CN102206229A - Silicon-containing benzocyclobutene monomers and preparation method thereof - Google Patents
Silicon-containing benzocyclobutene monomers and preparation method thereof Download PDFInfo
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- CN102206229A CN102206229A CN2011100926035A CN201110092603A CN102206229A CN 102206229 A CN102206229 A CN 102206229A CN 2011100926035 A CN2011100926035 A CN 2011100926035A CN 201110092603 A CN201110092603 A CN 201110092603A CN 102206229 A CN102206229 A CN 102206229A
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- bromobenzene
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Abstract
The invention discloses silicon-containing benzocyclobutene monomers, such as dimethyl vinyl benzocyclobuten-1-ylsiloxane, and a preparation method thereof. The preparation method of the compound comprises: adding magnesium, anhydrous lithium chloride and lithium aluminum hydride into a reactor under water-free, anaerobic and nitrogen-protection conditions; dripping the tetrahydrofuran solution of 1-bromobenzocyclobutene with stirring, dripping the tetrahydrofuran solution of methylvinyldichlorosilane after the magnesium is reacted completely, and reacting at -20 to 40 DEG C for 3 to 24 hours; and adding water to terminate reaction, extracting with an organic solvent, drying an organic phase by using an organic salt drying agent, concentrating, and subjecting the concentrated material to reduced-pressure distillation or silica column chromatography to obtain a product. The compound contains reactive vinylsilyl and hydrosilyl reaction groups, and the high polymer material formed by reaction has high comprehensive performance and has great development potential and application prospect in fields of microelectronics, aerospace and national defense.
Description
Technical field
The invention belongs to a kind of siliceous isocyclic compound and preparation method thereof, relate to a kind of silicon-containing benzocyclobutene monomer (dimethyl vinyl benzo cyclobutene-1-base silane or dimethylbiphenyl cyclobutene-4-base hydrogen silane) and preparation method thereof.The silicon-containing benzocyclobutene monomer of preparation is applicable in the fields such as microelectronics industry, aerospace and national defence.
Background technology
Benzocyclobutene (BCB) class material is owing to have excellent high and low temperature resistance, and weather-proof, resistance to air loss is good, and anti-irradiation particularly has characteristics such as excellent film forming properties and moisture resistance performance, has been widely applied to military, civilian a plurality of fields abroad.Common organosilicon macromolecule polymkeric substance has high-low temperature resistant, weather-proof, electrical isolation, anti-irradiation, fire-retardant, resistance to air loss is good, the corrosion-resistant good characteristic that waits, be widely used in a plurality of key areas such as aerospace, but general organosilicon material film forming properties is poor, need just can prepare film forming properties macromolecular material preferably by the modification of specific function group.In the prior art, existing report (
U.S. Pat. 5882836,1999Year) with in the middle of the BCB group introducing organosilicon molecule, for example: benzocyclobutene (DVSBCB) monomer of tetramethyl divinyl siloxanes bridging, can obtain the silicone resin of excellent combination property behind this monomer-polymer, wide application prospect be arranged in the microelectronics industry field.The present application people has synthesized new benzocyclobutene monomer 4-(1 ', 1 '-dimethyl-1 '-vinyl) silica-based benzocyclobutene (4-DMVSBCB), sees the Chinese invention patent application number:
200810044584.7Its polymkeric substance (
Journal of Polymer Science, Part A:Polymer Chemistry, 2011,49,381-391) shown excellent thermostability, chemical stability and electric property, shown wide application prospect in microelectronics industry.
The addition of silicon hydrogen is the reaction of the very important class of field of organic silicon, can provide new synthesis path for further introducing new functional group in the middle of silicon hydrogen group is directly introduced the benzocyclobutene parent nucleus.According to Y.Matsuta for 1,4-replaces establishing by cable of BCB derivative and encircles mechanism research, find to accelerate the BCB open loop when 1-position has β-Siliciumatom to exist, based on this conclusion, Siliciumatom is introduced the polymkeric substance that BCB is expected to obtain the low temperature open loop, for the Application Areas of expanding BCB family macromolecule material has significance.
Summary of the invention
Purpose of the present invention is intended to overcome deficiency of the prior art, and a kind of silicon-containing benzocyclobutene monomer (dimethyl vinyl benzo cyclobutene-1-base silane or dimethylbiphenyl cyclobutene-4-base hydrogen silane) and preparation method thereof is provided.The silicon-containing benzocyclobutene monomer of preparation has wide development potentiality and application prospect in fields such as microelectronics industry, aerospace and national defence.
Content of the present invention is: dimethyl vinyl benzo cyclobutene-1-base silane is characterized in that the chemical structural formula of this compound is:
The preparation method of the described dimethyl vinyl of content of the present invention benzo cyclobutene-1-base silane is characterized in that comprising the following steps:
A, batching: by magnesium: Lithium chloride (anhydrous): lithium aluminium hydride is that 1～2:1～2:0.1～1(optimum proportion is 1:1～2:0.2～0.5) molar ratio get each component; Get 1-bromobenzene and cyclobutene, 1-bromobenzene and cyclobutene are diluted wiring solution-forming with (exsiccant) tetrahydrofuran (THF) (or ether), Dilution ratio be volume ratio 1～40(promptly: the volume ratio of 1-bromobenzene and cyclobutene and tetrahydrofuran (THF) is 1:1～40, or the volume ratio of 1-bromobenzene and cyclobutene and ether is 1:1～40) (optimum proportion is 20～30); The mol ratio of 1-bromobenzene and cyclobutene and Lithium chloride (anhydrous) is that 1:1～5(optimum proportion is 1:1～3); Get the dimethyl vinyl chlorosilane, the mol ratio of 1-bromobenzene and cyclobutene and dimethyl vinyl chlorosilane is that 1:1～5(optimum proportion is 1:1～3), the dimethyl vinyl chlorosilane dilutes wiring solution-forming with (exsiccant) tetrahydrofuran (THF) (or ether), Dilution ratio be volume ratio 1～40(promptly: the volume ratio of dimethyl vinyl chlorosilane and tetrahydrofuran (THF) is 1:1～40, or the volume ratio of dimethyl vinyl chlorosilane and ether is 1:1～40) (optimum proportion is 10～20);
B, hybrid reaction: at anhydrous and oxygen-free, nitrogen (N
2) protect down (polishing) magnesium (bar), Lithium chloride (anhydrous), lithium aluminium hydride are put in the reactor, stir down, (slowly) is added dropwise to tetrahydrofuran (THF) (or ether) solution of 1-bromobenzene and cyclobutene, after magnesium rod reacts completely, again (slowly) be added dropwise to tetrahydrofuran (THF) (or ether) solution of dimethyl vinyl chlorosilane, after dripping, under-20～40 ℃ temperature of reaction (optimum temps is 0～30 ℃), reaction 3～24h;
C, separation are purified: add entry (distilled water or deionized water) stopped reaction, use organic solvent extraction again, organic phase with inorganic salt siccative drying (can standing over night) after, suction filtration is removed siccative, obtain light yellow transparent solution, after redistillation concentrate to remove and to desolvate, the material after concentrating through underpressure distillation (boiling point bp.:62～64 ℃/5 mmHg) or silica gel column chromatography, is obtained colourless transparent liquid---dimethyl vinyl benzo cyclobutene-1-base silane.
This dimethyl vinyl benzo cyclobutene-1-base silane is: colourless transparent liquid, boiling point bp.:62～64 ℃/5 mmHg, density: 0.862g/cm
3, gas-chromatography shows purity〉and 96%, structural characterization is as follows:
Proton nmr spectra
, 3.30 (SiCH), 2.94-3.07 (CH
2-), 5.67-5.99 (=CH
2), (SiCH=), (ArH), 7.09-7.25 is (ArH-C) for 6.94-7.01 for 6.07-6.15; (KBr's infrared spectra IR films, cm
-1): 2954,2919,1640,1454,1405,1248,1008,919,834,772.
Among the preparation method of described dimethyl vinyl benzo cyclobutene-1-base silane: the organic solvent of the usefulness of extraction described in the step c can be sherwood oil, ether, normal hexane, hexanaphthene, ethyl acetate, methylene dichloride, trichloromethane, benzene or toluene.
Among the preparation method of described dimethyl vinyl benzo cyclobutene-1-base silane: the siccative of inorganic salt described in the step c can be anhydrous Na
2SO
4Dry or anhydrous MgSO
4
Among the preparation method of described dimethyl vinyl benzo cyclobutene-1-base silane: the used solvent of column chromatography described in the step c can be for sherwood oil or/and normal hexane.
Another content of the present invention is: dimethylbiphenyl cyclobutene-4-base hydrogen silane is characterized in that the chemical structural formula of this compound is:
The preparation method of the described dimethylbiphenyl cyclobutene of another content of the present invention-4-base hydrogen silane is characterized in that comprising the following steps:
A, batching: by magnesium: Lithium chloride (anhydrous): lithium aluminium hydride is that the molar ratio of 1～2:1～2:0.1～1 is got each component (optimum proportion is 1:1～2:0.2～0.5); Get 4-bromobenzene and cyclobutene, with 4-bromobenzene and cyclobutene (exsiccant) tetrahydrofuran (THF) (or ether) wiring solution-forming, Dilution ratio be volume ratio 1～40(promptly: the volume ratio of 4-bromobenzene and cyclobutene and tetrahydrofuran (THF) is 1:1～40, or the volume ratio of 4-bromobenzene and cyclobutene and ether is 1:1～40) (optimum proportion is 20～30); The mol ratio of 4-bromobenzene and cyclobutene and Lithium chloride (anhydrous) is that 1:1～5(optimum proportion is 1:1～3); Get the dimethyl vinyl chlorosilane, the mol ratio of 4-bromobenzene and cyclobutene and dimethyl vinyl chlorosilane is that 1:1～5(optimum proportion is 1:1～3), dimethyl vinyl chlorosilane (exsiccant) tetrahydrofuran (THF) (or ether) wiring solution-forming, Dilution ratio be volume ratio 1～40(promptly: the volume ratio of dimethyl vinyl chlorosilane and tetrahydrofuran (THF) is 1:1～40, or the volume ratio of dimethyl vinyl chlorosilane and ether is 1:1～40) (optimum proportion is 10～20);
B, hybrid reaction: at anhydrous and oxygen-free, nitrogen (N
2) protect down (polishing) magnesium (bar), Lithium chloride (anhydrous), lithium aluminium hydride are put in the reactor, stir down, (slowly) is added dropwise to tetrahydrofuran (THF) (or ether) solution of 4-bromobenzene and cyclobutene, after magnesium rod reacts completely, again (slowly) be added dropwise to tetrahydrofuran (THF) (or ether) solution of dimethyl vinyl chlorosilane, after dripping, under-20～40 ℃ temperature of reaction (optimum temps is 0～30 ℃), reaction 3～24h;
C, separation are purified: add entry (distilled water or deionized water) stopped reaction, use organic solvent extraction again, organic phase with inorganic salt siccative drying (can standing over night) after, suction filtration is removed siccative, obtain light yellow transparent solution, after redistillation concentrate to remove and to desolvate, the material after concentrating through underpressure distillation (boiling point bp.:53～55 ℃/5 mmHg) or silica gel column chromatography, is obtained colourless transparent liquid---dimethylbiphenyl cyclobutene-4-base hydrogen silane.
This dimethylbiphenyl cyclobutene-4-base hydrogen silane is: colourless transparent liquid, and boiling point bp.:53～55 ℃/5 mmHg, gas-chromatography shows purity〉95%, density: 0.860g/cm
3, structural characterization is as follows: proton nmr spectra
1H NMR (400MHz, CDCl
3) δ: 7.31 ~ 7.33,7.17,6.99 ~ 7.00 (ArH), 4.316 ~ 4.353 (SiH), 3.122 (CH
2), 0.248 ~ 0.257 (SiCH
3).(KBr's infrared spectra IR films, cm
-1): 3067,2964,2930,2115,1631,1581,1454,1426,1400,1253,815.
Among the preparation method of the described dimethylbiphenyl cyclobutene of another content of the present invention-4-base hydrogen silane: the organic solvent of the usefulness of extraction described in the step c can be sherwood oil, ether, normal hexane, hexanaphthene, ethyl acetate, methylene dichloride, trichloromethane, benzene or toluene.
Among the preparation method of the described dimethylbiphenyl cyclobutene of another content of the present invention-4-base hydrogen silane: the siccative of inorganic salt described in the step c can be anhydrous Na
2SO
4Dry or anhydrous MgSO
4
Among the preparation method of the described dimethylbiphenyl cyclobutene of another content of the present invention-4-base hydrogen silane: the used solvent of column chromatography described in the step c can be for sherwood oil or/and normal hexane.
Compared with prior art, the present invention has following characteristics and beneficial effect:
(1) silicon-containing benzocyclobutene monomer provided by the invention is different from the 4-DMVSBCB monomer of having reported, and the silica-based functional group of its ethene is in the 4-position, and the silica-based functional group of monomer of the present invention (I) ethene is in the 1-position; Compound property is also different, novel benzocyclobutene monomer structure provided by the present invention is as (I) with (II), contain the silica-based and silica-based reactive group of hydrogen of the ethene that can react respectively, the addition of hydrogen silicon can take place, radical polymerization, reactions such as anionoid polymerization form novel high polymer material, can predict such macromolecular material and have the excellent comprehensive performance, wide development potentiality and application prospect also be arranged in fields such as microelectronics industry, aerospace and national defence;
(2) adopt the present invention, in the middle of this reaction system, having selected the Mg/LiCl system for use mainly is for following reason: (1) magnesium is the most cheap used metal of Grignard reagent, and toxicity is low, is widely used; (2) Lithium chloride (anhydrous) can fast reaction speed, reduces the generation of side reaction.The reaction initial feed is 1-BrBCB or 4-BrBCB, through metallization, generates corresponding Grignard reagent; The mol ratio of initial feed and Mg, LiCl is 1:1:1～1:5:5, and optimum proportion is 1:1:1～1:3:3.Used lithium aluminium hydride (LiAlH in the reaction
4) be activating reagent, mainly play the activation magnesium rod; The chlorosilane that adds and the Grignard reagent generation grignard reaction of generation generate final product, and its mol ratio is 1:1～1:5, and optimum proportion is 1:1～1:3; Used organic reagent is ether or tetrahydrofuran (THF) etc., and suitable dilution can make the side reaction of reaction reduce, and the dilution volume ratio is 1～40, and optimum proportion is 10～20; Entire reaction needs to carry out under nitrogen protection, and solvent for use all needs prior drying treatment;
(3) product preparation process of the present invention is simple, and operation is easy, and operation easily separates and purifies easily, and the productive rate height is practical.
Embodiment
Embodiment given below intends so that the invention will be further described; but can not be interpreted as it is limiting the scope of the invention; the person skilled in art to some nonessential improvement and adjustment that the present invention makes, still belongs to protection scope of the present invention according to the content of the invention described above.
Embodiment 1:
The preparation method of 1-dimethyl vinyl silanes base benzocyclobutene:
The side tube flask that will contain magnetic stir bar vacuumizes, inflated with nitrogen is repeatedly after three times, at nitrogen (N
2) protection down with magnesium (Mg) (264mg, 11mmol), Lithium chloride (anhydrous) (LiCl) (467.5mg, 11mmol), lithium aluminium hydride (LiAlH
4) (76mg 2mmol) adds in the side tube flask magnetic agitation for some time.Under nitrogen, add 1-BrBCB(1-bromobenzene and cyclobutene) (1.3mL, tetrahydrofuran solution 11mmol) (26mL).Stirred 2 hours fast under the room temperature, treat that magnesium rod almost completely reacts after, drip and enter the dimethyl vinyl chlorosilane (1.4mL, tetrahydrofuran (THF) 10mmol) (5mL) solution stirred 1 hour under the room temperature fast.Add a certain amount of water termination reaction, use extracted with diethyl ether, merge organic phase, use anhydrous MgSO
4Drying, standing over night, suction filtration separates purification with column chromatography.Get colourless transparent liquid 1.4g.
Embodiment 2:
The preparation method of 1-dimethyl vinyl silanes base benzocyclobutene:
The side tube flask that will contain magnetic stir bar vacuumizes, inflated with nitrogen is repeatedly after three times, at nitrogen (N
2) protection down with magnesium rod (2.64g, 110mmol), Lithium chloride (anhydrous) (LiCl) (467.5mg, 110mmol) and lithium aluminium hydride (LiAlH
4) (760mg 20mmol) adds in the side tube flask magnetic agitation for some time.Under nitrogen, add 1-BrBCB(1-bromobenzene and cyclobutene) (13mL, tetrahydrofuran solution 110mmol) (260mL).30 ℃ were stirred 5 hours down fast, treat that magnesium rod almost completely reacts after, drip and enter the dimethyl vinyl chlorosilane (30 ℃ were stirred 3 hours down fast for 14mL, tetrahydrofuran (THF) 100mmol) (50mL) solution.Add a certain amount of water termination reaction, use extracted with diethyl ether, merge organic phase, use anhydrous MgSO
4Drying, standing over night, suction filtration separates purification with column chromatography.Get colourless transparent liquid 14g.
Embodiment 3:
The preparation method of 1-dimethyl vinyl silanes base benzocyclobutene:
The side tube flask that will contain magnetic stir bar vacuumizes, inflated with nitrogen is repeatedly after three times, at nitrogen (N
2) protection down with magnesium rod (26.4mg, 1.1mmol), Lithium chloride (anhydrous) (LiCl) (46.7mg, 0.126 mmol) and lithium aluminium hydride (LiAlH
4) (7.6mg 0.2mmol) adds in the side tube flask magnetic agitation for some time.Under nitrogen, add 1-BrBCB(1-bromobenzene and cyclobutene) (0.13mL, tetrahydrofuran solution 1.1mmol) (0.4mL).Stirred 2 hours fast under the room temperature, treat that magnesium rod almost completely reacts after, drip and enter the dimethyl vinyl chlorosilane (0.14mL, tetrahydrofuran (THF) 1mmol) (1mL) solution stirred 1 hour under the room temperature fast.Add a certain amount of water termination reaction, use extracted with diethyl ether, merge organic phase, use anhydrous MgSO
4Drying, standing over night, suction filtration separates purification with column chromatography.Get colourless transparent liquid 0.14g.
Embodiment 4:
The preparation method of 4-dimethylsilyl benzocyclobutene:
The side tube flask that will contain magnetic stir bar vacuumizes, inflated with nitrogen is repeatedly after three times, at nitrogen (N
2) protection down with magnesium rod (264mg, 11mmol), Lithium chloride (anhydrous) (LiCl) (467.5mg, 11mmol) and lithium aluminium hydride (LiAlH
4) (76mg 2mmol) adds in the side tube flask magnetic agitation for some time.Under nitrogen, add 4-BrBCB(4-bromobenzene and cyclobutene) (1.3mL, diethyl ether solution 11mmol) (26mL).Stirred 2 hours fast under the room temperature, treat that magnesium rod almost completely reacts after, drip and enter dimethylchlorosilane (1.4mL, ether 10mmol) (5mL) solution stirred 1 hour under the room temperature fast.Add a certain amount of water termination reaction, use extracted with diethyl ether, merge organic phase, use anhydrous Na
2SO
4Drying, standing over night, suction filtration separates purification with column chromatography.Get colourless transparent liquid 113.4mg.
Embodiment: 5:
The preparation method of 4-dimethylsilyl benzocyclobutene:
The side tube flask that will contain magnetic stir bar vacuumizes, inflated with nitrogen is repeatedly after three times, at nitrogen (N
2) protection down with magnesium rod (2.64g, 0.11mol), Lithium chloride (anhydrous) (LiCl) (4.675g, 0.11mol) and lithium aluminium hydride (LiAlH
4) (152mg 4mmol) adds in the side tube flask magnetic agitation for some time.Under nitrogen, add 4-BrBCB(4-bromobenzene and cyclobutene) (13mL, diethyl ether solution 0.11mmol) (26mL).Stirred 2 hours fast under the room temperature, treat that magnesium rod almost completely reacts after, drip and enter dimethylchlorosilane (14mL, ether 0.1mol) (5mL) solution stirred 1 hour under the room temperature fast.Add a certain amount of water termination reaction, use extracted with diethyl ether, merge organic phase, use anhydrous Na
2SO
4Drying, standing over night, suction filtration separates purification with column chromatography.Get colourless transparent liquid 1.134g.
Embodiment 6:
The preparation method of 4-dimethylsilyl benzocyclobutene:
The side tube flask that will contain magnetic stir bar vacuumizes, inflated with nitrogen is repeatedly after three times, at nitrogen (N
2) protection down with magnesium rod (528mg, 22mmol), Lithium chloride (anhydrous) (LiCl) (935mg, 22mmol) and lithium aluminium hydride (LiAlH
4) (0.76g 20mmol) adds in the side tube flask magnetic agitation for some time.Under nitrogen, add 4-BrBCB(4-bromobenzene and cyclobutene) (2.6mL, diethyl ether solution 22mmol) (42mL).Stirred 2 hours fast under the room temperature, treat that magnesium rod almost completely reacts after, drip and enter dimethylchlorosilane (2.8mL, ether 20mol) (10mL) solution stirred 1 hour under the room temperature fast.Add a certain amount of water termination reaction, use extracted with diethyl ether, merge organic phase, use anhydrous Na
2SO
4Drying, standing over night, suction filtration separates purification with column chromatography.Get colourless transparent liquid 226.8mg.
Embodiment 7:
The preparation method of dimethyl vinyl benzo cyclobutene-1-base silane [chemical structural formula (I)] comprises the following steps:
A, batching: by magnesium: Lithium chloride (anhydrous): lithium aluminium hydride is that the molar ratio of 1:1:0.1 is got each component; Get 1-bromobenzene and cyclobutene, 1-bromobenzene and cyclobutene are diluted wiring solution-forming with (exsiccant) tetrahydrofuran (THF) (or ether), Dilution ratio be volume ratio 1(promptly: the volume ratio of 1-bromobenzene and cyclobutene and tetrahydrofuran (THF) is 1:1, or 1-bromobenzene and cyclobutene and ether and volume ratio be 1:1); The mol ratio of 1-bromobenzene and cyclobutene and Lithium chloride (anhydrous) is 1:1; Get the dimethyl vinyl chlorosilane, the mol ratio of 1-bromobenzene and cyclobutene and dimethyl vinyl chlorosilane is 1:1, the dimethyl vinyl chlorosilane dilutes wiring solution-forming with (exsiccant) tetrahydrofuran (THF) (or ether), Dilution ratio be volume ratio 1(promptly: the volume ratio of dimethyl vinyl chlorosilane and tetrahydrofuran (THF) is 1:1, or the volume ratio of dimethyl vinyl chlorosilane and ether is 1:1);
B, hybrid reaction: at anhydrous and oxygen-free, nitrogen (N
2) protect down (polishing) magnesium (bar), Lithium chloride (anhydrous), lithium aluminium hydride are put in the reactor, stir down, (slowly) is added dropwise to the solution of the tetrahydrofuran (THF) (or ether) of 1-bromobenzene and cyclobutene, after magnesium rod reacts completely, again (slowly) be added dropwise to tetrahydrofuran (THF) (or ether) solution of dimethyl vinyl chlorosilane, after dripping, under-20～40 ℃ temperature of reaction, reaction 3h;
C, separation are purified: add entry (distilled water or deionized water) stopped reaction, use organic solvent extraction again, organic phase with inorganic salt siccative drying (can standing over night) after, suction filtration is removed siccative, obtain light yellow transparent solution, after redistillation concentrate to remove and to desolvate, the material after concentrating through underpressure distillation (boiling point bp.:62～64 ℃/5 mmHg) or silica gel column chromatography, is obtained colourless transparent liquid---dimethyl vinyl benzo cyclobutene-1-base silane.
Embodiment 8:
The preparation method of dimethyl vinyl benzo cyclobutene-1-base silane [chemical structural formula (I)] comprises the following steps:
A, batching: by magnesium: Lithium chloride (anhydrous): lithium aluminium hydride is that the molar ratio of 2:2:1 is got each component; Get 1-bromobenzene and cyclobutene, 1-bromobenzene and cyclobutene are diluted wiring solution-forming with (exsiccant) tetrahydrofuran (THF) (or ether), Dilution ratio be volume ratio 40(promptly: the volume ratio of 1-bromobenzene and cyclobutene and tetrahydrofuran (THF) is 1:40, or the volume ratio of 1-bromobenzene and cyclobutene and ether is 1:40); The mol ratio of 1-bromobenzene and cyclobutene and Lithium chloride (anhydrous) is 1:5; Get the dimethyl vinyl chlorosilane, the mol ratio of 1-bromobenzene and cyclobutene and dimethyl vinyl chlorosilane is 1:5, the dimethyl vinyl chlorosilane dilutes wiring solution-forming with (exsiccant) tetrahydrofuran (THF) (or ether), Dilution ratio be volume ratio 40(promptly: the volume ratio of dimethyl vinyl chlorosilane and tetrahydrofuran (THF) is 1:40, or the volume ratio of dimethyl vinyl chlorosilane and ether is 1:40);
B, hybrid reaction: at anhydrous and oxygen-free, nitrogen (N
2) protect down (polishing) magnesium (bar), Lithium chloride (anhydrous), lithium aluminium hydride are put in the reactor, stir down, (slowly) is added dropwise to the solution of the tetrahydrofuran (THF) (or ether) of 1-bromobenzene and cyclobutene, after magnesium rod reacts completely, again (slowly) be added dropwise to tetrahydrofuran (THF) (or ether) solution of dimethyl vinyl chlorosilane, after dripping, under-20～40 ℃ temperature of reaction, reaction 24h;
C, separation are purified: add entry (distilled water or deionized water) stopped reaction, use organic solvent extraction again, organic phase with inorganic salt siccative drying (can standing over night) after, suction filtration is removed siccative, obtain light yellow transparent solution, after redistillation concentrate to remove and to desolvate, the material after concentrating through underpressure distillation (boiling point bp.:62～64 ℃/5 mmHg) or silica gel column chromatography, is obtained colourless transparent liquid---dimethyl vinyl benzo cyclobutene-1-base silane.
Embodiment 9:
The preparation method of dimethyl vinyl benzo cyclobutene-1-base silane [chemical structural formula (I)] comprises the following steps:
A, batching: by magnesium: Lithium chloride (anhydrous): lithium aluminium hydride is that the molar ratio of 1.5:1.5:0.5 is got each component; Get 1-bromobenzene and cyclobutene, 1-bromobenzene and cyclobutene are diluted wiring solution-forming with (exsiccant) tetrahydrofuran (THF) (or ether), Dilution ratio be volume ratio 20(promptly: the volume ratio of 1-bromobenzene and cyclobutene and tetrahydrofuran (THF) is 1:20, or the volume ratio of 1-bromobenzene and cyclobutene and ether is 1:20); The mol ratio of 1-bromobenzene and cyclobutene and Lithium chloride (anhydrous) is 1:2.5; Get the dimethyl vinyl chlorosilane, the mol ratio of 1-bromobenzene and cyclobutene and dimethyl vinyl chlorosilane is 1:2.5, the dimethyl vinyl chlorosilane dilutes wiring solution-forming with (exsiccant) tetrahydrofuran (THF) (or ether), Dilution ratio be volume ratio 1～40(promptly: the volume ratio of dimethyl vinyl chlorosilane and tetrahydrofuran (THF) is 1:20, or the volume ratio of dimethyl vinyl chlorosilane and ether is 1:20);
B, hybrid reaction: at anhydrous and oxygen-free, nitrogen (N
2) protect down (polishing) magnesium (bar), Lithium chloride (anhydrous), lithium aluminium hydride are put in the reactor, stir down, (slowly) is added dropwise to the solution of the tetrahydrofuran (THF) (or ether) of 1-bromobenzene and cyclobutene, after magnesium rod reacts completely, again (slowly) be added dropwise to tetrahydrofuran (THF) (or ether) solution of dimethyl vinyl chlorosilane, after dripping, under-20～40 ℃ temperature of reaction, reaction 13h;
C, separation are purified: add entry (distilled water or deionized water) stopped reaction, use organic solvent extraction again, organic phase with inorganic salt siccative drying (can standing over night) after, suction filtration is removed siccative, obtain light yellow transparent solution, after redistillation concentrate to remove and to desolvate, the material after concentrating through underpressure distillation (boiling point bp.:62～64 ℃/5 mmHg) or silica gel column chromatography, is obtained colourless transparent liquid---dimethyl vinyl benzo cyclobutene-1-base silane.
Embodiment 10:
The preparation method of dimethyl vinyl benzo cyclobutene-1-base silane [chemical structural formula (I)] comprises the following steps:
A, batching: by magnesium: Lithium chloride (anhydrous): lithium aluminium hydride is that the molar ratio of 1:1:0.2 is got each component; Get 1-bromobenzene and cyclobutene, 1-bromobenzene and cyclobutene are diluted wiring solution-forming with (exsiccant) tetrahydrofuran (THF) (or ether), Dilution ratio be volume ratio 20(promptly: the volume ratio of 1-bromobenzene and cyclobutene and tetrahydrofuran (THF) is 1:20, or the volume ratio of 1-bromobenzene and cyclobutene and ether is 1:20); The mol ratio of 1-bromobenzene and cyclobutene and Lithium chloride (anhydrous) is 1:1; Get the dimethyl vinyl chlorosilane, the mol ratio of 1-bromobenzene and cyclobutene and dimethyl vinyl chlorosilane is 1:1, the dimethyl vinyl chlorosilane dilutes wiring solution-forming with (exsiccant) tetrahydrofuran (THF) (or ether), Dilution ratio be volume ratio 10(promptly: the volume ratio of dimethyl vinyl chlorosilane and tetrahydrofuran (THF) is 1:10, or the volume ratio of dimethyl vinyl chlorosilane and ether is 1:10);
B, hybrid reaction: at anhydrous and oxygen-free, nitrogen (N
2) protect down (polishing) magnesium (bar), Lithium chloride (anhydrous), lithium aluminium hydride are put in the reactor, stir down, (slowly) is added dropwise to the solution of the tetrahydrofuran (THF) (or ether) of 1-bromobenzene and cyclobutene, after magnesium rod reacts completely, again (slowly) be added dropwise to tetrahydrofuran (THF) (or ether) solution of dimethyl vinyl chlorosilane, after dripping, under 0～30 ℃ temperature of reaction, reaction 3h;
C, separation are purified: add entry (distilled water or deionized water) stopped reaction, use organic solvent extraction again, organic phase with inorganic salt siccative drying (can standing over night) after, suction filtration is removed siccative, obtain light yellow transparent solution, after redistillation concentrate to remove and to desolvate, the material after concentrating through underpressure distillation (boiling point bp.:62～64 ℃/5 mmHg) or silica gel column chromatography, is obtained colourless transparent liquid---dimethyl vinyl benzo cyclobutene-1-base silane.
Embodiment 11:
The preparation method of dimethyl vinyl benzo cyclobutene-1-base silane [chemical structural formula (I)] comprises the following steps:
A, batching: by magnesium: Lithium chloride (anhydrous): lithium aluminium hydride is 1:2:0.5) molar ratio get each component; Get 1-bromobenzene and cyclobutene, 1-bromobenzene and cyclobutene are diluted wiring solution-forming with (exsiccant) tetrahydrofuran (THF) (or ether), Dilution ratio be volume ratio 30(promptly: the volume ratio of 1-bromobenzene and cyclobutene and tetrahydrofuran (THF) is 1:30, or the volume ratio of 1-bromobenzene and cyclobutene and ether is 1:30); The mol ratio of 1-bromobenzene and cyclobutene and Lithium chloride (anhydrous) is 1:3; Get the dimethyl vinyl chlorosilane, the mol ratio of 1-bromobenzene and cyclobutene and dimethyl vinyl chlorosilane is 1:3, the dimethyl vinyl chlorosilane dilutes wiring solution-forming with (exsiccant) tetrahydrofuran (THF) (or ether), Dilution ratio be volume ratio 20(promptly: the volume ratio of dimethyl vinyl chlorosilane and tetrahydrofuran (THF) is 1:20, or the volume ratio of dimethyl vinyl chlorosilane and ether is 1:20);
B, hybrid reaction: at anhydrous and oxygen-free, nitrogen (N
2) protect down (polishing) magnesium (bar), Lithium chloride (anhydrous), lithium aluminium hydride are put in the reactor, stir down, (slowly) is added dropwise to the solution of the tetrahydrofuran (THF) (or ether) of 1-bromobenzene and cyclobutene, after magnesium rod reacts completely, again (slowly) be added dropwise to tetrahydrofuran (THF) (or ether) solution of dimethyl vinyl chlorosilane, after dripping, under 0～30 ℃ temperature of reaction, reaction 24h;
C, separation are purified: add entry (distilled water or deionized water) stopped reaction, use organic solvent extraction again, organic phase with inorganic salt siccative drying (can standing over night) after, suction filtration is removed siccative, obtain light yellow transparent solution, after redistillation concentrate to remove and to desolvate, the material after concentrating through underpressure distillation (boiling point bp.:62～64 ℃/5 mmHg) or silica gel column chromatography, is obtained colourless transparent liquid---dimethyl vinyl benzo cyclobutene-1-base silane.
Embodiment 12:
The preparation method of dimethyl vinyl benzo cyclobutene-1-base silane [chemical structural formula (I)] comprises the following steps:
A, batching: by magnesium: Lithium chloride (anhydrous): lithium aluminium hydride is that the molar ratio of 1:1.5:0.4 is got each component; Get 1-bromobenzene and cyclobutene, 1-bromobenzene and cyclobutene are diluted wiring solution-forming with (exsiccant) tetrahydrofuran (THF) (or ether), Dilution ratio be volume ratio 25(promptly: the volume ratio of 1-bromobenzene and cyclobutene and tetrahydrofuran (THF) is 1:25, or 1-bromobenzene and cyclobutene and ether and volume ratio be 1:25); The mol ratio of 1-bromobenzene and cyclobutene and Lithium chloride (anhydrous) is 1:3; Get the dimethyl vinyl chlorosilane, the mol ratio of 1-bromobenzene and cyclobutene and dimethyl vinyl chlorosilane is 1:3, the dimethyl vinyl chlorosilane dilutes wiring solution-forming with (exsiccant) tetrahydrofuran (THF) (or ether), Dilution ratio be volume ratio 15(promptly: the volume ratio of dimethyl vinyl chlorosilane and tetrahydrofuran (THF) is 1:15, or the volume ratio of dimethyl vinyl chlorosilane and ether is 1:15);
B, hybrid reaction: at anhydrous and oxygen-free, nitrogen (N
2) protect down (polishing) magnesium (bar), Lithium chloride (anhydrous), lithium aluminium hydride are put in the reactor, stir down, (slowly) is added dropwise to the solution of the tetrahydrofuran (THF) (or ether) of 1-bromobenzene and cyclobutene, after magnesium rod reacts completely, again (slowly) be added dropwise to tetrahydrofuran (THF) (or ether) solution of dimethyl vinyl chlorosilane, after dripping, under 0～30 ℃ temperature of reaction, reaction 13h;
C, separation are purified: add entry (distilled water or deionized water) stopped reaction, use organic solvent extraction again, organic phase with inorganic salt siccative drying (can standing over night) after, suction filtration is removed siccative, obtain light yellow transparent solution, after redistillation concentrate to remove and to desolvate, the material after concentrating through underpressure distillation (boiling point bp.:62～64 ℃/5 mmHg) or silica gel column chromatography, is obtained colourless transparent liquid---dimethyl vinyl benzo cyclobutene-1-base silane.
Embodiment 13:
The preparation method of dimethyl vinyl benzo cyclobutene-1-base silane [chemical structural formula (I)] comprises the following steps:
A, batching: by magnesium: Lithium chloride (anhydrous): lithium aluminium hydride is that 1～2:1～2:0.1～1(optimum proportion is 1:1～2:0.2～0.5) molar ratio get each component; Get 1-bromobenzene and cyclobutene, 1-bromobenzene and cyclobutene are diluted wiring solution-forming with (exsiccant) tetrahydrofuran (THF) (or ether), Dilution ratio be volume ratio 1～40(promptly: the volume ratio of 1-bromobenzene and cyclobutene and tetrahydrofuran (THF) is 1:1～40, or the volume ratio of 1-bromobenzene and cyclobutene and ether is 1:1～40) (optimum proportion is 20～30); The mol ratio of 1-bromobenzene and cyclobutene and Lithium chloride (anhydrous) is that 1:1～5(optimum proportion is 1:1～3); Get the dimethyl vinyl chlorosilane, the mol ratio of 1-bromobenzene and cyclobutene and dimethyl vinyl chlorosilane is that 1:1～5(optimum proportion is 1:1～3), the dimethyl vinyl chlorosilane dilutes wiring solution-forming with (exsiccant) tetrahydrofuran (THF) (or ether), Dilution ratio be volume ratio 1～40(promptly: the volume ratio of dimethyl vinyl chlorosilane and tetrahydrofuran (THF) is 1:1～40, or the volume ratio of dimethyl vinyl chlorosilane and ether is 1:1～40) (optimum proportion is 10～20);
B, hybrid reaction: at anhydrous and oxygen-free, nitrogen (N
2) protect down (polishing) magnesium (bar), Lithium chloride (anhydrous), lithium aluminium hydride are put in the reactor, stir down, (slowly) is added dropwise to the solution of the tetrahydrofuran (THF) (or ether) of 1-bromobenzene and cyclobutene, after magnesium rod reacts completely, again (slowly) be added dropwise to tetrahydrofuran (THF) (or ether) solution of dimethyl vinyl chlorosilane, after dripping, under-20～40 ℃ temperature of reaction (optimum temps is 0～30 ℃), reaction 3～24h;
C, separation are purified: add entry (distilled water or deionized water) stopped reaction, use organic solvent extraction again, organic phase with inorganic salt siccative drying (can standing over night) after, suction filtration is removed siccative, obtain light yellow transparent solution, after redistillation concentrate to remove and to desolvate, the material after concentrating through underpressure distillation (boiling point bp.:62～64 ℃/5 mmHg) or silica gel column chromatography, is obtained colourless transparent liquid---dimethyl vinyl benzo cyclobutene-1-base silane.
Embodiment 14:
The preparation method [chemical structural formula (II)] of dimethylbiphenyl cyclobutene-4-base hydrogen silane comprises the following steps:
A, batching: by magnesium: Lithium chloride (anhydrous): lithium aluminium hydride is that the molar ratio of 1:1:0.1 is got each component; Get 4-bromobenzene and cyclobutene, with 4-bromobenzene and cyclobutene (exsiccant) tetrahydrofuran (THF) (or ether) wiring solution-forming, Dilution ratio be volume ratio 1(promptly: the volume ratio of 4-bromobenzene and cyclobutene and tetrahydrofuran (THF) is 1:1, or the volume ratio of 4-bromobenzene and cyclobutene and ether is 1:1); The mol ratio of 4-bromobenzene and cyclobutene and Lithium chloride (anhydrous) is 1:1; Get the dimethyl vinyl chlorosilane, the mol ratio of 4-bromobenzene and cyclobutene and dimethyl vinyl chlorosilane is 1:1, dimethyl vinyl chlorosilane (exsiccant) tetrahydrofuran (THF) (or ether) wiring solution-forming, Dilution ratio be volume ratio 1(promptly: the volume ratio of dimethyl vinyl chlorosilane and tetrahydrofuran (THF) is 1:1, or the volume ratio of dimethyl vinyl chlorosilane and ether is 1:1);
B, hybrid reaction: at anhydrous and oxygen-free, nitrogen (N
2) protect down (polishing) magnesium (bar), Lithium chloride (anhydrous), lithium aluminium hydride are put in the reactor, stir down, (slowly) is added dropwise to the solution of the tetrahydrofuran (THF) (or ether) of 4-bromobenzene and cyclobutene, after magnesium rod reacts completely, again (slowly) be added dropwise to tetrahydrofuran (THF) (or ether) solution of dimethyl vinyl chlorosilane, after dripping, under-20～40 ℃ temperature of reaction, reaction 3h;
C, separation are purified: add entry (distilled water or deionized water) stopped reaction, use organic solvent extraction again, organic phase with inorganic salt siccative drying (can standing over night) after, suction filtration is removed siccative, obtain light yellow transparent solution, after redistillation concentrate to remove and to desolvate, the material after concentrating through underpressure distillation (boiling point bp.:53～55 ℃/5 mmHg) or silica gel column chromatography, is obtained colourless transparent liquid---dimethylbiphenyl cyclobutene-4-base hydrogen silane.
Embodiment 15:
The preparation method [chemical structural formula (II)] of dimethylbiphenyl cyclobutene-4-base hydrogen silane comprises the following steps:
A, batching: by magnesium: Lithium chloride (anhydrous): lithium aluminium hydride is that the molar ratio of 2:2:1 is got each component; Get 4-bromobenzene and cyclobutene, with 4-bromobenzene and cyclobutene (exsiccant) tetrahydrofuran (THF) (or ether) wiring solution-forming, Dilution ratio be volume ratio 40(promptly: the volume ratio of 4-bromobenzene and cyclobutene and tetrahydrofuran (THF) is 1:40, or the volume ratio of 4-bromobenzene and cyclobutene and ether is 1:40); The mol ratio of 4-bromobenzene and cyclobutene and Lithium chloride (anhydrous) is 1:5; Get the dimethyl vinyl chlorosilane, the mol ratio of 4-bromobenzene and cyclobutene and dimethyl vinyl chlorosilane is 1:5, dimethyl vinyl chlorosilane (exsiccant) tetrahydrofuran (THF) (or ether) wiring solution-forming, Dilution ratio be volume ratio 40(promptly: the volume ratio of dimethyl vinyl chlorosilane and tetrahydrofuran (THF) is 1:40, or the volume ratio of dimethyl vinyl chlorosilane and ether is 1:40);
B, hybrid reaction: at anhydrous and oxygen-free, nitrogen (N
2) protect down (polishing) magnesium (bar), Lithium chloride (anhydrous), lithium aluminium hydride are put in the reactor, stir down, (slowly) is added dropwise to the solution of the tetrahydrofuran (THF) (or ether) of 4-bromobenzene and cyclobutene, after magnesium rod reacts completely, again (slowly) be added dropwise to tetrahydrofuran (THF) (or ether) solution of dimethyl vinyl chlorosilane, after dripping, under-20～40 ℃ temperature of reaction, reaction 24h;
C, separation are purified: add entry (distilled water or deionized water) stopped reaction, use organic solvent extraction again, organic phase with inorganic salt siccative drying (can standing over night) after, suction filtration is removed siccative, obtain light yellow transparent solution, after redistillation concentrate to remove and to desolvate, the material after concentrating through underpressure distillation (boiling point bp.:53～55 ℃/5 mmHg) or silica gel column chromatography, is obtained colourless transparent liquid---dimethylbiphenyl cyclobutene-4-base hydrogen silane.
Embodiment 16:
The preparation method [chemical structural formula (II)] of dimethylbiphenyl cyclobutene-4-base hydrogen silane comprises the following steps:
A, batching: by magnesium: Lithium chloride (anhydrous): lithium aluminium hydride is that the molar ratio of 1.5:1.5:0.55 is got each component; Get 4-bromobenzene and cyclobutene, with 4-bromobenzene and cyclobutene (exsiccant) tetrahydrofuran (THF) (or ether) wiring solution-forming, Dilution ratio be volume ratio 20(promptly: the volume ratio of 4-bromobenzene and cyclobutene and tetrahydrofuran (THF) is 1:20, or 4-bromobenzene and cyclobutene and ether and volume ratio are 1:20); The mol ratio of 4-bromobenzene and cyclobutene and Lithium chloride (anhydrous) is 1:2.5; Get the dimethyl vinyl chlorosilane, the mol ratio of 4-bromobenzene and cyclobutene and dimethyl vinyl chlorosilane is 1:2.5, dimethyl vinyl chlorosilane (exsiccant) tetrahydrofuran (THF) (or ether) wiring solution-forming, Dilution ratio be volume ratio 20(promptly: the volume ratio of dimethyl vinyl chlorosilane and tetrahydrofuran (THF) is 1:20, or the volume ratio of dimethyl vinyl chlorosilane and ether is 1:20);
B, hybrid reaction: at anhydrous and oxygen-free, nitrogen (N
2) protect down (polishing) magnesium (bar), Lithium chloride (anhydrous), lithium aluminium hydride are put in the reactor, stir down, (slowly) is added dropwise to the solution of the tetrahydrofuran (THF) (or ether) of 4-bromobenzene and cyclobutene, after magnesium rod reacts completely, again (slowly) be added dropwise to tetrahydrofuran (THF) (or ether) solution of dimethyl vinyl chlorosilane, after dripping, under-20～40 ℃ temperature of reaction, reaction 13h;
C, separation are purified: add entry (distilled water or deionized water) stopped reaction, use organic solvent extraction again, organic phase with inorganic salt siccative drying (can standing over night) after, suction filtration is removed siccative, obtain light yellow transparent solution, after redistillation concentrate to remove and to desolvate, the material after concentrating through underpressure distillation (boiling point bp.:53～55 ℃/5 mmHg) or silica gel column chromatography, is obtained colourless transparent liquid---dimethylbiphenyl cyclobutene-4-base hydrogen silane.
Embodiment 17:
The preparation method [chemical structural formula (II)] of dimethylbiphenyl cyclobutene-4-base hydrogen silane comprises the following steps:
A, batching: by magnesium: Lithium chloride (anhydrous): lithium aluminium hydride is that the molar ratio of 1:1:0.2 is got each component; Get 4-bromobenzene and cyclobutene, with 4-bromobenzene and cyclobutene (exsiccant) tetrahydrofuran (THF) (or ether) wiring solution-forming, Dilution ratio be volume ratio 20(promptly: the volume ratio of 4-bromobenzene and cyclobutene and tetrahydrofuran (THF) is 1:20, or the volume ratio of 4-bromobenzene and cyclobutene and ether is 1:20); The mol ratio of 4-bromobenzene and cyclobutene and Lithium chloride (anhydrous) is 1:1; Get the dimethyl vinyl chlorosilane, the mol ratio of 4-bromobenzene and cyclobutene and dimethyl vinyl chlorosilane is 1:1, dimethyl vinyl chlorosilane (exsiccant) tetrahydrofuran (THF) (or ether) wiring solution-forming, Dilution ratio be volume ratio 10(promptly: the volume ratio of dimethyl vinyl chlorosilane and tetrahydrofuran (THF) is 1:10, or the volume ratio of dimethyl vinyl chlorosilane and ether is 1:10);
B, hybrid reaction: at anhydrous and oxygen-free, nitrogen (N
2) protect down (polishing) magnesium (bar), Lithium chloride (anhydrous), lithium aluminium hydride are put in the reactor, stir down, (slowly) is added dropwise to the solution of the tetrahydrofuran (THF) (or ether) of 4-bromobenzene and cyclobutene, after magnesium rod reacts completely, again (slowly) be added dropwise to tetrahydrofuran (THF) (or ether) solution of dimethyl vinyl chlorosilane, after dripping, under 0～30 ℃ temperature of reaction, reaction 3h;
C, separation are purified: add entry (distilled water or deionized water) stopped reaction, use organic solvent extraction again, organic phase with inorganic salt siccative drying (can standing over night) after, suction filtration is removed siccative, obtain light yellow transparent solution, after redistillation concentrate to remove and to desolvate, the material after concentrating through underpressure distillation (boiling point bp.:53～55 ℃/5 mmHg) or silica gel column chromatography, is obtained colourless transparent liquid---dimethylbiphenyl cyclobutene-4-base hydrogen silane.
Embodiment 18:
The preparation method [chemical structural formula (II)] of dimethylbiphenyl cyclobutene-4-base hydrogen silane comprises the following steps:
A, batching: by magnesium: Lithium chloride (anhydrous): lithium aluminium hydride is that the molar ratio of 1:2:0.5 is got each component; Get 4-bromobenzene and cyclobutene, with 4-bromobenzene and cyclobutene (exsiccant) tetrahydrofuran (THF) (or ether) wiring solution-forming, Dilution ratio be volume ratio 30(promptly: the volume ratio of 4-bromobenzene and cyclobutene and tetrahydrofuran (THF) is 1:30, or the volume ratio of 4-bromobenzene and cyclobutene and ether is 1:30); The mol ratio of 4-bromobenzene and cyclobutene and Lithium chloride (anhydrous) is 1:3; Get the dimethyl vinyl chlorosilane, the mol ratio of 4-bromobenzene and cyclobutene and dimethyl vinyl chlorosilane is 1:3, dimethyl vinyl chlorosilane (exsiccant) tetrahydrofuran (THF) (or ether) wiring solution-forming, Dilution ratio be volume ratio 20(promptly: the volume ratio of dimethyl vinyl chlorosilane and tetrahydrofuran (THF) is 1:20, or the volume ratio of dimethyl vinyl chlorosilane and ether is 1:20);
B, hybrid reaction: at anhydrous and oxygen-free, nitrogen (N
2) protect down (polishing) magnesium (bar), Lithium chloride (anhydrous), lithium aluminium hydride are put in the reactor, stir down, (slowly) is added dropwise to the solution of the tetrahydrofuran (THF) (or ether) of 4-bromobenzene and cyclobutene, after magnesium rod reacts completely, again (slowly) be added dropwise to tetrahydrofuran (THF) (or ether) solution of dimethyl vinyl chlorosilane, after dripping, under 0～30 ℃ temperature of reaction, reaction 22h;
C, separation are purified: add entry (distilled water or deionized water) stopped reaction, use organic solvent extraction again, organic phase with inorganic salt siccative drying (can standing over night) after, suction filtration is removed siccative, obtain light yellow transparent solution, after redistillation concentrate to remove and to desolvate, the material after concentrating through underpressure distillation (boiling point bp.:53～55 ℃/5 mmHg) or silica gel column chromatography, is obtained colourless transparent liquid---dimethylbiphenyl cyclobutene-4-base hydrogen silane.
Embodiment 19:
The preparation method [chemical structural formula (II)] of dimethylbiphenyl cyclobutene-4-base hydrogen silane comprises the following steps:
A, batching: by magnesium: Lithium chloride (anhydrous): lithium aluminium hydride is that the molar ratio of 1:1.5:0.3 is got each component; Get 4-bromobenzene and cyclobutene, with 4-bromobenzene and cyclobutene (exsiccant) tetrahydrofuran (THF) (or ether) wiring solution-forming, Dilution ratio be volume ratio 25(promptly: the volume ratio of 4-bromobenzene and cyclobutene and tetrahydrofuran (THF) is 1:25, or the volume ratio of 4-bromobenzene and cyclobutene and ether is 1:25); The mol ratio of 4-bromobenzene and cyclobutene and Lithium chloride (anhydrous) is 1:2; Get the dimethyl vinyl chlorosilane, the mol ratio of 4-bromobenzene and cyclobutene and dimethyl vinyl chlorosilane is 1:2, dimethyl vinyl chlorosilane (exsiccant) tetrahydrofuran (THF) (or ether) wiring solution-forming, Dilution ratio be volume ratio 15(promptly: the volume ratio of dimethyl vinyl chlorosilane and tetrahydrofuran (THF) is 1:15, or the volume ratio of dimethyl vinyl chlorosilane and ether is 1:15);
B, hybrid reaction: at anhydrous and oxygen-free, nitrogen (N
2) protect down (polishing) magnesium (bar), Lithium chloride (anhydrous), lithium aluminium hydride are put in the reactor, stir down, (slowly) is added dropwise to the solution of the tetrahydrofuran (THF) (or ether) of 4-bromobenzene and cyclobutene, after magnesium rod reacts completely, again (slowly) be added dropwise to tetrahydrofuran (THF) (or ether) solution of dimethyl vinyl chlorosilane, after dripping, under 0～30 ℃ temperature of reaction, reaction 13h;
C, separation are purified: add entry (distilled water or deionized water) stopped reaction, use organic solvent extraction again, organic phase with inorganic salt siccative drying (can standing over night) after, suction filtration is removed siccative, obtain light yellow transparent solution, after redistillation concentrate to remove and to desolvate, the material after concentrating through underpressure distillation (boiling point bp.:53～55 ℃/5 mmHg) or silica gel column chromatography, is obtained colourless transparent liquid---dimethylbiphenyl cyclobutene-4-base hydrogen silane.
Embodiment 20:
The preparation method [chemical structural formula (II)] of dimethylbiphenyl cyclobutene-4-base hydrogen silane comprises the following steps:
A, batching: by magnesium: Lithium chloride (anhydrous): lithium aluminium hydride is that the molar ratio of 1～2:1～2:0.1～1 is got each component (optimum proportion is 1:1～2:0.2～0.5); Get 4-bromobenzene and cyclobutene, with 4-bromobenzene and cyclobutene (exsiccant) tetrahydrofuran (THF) (or ether) wiring solution-forming, Dilution ratio be volume ratio 1～40(promptly: the volume ratio of 4-bromobenzene and cyclobutene and tetrahydrofuran (THF) is 1:1～40, or the volume ratio of 4-bromobenzene and cyclobutene and ether is 1:1～40) (optimum proportion is 20～30); The mol ratio of 4-bromobenzene and cyclobutene and Lithium chloride (anhydrous) is that 1:1～5(optimum proportion is 1:1～3); Get the dimethyl vinyl chlorosilane, the mol ratio of 4-bromobenzene and cyclobutene and dimethyl vinyl chlorosilane is that 1:1～5(optimum proportion is 1:1～3), dimethyl vinyl chlorosilane (exsiccant) tetrahydrofuran (THF) (or ether) wiring solution-forming, Dilution ratio be volume ratio 1～40(promptly: the volume ratio of dimethyl vinyl chlorosilane and tetrahydrofuran (THF) is 1:1～40, or the volume ratio of dimethyl vinyl chlorosilane and ether is 1:1～40) (optimum proportion is 10～20);
B, hybrid reaction: at anhydrous and oxygen-free, nitrogen (N
2) protect down (polishing) magnesium (bar), Lithium chloride (anhydrous), lithium aluminium hydride are put in the reactor, stir down, (slowly) is added dropwise to the solution of the tetrahydrofuran (THF) (or ether) of 4-bromobenzene and cyclobutene, after magnesium rod reacts completely, again (slowly) be added dropwise to tetrahydrofuran (THF) (or ether) solution of dimethyl vinyl chlorosilane, after dripping, under-20～40 ℃ temperature of reaction (optimum temps is 0～30 ℃), reaction 3～24h;
C, separation are purified: add entry (distilled water or deionized water) stopped reaction, use organic solvent extraction again, organic phase with inorganic salt siccative drying (can standing over night) after, suction filtration is removed siccative, obtain light yellow transparent solution, after redistillation concentrate to remove and to desolvate, the material after concentrating through underpressure distillation (boiling point bp.:53～55 ℃/5 mmHg) or silica gel column chromatography, is obtained colourless transparent liquid---dimethylbiphenyl cyclobutene-4-base hydrogen silane.
In the foregoing description: the organic solvent of the usefulness of extraction described in the step c can be sherwood oil, ether, normal hexane, hexanaphthene, ethyl acetate, methylene dichloride, trichloromethane, benzene or toluene.
In the foregoing description: the siccative of inorganic salt described in the step c can be anhydrous Na
2SO
4Dry or anhydrous MgSO
4
In the foregoing description: the used solvent of column chromatography described in the step c can be for sherwood oil or/and normal hexane.
The related parameter that has of the dimethyl vinyl benzo cyclobutene-1-base silane [chemical structural formula (I)] of the foregoing description preparation is: colourless transparent liquid, boiling point bp.:62～64 ℃/5 mmHg, density: 0.862g/cm
3, gas-chromatography shows purity〉and 96%, structural characterization is as follows:
Proton nmr spectra
1H NMR (400MHz, CDCl
3) δ: 0.043-0.076 (SiCH
3), 3.30 (SiCH), 2.94-3.07 (CH
2-), 5.67-5.99 (=CH
2), (SiCH=), (ArH), 7.09-7.25 is (ArH-C) for 6.94-7.01 for 6.07-6.15; (KBr's infrared spectra IR films, cm
-1): 2954,2919,1640,1454,1405,1248,1008,919,834,772.
The dimethylbiphenyl cyclobutene of the foregoing description preparation-4-base hydrogen silane [chemical structural formula (II)] has related parameter to be: colourless transparent liquid, and boiling point bp.:53～55 ℃/5 mmHg, gas-chromatography shows purity〉95%, density: 0.860g/cm
3, structural characterization is as follows:
Proton nmr spectra
1H NMR (400MHz, CDCl
3) δ: 7.31 ~ 7.33,7.17,6.99 ~ 7.00 (ArH), 4.316 ~ 4.353 (SiH), 3.122 (CH
2), 0.248 ~ 0.257 (SiCH
3).(KBr's infrared spectra IR films, cm
-1): 3067,2964,2930,2115,1631,1581,1454,1426,1400,1253,815.
In the foregoing description: the processing parameter in each step and each amounts of components numerical value etc. are scope, and any point is all applicable.
The not concrete same prior art of narrating of technology contents in content of the present invention and the foregoing description.
The invention is not restricted to the foregoing description, content of the present invention is described all can implement and have described good result.
Claims (10)
1. dimethyl vinyl benzo cyclobutene-1-base silane is characterized in that the chemical structural formula of this compound is:
。
2. the preparation method of dimethyl vinyl benzo cyclobutene-1-base silane is characterized in that comprising the following steps:
A, batching: by magnesium: Lithium chloride (anhydrous): lithium aluminium hydride is that the molar ratio of 1～2:1～2:0.1～1 is got each component; Get 1-bromobenzene and cyclobutene, 1-bromobenzene and cyclobutene are diluted wiring solution-forming with tetrahydrofuran (THF), Dilution ratio is a volume ratio 1～40; The mol ratio of 1-bromobenzene and cyclobutene and Lithium chloride (anhydrous) is 1:1～5; Get the dimethyl vinyl chlorosilane, the mol ratio of 1-bromobenzene and cyclobutene and dimethyl vinyl chlorosilane is 1:1～5, and the dimethyl vinyl chlorosilane dilutes wiring solution-forming with tetrahydrofuran (THF), and Dilution ratio is a volume ratio 1～40;
B, hybrid reaction: under anhydrous and oxygen-free, nitrogen protection, magnesium, Lithium chloride (anhydrous), lithium aluminium hydride are put in the reactor, stir down, be added dropwise to the tetrahydrofuran solution of 1-bromobenzene and cyclobutene, after magnesium rod reacts completely, be added dropwise to the tetrahydrofuran solution of dimethyl vinyl chlorosilane again, after dripping, under-20～40 ℃ temperature of reaction, reaction 3～24h;
C, separation are purified: add the entry stopped reaction, use organic solvent extraction again, after organic phase is used inorganic salt siccative drying, suction filtration is removed siccative, obtain light yellow transparent solution, redistillation concentrates except that after desolvating, and the material after concentrating through underpressure distillation or silica gel column chromatography, is obtained colourless transparent liquid---dimethyl vinyl benzo cyclobutene-1-base silane.
3. by the preparation method of the described dimethyl vinyl of claim 2 benzo cyclobutene-1-base silane, it is characterized in that: the organic solvent of the usefulness of extraction described in the step c is sherwood oil, ether, normal hexane, hexanaphthene, ethyl acetate, methylene dichloride, trichloromethane, benzene or toluene.
4. by the preparation method of the described dimethyl vinyl of claim 2 benzo cyclobutene-1-base silane, it is characterized in that: the siccative of inorganic salt described in the step c is an anhydrous Na
2SO
4Dry or anhydrous MgSO
4
5. by the preparation method of the described dimethyl vinyl of claim 2 benzo cyclobutene-1-base silane, it is characterized in that: the used solvent of column chromatography described in the step c is that sherwood oil is or/and normal hexane.
6. dimethylbiphenyl cyclobutene-4-base hydrogen silane is characterized in that the chemical structural formula of this compound is:
。
7. the preparation method of dimethylbiphenyl cyclobutene-4-base hydrogen silane is characterized in that comprising the following steps:
A, batching: by magnesium: Lithium chloride (anhydrous): lithium aluminium hydride is that the molar ratio of 1～2:1～2:0.1～1 is got each component; Get 4-bromobenzene and cyclobutene, with 4-bromobenzene and cyclobutene tetrahydrofuran (THF) wiring solution-forming, Dilution ratio is a volume ratio 1～40; The mol ratio of 4-bromobenzene and cyclobutene and Lithium chloride (anhydrous) is 1:1～5; Get the dimethyl vinyl chlorosilane, the mol ratio of 4-bromobenzene and cyclobutene and dimethyl vinyl chlorosilane is 1:1～5, dimethyl vinyl chlorosilane tetrahydrofuran (THF) wiring solution-forming, and Dilution ratio is a volume ratio 1～40;
B, hybrid reaction: under anhydrous and oxygen-free, nitrogen protection, magnesium, Lithium chloride (anhydrous), lithium aluminium hydride are put in the reactor, stir down, be added dropwise to the tetrahydrofuran solution of 4-bromobenzene and cyclobutene, after magnesium rod reacts completely, be added dropwise to the tetrahydrofuran solution of dimethyl vinyl chlorosilane again, after dripping, under-20～40 ℃ temperature of reaction, reaction 3～24h;
C, separation are purified: add the entry stopped reaction, use organic solvent extraction again, after organic phase is used inorganic salt siccative drying, suction filtration is removed siccative, obtain light yellow transparent solution, redistillation concentrates except that after desolvating, and the material after concentrating through underpressure distillation or silica gel column chromatography, is obtained colourless transparent liquid---dimethylbiphenyl cyclobutene-4-base hydrogen silane.
8. by the preparation method of the described dimethylbiphenyl cyclobutene of claim 7-4-base hydrogen silane, it is characterized in that: the organic solvent of the usefulness of extraction described in the step c is sherwood oil, ether, normal hexane, hexanaphthene, ethyl acetate, methylene dichloride, trichloromethane, benzene or toluene.
9. by the preparation method of the described dimethylbiphenyl cyclobutene of claim 7-4-base hydrogen silane, it is characterized in that: the siccative of inorganic salt described in the step c is an anhydrous Na
2SO
4Dry or anhydrous MgSO
4
10. by the preparation method of the described dimethylbiphenyl cyclobutene of claim 7-4-base hydrogen silane, it is characterized in that: the used solvent of column chromatography described in the step c is that sherwood oil is or/and normal hexane.
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