CN112920215A - Synthetic method of 3- (pentafluorophenyl) propyl-trimethoxy silane - Google Patents
Synthetic method of 3- (pentafluorophenyl) propyl-trimethoxy silane Download PDFInfo
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- CN112920215A CN112920215A CN201911128010.2A CN201911128010A CN112920215A CN 112920215 A CN112920215 A CN 112920215A CN 201911128010 A CN201911128010 A CN 201911128010A CN 112920215 A CN112920215 A CN 112920215A
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- pentafluorophenyl
- propyl
- pentafluorobenzene
- trimethoxysilane
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- ATBYFXZUTXZYMA-UHFFFAOYSA-N trimethoxy-[3-(2,3,4,5,6-pentafluorophenyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCC1=C(F)C(F)=C(F)C(F)=C1F ATBYFXZUTXZYMA-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000010189 synthetic method Methods 0.000 title abstract description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims abstract description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 28
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 26
- IIYGDQPZCDZFKG-UHFFFAOYSA-N 1-(3-bromopropyl)-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(CCCBr)C(F)=C1F IIYGDQPZCDZFKG-UHFFFAOYSA-N 0.000 claims abstract description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- WACNXHCZHTVBJM-UHFFFAOYSA-N 1,2,3,4,5-pentafluorobenzene Chemical compound FC1=CC(F)=C(F)C(F)=C1F WACNXHCZHTVBJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229940043279 diisopropylamine Drugs 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims abstract description 12
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 claims abstract description 11
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 229910052786 argon Inorganic materials 0.000 claims abstract description 8
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- 239000011541 reaction mixture Substances 0.000 claims abstract description 8
- 150000007530 organic bases Chemical class 0.000 claims abstract description 7
- -1 dicarbonyl acetylacetone rhodium Chemical compound 0.000 claims abstract description 5
- 238000001308 synthesis method Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 7
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical group COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 abstract description 5
- 239000002000 Electrolyte additive Substances 0.000 abstract description 4
- 238000004321 preservation Methods 0.000 abstract 3
- 238000001228 spectrum Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000004451 qualitative analysis Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 101100234822 Caenorhabditis elegans ltd-1 gene Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
A synthetic method of 3- (pentafluorophenyl) propyl-trimethoxy silane belongs to the technical field of battery electrolyte additives, takes pentafluorobenzene as a raw material for preparation, and comprises the following steps: A. under the protection of argon, adding THF and diisopropylamine into a reaction kettle, stirring and cooling to a temperature T of less than or equal to-45 ℃, dropwise adding n-butyllithium, carrying out dropwise adding, carrying out heat preservation, dropwise adding pentafluorobenzene, carrying out dropwise adding, carrying out heat preservation, dropwise adding 1, 3-dibromopropane, carrying out dropwise adding, carrying out heat preservation, washing to be neutral, carrying out liquid separation, washing, drying after liquid separation, carrying out suction filtration, and concentrating to obtain 1- (3-bromopropyl) pentafluorobenzene; B. adding 1- (3-bromopropyl) pentafluorobenzene, trimethoxy silane and N, N-dimethylformamide into a reactor under argon atmosphere, stirring, adding an organic base and tetrabutylammonium bromide, adding dicarbonyl acetylacetone rhodium (I), heating the reaction mixture to 80-90 ℃, continuously stirring, standing, cooling to room temperature, and concentrating to obtain 3- (pentafluorophenyl) propyl-trimethoxy silane. The product obtained by the synthesis method has high yield and high purity.
Description
Technical Field
The invention belongs to the technical field of battery electrolyte additives, and relates to a synthesis method of battery-grade 3- (pentafluorophenyl) propyl-trimethoxy silane used as a battery electrolyte additive. The product obtained by the synthesis method has high yield and high purity.
Background
With the continuous expansion of the application range of the lithium ion battery, the safety performance of the lithium ion battery becomes a bottleneck restricting development, the functional additive of the battery additive becomes a new technical development direction, certain performances of the battery can be pertinently changed by using less dosage, and the lithium ion battery has considerable development prospect.
At present, no synthetic method for battery-grade 3- (pentafluorophenyl) propyl-trimethoxysilane exists, and the research on the synthetic method for the battery-grade 3- (pentafluorophenyl) propyl-trimethoxysilane has important significance in development.
Disclosure of Invention
The invention aims to provide a method for synthesizing battery-grade 3- (pentafluorophenyl) propyl-trimethoxysilane, which is used for synthesizing the battery-grade 3- (pentafluorophenyl) propyl-trimethoxysilane used as a battery electrolyte additive, so that the synthesized battery-grade 3- (pentafluorophenyl) propyl-trimethoxysilane meets the requirements of battery grade.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the synthesis method of 3- (pentafluorophenyl) propyl-trimethoxy silane takes pentafluorobenzene as a raw material for preparation, and comprises the following steps:
A. under the protection of argon, adding THF and diisopropylamine into a dry reaction kettle, stirring and cooling to a temperature T of less than or equal to-45 ℃, beginning to dropwise add n-butyllithium, keeping the temperature for 1-1.5h after dropwise adding the n-butyllithium for 2-3h, then dropwise adding pentafluorobenzene, keeping the temperature for 2-2.5h, keeping the temperature for 1.5-2h, beginning to dropwise add 1, 3-dibromopropane, keeping the temperature for 1-1.5h, keeping the temperature for 50-80min, washing the system to be neutral, separating liquid, washing with saturated sodium chloride for 20-30min, drying, filtering and concentrating after liquid separation to obtain 1- (3-bromopropyl) pentafluorobenzene;
B. and D, under the argon atmosphere, adding 1- (3-bromopropyl) pentafluorobenzene, trimethoxy silane and N, N-dimethylformamide obtained in the step A into a reactor, stirring, adding an organic base and tetrabutylammonium bromide, adding dicarbonyl acetylacetone rhodium (I), heating the reaction mixture to 80-90 ℃, continuously stirring for 6-10 hours, standing, cooling to room temperature, and concentrating to obtain 3- (pentafluorophenyl) propyl-trimethoxy silane.
In the step A, the molar ratio of pentafluorobenzene, diisopropylamine, n-butyllithium to 1, 3-dibromopropane is 1: (1.05-1.1): (1.3-1.6): (1.05:1.1).
In step A, THF was added in an amount of 300 to 500ml based on 100g of diisopropylamine.
In the step A, the concentration condition is that the concentration is carried out for 1 to 1.5 hours under the vacuum degree of 0.093MPa and the temperature of 40 to 55 ℃.
In the step B, the mol ratio of 1- (3-bromopropyl) pentafluorobenzene, trimethoxy silane, organic base and tetrabutylammonium bromide is 1: (1-1.6): (1.05-1.2): (0.005-0.01).
In the step B, the organic base is triethylamine or pyridine.
In the step B, the mass ratio of the 1- (3-bromopropyl) pentafluorobenzene to the dicarbonyl acetylacetone rhodium (I) catalyst is 1: (0.03-0.05).
In the step B, the concentration condition is that the mixture is concentrated for 1 to 1.5 hours under the vacuum degree of minus 0.095MPa and the temperature of 65 to 70 ℃.
The invention has the beneficial effects that:
the yield of the final product obtained by the synthetic method of the invention is more than 70%, and the purity is more than 99%.
Drawings
FIG. 1 is a graph of the H spectrum of 3- (pentafluorophenyl) propyl-trimethoxysilane of the present invention.
FIG. 2 is a C spectrum of 3- (pentafluorophenyl) propyl-trimethoxysilane according to the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
Detailed description of the preferred embodiments
1. Reagent
| Name of reagent | Grade specification | Suppliers of goods |
| Diisopropylamine | Analytical purity | Shanghai Bang chemical industry Co., Ltd |
| N-butyl lithium | Analytical purity | Zhengzhou alpha chemical Co., Ltd |
| Pentafluorobenzene | Analytical purity | Beijing coupled technologies Ltd |
| 1, 3-dibromopropane | Analytical purity | GUANGDONG WENGJIANG CHEMICAL REAGENT Co.,Ltd. |
| Trimethoxy silane | Analytical purity | Qufuchenguang chemical Co Ltd |
| N, N-dimethylformamide | Analytical purity | Taya-Tay Co Ltd, tin-free City |
| Triethylamine | Analytical purity | Tianjin City Jing Jiang Gong Ltd |
| Pyridine compound | Analytical purity | TIANJIN DAMAO CHEMICAL REAGENT FACTORY |
| Tetrabutylammonium bromide | Analytical purity | Guangzhou Jiang shun Kouchi Co Ltd |
| Dicarbonyl acetylacetonatorhodium (I) | Analytical purity | GUANGDONG WENGJIANG CHEMICAL REAGENT Co.,Ltd. |
| Sodium bicarbonate | Analytical purity | Taya-Tay Co Ltd, tin-free City |
| Sodium chloride | Analytical purity | TIANJIN DAMAO CHEMICAL REAGENT FACTORY |
| THF | Analytical purity | Shandong Deg chemical engineering Co Ltd |
2. Instrument for measuring the position of a moving object
| Name of instrument | Suppliers of goods |
| Reactor with a reactor shell | Acciaierie e Ltd |
| Electronic balance | Shijiazhuang Botong high-tech limited |
| Separating funnel | Shijiazhuang Botong high-tech limited |
| Rotary evaporator | Shanghai' an pavilion electronic instrument factory |
| Low-temperature constant-temperature bath | Nanjing Shunhma instruments and Equipment Co., Ltd |
| Heat collection type magnetic stirrer | Zhengzhou purple Tuo instruments & Equipment Co Ltd |
| Nuclear magnetic resonance apparatus | Bruke (Beijing) science and technology Co., Ltd |
Example 1
Under the protection of argon, adding 106.3g of 504mL of THF and diisopropylamine into a dry reaction kettle, stirring and cooling to-45 ℃, beginning to dropwise add 83.3g of n-butyllithium, ending dropwise adding for 2h, preserving heat for 1h, then dropwise adding 168.1g of pentafluorobenzene, ending dropwise adding for 2h, preserving heat for 1.5h, beginning to dropwise add 212g of 1, 3-dibromopropane, ending dropwise adding for 1h, preserving heat for 1h, washing the system to be neutral by using an aqueous solution of sodium bicarbonate, separating liquid, washing for 20min by using saturated sodium chloride, drying after liquid separation, performing suction filtration, and concentrating at 50 ℃ for 1h under the vacuum degree of 0.093MPa to obtain colorless liquid, wherein 226.73g of 1- (3-bromopropyl) pentafluorobenzene is obtained.
144.4g of trimethoxysilane, 61.1g of trimethoxysilane and N, N-dimethylformamide are weighed from the 1- (3-bromopropyl) pentafluorobenzene obtained in the above manner and added into a reactor under an argon atmosphere for stirring, 53.6g of triethylamine, tetrabutylammonium bromide and 4.4g of rhodium (I) dicarbonylacetylacetonate are added as catalysts, the reaction mixture is heated to 80 ℃, continuously stirred for 10 hours, kept stand, cooled to room temperature and concentrated for 1.5 hours at a vacuum degree of-0.095 MPa and a temperature of 65 ℃ to obtain 154.09g of 3- (pentafluorophenyl) propyl-trimethoxysilane.
The product is detected, the detection purity is 99.1%, the total yield is 73.2%, the specific structure representation is carried out by using a C spectrum and an H spectrum through qualitative analysis, referring to a figure 1 and a figure 2, the obtained product is identified to be 3- (pentafluorophenyl) propyl-trimethoxy silane, and the structural formula is as follows:
example 2
Adding 107.2g of 600mL of THF and diisopropylamine into a dry reaction kettle under the protection of argon, stirring and cooling to-48 ℃, beginning to dropwise add 89.7g of n-butyllithium, ending dropwise adding for 3h, preserving heat for 1.5h, then dropwise adding 168.1g of pentafluorobenzene, ending dropwise adding for 2.5h, preserving heat for 2h, beginning to dropwise add 214g of 1, 3-dibromopropane, ending dropwise adding for 1.5h, preserving heat for 1h, washing the system to be neutral by using an aqueous solution of sodium bicarbonate, separating, washing for 30min by using saturated sodium chloride, drying and filtering after separating, concentrating at 40 ℃ under the vacuum degree of 0.093MPa, and obtaining 230.60g of 1- (3-bromopropyl) pentafluorobenzene.
Under argon atmosphere, 144.4g of the 1- (3-bromopropyl) pentafluorobenzene, 73.3g of trimethoxy silane and N, N-dimethylformamide obtained above were added to a reactor and stirred, 43.5g of pyridine and tetrabutylammonium bromide and 5.5g of rhodium dicarbonylacetoacetone (I) were added as catalysts, the reaction mixture was heated to 90 ℃ and stirred for 6 hours, allowed to stand, cooled to room temperature, and concentrated at a vacuum degree of-0.095 MPa and a temperature of 70 ℃ for 1 hour to obtain 155.41g of 3- (pentafluorophenyl) propyl-trimethoxy silane.
The product is detected, the detection purity is 99.3%, the total yield is 75.1%, and the product is identified to be 3- (pentafluorophenyl) propyl-trimethoxy silane by qualitative analysis and specific structural characterization by using a C spectrum and an H spectrum, and the structural formula is as follows:
example 3
Under the protection of argon, 680mL of THF and 108.3g of diisopropylamine are added into a dry reaction kettle, the temperature is reduced to-50 ℃ under stirring, 96.1g of n-butyllithium is added dropwise, the temperature is maintained for 70min after 2.5h of dropwise addition, 168.1g of pentafluorobenzene is added dropwise, the temperature is maintained for 110min after 140min of dropwise addition, 216g of 1, 3-dibromopropane is added dropwise, the temperature is maintained for 1h after 80min of dropwise addition, the system is washed to be neutral by using an aqueous solution of sodium bicarbonate, liquid separation is carried out, the system is washed by using saturated sodium chloride for 25min, and drying and suction filtration are carried out after liquid separation, and the concentrated solution is concentrated for 70min at the temperature of 45 ℃ under the vacuum degree of 0.093MPa, so that 229.82g of 1- (3-bromo.
Under argon atmosphere, 144.4g of 1- (3-bromopropyl) pentafluorobenzene, 85.5g of trimethoxy silane and N, N-dimethylformamide obtained above were added to a reactor and stirred, 57.6g of triethylamine and tetrabutylammonium bromide were added, 6.2g of rhodium (I) dicarbonylacetylacetonate was used as a catalyst, the reaction mixture was heated to 85 ℃ and stirred for 8 hours, allowed to stand, cooled to room temperature, and concentrated at 68 ℃ under a vacuum degree of-0.095 MPa for 75 minutes to obtain 154.92g of 3- (pentafluorophenyl) propyl-trimethoxy silane.
The product is detected, the detection purity is 99.5%, the total yield is 74.6%, and the product is identified to be 3- (pentafluorophenyl) propyl-trimethoxy silane by qualitative analysis and specific structural characterization by using a C spectrum and an H spectrum, and the structural formula is as follows:
example 4
Under the protection of argon, adding 110.2g of THF and diisopropylamine of 760mL into a dry reaction kettle, stirring and cooling to-47 ℃, beginning to dropwise add 92.9g of n-butyllithium, ending dropwise adding after 150min, preserving heat for 80min, then dropwise adding 168.1g of pentafluorobenzene, ending dropwise adding after 130min, preserving heat for 100min, beginning to dropwise add 218g of 1, 3-dibromopropane, ending dropwise adding after 80min, preserving heat for 1h, washing the system with an aqueous solution of sodium bicarbonate to be neutral, separating liquid, washing with saturated sodium chloride for 26min, drying after separating liquid, performing suction filtration, and concentrating at the temperature of 53 ℃ under the vacuum degree of 0.093MPa for 65min to obtain 227.48g of 1- (3-bromopropyl) pentafluorobenzene.
Under argon atmosphere, 144.4g of 1- (3-bromopropyl) pentafluorobenzene, 97.7g of trimethoxy silane and N, N-dimethylformamide obtained above were added to a reactor and stirred, 45.8g of pyridine and tetrabutylammonium bromide and 7.23g of rhodium dicarbonylacetylacetonate (I) were added as catalysts, the reaction mixture was heated to 87 ℃ and stirred for 9 hours, allowed to stand, cooled to room temperature, and concentrated at 66 ℃ under a vacuum degree of-0.095 MPa for 85min to obtain 150.82g of 3- (pentafluorophenyl) propyl-trimethoxy silane.
The product is detected, the detection purity is 99.2%, the total yield is 71.8%, and the product is identified to be 3- (pentafluorophenyl) propyl-trimethoxy silane by qualitative analysis and specific structural characterization by using a C spectrum and an H spectrum, and the structural formula is as follows:
example 5
Under the protection of argon, 840mL of THF and 111.3g of diisopropylamine are added into a dry reaction kettle, the temperature is reduced to-48 ℃ under stirring, 102.4g of n-butyllithium is added, 2h of dropwise addition is completed, the temperature is kept for 1.5h, 168.1g of pentafluorobenzene is added, 2h of dropwise addition is completed, the temperature is kept for 2h, 222g of 1, 3-dibromopropane is added, 1.5h of dropwise addition is completed, the temperature is kept for 1h, the system is washed to be neutral by using an aqueous solution of sodium bicarbonate, liquid separation is carried out, saturated sodium chloride is used for washing for 30min, drying and suction filtration are carried out after liquid separation, and the 1- (3-bromopropyl) pentafluorobenzene is concentrated for 1.5h at 49 ℃ under the vacuum degree of 0.093MPa, so as to obtain 228.76 g.
144.4g of the 1- (3-bromopropyl) pentafluorobenzene, 89.2g of trimethoxysilane and N, N-dimethylformamide obtained in the above were added to a reactor under an argon atmosphere and stirred, 60.7g of triethylamine and tetrabutylammonium bromide and 6.8g of rhodium (I) dicarbonylacetylacetonate were added as catalysts, and the reaction mixture was heated to 88 ℃ and continuously stirred for 7 hours, allowed to stand, cooled to room temperature and concentrated at 69 ℃ under a vacuum degree of-0.095 MPa for 1.5 hours to obtain 155.02g of 3- (pentafluorophenyl) propyl-trimethoxysilane.
The product is detected, the detection purity is 99.1%, the total yield is 74.3%, and the product is identified to be 3- (pentafluorophenyl) propyl-trimethoxy silane by qualitative analysis and specific structural characterization by using a C spectrum and an H spectrum, and the structural formula is as follows:
Claims (9)
- the synthesis method of 3- (pentafluorophenyl) propyl-trimethoxy silane takes pentafluorobenzene as a raw material for preparation, and is characterized by comprising the following steps:A. under the protection of argon, adding THF and diisopropylamine into a dry reaction kettle, stirring and cooling to a temperature T of less than or equal to-45 ℃, beginning to dropwise add n-butyllithium, keeping the temperature for 1-1.5h after dropwise adding the n-butyllithium for 2-3h, then dropwise adding pentafluorobenzene, keeping the temperature for 2-2.5h, keeping the temperature for 1.5-2h, beginning to dropwise add 1, 3-dibromopropane, keeping the temperature for 1-1.5h, keeping the temperature for 50-80min, washing the system to be neutral, separating liquid, washing with saturated sodium chloride for 20-30min, drying, filtering and concentrating after liquid separation to obtain 1- (3-bromopropyl) pentafluorobenzene;B. and D, under the argon atmosphere, adding 1- (3-bromopropyl) pentafluorobenzene, trimethoxy silane and N, N-dimethylformamide obtained in the step A into a reactor, stirring, adding an organic base and tetrabutylammonium bromide, adding dicarbonyl acetylacetone rhodium (I), heating the reaction mixture to 80-90 ℃, continuously stirring for 6-10 hours, standing, cooling to room temperature, and concentrating to obtain 3- (pentafluorophenyl) propyl-trimethoxy silane.
- 2. A method of synthesizing 3- (pentafluorophenyl) propyl-trimethoxysilane as claimed in claim 1, wherein in step a, the molar ratio of pentafluorobenzene, diisopropylamine, n-butyllithium to 1, 3-dibromopropane is 1: (1.05-1.1): (1.3-1.6): (1.05:1.1).
- 3. A process for the synthesis of 3- (pentafluorophenyl) propyl-trimethoxysilane as claimed in claim 1, wherein in step A, THF is added in an amount of 300 to 500ml, based on 100g of diisopropylamine.
- 4. A process for synthesizing 3- (pentafluorophenyl) propyl-trimethoxysilane as claimed in claim 1, wherein in step A, the concentration is carried out under a vacuum of 0.093MPa at 40-55 ℃ for 1-1.5 h.
- 5. A method of synthesizing 3- (pentafluorophenyl) propyl-trimethoxysilane as claimed in claim 1, wherein in step B, the molar ratio of 1- (3-bromopropyl) pentafluorobenzene, trimethoxysilane, organic base and tetrabutylammonium bromide is 1: (1-1.6): (1.05-1.2): (0.005-0.01).
- 6. A method of synthesizing 3- (pentafluorophenyl) propyl-trimethoxysilane as claimed in claim 1, wherein the organic base in step B is triethylamine or pyridine.
- 7. A method for synthesizing 3- (pentafluorophenyl) propyl-trimethoxysilane as claimed in claim 1, wherein in step B, the mass ratio of 1- (3-bromopropyl) pentafluorobenzene to rhodium (I) dicarbonyl acetylacetonate catalyst is 1: (0.03-0.05).
- 8. A process for synthesizing 3- (pentafluorophenyl) propyl-trimethoxysilane as claimed in claim 1, wherein in step B, the concentration is carried out under vacuum of-0.095 MPa at 65-70 ℃ for 1-1.5 h.
- 9. A method of synthesizing 3- (pentafluorophenyl) propyl-trimethoxysilane as claimed in claim 1, wherein in the step B, N-dimethylformamide is used in an amount of 10 to 15 times the mass of 1- (3-bromopropyl) pentafluorobenzene.
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