CN112920215B - Synthesis method of 3- (pentafluorophenyl) propyl-trimethoxy silane - Google Patents
Synthesis method of 3- (pentafluorophenyl) propyl-trimethoxy silane Download PDFInfo
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- CN112920215B CN112920215B CN201911128010.2A CN201911128010A CN112920215B CN 112920215 B CN112920215 B CN 112920215B CN 201911128010 A CN201911128010 A CN 201911128010A CN 112920215 B CN112920215 B CN 112920215B
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- pentafluorophenyl
- propyl
- trimethoxysilane
- temperature
- bromopropyl
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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 33
- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- 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 22
- 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
- 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 14
- 229940043279 diisopropylamine Drugs 0.000 claims abstract description 13
- 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
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims abstract description 10
- 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
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- 239000011541 reaction mixture Substances 0.000 claims abstract description 8
- 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 abstract description 7
- 150000007530 organic bases Chemical class 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- -1 1- (3-bromopropyl) pentafluorophenyl Chemical group 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound 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
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 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 description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000002000 Electrolyte additive Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 11
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000004451 qualitative analysis Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000001514 detection method Methods 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
- 239000000126 substance Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 101100234822 Caenorhabditis elegans ltd-1 gene Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 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
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000000967 suction filtration 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
- 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
The synthesis process of 3- (pentafluorophenyl) propyl-trimethoxy silane belongs to the field of battery electrolyte additive technology, and includes the following steps: A. adding THF and diisopropylamine into a reaction kettle under the protection of argon, stirring and cooling to a temperature T which is less than or equal to minus 45 ℃, dropwise adding n-butyllithium, keeping the temperature, dropwise adding pentafluorophenyl, keeping the temperature, dropwise adding 1, 3-dibromopropane, keeping the temperature, washing to be neutral, separating liquid, washing, drying, suction filtering and concentrating to obtain 1- (3-bromopropyl) pentafluorobenzene; B. under the argon atmosphere, adding 1- (3-bromopropyl) pentafluorobenzene, trimethoxysilane and N, N-dimethylformamide into a reactor, stirring, adding organic base and tetrabutylammonium bromide, adding rhodium (I) dicarbonyl acetylacetonate, heating the reaction mixture to 80-90 ℃, continuously stirring, standing, cooling to room temperature, and concentrating to obtain the 3- (pentafluorophenyl) propyl-trimethoxysilane. The product obtained by the synthesis method has higher 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 higher 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 for restricting development, the functional additive of the battery additive becomes a new technical development direction, and certain performances of the battery can be changed in a targeted manner by using a small dosage, so that the lithium ion battery has a considerable development prospect.
At present, no synthesis method for battery grade 3- (pentafluorophenyl) propyl-trimethoxy silane is studied, and the research on the synthesis method for battery grade 3- (pentafluorophenyl) propyl-trimethoxy silane is of great significance in development.
Disclosure of Invention
The invention aims to provide a method for synthesizing battery grade 3- (pentafluorophenyl) propyl-trimethoxysilane, which is used as an additive of battery electrolyte, so that the synthesized battery grade 3- (pentafluorophenyl) propyl-trimethoxysilane meets the battery grade requirement.
The technical scheme adopted by the invention for achieving the purpose is as follows:
the synthesis method of 3- (pentafluorophenyl) propyl-trimethoxy silane takes pentafluorophenyl as a raw material for preparation, and comprises the following steps:
A. adding THF and diisopropylamine into a dry reaction kettle under the protection of argon, stirring and cooling to a temperature T which is less than or equal to-45 ℃, beginning to dropwise add n-butyllithium, after 2-3 hours of dropwise addition, preserving heat for 1-1.5 hours, then dropwise adding pentafluorophenyl, after 2-2.5 hours of dropwise addition, preserving heat for 1.5-2 hours, beginning to dropwise add 1, 3-dibromopropane, after 1-1.5 hours of dropwise addition, preserving heat for 50-80 minutes, washing the system to be neutral, separating liquid, washing with saturated sodium chloride for 20-30 minutes, and drying, suction filtering and concentrating after liquid separation to obtain 1- (3-bromopropyl) pentafluorophenyl;
B. and (3) adding the 1- (3-bromopropyl) pentafluorobenzene, trimethoxysilane and N, N-dimethylformamide obtained in the step A into a reactor under the argon atmosphere, stirring, adding organic base and tetrabutylammonium bromide, adding rhodium (I) dicarbonyl acetylacetonate, heating the reaction mixture to 80-90 ℃, continuously stirring for 6-10h, standing, cooling to room temperature, and concentrating to obtain the 3- (pentafluorophenyl) propyl-trimethoxysilane.
In the step A, the molar ratio of the pentafluorobenzene, the diisopropylamine, the n-butyllithium and the 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 molar ratio of the 1- (3-bromopropyl) pentafluorobenzene, trimethoxysilane, 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 acetyl acetone rhodium (I) catalyst is 1: (0.03-0.05).
In the step B, the concentration condition is that the concentration is carried out for 1 to 1.5 hours under the vacuum degree of-0.095 MPa and the temperature of 65 to 70 ℃.
The beneficial effects of the invention are as follows:
the final product obtained by the synthesis method has the yield of more than 70 percent and the purity of more than 99 percent.
Drawings
FIG. 1 is an H spectrum of 3- (pentafluorophenyl) propyl-trimethoxysilane of the present invention.
FIG. 2 is a graph of C of 3- (pentafluorophenyl) propyl-trimethoxysilane according to the present invention.
Detailed Description
The invention will be further illustrated with reference to specific examples.
1. Detailed description of the preferred embodiments
1. Reagent(s)
| Reagent name | Grade specification | SupplyingCommercial products |
| Diisopropylamine | Analytical grade | Shanghai Pont chemical industry Co.Ltd |
| N-butyllithium | Analytical grade | Zhengzhou alpha chemical Co., ltd |
| Pentafluorobenzene | Analytical grade | Beijing coupling technologies Co Ltd |
| 1, 3-dibromopropane | Analytical grade | GUANGDONG WENGJIANG CHEMICAL REAGENT Co.,Ltd. |
| Trimethoxysilane | Analytical grade | Mono Chenfuga Limited |
| N, N-dimethylformamide | Analytical grade | Tin-free city Yatai Joint chemical Co.Ltd |
| Triethylamine | Analytical grade | Tianjin City Co.Ltd |
| Pyridine compound | Analytical grade | TIANJIN DAMAO CHEMICAL REAGENT FACTORY |
| Tetrabutylammonium bromide | Analytical grade | Guangzhou city Jiang Shunhua engineering Co., ltd |
| Rhodium dicarbonyl acetylacetonate (I) | Analytical grade | GUANGDONG WENGJIANG CHEMICAL REAGENT Co.,Ltd. |
| Sodium bicarbonate | Analytical grade | Tin-free city Yatai Joint chemical Co.Ltd |
| Sodium chloride | Analytical grade | TIANJIN DAMAO CHEMICAL REAGENT FACTORY |
| THF | Analytical grade | Shandong Deyan chemical Co., ltd |
2. Instrument for measuring and controlling the intensity of light
| Instrument name | Suppliers (suppliers) |
| Reactor for producing a catalyst | Instrument Co., ltd |
| Electronic balance | Shijia zhuang Botong high-tech Co., ltd |
| Separating funnel | Shijia zhuang Botong high-tech Co., ltd |
| Rotary evaporator | Shanghai's pavilion electronic instrument factory |
| Low temperature constant temperature bath | Nanjing Shunma Instrument Co., ltd |
| Heat collection type magnetic stirrer | Zhengzhou purple Tuo instruments and Equipment Co., ltd |
| Nuclear magnetic resonance apparatus | Bruk (Beijing) technology Co., ltd |
Example 1
Under the protection of argon, 504mL of THF and 106.3g of diisopropylamine are added into a dry reaction kettle, stirred and cooled to-45 ℃, 83.3g of n-butyllithium is added dropwise after 2 hours of dropwise addition, the temperature is kept for 1 hour, 168.1g of pentafluorophenyl is added dropwise after 2 hours of dropwise addition, the temperature is kept for 1.5 hours, 212g of 1, 3-dibromopropane is added dropwise after 1 hour of dropwise addition, the system is washed to be neutral by sodium bicarbonate aqueous solution, liquid separation is carried out, saturated sodium chloride is used for washing for 20 minutes, and after liquid separation, drying and suction filtration are carried out, and 226.73g of 1- (3-bromopropyl) pentafluorobenzene is obtained after concentration for 1 hour under the vacuum degree of 0.093MPa and the temperature of 50 ℃.
144.4g of 1- (3-bromopropyl) pentafluorobenzene obtained above, 61.1g of trimethoxysilane and N, N-dimethylformamide were weighed into a reactor under an argon atmosphere, and 53.6g of triethylamine and 4.4g of tetrabutylammonium bromide were added as catalysts, and the reaction mixture was heated to 80℃with continuous stirring for 10 hours, allowed to stand, cooled to room temperature, and concentrated at a vacuum of-0.095 MPa and a temperature of 65℃for 1.5 hours to give 154.09g of 3- (pentafluorophenyl) propyl-trimethoxysilane.
The product is detected to have the purity of 99.1 percent and the total yield of 73.2 percent, and the specific structural characterization is carried out by using a C spectrum and an H spectrum through qualitative analysis, referring to fig. 1 and 2, the obtained product is identified to be 3- (pentafluorophenyl) propyl-trimethoxysilane, and the structural formula is as follows:
example 2
600mL of THF and 107.2g of diisopropylamine are added into a dry reaction kettle under the protection of argon, stirred and cooled to-48 ℃, 89.7g of n-butyllithium is added dropwise after 3h of dropwise addition, the temperature is kept for 1.5h, 168.1g of pentafluorophenyl is added dropwise after 2.5h of dropwise addition, the temperature is kept for 2h, 214g of 1, 3-dibromopropane is added dropwise after 1.5h of dropwise addition, the temperature is kept for 1h, the system is washed to be neutral by sodium bicarbonate aqueous solution, separated liquid is washed by saturated sodium chloride for 30min, and after separated liquid, the mixture is dried and filtered by suction, and is concentrated for 1.5h at the vacuum degree of 0.093MPa and the temperature of 40 ℃ to obtain 230.60g of 1- (3-bromopropyl) pentafluorophenyl.
144.4g of the 1- (3-bromopropyl) pentafluorobenzene, 73.3g of trimethoxysilane and N, N-dimethylformamide obtained above were taken under an argon atmosphere, stirred in a reactor, 43.5g of pyridine and 5.5g of tetrabutylammonium bromide were added, rhodium (I) dicarbonyl acetylacetonate was used as a catalyst, the reaction mixture was heated to 90℃under continuous stirring for 6 hours, left to stand, cooled to room temperature, and concentrated at a vacuum of-0.095 MPa and a temperature of 70℃for 1 hour to obtain 155.41g of 3- (pentafluorophenyl) propyl-trimethoxysilane.
The product is detected, the detection purity is 99.3%, the total yield is 75.1%, the specific structural characterization is carried out by using C spectrum and H spectrum through qualitative analysis, and the obtained product is identified to be 3- (pentafluorophenyl) propyl-trimethoxysilane, 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 minus 50 ℃ by stirring, 96.1g of n-butyllithium is started to be added dropwise, the temperature is kept for 70min after 2.5h of dropwise addition, 168.1g of pentafluorophenyl is then dropwise added, 140min of dropwise addition is completed, the temperature is kept for 110min, 216g of 1, 3-dibromopropane is started to be added dropwise after 80min of dropwise addition, the temperature is kept for 1h, the system is washed to be neutral by sodium bicarbonate aqueous solution, liquid is separated, the system is washed by saturated sodium chloride for 25min, and after liquid separation, the system is dried and filtered by suction, and is concentrated for 70min at the temperature of 45 ℃ under the vacuum degree of 0.093MPa, thus obtaining 229.82g of 1- (3-bromopropyl) pentafluorophenyl.
144.4g of the 1- (3-bromopropyl) pentafluorobenzene, 85.5g of trimethoxysilane and N, N-dimethylformamide obtained above were added to a reactor under an argon atmosphere, stirred, 57.6g of triethylamine and 6.2g of tetrabutylammonium bromide were added, and the reaction mixture was heated to 85℃under continuous stirring for 8 hours, allowed to stand, cooled to room temperature and concentrated at a vacuum of-0.095 MPa and a temperature of 68℃for 75 minutes to give 154.92g of 3- (pentafluorophenyl) propyl-trimethoxysilane.
The product is detected, the detection purity is 99.5%, the total yield is 74.6%, the specific structural characterization is carried out by using C spectrum and H spectrum through qualitative analysis, and the obtained product is identified to be 3- (pentafluorophenyl) propyl-trimethoxysilane, and the structural formula is as follows:
example 4
Under the protection of argon, 760mL of THF and 110.2g of diisopropylamine are added into a dry reaction kettle, the temperature is reduced to-47 ℃ under stirring, 92.9g of n-butyllithium is started to be added dropwise, 150min is finished, the temperature is kept for 80min, 168.1g of pentafluorophenyl is then added dropwise, 130min is finished, the temperature is kept for 100min, 218g of 1, 3-dibromopropane is started to be added dropwise, 80min is finished, the temperature is kept for 1h, the system is washed to be neutral by sodium bicarbonate aqueous solution, liquid is separated, then is washed by saturated sodium chloride for 26min, and is dried and filtered after liquid separation, and is concentrated for 65min at the temperature of 53 ℃ under the vacuum degree of 0.093MPa, thus obtaining 227.48g of 1- (3-bromopropyl) pentafluorophenyl.
144.4g of the 1- (3-bromopropyl) pentafluorobenzene, 97.7g of trimethoxysilane and N, N-dimethylformamide obtained above were added to a reactor under an argon atmosphere, stirred, 45.8g of pyridine and 7.23g of tetrabutylammonium bromide were added, rhodium (I) dicarbonyl acetylacetonate was used as a catalyst, the reaction mixture was heated to 87℃and stirred continuously for 9 hours, left to stand, cooled to room temperature, and concentrated at 66℃under a vacuum of-0.095 MPa for 85min to obtain 150.82g of 3- (pentafluorophenyl) propyl-trimethoxysilane.
The product is detected, the detection purity is 99.2%, the total yield is 71.8%, the specific structural characterization is carried out by using C spectrum and H spectrum through qualitative analysis, and the obtained product is identified to be 3- (pentafluorophenyl) propyl-trimethoxysilane, 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, stirred and cooled to-48 ℃, 102.4g of n-butyllithium is added dropwise after 2 hours of dropwise addition, the temperature is kept for 1.5 hours, 168.1g of pentafluorophenyl is added dropwise after 2 hours of dropwise addition, the temperature is kept for 2 hours, 222g of 1, 3-dibromopropane is added dropwise after 1.5 hours of dropwise addition, the temperature is kept for 1 hour, the system is washed to be neutral by sodium bicarbonate aqueous solution, separated liquid is washed by saturated sodium chloride for 30 minutes, and after separated liquid, the system is dried and filtered by suction, and concentrated for 1.5 hours at the vacuum degree of 0.093MPa and the temperature of 49 ℃ to obtain 228.76g of 1- (3-bromopropyl) pentafluorophenyl.
144.4g of the 1- (3-bromopropyl) pentafluorobenzene, 89.2g of trimethoxysilane and N, N-dimethylformamide obtained above were added to a reactor under an argon atmosphere, stirred, 60.7g of triethylamine and 6.8g of tetrabutylammonium bromide were added, and the reaction mixture was heated to 88℃under continuous stirring for 7 hours, allowed to stand, cooled to room temperature and concentrated at a vacuum of-0.095 MPa and a temperature of 69℃for 1.5 hours to give 155.02g of 3- (pentafluorophenyl) propyl-trimethoxysilane.
The product is detected, the detection purity is 99.1%, the total yield is 74.3%, the specific structural characterization is carried out by using C spectrum and H spectrum through qualitative analysis, and the obtained product is identified to be 3- (pentafluorophenyl) propyl-trimethoxysilane, and the structural formula is as follows:
Claims (9)
- the synthesis method of 3- (pentafluorophenyl) propyl-trimethoxy silane takes pentafluorophenyl as a raw material for preparation, and is characterized by comprising the following steps:A. adding THF and diisopropylamine into a dry reaction kettle under the protection of argon, stirring and cooling to a temperature T which is less than or equal to-45 ℃, beginning to dropwise add n-butyllithium, after 2-3 hours of dropwise addition, preserving heat for 1-1.5 hours, then dropwise adding pentafluorophenyl, after 2-2.5 hours of dropwise addition, preserving heat for 1.5-2 hours, beginning to dropwise add 1, 3-dibromopropane, after 1-1.5 hours of dropwise addition, preserving heat for 50-80 minutes, washing the system to be neutral, separating liquid, washing with saturated sodium chloride for 20-30 minutes, and drying, suction filtering and concentrating after liquid separation to obtain 1- (3-bromopropyl) pentafluorophenyl;B. and (3) adding the 1- (3-bromopropyl) pentafluorobenzene, trimethoxysilane and N, N-dimethylformamide obtained in the step A into a reactor under the argon atmosphere, stirring, adding organic base and tetrabutylammonium bromide, adding rhodium (I) dicarbonyl acetylacetonate, heating the reaction mixture to 80-90 ℃, continuously stirring for 6-10h, standing, cooling to room temperature, and concentrating to obtain the 3- (pentafluorophenyl) propyl-trimethoxysilane.
- 2. The method for synthesizing 3- (pentafluorophenyl) propyl-trimethoxysilane according to 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. The method for synthesizing 3- (pentafluorophenyl) propyl-trimethoxysilane according to claim 1, wherein in step a, THF is added in an amount of 300-500ml based on 100g diisopropylamine.
- 4. The method for synthesizing 3- (pentafluorophenyl) propyl-trimethoxysilane according to claim 1, wherein in step a, the concentration is performed under vacuum of 0.093MPa at a temperature of 40-55 ℃ for 1-1.5h.
- 5. The method for synthesizing 3- (pentafluorophenyl) propyl-trimethoxysilane according to claim 1, wherein in step B, the molar ratio of 1- (3-bromopropyl) pentafluorobenzene, trimethoxysilane, organic base to tetrabutylammonium bromide is 1: (1-1.6): (1.05-1.2): (0.005-0.01).
- 6. The method for synthesizing 3- (pentafluorophenyl) propyl-trimethoxysilane according to claim 1, wherein in step B, the organic base is triethylamine or pyridine.
- 7. The method for synthesizing 3- (pentafluorophenyl) propyl-trimethoxysilane according to 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. The method for synthesizing 3- (pentafluorophenyl) propyl-trimethoxysilane according to claim 1, wherein in step B, the concentration is performed under vacuum of 0.095MPa at a temperature of 65-70 ℃ for 1-1.5h.
- 9. The method for synthesizing 3- (pentafluorophenyl) propyl-trimethoxysilane according to claim 1, wherein in step B, N-dimethylformamide is used in an amount of 10 to 15 times the mass of 1- (3-bromopropyl) pentafluorophenyl.
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