* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
With potassium hexamethylsilazane In neat liquid at 30℃; for 2 h; Schlenk technique; Inert atmosphere
General procedure: Catalyzed CDC reactions were carried out using the following standard protocol. In the glove box, the chosen pre-catalyst (0.05 mmol) was loaded into a Schlenk tube, and subsequently the alcohol (n x 0.05 mmol, n equiv.) followed by silane (n' x 0 0.05 mmol, n' equiv.) were added. The reaction mixture was stirred at the desired temperature (30°C), which was controlled by an oil bath. After the required period, the reaction was quenched by adding CDCl3 to the mixture. Substrate conversion was monitored by examination of the 1H NMR spectrum of the reaction mixture and comparing relative intensities of resonance characteristics of the substrates and products.
Reference：
[1] Australian Journal of Chemistry, 2017, vol. 70, # 6, p. 724 - 730
[2] Chemische Berichte, 1995, vol. 128, # 12, p. 1267 - 1270
[3] Journal of Organometallic Chemistry, 2004, vol. 689, # 20, p. 3258 - 3264
[4] ACS Catalysis, 2018, vol. 8, # 3, p. 2558 - 2566
[5] Chemistry Letters, 1973, p. 501 - 504
[6] Journal of Organometallic Chemistry, 1976, vol. 114, p. 135 - 144
[7] Advanced Synthesis and Catalysis, 2009, vol. 351, # 9, p. 1405 - 1411
[8] Chemistry - An Asian Journal, 2014, vol. 9, # 2, p. 612 - 619
[9] Angewandte Chemie - International Edition, 2014, vol. 53, # 46, p. 12581 - 12586[10] Angew. Chem., 2014, vol. 126, # 46, p. 12789 - 12794,6
[11] Chemical Communications, 2016, vol. 52, # 13, p. 2725 - 2728
[12] Chemistry - A European Journal, 2017, vol. 23, # 45, p. 10815 - 10821
2
[ 681-84-5 ]
[ 20699-69-8 ]
[ 2996-92-1 ]
[ 6843-66-9 ]
Yield
Reaction Conditions
Operation in experiment
77%
at 80℃; for 2 h; Inert atmosphere; Schlenk technique
In a nitrogen-filled drybox, aryl manganese compound represented by the followingformula into a glass vial (30.0 mg, 0.039 mmol) and the internal standard eicosane (10.0 mg,0.035 mmol) was charged and added toluene 1mL and the. It was prepared in a separate vial Si(OEt) 4 and (16.0mg, 0.077mmol) was added thereto using a toluene 1 mL. The reaction wascarried out with stirring for 24 hours at 100 ° C. By Shimadzu GC-2010 gas chromatograph,SiPh (OEt) 3 is 80percent, SiPh 2 (OEt) 2, it was confirmed that have generated 11percent.
Reference：
[1] Patent: JP2016/34912, 2016, A, . Location in patent: Paragraph 0031
3
[ 108-86-1 ]
[ 2996-92-1 ]
[ 6843-66-9 ]
Yield
Reaction Conditions
Operation in experiment
232 g
With magnesium In tetrahydrofuran; toluene at 60 - 70℃; for 1 h; Inert atmosphere
[0048] Practical Example 1 24.3 g (1.0 mol) of flake-like magnesium produced by Wako Pure Chemical Industries, Ltd. (1.74 specific gravity), 54.0 g (0.75 mol) of tetrahydrofuran produced by Tokyo Chemical Industry Co., Ltd., 92.1 g (1.0 mol) of toluene produced by Tokyo Chemical Industry Co., Ltd., and 198.3 g (1.0 mol) of phenyltrimethoxysilane (Z-6126 SILANE) produced by Dow Corning were loaded into a 1 L 4-neck flask equipped with a nitrogen gas feed tube, thermometer, Dimroth type condenser, and dripping funnel. While the mixture was stirred, the mixture was heated to 60°C. Thereafter, 157.0 g (1.0 mol) of phenyl bromide produced by Sigma-Aldrich was added dropwise at 60 to 70°C. After completion of trickling addition, the mixture was further stirred for 1 h, and then was cooled to 30°C. The generated slurry was suction filtered using glass filter paper GC90 manufactured by Advantec, and the byproduct methoxymagnesium bromide was removed by filtration. The tetrahydrofuran was removed by distillation using an evaporator to obtain 232.0 g of the product. The product was confirmed by GC-MS to be diphenyldimethoxysilane (86.8percent purity).
[0047] Comparative Example 1 500 mL of a phenyl magnesium chloride solution (produced by Sigma-Aldrich, 32 percent by weight tetrahydrofuran solution, 2 mol/L, 1.0 mol equivalents of phenyl magnesium chloride) was loaded into a 1 L 4-neck flask equipped with a nitrogen gas feed tube, thermometer, Dimroth type condenser, and dripping funnel. While the mixture was stirred, the mixture was heated to 60°C. Thereafter, 193.8 g (1.0 mol) of phenyltrimethoxysilane was added dropwise at 60 to 70°C. After completion of trickling addition, the mixture was further stirred for 1 h at 70°C, and then was cooled to 30°C. The generated slurry was suction filtered using glass filter paper GC90 manufactured by Advantec, and the byproduct methoxymagnesium bromide was removed by filtration. The tetrahydrofuran was removed by distillation using an evaporator to obtain 200.2 g of the product. The product was confirmed by MS-GC to be diphenyldimethoxysilane(66.1 percent purity).
Reference：
[1] Chalmers Doktorsavhandl., 1951, # 6, p. 63,64
[2] Research on Chemical Intermediates, 2010, vol. 36, # 1, p. 181 - 191
[3] Research on Chemical Intermediates, 2010, vol. 36, # 1, p. 181 - 191
poly(dimethylsiloxane-co-diphenylsiloxane)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With hydrogenchloride; water; for 2h;Heating / reflux;
1,3-bis (hydroxybutyl) tetramethyl disiloxane (33.70 g, 0.118 mole),dimethyidimethoxysilane (403.18 g, 3.25 moles) anddiphenyidimethoxysilane <Desc/Clms Page number 14>(272.33 g, 1. 08 moles) were added in a one-liter round bottom flask. Water (78.29 g) and concentrated hydrochloric acid (11.9 mL) were then slowly added to the flask. The contents of the flask wererefluxed for one hour. Methanol (253.3 mL) was distilled from the contents. Water (160 mL) and concentrated hydrochloric acid (130 mL) was added to the flask. The contents of the flask were refluxed for one hour. The contents of the flask were then poured into a separatory funnel. The silicone layer was separated, diluted with 500 mL ether and washed once with 250 mL water, twice with 250 mL 5-percent sodium bicarbonate aqueous solution and twice with 250 mL water. The final organic layer was dried with magnesium sulfate, and then vacuum stripped at 80 degrees Celsius (0.1 mm Hg) to give the crude product. The crude product was then dissolved in 50/50cyclohexane/methylene chloride and then passed through a silica gel column with the same solvent mixture. The final product was collected in tetrahydrofuran (THF) by passing THF through the silica gel column. The THF fractions were combined, dried and vacuum stripped to give the final product. Size Exclusion Chromatography (SEC) measurements of the final product indicated less than three percent cyclics and a molecular weight of 2821 by titration.
EXAMPLE 3 In the manner described above, a mixture of 3.24 g (0.036 g mole) of dimethyl carbonate, 3.96 g (0.015 g mole) of 96 percent diphenyldichlorosilane, and 0.5 g of tetra-n-butyl phosphonium bromide in 15 ml of sulfolane was heated at 150 C. for 16 hours. The reaction mixture was then added to 200 ml of icewater and the organic portion was extracted with two 25-ml portions of hexane. After the extract was dried over anhydrous MgSO4, the solvent was distilled off and the residual material was distilled under reduced pressure to obtain 2.87 g (78 percent yield) of diphenyldimethoxysilane, b.p. 93 C.-94 C./0.1 mm Hg.
hydroxybutyl-terminated copolymer of dimethylsiloxane and diphenylsiloxane[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With hydrogenchloride; In water; for 2h;Heating / reflux;
1,3-bis(hydroxybutyl)tetramethyl disiloxane (33.70 g, 0.118 mole), dimethyldimethoxysilane (403.18 g, 3.25 moles) and <strong>[6843-66-9]<strong>[6843-66-9]diphenyldimethoxysilan</strong>e</strong> (272.33 g, 1.08 moles) were added in a one-liter round bottom flask. Water (78.29 g) and concentrated hydrochloric acid (11.9 mL) were then slowly added to the flask. The contents of the flask were refluxed for one hour. Methanol (253.3 mL) was distilled from the contents. Water (160 mL) and concentrated hydrochloric acid (130 mL) was added to the flask. The contents of the flask were refluxed for one hour. The contents of the flask were then poured into a separatory funnel. The silicone layer was separated, diluted with 500 mL ether and washed once with 250 mL water, twice with 250 mL 5-percent sodium bicarbonate aqueous solution and twice with 250 mL water. The final organic layer was dried with magnesium sulfate, and then vacuum stripped at 80 degrees Celsius (0.1 mm Hg) to give the crude product. The crude product was then dissolved in 50/50 cyclohexane/methylene chloride and then passed through a silica gel column with the same solvent mixture. The final product was collected in tetrahydrofuran (THF) by passing THF through the silica gel column. The THF fractions were combined, dried and vacuum stripped to give the final product. Size exclusion chromatography (SEC) measurements of the final product indicated less than three percent cyclics and a molecular weight of 2821 by titration.
hydroxybutyl-terminated copolymer of dimethylsiloxane and diphenylsiloxane with a 27:9 ratio of methyl/phenyl and a molecular weight of 4000[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
The preparation procedure, ingredients and ingredient feed ratio used in the present example were the same as those of Example 1, except preparative SEC was used to purify the crude product. In so doing, the crude product was dissolved in THF (10% w/v) and passed through a preparative SEC unit. The final product, after stripping off all solvent, was over 97 percent pure, with less than 3 percent cyclic impurities. The molecular weight of the final product as determined by titration was 4158.
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