* 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.
Reference：
[1] Journal of Organic Chemistry, 2002, vol. 67, # 15, p. 5327 - 5332
2
[ 75-77-4 ]
[ 6999-03-7 ]
[ 13183-70-5 ]
Reference：
[1] Nippon Kagaku Zasshi, 1958, vol. 79, p. 1307[2] Chem.Abstr., 1960, p. 5525
[3] Nippon Kagaku Zasshi, 1958, vol. 79, p. 1307[4] Chem.Abstr., 1960, p. 5525
3
[ 462-06-6 ]
[ 6999-03-7 ]
[ 398-21-0 ]
Reference：
[1] Science (Washington, DC, United States), 2012, vol. 337, # 6102, p. 1644 - 1648,5
4
[ 75-77-4 ]
[ 106-37-6 ]
[ 6999-03-7 ]
Yield
Reaction Conditions
Operation in experiment
96%
Stage #1: With n-butyllithium In tetrahydrofuran; diethyl ether at -78℃; Stage #2: at -78℃;
The photoinitiator PI-1 was synthesized according to Scheme 1 as shown below. In a 500 mL flask equipped with a thermometer, cooling device and dropping funnel, 1 ,4-dibromobenzene (23.6 g , 100 mmol) in 200 mL of Et.20 was treated with n-BuLi (41.7 mL, 2.4 M in THF) at -78 °C, and then the reaction was quenched with TMSCI (5.2 mL, 40 mmol) at -78 °C, and IM-1 (22 g, 96percent yield) was obtained as oil.
93%
Stage #1: With n-butyllithium In tetrahydrofuran; pentane at -78 - 0℃; for 1 h; Stage #2: at 0 - 20℃; for 1 h;
[Preparative Example 6] Preparation of Compound F[74] Dibromobenzene (20 g, 84.78 mmol) was dissolved in dry tetrahydrofuran (THF,200 mL) at room temperature under a nitrogen atmosphere. The solution was cooled to -78°C. n-butyl lithium (34 mL, 2.5 M pentane solution) was added slowly to the solution at -78°C, and the temperature of the mixture was slowly raised to 0°C for about 1 hour. To the mixture, chlorotrimethylsilane (13 ml, 101.74 mmol) was added, and the temperature of the mixture was raised to normal temperature over 1 hour. After confirmation of completion of the reaction, the mixture was extracted from ethyl acetate, dried over magnesium sulfate, and distilled off under reduced pressure to obtain Compound F (18 g, 93percent).[75] MS (M+) = 229
93%
Stage #1: With n-butyllithium In tetrahydrofuran; pentane at -78 - 0℃; for 1 h; Stage #2: at 0 - 20℃; for 1 h;
Preparation Example 4: Preparation of compound D. Dibromobenzene (20 g, 84.78 mmol) was dissolved in anhydroustetrahydrofuran (THF, 200 mL) at room temperature under nitrogenatmosphere. The solution was cooled to -78°C . n-butyl lithium (34 mL,2.5 M pentane solution) was added slowly to the solution at -78°C, andthe temperature of the mixture was slowly raised to 0°C for about 1 hour.To the mixture, chlorotrimethylsilane (13 ml, 101.74 mmol) was added, andthe temperature of the mixture was raised to room temperature over 1 hour.After confirmation of completion of the reaction, the mixture wasextracted from ethyl acetate, dried over magnesium sulfate, and distilledoff under reduced pressure to obtain a compound D (18 g, 93percent). MS (M+)= 229.
93%
Stage #1: With n-butyllithium In tetrahydrofuran; pentane at -78 - 0℃; for 1 h; Stage #2: at 0 - 20℃; for 1 h;
Dibromobenzene (20 g, 84.78 mmol) was dissolved in anhydrous tetrahydrofuran(THF, 200 mL) at room temperature under nitrogen atmosphere. The solution was cooled to -78°C. N-butyllithium (34 mL, 2.5 M pentane solution) was added slowly to the solution at -78°C, and the temperature of the mixture was slowly raised to 0°C for about 1 hour. To the mixture, chlorotrimethylsilane (13 ml, 101.74 mmol) was added, and the temperature of the mixture was raised to room temperature over 1 hour. After confirmation of completion of the reaction, the mixture was extracted from ethyl acetate, dried over magnesium sulfate, and distilled off under reduced pressure to obtain a compound K (18 g, 93percent).[87] MS [M] = 229
89.5%
Stage #1: With n-butyllithium In tetrahydrofuran at -78℃; for 1 h; Stage #2: at 20℃; for 12 h;
20.0 g (0.0848 mol) of 1,4-dibromobenzene and 200 mL of tetrahydrofuran were added to a 500 mL round bottom flask, and 28.2 g (0.1017 mol) of n-butyllithium was slowly added thereto at -78 ° C and stirred at the same temperature for 1 hour Then, 11.0 g (0.1017 mol) of trichloromethylsilane was added and stirred at room temperature for 12 hours. The reaction mixture was extracted with ethyl acetate and water, and the organic layer was concentrated under reduced pressure. The residue was purified by column chromatography using hexane as eluent to obtain 17.3 g (89.5) of the compound represented by the formula 6-a.
Reference：
[1] Journal of the American Chemical Society, 2003, vol. 125, # 20, p. 6058 - 6059
[2] Bulletin of the Chemical Society of Japan, 2004, vol. 77, # 11, p. 2071 - 2080
[3] Angewandte Chemie - International Edition, 2018, vol. 57, # 36, p. 11688 - 11691[4] Angew. Chem., 2018, vol. 130, # 36, p. 11862 - 11865,4
[5] European Journal of Organic Chemistry, 1999, # 9, p. 2079 - 2085
[6] Patent: WO2016/29439, 2016, A1, . Location in patent: Page/Page column 11
[7] Patent: WO2007/105917, 2007, A1, . Location in patent: Page/Page column 18
[8] Patent: WO2007/108666, 2007, A1, . Location in patent: Page/Page column 34
[9] Patent: WO2007/123339, 2007, A1, . Location in patent: Page/Page column 20
[10] Journal of Heterocyclic Chemistry, 2003, vol. 40, # 5, p. 845 - 850
[11] Patent: KR101791161, 2017, B1, . Location in patent: Paragraph 0372-0378
[12] Tetrahedron, 2003, vol. 59, # 20, p. 3593 - 3601
[13] Journal of the American Chemical Society, 2017, vol. 139, # 36, p. 12386 - 12389
[14] Chemistry - A European Journal, 2015, vol. 21, # 50, p. 18128 - 18137
[15] Molecular Crystals and Liquid Crystals, 2009, vol. 513, p. 163 - 178
[16] Doklady Chemistry, 1966, vol. 168, p. 541 - 542[17] Doklady Akademii Nauk SSSR, 1966, vol. 168, # 3, p. 613 - 614
[18] Journal of Organic Chemistry, 1990, vol. 55, # 4, p. 1311 - 1321
[19] Journal of Organic Chemistry, 1981, vol. 46, # 7, p. 1243 - 1247
[20] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1988, p. 697 - 700
[21] Journal of Labelled Compounds and Radiopharmaceuticals, 1994, vol. 34, # 3, p. 213 - 220
[22] Journal of Organometallic Chemistry, 1987, vol. 319, p. 29 - 40
[23] Journal of the American Chemical Society, 1994, vol. 116, # 26, p. 11723 - 11736
[24] Synthetic Communications, 1995, vol. 25, # 17, p. 2599 - 2612
[25] Journal of Organic Chemistry, 1996, vol. 61, # 20, p. 6906 - 6921
[26] Macromolecules, 2005, vol. 38, # 20, p. 8327 - 8332
[27] Journal of the American Chemical Society, 2006, vol. 128, # 46, p. 14845 - 14853
[28] Journal of Organometallic Chemistry, 2010, vol. 695, # 21, p. 2329 - 2337
[29] Journal of Organometallic Chemistry, 2013, vol. 735, p. 58 - 64
[30] European Journal of Inorganic Chemistry, 2013, # 13, p. 2368 - 2381
[31] Journal of Porphyrins and Phthalocyanines, 2014, vol. 18, # 3, p. 209 - 220
[32] Journal of Organometallic Chemistry, 2014, vol. 772, p. 79 - 83
5
[ 75-77-4 ]
[ 589-87-7 ]
[ 6999-03-7 ]
Reference：
[1] Journal of Organic Chemistry, 2000, vol. 65, # 13, p. 3885 - 3893
[2] Journal of Organic Chemistry, 1986, vol. 51, # 21, p. 3996 - 4000
[3] Journal of Organometallic Chemistry, 1985, vol. 284, p. C33 - C35
[4] Applied Organometallic Chemistry, 2016, vol. 30, # 11, p. 905 - 910
6
[ 75-77-4 ]
[ 60-29-7 ]
[ 106-37-6 ]
[ 6999-03-7 ]
Yield
Reaction Conditions
Operation in experiment
92%
With n-butyllithium; magnesium sulfate In water
(3) Synthesis of (4-Bromo-phenyl)-trimethyl-silane First, a dropping funnel is provided at the 3-necks-r.b.f. and the round-floor flask is dried under decompression. 1,4-Dibromobenzene (12.7 g, 0.053 mol) and the dried diethylether (300 mL) are dissolved in the round-floor flask. A dryice bath is provided at the round-floor flask, n-BuLi (33.58 mL, 0.0537 mol) is put into the dropping funnel and n-BuLi is slowly dropped, and a temperature is slowly raised from -78° C. to 0° C. Next, chloro trimethylsilane (7.51 mL, 0.059 mol) is slowly dropped at 0° C. and then the temperature is raised again to the normal temperature for over a period of one hour. When the reaction is finished, sediment is extracted by using diethylether and water is removed from the result by using MgSO4. And then, after solvent is removed from the result, when the solvent is fractionally distilled under decompression, (4-Bromo-phenyl)-trimethyl-silane (11.3 g, 92percent) is obtained.
Reference：
[1] Patent: US2010/155714, 2010, A1,
7
[ 106-37-6 ]
[ 6999-03-7 ]
Yield
Reaction Conditions
Operation in experiment
1 mole, 47%
With n-butyllithium; chloro-trimethyl-silane; triethylamine In tetrahydrofuran; methanol; dichloromethane; water
5(a): Synthesis of 4-trimethylsilyl-1-bromobenzene 1,4-Dibromobenzene (500 g, 2.12 moles) was dissolved in THF (3.5 L) in a four-neck round-bottom flask. The flask was cooled to -78° C., and then 1.6M n-BuLi (1,600 ml, 2.56, moles) was rapidly added dropwise thereto. At the same temperature, the mixture was allowed to react for 2 hours. Thereafter, chlorotrimethylsilane (362 ml, 2.86 moles) was slowly added dropwise to the reaction mixture. The resulting mixture was reacted for 5 hours while warming to room temperature. After completion of the reaction, a mixture of triethylamine (100 ml) and methanol (200 ml) was added to the reaction mixture. The resulting mixture was stirred for one hour to obtain a crystal. The crystal was filtered, and then the filtrate was concentrated under reduced pressure at 60° C. to obtain a crystal. The crystal was filtered off and the filtrate was diluted with dichloromethane. The dichloromethane solution was subjected to phase separation using water. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure at 60° C. The concentrate in the form of liquid organic matter was distilled to yield 230 g (1 mole, 47percent) of the pure title product.
Reference：
[1] Journal of the American Chemical Society, 1954, vol. 76, p. 3219
[2] Patent: US2008/203905, 2008, A1,
8
[ 75-77-4 ]
[ 22480-64-4 ]
[ 6999-03-7 ]
Reference：
[1] Journal of Organometallic Chemistry, 1995, vol. 496, # 1, p. 117 - 126
[2] Patent: WO2008/133459, 2008, A1, . Location in patent: Page/Page column 55
9
[ 75-77-4 ]
[ 18620-02-5 ]
[ 6999-03-7 ]
Reference：
[1] Journal of the American Chemical Society, 1946, vol. 68, p. 2103
[2] Journal of the American Chemical Society, 1951, vol. 73, p. 5817
[3] , Gmelin Handbook: Si: MVol.C, 22, page 68 - 71,
[4] Journal of the American Chemical Society, 1946, vol. 68, p. 2103
[5] Chemistry Letters, 2011, vol. 40, # 9, p. 1050 - 1052
10
[ 18164-08-4 ]
[ 6999-03-7 ]
Reference：
[1] Collection of Czechoslovak Chemical Communications, [2] Collection of Czechoslovak Chemical Communications, 1951, vol. 16, p. 580 - 590
[3] , Gmelin Handbook: Si: MVol.C, 22, page 68 - 71,
11
[ 75-77-4 ]
[ 106-37-6 ]
[ 13183-70-5 ]
[ 6999-03-7 ]
Reference：
[1] Journal of Organic Chemistry, 2002, vol. 67, # 15, p. 5327 - 5332
12
[ 18164-08-4 ]
[ 676-58-4 ]
[ 6999-03-7 ]
Reference：
[1] Collection of Czechoslovak Chemical Communications, 1951, vol. 16/17, p. 580,582,585
13
[ 6999-03-7 ]
[ 68-12-2 ]
[ 2199-32-8 ]
Yield
Reaction Conditions
Operation in experiment
100%
Stage #1: With n-butyllithium In tetrahydrofuran; hexane; N,N-dimethyl-formamide at -78 - -70℃; for 0.25 h; Stage #2: at -78 - -68℃; for 0.25 h;
Bromo-4-(trimethylsilyl)benzene (1.15 g, 5 mmol) was dissolved in THF (30 ml) and cooled to -78° C. Under argon a 1.6 M solution of n-butyl lithium in hexane (3.13 ml, 5 mmol) was added dropwise keeping the temperature below -70° C. The clear colorless solution was stirred at -78° C. for 15 min and DMF (1.156 ml, 15 mmol) was added quickly. The reaction temperature increased to -68° C. The reaction was stirred for additional 15 min at -78° C., quenched with 1N aqueous hydrogen chloride solution and extracted twice with diethyl ether. The combined organic layers were washed twice with water and once with saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered and the solvent was evaporated to leave the product as a colorless oil (920 mg, 100percent). The product was pure enough to be used directly in the next step. MS (ISP) 179.2 (M+H+). 1H NMR (CDCl3, 300 MHz): δ 10.02 (s, 1H) 7.84 (d, 2H), 7.69 (d, 2H), 0.31 (s, 9H).
Reference：
[1] Patent: US2007/185058, 2007, A1, . Location in patent: Page/Page column 9
[2] Dyes and Pigments, 2017, vol. 141, p. 128 - 136
[3] Macromolecules, 2003, vol. 36, # 18, p. 6807 - 6816
[4] Tetrahedron, 2003, vol. 59, # 20, p. 3593 - 3601
[5] Organic Letters, 2010, vol. 12, # 21, p. 4728 - 4731
[6] Journal of Organometallic Chemistry, 1995, vol. 496, # 1, p. 117 - 126
[7] Dalton Transactions, 2014, vol. 43, # 21, p. 7868 - 7888
[8] Journal of Porphyrins and Phthalocyanines, 2014, vol. 18, # 3, p. 209 - 220
14
[ 6999-03-7 ]
[ 2199-32-8 ]
Yield
Reaction Conditions
Operation in experiment
100%
Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -78 - -70℃; for 0.25 h; Stage #2: at -78 - -68℃; for 0.25 h;
1-Bromo-4-(trimethylsilyl)benzene (1.15g, 5 mmol) was dissolved in THF (30 ml) and cooled to -78° C. Under argon a 1.6 M solution of n-butyl lithium in hexane (3.13 ml, 5 mmol) was added dropwise keeping the temperature below -70° C. The clear colorless solution was stirred at -78° C. for 15 min and DMF (1.16ml, 15 mmol) was added quickly. The reaction temperature raised to -68° C. The reaction was stirred for additional 15 min at -78° C., quenched with 1N aq. HCl solution and extracted twice with diethyl ether. The combined organic layers were washed twice with water and once with sat. aq. NaCl solution, dried over sodium sulfate, filtered and the solvent was evaporated to yield 4' trimethylsilanyl-benzaldehyde (920 mg, 100percent) as a colorless oil. The product was pure enough to be used directly in the next step. MS (ISP): 179.2 (M+H)+. 1H NMR (CDCl3, 300 MHz): δ 10.02 (s, 1H) 7.84 (d, 2H), 7.69 (d, 2H), 0.31 (s, 9H).
Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1.5 h; Inert atmosphere Stage #2: With Trimethyl borate In tetrahydrofuran; hexane at -78 - 20℃; Stage #3: With water In tetrahydrofuran; hexane; ethyl acetate
l-Bromo-4-(trimethylsilyl)benzene (25 g, 0.10 mol) was added to a 1-bulb flask and an argon atmosphere was established. After adding tetrahydrofuran (500 mL), the mixture was stirred at -78 0C for 10 minutes. After adding n-BuLi (2.5 M in hexane, 43.6 mL, 0.10 mol) dropwise, the mixture was stirred for 1 hour and 30 minutes at -78 0C. Then, trimethyl borate (13.6 mL, 0.11 mol) was added at -78 0C. After stirring for 30 minutes at -78 0C, the mixture was stirred at room temperature for 4 hours. After the reaction was completed, extraction was performed using distilled water and EA. The organic layer was dried with MgSO4 and the solvent was removed using a rotary evaporator. Pure Compound A (18 g, 85percent) was separated by column chromatography using hexane and EA as an eluent.
Reference：
[1] Patent: WO2010/140801, 2010, A1, . Location in patent: Page/Page column 18
[2] Macromolecules, 2003, vol. 36, # 7, p. 2327 - 2332
[3] Organic and Biomolecular Chemistry, 2003, vol. 1, # 9, p. 1609 - 1624
Stage #1: 1.4-dibromobenzene With n-butyllithium In diethyl ether; hexane at -78℃; for 4h;
Stage #2: chloro-trimethyl-silane In diethyl ether; hexane at -78 - 20℃; for 2.16667h;
100%
Stage #1: 1.4-dibromobenzene With n-butyllithium In diethyl ether; hexane at -78℃; for 0.25h; Inert atmosphere;
Stage #2: chloro-trimethyl-silane In diethyl ether; hexane at 20℃; for 2h; Inert atmosphere;
100%
Stage #1: 1.4-dibromobenzene With n-butyllithium In diethyl ether at -78℃; for 4h; Inert atmosphere; Schlenk technique;
Stage #2: chloro-trimethyl-silane In diethyl ether at -78 - 20℃; Inert atmosphere; Schlenk technique;
98%
With n-butyllithium In diethyl ether; hexane at 20℃; for 1h;
96%
Stage #1: 1.4-dibromobenzene With n-butyllithium In tetrahydrofuran; diethyl ether at -78℃;
Stage #2: chloro-trimethyl-silane In diethyl ether at -78℃;
1 Synthesis of photoinitiator PI-1
The photoinitiator PI-1 was synthesized according to Scheme 1 as shown below. In a 500 mL flask equipped with a thermometer, cooling device and dropping funnel, 1 ,4-dibromobenzene (23.6 g , 100 mmol) in 200 mL of Et.20 was treated with n-BuLi (41.7 mL, 2.4 M in THF) at -78 °C, and then the reaction was quenched with TMSCI (5.2 mL, 40 mmol) at -78 °C, and IM-1 (22 g, 96% yield) was obtained as oil.
93%
Stage #1: 1.4-dibromobenzene With n-butyllithium In tetrahydrofuran; pentane at -78 - 0℃; for 1h;
Stage #2: chloro-trimethyl-silane In tetrahydrofuran; pentane at 0 - 20℃; for 1h;
6
[Preparative Example 6] Preparation of Compound F[74] Dibromobenzene (20 g, 84.78 mmol) was dissolved in dry tetrahydrofuran (THF,200 mL) at room temperature under a nitrogen atmosphere. The solution was cooled to -78°C. n-butyl lithium (34 mL, 2.5 M pentane solution) was added slowly to the solution at -78°C, and the temperature of the mixture was slowly raised to 0°C for about 1 hour. To the mixture, chlorotrimethylsilane (13 ml, 101.74 mmol) was added, and the temperature of the mixture was raised to normal temperature over 1 hour. After confirmation of completion of the reaction, the mixture was extracted from ethyl acetate, dried over magnesium sulfate, and distilled off under reduced pressure to obtain Compound F (18 g, 93%).[75] MS (M+) = 229
93%
Stage #1: 1.4-dibromobenzene With n-butyllithium In tetrahydrofuran; pentane at -78 - 0℃; for 1h;
Stage #2: chloro-trimethyl-silane In tetrahydrofuran; pentane at 0 - 20℃; for 1h;
4
Preparation Example 4: Preparation of compound D. Dibromobenzene (20 g, 84.78 mmol) was dissolved in anhydroustetrahydrofuran (THF, 200 mL) at room temperature under nitrogenatmosphere. The solution was cooled to -78°C . n-butyl lithium (34 mL,2.5 M pentane solution) was added slowly to the solution at -78°C, andthe temperature of the mixture was slowly raised to 0°C for about 1 hour.To the mixture, chlorotrimethylsilane (13 ml, 101.74 mmol) was added, andthe temperature of the mixture was raised to room temperature over 1 hour.After confirmation of completion of the reaction, the mixture wasextracted from ethyl acetate, dried over magnesium sulfate, and distilledoff under reduced pressure to obtain a compound D (18 g, 93%). MS (M+)= 229.
93%
Stage #1: 1.4-dibromobenzene With n-butyllithium In tetrahydrofuran; pentane at -78 - 0℃; for 1h;
Stage #2: chloro-trimethyl-silane In tetrahydrofuran; pentane at 0 - 20℃; for 1h;
11
Dibromobenzene (20 g, 84.78 mmol) was dissolved in anhydrous tetrahydrofuran(THF, 200 mL) at room temperature under nitrogen atmosphere. The solution was cooled to -78°C. N-butyllithium (34 mL, 2.5 M pentane solution) was added slowly to the solution at -78°C, and the temperature of the mixture was slowly raised to 0°C for about 1 hour. To the mixture, chlorotrimethylsilane (13 ml, 101.74 mmol) was added, and the temperature of the mixture was raised to room temperature over 1 hour. After confirmation of completion of the reaction, the mixture was extracted from ethyl acetate, dried over magnesium sulfate, and distilled off under reduced pressure to obtain a compound K (18 g, 93%).[87] MS [M] = 229
90%
Stage #1: 1.4-dibromobenzene With n-butyllithium In diethyl ether at -10℃; for 1h;
Stage #2: chloro-trimethyl-silane In diethyl ether at -10 - 20℃; for 1h;
89.5%
Stage #1: 1.4-dibromobenzene With n-butyllithium In tetrahydrofuran at -78℃; for 1h;
Stage #2: chloro-trimethyl-silane In tetrahydrofuran at 20℃; for 12h;
6.1 1) Synthesis of Compound Represented by Formula 6-a
20.0 g (0.0848 mol) of 1,4-dibromobenzene and 200 mL of tetrahydrofuran were added to a 500 mL round bottom flask, and 28.2 g (0.1017 mol) of n-butyllithium was slowly added thereto at -78 ° C and stirred at the same temperature for 1 hour Then, 11.0 g (0.1017 mol) of trichloromethylsilane was added and stirred at room temperature for 12 hours. The reaction mixture was extracted with ethyl acetate and water, and the organic layer was concentrated under reduced pressure. The residue was purified by column chromatography using hexane as eluent to obtain 17.3 g (89.5) of the compound represented by the formula 6-a.
88%
Stage #1: 1.4-dibromobenzene With n-butyllithium In diethyl ether; hexane at -78℃; for 0.5h;
Stage #2: chloro-trimethyl-silane In diethyl ether; hexane at -78 - 20℃; for 1.5h;
87%
Stage #1: 1.4-dibromobenzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; Inert atmosphere; Schlenk technique;
Stage #2: chloro-trimethyl-silane In tetrahydrofuran; hexane at -78 - 20℃; for 18h; Inert atmosphere; Schlenk technique;
74.7%
Stage #1: 1.4-dibromobenzene With n-butyllithium In tetrahydrofuran at -78℃; Schlenk technique;
Stage #2: chloro-trimethyl-silane In tetrahydrofuran at 20℃;
1.1 Preparation of p-trimethylsilyl bromobenzene:
Weigh 2.9 g of p-dibromobenzene into a Schlenk reaction flask, add 100 ml of anhydrous THF to dissolve it, and slowly add 5 ml of n-BuLi (2.5M) after stirring at -78 ° C.After the dropwise addition, continue to stir at -78 ° C.Subsequently, 1.8 ml of trimethylchlorosilane was added dropwise.The temperature was gradually raised to room temperature. After adding saturated NH4Cl solution, it was extracted with ethyl acetate (30mL × 3)Combine the organic phases and wash with saturated sodium chloride solution.Dry over anhydrous sodium sulfate. The solvent was removed under reduced pressure and purified by column chromatography.The title compound was obtained as a colorless oil with a yield of 74.7%.
70%
Stage #1: 1.4-dibromobenzene With n-butyllithium In hexane; tert-butyl methyl ether at 0℃; for 0.25h; Inert atmosphere;
Stage #2: chloro-trimethyl-silane at 25℃; for 1.5h; Inert atmosphere;
64.7%
Stage #1: 1.4-dibromobenzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2h; Inert atmosphere; Schlenk technique;
Stage #2: chloro-trimethyl-silane In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere; Schlenk technique;
4.1.1. Synthesis of (4-bromophenyl)trimethylsilane 2
1,4-dibromobenzene (1) (12.5 mmol) was dissolved with anhydroustetrahydrofuran (100 mL) in pre-dried Schlenk tube (charged withArgon) and cooled to -78 °C, then n-BuLi (2.5 M in hexane, 5 mL,12.5 mmol) was added dropwise. The solution was stirred at -78 °C for2 h, then chlorotrimethylsilane (15 mmol) was added and the reactionwas allowed to warm to room temperature gradually. Saturated NH4Clsolution was added and the residue was taken up in ether twice. Thecombined organic layer was washed with brine and dried with Na2SO4,filtered and concentrated under reduced pressure. After column chromatographythe target compound was obtained. Yield 64.7%, colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.48 (d, J = 8.2 Hz, 2H), 7.37 (d,J = 8.3 Hz, 2H), 0.25 (s, 9H) ppm.
54%
Stage #1: 1.4-dibromobenzene With n-butyllithium In diethyl ether; hexane at 0℃; Inert atmosphere;
Stage #2: chloro-trimethyl-silane In diethyl ether; hexane at 0℃; Inert atmosphere;
(i) nBuLi, (ii) /BRN= 1209232/; Multistep reaction;
With n-butyllithium 1.) THF, hexane, -78 deg C, 1.5 h, 2.) THF, hexane, from -78 deg C to RT, 1 h; Yield given. Multistep reaction;
With n-butyllithium 1.) t-BuOMe, hexane, from 5 deg C to 10 deg C, 15 min, 2.) t-BuOMe, hexane, from 20 deg C to 22 deg C, 1.5 h; Yield given. Multistep reaction;
Stage #1: 1.4-dibromobenzene With n-butyllithium In diethyl ether; hexane for 0.5h;
Stage #2: chloro-trimethyl-silane In diethyl ether; hexane for 0.5h; Further stages.;
Stage #1: 1.4-dibromobenzene With n-butyllithium In hexanes; diethyl ether at -78℃; Inert atmosphere;
Stage #2: chloro-trimethyl-silane In hexanes; diethyl ether at -78 - 20℃;
Stage #1: 1.4-dibromobenzene With n-butyllithium In diethyl ether at -78℃; for 1h; Inert atmosphere;
Stage #2: chloro-trimethyl-silane In diethyl ether at -78 - 20℃; Inert atmosphere;
Synthesis of (4-bromophenyl)silane (4a-f) and (3-bromophenyl)silane (5a-c)
General procedure: (4-Bromophenyl)silane (4a-f) and (3-bromophenyl)silane (5a-c) were synthesized as our previous reports [44]. The typical synthetic procedure for the bromophenylsilanes is mentioned below. 1,4-Dibromobenzene or 1,3-dibromobenzene (1 equiv) was dissolved in dry Et2O and cooled to 78 °C under argon. n-BuLi (1.05 equiv) was added into this solution dropwise and stirred for another 1 h at 78 °C. Chlorosilane (chlorotrimethylsilane: 1 equiv; dichlorodimethylsilane or dichlorodiphenylsilane: 0.5 equiv; trichloromethylsilane or trichlorophenylsilane: 0.33 equiv; tetrachlorosilane: 0.25 equiv) was then added dropwise at this temperature. After the end of the addition, the reaction mixture was slowly raised to room temperature and stirred overnight. Then the reaction was quenched by H2O and the organic layer was separated. The water layer was washed twice by Et2O. The organic layers were combined, washed by brine, dried over anhydrous MgSO4 and then filtered. Removal of the solvents under vacuum gave the crude product and the pure products were obtained by column chromatography or recrystallization. The physical and spectroscopic data of 4aef were shown in our previous report [44].
Stage #1: 1.4-dibromobenzene With n-butyllithium In diethyl ether; hexane at -78℃; for 0.25h; Inert atmosphere; Schlenk technique;
Stage #2: chloro-trimethyl-silane In diethyl ether; hexane at -78 - 20℃; for 4h; Inert atmosphere; Schlenk technique;
Stage #1: 1,4-bromoiodobenzene With tert.-butyl lithium In hexane; pentane at 0℃; for 1h;
Stage #2: chloro-trimethyl-silane In tetrahydrofuran; Petroleum ether at 20℃; Further stages.;
60%
With tetraethylammonium tosylate In N,N-dimethyl-formamide Ambient temperature; electrochemical reduction;
60%
With tetraethylammonium tosylate In N,N-dimethyl-formamide Ambient temperature; electrochemical reduction (H-type cell with Pt electrodes);
Stage #1: 1,4-bromoiodobenzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Schlenk technique; Inert atmosphere;
Stage #2: chloro-trimethyl-silane In tetrahydrofuran; hexane at -78 - 20℃; for 4h; Inert atmosphere; Schlenk technique;
With n-butyllithium 1.) THF, hexane, -78 deg C, 1 h, 2.) THF, hexane, a) -78 deg C, 15 min, b) from -78 deg C to RT; Yield given. Multistep reaction;
Stage #1: 1-bromo-4-(trimethylsilyl)benzene With n-butyllithium In tetrahydrofuran; hexanes at -78℃; for 0.25h;
Stage #2: carbon dioxide In tetrahydrofuran; hexanes at -78 - 20℃; for 1h;
Stage #3: With hydrogenchloride; water In ethyl acetate
1.F
4-(Trimethylsilyl)benzoic acid. A solution of 4-trimethylsilylphenylbromide (500 mg, 2.18 mmol) and THF (21.8 mL) was cooled to -78 0C and nBuLi (0.960 mL, 2.40 mmol, 2.5M in hexanes) was added dropwise. Fifteen minutes after the addition was complete an excess of crushed dry ice was added, the cold bath was removed, and the mixture stirred while warming for Ih. The reaction was concentrated and the residue partitioned between IM aq. HCl and EtOAc. The layers were separated and the aqueous layer was extracted with EtOAc twice. The combined organic layers were dried (MgSO4) and concentrated to afford the title compound as a white solid. 1H νMR (d6-DMSO, 600 MHz) δ 12.9 (br s, IH), 7.88 (d, J = 8.2 Hz, 2H), 7.62 (d, J = 7.9 Hz, 2H), 0.02 (s, 9H).
Stage #1: 1-bromo-4-(trimethylsilyl)benzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1.5h;
Stage #2: carbon dioxide In tetrahydrofuran; hexane at -78℃; for 0.416667h;
Stage #3: With hydrogenchloride In tetrahydrofuran; hexane; water; ethyl acetate
28
Example 28.; To l-bromo-4-(trimethylsilyl)-benzene (Aldrich) (6.42g, 28.04mmol) in a clean, dry 25OmL round-bottom flask was added THF (10OmL) and the mixture was cooled to -78 0C with stirring for 10 minutes under nitrogen. Then, a 2.5 M solution of n-butyllithium in hexanes (13.46mL, 1.2eq) was added slowly over about seven minutes. The resulting mixture was stirred at -780C for 1.5 hours (solution turned light yellow). Then, at -780C an excess of dry ice (4 large pieces) were added to the reaction mixture (solution turned color, then became clear) and the dry ice bath was removed and stirred for 15 minutes. TLC confirmed that the reaction was complete, and after stirring an additional 10 minutes at -780C, the reaction was quenched with water (10OmL). Ethyl acetate (500 mL) was then added and with stirring 4N HCl was added to pH = 2. The layers were separated and then washed the ethyl acetate layer with brine (1X250 mL) and finally the organic layer was dried over magnesium sulfate, filtered, concentrated and pumped to give 4- Trimethylsilanyl-benzoic acid as a white solid (5.49g).
284 mg
Stage #1: 1-bromo-4-(trimethylsilyl)benzene With magnesium; lithium chloride; zinc(II) chloride In tetrahydrofuran at 25℃; for 2h; Inert atmosphere;
Stage #2: carbon dioxide In tetrahydrofuran at 25℃; for 6h;
Stage #1: 1-bromo-4-(trimethylsilyl)benzene With n-butyllithium In tetrahydrofuran; hexane; N,N-dimethyl-formamide at -78 - -70℃; for 0.25h;
Stage #2: N,N-dimethyl-formamide In tetrahydrofuran; hexane at -78 - -68℃; for 0.25h;
S6.A
Bromo-4-(trimethylsilyl)benzene (1.15 g, 5 mmol) was dissolved in THF (30 ml) and cooled to -78° C. Under argon a 1.6 M solution of n-butyl lithium in hexane (3.13 ml, 5 mmol) was added dropwise keeping the temperature below -70° C. The clear colorless solution was stirred at -78° C. for 15 min and DMF (1.156 ml, 15 mmol) was added quickly. The reaction temperature increased to -68° C. The reaction was stirred for additional 15 min at -78° C., quenched with 1N aqueous hydrogen chloride solution and extracted twice with diethyl ether. The combined organic layers were washed twice with water and once with saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered and the solvent was evaporated to leave the product as a colorless oil (920 mg, 100%). The product was pure enough to be used directly in the next step. MS (ISP) 179.2 (M+H+). 1H NMR (CDCl3, 300 MHz): δ 10.02 (s, 1H) 7.84 (d, 2H), 7.69 (d, 2H), 0.31 (s, 9H).
93%
Stage #1: 1-bromo-4-(trimethylsilyl)benzene With n-butyllithium In tetrahydrofuran at -78℃;
Stage #2: N,N-dimethyl-formamide With hydrogenchloride
89%
Stage #1: 1-bromo-4-(trimethylsilyl)benzene With n-butyllithium In tetrahydrofuran at -76℃; for 0.5h;
Stage #2: N,N-dimethyl-formamide In tetrahydrofuran at -76 - -30℃; for 1h;
75%
Stage #1: 1-bromo-4-(trimethylsilyl)benzene With n-butyllithium In diethyl ether; hexane at 0 - 20℃; for 2h;
Stage #2: N,N-dimethyl-formamide In diethyl ether; hexane
Stage #3: With hydrogenchloride In diethyl ether; hexane; water
75%
Stage #1: 1-bromo-4-(trimethylsilyl)benzene With n-butyllithium In tetrahydrofuran at -78℃; for 0.25h; Inert atmosphere; Schlenk technique;
Stage #2: N,N-dimethyl-formamide In tetrahydrofuran at -78 - 20℃; Inert atmosphere; Schlenk technique;
52%
Stage #1: 1-bromo-4-(trimethylsilyl)benzene With n-butyllithium In tetrahydrofuran; hexane at -78℃;
Stage #2: N,N-dimethyl-formamide In tetrahydrofuran; hexane at -78 - 20℃; for 5h;
With hydrogenchloride; tert.-butyl lithium; triphenylphosphine;Zinc chloride; In tetrahydrofuran; pentane;
2,2',7,7'-Tetrakis(p-trimethylsilylphenyl)-9,9'-spirobifluorene (unoptimized). To a solution of 4-(trimethylsilyl)bromobenzene (1.88 g, 8.2 mmol) in ether (15 mL) was added at -78 C. t-butyllithium (10.1 mL, 17.2 mmol, 1.7M in pentane). The solution was stirred at -78 C. for 1 h and transferred via cannula into anhydrous zinc chloride (1.56 g, 11.5 mmol) in THF (10 mL) at room temperature. The resulting slurry was stirred for 1 h at room temperature and then transferred via cannula into tetrakis(triphenylphosphine)palladium(0) [made from tris(dibenzylideneacetone)bispalladium(0) chloroform complex (15 mg, 0.014 mmol), and triphenylphosphine (26 mg, 0.1 mmol) in THF (2 mL)] and <strong>[128055-74-3]2,2',7,7'-tetrabromo-9,9'-spirobifluorene</strong> (0.312 g. 0.5 mmol) in THF (5 mL). The solution was heated to 55 C. for 16 h and cooled to room temperature. The solution was poured into water and the aqueous layer was extracted with chloroform (3*5 mL). The combined organic layers were rinsed with 3N hydrochloric acid, and then water, before drying over magnesium sulfate. The solvent was removed in vacuo and the resulting solid was purified by flash chromatography on silica gel with hexane (4 column volumes) followed by 30:1 hexane:ether to aford 0.18 g (40%) of the title compound as a white solid. IR (KBr) 2954, 1598, 1464, 1385, 1248, 1112, 850, 808 cm-1. 1 H NMR (300 MHz, CDCl3)delta 7.91 (d, J=8.0 Hz, 4H), 7.61 (d, J=7.9 Hz, 4H), 7.45 (1/2ABq, J=8.3 Hz, 8H), 7.40 (1/2 ABq, J=8.8 Hz, 8H), 6.98 (s, 4H), 0.20 (s, 36 H).
Stage #1: 1-bromo-4-(trimethylsilyl)benzene With iodine; magnesium In tetrahydrofuran for 6h; Heating;
Stage #2: allyl bromide In tetrahydrofuran at 20℃; for 2h; Further stages.;
l-Bromo-4-(trimethylsilyl)benzene (25 g, 0.10 mol) was added to a 1-bulb flask and an argon atmosphere was established. After adding tetrahydrofuran (500 mL), the mixture was stirred at -78 0C for 10 minutes. After adding n-BuLi (2.5 M in hexane, 43.6 mL, 0.10 mol) dropwise, the mixture was stirred for 1 hour and 30 minutes at -78 0C. Then, trimethyl borate (13.6 mL, 0.11 mol) was added at -78 0C. After stirring for 30 minutes at -78 0C, the mixture was stirred at room temperature for 4 hours. After the reaction was completed, extraction was performed using distilled water and EA. The organic layer was dried with MgSO4 and the solvent was removed using a rotary evaporator. Pure Compound A (18 g, 85%) was separated by column chromatography using hexane and EA as an eluent.
With tri-tert-butyl phosphine; potassium <i>tert</i>-butylate; bis(dibenzylideneacetone)-palladium(0) In toluene at 60℃; for 2h; Inert atmosphere;
87%
With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; potassium <i>tert</i>-butylate In toluene at 80℃; for 0.15h; Inert atmosphere; Microwave irradiation;
82%
With bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate In toluene at 80℃; Inert atmosphere;
55%
With tris-(dibenzylideneacetone)dipalladium(0); potassium <i>tert</i>-butylate; tris-(o-tolyl)phosphine In toluene at 90℃; for 27h;
2-furyl [4-(trimethylsilyl)phenyl]methanol[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
92%
Stage #1: 1-bromo-4-(trimethylsilyl)benzene With TurboGrignard In tetrahydrofuran; 1,4-dioxane at 25℃; for 24h;
Stage #2: furfural In tetrahydrofuran; 1,4-dioxane at 0℃; for 0.0833333h;
With potassium carbonate In ethanol; water; toluene at 80℃; for 4h;
1.1; 17.1
A solution of dibenzofuran-4-yl-boronic acid (20.0 g, 94.3 mmol), (4-bromo-phenyl) -trimethyl-silane (21.62 g, 94.3 mmol), K2CO3 (39.1 g, 3 equiv. , 283 mmol) in toluene (100 mL), ethanol (60 mL) and water (30 mL) was purged with nitrogen for 5 min (bubbled into solution) and treated with Pd (PPH3) 4 (3.59 g, 2.9 mmol). After heating to 80 °C for 4 h, the solution was cooled to room temperature, poured into water (300 mL) and extracted with ethyl acetate (300 ML). The organic phase was washed with sat'd aq NACL, dried over anhydrous MGS04, filtered and concentrated in vacuo. Purification by flash column chromatography (5-20% ethyl acetate in heptane) afforded (4- dibenzofuran-4-yl-phenyl) -trimethyl-silane as a colorless oil (28.9 g, 96%).A solution of dibenzofuran-4-yl-boronic acid (20.0 g, 94.3 mmol), (4-bromo-phenyl)-trimethyl-silane (21. 62 G, 94.3 mmol), K2CO3 (39.1 g, 3 equiv. , 283 mmol) in toluene (100 mL), ethanol (60 mL) and water (30 mL) was purgged with nitrogen for 5 min (bubbled into solution) and treated with Pd (PPH3) 4 (3. 59 g, 2.9 mmol). After heating to 80 °C for 4 h, the solution was cooled to room temperature, poured into water (300 mL) and extracted with ethyl acetate (300 mL). The organic phase was washed with sat'd aq NaCl, dried over anhydrous MGSO4, filtered and concentrated in vacuo. Purification by flash column chromatography (5-20% ethyl acetate in heptane) afforded (4- dibenzofuran-4-yl-phenyl) -trimethyl-silane as a colorless oil (28.9 g, 96%).
96%
Stage #1: 4-dibenzofurylboronic acid; 1-bromo-4-(trimethylsilyl)benzene With potassium carbonate In ethanol; water; toluene for 0.0833333h;
Stage #2: In ethanol; water; toluene at 80℃; for 4h;
1.1; 17.1
Example 1. Preparation of 4-Dibenzofuran-4-yl-phenyl- boronic acid; Step 1: (4-Dibenzofuran-4-yl-phenyl) -trimethyl-silane; A solution of dibenzofuran-4-yl-boronic acid (20.0 g, 94.3 mmol), (4-bromo-phenyl) -trimethyl-silane (21.62 g, 94.3 mmol) , K2CO3 (39.1 g, 3 equiv., 283 mmol) in toluene (100 ϖiL) , ethanol (60 mL) and water (30 mL) was purged with nitrogen for 5 min (bubbled into solution) and treated with Pd (PPh3) 4 (3.59 g, 2.9 mmol) . After heating to 80 0C for 4 h, the solution was cooled to room temperature, poured into water (300 mL) and extracted with ethyl acetate (300 mL) . The organic phase was washed with sat'd aq NaCl, dried over anhydrous MgSO4, filtered and concentrated in vacuo. Purification by flash column chromatography (5-20% ethyl acetate in heptane) afforded (4- dibenzofuran-4-yl-phenyl) -trimethyl-silane as a colorless oil (28.9 g, 96%) .; Example 17 . ( 4-Dibenzofuran-4-yl-phenyl ) boronic acid; Step 1 : (4-Dibenzofuran-4-yl~phenyl) -trimethyl-silane; A solution of dibenzofuran-4-yl-boronic acid (20.0 g, 94.3 mmol) , (4-bromo-phenyl) -trimethyl-silane (21.62 g, 94.3 mmol) , K2CO3 (39.1 g, 3 equiv., 283 mmol) in toluene (100 inL) , ethanol (60 mL) and water (30 mL) was purgged with nitrogen for 5 min (bubbled into solution) and treated with Pd(PPh3) 4 (3.59 g, 2.9 mmol) . After heating to 80 0C for 4 h, the solution was cooled to room temperature, poured into water (300 mL) and extracted with ethyl acetate (300 mL) . The organic phase was washed with sat'd aq NaCl, dried over anhydrous MgSO4, filtered and concentrated in vacuo. Purification by flash column chromatography (5-20% ethyl acetate in heptane) afforded (4- dibenzofuran-4-yl-phenyl) -trimethyl-silane as a colorless oil (28.9 g, 96%) .
96%
With potassium carbonate In ethanol; water; toluene at 80℃; for 4h;
117.1
Example 117; 4-Dibenzofuran-4-yl-phenyl-boronic acid; Step 1; (4-Dibenzofuran-4-yl-phenyl) -trimethyl-silane; A solution of dibenzofuran-4-yl-boronic acid (20.0 g,94.3 mmol) , (4-bromo-phenyl) -trimethyl-silane (21.62 g, 94.3 itimol) , K2CO3 (39.1 g, 3 equiv. , 283 mmol) in toluene (100 mL) , ethanol (60 mL) and water (30 mL) was purged with nitrogen for 5 min (bubbled into solution) and treated with Pd(PPh3) 4 (3.59 g, 2.9 mmol) . After heating to 80 0C for 4 h, the solution was cooled to room temperature, poured into water (300 mL) and extracted with ethyl acetate (300 mL) . The organic phase was washed with sat'd aq NaCl, dried over anhydrous MgSO4, filtered and concentrated in vacuo. Purification by flash column chromatography (5-20% ethyl acetate in heptane) afforded (4- dibenzofuran-4-yl-phenyl) -trimethyl-silane as a colorless oil (28.9 g, 96%) .
96%
With potassium carbonate In ethanol; water; toluene at 80℃; for 4h;
4.1
A solution of dibenzofuran-4-yl-boronic acid (20.0 g, 94.3 mmol), (4-bromo-phenyl)-trimethyl-silane (21.62 G, 94.3 mmol), K2CO3 (39.1 g, 3 equiv. , 283 mmol) in toluene (100 mL), ethanol (60 mL) and water (30 mL) was purged with nitrogen for 5 min (bubbled into solution) and treated with Pd (PPH3) 4 (3. 59 g, 2.9 mmol). After heating to 80 °C for 4 h, the solution was cooled to room temperature, poured into water (300 mL) and extracted with ethyl acetate (300 mL). The organic phase was washed with sat'd aq NACL, dried over anhydrous MGSO4, filtered and concentrated in vacuo. Purification by flash column chromatography (5-20% ethyl acetate in heptane) afforded (4- dibenzofuran-4-yl-phenyl) -trimethylsilane as a colorless oil (28.9 g, 96%).
96%
With potassium carbonate In ethanol; water; toluene at 80℃; for 4.08333h;
4.1
A solution of dibenzofuran-4-yl-boronic acid (20.0 g, 94.3 mmol), (4-bromo-phenyl)-trimethyl-silane (21.62 g, 94.3 mmol), K2CO3 (39.1 g, 3 equiv., 283 mmol) in toluene (100 mL), ethanol (60 mL) and water (30 mL) was purged with nitrogen for 5 min (bubbled into solution) and treated with Pd(PPh3)4 (3.59 g, 2.9 mmol). After heating to 80° C. for 4 h, the solution was cooled to room temperature, poured into water (300 mL) and extracted with ethyl acetate (300 mL). The organic phase was washed with sat'd aq NaCl, dried over anhydrous MgSO4, filtered and concentrated in vacuo. Purification by flash column chromatography (5-20% ethyl acetate in heptane) afforded (4-dibenzofuran-4-yl-phenyl)-trimethylsilane as a colorless oil (28.9 g, 96%).
96%
With potassium carbonate In ethanol; water; toluene at 80℃; for 4h;
117.1
A solution of dibenzofuran-4-yl-boronic acid (20.0 g, 94.3 mmol), (4-bromo-phenyl) -trimethyl-silane (21.62 g, 94.3 mmol), K2CO3 (39.1 g, 3 equiv. , 283 mmol) in toluene (100 mL), ethanol (60 mL) and water (30 mL) was purged with nitrogen for 5 min (bubbled into solution) and treated with Pd (PPH3) 4 (3.59 G, 2.9 mmol). After heating to 80 °C for 4 h, the solution was cooled to room temperature, poured into water (300 mL) and extracted with ethyl acetate (300 mL). The organic phase was washed with sat'd aq NaCl, dried over anhydrous MGS04, filtered and concentrated in vacuo. Purification by flash column chromatography (5-20% ethyl acetate in heptane) afforded (4- dibenzofuran-4-yl-phenyl) -trimethyl-silane as a colorless oil (28.9 g, 96%).
Stage #1: 1-bromo-4-(trimethylsilyl)benzene With n-butyllithium In tetrahydrofuran; hexane at -78 - -70℃; for 0.25h;
Stage #2: In tetrahydrofuran; hexane at -78 - -68℃; for 0.25h;
1
1-Bromo-4-(trimethylsilyl)benzene (1.15g, 5 mmol) was dissolved in THF (30 ml) and cooled to -78° C. Under argon a 1.6 M solution of n-butyl lithium in hexane (3.13 ml, 5 mmol) was added dropwise keeping the temperature below -70° C. The clear colorless solution was stirred at -78° C. for 15 min and DMF (1.16ml, 15 mmol) was added quickly. The reaction temperature raised to -68° C. The reaction was stirred for additional 15 min at -78° C., quenched with 1N aq. HCl solution and extracted twice with diethyl ether. The combined organic layers were washed twice with water and once with sat. aq. NaCl solution, dried over sodium sulfate, filtered and the solvent was evaporated to yield 4' trimethylsilanyl-benzaldehyde (920 mg, 100%) as a colorless oil. The product was pure enough to be used directly in the next step. MS (ISP): 179.2 (M+H)+. 1H NMR (CDCl3, 300 MHz): δ 10.02 (s, 1H) 7.84 (d, 2H), 7.69 (d, 2H), 0.31 (s, 9H).
Stage #1: 1-bromo-4-(trimethylsilyl)benzene; aniline With sodium t-butanolate In toluene for 3h; Heating / reflux;
Stage #2: With water In tetrahydrofuran; toluene at 20℃;
18
Under nitrogen atmosphere, the compound Q (15 g, 65.45 mmol), aniline (6.6 ml, 72 mmol), Pd(dba) (0.125 g, 0.13 mmol), P(t-Bu) (0.04 g, 0.2 mmol) and sodium t - butoxide (1.8O g, 18.7 mmol) were added to toluene (200 mL), and refluxed for about 3 hrs. After completion of the reaction, the reaction mixture was cooled to room temperature, and added to a mixture of THF and H O. The organic layer was separated, dried over magnesium sulfate, and concentrated. The residue was purified by column chromatography to obtain a compound R (15 g, 86%). [158] MS: [M] = 143.
86%
With sodium t-butanolate In toluene for 3h; Heating / reflux;
7
[Preparative Example 7] Preparation of Compound G[77] Compound F (15 g, 65.45 mmol), aniline (6.6 ml, 72 mmol), pd(dba) (0.125 g,0.13 mmol), P(t-Bu) (0.04 g, 0.2 mmol) and sodium t-butoxide (1.80 g, 18.7 mmol) were added to toluene (200 mL), and the mixture was refluxed for about 3 hours. After completion of the reaction, the mixture was cooled to room temperature, and the reaction mixture was added to a mixed solution of THF and H O. The organic layer was subject to phase separation, dried over MgSO 4 , concentrated, and then separated by column chromatography to obtain Compound G (15 g, 86%). [78] MS [M] = 143
86%
With tri-tert-butyl phosphine; sodium t-butanolate In toluene for 3h; Heating / reflux;
5
Preparation Example 5: Preparation of compound E. The compound D (15 g, 65.45 mmol), aniline (6.6ml , 72 mmol), pd(dba)2(0.125 g, 0.13 mmol), PCt-Bu)3 (0.04 g, 0.2 mmol) and sodium t-butoxide (1.80 g, 18.7 mmol) were added to toluene (200 mL) under nitrogenatmosphere, and the mixture was refluxed for about 3 hours. Aftercompletion of the reaction, the mixture was cooled to room temperature,and the reaction mixture was added to a mixed solution of THF and H2O. Theorganic layer was separated, dried over magnesium sulfate, and thenconcentrated. The residue was separated by column chromatography toobtain a compound E (15 g, 86%). MS [M] = 143.
86%
With tri-tert-butyl phosphine; sodium t-butanolate In toluene for 3h; Heating / reflux;
12
The compound K (15 g, 65.45 mmol), aniline (6.6 ml, 72 mmol), pd(dba) (0.125 g,0.13 mmol), P(t-Bu) (0.04 g, 0.2 mmol), and sodium t-butoxide (1.80 g, 18.7 mmol) were added to toluene (200 mL), and the mixture was refluxed for about 3 hours. After completion of the reaction, the mixture was cooled to room temperature, and the reaction mixture was added to a mixed solution of THF and H O. The organic layer was separated, dried over MgSO 4 , and concentrated. The residue was separated by column chromatography to obtain a compound L (15 g, 86%). [90] MS [M] = 143
With sodium t-butanolate In toluene at 100℃; for 6h; Inert atmosphere;
1-1
In an argon stream, 1000 mL-recovery flask was charged with 27.5 g of 1-bromo-4-(trimethylsilyl)benzene, 33.5 g of aniline, 1.65 g of tris(dibenzylideneacetone)dipalladium (0), 2.24 g of 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, 23.0 g of sodium tert-butoxide and toluene. The resultant was allowed to react at 100°C for 6 hours. After cooling, the reaction solution was filtered through Celite, and the filtrate was concentrated. The concentrated filtrate was purified by silica gel chromatography (toluene/hexane (15/85)), and dried under reduced pressure, whereby 23.1 g of colorless, transparent liquid was obtained. As a result of the measurement by FD-MS (field desorption mass spectrometry), the compound was confirmed to be intermediate 1.
0.3 g
With tris-(dibenzylideneacetone)dipalladium(0); 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In toluene at 100℃; for 24h;
2.1 (1) Fabrication of 4-(trimethylsilyl)-N-phenylbenzeneamine
Aniline (127.5 m mol)), (4-bromophenyl)trimethylsilane (102 m mol)), tris(dibenzylideneaceton)dipalladium(O) (1.53 m mol)), BINAP(2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (3.06 m mol)), and sodium-tert-butoxide (132.6 m mol)) were dissolved in toluene (100 ml) in a 250 ml tri-neck-round bottom flask and then stirred in a bath of 100° C. for 24 hours. After the reaction was terminated, the toluene was removed from the solution. After extraction was performed on the solution using dichloromethane and water, the resulting solution was reduced in pressure and distilled. After a silica gel column chromatography, the solvent was reduced in pressure and distilled, thereby obtaining 4-(trimethylsilyl)-N-phenylbenzeneamine liquid having 0.3 g.
With tri-tert-butyl phosphine; sodium t-butanolate In toluene for 3h; Heating / reflux;
12
Preparation Example 12: Preparation of compound L- The compound D of Preparation Example 4 (15 g, 65.45 mmol),aniline-2,3,4,5,6-D5 (6.6 ml, 72 mmol), pd(dba)2 (0.125 g, 0.13 mmol),PCt-Bu)3 (0.04 g, 0.2 mmol) and sodium t-butoxide (1.80 g, 18.7 mmol) wereadded to toluene (80 mL) under nitrogen atmosphere, and the mixture wasrefluxed for about 3 hours. After completion of the reaction, the mixture was cooled to room temperature, and the reaction mixture was added to amixed solution of THF and H2O. The organic layer was separated, dried overmagnesium sulfate, and then concentrated. The residue was separated bycolumn chromatography to obtain a compound L (16 g, 85%). MS [M] = 246.
With piperidine; bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide at 80℃; for 11h; Inert atmosphere;
3 (1) Synthesis of trimethyl(4-((trimethylsilyl)ethynyl)phenyl)silane
(4-bromophenyl)trimethylsilane (2.0 g, 8.7 mmol), trimethylsilylacetylene (1.29 g, 13.1 mmol), copper iodide (I) (0.05 g, 0.26 mmol), bis (triphenylphosphine) palladium (II) dichloride (0.09 g, 0.13mmol), piperidine (10 mL) under a nitrogen atmosphere, the mixture was stirred at 80 11 hours. After cooling to room temperature, water was added, and the mixture was extracted with ethyl acetate to the reaction solution. The organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the solvent was evaporated under reduced pressure and the residue was purified by flash chromatography was purified (eluent n- heptane / ethyl acetate), the desired product (2.2 g, 100% yield) Obtained.
55%
With copper(l) iodide; diisopropylamine In 1,4-dioxane; hexane
1
Example 1Trimethyl{4-[(trimethylsilyl)ethynyl]phenyl}silane; Dichlorobis(benzonitrile)palladium(II) (88 mg, 0.23 mmol), copper(I) iodide (29 mg, 0.15 mmol), tri-tert-butylphosphine (0.9 g, 10 wt % solution in hexane, 0.459 mmol) and diisopropylamine (1.3 mL, 9.19 mmol) were dissolved in anhydrous dioxane (9 mL) under an atmosphere of argon. 1-Bromo-4-(trimethylsilyl)benzene (1.5 mL, 7.66 mmol) and (trimethylsilyl)acetylene (1.27 mL, 9.19 mmol) were added to the above solution and the reaction mixture was stirred overnight. The mixture was diluted with ethyl acetate (40 mL), filtered through a small pad of silica gel, concentrated and purified by column chromatography using n-heptane as the eluent, to give 1.03 g (55% yield) of the title compound: GC-MS (EI) m/z 246 [M]+.
With magnesium In tetrahydrofuran at 20℃; for 4.5h; Reflux; Inert atmosphere;
2
Magnesium (0.583 g, 24.0 mmol) was added to a solution of (4- bromophenyl)(trimethyl)silane (5 g, 20 mmol) and iodine (6 mg, 0.02 mmol) in tetrahydrofuran (40 ml_), and the reaction was stirred at room temperature for2 hours. The suspension was then heated to reflux for 2.5 hours, until almost all of the magnesium had been consumed. The solution was cooled to room temperature to provide a 0.5 M solution of the title compound in tetrahydrofuran.
With iodine; magnesium In tetrahydrofuran for 2h; Inert atmosphere; Reflux;
With magnesium; lithium chloride In tetrahydrofuran at 0 - 20℃; Inert atmosphere;
4 (4)
(4) Synthesis of (4-tert-Butyl-phenyl)-(4-trimethylsilanyl-phenyl)-amine 4-tert-Butyl-phenylamine (1.2 mL, 0.0076 mol), (4-Bromo-phenyl)-trimethyl-silane (1 g, 0.0044 mol), BINAP (0.03 g, 1% mol), Pd(OAc)2(0.01 g, 1% mol) and NaOtBu (1.5 g, 0.016 mol) are dissolved into toluene (50 mL) in the 2-necks-r.b.f. so as to be refluxed for about 2 hours. When the reaction is finished, the 2-necks-r.b.f. is cooled and toluene, which is reaction solvent, is removed. Next, when the sediment is filtered, the white solid matter such as (4-tert-Butyl-phenyl)-(4-trimethylsilanyl-phenyl)-amine (1.12 g, 86%) is obtained.
72%
With tris-(dibenzylideneacetone)dipalladium(0); 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In toluene for 3h; Reflux;
3-(12) Synthesis Example 3-(12): Synthesis of Intermediate 3-l
To a 250 ml round-bottomed flask was added 1-bromo-4- (trimethylsilyl) benzene (8.0 g, 0.035 mol) 4-tert-Butylaniline (5.8 g, 0.039 mol),Tris (dibenzylideneacetone) dipalladium (0) (0.65 g, 0.0007 mol),Sodium tertiary butoxide (6.79 g, 0.0706 mol), 100 ml of 2,2'-bis (diphenylphosphino) -1,1'-binaphthalene (0.44 g, 0.0007 mol) toluene was added and the mixture was stirred under reflux for 3 hours.After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with ethyl acetate and water.The organic layer was separated, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.The reaction mixture was separated by column chromatography to obtain (7.5 g, 72%).
3 (3)
(3) Synthesis of (4-Bromo-phenyl)-trimethyl-silane First, a dropping funnel is provided at the 3-necks-r.b.f. and the round-floor flask is dried under decompression. 1,4-Dibromobenzene (12.7 g, 0.053 mol) and the dried diethylether (300 mL) are dissolved in the round-floor flask. A dryice bath is provided at the round-floor flask, n-BuLi (33.58 mL, 0.0537 mol) is put into the dropping funnel and n-BuLi is slowly dropped, and a temperature is slowly raised from -78° C. to 0° C. Next, chloro trimethylsilane (7.51 mL, 0.059 mol) is slowly dropped at 0° C. and then the temperature is raised again to the normal temperature for over a period of one hour. When the reaction is finished, sediment is extracted by using diethylether and water is removed from the result by using MgSO4. And then, after solvent is removed from the result, when the solvent is fractionally distilled under decompression, (4-Bromo-phenyl)-trimethyl-silane (11.3 g, 92%) is obtained.
With tetrakis(triphenylphosphine) palladium(0) In 1,4-dioxane at 100℃; for 2h; Inert atmosphere;
Bis(4-trimethylsilylphenyl)acetylene (6).
Tetrakis(triphenylphosphino) palladium(0) (0.608 g, 1.6 mol%), triphenylphosphine (20 mg, 0.23 mol%), 1-bromo-4-trimethylsilylbenzene1 (13.29 mL, 68.0 mmol, 2.05 eq.), 1 (20.1 g, 33.2 mmol) and p-dioxane (25 mL) were combined in a Schlenk flask and heated to 100 °C for 2 h. The volume of the solution was reduced to 20 mL, hexanes solvent (200 mL) was added, and the solution was heated to reflux for 5 minutes. A dark oil accumulated at the bottom of the flask, so the solution was decanted away from the oil. The solvent was allowed to evaporate, giving yellow crystals. These were recrystallized again from hot hexanes to give colorless crystals of 6 (5.42 g, 49%). m. p.: 134-137 °C. 1H NMR (CDCl3; 300.17 MHz): d 7.50 (s, 8 H), 0.27 (s, 18 H). 13C NMR (CDCl3; 75.486 MHz): d 142.3, 134.4 (C-H), 131.9 (C-H), 124.9, 91.2 (acetylene), 1.2 (Si(CH3)3). UV/Vis (toluene): lmax 313 nm (e = 53,300). HR-MS (EI): for C20H26Si2: calc’d: 322.1573; found: 322.1580.
With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; bis(eta3-allyl-mu-chloropalladium(II)); In 1,3,5-trimethyl-benzene; at 140℃;Inert atmosphere;
Weigh 37mg of allyl palladium chloride,123mg of 2-dicyclohexylphosphine-2 ', 6'-dimethoxybiphenyl,800 mg of <strong>[1071-36-9]sodium cyanoacetate</strong> was added to a two-necked bottle.After three times of argon ventilation, 1.15 g of p-trimethylsilyl bromide and 10 ml of mesitylene were added with a syringe, and the reaction was heated at 140 C after stirring at room temperature.At the end of the reaction, it was cooled to room temperature and purified by column chromatography to obtain a yellow oil with a yield of 73.2%.
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride In tetrahydrofuran Reflux; Inert atmosphere;
2.1.1. Synthesis of 1-trimethylsilyl-4-(3,7-dimethyloctyl)benzene (3)
In a 300-mL round bottom flask, 22 mL of a 1 M solution of 3,7-dimethyloctanyl-1-magnesiumbromide was added dropwise to a solution of 2.5 g (10.9 mmol) 1-bromo-4-trimethylsilylbenzene dissolved in 150 mL of dry THF and 250 mg [PdCl2(dppf)] catalyst. The resulting mixture was stirred under reflux in an inert atmosphere overnight. The reaction was quenched with methanol and the solvent removed under reduced pressure. Purification using column chromatography on silica gel with petroleum ether as the eluent afforded 2.8 g 1-trimethylsilyl-4-(3,7-dimethyloctyl) benzene as a colorless oil. Yield: 90%. 1H NMR (CDCl3) d (ppm) 7.46 (d, J = 8.4 Hz, 2H, ArH), 7.20 (d, J = 7.5 Hz, 2H, ArH), 2.71-2.52 (m, 2H, -CH2), 1.70-1.04 (m, 10H, -CH2, CH, CH2, CH2, CH2, CH), 0.95 (d, J = 6.0 Hz, 3H, CH3), 0.89 (d, J = 6.0 Hz, 6H, CH3), 0.28 (s, 9H, CH3). 13C NMR (CDCl3) d (ppm) 143.9, 137.0, 133.3, 127.8, 39.3, 38.8, 37.1, 33.5, 32.6, 27.9, 24.6, 22.7, 22.6, 19.6, -1.0. Mass data (TOF MS EI+): calculated for C19H34Si [M+] 290.24, found: 290.24. Compound was analyzed for C19H34Si (calculated C 78.54, H 11.79, Si 9.67%; found C 78.42, H 11.67, Si 9.65%). IR absorptions (KBr, cm-1): 2953 (s), 2925 (m), 2868 (w), 1716 (m), 1601 (w), 1462 (m), 1396 (w), 1364 (m), 1247 (s), 1218 (m), 1108 (s), 850 (s), 836 (s), 804 (m), 754 (m), 720 (w), 691 (w).
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride In tetrahydrofuran
Stage #1: 1-bromo-4-(trimethylsilyl)benzene With iodine; magnesium In tetrahydrofuran at 68℃; for 1.5h; Inert atmosphere;
Stage #2: tert-butyl 3-oxoazetidine-1-carboxylate In tetrahydrofuran at 0℃; for 3h; Inert atmosphere;
3 Preparation 3: tert-butyl 3-hydroxy-3-(4-(trimethylsilyl)phenyl)azetidine-1-carboxylate
A 2 L-3neck flask equipped with mechanical stirrer, thermocouple, addition funnel and nitrogen inlet was charged with (4-bromophenyl)trimethylsilane (80.4 g, 0.35 mol), THF (600 mL), Mg (8.5 g), and I2 (catalytic amount). The suspension was refluxed at 68° C. for 1.5 hours until all magnesium disappeared. The solution was cooled to 0° C. in ice-bath. Then, a solution of tert-butyl 3-oxoazetidine-1-carboxylate (Preparation 2, 30 g, 0.17 mol) in THF (200 mL) was added slowly via addition funnel. The solution was stirred at 0° C. for 3 hours. LC/MS indicated the formation of desired product. The reaction was quenched with brine at 0° C. The aqueous layer was extracted with EtOAc (2×800 mL). The combined organics were dried over sodium sulfate, filtered and concentrated to give the desired product (47.4 g, 84% yield). 1H NMR (CDCl3) δ 7.3 (d, 2H), 7.2 (d, 2H), 4.0 (d, 2 H), 3.9 (d, 2H), 2.9 (s, 1H), 1.2 (s, 9H), 0.0 (s, 9H).
84%
Stage #1: 1-bromo-4-(trimethylsilyl)benzene With iodine; magnesium In tetrahydrofuran at 68℃; for 1.5h; Inert atmosphere;
Stage #2: tert-butyl 3-oxoazetidine-1-carboxylate In tetrahydrofuran at 0℃; for 3h; Inert atmosphere;
3a Preparation 3a: tert-butyl 3-hydroxy-3-(4-(trimethylsilyl)phenyl)azetidine-1- carboxylate
2L-3neck flask equipped with mechanical stirrer, thermocouple, addition funnel and nitrogen inlet was charged with (4-bromophenyl)trimethylsilane (80.4 g, 0.35 mol), THF (600 ml_), Mg (8.5 g), and l2 (catalytic amount). The suspension was refluxed at 68°C for 1.5 hours until all magnesium disappeared. The solution was cooled to 0°C in an ice-bath. Then, a solution of tert-butyl 3- oxoazetidine-1-carboxylate (Preparation 2a, 30 g, 0.17 mol) in THF (200 mL) was added slowly via addition funnel. The solution was stirred at 0°C for 3 hours. LC/MS indicated the formation of desired product. The reaction was quenched with brine at 0°C. The aqueous layer was extracted with EtOAc (2 x 800 mL). The combined organics were dried over sodium sulfate, filtered and concentrated to give the desired product (47.4 g, 84% yield). 1H NMR (CDCI3) δ 7.3 (d, 2 H), 7.2 (d, 2 H), 4.0 (d, 2 H), 3.9 (d, 2 H), 2.9 (s, 1 H), 1.2 (s, 9 H), 0.0 (s, 9 H).
84%
Stage #1: 1-bromo-4-(trimethylsilyl)benzene With iodine; magnesium In tetrahydrofuran at 0 - 68℃; for 1.5h; Inert atmosphere; Cooling with ice;
Stage #2: tert-butyl 3-oxoazetidine-1-carboxylate In tetrahydrofuran at 0℃; for 3h;
3a Preparation 3a: tert-butyl 3-hydroxy-3-(4-(trimethylsilyl)phenylazetidine-1 - carboxylate; (3-hydroxy-3-(4-trimiethylsilyl)phenyl-azetidine-1 -carboxylic acid tert-butyl ester)
Preparation 3a: tert-butyl 3-hydroxy-3-(4-(trimethylsilyl)phenylazetidine-1 - carboxylate; (3-hydroxy-3-(4-trimiethylsilyl)phenyl-azetidine-1 -carboxylic acid tert-butyl ester) A 2L-3neck flask equipped with mechanical stirrer, thermocouple, addition funnel and nitrogen inlet was charged with (4-bromophenyl)trimethylsilane (80.4 g, 0.35 mol), THF (600 mL), Mg (8.5 g), and l2 (catalytic amount). The suspension was refluxed at 68°C for 1 .5 hours until all magnesium disappeared. The solution was cooled to 0°C in an ice-bath. Then, a solution of tert-butyl 3- oxoazetidine-1 -carboxylate (Preparation 2a, 30 g, 0.17 mol) in THF (200 mL) was added slowly via addition funnel. The solution was stirred at 0°C for 3 hours. LC/MS indicated the formation of desired product. The reaction was quenched with brine at 0°C. The aqueous layer was extracted with EtOAc (2 x 800 mL). The combined organics were dried over sodium sulfate, filtered and concentrated to give the desired product (47.4 g, 84% yield). H NMR (CDCI3) δ 7.3 (d, 2 H), 7.2 (d, 2 H), 4.0 (d, 2 H), 3.9 (d, 2 H), 2.9 (s, 1 H), 1 .2 (s, 9 H), 0.0 (s, 9 H).
Stage #1: 1-bromo-4-(trimethylsilyl)benzene With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Inert atmosphere;
Stage #2: trichlorovinylsilane In tetrahydrofuran at -78℃; for 1h;
Synthesis of tris(4-trimethylsilylphenyl)vinylsilane (3)
1.6 M solution of n-BuLi in hexane (24.5 mL, 0.039 mol) was added dropwise to solution of 4-trimethylsilylbromobenzene 2 (9 g, 0.039 mol) in absolute THF (90 mL) at 78 °C in argon under stirring. The reaction mixture was stirred at 78 °C for 1 h. A solution of trichlorovinylsilane (1.65 mL, 0.013 mol) in THF (5 mL) was added, and the mixture was stirred at 78 °C for 1 h. After allowing the reaction mixture to warm up to room temperature 150 mL of water was added under stirring. The aqueous layer was extracted twice with ethylacetate and washed by water. After drying over Na2SO4 the solvent was evaporated in vacuo to yield compound 3 as colorless solid. The product was purified by recrystallization from hexane. As a result 4.91 g of white powder with 75% yield was obtained. IR (KBr): 850, 1134, 1248, 1680, 1640, 3047 cm-1. 1H NMR(δd ppm, J Hz, CDCl3): 7.58 (broad singlet, 12H, ArH), 6.75 (dd, 2J 20.2, 3J 14.6, 1H, ]CH-trans), 6.36 (dd, 3J 14.6, 3J 3.6, 1H,SiCHe), 5.88 (dd, 2J 20.2, 3J 3.6, 1H, ]CH-cis), 0.33 (s, 27H, SiCH3). 13C NMR (d ppm, CDCl3): 141.85 (3C, CeSiMe3), 136.78 (1C,]CH2), 135.12 (6C, HCCSiMe3), 134.57 (3C, CSiAr2Vin), 133.77 (1C,SiCH]CH2), 132.64 (6C, HCCSiAr2Vin), 1.19 (9C, SiCH3). 29Si NMR ((dppm, CDCl3)): 4.0 (3Si, Me3Si), 17.7 (1Si, Ar3SiVin). Anal. Calc. (%)for C29H42Si4: C, 69.25; H, 8.42; Si, 22.34. Found: C, 69.19; H, 8.41; Si,22.40.
Stage #1: 1-bromo-4-(trimethylsilyl)benzene With n-butyllithium In diethyl ether; hexane at 0 - 20℃; for 2.5h;
Stage #2: antimony(III) chloride In diethyl ether; hexane at 0 - 20℃;
Synthesis of tris(4-trimethylsilylphenyl)stibane (1e)
To a solution of (4-Bromophenyl)trimethylsilane (2.29 g, 10.0 mmol) in ether (15 mL), BuLi (1.63 M in hexane, 6.3 mL, 10.3 mmol) was added using syringe through septum cap at 0 °C for 30 min, and the mixture was stirred for 1 h at 0 °C. After the mixture was raised gradually to room temperature, the stirring was continued for 1.5 h. To the reaction mixture a solution of antimony(III) chloride (684 mg, 3.0 mmol) in ether (8 mL) was added dropwise at 0 °C, and the resulting mixture was gradually raised to room temperature and stirred overnight. The reaction mixture was diluted with dichloromethane (20 mL), and quenched with water. The mixture was extracted with dichloromethane (20 mL). The combined extracts were washed with brine and dried over anhydrous magnesium sulfate. The dried organic layer was concentrated under reduced pressure. The residue was purified by recrystallization to give 1e (1.0 g, 59 % yield). Colorless prisms (mp 209-211 °C). 1H NMR (400 MHz, CDCl3) δ: 0.29 (27H, s), 7.48 (6H, d, J = 7.3 Hz), 7.51 (6H, d, J = 7.3 Hz). 13C NMR (100 MHz, CDCl3) δ: 1.20 (q), 133.63 (d), 135.53 (d), 138.98 (s), 140.76 (s). LRMS (EI) m/z: 568 (14), 533 (7), 480 (6), 417 (6), 346 (21), 283 (100), 270 (23), 207 (18). Anal. Calc. for C27H39SbSi: C, 56.93; H, 6.90. Found: C,56.53; H, 6.63.
dimethyl (1-(4-(trimethylsilyl)phenyl)vinyl)phosphonate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
87%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane at 90℃; for 3h; Inert atmosphere;
31 synthesis of 1-(4-trimethylsilylphenyl) vinyl dimethyl phosphonate
To a 10 mL reaction tube was added 64. Omg (i.e., 0.20 mml) of dimethyl acetyl phosphate p-toluenesulfonylhydrazone,(I.e., 0.50 mmol), and then weighed 11.5 mg (i.e., 5 mol% of Dimethyl acetyl phosphate p-MethylbenzenesulfonHydrazone) tetrakis (triphenylphosphine) palladium, and the reaction tube was sealed and the system was replaced To a nitrogen atmosphere, 1.5 mL of 4-dioxane was added followed by 72.9 mg (0.30 mmo 1)4-trimethylbaromobenzene,Reaction at 90 ° C for 3 hours. After the reaction, the mixture was filtered, washed with ethyl acetate and concentrated to give 1-(4-trimethylsilylphenyl) vinyl dimethyl phosphate by using a column eluting with petroleum ether: ethyl acetate in a 1: 1 by volume ratio Dimethyl phosphonate, The compound as a colorless liquid, 81% yield
81%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane at 90℃; for 3h; Inert atmosphere; Schlenk technique;
4,7-diphenyl-2-(4-(triphenylsilyl)phenyl)-1,10-phenanthroline[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
48%
Stage #1: 1-bromo-4-(trimethylsilyl)benzene With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; for 2h; Inert atmosphere;
Stage #2: bathophenanthroline In tetrahydrofuran; hexane for 24h; Reflux; Inert atmosphere;
2 2.2.1. Synthesis of 4,7-diphenyl-2-(4-(trimethylsilyl)phenyl)-1,10-phenanthro-line (Bath-1)
General procedure: BrPhSiMe3 (0.824 g, 3.6 mmol) was dissolved in 80 mL freshly distilled THF in a 200 mL flask under N2 at 78°C, then n-butyllithium (2.5 mL, 4.0 mmol, 1.6 M in hexane) was added dropwise in 1 h and stirred 1 h at room temperature. Bath (0.720 g,3.6 mmol) was added into the mixture which was then refluxed for 24 h and then quenched with water. The resulting mixture was extracted with CH2Cl2. The organic layer was stirred with the activated MnO2 (1.910 g) for 12 h and then dried over MgSO4. After removing the solvent, the residue was purified by column chromatography on silica gel using ethyl acetate/petroleum ether (v/v 1/3) as the eluent, which was then recrystallized from n-hexane and diethyl ether (v/v 1/1) to give a yellow solid. Yield: 0.829 g,48.0%. 1H NMR (CDCl3, 400 MHz, ppm): 9.718 (s, 1H), 8.714 (s, 2H),8.223 (s, 1H), 8.017 (s, 1H), 7.909 (d, 2H), 7.786 (d, 2H), 7.593 (m,10H), 0.331 (s, 9H). 13C NMR (CDCl3, 400 MHz, ppm): 157.04, 149.76,149.07, 148.36, 146.95, 146.80, 144.71, 140.01, 138.29, 138.01, 133.71,129.61, 128.56, 128.51, 128.38, 127.16, 126.72, 125.39, 123.86, 123.62,123.25, 121.17, 1.17. FT-IR (KBr, cm1): 3060, 2957, 2858, 1727,1540, 1249, 835, 702.
Stage #1: C8H15NO2 With n-butyllithium In tetrahydrofuran; hexane; toluene at -35 - -30℃; for 0.5h; Inert atmosphere;
Stage #2: 1-bromo-4-(trimethylsilyl)benzene With n-butyllithium In tetrahydrofuran; hexane; toluene at -30 - -5℃; Inert atmosphere;
1 Synthesis of photoinitiator PI-1
In a 100 mL flask equipped with a thermometer, cooling device and dropping funnel, 1 1 g B-1 was added to a solvent mixture of THF 2 mL and toluene 12 mL. The solution was degassed by vacuum/N2 purge. The mixture was cooled to -35 to -30°C, and n-BuLi (2.4 M in hexane, 2 mL, 4.8 mol) was added slowly over 0.5 h, keeping the temperature below -30°C. In another 100 mL flask equipped with a thermometer, cooling device and dropping funnel, (4-bromophenyl)trimethylsilane (1.0 g, 4.8 mmol) was dissolved in a solvent mixture of THF 2 mL and toluene 12 ml. and cooled to -35 °C. The solution was also degassed thoroughly. n-BuLi (2.4 M in hexane, 2 ml_, 4.8 mol) was added slowly to the cold solution, keeping the temperature below -30 °C. The amide-alkoxide solution was transferred into the aryllithium slurry over a 30 min period via cannula. The resulting solution was warmed to -15°C over 1 h and then to -5°C over 1 h period. The mixture was aged at -5°C until the reaction was complete as determined by TLC. The reaction was quenched by aqueous 2N hydrochloric acid with vigorous stirring. This affords 0.620 g (61 %) of IM-2 as colorless oil. Scale up also was achieved, and 24 g IM-2 was obtained totally.
With 1-hydroxy-1,2-benzodioxol-3-(1H)-one; camphor-10-sulfonic acid; [gold(I)Cl(1-(2,4,6-Me3C6H2)-3,5-di(2,6-Me2C6H3) 2-pyridylidene)]; In methanol; chloroform; at 65℃; for 18h;Inert atmosphere; Sealed tube;
General procedure: Triarylpyridylidene-gold complex AuCl(PyC) (6.4 mg, 10 mumol, 5 mol %), heteroarene (0.20 mmol), and aryl(trimethyl)silane (0.20 mmol), 2-iodosobenzoic acids (IBA) (53 mg, 0.20 mmol), (+)-10-camphorsulfonic acid (CSA) (47 mg, 0.20 mmol) and a stirring bar were placed in a screw test tube, and dry chloroform/methanol (1.0 mL/0.10 mL) was added under N2 atmosphere. The tube was sealed with a cap equipped with a Teflon-coated silicon rubber septum, and the mixture was stirred at 65 C for 18-48 h. The reaction was quenched by addition of excess saturated NaHCO3 aq, the aqueous layer was extracted with dichloromethane and the combined organic layers were dried over Na2SO4, filtrated, and concentrated under reduced pressure. The residue was purified by flash chromatography (FC) to afford the coupling product.
With 1-hydroxy-1,2-benzodioxol-3-(1H)-one; camphor-10-sulfonic acid; [gold(I)Cl(1-(2,4,6-Me3C6H2)-3,5-di(2,6-Me2C6H3) 2-pyridylidene)]; In methanol; chloroform; at 65℃; for 24h;Inert atmosphere; Sealed tube;
General procedure: Triarylpyridylidene-gold complex AuCl(PyC) (6.4 mg, 10 mumol, 5 mol %), heteroarene (0.20 mmol), and aryl(trimethyl)silane (0.20 mmol), 2-iodosobenzoic acids (IBA) (53 mg, 0.20 mmol), (+)-10-camphorsulfonic acid (CSA) (47 mg, 0.20 mmol) and a stirring bar were placed in a screw test tube, and dry chloroform/methanol (1.0 mL/0.10 mL) was added under N2 atmosphere. The tube was sealed with a cap equipped with a Teflon-coated silicon rubber septum, and the mixture was stirred at 65 C for 18-48 h. The reaction was quenched by addition of excess saturated NaHCO3 aq, the aqueous layer was extracted with dichloromethane and the combined organic layers were dried over Na2SO4, filtrated, and concentrated under reduced pressure. The residue was purified by flash chromatography (FC) to afford the coupling product.
With 1-hydroxy-1,2-benzodioxol-3-(1H)-one; camphor-10-sulfonic acid; [gold(I)Cl(1-(2,4,6-Me3C6H2)-3,5-di(2,6-Me2C6H3) 2-pyridylidene)]; In methanol; chloroform; at 65℃; for 48h;Inert atmosphere; Sealed tube;
General procedure: Triarylpyridylidene-gold complex AuCl(PyC) (6.4 mg, 10 mumol, 5 mol %), heteroarene (0.20 mmol), and aryl(trimethyl)silane (0.20 mmol), 2-iodosobenzoic acids (IBA) (53 mg, 0.20 mmol), (+)-10-camphorsulfonic acid (CSA) (47 mg, 0.20 mmol) and a stirring bar were placed in a screw test tube, and dry chloroform/methanol (1.0 mL/0.10 mL) was added under N2 atmosphere. The tube was sealed with a cap equipped with a Teflon-coated silicon rubber septum, and the mixture was stirred at 65 C for 18-48 h. The reaction was quenched by addition of excess saturated NaHCO3 aq, the aqueous layer was extracted with dichloromethane and the combined organic layers were dried over Na2SO4, filtrated, and concentrated under reduced pressure. The residue was purified by flash chromatography (FC) to afford the coupling product.
With 1-hydroxy-1,2-benzodioxol-3-(1H)-one; camphor-10-sulfonic acid; [gold(I)Cl(1-(2,4,6-Me3C6H2)-3,5-di(2,6-Me2C6H3) 2-pyridylidene)] In methanol; chloroform at 65℃; for 48h; Inert atmosphere; Sealed tube;
General procedure for triarylpyridylidene-gold-catalyzed oxidative C-H arylation of heteroarenes with arylsilanes
General procedure: Triarylpyridylidene-gold complex AuCl(PyC) (6.4 mg, 10 μmol, 5 mol %), heteroarene (0.20 mmol), and aryl(trimethyl)silane (0.20 mmol), 2-iodosobenzoic acids (IBA) (53 mg, 0.20 mmol), (+)-10-camphorsulfonic acid (CSA) (47 mg, 0.20 mmol) and a stirring bar were placed in a screw test tube, and dry chloroform/methanol (1.0 mL/0.10 mL) was added under N2 atmosphere. The tube was sealed with a cap equipped with a Teflon-coated silicon rubber septum, and the mixture was stirred at 65 °C for 18-48 h. The reaction was quenched by addition of excess saturated NaHCO3 aq, the aqueous layer was extracted with dichloromethane and the combined organic layers were dried over Na2SO4, filtrated, and concentrated under reduced pressure. The residue was purified by flash chromatography (FC) to afford the coupling product.
With 1-hydroxy-1,2-benzodioxol-3-(1H)-one; camphor-10-sulfonic acid; [gold(I)Cl(1-(2,4,6-Me3C6H2)-3,5-di(2,6-Me2C6H3) 2-pyridylidene)] In methanol; chloroform at 65℃; for 48h; Inert atmosphere; Sealed tube;
General procedure for triarylpyridylidene-gold-catalyzed oxidative C-H arylation of heteroarenes with arylsilanes
General procedure: Triarylpyridylidene-gold complex AuCl(PyC) (6.4 mg, 10 μmol, 5 mol %), heteroarene (0.20 mmol), and aryl(trimethyl)silane (0.20 mmol), 2-iodosobenzoic acids (IBA) (53 mg, 0.20 mmol), (+)-10-camphorsulfonic acid (CSA) (47 mg, 0.20 mmol) and a stirring bar were placed in a screw test tube, and dry chloroform/methanol (1.0 mL/0.10 mL) was added under N2 atmosphere. The tube was sealed with a cap equipped with a Teflon-coated silicon rubber septum, and the mixture was stirred at 65 °C for 18-48 h. The reaction was quenched by addition of excess saturated NaHCO3 aq, the aqueous layer was extracted with dichloromethane and the combined organic layers were dried over Na2SO4, filtrated, and concentrated under reduced pressure. The residue was purified by flash chromatography (FC) to afford the coupling product.
bicyclo(2.2.1)hept-5-ene-2,3-diyl-bis(diphenylphosphine oxide)[ No CAS ]
(7,10-bis(trimethylsilyl)-1,2,3,4,4a,12b-hexahydro-1,4-methanotriphenylene-2,3-diyl)bis(diphenylphosphineoxide)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
78%
With MeOSym-Phos; palladium diacetate; caesium carbonate In N,N-dimethyl-formamide at 105℃; for 72h; Inert atmosphere;
Typical procedure for the coupling reaction.
General procedure: Pd(OAc)2 (1.82 mg, 4% mol) and phosphine ligand (8% mol) were placed in a Schlenk tube under argon. Dry DCM was added (2 mL) andthe mixture was stirred for 15 minutes. After this time, solvent was evaporated off under the reduced pressure, reactor backfilled with argon, charged with NORPHOS-O2 (100 mg, 0.20mmol), 4-bromoarene (0.6 mmol), Cs2CO3 (0.6 mmol) and DMF. The reaction was carried out under the continuous stirring at 105 °C for 72 h. Then, the mixture was cooled down to RT. The solvent was evaporated and 20 mL of water was added. The products were extracted withDCM (3x20 mL). The combined organic phase was dried over MgSO4, filtered and evaporated. The product was purified by silica-gel column chromatography (Hexane/EtOAc/MeOH=5/3/0.1) and finally recrystallised from appropriate solvent mixture.
With tris-(dibenzylideneacetone)dipalladium(0); 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate; In toluene; for 12h;Reflux;
500mL 4-neckround bottom flask, 1bromo4methylgive silyl benzene (1bromo4trimethylsilylbenzene)12 g (0.052 mole) and6methylaniline7.1 g 2fluoro(0.058 mole) and Pd2 (dba) 31.0 g (0.001 mole) and sodium tbutoxide10.1 g (0.105 mole)and 0.7 g BINAP (0.001 mole) and the mixture, 200 mL of toluene were put into 12 sigan under reflux. To complete the reaction, and the organic layer was separated and the water layer was extracted twice with 100 mL toluene. Formed organiclayer was concentrated under reduced pressure. Intermediate 1d(11 g, 76.9%) was obtained as a column chromatography
With tris-(dibenzylideneacetone)dipalladium(0); 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In toluene for 12h; Reflux;
2-(2) Synthesis of intermediate 2-b
500mL 4neckround bottom flask was charged with intermediate 2-a 21.0 g (0.112 mole) and 4trimethylsilylbromobenzene24.7g (0.112 mole), Pd2 (dba) 32.3 g (0.003 mole) and sodium tbutoxide24.5 g ( 0.25 mole) and put into a 1.6 g BINAP (0.003mole), put into a 300 mL toluene was stirred under reflux for 12 hours. To complete the reaction, and the organic layer wasseparated and the water layer was extracted twice with 100 mL toluene. Formed organic layer was concentrated underreduced pressure. Column (27.1 g, 72.0%) intermediate 2-b by chromatography
With tris-(dibenzylideneacetone)dipalladium(0); 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In toluene for 12h; Reflux;
3-(2) Synthesis of intermediate 3b
500mL 4neckround bottom flask was charged with intermediate 3a26.6 g (0.112 mole) and 4trimethylsilylbromobenzene24.7g (0.112 mole), Pd2 (dba) 32.3 g (0.003 mole) and sodium tbutoxide24.5 g ( 0.25 mole) and put into a 1.6 g BINAP (0.003mole), put into a 300 mL toluene was stirred under reflux for 12 hours. To complete the reaction, and the organic layer wasseparated and the water layer was extracted twice with 100 mL toluene. Formed organic layer was concentrated underreduced pressure. To give the intermediate 3b(30.7 g, 71.0%) by column chromatography.
With tris-(dibenzylideneacetone)dipalladium(0); 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In toluene for 12h; Reflux;
7-(2) Synthesis of intermediate 7-b
500mL 4neckround bottom flask was charged with intermediate 7-a3 4.7 g (0.127 mole) and 4-trimethylsilylbromobenzene 29.1 g (0.127 mole), Pd2 (dba) 32.3 g (0.003 mole) and sodium tbutoxide24.5 g ( 0.25 mole) and put into a 1.6 g BINAP(0.003 mole), put into a 300 mL toluene was stirred under reflux for 12 hours. To complete the reaction, and the organic layerwas separated and the water layer was extracted twice with 100 mL toluene. Formed organic layer was concentrated underreduced pressure. Columns of intermediate 7bby chromatography to obtain (40.2 g, 75.0%).
With tris-(dibenzylideneacetone)dipalladium(0); 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In toluene for 12h; Reflux;
8-(1) Synthesis of the intermediate 8-a
500mL 4 neckround bottom flask was charged with 2-fluoroaniline15.0 g (0.135 mole) and 4-trimethylsilylbromobenzene29.1g (0.127 mole), Pd2 (dba) 32.3 g (0.003 mole) and sodium tbutoxide24.5 g (0.25 mole) and put into a 1.6 g BINAP (0.003mole), put into a 300 mL toluene was stirred under reflux for 12 hours. To complete the reaction, and the organic layer wasseparated and the water layer was extracted twice with 100 mL toluene. Formed organic layer was concentrated underreduced pressure. Intermediate a8(23.7 g, 70.0%) by column chromatography
With tris-(dibenzylideneacetone)dipalladium(0); 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In toluene for 12h; Reflux;
4-(1) Synthesis of intermediate 4-a
500mL 4-neckround bottom flask was added the intermediate 1-a 31.2 g (0.127 mole) and 4trimethylsilylbromobenzene 29.1 g(0.127 mole), Pd2 (dba) 32.3 g (0.003 mole) and sodium tbutoxide24.5 g ( 0.25 mole) and put into a 1.6 g BINAP (0.003mole), put into a 300 mL toluene was stirred under reflux for 12 hours. To complete the reaction, and the organic layer wasseparated and the water layer was extracted twice with 100 mL toluene. Formed organic layer was concentrated underreduced pressure. Intermediates a4(38.5 g, 77.0%) by column chromatography
With bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate In toluene at 95℃; for 4h;
3.1 Synthesis of intermediate 3-1
1,3-Diiodobenzene (3.3 g, 0.010 mol) to 3-bromo-9H-carbazole (5.4 g, 0.022 mol),Pd (dba) 2 (0.5 g, 0.0005 mol), sodium-tert-butoxide (1.9 g, 0.020 the mol) into a 100mL Toluene then it was reacted with stirring for 4 hours at 95 ° C. After the layer separationin the MC column purification (N-HEXANE:: MC) after the end of the reaction H20 to Intermediate 1-1 ; 3.5 g (62% yield) was obtained. (M / z = 566) 3,5-Dimethylaniline (1.2 g, 0.010 mol) for (4-bromophenyl) trimethylsilane (2.5 g,0.011 mol) and the mixture in Example 1-Preparation Example 1 in the same manner asin synthesis To give the 2.0 g (76% yield). (M / z = 269)
76%
With bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate In toluene at 95℃; for 4h;
3.1 Synthesis of intermediates 1-1
1,3-dibromobenzene (2.4 g, 0.010 mol) to 3-chloro-9H-carbazole (4.2 g, 0.022 mol), Pd (dba) 2 (0.5 g, 0.0005mol), sodium-tert-butoxide (1.9 g, 0.020 mol) in 90 mL Toluene was put into the reaction stirred for 4 hours at 95 . After the end of the reaction H2O: after the layer separation in the MC column purification (N-HEXANE: MC) to give 3.0 g (yield 62%).
((4-(N-3-cyanocarbazolyl)phenyl)trimethylsilane)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
65%
With copper(l) iodide; potassium carbonate In 1,2-dichloro-benzene at 210℃; for 12h;
4 Synthesis of 4-(N-3-cyanocarbazolyl)phenyl)trimethylsilane
As shown in Reaction Scheme 4, a reaction vessel was charged with (4-bromophenyl) trimethylsilane((4-bromophenyl) trimethyl silane) (6.61 g, 29 mmol),3-Cyano-carbazole (4.61 g, 24 mmol), copper iodide (9.30 g, 49 mmol), potassium carbonate (13.10 g, 95 mmol) - Dichlorobenzene (1,2-dichlorobenzene) is heated at 210° C for 12 hours.After completion of the reaction, the reaction mixture was extracted with dichloromethane, and the organic solvent was evaporated using a rotary vacuum evaporator. The resultant was subjected to silica gel column chromatography to obtain a white solid in a yield of 65% (6.41 g). The results are as follows.
With palladium diacetate; caesium carbonate; tricyclohexylphosphine tetrafluoroborate In isopropyl alcohol; toluene at 80℃; for 12h; Inert atmosphere; Schlenk technique;
Palladium-Catalyzed Reductive Coupling Reaction for the Synthesisof Diarylmethanes; 4-Benzyl-1,1′-biphenyl (3a); Typical Procedure3
General procedure: Under an argon atmosphere, Pd(OAc)2 (3.3 mg, 0.015 mmol, 5 mol%),PCy3·HBF4 (22.1 mg, 0.06 mmol, 20 mol%), benzaldehyde N-tosylhydrazone1a (99 mg, 0.36 mmol), 4-bromo-1,1′-biphenyl (2a; 70 mg,0.3 mmol), and Cs2CO3 (195 mg, 0.6 mmol) were successively addedto a flame-dried 25 mL Schlenk flask. The reaction flask was degassedthree times with argon. Then anhyd toluene (2.7 mL) and i-PrOH (0.3mL) were added with a syringe. Note that the aryl bromide in oil formwas added to the reaction flask prior to i-PrOH. The reaction washeated at 80 °C with stirring for about 12 h, then it was cooled to r.t.,and filtered through a short pad of neutral alumina with EtOAc (25mL) as eluent. Solvent was then removed in vacuo to leave a crudemixture, which was purified by silica gel column chromatography(eluent: PE) to give 3a3d as a white solid (59 mg, 80%)
1,4-bis{2-[4-(trimethylsilyl)phenyl]-1,3-oxazol-5-yl}benzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
74%
With tetrakis(triphenylphosphine) palladium(0); lithium tert-butoxide In 1,4-dioxane for 1h; Reflux;
General procedure: Solutions oflithium tert-butoxide (0.94 g, 12 mmol, 5 equiv.), 1,4-bis(1,3-oxazol-5-yl)benzene (2) (0.5 g, 2.4 mmol, 1 equiv.), bromobenzene (0.89 g,5.6 mmol, 2.3 equiv.) and Pd(PPh3)4 (54 mg, 0.047 mmol, 2%) in 1,4-dioxane (60 mL) was heated to boiling. The reaction mixture wasrefluxed for 1 h. Progress of the reaction was monitored by GPCanalysis. After completeness of the reaction, the reaction mixturewas cooled to room temperature (23 °C) and poured into water(200 mL), filtered off and thoroughly washed with water andacetone. The crude product was passed over a short column of silicagel in toluene: ethyl acetate 10:1 mixture to remove the rest of thecatalyst. The product was purified by recrystallization from tolueneto give a pure compound (686 mg, yield 80%) as yellowish needlecrystals
trimethyl(4-(prop-1-yn-1-yl)phenyl)silane[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
72%
With bis-triphenylphosphine-palladium(II) chloride; 1,8-diazabicyclo[5.4.0]undec-7-ene; 1,4-di(diphenylphosphino)-butane In dimethyl sulfoxide at 110℃; for 1h; Schlenk technique;
72%
With bis-triphenylphosphine-palladium(II) chloride; 1,8-diazabicyclo[5.4.0]undec-7-ene; 1,4-di(diphenylphosphino)-butane In dimethyl sulfoxide at 110℃; for 1h; Inert atmosphere;
With copper(l) iodide; caesium carbonate; ethylenediamine In toluene for 24h; Reflux;
19
Intermediate e (17.7 g, 41 mmol), (4-bromophenyl)silane (14.02 g, 61.5 mmol),Cuprous iodide (3.9 g, 20.5 mmol), ethylenediamine (1.4 mL, 20.5 mmol) and cesium carbonate (40 g, 123 mmol) were sequentially added to toluene (250 mL) and then stirred under reflux.Extraction with ethyl acetate under reduced pressure and dichloromethane and hexanes were applied to the residue to afford compound 19-1 (19.75 g, 83%).
5,9-dibromo-7,7-dimethyl-7H-benzo[c]fluorene[ No CAS ]
[ 62-53-3 ]
C49H50N2Si2[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
18%
Stage #1: 5,9-dibromo-7,7-dimethyl-7H-benzo[c]fluorene; aniline With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate In toluene at 50℃; for 2h; Inert atmosphere;
Stage #2: 1-bromo-4-(trimethylsilyl)benzene With palladium diacetate; sodium t-butanolate In toluene at 80℃; for 4h; Inert atmosphere;
Synthesis example of compound (BD-1)
Under a nitrogen atmosphere,Dissolving 5,9-dibromo-7,7-dimethyl-7H-benzo[c]indole (9.5 g) and aniline (4.5 g) in dehydrated toluene (80 ml), adding bis(dibenzylidene) Acetone) palladium (140 mg), sodium butoxide (7.0 g) and tris(t-butyl)phosphine (0.15 g) were heated at 50 °C for 2 hours.After the reaction, 1-bromo-4-(trimethylsilyl)benzene (11 g), palladium acetate (27 mg) and sodium butoxide (7.0 g) were added, and the mixture was heated at 80 ° C for 4 hours. 100 ml of water was added, and the organic layer was washed with water using a separatory funnel.After the aqueous layer was removed, the organic layer was collected and concentrated using a rotary evaporator to obtain a crude product. This crude product was subjected to column purification (solvent: heptane/toluene = 5/1 (volume ratio)) using yttrium gel, and sublimation purification was carried out to obtain a compound (BD-1): 3.1 g (yield: 18%).
5,9-dibromo-7,7-dimethyl-7H-benzo[c]fluorene[ No CAS ]
[ 540-23-8 ]
C51H54N2Si2[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
46%
Stage #1: 5,9-dibromo-7,7-dimethyl-7H-benzo[c]fluorene; p-toluidine hydrochloride With (4-(N,N-dimethylamino)phenyl)-di-tert-butylphosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate In toluene at 80℃; for 2h; Inert atmosphere;
Stage #2: 1-bromo-4-(trimethylsilyl)benzene In toluene at 80℃; for 4h; Inert atmosphere;
Synthesis example of compound (BD-2)
Under a nitrogen atmosphere, 5,9-dibromo-7,7-dimethyl-7H-benzo[c]fluorene (8.0 g) and p-methylaniline hydrochloride (5.7 g) were dissolved in dehydrated toluene (200 ml), added Bis(dibenzylideneacetone)palladium (115 mg), sodium butoxide (15 g), and (4-(N,N-dimethylamino)phenyl)di-tert-butylphosphine (0.160 g) Heating was carried out at 80 ° C for 2 hours.After the reaction, 1-bromo-4-(trimethylsilyl)benzene (10 g) was added, and the mixture was heated at 80 ° C for 4 hours.100 ml of water was added thereto, and the organic layer was washed with water using a separatory funnel. After the aqueous layer was removed, the organic layer was collected and concentrated using a rotary evaporator to obtain a crude product.This crude product was subjected to column purification (solvent: heptane / toluene = 5 / 1 (volume ratio)) using alumina, and then subjected to sublimation purification to obtain Compound (BD-2) 6.9 g (yield: 46%).
With tris-(dibenzylideneacetone)dipalladium(0); 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate; In toluene; at 100℃; for 24h;
<strong>[7293-45-0]4-amino-p-terphenyl</strong> (3.00 g, 12.23 mmol), (4-bromophenyl)trimethylsilane (2.71 g, 11.81 mmol), Tris(dibenzylideneacetone)dipalladium (0) (0.17 g, 0.18 mmol) (±) -2,2'-Bis(diphenylphosphino)-1,1'-binaphthalene (BINAP) (0.25 g, 0.37 mmol) and sodium tert-butoxide (1.65 g, 17.12 mmol) were dissolved in 120 mL of toluene and stirred at 100 C for 24 hours. After completion of the reaction, toluene was removed, And water, and the mixture was distilled under reduced pressure. After the silica gel column, the solvent was distilled off under reduced pressure to obtain Compound B1 (3.52 g, 8.94 mmol).
2-fluoro-N-methyl-N-methyloxy-2-(1,2,4-triazole-1-yl)acetamide[ No CAS ]
2-fluoro-2-(1,2,4-triazol-1-yl)-1-[4-(trimethylsilyl)phenyl]ethanone[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
87%
Stage #1: 1-bromo-4-(trimethylsilyl)benzene With isopropylmagnesium chloride; lithium chloride In tetrahydrofuran at 20℃; for 24h; Inert atmosphere;
Stage #2: 2-fluoro-N-methyl-N-methyloxy-2-(1,2,4-triazole-1-yl)acetamide In tetrahydrofuran at 0℃; for 0.166667h; Inert atmosphere;
35 Reference example-35
Under an argon atmosphere,To a suspension of lithium chloride (113 mg, 2.66 mmol) in THF (5.3 mL) was added isopropyl magnesium chloride in THF solution (2 M, 1.33 mL, 2.66 mmol)And 1-bromo-4- (trimethylsilyl) benzene (0.540 mL, 2.76 mmol) were added at room temperature,And the mixture was stirred for 24 hours.2-fluoro-N-methyl-N-methyloxy-2- (1,2,4-triazol-1-yl) acetamide (200 mg, 1.06 mmol)In THF (3.5 mL) at 0 ° C.,And the mixture was stirred at that temperature for 10 minutes.Saturated ammonium chloride aqueous solution was added to the reaction solution, and the mixture was extracted with ethyl acetate.The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure.The obtained crude product was purified by column chromatography (hexane: ethyl acetate = 10: 1 to 1: 1)2-fluoro-2- (1,2,4-triazol-1-yl) -1- [4- (trimethylsilyl) phenyl] ethanoneOf pale yellow oil (258 mg, yield: 87%
[7,10-bis(trimethylsilyl)-1,2,3,4,4a,12b-hexahydro-1,4-methanotriphenylene-2,3-diyl]bis(diphenylphosphane) dioxide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
63%
With tetrakis(triphenylphosphine) palladium(0); caesium carbonate In N,N-dimethyl-formamide at 105℃; for 48h; Schlenk technique; Inert atmosphere; stereoselective reaction;
General procedure for the coupling reaction.
General procedure: 1 (0.2 mmol), 2 (0.24 mmol), Cs2CO3 (0.6mmol), Pd(PPh3)4 (0.01 mmol) were placed in a Schlenk tube under argon. Dry DMF (2 mL)was added and the mixture was stirred at 105 °C for 18-24 h. Then, the mixture was cooleddown to RT. The DMF was evaporated under reduced pressure and 20 mL of water was added.The products were extracted with DCM (3 x 20 mL). The combined organic phase was driedover MgSO4, drying agent was filtered off and DCM was evaporated. The product was purifiedby silica-gel column chromatography (Hexane/iPrOH 50/1) and finally crystallised and finallyrecrystallized from appropriate solvent mixture.
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 1h;Sealed tube;
Gold catalyst 1a (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.02 mmol), PhI(OAc) 2 (84 mg, 0.26 mmol) and C2H3Cl3 (1 ml) were added to the dried tube and stirred vigorously at room temperature. 30min. Subsequently, a mixed solution of (45.8 mg, 0.2 mmol) and (57.2 mg, 0.26 mmol) of C2H3Cl3 (1 ml) was dropped into a sealed tube and reacted at 110 C for 1 h. The reaction solution was concentrated, dried, and purified by column chromatography to give the product 38.4 mg ( petroleum ether: ethyl acetate = 100:1), yield 73%.
73%
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 1h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
(sulfonylbis(4,1-phenylene))bis(trimethylsilane)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
71%
With potassium pyrosulfite; palladium diacetate; N-ethyl-N,N-diisopropylamine; tri tert-butylphosphoniumtetrafluoroborate In N,N-dimethyl-formamide at 100℃; for 20h; Inert atmosphere;
Typical procedure for synthesis of symmetrical diaryl sulfones
General procedure: K2S2O5 (33.3 mg, 0.150 mmol, 0.75 equiv), Pd(OAc)2 (4.5 mg, 20.0 μmol, 10 mol%), P(t-Bu)3HBF4 (11.6 mg, 40.0 μmol, 20 mol%), and 4-iodoanisole (93.6 mg, 0.400 mmol, 2.0 equiv)were added into a screw-capped 10-mL test tube containing a magnetic stirring bar. The tube wascapped with a septum, evacuated, and backfilled with Ar three times. DMF (0.40 mL) and iPr2NEt(77.5 mg, 0.600 mmol, 3.0 equiv) were added to the tube. The septum was replaced with a screwcap. The tube was warmed to 100 °C in an oil bath and stirred for 20 h. The reaction mixture wascooled to rt, diluted with EtOAc, washed with H2O and brine, dried over Na2SO4, filtered, andconcentrated. The residue was purified by preparative TLC (SiO2, hexane/CHCl3 = 1/3) to afford2 (44.7 mg, 0.161 mmol, 81%).
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate In 1,1,2-trichloroethane at 110℃; for 2h; Schlenk technique; Inert atmosphere;
2. General procedure and conditions optimization for organometallic crosscoupling
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 2h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
trimethyl(9-phenylphenanthren-3-yl)silane[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
64%
With palladium diacetate; potassium carbonate; bis[2-(diphenylphosphino)phenyl] ether In 1,4-dioxane at 130℃; for 5h; Inert atmosphere; Schlenk technique; Sealed tube; regioselective reaction;
64%
With palladium diacetate; potassium carbonate; bis[2-(diphenylphosphino)phenyl] ether In 1,4-dioxane at 130℃; for 5h; Inert atmosphere; Sealed tube;
1
General procedure: In a dry sealed tube, protected by argon, add 3.4mg Pd(OAc)2, 16.2mg DPEPhos, 77.4mg 1a(0.3mmol), 47.1μL 2a(0.45mmol), 82.8mg K2CO3, 1.5mL dioxane, and heat to 130 , stir for 5h. It was cooled to room temperature and concentrated. The residue was column chromatographed with n-hexane as the eluent, and the product band was collected to obtain 65 mg of 3aa white solid with a yield of 85%.
1,4-bis{(E)-2-[4-(trimethylsilyl)phenyl]ethenyl}benzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
87%
With potassium phosphate; palladium diacetate In N,N-dimethyl acetamide at 140℃; for 4h; Inert atmosphere;
1,4-Bis{(E)-2-[4-(trimethylsylyl)phenyl]ethenyl}-benzene (3).
b. A mixture of 0.3 g (2.3 mmol) of 1,4-divinylbenzene (6), 1.27 g (5.5 mmol) of (4-bromophenyl)-trimethylsilane (7), 1.37 g (6.45 mmol) of K3PO4, and 10.3 mg (0.046 mmol) of Pd(OAc)2 in 6 mL of DMA was stirred for 4 h at 140°C. The mixture was cooled, diluted with 30 mL of water, and extracted with toluene (3 × 15 mL). The combined extracts were washed with water (3 × 10 mL) and dried over Na2SO4, the solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography using toluene-hexane (1 : 5) as eluent. The product was recrystallized from cyclohexane and dried at 80°C under reduced pressure. Yield 483 mg (89%, a), 856 mg (87%, b); yellow-green crystals, mp 261°C. 1H NMR spectrum, δ, ppm:0.30 s [18H, Si(CH3)3], 7.13 s (4H, CH=CH), 7.48-7.54 m (12H, Harom). 13C NMR spectrum, δC, ppm:-1.3 [Si(CH3)3], 125.8, 126.8, 128.6, 128.7, 133.6,136.9, 137.8, 140.0. 29Si NMR spectrum: δSi -4.3 ppm. Found, %: C 78.91; H 8.07; Si 12.97. C28H34Si2. Calculated,%: C 78.81; H 8.03; Si 13.16.
trimethyl(4-(triethylgermyl)phenyl)silane[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
93%
Stage #1: 1-bromo-4-(trimethylsilyl)benzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere;
Stage #2: triethylchlorogermane In tetrahydrofuran; hexane at 20℃; Inert atmosphere;
With tris-(dibenzylideneacetone)dipalladium(0); nitrogen; tetrabutylammomium bromide; lithium; sodium t-butanolate; ruphos In 1,4-dioxane at 150℃; for 24h;
4 Example 4
The method for synthesizing tris(4-(trimethylsilyl)phenyl)amine using nitrogen as nitrogen source, the steps are as follows:Add 42.0mg of lithium powder to a 25mL reaction tube, and react at 150°C for 4 hours under a nitrogen atmosphere.Then add 114.6mg of 1-bromo-4-trimethylsilylbenzene, 96.1mg of sodium tert-butoxide,Tris(dibenzylideneacetone)dipalladium 11.4mg, 2-Dicyclohexylphosphino-2′,6′-diisopropoxy-1,1′-biphenyl 23.3mg,161.0 mg of tetrabutylammonium bromide and 2 mL of 1,4-dioxane were used to obtain a mixed solution. The mixed solution was reacted at 150°C for 24 hours. Cool to room temperature, remove the solvent, and add saturated brine and ethyl acetate to separate the layers. The aqueous phase was extracted 3 times with ethyl acetate. The organic layers were combined, dried over Na2SO4 and filtered. The solvent was removed under reduced pressure. Finally, the product was purified by column chromatography. Column chromatography obtained 46.1 mg of the corresponding target product with a yield of 60%.
With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate In 5,5-dimethyl-1,3-cyclohexadiene; toluene for 12h; Reflux;
7 Example 7: Synthesis of compound 3-27 (LT19-35-220)
Intermediate (1) 3.5 g (10.8 mmol), 4- (bromophenyl) trimethylsilane ((4-bromophenyl) trimethylsilane) 5.4 g (23.7 mmol), tert-butoxy sodium 3.1 g (32.4 mmol), Pd (dba) ) 20.4 g (0.7 mmol), tri-tert-butylphosphine 0.4 g (0.9 mmol, 50wt% toluene solution) and 150 mL of xylene were stirred under reflux for 12 hours. The reaction mixture was cooled to room temperature and then concentrated under reduced pressure. To the resulting mixture, 500 mL of chloroform was added, stirred, and filtered through a pad of Celite. The filtrate was concentrated under reduced pressure, and the obtained compound was purified by column chromatography to obtain 4.6 g (yield: 68.6%) of a white solid compound 3-27 (LT19-35-220).
6-phenyl-12-(4-(trimethylsilyl)phenyl)-5,6,7,12-tetrahydrodibenzo[c,f][1,5]azastibocine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
85%
With 1,2-bis(diphenylphosphino)ethane nickel(II) chloride; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; lithium iodide; zinc In tetrahydrofuran at 100℃; for 12h;
With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In ethanol; toluene for 12h; Reflux;
18 Synthesis of Intermediate (32)
(4-bromophenyl)trimethylsilane 20.0 g (87.3 mmol), 4-chlorophenyl)boronic acid 13.7 g (87.3 mmol), Pd(PPh3)4 5.0 g (4.4 mmol), 2 M K2CO3 87.3 mL (174.5 mmol), toluene 436 mL and 218 mL of ethanol were mixed and stirred under reflux for 12 hours.After completion of the reaction, the mixture was cooled to room temperature, added with water, extracted with ethyl acetate, and the solvent was removed under reduced pressure.The obtained reaction mixture was purified by silica gel column chromatography (CHCl3) and solidified with a mixed solution (DCM/Hex) to obtain 18.5 g (yield: 81.3%) of the compound as a white solid (intermediate (32)).
With 1,1'-bis(diphenylphosphanyl)ferrocene; tris-(dibenzylideneacetone)dipalladium(0); sodium tertiary butoxide In toluene at 120℃; for 12h; Inert atmosphere;
9 Example 9 Synthesis and preparation of luminescent compound (1-2-73)
Under nitrogen atmosphere, [1,1'-binaphthyl]-2,2'-diamine (2.7 g, 9.5 mmol, 1 eq), 1-bromo-4-(trimethylsilyl)benzene (4.8 g , 20.9mmol, 2.2eq), tris(dibenzylideneacetone)dipalladium (173mg, 0.19mmol, 0.02eq), 1,1'-bis(diphenylphosphino)ferrocene (107mg, 0.19mmol, 0.02 eq) and sodium tert-butoxide (2.6 g, 28.4 mmol, 3 eq) were dispersed in 20 mL of toluene.The reaction was carried out at 120°C for 12 hours.After the reaction, the solvent was spun dry and the crude product was further purified by column chromatography using petroleum ether:dichloromethane (75:25).The intermediate product P-15 was obtained in a yield of 4.9 g (90% yield).
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