* 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.
Stage #1: With iodine; magnesium In tetrahydrofuran at 70℃; Stage #2: With N,N-dimethyl-formamide In tetrahydrofuran at 0℃; for 2 h; Stage #3: With ammonia; iodine In tetrahydrofuran; water at 20℃; for 2 h;
General procedure: To a flask containing Mg turnings (0.29 g, 12 mmol) was added1-bromo-4-methylbenzene (1.37 g, 8.0 mmol) in THF (8 mL) at room temperature. After being stirred for 2 h, DMF (1.3 mL,12 mmol) was added to the reaction mixture. The obtained mixturewas stirred for 2 h at 0 ° C. Then, aq NH3 (7 mL, 28-30percent) and I2 (4.06 g, 16 mmol) were added to the reaction mixture. After beingstirred for 2 h at room temperature, the reaction mixture waspoured into satd aq Na2SO3 solution and was extracted with CHCl3 (3*30 mL). The organic layer was dried over Na2SO4 and filtered.After removal of the solvent, the residue was purified by shortcolumn chromatography on silica gel (eluent: hexane/ethylacetate=9:1, v/v) to provide pure 4-methyl-1-benzonitrile (0.77 g) in 82percent yield.
With sulfuric acid; diisobutylaluminium hydride; In water; ethyl acetate; toluene;
(a) A solution of 6.23 g of 4'-pentyl-4-cyanobiphenyl in 50 ml of absolute toluene was placed at 0 C. in a sulphonation flask under argon gasification and treated within 10 minutes with 27 ml of a 1.36N solution of diisobutylaluminium hydride in toluene. After completion of the addition, the mixture was stirred at room temperature for a further 22 hours, then poured cautiously into 50 ml of 1N sulphuric acid and extracted three times with 100 ml of diethyl ether each time. The organic phases were washed once with 50 ml of 1N sulphuric acid and twice with 50 ml of water each time, dried over magnesium sulphate and concentrated. Low-pressure chromatography (0.5 bar) of the oily residue (6.0 g on silica gel with 10% ethyl acetate/petroleum ether gave 5.86 g (93%) of 4-formyl-4'-pentylbiphenyl as a colourless viscous oil (purity 99.7%).
98%
With hydrogenchloride; diisobutylaluminium hydride; In dichloromethane; water; ethyl acetate; toluene;
(a) A solution of 10 g of 4-cyano-4'-pentylbiphenyl in 150 ml of methylene chloride was placed at -78 C. in a sulphonation flask under argon gasification and treated within 15 minutes with 54 ml of a 1.5N solution of diisobutylaluminium hydride in toluene. Subsequently, the mixture was stirred at -78 C. for a further 30 minutes, then poured cautiously into 50 ml of 2N hydrochloric acid and extracted three times with 100 ml of methylene chloride each time. The organic phases were washed a further twice with 100 ml of water each time, dried over magnesium sulphate and concentrated. Low-pressure chromatography (0.5 bar) of the oily residue (22.0 g) on silica gel with 3% ethyl acetate/petroleum ether gave 10.0 g (99%) of 4'-pentyl-4-biphenylylcarboxaldehyde as a colourless viscous oil (purity 98%).
Specific examples of compounds within these families are: 4-cyano-4'-pentylbiphenyl, 4-cyano-4'-hexyloxybiphenyl, trans-4-pentyl-(4'-cyanophenyl)cyclohexane, trans-4-hexyl-(4'-cyanobiphenyl)cyclohexane, 4-cyanophenyl-4'-propylbenzoate, 4-pentyloxyphenyl-4'-cyanobenzoate, 4-hexylphenyl-4'-cyanobenzoate, 1-(4'-pentylphenyl)-4-butylpyrimidine, 1-(4'-butyloxyphenyl)-4-cyanopyrimidine, ...
11
[ 103-11-7 ]
[ 40817-08-1 ]
polymer, Mw ca. 9.4E4 Da, Mn ca. 3.8E4 Da, Mw/Mn ca. 2.5; monomer(s): 2-ethylhexyl acrylate; 4-cyano-4\-n-pentylbiphenyl, 10 wt percent[ No CAS ]
4-(E-2-fluoro-1-ethenyl)-4'-pentylbiphenyl[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
EXAMPLE 5 Preparation of 4-pentyl-4'-(E-2-fluoro-1-ethenyl)biphenyl Using <strong>[40817-08-1]4-pentyl-4'-cyanobiphenyl</strong> as a starting raw material and similarly to the procedure in Example 3, (i), (ii) and (iii), 4-pentyl-4'-(E-2-fluoro-1-ethenyl)biphenyl was prepared. This compound exhibited an SI point of 123 C.
General procedure: To a flask containing Mg turnings (0.29 g, 12 mmol) was added1-bromo-4-methylbenzene (1.37 g, 8.0 mmol) in THF (8 mL) at room temperature. After being stirred for 2 h, DMF (1.3 mL,12 mmol) was added to the reaction mixture. The obtained mixturewas stirred for 2 h at 0 C. Then, aq NH3 (7 mL, 28-30%) and I2 (4.06 g, 16 mmol) were added to the reaction mixture. After beingstirred for 2 h at room temperature, the reaction mixture waspoured into satd aq Na2SO3 solution and was extracted with CHCl3 (3*30 mL). The organic layer was dried over Na2SO4 and filtered.After removal of the solvent, the residue was purified by shortcolumn chromatography on silica gel (eluent: hexane/ethylacetate=9:1, v/v) to provide pure 4-methyl-1-benzonitrile (0.77 g) in 82% yield.
2,4-bis(trichloromethyl)-6-(4'-pentylbiphenyl)-s-triazine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
68%
With hydrogenchloride; aluminum tri-bromide; at 0 - 23℃; for 15h;Inert atmosphere;
4'-Pentyl-4-biphenylcarbonitrile 1a(10.0 g, 40.10 mmol) was reacted with trichloroacetonitrile(92.64 g, 641.64 mmol) was added aluminum bromide(1.06 g, 4.01 mmol). Hydrogen chloride gas, which had been dried through a dip tube, was poured into the mixture at 0 C for 3 hours and stirred at room temperature (23 C) for 12 hours. 2,4,6-Tris (trichloromethyl) -s-triazine was dissolved and removed by using n-hexane to crystallize the product 1b (14.67 g, yield = 68%).
General procedure: Under nitrogen atmosphere, Cu2O (10 mol %), DABCO (25 mol %), and a stirring bar were added into a 10 mL oven-dried sealed glass tube (as shown in Figure S1). Then NMP (0.5 mL), aryl iodides (0.125 mmol, 1.0 equiv.) and PhSiH3 (0.75 mmol, 6 equiv.) were injected by syringe. The tube wasthen sealed and CO2 (0.67 mmol, 5.4 equiv., 15 mL) as well as NH3 (0.67 mmol, 5.4 equiv., 15 mL) were injected by syringe after N2 was removed under vacuum. Finally, the mixture was stirred for 24 hr in a pre-heated-to-130 C alloyed block. After the reaction was finished, the tube was cooled to room temperature and the pressure was carefully released. The yield of were measured by GC analysis using dodecane as the internal standard or by flash chromatography on silica gel (petroleumether/ethyl acetate).
General procedure: To a solution of 4-bromobiphenyl 1a (3.0 mmol, 699.3 mg) in THF (3.0 mL) was added n-BuLi (4.5 mmol, 1.55 M in hexane, 2.87 mL) at 50 C. The obtained mixture was stirred for 30 min at 50 C under an argon atmosphere. Pivalonitrile (6.0 mmol, 498.8 mg) in THF (2.0 mL) was added to the mixture at 50 C and the obtained mixture was stirred for 30 min in the temperature range of 50 C to room temperature. MeOH (2.0 mL) was added to the mixture. Then, I2 (12.0 mmol, 3045.6 mg) and K2CO3 (12.0 mmol, 1658.4 mg) were added to the mixture at room temperature, and the obtained mixture was stirred for 6 h at 70 C. Sat. aq. Na2SO3 solution (20.0 mL) was added to the reaction mixture, and the product was extracted with AcOEt (10.0 mL x 3). The organic layer was dried over Na2SO4. After filtration and removal of the solvent, the residue was purified by silica-gel column chromatography (chloroform: n-hexane 1:1) to give 4-cyanobiphenyl 2a (451.6 mg, 84%).