CN116444556A - Preparation method of organosilicon intermediate 4-benzonitrile oxyalkyl trialkoxy silane - Google Patents
Preparation method of organosilicon intermediate 4-benzonitrile oxyalkyl trialkoxy silane Download PDFInfo
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- CN116444556A CN116444556A CN202310297044.4A CN202310297044A CN116444556A CN 116444556 A CN116444556 A CN 116444556A CN 202310297044 A CN202310297044 A CN 202310297044A CN 116444556 A CN116444556 A CN 116444556A
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- benzonitrile
- oxyalkyl
- trialkoxysilane
- reaction solvent
- alkenylalkoxy
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- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Substances N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- CVNOWLNNPYYEOH-UHFFFAOYSA-N 4-cyanophenol Chemical compound OC1=CC=C(C#N)C=C1 CVNOWLNNPYYEOH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000004440 column chromatography Methods 0.000 claims abstract description 16
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 15
- 125000005819 alkenylalkoxy group Chemical group 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 10
- -1 trialkoxysilane Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000012670 alkaline solution Substances 0.000 claims abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229920001296 polysiloxane Polymers 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002346 iodo group Chemical group I* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract 1
- 125000005429 oxyalkyl group Chemical group 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 description 17
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 14
- 239000012074 organic phase Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- IUXHPSPHPKXTPA-UHFFFAOYSA-N 1-bromobut-1-ene Chemical compound CCC=CBr IUXHPSPHPKXTPA-UHFFFAOYSA-N 0.000 description 6
- NEFWHNGRRGVCEW-UHFFFAOYSA-N 4-prop-2-enoxybenzonitrile Chemical compound C=CCOC1=CC=C(C#N)C=C1 NEFWHNGRRGVCEW-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 4
- DUDKKPVINWLFBI-UHFFFAOYSA-N 1-chlorobut-1-ene Chemical compound CCC=CCl DUDKKPVINWLFBI-UHFFFAOYSA-N 0.000 description 3
- QYQQTZFOFMPYCA-UHFFFAOYSA-N 1-iodoprop-1-ene Chemical group CC=CI QYQQTZFOFMPYCA-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 3
- 238000006459 hydrosilylation reaction Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 229940124558 contraceptive agent Drugs 0.000 description 1
- 239000003433 contraceptive agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003163 gonadal steroid hormone Substances 0.000 description 1
- 230000003054 hormonal effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000000816 peptidomimetic Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- 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
-
- 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
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention relates to an organosilicon intermediate 4-benzonitrile oxyalkyl trialkoxy silane and a preparation method thereof, wherein the preparation method is as follows: s1: placing 4-hydroxy benzonitrile, an alkaline solution, a reaction solvent and haloalkylene into a wide-mouth bottle, stirring overnight at room temperature, screwing off the reaction solvent and excessive haloalkylene, then adding DCM, and purifying by EA/PE=0-5% column chromatography after treatment to obtain 4- (alkenylalkoxy) benzonitrile; s2: sequentially adding 4- (alkenylalkoxy) benzonitrile, trialkoxysilane, catalyst and reaction solvent into a single-mouth bottle, and adding the mixture into a single-mouth bottle in N 2 Stirring overnight under protection, cooling to room temperature, spin-drying with a rotary evaporator, and purifying with EA/PE=0-5% column chromatography to obtain 4-benzonitrile-group oxyalkyl trialkoxysilane as colorless oily product. The invention has low cost of raw materials, simple operation, convenient extraction and purification and higher product yield, and the obtained product is modified in metal organic complex, high molecular compound and novel organic molecular structureThe method has important application in the aspect.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a preparation method of an organosilicon intermediate 4-benzonitrile oxygen alkyl trialkoxy silane.
Background
Silicon is the second most abundant element in the crust (about 28% by mass) next to oxygen, and therefore silicon-based materials are widely used in a number of consumer and commodity chemicals including polymers (adhesives, coating agents, sealants, gels, foams, aerosols, encapsulants and preservatives), semiconductors, pesticides and biomedical formulations. Furthermore, silicon substitution of bioactive molecules, also known as "silicon switching", has become an increasingly popular application in pharmaceutical chemistry, particularly in the preparation of silicon-based peptidomimetic analogs. This trend has re-activated hydrosilylation reactions as a strategic route to a large number of key silane intermediates. While many metal catalysts have been used to achieve these reactions, the continual need for more selective, cleaner, and sustainable conversions has motivated. The transition metal catalyzed hydrosilylation of olefins has the advantages of direct and atomic economy, and is a well-known reaction for preparing organosilane. In industry, organosilicon is a prominent catalyst for hydrosilylation reactions of olefins due to its high efficiency and selectivity, either as a precursor to alcohols or as a basis for platinum-based silicon-based polymerization catalysts.
The organosilicon intermediate 4-benzonitrile oxyalkyl trialkoxy silane synthesized by the invention has the universality of organic ligands and has important application in the aspect of metal organic complexes. In addition, dow Corning corporation of the United states found that certain phenyl-containing polysiloxanes have considerable sex hormone activity, and that such drugs are very toxic and are currently being incorporated into the patent as contraceptives. With the development of organic chemistry of elements, the synthesis of compounds with special structures, stereospecific compounds, optically active compounds and compounds with complex structures with physiological activity by using organosilicon compounds will attract more and more attention from organic chemists.
Disclosure of Invention
The technical problems to be solved are as follows: the invention aims to provide a preparation method of an organosilicon intermediate 4-benzonitrile oxygen alkyl trialkoxysilane, which has the advantages of few steps, simple operation, convenient extraction and purification, higher yield of the organosilicon intermediate 4-benzonitrile oxygen alkyl trialkoxysilane, and very important application of the obtained product in the aspects of metal organic complexes, high polymer compounds and new organic molecular structure modification.
The technical scheme is as follows: an organosilicon intermediate 4-benzonitrile oxyalkyl trialkoxy silane, wherein the structural general formula I of the organosilicon intermediate is shown as follows:
wherein R is one of methyl, ethyl and propyl, and n represents an integer of 1-4.
Further, the specific preparation steps are as follows:
s1: placing 4-hydroxy benzonitrile, alkaline solution and reaction solvent into a wide-mouth bottle, cooling to-10-40 ℃, adding haloalkylene, stirring at room temperature for reaction, post-treating, and purifying by column chromatography to obtain 4- (alkenylalkoxy) benzonitrile;
s2: sequentially adding 4- (alkenylalkoxy) benzonitrile, trialkoxysilane, catalyst and reaction solvent into a single-mouth bottle, and adding the mixture into a single-mouth bottle in N 2 Stirring overnight at 80-130 ℃ under protection, cooling to room temperature, spin-drying with a rotary evaporator, and purifying by column chromatography to obtain the colorless oily product 4-benzonitrile oxyalkyl trialkoxysilane.
Further, the alkaline solution in the step S1 comprises one of sodium hydroxide, potassium hydroxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydrogen and sodium carbonate.
Further, the reaction solvent in the step S1 comprises one of DMF, acetonitrile, tetrahydrofuran and water.
Further, the haloalkylene in S1 includes one of chloro, bromo and iodo.
Further, in the S1, the molar ratio of the 4-hydroxybenzonitrile to the alkaline solution to the haloalkylene is 1 (1-2) (2-5), and the mass volume ratio of the 4-hydroxybenzonitrile to the reaction solvent is 1g (8-40 mL).
Further, the reaction solvent in the step S2 comprises one or more of toluene, xylene and 1, 4-dioxane.
Further, the catalyst in the step S2 comprises methyltriethoxysilane platinum and chloroplatinic acid.
Further, in the S2, the molar ratio of the 4- (alkenylalkoxy) benzonitrile to the trialkoxysilane to the catalyst is 1 (1-3) (0.02-0.05), and the mass volume ratio of the 4- (alkenylalkoxy) benzonitrile to the reaction solvent is 1g (8-40 mL).
The beneficial effects are that:
1. the invention provides a preparation method of organosilicon intermediate 4-benzonitrile oxyalkyl trialkoxy silane, 4-hydroxy benzonitrile and optional halogenated olefin are substituted to obtain benzonitrile oxy ether intermediate with one end being optional olefin, and then the benzonitrile oxy ether intermediate and optional trialkoxy silane are added and reacted under the action of catalyst to generate target product, the raw material 4-hydroxy benzonitrile adopted in the preparation process has low cost, and the preparation process only involves two steps of chemical reaction, so that the preparation method has the advantages of few synthesis steps and simple operation.
2. The preparation method provided by the invention is simple and convenient to extract and purify, the yield of the final organosilicon intermediate 4-benzonitrile oxyalkyl trialkoxy silane is higher, and the prepared organosilicon intermediate 4-benzonitrile oxyalkyl trialkoxy silane has very important application in the aspects of metal organic complexes, high molecular compounds and new organic molecular structure modification.
Drawings
FIG. 1 shows nuclear magnetic resonance hydrogen spectra of 4-benzonitrile oxypropyl triethoxysilane prepared in example 1 and example 4.
Detailed Description
Example 1 synthesis of organosilicon intermediate 4-benzonitrile oxypropyl triethoxysilane, the specific preparation steps are as follows:
s1: 25.00g of 4-hydroxybenzonitrile, sodium hydroxide and 200mL of tetrahydrofuran are added into a wide-mouth bottle with the capacity of 1L, 3-bromopropene is added after the temperature is reduced to minus 10 ℃, the molar ratio of the 4-hydroxybenzonitrile, the sodium hydroxide and the 3-bromopropene is 1:1:2, stirring is carried out at room temperature overnight, tetrahydrofuran and excessive 3-bromopropene are removed by screwing, DCM is then added, deionized water and saturated saline are used for extracting an organic phase, the organic phase is dried by anhydrous sodium sulfate, most of solvent is removed by a rotary evaporator, residues are stirred, and finally, EA/PE=1% column chromatography is used for purifying to obtain 26.70g of white solid 4- (allyloxy) benzonitrile with the yield of 80.1%;
s2: 10.00g of 4- (allyloxy) benzonitrile, triethoxysilane, platinum methyltriethoxysilane as a catalyst and 80mL of toluene were sequentially added to a single-necked flask, wherein the molar ratio of 4- (allyloxy) benzonitrile, triethoxysilane and platinum methyltriethoxysilane as a catalyst was 1:1:0.02, and the reaction solution was in N 2 Stirring overnight at 80 ℃ under protection, cooling the reaction liquid to room temperature, spin-drying and stirring the sample by a rotary evaporator, and finally purifying by EA/PE=1% column chromatography to obtain 20.30g of colorless oily product, wherein the yield is 91.7%, and the 4-benzonitrile oxypropyl triethoxysilane is identified by nuclear magnetic resonance hydrogen spectrum.
Example 2 synthesis of organosilicon intermediate 4-benzonitrile oxybutyl triethoxysilane, the specific preparation steps are as follows:
s1: 25.00g of 4-hydroxybenzonitrile, potassium hydroxide and 250mL of acetonitrile are added into a wide-mouth bottle with the capacity of 1L, the temperature is reduced to 10 ℃, then bromonormal butene is added, wherein the molar ratio of the 4-hydroxybenzonitrile to the bromonormal butene to the potassium hydroxide is 1:2:2, the mixture is stirred at room temperature overnight, acetonitrile and excessive bromonormal butene are removed by rotation, DCM is then added, the organic phase is extracted by deionized water and saturated saline, the organic phase is dried by anhydrous sodium sulfate, most of the solvent is removed by a rotary evaporator, the residue is stirred, and finally, the mixture is purified by EA/PE=2% column chromatography to obtain 28.70g of white solid 4- (alkene butoxy) benzonitrile with the yield of 79.0 percent;
s2: 10.00g of 4- (enebutoxy) benzonitrile, triethoxysilane, platinum catalyst methyltriethoxysilane and 100mL of xylene were sequentially added to a single-necked flask, wherein the molar ratio of 4- (enebutoxy) benzonitrile, triethoxysilane and platinum catalyst methyltriethoxysilane was 1:2:0.03, and the reaction solution was in N 2 Stirring overnight at 100deg.C under protection, cooling to room temperature, spin-drying with rotary evaporator, and purifying with EA/PE=2% column chromatography to obtain 17.00g colorless oily product with yield of 87.5%, and identifying to be 4-benzonitrile oxybutyl triethoxysilane by nuclear magnetic resonance hydrogen spectrum.
Example 3 synthesis of organosilicon intermediate 4-benzonitrile oxypropyl trimethoxysilane, the specific preparation steps are as follows:
s1: 25.00g of 4-hydroxybenzonitrile, sodium tert-butoxide and 625mL of tetrahydrofuran are added into a wide-mouth bottle with the capacity of 1L, bromobutene is added after the temperature is reduced to 20 ℃, wherein the molar ratio of 4-hydroxybenzonitrile, bromobutene and potassium hydroxide is 1:2:3, the mixture is stirred at room temperature overnight, acetonitrile and excessive bromobutene are removed by rotation, DCM is then added, the organic phase is extracted by deionized water and saturated saline, the organic phase is dried by anhydrous sodium sulfate, most of the solvent is removed by a rotary evaporator, the residue is stirred, and finally, the mixture is purified by EA/PE=3% column chromatography to obtain 27.50g of 4- (alkene-butoxy) benzonitrile as a white solid product with the yield of 82.8%;
s2: 10.00g of 4- (enebutoxy) benzonitrile, trimethoxysilane, catalyst chloroplatinic acid and 250ml of 1, 4-dioxane are added into a single-mouth bottle in sequence, wherein the mol ratio of the 4- (enebutoxy) benzonitrile, the trimethoxysilane and the catalyst chloroplatinic acid is 1:2:0.04, and the reaction solution is in N 2 Stirring overnight at 115 ℃ under protection, cooling the reaction liquid to room temperature, spin-drying and stirring the sample by a rotary evaporator, and finally purifying by EA/PE=3% column chromatography to obtain 14.44g of colorless oily product, wherein the yield is 81.7%, and the 4-benzonitrile oxypropyl trimethoxysilane is identified by nuclear magnetic resonance hydrogen spectrum.
Example 4 hasThe synthesis of the organosilicon intermediate 4-benzonitrile oxypropyl triethoxysilane comprises the following specific preparation steps:
s1: 25.00g of 4-hydroxybenzonitrile, potassium hydroxide and 750mL of acetonitrile are added into a wide-mouth bottle with the capacity of 1L, the temperature is reduced to 30 ℃, iodopropylene is added, wherein the molar ratio of the 4-hydroxybenzonitrile to the iodopropylene to the potassium hydroxide is 1:2:4, stirring is carried out at room temperature overnight, acetonitrile and excessive iodopropylene are removed by rotation, DCM is then added, an organic phase is extracted by deionized water and saturated saline solution successively, the organic phase is dried by anhydrous sodium sulfate, most of solvents are removed by a rotary evaporator, the residue is stirred, and finally, EA/PE=4% column chromatography is used for purification, so that 30.30g of white solid product 4- (allyloxy) benzonitrile is obtained, and the yield is 90.8%;
s2: 10.00g of 4- (allyloxy) benzonitrile, triethoxysilane, catalyst chloroplatinic acid and 300mL of toluene are sequentially added into a single-port bottle, wherein the mol ratio of the 4- (allyloxy) benzonitrile, the triethoxysilane and the catalyst chloroplatinic acid is 1:1:0.04, and the reaction solution is formed in N 2 Stirring overnight at 120 ℃ under protection, cooling the reaction liquid to room temperature, spin-drying and stirring the sample by a rotary evaporator, and finally purifying by EA/PE=4% column chromatography to obtain 16.80g colorless oily product, wherein the yield is 83.5%, and the 4-benzonitrile oxypropyl triethoxysilane is identified by nuclear magnetic resonance hydrogen spectrum.
Example 5
S1: 25.00g of 4-hydroxybenzonitrile, sodium hydrogen and 600mL of tetrahydrofuran are added to a wide-mouth bottle with a capacity of 1L, the temperature is reduced to 0 ℃ and then chlorobutene is added, wherein the molar ratio of 4-hydroxybenzonitrile, chlorobutene and potassium hydroxide is 1:1:5, the mixture is stirred at room temperature overnight, acetonitrile and excessive chlorobutene are removed by rotation, DCM is then added, the organic phase is extracted with deionized water and saturated saline in sequence, the organic phase is dried with anhydrous sodium sulfate and rotatedRemoving most of the solvent by an evaporator, mixing the residue, and finally purifying by EA/PE=5% column chromatography to obtain 29.20g of a white solid product 4- (alkene butoxy) benzonitrile with the yield of 87.4%; s2: 10.00g of 4- (enebutoxy) benzonitrile, trimethoxysilane, platinum methyltriethoxysilane as a catalyst and 400mL of xylene were sequentially added to a single-necked flask, wherein the molar ratio of 4- (enebutoxy) benzonitrile, trimethoxysilane and platinum methyltriethoxysilane as a catalyst was 1:3:0.05, and the reaction solution was prepared in the presence of N 2 Stirring overnight at 130 ℃ under protection, cooling the reaction liquid to room temperature, spin-drying and stirring the sample by a rotary evaporator, and finally purifying by EA/PE=5% column chromatography to obtain 17.46g colorless oily product, wherein the yield is 89.6%, and the 4-benzonitrile oxybutyl triethoxysilane is identified by nuclear magnetic resonance hydrogen spectrum.
The physical properties and spectrum data of 4-4- (3- (ethoxysilyl) propoxy) benzonitrile prepared from example 1 and example 4 are as follows: colorless oil, LC-MS-PH-ABD-043-A-0 (ES, m/z): 176[ M+H ] +
Nuclear magnetic hydrogen spectrum: H-NMR-19012-0 (400 MHz, CDCl3, ppm) δ:7.56 (d, J=6.0 Hz, 2H), 6.93 (d, J= 6.0,2H), 3.99 (t, J1=6.0 Hz, 1H), 3.83 (q, J1=10.0 Hz, J2=4.0 Hz, 6H), 1.95-1.88 (m, 2H), 1.22 (t, J1=8.0 Hz, 9H), 0.75 (t, J1=8.0 Hz, 1H).
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (9)
1. An organosilicon intermediate 4-benzonitrile oxyalkyl trialkoxy silane, which is characterized in that: the structural general formula I of the organosilicon intermediate is shown as follows:
wherein R is one of methyl, ethyl and propyl, and n represents an integer of 1-4.
2. A silicone intermediate 4-benzonitrile oxyalkyl trialkoxysilane according to claim 1, wherein: the preparation method comprises the following specific steps:
s1: placing 4-hydroxy benzonitrile, alkaline solution and reaction solvent into a wide-mouth bottle, cooling to-10-40 ℃, adding haloalkylene, stirring at room temperature for reaction, post-treating, and purifying by column chromatography to obtain 4- (alkenylalkoxy) benzonitrile;
s2: sequentially adding 4- (alkenylalkoxy) benzonitrile, trialkoxysilane, catalyst and reaction solvent into a single-mouth bottle, and adding the mixture into a single-mouth bottle in N 2 Stirring overnight at 80-130 ℃ under protection, cooling to room temperature, spin-drying with a rotary evaporator, and purifying by column chromatography to obtain the colorless oily product 4-benzonitrile oxyalkyl trialkoxysilane.
3. A silicone intermediate 4-benzonitrile oxyalkyl trialkoxysilane according to claim 2, characterized in that: the alkaline solution in the step S1 comprises one of sodium hydroxide, potassium hydroxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydrogen and sodium carbonate.
4. A silicone intermediate 4-benzonitrile oxyalkyl trialkoxysilane according to claim 2, characterized in that: the reaction solvent in S1 comprises one of DMF, acetonitrile, tetrahydrofuran and water.
5. A silicone intermediate 4-benzonitrile oxyalkyl trialkoxysilane according to claim 2, characterized in that: the haloalkylene in S1 comprises one of chloro, bromo and iodo.
6. A silicone intermediate 4-benzonitrile oxyalkyl trialkoxysilane according to claim 2, characterized in that: the molar ratio of the 4-hydroxybenzonitrile to the alkaline solution to the haloalkylene in the S1 is 1 (1-2) (2-5), and the mass volume ratio of the 4-hydroxybenzonitrile to the reaction solvent is 1g (8-40 mL).
7. A silicone intermediate 4-benzonitrile oxyalkyl trialkoxysilane according to claim 2, characterized in that: the reaction solvent in the S2 comprises one or more of toluene, xylene and 1, 4-dioxane.
8. A silicone intermediate 4-benzonitrile oxyalkyl trialkoxysilane according to claim 2, characterized in that: the catalyst in the S2 comprises methyltriethoxysilane platinum and chloroplatinic acid.
9. A silicone intermediate 4-benzonitrile oxyalkyl trialkoxysilane according to claim 2, characterized in that: the molar ratio of the 4- (alkenylalkoxy) benzonitrile to the trialkoxysilane to the catalyst in the S2 is 1 (1-3) (0.02-0.05), and the mass volume ratio of the 4- (alkenylalkoxy) benzonitrile to the reaction solvent is 1g (8-40 mL).
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