CN110003265A - A kind of preparation method of 1,4- butine two (trialkyl silyl) ester - Google Patents
A kind of preparation method of 1,4- butine two (trialkyl silyl) ester Download PDFInfo
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- CN110003265A CN110003265A CN201910290253.XA CN201910290253A CN110003265A CN 110003265 A CN110003265 A CN 110003265A CN 201910290253 A CN201910290253 A CN 201910290253A CN 110003265 A CN110003265 A CN 110003265A
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- China
- Prior art keywords
- butine
- ester
- nitrae
- isosorbide
- trialkyl silyl
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- 150000002148 esters Chemical class 0.000 title claims abstract description 59
- 125000004665 trialkylsilyl group Chemical group 0.000 title claims abstract description 38
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000012043 crude product Substances 0.000 claims abstract description 21
- 239000000706 filtrate Substances 0.000 claims abstract description 20
- 239000005046 Chlorosilane Substances 0.000 claims abstract description 14
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 11
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 6
- WZHKCFDUDKJGBA-UHFFFAOYSA-N N1CCNCC1.S1C=CC=C1 Chemical group N1CCNCC1.S1C=CC=C1 WZHKCFDUDKJGBA-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- -1 cyclic carboxylic esters Chemical class 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- JSPXPZKDILSYNN-UHFFFAOYSA-N but-1-yne-1,4-diol Chemical class OCCC#CO JSPXPZKDILSYNN-UHFFFAOYSA-N 0.000 claims description 4
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000004255 Butylated hydroxyanisole Substances 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 235000019282 butylated hydroxyanisole Nutrition 0.000 claims description 3
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 claims description 3
- 229940043253 butylated hydroxyanisole Drugs 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003233 pyrroles Chemical class 0.000 claims description 3
- DCSOPUDOZMRWRP-UHFFFAOYSA-N Cc1cc(C)cc([SiH2]Cl)c1 Chemical compound Cc1cc(C)cc([SiH2]Cl)c1 DCSOPUDOZMRWRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- YCXVDEMHEKQQCI-UHFFFAOYSA-N chloro-dimethyl-propan-2-ylsilane Chemical compound CC(C)[Si](C)(C)Cl YCXVDEMHEKQQCI-UHFFFAOYSA-N 0.000 claims description 2
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 claims description 2
- 150000004292 cyclic ethers Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical group CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims 1
- BGPCFXZWLWDDDU-UHFFFAOYSA-N chloro(propyl)silane Chemical compound CCC[SiH2]Cl BGPCFXZWLWDDDU-UHFFFAOYSA-N 0.000 claims 1
- GSXJAPJSIVGONK-UHFFFAOYSA-N chloro-ethenyl-methyl-phenylsilane Chemical compound C=C[Si](Cl)(C)C1=CC=CC=C1 GSXJAPJSIVGONK-UHFFFAOYSA-N 0.000 claims 1
- 239000004250 tert-Butylhydroquinone Chemical group 0.000 claims 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 abstract description 3
- 238000005292 vacuum distillation Methods 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000003292 diminished effect Effects 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 5
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 3
- XVSBWQYHSLNOCU-UHFFFAOYSA-N ethenyl(dimethyl)silicon Chemical compound C[Si](C)C=C XVSBWQYHSLNOCU-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000005103 alkyl silyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KQIADDMXRMTWHZ-UHFFFAOYSA-N chloro-tri(propan-2-yl)silane Chemical compound CC(C)[Si](Cl)(C(C)C)C(C)C KQIADDMXRMTWHZ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101100537779 Homo sapiens TPM2 gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 102100036471 Tropomyosin beta chain Human genes 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- UZBDLHYCYNXFRF-UHFFFAOYSA-N chloro(prop-1-enyl)silane Chemical class C(=CC)[SiH2]Cl UZBDLHYCYNXFRF-UHFFFAOYSA-N 0.000 description 1
- HXVPUKPVLPTVCQ-UHFFFAOYSA-N chloro-dimethyl-propylsilane Chemical compound CCC[Si](C)(C)Cl HXVPUKPVLPTVCQ-UHFFFAOYSA-N 0.000 description 1
- PBQIUJYTGLIUQL-UHFFFAOYSA-N chloro-ethenyl-phenylsilane Chemical compound Cl[SiH](C=C)c1ccccc1 PBQIUJYTGLIUQL-UHFFFAOYSA-N 0.000 description 1
- MVOOLFHHNLABLE-UHFFFAOYSA-N chloro-methyl-prop-1-enylsilane Chemical compound C(=CC)[SiH](Cl)C MVOOLFHHNLABLE-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- OIIWPAYIXDCDNL-UHFFFAOYSA-M sodium 3-(trimethylsilyl)propionate Chemical compound [Na+].C[Si](C)(C)CCC([O-])=O OIIWPAYIXDCDNL-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VMZOBROUFBEGAR-UHFFFAOYSA-N tris(trimethylsilyl) phosphite Chemical compound C[Si](C)(C)OP(O[Si](C)(C)C)O[Si](C)(C)C VMZOBROUFBEGAR-UHFFFAOYSA-N 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 Table
- 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
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses one kind 1, the preparation method of 4- butine two (trialkyl silyl) ester, include the following steps: that a certain proportion of 1 is added in nonaqueous solvents, 4- butynediols and acid binding agent A, and then a certain proportion of edittrialkyl chlorosilane is added thereto, reaction controlling in certain temperature and is reacted, it is separated by solid-liquid separation after complete reaction, filtrate is obtained after filtering, gained filtrate is subjected to vacuum distillation and removes solvent, after unreacted raw material and impurity, obtain 1, 4- butine two (trialkyl silyl) ester crude product, then to 1, a certain proportion of stabilizer B is added in 4- butine two (trialkyl silyl) ester crude product, and then rectification under vacuum is carried out to it, obtain 1, 4- butine two (trialkyl silyl) ester fine work.Present invention process is simple, low in cost, and reaction condition is mild, high production efficiency, and product is expected to use as lithium-ion battery electrolytes additive.
Description
Technical field
The present invention relates to chemical production technology technical field, in particular to a kind of Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester
Preparation method.
Background technique
Lithium ion battery technology is quickly grown in recent years, be widely used in portable digital equipment, electric car and
The fields such as energy storage device.However its energy density and power density are not met by the growing use demand of people.Anode
One of an important factor for material is decision existing lithium ion battery energy density improves the voltage of positive electrode and using nickel content
The nickel cobalt manganese or nickel cobalt aluminium ternary material of continuous improvement can be obviously improved the energy density of battery, but matched resistance to height
The exploitation of voltage and the electrolyte of resistance to breakdown type then falls behind relatively.
Electrolysis additive forms a film prior to solvent at electrode material interface during the initial charge of battery, can be effective
The interface stability of electrode material is improved, to reduce electrolyte decomposition, reduces battery irreversible capacity, improves battery head effect,
Improve the high and low temperature of battery, multiplying power and cycle performance.
Alkyl silicon compound (such as TMSP, TMSB, TMSPi) is a kind of important lithium-ion battery electrolytes additive,
It can be acted on the inorganic LiF ingredient in cathode SEI, reduce the content of LiF, to reduce the internal resistance of battery, improve battery
Multiplying power and cryogenic property.In patent CN101442140B, the silane compound by boiling point not less than 150 DEG C is used as addition
Agent can significantly improve the high temperature safe performance of battery；In patent CN104425841B, fluoric alkoxy silane is used as non-aqueous
Organic electrolyte high voltage additive, it is oxidized decomposition during the charging process, promotes the formation of positive electrode surface protection film,
The cycle performance and discharge capacity of lithium ion secondary battery under high voltage can be improved.In addition, introducing carbon-carbon double bond in additive
Or three unsaturated functional groups such as key, dielectric film (CEI) can be formed in positive electrode surface, to improve the stability of battery.This hair
Bright to combine alkyl silyl functional group with alkenyl or alkynyl functional group, design synthesizes two (trialkyl silica of unsaturated Isosorbide-5-Nitrae-butine
Base) it ester and is used as lithium-ion battery electrolytes additive, there is very big theoretical and actual production meaning.
Summary of the invention
The purpose of the present invention is to provide a kind of simple process and low costs, and reaction condition is mild, the system of high production efficiency
The method of standby 1,4- butine two (trialkyl silyl) ester.
In order to solve the above-mentioned technical problem, the technical solution of the present invention is as follows:
A kind of preparation method of Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester, comprising the following steps:
(1) 1,4- butynediols is mixed with acid binding agent A in nonaqueous solvents；
(2) edittrialkyl chlorosilane is added into the mixed liquor；
(3) after complete reaction, it is separated by solid-liquid separation, filtrate is obtained after filtering；
(4) filtrate is evaporated under reduced pressure, after removing solvent, unreacted raw material and impurity, obtains Isosorbide-5-Nitrae-butine two (three
Alkyl silyl) ester crude product；
(5) stabilizer B is added into gained Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester crude product, then carries out rectification under vacuum,
Obtain 1,4- butine two (trialkyl silyl) ester fine work.
(structural formula I；R1, R2 and R3 are respectively methyl, ethyl, propyl, isopropyl, 3- cyanogen propyl, phenyl, vinyl, third
Any one of alkenyl)
Scheme as a further preference, the nonaqueous solvents are selected from chain carboxylate, cyclic carboxylic esters, chain carbonic acid
One of rouge, chain ether, cyclic ether, nitrile, chloralkane or a variety of mixing.
The molar ratio of scheme as a further preference, the Isosorbide-5-Nitrae-butynediols and acid binding agent A are 1:2.2-1:3.
Scheme as a further preference, the acid binding agent A are one of triethylamine, trimethylamine, pyridine, pyrroles or more
Kind.
The molar ratio of scheme as a further preference, the Isosorbide-5-Nitrae-butynediols and edittrialkyl chlorosilane is 1:2.05-
1:2.20；The addition edittrialkyl chlorosilane and -20-50 DEG C of temperature of range when making its reaction, preferably -0-30 DEG C.
Scheme as a further preference, the edittrialkyl chlorosilane are trim,ethylchlorosilane, dimethyl ethenyl chlorine silicon
Alkane, dimethyl propylene alkenyl chlorosilane, dimethyl propyl chlorosilane, dimethylisopropyl chlorosilane, 3,5-dimethylphenyl chlorosilane, first
Any one of base phenyl vinyl chlorosilane, tri isopropyl chlorosilane and (3- cyanogen propyl) dimethylchlorosilane.
Scheme as a further preference, the stabilizer B are thiophene piperazine, 2,6-di-tert-butyl p-methylphenol, special fourth
Any one of base hydroquinone, butylated hydroxy anisole.
Scheme as a further preference, the additive amount of the stabilizer B are that Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester is thick
The 2 ‰ -2% of product.
Scheme as a further preference, time required for the fully reacting are 5h-8h；
The structural formula of described two (trialkyl silyl) ester of 1,4- butine obtained are as follows:
(R1, R2 and R3 are respectively methyl, ethyl, propyl, isopropyl, 3- cyanogen third
Any one of base, phenyl, vinyl, acrylic)
The present invention by adopting the above technical scheme, by the way that a certain proportion of Isosorbide-5-Nitrae-butynediols is added in nonaqueous solvents and ties up
Sour agent A, and then a certain proportion of edittrialkyl chlorosilane is added thereto, reaction controlling in certain temperature and is reacted, to
It is separated by solid-liquid separation after fully reacting, filtrate is obtained after filtering, gained filtrate is subjected to vacuum distillation and removes solvent, unreacted
After raw material and impurity, Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester crude product is obtained, then to Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester
A certain proportion of stabilizer B is added in crude product, and then rectification under vacuum is carried out to it, obtains Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester
Fine work.Present invention process is simple, low in cost, and reaction condition is mild, Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester yield obtained
Height, high production efficiency.
Specific embodiment
Below with reference to embodiment, specific embodiments of the present invention will be further explained.It should be noted that right
It is used to help understand the present invention in the explanation of these embodiments, but and does not constitute a limitation of the invention.In addition, being retouched below
Technical characteristic involved in each embodiment of the present invention stated can be combined with each other as long as they do not conflict with each other.
Embodiment one
A kind of preparation method of Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester, comprising the following steps: to 1000mL three-necked flask
Then middle investment 400g ethyl acetate puts into 18.69g1,4- butynediols and 48.32g triethylamine thereto, is put into stirrer,
Three-necked flask is immersed in ice-water bath and is opened magnetic stirring apparatus, is sufficiently stirred, while being passed through nitrogen thereto, flask is replaced
In air.
Reaction temperature is adjusted to 0 DEG C, 49.52g tri- is then added dropwise into above-mentioned mixed liquor using constant pressure separatory funnel
Methylchlorosilane, time for adding 1h.White precipitate triethylamine hydrochloride is constantly generated in solution during dropwise addition, with three
The increase of methylchlorosilane additional amount, white precipitate gradually increase, and react and constantly carry out.After completion of dropwise addition, after the reaction was continued 5h
Stop reaction.
It is filtered under diminished pressure to liquid is produced, removes white precipitate and obtain filtrate, then filtrate is evaporated under reduced pressure, is distillated molten
(trimethyl silicon substrate) the ester crude product of 1,4- butine two 47.62g is obtained after agent, unreacted raw material and impurity.
Thiophene piperazine 0.48g is added into Isosorbide-5-Nitrae-butine two (trimethyl silicon substrate) ester crude product, decompression essence is carried out after being sufficiently stirred
It evaporates, obtains Isosorbide-5-Nitrae-butine two (trimethyl silicon substrate) ester fine work 45.96g, purity 99.6%, yield 91.92%.
Embodiment two
A kind of preparation method of Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester, comprising the following steps: to 1000mL three-necked flask
Then middle investment 400g methylene chloride puts into 16.88g1,4- butynediols and 34.12g pyridine thereto, is put into stirrer, will
Three-necked flask is immersed in ice-water bath and opens magnetic stirring apparatus, is sufficiently stirred, while being passed through nitrogen thereto, replaces in flask
Air.
Reaction temperature is adjusted to 0 DEG C, 49.68g bis- is then added dropwise into above-mentioned mixed liquor using constant pressure separatory funnel
Methylvinyl-chlorosilanes, time for adding 1h.White precipitate pyridine hydrochloride is constantly generated in solution during dropwise addition, with
The increase of dimethyl vinyl chlorosilane additional amount, white precipitate gradually increase, react constantly carry out.After completion of dropwise addition, after
Stop reaction after continuous reaction 5h.
It is filtered under diminished pressure to liquid is produced, removes white precipitate and obtain filtrate, then filtrate is evaporated under reduced pressure, is distillated molten
(dimethyl ethenyl silicon substrate) the ester crude product of 1,4- butine two 47.25g is obtained after agent, unreacted raw material and impurity.
Thiophene piperazine 0.47g is added into Isosorbide-5-Nitrae-butine two (dimethyl ethenyl silicon substrate) ester crude product, is carried out after being sufficiently stirred
Rectification under vacuum obtains Isosorbide-5-Nitrae-butine two (dimethyl ethenyl silicon substrate) ester fine work 46.27g, purity 99.5%, yield 92.54%.
Embodiment three
A kind of preparation method of Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester, comprising the following steps: to 1000mL three-necked flask
Then middle investment 400g dimethyl carbonate puts into 15.24g1,4- butynediols and 26.13g pyrroles thereto, is put into stirrer,
Three-necked flask is immersed in ice-water bath and is opened magnetic stirring apparatus, is sufficiently stirred, while being passed through nitrogen thereto, flask is replaced
In air.
Reaction temperature is adjusted to 0 DEG C, 50.07g bis- is then added dropwise into above-mentioned mixed liquor using constant pressure separatory funnel
Methylpropenyl chlorosilane, time for adding 1h.White precipitate pyridine hydrochloride is constantly generated in solution during dropwise addition, with
The increase of dimethyl propylene alkenyl chlorosilane additional amount, white precipitate gradually increase, react constantly carry out.After completion of dropwise addition, after
Stop reaction after continuous reaction 5h.
It is filtered under diminished pressure to liquid is produced, removes white precipitate and obtain filtrate, then filtrate is evaporated under reduced pressure, is distillated molten
1,4- butine two (dimethyl propylene alkenyl silicon substrate) ester crude product 46.43g is obtained after agent, unreacted raw material and impurity.
Thiophene piperazine 0.46g is added into Isosorbide-5-Nitrae-butine two (dimethyl propylene alkenyl silicon substrate) ester crude product, is carried out after being sufficiently stirred
Rectification under vacuum obtains Isosorbide-5-Nitrae-butine two (dimethyl propylene alkenyl silicon substrate) ester fine work 45.22g, purity 99.5%, yield 90.44%.
Example IV
A kind of preparation method of Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester, comprising the following steps: to 1000mL three-necked flask
Then middle investment 300g acetonitrile puts into 12.79g1,4- butynediols and 19.32g trimethylamine thereto, stirrer is put into, by three
Mouth flask is immersed in ice-water bath and opens magnetic stirring apparatus, is sufficiently stirred, while being passed through nitrogen thereto, replaces in flask
Air.
Reaction temperature is adjusted to 0 DEG C, 50.46g (3- is then added dropwise into above-mentioned mixed liquor using constant pressure separatory funnel
Cyanogen propyl) dimethylchlorosilane, time for adding 1h.White precipitate pyridine hydrochloric acid is constantly generated in solution during dropwise addition
Salt, with the increase of (3- cyanogen propyl) dimethylchlorosilane additional amount, white precipitate gradually increases, and reacts and constantly carries out.It is added dropwise
After, stop reaction after the reaction was continued 5h.
It is filtered under diminished pressure to liquid is produced, removes white precipitate and obtain filtrate, then filtrate is evaporated under reduced pressure, is distillated molten
1,4- butine two ((3- cyanogen propyl) dimethyl silicon substrate) ester crude product 47.19g is obtained after agent, unreacted raw material and impurity.
Thiophene piperazine 0.47g is added into Isosorbide-5-Nitrae-butine two ((3- cyanogen propyl) dimethyl silicon substrate) ester crude product, after being sufficiently stirred
Rectification under vacuum is carried out, Isosorbide-5-Nitrae-butine two ((3- cyanogen propyl) dimethyl silicon substrate) ester fine work 45.57g, purity 99.6%, yield are obtained
91.14%.
Embodiment five
A kind of preparation method of Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester, comprising the following steps: to 1000mL three-necked flask
Then middle investment 400g ethyl acetate puts into 18.69g1,4- butynediols and 48.32g triethylamine thereto, is put into stirrer,
Three-necked flask is immersed in ice-water bath and is opened magnetic stirring apparatus, is sufficiently stirred, while being passed through nitrogen thereto, flask is replaced
In air.
Reaction temperature is adjusted to 50 DEG C, 49.52g tri- is then added dropwise into above-mentioned mixed liquor using constant pressure separatory funnel
Methylchlorosilane, time for adding 1h.White precipitate triethylamine hydrochloride is constantly generated in solution during dropwise addition, with three
The increase of methylchlorosilane additional amount, white precipitate gradually increase, and react and constantly carry out.After completion of dropwise addition, after the reaction was continued 4h
Stop reaction.
It is filtered under diminished pressure to liquid is produced, removes white precipitate and obtain filtrate, then filtrate is evaporated under reduced pressure, is distillated molten
(trimethyl silicon substrate) the ester crude product of 1,4- butine two 40.55g is obtained after agent, unreacted raw material and impurity.
2,6-di-tert-butyl p-methylphenol 0.41g is added into Isosorbide-5-Nitrae-butine two (trimethyl silicon substrate) ester crude product, sufficiently
Rectification under vacuum is carried out after stirring, obtains Isosorbide-5-Nitrae-butine two (trimethyl silicon substrate) ester fine work 38.70g, purity 99.0%, yield
77.4%.
Embodiment six
A kind of preparation method of Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester, comprising the following steps: to 1000mL three-necked flask
Then middle investment 400g ethyl acetate puts into 18.69g1,4- butynediols and 48.32g triethylamine thereto, is put into stirrer,
Three-necked flask is immersed in ice-water bath and is opened magnetic stirring apparatus, is sufficiently stirred, while being passed through nitrogen thereto, flask is replaced
In air.
Reaction temperature is adjusted to -10 DEG C, 49.52g is then added dropwise into above-mentioned mixed liquor using constant pressure separatory funnel
Trim,ethylchlorosilane, time for adding 1h.White precipitate triethylamine hydrochloride is constantly generated in solution during dropwise addition, with
The increase of trim,ethylchlorosilane additional amount, white precipitate gradually increase, and react and constantly carry out.After completion of dropwise addition, the reaction was continued 7h
Stop reaction afterwards.
It is filtered under diminished pressure to liquid is produced, removes white precipitate and obtain filtrate, then filtrate is evaporated under reduced pressure, is distillated molten
(trimethyl silicon substrate) the ester crude product of 1,4- butine two 45.13g is obtained after agent, unreacted raw material and impurity.
Butylated hydroxy anisole 0.45g is added into Isosorbide-5-Nitrae-butine two (trimethyl silicon substrate) ester crude product, is sufficiently stirred laggard
Row rectification under vacuum obtains Isosorbide-5-Nitrae-butine two (trimethyl silicon substrate) ester fine work 43.66g, purity 99.3%, yield 87.32%.
The structural formula of 1,4- butine two (trialkyl silyl) ester made from above embodiments is equal are as follows:
(R1, R2 and R3 are respectively methyl, ethyl, propyl, isopropyl, 3- cyanogen third
Any one of base, phenyl, vinyl, acrylic).
By all of above embodiment it is found that the reaction of two (trialkyl silyl) ester of Isosorbide-5-Nitrae-butine prepared by the present invention is by non-
A certain proportion of Isosorbide-5-Nitrae-butynediols and acid binding agent A are added in aqueous solvent, acid binding agent A is capable of the chlorination of rapid capture reaction generation
Hydrogen generates lewis acid alkali adduct, and then effectively inhibits chloride ion and Isosorbide-5-Nitrae-butynediols halogenating reaction, and improves main anti-
The reaction rate answered, reaction condition is mild, and the raw material of synthesis is simple and easy to get, low in cost, and the high income of obtained product.
The embodiments of the present invention are described in detail in conjunction with the embodiments above, but the present invention is not limited to described realities
Apply mode.For a person skilled in the art, in the case where not departing from the principle of the invention and spirit, to these embodiment party
Formula carries out a variety of change, modification, replacement and modification, still falls in protection scope of the present invention.
Claims (9)
1. a kind of preparation method of Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester, it is characterised in that: the following steps are included:
(1) 1,4- butynediols is mixed with acid binding agent A in nonaqueous solvents；
(2) edittrialkyl chlorosilane is added into the mixed liquor；
(3) after complete reaction, it is separated by solid-liquid separation, filtrate is obtained after filtering；
(4) filtrate is evaporated under reduced pressure, after removing solvent, unreacted raw material and impurity, obtains two (trialkyl of Isosorbide-5-Nitrae-butine
Silicon substrate) ester crude product；
(5) stabilizer B is added into gained Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester crude product, then carries out rectification under vacuum, obtains
1,4- butine two (trialkyl silyl) ester fine work.
2. the method according to claim 1 for preparing Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester, it is characterised in that: described
Nonaqueous solvents is in chain carboxylate, cyclic carboxylic esters, chain carbonic ether, chain ether, cyclic ether, nitrile, chloralkane
One or more mixing.
3. the preparation method of Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester according to claim 1, it is characterised in that: described
The molar ratio of 1,4- butynediols and acid binding agent A are 1:2.2-1:3.
4. according to the preparation method of Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester described in claims 1,3 and 4, feature exists
In: the acid binding agent A be one of triethylamine, trimethylamine, pyridine, pyrroles or a variety of.
5. the method according to claim 1 for preparing Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester, it is characterised in that: described
The molar ratio of 1,4- butynediols and edittrialkyl chlorosilane is 1:2.05-1:2.20；The addition edittrialkyl chlorosilane simultaneously makes it
Temperature when reaction is 0-30 DEG C.
6. according to the preparation method of Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester described in claims 1,4,6 and 7, feature exists
In: the edittrialkyl chlorosilane is trim,ethylchlorosilane, dimethyl vinyl chlorosilane, dimethyl propylene alkenyl chlorosilane, diformazan
Base propyl chlorosilane, dimethylisopropyl chlorosilane, 3,5-dimethylphenyl chlorosilane, methyl phenyl vinyl chlorosilane, three isopropyls
Any one of base chlorosilane and (3- cyanogen propyl) dimethylchlorosilane.
7. the preparation method of Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester according to claim 1, it is characterised in that: described
Stabilizer B is thiophene piperazine, 2,6- di-tert-butyl methyl phenol, tert-butylhydroquinone, any in butylated hydroxy anisole
Kind.
8. the preparation method of Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester according to claim 1, it is characterised in that: described
The additive amount of stabilizer B is the 2 ‰ -2% of 1,4- butine two (trialkyl silyl) ester crude product.
9. the preparation method of Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester according to claim 1, it is characterised in that: described
Time required for fully reacting is 5h-8h, the structural formula of described Isosorbide-5-Nitrae-butine two (trialkyl silyl) ester obtained are as follows:(R1, R2 and R3 are respectively methyl, ethyl, propyl, isopropyl, 3- cyanogen propyl, phenyl, second
Any one of alkenyl, acrylic).
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