0.5mL) into a reaction vessel, stirring and mixing, reacting at 80 ℃ for 24 hours after uniform mixing, filtering and purifying to obtain a product; the product isolation yield was 89%.
1H NMR(500MHz,CDCl3)δ7.41-7.37(m,3H),7.15(d,J＝8.0Hz,2H),6.12(d,J＝18.5Hz,1H)2.62(q,J＝8.0Hz,2H),1.32(s,12H),1.21(t,J＝8.0Hz,3H).13C NMR(125MHz,CDCl3)δ149.6,145.3,135.1,128.1,127.2,115.4(br,C-B),83.3,28.8,24.9,15.5.
Example 4
(E) Preparation of (E) -2- (4- (tert-butyl) styryl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane, structural formula:
the preparation method comprises the following steps: under the protection of nitrogen, adding raw materials of 4-tert-butyl phenylacetylene (0.5mmol), pinacolborane (0.6mmol), a catalyst LHMDS (7 mol%) and an organic solvent of toluene (0.5mL) into a reaction vessel, stirring and mixing, reacting at 80 ℃ for 24 hours after uniform mixing, filtering and purifying to obtain a product; the product isolation yield was 88%.
1H NMR(500MHz,CDCl3)δ7.45-7.35(m,5H),6.12(d,J＝18.5Hz,1H),1.31(s,21H).13C NMR(125MHz,CDCl3)δ152.2,149.5,134.9,126.9,125.6,83.4,34.8,31.4,24.9.
Example 5
(E) Preparation of (E) -2- (2- ([1,1' -biphenyl ] -4-yl) vinyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane of the formula:
the preparation method comprises the following steps: under the protection of nitrogen, adding raw materials of 4-phenyl phenylacetylene (0.5mmol), pinacol borane (0.6mmol), a catalyst LHMDS (7 mol%) and an organic solvent toluene (0.5mL) into a reaction vessel, stirring and mixing, reacting at 80 ℃ for 24h after uniform mixing, filtering and purifying to obtain a product; the product isolation yield was 90%.
1H NMR(500MHz,CDCl3)δ7.60-7.55(m,6H),7.46-7.41(m,3H),7.35-7.32(m,1H),6.21(d,J＝18.5,1H),1.32(s,12H).13C NMR(125MHz,CDCl3)δ149.1,141.7,140.6,136.6,128.9,127.6,127.5,127.3,127.0,83.4,24.9.
Example 6
(E) Preparation of (E) -2- (4-fluorophenylvinyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane, structural formula:
the preparation method comprises the following steps: under the protection of nitrogen, adding raw materials of 4-fluoroacetylene (0.5mmol), pinacolborane (0.6mmol), a catalyst LHMDS (7 mol%) and an organic solvent of toluene (0.5mL) into a reaction vessel, stirring and mixing, reacting at 80 ℃ for 24h after uniform mixing, filtering and purifying to obtain a product; the product isolation yield was 97%.
1H NMR(500MHz,CDCl3):δ7.47–7.44(m,2H),7.35(d,J＝18.5Hz,1H),7.02(t,J＝8.0Hz,2H),6.07(d,J＝18.5Hz,1H),1.31(s,12H).13C NMR(125MHz,CDCl3):δ163.3(d,J＝248.3Hz),148.3,133.9,128.8(d,J＝8.3Hz),115.7(d,J＝21.6Hz),83.5,24.9.
Example 7
Preparation of 1, 4-bis ((E) -2- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) vinyl) benzene, structural formula:
the preparation method comprises the following steps: under the protection of nitrogen, adding raw materials of 1, 4-phenylacetylene (0.5mmol), pinacolborane (1.2mmol), a catalyst LHMDS (7 mol%) and an organic solvent of toluene (0.5mL) into a reaction vessel, stirring and mixing, reacting at 100 ℃ for 24 hours after uniform mixing, filtering and purifying to obtain a product; the product isolation yield was 78%.
1H NMR(500MHz,CDCl3)δ7.45(s,4H),7.36(d,J＝18.5Hz,2H),6.16(d,J＝18.5Hz,2H),1.31(s,24H)；13C NMR(125MHz,CDCl3)δ148.7,137.8,127.2,119.6(br,C-B),83.8,24.8.
Example 8
(E) Preparation of (E) -2- (4-methoxystyryl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane, structural formula:
the preparation method comprises the following steps: under the protection of nitrogen, adding raw materials of 4-methoxy phenylacetylene (0.5mmol), pinacol borane (0.6mmol), a catalyst LHMDS (7 mol%) and an organic solvent toluene (0.5mL) into a reaction vessel, stirring and mixing, reacting at 100 ℃ for 24h after uniform mixing, filtering and purifying to obtain a product; the product isolation yield was 98%.
1H NMR(500MHz,CDCl3)δ7.49–7.39(m,2H),7.35(d,J＝18.5Hz,1H),6.92–6.80(m,2H),6.01(d,J＝18.5Hz,1H),3.81(s,3H),1.31(s,12H).13CNMR(125MHz,CDCl3)δ160.3,149.0,130.4,128.4,113.9,83.2,55.3,24.8.
Example 9
(E) Preparation of (E) -2- (3, 3-dimethylbut-1-en-1-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane of the formula:
the preparation method comprises the following steps: under the protection of nitrogen, raw materials of tert-butyl acetylene (0.5mmol), pinacolborane (0.6mmol), a catalyst LHMDS (7 mol%) and an organic solvent of toluene (0.5mL) are added into a reaction vessel, stirred and mixed, reacted for 24 hours at 100 ℃ after uniform mixing, filtered and purified to obtain a product, and the separation yield of the product is 80%.
1H NMR(500MHz,CDCl3)δ6.64(d,J＝18.5Hz,1H),5.35(d,J＝18.5Hz,1H),1.28(s,12H),1.02(s,9H).13C NMR(125Mz,CDCl3)δ164.5,112.6(C-B),83.1,35.1,28.9,24.9.
Example 10
(E) Preparation of (E) -2- (2- (cyclohex-1-en-1-yl) vinyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane of the formula:
the preparation method comprises the following steps: under the protection of nitrogen, adding raw materials of cyclohexenyl acetylene (0.5mmol), pinacol borane (0.6mmol), a catalyst LHMDS (7 mol%) and an organic solvent toluene (0.5mL) into a reaction vessel, stirring and mixing, reacting at 100 ℃ for 24h after uniform mixing, filtering and purifying to obtain a product; the product isolation yield was 80%.
1H NMR(500MHz,CDCl3)δ7.02(d,J＝18.5Hz,1H),5.96(t,J＝3.9Hz,1H),5.42(d,J＝18.5Hz,1H),2.22–2.07(m,4H),1.76–1.47(m,4H),1.27(s,12H).13C NMR(125MHz,CDCl3)δ153.2,137.1,134.3,83.0,26.2,24.8,23.7,22.4,22.3.
The method can directly synthesize the target product, does not need to separate intermediate products, can obtain the target product only by stirring and reacting under normal pressure, has the highest yield of 98 percent, greatly simplifies process engineering, reduces energy consumption and has 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 method reduces the discharge of the waste solution, and has the advantages of protecting the environment and ensuring the health of operators; the toxicity of the substances used in the invention is low, thus ensuring the health of operators; in addition, a series of alkenyl borate substances can be prepared, the method has stronger substrate universality, and better guarantee is provided for developing the alkenyl 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 embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (6)
1. A method for synthesizing alkenyl borate is characterized in that: under the nitrogen atmosphere, adding alkyne substances, pinacol borane and lithium amide catalyst into a reaction vessel filled with an organic solvent, stirring and mixing, uniformly mixing, reacting at the temperature of 70-110 ℃ for 18-28h, and filtering and purifying after the reaction is finished to obtain the alkenyl borate.
2. The method for synthesizing an alkenyl borate according to claim 1, wherein: the lithium amide catalyst is lithium bis (trimethylsilyl) amide.
3. The method for synthesizing an alkenyl borate according to claim 1, wherein: the alkyne substance is any one of phenylacetylene, 4-methyl phenylacetylene, 4-ethyl phenylacetylene, 4-tert-butyl phenylacetylene, 4-phenyl phenylacetylene, 4-fluorobenzene acetylene, 1, 4-phenylacetylene, 4-methoxy phenylacetylene, tert-butyl acetylene and cyclohexenyl acetylene.
4. The method for synthesizing an alkenyl borate according to claim 1, wherein: the molar ratio of the alkyne substance to the pinacol borane is 1: 1.1-1.5.
5. The method for synthesizing an alkenyl borate according to claim 1, wherein: the molar ratio of the alkyne substance to the lithium amide catalyst is 1: 0.04-0.10.
6. The method for synthesizing an alkenyl borate according to claim 1, wherein: the organic solvent is toluene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111012403.4A CN113563372B (en) | 2021-08-31 | 2021-08-31 | Alkenyl borate synthesis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111012403.4A CN113563372B (en) | 2021-08-31 | 2021-08-31 | Alkenyl borate synthesis method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113563372A true CN113563372A (en) | 2021-10-29 |
| CN113563372B CN113563372B (en) | 2023-12-12 |
Family
ID=78173247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111012403.4A Active CN113563372B (en) | 2021-08-31 | 2021-08-31 | Alkenyl borate synthesis method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113563372B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113880688A (en) * | 2021-11-02 | 2022-01-04 | 温州大学新材料与产业技术研究院 | Method for synthesizing diol |
| CN115025820A (en) * | 2022-07-08 | 2022-09-09 | 安徽大学 | Efficient catalyst for alkynyl hydroboration and application thereof in alkynyl hydroboration |
| CN115043866A (en) * | 2022-05-26 | 2022-09-13 | 宁波大学 | Synthetic method and application of organic aluminum hydrogen reagent |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1617706A (en) * | 2002-01-18 | 2005-05-18 | 巴斯福股份公司 | Cosmetic or dermatological preparations for preventing damages to skin caused by peroxides |
| US20060025623A1 (en) * | 2004-07-29 | 2006-02-02 | Basf Aktiengesellschaft | Process for preparing alkylboronic esters |
| CN103408573A (en) * | 2013-07-12 | 2013-11-27 | 上海工程技术大学 | Boric acid derivatives, and preparation method and application thereof |
| CN110590823A (en) * | 2019-09-24 | 2019-12-20 | 新乡市润宇新材料科技有限公司 | Method for synthesizing borate derivatives under catalysis of non-transition metals |
| CN111217844A (en) * | 2020-03-30 | 2020-06-02 | 中国科学院兰州化学物理研究所 | Method for preparing gem-diboron compound by selectively 1, 1-diboronating olefin |
-
2021
- 2021-08-31 CN CN202111012403.4A patent/CN113563372B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1617706A (en) * | 2002-01-18 | 2005-05-18 | 巴斯福股份公司 | Cosmetic or dermatological preparations for preventing damages to skin caused by peroxides |
| US20060025623A1 (en) * | 2004-07-29 | 2006-02-02 | Basf Aktiengesellschaft | Process for preparing alkylboronic esters |
| CN103408573A (en) * | 2013-07-12 | 2013-11-27 | 上海工程技术大学 | Boric acid derivatives, and preparation method and application thereof |
| CN110590823A (en) * | 2019-09-24 | 2019-12-20 | 新乡市润宇新材料科技有限公司 | Method for synthesizing borate derivatives under catalysis of non-transition metals |
| CN111217844A (en) * | 2020-03-30 | 2020-06-02 | 中国科学院兰州化学物理研究所 | Method for preparing gem-diboron compound by selectively 1, 1-diboronating olefin |
Non-Patent Citations (1)
| Title |
|---|
| JIMENEZ-ALIGAGA, KARIM ET AL.: "Discovery of alkenylboronic acids as neuroprotective agents affecting multiple biological targets involved in Alzheimer\'s disease", 《BIOORGANIC & MEDICINAL CHEMISTRY LETTERS》, vol. 23, no. 2, pages 426 - 429 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113880688A (en) * | 2021-11-02 | 2022-01-04 | 温州大学新材料与产业技术研究院 | Method for synthesizing diol |
| CN113880688B (en) * | 2021-11-02 | 2023-09-08 | 温州大学新材料与产业技术研究院 | Synthesis method of diol |
| CN115043866A (en) * | 2022-05-26 | 2022-09-13 | 宁波大学 | Synthetic method and application of organic aluminum hydrogen reagent |
| CN115025820A (en) * | 2022-07-08 | 2022-09-09 | 安徽大学 | Efficient catalyst for alkynyl hydroboration and application thereof in alkynyl hydroboration |
| CN115025820B (en) * | 2022-07-08 | 2023-11-14 | 安徽大学 | Alkynyl borohydride catalyst and application thereof in alkynyl borohydride |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113563372B (en) | 2023-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113563372A (en) | Synthesis method of alkenyl borate | |
| Zhao et al. | A new copper-based metal–organic framework as a promising heterogeneous catalyst for chemo-and regio-selective enamination of β-ketoesters | |
| Lee et al. | Copper-catalyzed addition of diboron reagents to α, β-acetylenic esters: efficient synthesis of β-boryl-α, β-ethylenic esters | |
| Xu et al. | Palladium catalyzed selective arylation of o-carboranes via B (4)–H activation: amide induced regioselectivity reversal | |
| CN1333777A (en) | Organoboron derivatives and process for coupling organic compounds | |
| CN1275984A (en) | Process for preparing organic acid derivatives using diboronic acid | |
| Amoroso et al. | An attractive route to olefin metathesis catalysts: Facile synthesis of a ruthenium alkylidene complex containing labile phosphane donors | |
| CN111763135A (en) | Application of deprotonated phenyl bridged beta-ketimine lithium compound in preparation of alcohol from ester | |
| Ohmiya et al. | Copper-catalyzed Conjugate Additions of Alkylboranes to Aryl α, β-Unsaturated Ketones | |
| WO2012085169A1 (en) | Metallic amidoborates for functionalizing organic compounds | |
| US9284270B2 (en) | Boronic acid catalysts and methods of use thereof for activation and transformation of carboxylic acids | |
| CN113683633B (en) | Preparation method of alkyl borate | |
| CN111744551A (en) | Application of lithium complex in hydroboration reaction of nitrile | |
| CN112679299B (en) | Preparation method of diarylmethane and derivatives thereof | |
| Huo et al. | Highly Efficient Bulky α‐Diimine Palladium Complexes for Suzuki‐Miyaura Cross‐Coupling Reaction | |
| CN110878099A (en) | Preparation method of pyrrole [1,2, α ] indole alkaloid derivative | |
| Farinola et al. | A novel and efficient route to (E)-alk-1-enyl boronic acid derivatives from (E)-1-(trimethylsilyl) alk-1-enes and a formal Suzuki–Miyaura cross-coupling reaction starting with vinylsilanes | |
| CN102827192B (en) | A kind of Zn complex | |
| CN101602774B (en) | Method for preparing silylene by carbene-induced halogenated silane dehydrohalogenation | |
| CN114308121A (en) | Phosphine oxide catalyst and preparation method and application thereof | |
| CN100588656C (en) | Forcipated diimidazoline palladium compound and its application in Suzuki reaction | |
| CN105073257A (en) | Catalyst and method for producing optically active anti-1,2-nitroalkanol compound | |
| CN114085242A (en) | Synthesis method of iron-catalyzed alkyl internal alkyne compound | |
| CN101775029A (en) | Convenient synthesis method for alkyl substitution phenyloboricacid | |
| US6268537B1 (en) | Method of synthesis of lithium substituted borohydride reagents and method of synthesis of reactive lithium hydride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |