CN114409691A - Preparation method of benzo-siloxaboron heterocyclic compound - Google Patents
Preparation method of benzo-siloxaboron heterocyclic compound Download PDFInfo
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- CN114409691A CN114409691A CN202210126983.8A CN202210126983A CN114409691A CN 114409691 A CN114409691 A CN 114409691A CN 202210126983 A CN202210126983 A CN 202210126983A CN 114409691 A CN114409691 A CN 114409691A
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- Prior art keywords
- benzo
- siloxaboron
- reaction
- heterocyclic compound
- compound
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- 150000002391 heterocyclic compounds Chemical class 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 125000005605 benzo group Chemical group 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- -1 heterocycle compound Chemical class 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229910015844 BCl3 Inorganic materials 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 150000001639 boron compounds Chemical class 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 150000003967 siloles Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
A process for preparing the benzo siloxaboron heterocyclic compound includes such steps as adding 2-allylphenylsilane compound and 1, 2-dichloroethane as solvent to flask, stirring while adding BCl3Stirring for reaction, and separating and purifying after the reaction to obtain the benzo siloxaboron heterocyclic compound. The invention realizes the synthesis of the benzo-siloxaboron heterocyclic compound, and the method of the invention is mainly characterized in that BCl is used3The method has the advantages of no need of metal to participate in the reaction, mild reaction conditions, simple operation, rapidness and high efficiency, great popularization and application values, contribution to industrial production and high product conversion rate which can reach more than 80 percent in some cases.
Description
Technical Field
The invention relates to preparation of a heterocyclic compound, in particular to a preparation method of a benzo-siloxaboron heterocyclic compound, and belongs to the technical field of chemistry.
Background
The organic boron compound and the organic silicon compound have important functions in organic synthesis and drug synthesis, and the organic silicon boron compound containing silicon and boron has important functions in organic synthesis and drug synthesis.
The synthesis of the organic silicon boron compound is realized by respectively constructing a C-Si bond and a C-B bond by adopting multi-step reaction. In recent years, a series of methods for constructing organosilicon boron compounds by boronization and silicidation of unsaturated C-C bonds have been developed. The methods usually need transition metal as a catalyst, are complex to operate, only realize intermolecular boronization and silicification reaction of C-C unsaturated bonds, and have no report of intramolecular reaction.
Disclosure of Invention
The invention aims to overcome the problems in the preparation of the prior organosilicon boron compound and provide a preparation method of a benzo-siloxano-boron heterocyclic compound.
In order to realize the purpose of the invention, the following technical scheme is adopted: a preparation method of a benzo siloxaboron heterocyclic compound, wherein the benzo siloxaboron heterocyclic compound has a structure shown in a formula II, and the benzo siloxaboron heterocyclic compound is prepared by the following method: adding 2-allyl phenylsilane compound shown in formula I and 1, 2-dichloroethane as solvent into a flask, adding BCl under stirring3Stirring for reaction, and separating and purifying after the reaction to obtain the benzo siloxyboron heterocyclic compound shown in the formula II, wherein the reaction formula is as follows:
in the reaction formula, R is hydrogen, or alkyl with 1-5 carbon atoms, or alkoxy with 1-2 carbon atoms, or benzyl, or halogen; [ Si ]]Is SiHMe2Or SiHEt2Or SiHPhMe or SiHPhET.
Further, the method comprises the following steps of; BCl used in the reaction3The number of ml of (b) is 1.2 times of the number of mmol of the 2-allylphenylsilane compound.
The invention has the positive and beneficial technical effects that: the invention realizes the synthesis of the benzo-siloxaboron heterocyclic compound, and the method of the invention is mainly characterized in that BCl is used3The method has the advantages of no need of metal to participate in the reaction, mild reaction conditions, simple operation, rapidness and high efficiency, great popularization and application values, contribution to industrial production and high product conversion rate which can reach more than 80 percent in some cases.
Detailed Description
In order to more fully explain the implementation of the present invention, the implementation examples of the present invention are provided, which are merely illustrative of the present invention and do not limit the scope of the present invention.
Example 1:
in a reaction flaskSubstrate 2-allylphenyl-dimethylsilane (0.2 mmol) and 1, 2-dichloroethane (2 mL) were added and BCl was added with stirring3(0.24 mL); after stirring at room temperature for 3 hours, water (2 mL) was added, the organic phase was separated, the aqueous phase was extracted with dichloromethane (5 mL), the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated to give a crude product, which was separated by column chromatography (ethyl acetate: petroleum ether volume ratio = 1: 10) to give a benzo-siloxanone heterocyclic compound as a yellow oil 35 mg with a yield of 80%. The reaction formula of this example is as follows:
example 2:
the substrates 2-allylphenyl-diethylsilane (0.2 mmol) and 1, 2-dichloroethane (2 mL) were added to a reaction flask and BCl was added with stirring3(0.24 mL); after stirring at room temperature for 3 hours, water (2 mL) was added, the organic phase was separated, the aqueous phase was extracted with dichloromethane (5 mL), the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated to give a crude product, which was separated by column chromatography (ethyl acetate: petroleum ether volume ratio = 1: 10) to give a benzo-siloxanone heterocyclic compound as a yellow oil 30 mg with a yield of 60%. The reaction formula of this example is as follows:
example 3:
the substrates 2-allyl-4-methylphenyl-dimethylsilane (0.2 mmol) and 1, 2-dichloroethane (2 mL) were added to a reaction flask, and BCl was added with stirring3(0.24 mL); after stirring at room temperature for 3 hours, water (2 mL) was added, the organic phase was separated, the aqueous phase was extracted with dichloromethane (5 mL), the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated to give a crude product, which was separated by column chromatography (ethyl acetate: petroleum ether volume ratio = 1: 10) to give a benzo-siloxanone heterocyclic compound as a yellow oil 30 mg with a yield of 64%. The reaction formula of this example is as follows:
the starting materials of formula I in the present application can be obtained by the prior art, for example, by synthesis according to the following literature procedures: ilies, L.; Tsuji, H.; Nakamura, E., Synthesis of Benzo [ b ] siloles via KH-catalyzed Cyclization of (2-allyl phenyl) silanes, org. Lett. 2009, 11 (17), 3966-.
After the embodiments of the present invention have been described in detail, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention, and it is intended that all simple modifications, equivalent changes and modifications made to the above embodiments based on the technical spirit of the present invention shall fall within the technical scope of the present invention, and the present invention shall not be limited to the embodiments illustrated in the description.
Claims (2)
1. A preparation method of a benzo siloxaboron heterocyclic compound, wherein the benzo siloxaboron heterocyclic compound has a structure shown in a formula II, and is characterized in that: the benzo siloxaboron heterocyclic compound is prepared by the following method: adding 2-allyl phenylsilane compound shown in formula I and 1, 2-dichloroethane as solvent into a flask, adding BCl under stirring3Stirring for reaction, and separating and purifying after the reaction to obtain the benzo siloxyboron heterocyclic compound shown in the formula II, wherein the reaction formula is as follows:
in the reaction formula, R is hydrogen, or alkyl with 1-5 carbon atoms, or alkoxy with 1-2 carbon atoms, or benzyl, or halogen; [ Si ]]Is SiHMe2Or SiHEt2Or SiHPhMe or SiHPhET.
2. The method of claim 1, wherein the benzo siloxaboron heterocycle compound comprises: in the reaction ofBCl for use3The number of ml of (b) is 1.2 times of the number of mmol of the 2-allylphenylsilane compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210126983.8A CN114409691A (en) | 2022-02-11 | 2022-02-11 | Preparation method of benzo-siloxaboron heterocyclic compound |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210126983.8A CN114409691A (en) | 2022-02-11 | 2022-02-11 | Preparation method of benzo-siloxaboron heterocyclic compound |
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|---|---|
| CN114409691A true CN114409691A (en) | 2022-04-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210126983.8A Pending CN114409691A (en) | 2022-02-11 | 2022-02-11 | Preparation method of benzo-siloxaboron heterocyclic compound |
Country Status (1)
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| CN (1) | CN114409691A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679460A (en) * | 2007-06-15 | 2010-03-24 | 陶氏康宁公司 | Method for the production of cyclic polysiloxanes |
| US20120165550A1 (en) * | 2010-12-28 | 2012-06-28 | Semiconductor Energy Laboratory Co., Ltd. | Organoboron Compound and Method for Manufacturing the Same |
| CN104479606A (en) * | 2014-12-24 | 2015-04-01 | 中科院广州化学有限公司 | High-temperature-resistant high-thermal-conductivity boron-dopedorganosilicon epoxy pouring sealant as well as preparation method and application thereof |
| CN105585590A (en) * | 2015-12-02 | 2016-05-18 | 杭州师范大学 | Method for preparing hybrid cyclo-boron siloxane |
| CN108822030A (en) * | 2018-07-31 | 2018-11-16 | 安阳师范学院 | A method of synthesis 1,2,3,4- Tetrahydroquinolinesas |
| CN111363158A (en) * | 2020-04-27 | 2020-07-03 | 福建师范大学 | Epoxy group-containing polysiloxane borane hyperbranched polymer and preparation method thereof |
-
2022
- 2022-02-11 CN CN202210126983.8A patent/CN114409691A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679460A (en) * | 2007-06-15 | 2010-03-24 | 陶氏康宁公司 | Method for the production of cyclic polysiloxanes |
| US20120165550A1 (en) * | 2010-12-28 | 2012-06-28 | Semiconductor Energy Laboratory Co., Ltd. | Organoboron Compound and Method for Manufacturing the Same |
| CN104479606A (en) * | 2014-12-24 | 2015-04-01 | 中科院广州化学有限公司 | High-temperature-resistant high-thermal-conductivity boron-dopedorganosilicon epoxy pouring sealant as well as preparation method and application thereof |
| CN105585590A (en) * | 2015-12-02 | 2016-05-18 | 杭州师范大学 | Method for preparing hybrid cyclo-boron siloxane |
| CN108822030A (en) * | 2018-07-31 | 2018-11-16 | 安阳师范学院 | A method of synthesis 1,2,3,4- Tetrahydroquinolinesas |
| CN111363158A (en) * | 2020-04-27 | 2020-07-03 | 福建师范大学 | Epoxy group-containing polysiloxane borane hyperbranched polymer and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| ATSUSHI KAWACHI等: "Intramolecular Reaction of Silanol and Triarylborane: Boron-Aryl Bond Cleavage and Formation of a Si-O-B Heterocyle", 《ORGANOMETALLICS》, vol. 27, no. 18, pages 4691 - 4696 * |
| KRZYSZTOF DURKA等: "Expedient Synthesis of Oxaboracyclic Compounds Based on Naphthalene and Biphenyl Backbone and Phase- Dependent Luminescence of their Chelate Complexes", 《CHEM. EUR. J.》, pages 1 - 15 * |
| 陈勇等: "基于２′，４′－二氟联苯基的新型１，２，４－三氮唑类 化合物的合成及其抗真菌活性", 《华中师范大学学报（自然科学版）》, vol. 54, no. 6, pages 982 - 989 * |
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Application publication date: 20220429 |