* 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] Molecular crystals and liquid crystals, 1981, vol. 75, # 1-4, p. 233 - 247
2
[ 110-53-2 ]
[ 29558-77-8 ]
[ 63619-51-2 ]
Yield
Reaction Conditions
Operation in experiment
95.9%
With potassium carbonate In butanone for 8 h; Reflux
General procedure: A suspension of 4-bromo-4'-hydroxybiphenyl (13) (3.5 g, 14.11 mmol), 1-bromoheptane (3.75 g, 21.05 mmol) and K2CO3 (4.9 g, 35.28 mmol) in 2-butanone (25 mL) was refluxed for 8 h. After cooling, the reaction mixture was diluted by CH2Cl2 (50 mL). After filtration, the organic layer was washed by H2O (50 mL) and saturated brine (50 mL), dried over anhydrous Na2SO4, and filtrated. The solvent was condensed to 15 mL under reduced pressure, and the residue was collected and washed by cool hexane (0 °C) to afford 14c (4.6 g, yield 94.3percent) as white solid.
Reference：
[1] European Journal of Medicinal Chemistry, 2012, vol. 50, p. 196 - 208
[2] Chemistry Letters, 2010, vol. 39, # 5, p. 513 - 515
[3] Bioorganic and Medicinal Chemistry Letters, 2008, vol. 18, # 4, p. 1474 - 1477
[4] Molecular Crystals and Liquid Crystals Science and Technology Section A: Molecular Crystals and Liquid Crystals, 2000, vol. 339, p. 145 - 158
[5] Patent: US5948753, 1999, A,
[6] Patent: US5514651, 1996, A,
[7] Patent: US5516756, 1996, A,
[8] Patent: US5646245, 1997, A,
[9] Patent: US5741775, 1998, A,
[10] Patent: US5854213, 1998, A,
[11] Patent: US6268338, 2001, B1,
3
[ 628-17-1 ]
[ 29558-77-8 ]
[ 63619-51-2 ]
Yield
Reaction Conditions
Operation in experiment
96%
With sodium hydroxide; tetrabutylammomium bromide In water
Alternative Preparation of 4-bromo-4'-pentyloxybiphenyl 1(a): 4-Bromo-4'-hydroxybiphenyl (12.5 g, 50.2 mmol) was added to a solution of NaOH (2.28 g, 97percent pure, 55.2 mmol) in deionized H2O (150 ml), followed by the addition of 1-iodopentane (11.9 g, 60.2 mmol) and tetrabutylammonium bromide (0.82 g, 2.5 mmol). The mixture was stirred at 90° C. for 3.75 h until the solids went into solution. Then, as the reaction proceeded, the desired product began to precipitate. The mixture was slowly cooled and then filtered to provide a solid which was washed with deionized water until the pH of the filtrate was neutral and then dried for 16 h in a vacuum oven at 30° C. Yield: 15.41 g (96percent) of 5a. Rf 0.5 (97:3 hexanes/EtOAc). 1H NMR: δ 0.93 (t, 3H, J=6.9 Hz); 1.41 (m, 4H); 1.79 (m, 2H); 3.97 (t, 2H, J=6.6 Hz); 6.98 (m, 2H); 7.23 (m,6H). 13C NMR: δ 14.03; 22.43; 28.22; 28.98; 68.12; 114.91; 120.71; 127.93; 128.27; 131.77; 132.24; 139.82; 159.03. MS(FAB+): m/z 320. IR(CHCl3): 2960, 2936, 2874, 1608, 1518, 1485, 1475 cm-1 Analysis for C17H19BrO: Calcd: C, 63.96; H. 6.00; Br, 25.0; Found: C, 64.10; H. 5.97; Br, 25.28.
96%
With sodium hydroxide; tetrabutylammomium bromide In water
Alternative Preparation of 4-bromo-4'-pentyloxybiphenyl 1(a): 4-Bromo-4'-hydroxybiphenyl (12.5 g, 50.2 mmol) was added to a solution of NaOH (2.28 g, 97percent pure, 55.2 mmol) in deionized H2O (150 ml), followed by the addition of 1-iodopentane (11.9 g, 60.2 mmol) and tetrabutylammonium bromide (0.82 g, 2.51 mmol). The mixture was stirred at 90° C. for 3.75 h until the solids went into solution. Then, as the reaction proceeded, the desired product began to precipitate. The mixture was slowly cooled and then filtered to provide a solid which was washed with deionized water until the pH of the filtrate was neutral and then dried for 16 h in a vacuum oven at 30° C. Yield: 15.41 g (96percent) of 5a. Rf 0.5 (97:3 hexanes/EtOAc). 1H NMR: δ0.93 (t, 3H, J=6.9 Hz); 1.41 (m, 4H); 1.79 (m, 2H); 3.97 (t, 2H, J=6.6 Hz); 6.98 (m, 2H); 7.23 (m, 6H). 13C NMR: δ14.03; 22.43; 28.22; 28.98; 68.12; 114.91; 120.71; 127.93; 128.27; 131.77; 132.24; 139.82; 159.03. MS(FAB+): m/z 320. IR(CHC13): 2960, 2936, 2874, 1608, 1518, 1485, 1475 cm-1. Analysis for C17H19BrO: Calcd: C, 63.96; H. 6.00; Br, 25.0; Found: C, 64.10; H. 5.97; Br, 25.28.
Reference：
[1] Doklady Chemistry, 1993, vol. 332, # 1-3, p. 195 - 197[2] Dokl. Akad. Nauk SSSR Ser. Khim., 1993, vol. 332, # 1, p. 48 - 49
6
[ 106-37-6 ]
[ 115171-02-3 ]
[ 63619-51-2 ]
Reference：
[1] Russian Journal of Organic Chemistry, 1995, vol. 31, # 11, p. 1480 - 1486[2] Zhurnal Organicheskoi Khimii, 1995, vol. 31, # 11, p. 1650 - 1656
7
[ 148-86-7 ]
[ 63619-51-2 ]
Reference：
[1] Molecular Crystals and Liquid Crystals Science and Technology Section A: Molecular Crystals and Liquid Crystals, 2000, vol. 339, p. 145 - 158
8
[ 92-69-3 ]
[ 63619-51-2 ]
Reference：
[1] Molecular Crystals and Liquid Crystals Science and Technology Section A: Molecular Crystals and Liquid Crystals, 2000, vol. 339, p. 145 - 158
9
[ 84244-98-4 ]
[ 63619-51-2 ]
Reference：
[1] Molecular Crystals and Liquid Crystals Science and Technology Section A: Molecular Crystals and Liquid Crystals, 2000, vol. 339, p. 145 - 158
10
[ 110-53-2 ]
[ 78079-08-0 ]
[ 63619-51-2 ]
Reference：
[1] Molecular crystals and liquid crystals, 1981, vol. 75, # 1-4, p. 233 - 247
11
[ 14047-29-1 ]
[ 63619-51-2 ]
[ 158938-08-0 ]
Reference：
[1] Bioorganic and Medicinal Chemistry Letters, 2003, vol. 13, # 3, p. 489 - 493
12
[ 63619-51-2 ]
[ 158938-08-0 ]
Reference：
[1] Journal of Medicinal Chemistry, 1995, vol. 38, # 17, p. 3271 - 3281
[2] European Journal of Medicinal Chemistry, 2012, vol. 50, p. 196 - 208
13
[ 63619-51-2 ]
[ 158937-25-8 ]
Yield
Reaction Conditions
Operation in experiment
94.4%
Stage #1: With n-butyllithium In tert-butyl methyl ether at -20℃; for 2 h; Inert atmosphere Stage #2: With Triisopropyl borate In tetrahydrofuran; tert-butyl methyl ether at -60 - 20℃; Stage #3: With hydrogenchloride; water In tetrahydrofuran; tert-butyl methyl ether at 20℃; for 0.166667 h;
General procedure: n-BuLi (2.5 M, 7.4 mL, 18 mmol) was added dropwise to a solution of compound 14c (4.5 g, 13 mmol) in MTBE (50 mL) at -20 °C under nitrogen atmosphere. After stirring for 2 h, the reaction mixture was cooled to -60 °C and was added THF (6 mL). Then, a solution of (i-PrO)3B (6.1 mL, 26 mmol) in MTBE (8 mL) was added dropwise to the resulting mixture and was stirred for 1 h. The reaction mixture was allowed to warm to room temperature, stirred overnight and treated with 2 M HCl (50 mL) for 10 min. The organic layer was separated and the solvent was evaporated under reduced pressure. The residue was added hexane (40 mL) and stirred for 10 min. After filtration, the filter cake was washed by hexane-MTBE (8: 1) to give 15c (3.7 g, yield 91.4percent) as white solid.
Reference：
[1] European Journal of Medicinal Chemistry, 2012, vol. 50, p. 196 - 208
[2] Molecular Crystals and Liquid Crystals Science and Technology Section A: Molecular Crystals and Liquid Crystals, 2000, vol. 339, p. 145 - 158
14
[ 5419-55-6 ]
[ 63619-51-2 ]
[ 158937-25-8 ]
Yield
Reaction Conditions
Operation in experiment
91%
Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -78 - -65℃; for 2.25 h; Stage #2: at -78 - 20℃; for 1.16667 h; Stage #3: With hydrogenchloride; water In tetrahydrofuran; hexane
31,9 g (0,1 mol) 4-Brom-4'-n-pentoxy[1,1']biphenyl werden unter Stickstoffatmosphaere in 640 ml Tetrahydrofuran geloest, auf -78°C gekuehlt und innerhalb von 2 Stunden tropfenweise mit 67 ml (0,11 mol) einer 15percentigen Loesung von n-Butyilithium in Hexan versetzt. Dabei wird die Innentemperatur in einem Bereich von -78°C bis -65°C gehalten. Nach beendeter Zugabe wird die dicke, milchige Suspension weitere 15 Minuten bei -78°C geruehrt und im Anschluss daran mit 25,5 ml (0,11 mol) Triisopropylborat innerhalb 15 Minuten bei -78°C tropfenweise versetzt. Nach beendeter Boratzugabe erhaelt man eine klare Loesung, welche 15 Minuten bei -78°C nachgeruehrt wird. Im Anschluss daran wird das Kaeltebad entfernt und nach 40 Minuten die Loesung mit 100 ml 2N Salzsaeure auf pH 2 gestellt. Die Phasen werden getrennt, die organische Phase mit Wasser und gesaettigter Kochsalzloesung gewaschen und im Anschluss daran werden die Loesungsmittel unter Zusatz von 200 ml Wasser destillativ entfernt. Der ausgefallene Feststoff wird abfiltriert und getrocknet. Man erhaelt 25,8 g (91 percent) 4'-n-Pentoxy[1,1']biphenyl-4-boronsaeure vom Schmelzpunkt 148-150°C.
Reference：
[1] Patent: EP1156997, 2004, B1, . Location in patent: Page 12
[2] Patent: US5516756, 1996, A,
With sodium hydroxide; tetrabutylammomium bromide; In water;
Alternative Preparation of 4-bromo-4'-pentyloxybiphenyl 1 (a) 4-Bromo-4'-hydroxybiphenyl (12.5 g 50.2 mmol) was added to a solution of NaOH (2.28 g. 97% pure. 55.2 mmol) in deionized H2O (150 ml). followed by the addition of 1-iodopentane (11.9 g, 60.2 mmol) and tetrabutylammonium bromide (0.82 g. 2.51 mmol). The mixture was stirred at 90 C. for 3.75 h until the solids went into solution. Then, as the reaction proceeded, the desired product began to precipitate. The mixture was slowly cooled and then filtered to provide a solid which was washed with deionized water until the pH of the filtrate was neutral and then dried for 16 h in a vacuum oven at 30 C. Yield: 15.41 g (96%) of 5a. Rf0.5 (97:3 hexaneslEtOAc). 1H NMR: delta0.93 (t, 3H, J=6.9 Hz); 1.41 (m, 4H); 1.79 (mn. 2H): 3.97 (t, 2H. J=6.6 Hz); 6.98 (m. 2H); 7.23 (m,6H). 13C NMR: delta14.03; 22.43; 28.22 28.98; 68.12; 114.91; 120.71; 127.93; 128.27; 131.77; 132.24; 139.82; 159.03. MS(FAB+): m/z 320. IR(CHCl3): 2960. 2936, 2874 1608, 1518, 1485, 1475 cm-1. Analysis for C17H19BrO: Calcd: C, 63.96; H. 6.00; Br. 25.0; Found: C, 64.10; H. 5.97; Br, 25.28.
15.41 g (96%)
With sodium hydroxide; tetrabutylammomium bromide; In water;
Alternative Preparation of 4-bromo-4'-pentyloxybiphenyl 1(a): 4-Bromo-4'-hydroxybiphenyl (12.5 g, 50.2 mmol) was added to a solution of NaOH (2.28 g, 97% pure, 55.2 mmol) in deionized H2O (150 ml), followed by the addition of 1-iodopentane (11.9 g, 60.2 mmol) and tetrabutylammonium bromide (0.82 g, 2.5 mmol). The mixture was stirred at 90 C. for 3.75 h until the solids went into solution. Then, as the reaction proceeded, the desired product began to precipitate. The mixture was slowly cooled and then filtered to provide a solid which was washed with deionized water until the pH of the filtrate was neutral and then dried for 16 h in a vacuum oven at 30 C. Yield: 15.41 g (96%) of 5a. Rf 0.5 (97:3 hexanes/EtOAc). 1H NMR: delta 0.93 (t, 3H, J=6.9 Hz); 1.41 (m, 4H); 1.79 (m, 2H); 3.97 (t, 2H, J=6.6 Hz); 6.98 (m, 2H); 7.23 (m,6H). 13C NMR: delta 14.03; 22.43; 28.22; 28.98; 68.12; 114.91; 120.71; 127.93; 128.27; 131.77; 132.24; 139.82; 159.03. MS(FAB+): m/z 320. IR(CHCl3): 2960, 2936, 2874, 1608, 1518, 1485, 1475 cm-1 Analysis for C17H19BrO: Calcd: C, 63.96; H. 6.00; Br, 25.0; Found: C, 64.10; H. 5.97; Br, 25.28.
15.41 g (96%)
With sodium hydroxide; tetrabutylammomium bromide; In water;
Alternative Preparation of 4-bromo-4'-pentyloxybiphenyl 1(a): 4-Bromo-4'-hydroxybiphenyl (12.5 g, 50.2 mmol) was added to a solution of NaOH (2.28 g, 97% pure, 55.2 mmol) in deionized H2O (150 ml), followed by the addition of 1-iodopentane (11.9 g, 60.2 mmol) and tetrabutylammonium bromide (0.82 g, 2.51 mmol). The mixture was stirred at 90 C. for 3.75 h until the solids went into solution. Then, as the reaction proceeded, the desired product began to precipitate. The mixture was slowly cooled and then filtered to provide a solid which was washed with deionized water until the pH of the filtrate was neutral and then dried for 16 h in a vacuum oven at 30 C. Yield: 15.41 g (96%) of 5a. Rf 0.5 (97:3 hexanes/EtOAc). 1H NMR: delta0.93 (t, 3H, J=6.9 Hz); 1.41 (m, 4H); 1.79 (m, 2H); 3.97 (t, 2H, J=6.6 Hz); 6.98 (m, 2H); 7.23 (m, 6H). 13C NMR: delta14.03; 22.43; 28.22; 28.98; 68.12; 114.91; 120.71; 127.93; 128.27; 131.77; 132.24; 139.82; 159.03. MS(FAB+): m/z 320. IR(CHC13): 2960, 2936, 2874, 1608, 1518, 1485, 1475 cm-1. Analysis for C17H19BrO: Calcd: C, 63.96; H. 6.00; Br, 25.0; Found: C, 64.10; H. 5.97; Br, 25.28.
With sodium hydroxide; tetrabutylammomium bromide; In water;
Alternative Preparation of 4-bromo-4'-pentyloxybiphenyl 4-Bromo-4'-hydroxybiphenyl (12.5g, 50.2mmol) was added to a solution of NaOH (2.28g, 97% pure, 55.2mmol) in deionized H2O (150mL), followed by the addition of 1-iodopentane (11.9g, 60.2mmol) and tetrabutylammonium bromide (0.82g, 2.51mmol). The mixture was stirred at 90C for 3.75h until the solids went into solution. Then, as the reaction proceeded, the desired product began to precipitate. The mixture was slowly cooled and then filtered to provide a solid which was washed with deionized water until the pH of the filtrate was neutral and then dried for 16h in a vacuum oven at 30C. Yield: 15.41g (96%) of 5a. Rf0.5 (97:3 hexanes/EtOAc). 1H NMR: delta 0.93 (t, 3H, J=6.9Hz); 1.41 (m, 4H); 1.79 (m, 2H); 3.97 (t, 2H, J= 6.6Hz); 6.98 (m, 2H); 7.23 (m, 6H). 13C NMR: delta 14.03; 22.43; 28.22; 28.98; 68.12; 114.91; 120.71; 127.93; 128.27; 131.77; 132.24; 139.82; 159.03. MS(FAB+): m/z 320. IR(CHCl3): 2960, 2936, 2874, 1608, 1518, 1485, 1475 cm-1.
With potassium carbonate; In butanone; for 8h;Reflux;
General procedure: A suspension of <strong>[29558-77-8]4-bromo-4'-hydroxybiphenyl</strong> (13) (3.5 g, 14.11 mmol), 1-bromoheptane (3.75 g, 21.05 mmol) and K2CO3 (4.9 g, 35.28 mmol) in 2-butanone (25 mL) was refluxed for 8 h. After cooling, the reaction mixture was diluted by CH2Cl2 (50 mL). After filtration, the organic layer was washed by H2O (50 mL) and saturated brine (50 mL), dried over anhydrous Na2SO4, and filtrated. The solvent was condensed to 15 mL under reduced pressure, and the residue was collected and washed by cool hexane (0 C) to afford 14c (4.6 g, yield 94.3%) as white solid.
87%
Add 1450 mL of water to a 2 L three-neck bottle. 21.2 g of sodium hydroxide, After stirring and dissolving, 120 g of 4-hydroxy-4'-bromobiphenyl and 6 g of tetrabutylammonium bromide were added. After stirring at room temperature for 10 min, 87.2 g of 1-bromopentane was added dropwise. After the completion of the dropwise addition, reflux for 5 hours. After the reaction is cooled to room temperature, it is filtered by suction. The filter cake was washed with 400 mL of water. The solid was hot beaten with 600 mL of a n-heptane/water (1:1) mixed solution. Filter by suction and wash the filter cake with 60 mL of n-heptane. The obtained solid was vacuum dried at 60 C for 5 hours in a yield of 87%.
With sodium hydroxide; In water; dimethyl sulfoxide; ethyl acetate;
Part A 4-(4-n-Pentyloxyphenyl) bromobenzene To a stirred solution of 25.5 g of 4-(4-bromophenyl)phenol. (Compound (a)) in 400 mL of dimethylsulfoxide was added 40.9 mL of 2.5 N NaOH, followed by 12.7 mL of n-pentyl bromide, and the resulting mixture heated at 70 C. for 18 hours to obtain in the mixture, compound (b). The mixture was partitioned between 1000 mL of ethyl acetate and 500 mL water and from the organic phase after washing with water and brine, and drying was obtained 30.9 grams of Compound (b) as a white solid.
With sodium hydroxide; In water; dimethyl sulfoxide; ethyl acetate;
Part A: 4-(4-n-Pentyloxyphenyl) bromobenzene To a stirred solution of 25.5 g of 4-(4-bromophenyl)phenol (Compound (a)) in 400 mL of dimethylsulfoxide was added 40.9 mL of 2.5 N NaOH, followed by 12.7 mL of n-pentyl bromide, and the resulting mixture heated at 70 C. for 18 hours to obtain in the mixture, compound (b). The mixture was partitioned between 1000 mL of ethyl acetate and 500 mL water and from the organic phase after washing with water and brine, and drying was obtained 30.9 grams of Compound (b) as a whim solid. 1 H NMR (400 MHz, DMSO-d6) delta0.93 (t, J=7.2 Hz, 3H), 1.41 (m, 4H), 1.79 (m, 2H), 3.97 (t, J=6.6 Hz, 2H), 6.94 (d, J=8.8 Hz, 2H), 7.39 (d, J=8.6 Hz, 2H), 7.45 (d, J=8.8 Hz, 2H), 7.51 (d, J=8.6 Hz, 2H).
With sodium hydroxide; In dimethyl sulfoxide;
Step 1: 4-(4-n-Pentoxyphenyl)bromobenzene To a stirred solution of 4-(4-bromophenyl)phenol (25.5 g, 0.102 mol) in 400 mL of dimethylsulfoxide was added 2.5N NaOH (40.9 ml, 0.102 mol) followed by n-pentyl bromide (12.7 mL, 0.102 mol). The resulting mixture was heated at 70 C. for a period of 18 h. After cooling, the yellow solution was partitioned between ethyl acetate (1000 ml) and water (500 ml). The organic phase was washed with water (3*) and brine and dried with magnesium sulfate. The solvent was removed in vacuo to give 4-(4-n-pentoxyphenyl)bromobenzene (30.9 g): 1 H NMR (400 MHz, DMSO-d6) delta 0.93 (t, 3, J=7.2 Hz), 1.41 (m, 4), 1.79 (m, 2), 3.97 (t, 2, J=6.6 Hz), 6.94 (d, 2, J=8.8 Hz), 7.39 (d, 2, J=8.6 Hz), 7.45 (d, 2, J=8.8 Hz), 7.51 (d, 2, J=8.6 Hz).
With sodium hydroxide; In dimethyl sulfoxide;
Step 2 4-(4-n-Pentoxyphenyl)bromobenzene To a stirred solution of 4-(4-bromophenyl)phenol (25.5 g, 0.102 mol) in 400 mL of dimethylsulfoxide was added 2.5N NaOH (40.9 ml, 0.102 mol) followed by n-pentyl bromide (12.7 mL, 0.102 mol). The resulting mixture was heated at 70 C. for a period of 18 h. After cooling, the solution was partitioned between ethyl acetate (1000 ml) and water (500 ml). The organic phase was washed with water (3*) and brine and dried with magnesium sulfate. The solvent was removed in vacuo to give 30.9 g of 4-(4-n-pentoxyphenyl)-bromobenzene: 1 H NMR (400 MHz, DMSO-d6) delta0.93 (t, 3H, J=7.2 Hz), 1.41 (m, 4H), 1.79 (m, 2H), 3.97 (t, 2H, J=6.6 Hz), 6.94 (d, 2H, J=8.8 Hz), 7.39 (d, 2H, J=8.6 Hz), 7.45 (d, 2H, J=8.8 Hz), 7.51 (d, 2H, J=8.6 Hz).
With sodium hydroxide; In water; dimethyl sulfoxide; ethyl acetate;
Part A: 4-(4-n-Pentyloxyphenyl) bromobenzene. To a stirred solution of 25.5 g of 4-(4-bromophenyl)phenol (Compound (a)) in 400 mL of dimethylsulfoxide was added 40.9 mL of 2.5N NaOH, followed by 12.7 mL of n-pentyl bromide, and the resulting mixture heated at 70 C. for 18 hours to obtain in the mixture, compound (b). The mixture was partitioned between 1000 mL of ethyl acetate and 500 mL water and from the organic phase after washing with water and brine, and drying was obtained 30.9 grams of Compound (b) as a white solid.
With sodium hydroxide; In water; dimethyl sulfoxide; ethyl acetate;
A. Preparation of pentyloxy-substituted-terphenyl-carboxylic acid STR30 Part A: 4-(4-n-Pentyloxyphenyl)bromobenzene To a stirred solution of 25.5 g of 4-(4-bromophenyl)phenol (Compound (a)) in 400 mL of dimethylsulfoxide was added 40.9 mL of 2.5N NaOH, followed by 12.7 mL of n-pentyl bromide, and the resulting mixture heated at 70 C. for 18 hours to obtain in the mixture, compound (b). The mixture was partitioned between 1000 mL of ethyl acetate and 500 mL water and from the organic phase after washing with water and brine, and drying was obtained 30.9 grams of Compound (b) as a white solid.
With sodium hydroxide; In water; dimethyl sulfoxide; ethyl acetate;
Part A: 4-(4-n-Pentyloxyphenyl)bromobenzene. To a stirred solution of 25.5 g of 4-(4-bromophenyl)phenol. (Compound (a)) in 400 mL of dimethylsulfoxide was added 40.9 mL of 2.5 N NaOH, followed by 12.7 mL of n-pentyl bromide, and the resulting mixture heated at 70 C. for 18 hours to obtain in the mixture, compound (b). The mixture was partitioned between 1000 mL of ethyl acetate and 500 mL water and from the organic phase after washing with water and brine, and drying was obtained 30.9 grams of Compound (b) as a white solid.
General procedure: n-BuLi (2.5 M, 7.4 mL, 18 mmol) was added dropwise to a solution of compound 14c (4.5 g, 13 mmol) in MTBE (50 mL) at -20 C under nitrogen atmosphere. After stirring for 2 h, the reaction mixture was cooled to -60 C and was added THF (6 mL). Then, a solution of (i-PrO)3B (6.1 mL, 26 mmol) in MTBE (8 mL) was added dropwise to the resulting mixture and was stirred for 1 h. The reaction mixture was allowed to warm to room temperature, stirred overnight and treated with 2 M HCl (50 mL) for 10 min. The organic layer was separated and the solvent was evaporated under reduced pressure. The residue was added hexane (40 mL) and stirred for 10 min. After filtration, the filter cake was washed by hexane-MTBE (8: 1) to give 15c (3.7 g, yield 91.4%) as white solid.
(i) Synthesis of 4'-n-pentyloxy-4-bromobiphenyl 4'-n-pentyloxy-4-bromobiphenyl was obtained in the same manner as in the step (i) of the Example 27, except for using 4'-hydroxy-4-bromobiphenyl, n-pentyl bromide, and ethanol as the recrystallization solvent instead of 4-(benzyloxy)phenol, n-propyl bromide, and methanol, respectively.
B. 4-Boronic acid-4'-pentyloxybiphenyl To a cold (-20C) mixture of Preparation 8A (100g, 0.31mol) in MTBE (1L), was slowly added n-butyl lithium (150mL of a 2.5M hexanes solution, 0.37mol) dropwise under N2, while maintaining the internal temperature between -19 and -18C. The resultant mixture was stirred for 3.5h between -17 and -16C which resulted in light yellow-green solution. This solution was cooled to -78C and diluted with 100mL of anhydrous THF which resulted in a white precipitate.
21
[ 63619-51-2 ]
4'-n-pentyloxy-4-(2-tert-butoxycarbonylvinyl)biphenyl[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
(ii) Synthesis of 4'-n-pentyloxy-4-(2-tert-butoxycarbonylvinyl)biphenyl 4'-n-pentyloxy-4-(2-tert-butoxycarbonylvinyl)biphenyl was obtained in the same manner as in the Example 44, except for using 4'-n-pentyloxy-4-bromobiphenyl synthesised in the step (i) and hexane as the recrystallization solvent instead of 4-(tert-butoxycarbonyloxy)-4'-bromobiphenyl and methanol, respectively. 1H-NMR(CDCl3) ppm: 0.94(t, 3H, CH3), 1.30-1.55(m, 4H, C2H4), 1.55(s, 9H, tert-Bu), 1.74-1.90(m, 2H, CH2), 4.00(t, 2H, OCH2), 6.39(d, 1H, CH=CH), 6.98(d, 2H, C6H4), 7.50-7.61(d, 6H, C6H4), 7.61(d, 1H, CH=CH).
Preparation of 4-Bromo-4'-pentyloxybiphenyl 1(a): Anhydrous K2CO3 (416 g, 3 mol) was added to a mixture of 4-bromo-4'-hydroxybiphenyl (300 g, 1. 2 mol), 1-iodopentane (234 ml, 1.79 mol) and 2-butanone (600 ml). The reaction mixture was refluxed for 44 h until TLC (85:15 hexanes/EtOAc) showed complete consumption of the bromo alcohol. The mixture was cooled to about 30 C., diluted with CH2Cl2 (600 ml) and then filtered. The filtrate was washed twice with H2O and twice with a saturated aqueous NaCl solution, dried over anhydrous Na2SO4, filtered and then dried at reduced pressure to provide a solid. This solid was isolated by filtration, washed repeatedly with a total of 2L of ice-cold heptane to remove all traces of iodopentane and then dried overnight under high vacuum. Yield: 340 g (88%) of a white powder.
With potassium carbonate;
Preparation of 4-Bromo-4'-pentyloxybiphenyl 1(a): Anhydrous K2CO3 (416g, 3 mol) was added to a mixture of 4-bromo-4'-hydroxybiphenyl (300 g, 1.2 mol), 1-iodopentane (234 ml, 1.79 mol) and 2-butanone (600 ml). The reaction mixture was refluxed for 44 h until TLC (85:15 hexanes/EtOAc) showed complete consumption of the bromo alcohol. The mixture was cooled to about 30 C., diluted with CH2C12 (600 ml) and then filtered. The filtrate was washed twice with H2O and twice with a saturated aqueous NaCl solution, dried over anhydrous Na2SO4, filtered and then dried at reduced pressure to provide a solid. This solid was isolated by filtration, washed repeatedly with a total of 2 L of ice-cold heptane to remove all traces of iodopentane and then dried overnight under high vacuum. Yield: 340 g (88%) of a white powder.
With potassium carbonate;
A. 4-Bromo-4'-pentyloxybiphenyl Anhydrous K2CO3(416g, 3mol) was added to a mixture of 4-bromo-4'-hydroxybiphenyl (300g, 1.2mol), 1-iodopentane (234mL, 1.79mol) and 2-butanone (600mL). The reaction mixture was refluxed for 44h until TLC (85:15 hexanes/EtOAc) showed complete consumption of the bromo alcohol. The mixture was cooled to about 30C, diluted with CH2Cl2(600mL) and then filtered. The filtrate was washed twice with H2O and twice with a saturated aqueous NaCl solution, dried over anhydrous Na2SO4, filtered and then dried at reduced pressure to provide a solid. This solid was isolated by filtration, washed repeatedly with a total of 2L of ice-cold heptane to remove all traces of iodopentane and then dried overnight under high vacuum. Yield: 340g (88%) of a white powder.
31,9 g (0,1 mol) 4-Brom-4'-n-pentoxy[1,1']biphenyl werden unter Stickstoffatmosphaere in 640 ml Tetrahydrofuran geloest, auf -78C gekuehlt und innerhalb von 2 Stunden tropfenweise mit 67 ml (0,11 mol) einer 15%igen Loesung von n-Butyilithium in Hexan versetzt. Dabei wird die Innentemperatur in einem Bereich von -78C bis -65C gehalten. Nach beendeter Zugabe wird die dicke, milchige Suspension weitere 15 Minuten bei -78C geruehrt und im Anschluss daran mit 25,5 ml (0,11 mol) Triisopropylborat innerhalb 15 Minuten bei -78C tropfenweise versetzt. Nach beendeter Boratzugabe erhaelt man eine klare Loesung, welche 15 Minuten bei -78C nachgeruehrt wird. Im Anschluss daran wird das Kaeltebad entfernt und nach 40 Minuten die Loesung mit 100 ml 2N Salzsaeure auf pH 2 gestellt. Die Phasen werden getrennt, die organische Phase mit Wasser und gesaettigter Kochsalzloesung gewaschen und im Anschluss daran werden die Loesungsmittel unter Zusatz von 200 ml Wasser destillativ entfernt. Der ausgefallene Feststoff wird abfiltriert und getrocknet. Man erhaelt 25,8 g (91 %) 4'-n-Pentoxy[1,1']biphenyl-4-boronsaeure vom Schmelzpunkt 148-150C.
With n-butyllithium; In tetrahydrofuran;
Step 2; 4-(4-n-Pentoxyphenyl)phenylboronic acid To a stirred suspension of 4-(4-n-pentoxyphenyl)bromobenzene (1.0 g, 3.13 mmol) in anhydrous tetrahydrofuran (20 ml) at -78 C. under a nitrogen atmosphere was added n-butyllithium in hexanes (2.5M, 1.32 ml, 3.30 mmol). After a period of 15 min, triisopropylborate (760 mul, 3.30 mmol) was added. Stirring at -78 C. was continued for 15 min and then at 25 C. for 40 min. The mixture was acidified with 0.5N HCl (20 mL) and then partitioned between ether (50 ml) and water (40 ml). The organic phase was washed with water (3*) and brine and dried with magnesium sulfate. The solvent was removed in vacuo to give 4-(4-n-pentoxyphenyl)phenylboronic acid (750 mg) as a white solid: 1 H NMR (400 MHZ, DMSO-d6) delta 0.89 (t, 3, J=7.2 Hz), 1.38 (m, 4), 1.72 (m, 2), 3.99 (t, 2, J=6.5 Hz), 6.99 (d, 2, J=8.8 Hz), 7.57 (d, 2, J=8.2 Hz), 7.60 (d, 2, J=8.8 Hz), 7.83 (d, 2, J=8.2 Hz).
With potassium acetate; palladium diacetate; tris-(o-tolyl)phosphine; In tetrahydrofuran; methanol; at 0 - 20℃;Inert atmosphere;
Example 3 Synthesis of 4-pentyloxy-4'-biphenylboronic acid under nitrogen protection, Add 5g of 4'-bromo-4-n-pentyloxybiphenyl to a 100mL three-necked flask. 88 mg of palladium acetate, 4.6 g of potassium acetate, 144 mg of tris(o-methylphenyl)phosphine and 15 mL of tetrahydrofuran, The ice water bath is cooled to 0-10 C. 1.84 g of tetrahydroxydiboron was dissolved in 10 mL of methanol and added dropwise to the reaction. Stir the reaction at room temperature, After the raw materials disappeared, add 30mL of ethanol to dilute. Filtering, The filter cake was washed with 10 mL of ethanol. The filtrate was spun dry, and then 80 ml of a dichloromethane/water mixed solvent (1:1) was added and hot-battered at 40 C for 1 h. After cooling to room temperature, suction filtration, The filter cake was washed sequentially with 5 mL of water and 5 mL of dichloromethane. Drying at 50 C under vacuum gave 2.84 g of a white solid. The yield was 64%.
4-(1,1-difluoroethyl)-4'-(pentyloxy)-1,1'-biphenyl[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
56%
With dmap; bis(tricyclohexylphosphine)nickel(II) dichloride; 4,4'-diamino-2,2'-bipyridyl; magnesium chloride; zinc; In dimethyl sulfoxide; at 110℃; for 10h;Schlenk technique;
To a 10 ml Schlenk reaction tube, add <strong>[63619-51-2]4-bromo-4 '-(pentyloxy) biphenyl</strong> (0.2 mmol),Bis (tricyclohexylphosphine) nickel dichloride (10 mol%), 4,4?-diamino-2,2?-bipyridine (10 mol%),4-dimethylaminopyridine (20mol%), magnesium chloride (3 equivalents), zinc powder (2 equivalents),In other vacuum with nitrogen, and then the reaction solution was dissolved in DMSO 1(Be prepared before the reaction, slowly pass reactant 1 into DMSO, until the total volume does not increase, after 19F NMR detection concentration is 0.7mol / L) Add 1mL,The reaction was carried out at 110 C for 10h. After the reaction was completed, the reaction was detected by TLC, and the target product was obtained by column chromatography (56%)
Chemistry
Pharmaceutical Intermediates
Inhibitors/Agonists
Material Science
For Research Only
110K+ Compounds
Competitive Price
1-2 Day Shipping
