1-bromo-4-but-3-enylbenzene

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: About 20.0 g (95 mMol) of 4-(3-butenyl)-1-bromobenzene [which can be prepared, for example, by the method of P. E. Peterson et al, J. Org. Chem. 33, 972 (1968)] were dissolved in 40 ml of toluene, 2 ml of a platinum catalyst solution (0.5 percent solution of cyclopentadiene-platinum dichloride in dichloromethane) were added, and the mixture was added dropwise to a stirred solution containing 16 g (0.18 Mol) of commercially available dimethylethylsilane in 20 ml of toluene. The mixture was stirred at 50° to 70° C. for 3 hours and then cooled, and the solvent was removed by distillation. The residue was fractionated under reduced pressure. Approximately 19.4 g of 4-[4-(dimethylethylsilyl)butyl]-1-bromobenzene (67.9 percent yield) were obtained at a pressure of 0.05 hPa and at a temperature of 110° to 112° C. A mixture containing 18 g (0.06 Mol) of this derivative, 6.3 g (0.07 Mol) of CuCN and 10 ml of dimethylformamide was heated at 160° C. for 8 hours. The mixture, still hot at 80° C., was poured into a mixture containing 30 g of iron(III) chloride, 7.5 ml of concentrated hydrochloric acid and 90 ml of water, and the full mixture was stirred at 70° C. for 75 minutes. The product was then extracted with tert-butyl methyl ether, the extract was washed, dried and evaporated, and the residue was fractionated. About 9.9 g of 4-[4-(dimethylethylsilyl)butyl]benzonitrile were obtained at 0.02 hPa and at 114° to 116° C. (66.6 percent yield). the mixture was added dropwise to a stirred solution cooled the solvent was removed by distillation

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: About 20.0 g (95 mMol) of 4-(3-butenyl)-1-bromobenzene [which can be prepared, for example, by the method of P. E. Peterson et al, J. Org. Chem. 33, 972 (1968)] were dissolved in 40 ml of toluene, 2 ml of a platinum catalyst solution (0.5 percent solution of cyclopentadiene-platinum dichloride in dichloromethane) were added, and the mixture was added dropwise to a stirred solution containing 16 g (0.18 Mol) of commercially available dimethylethylsilane in 20 ml of toluene. The mixture was stirred at 50° to 70° C. for 3 hours and then cooled, and the solvent was removed by distillation. The residue was fractionated under reduced pressure. Approximately 19.4 g of 4-[4-(dimethylethylsilyl)butyl]-1-bromobenzene (67.9 percent yield) were obtained at a pressure of 0.05 hPa and at a temperature of 110° to 112° C. A mixture containing 18 g (0.06 Mol) of this derivative, 6.3 g (0.07 Mol) of CuCN and 10 ml of dimethylformamide was heated at 160° C. for 8 hours. The mixture, still hot at 80° C., was poured into a mixture containing 30 g of iron(III) chloride, 7.5 ml of concentrated hydrochloric acid and 90 ml of water, and the full mixture was stirred at 70° C. for 75 minutes. The product was then extracted with tert-butyl methyl ether, the extract was washed, dried and evaporated, and the residue was fractionated. About 9.9 g of 4-[4-(dimethylethylsilyl)butyl]benzonitrile were obtained at 0.02 hPa and at 114° to 116° C. (66.6 percent yield). the mixture was added dropwise to a stirred solution cooled the solvent was removed by distillation

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of Pd2(dba)3 (517.6 mg, 5 mol % Pd), BINAP (1.06 g, 1.5 eq of Pd), and potassium tert-butoxide (3.05 g, 27.13 mmol) in 80 ml toluene was prepared in a round-bottom flask in a glove box. The 4-(4-bromophenyl)-1-butene (5.00 g, 22.6 mmol) and 2,4,6-trimethylaniline (3.80 ml, 27.13 mmol) were added by syringe, and the reaction mixture was stirred at 80° C. oil bath for 12 h. The mixture was quenched with a saturated NaHCO3(aq) solution and then concentrated under reduced pressure. The crude product was purified by column chromatography (t-butyl methyl ether/heptane (v/v)=3/97, Rf=0.3) to afford N-(4-(but-3-en-1-yl)phenyl)-2,4,6-trimethylaniline (4.83 g, 76.7%). 1H NMR (300 MHz, CDCl3): δ 6.95 (m, 4H), 6.44 (s, 1H), 6.42 (s, 1H), 5.87 (m, 1H), 5.01 (m, 2H+NH), 2.60 (t, 2H), 2.30 (s, 1H), 2.17 (s, 6H). 13C NMR (100 MHz, CDCl3): δ 144.7, 138.8, 135.6, 135.2 (2C), 134.8, 131.5, 129.4 (2C), 129.2 (2C), 114.8, 113.6 (2C), 36.1, 34.8, 21.1, 18.5 (2C). MS (EI): m/z: calc. for C19H23N: 265.18. found 265.18. was prepared in a round-bottom flask in a glove box The mixture was quenched with a saturated NaHCO3(aq) solution concentrated under reduced pressure The crude product was purified by column chromatography (t-butyl methyl ether/heptane (v/v)=3/97, Rf=0.3)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 250 ml two-necked round-bottom flask, equipped with an additional funnel and condenser, was charged with 4-bromo-benzyl bromide (20.0 g, 80 mmol) in 50 ml dry ether at 0° C. ice bath for 10 min. The allylmagnesium chloride (48.0 ml of a 2.0 M solution in ether, 96 mmol) was added dropwisely via an additional funnel over a period of 30 min at 0° C. Subsequently, the mixture was stirred at room temperature for 2 h and refluxed for another 3 h. The reaction was monitored by TLC analysis. After the starting material disappeared, the reaction was quenched by water and transferred to a separation funnel. The organic layer was washed with brine, dried over anhydrous MgSO4, and then concentrated under vacuum to yield a yellow crude liquid. The product was purified by Kugelrhor distillation to obtain the final product as a transparent liquid (14.10 g, 83%), whose 1H and 13C NMR spectra matched with the earlier reported literature data [7]. A 250 ml two-necked round-bottom flask, equipped with an additional funnel and condenser refluxed for another 3 h the reaction was quenched by water transferred to a separation funnel The organic layer was washed with brine dried over anhydrous MgSO4 concentrated under vacuum to yield a yellow crude liquid The product was purified by Kugelrhor distillation

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 250 ml two-necked round-bottom flask, equipped with an additional funnel and condenser, was charged with 4-bromo-benzyl bromide (20.0 g, 80 mmol) in 50 ml dry ether at 0° C. ice bath for 10 min. The allylmagnesium chloride (48.0 ml of a 2.0 M solution in ether, 96 mmol) was added dropwisely via an additional funnel over a period of 30 min at 0° C. Subsequently, the mixture was stirred at room temperature for 2 h and refluxed for another 3 h. The reaction was monitored by TLC analysis. After the starting material disappeared, the reaction was quenched by water and transferred to a separation funnel. The organic layer was washed with brine, dried over anhydrous MgSO4, and then concentrated under vacuum to yield a yellow crude liquid. The product was purified by Kugelrhor distillation to obtain the final product as a transparent liquid (14.10 g, 83%), whose 1H and 13C NMR spectra matched with the earlier reported literature data [7]. A 250 ml two-necked round-bottom flask, equipped with an additional funnel and condenser refluxed for another 3 h the reaction was quenched by water transferred to a separation funnel The organic layer was washed with brine dried over anhydrous MgSO4 concentrated under vacuum to yield a yellow crude liquid The product was purified by Kugelrhor distillation

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 15.6 g of a monohydrate of hydrazine was added a solution of 5.0 g of 4-(3-butenyl)benzaldehyde (synthesized by reacting 1-(3-butenyl)-4-bromobenzene with magnesium to prepare a Grignard reagent which is then reacted with DMF) in 20 ml of ethanol. The mixture was stirred at room temperature for 30 minutes. To the mixture was then added 20 ml of saturated aqueous solution of sodium bicarbonate. To the mixture was then added 10 ml of dichloromethane. The mixture was then washed with 10 ml of saturated aqueous solution of sodium bicarbonate twice. To the resulting organic phase was then added 3.5 ml of triethylamine. The mixture was then dehydrated and dried over anhydrous sodium sulfate. The solvent was then distilled off under reduced pressure. To the residue was then added 3.5 ml of triethylamine. To the mixture were then added 20 ml of ethanol and 3.75 g of 4-methylbenzaldehyde. The mixture was then stirred at room temperature for 3 hours. To the mixture was then added 20 ml of saturated aqueous solution of sodium bicarbonate. To the mixture was then added 10 ml of dichloromethane. The mixture was then washed with 10 ml of saturated aqueous solution of sodium bicarbonate. The solvent was then distilled off under reduced pressure. The residue was purified through alumina (basic) column chromatography (dichloromethane), and then recrystallized from methanol to obtain 7.0 g of 1-[4-(3-butenyl)benzylidene]-2-(4-methylbenzylidene)hydrazine. The compound thus obtained had a melting point of 82° C. and exhibited nematic phase up to 103° C. synthesized The mixture was then washed with 10 ml of saturated aqueous solution of sodium bicarbonate twice To the resulting organic phase was then added 3.5 ml of triethylamine dried over anhydrous sodium sulfate The solvent was then distilled off under reduced pressure To the residue was then added 3.5 ml of triethylamine To the mixture were then added 20 ml of ethanol and 3.75 g of 4-methylbenzaldehyde The mixture was then stirred at room temperature for 3 hours To the mixture was then added 20 ml of saturated aqueous solution of sodium bicarbonate To the mixture was then added 10 ml of dichloromethane The mixture was then washed with 10 ml of saturated aqueous solution of sodium bicarbonate The solvent was then distilled off under reduced pressure The residue was purified through alumina (basic) column chromatography (dichloromethane) recrystallized from methanol

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 2M solution of allylmagnesium chloride in THF (24 mL, 48.00 mmol, 1.5 equiv) at 0° C. was added, under an atmosphere of N2, 4-bromobenzyl bromide (8.00 g, 32.01 mmol, 1.0 equiv) neat in 10 portions over a period of 5 min. The mixture was stirred for 1 h at 0° C. and then at rt for 28 h. The mixture was carefully quenched with water (100 mL) and then extracted with ethyl acetate (3×150 mL). The combined extracts were washed with brine (2×50 mL), dried over anhydrous Na2SO4, and concentrated. High-vacuum drying gave 11a (6.51 g, 30.84 mmol, 96%) as a clear oil: Rf=0.94 (ethyl acetate); 1H NMR (400 MHz, CDCl3): δ 2.32-2.38 (m, 2H), 2.67 (t, J=7.8 Hz, 2H), 4.98-5.06 (m, 2H), 5.78-5.86 (m, 1H), 7.06 (d, J=8.4 Hz, 2H), 7.40 (d, J=8.4 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 34.9, 35.4, 115.4, 119.7, 130.4, 131.5, 137.7, 140.9; HRMS (EI) Calcd. for C10H11Br: 210.0044 (M+). Found: 210.0053. at rt for 28 h The mixture was carefully quenched with water (100 mL) extracted with ethyl acetate (3×150 mL) The combined extracts were washed with brine (2×50 mL) dried over anhydrous Na2SO4 concentrated High-vacuum drying

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 2M solution of allylmagnesium chloride in THF (24 mL, 48.00 mmol, 1.5 equiv) at 0° C. was added, under an atmosphere of N2, 4-bromobenzyl bromide (8.00 g, 32.01 mmol, 1.0 equiv) neat in 10 portions over a period of 5 min. The mixture was stirred for 1 h at 0° C. and then at rt for 28 h. The mixture was carefully quenched with water (100 mL) and then extracted with ethyl acetate (3×150 mL). The combined extracts were washed with brine (2×50 mL), dried over anhydrous Na2SO4, and concentrated. High-vacuum drying gave 11a (6.51 g, 30.84 mmol, 96%) as a clear oil: Rf=0.94 (ethyl acetate); 1H NMR (400 MHz, CDCl3): δ 2.32-2.38 (m, 2H), 2.67 (t, J=7.8 Hz, 2H), 4.98-5.06 (m, 2H), 5.78-5.86 (m, 1H), 7.06 (d, J=8.4 Hz, 2H), 7.40 (d, J=8.4 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 34.9, 35.4, 115.4, 119.7, 130.4, 131.5, 137.7, 140.9; HRMS (EI) Calcd. for C10H11Br: 210.0044 (M+). Found: 210.0053. at rt for 28 h The mixture was carefully quenched with water (100 mL) extracted with ethyl acetate (3×150 mL) The combined extracts were washed with brine (2×50 mL) dried over anhydrous Na2SO4 concentrated High-vacuum drying

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: About 20.0 g (95 mMol) of 4-(3-butenyl)-1-bromobenzene [which can be prepared, for example, by the method of P. E. Peterson et al, J. Org. Chem. 33, 972 (1968)] were dissolved in 40 ml of toluene, 2 ml of a platinum catalyst solution (0.5 percent solution of cyclopentadiene-platinum dichloride in dichloromethane) were added, and the mixture was added dropwise to a stirred solution containing 16 g (0.18 Mol) of commercially available dimethylethylsilane in 20 ml of toluene. The mixture was stirred at 50° to 70° C. for 3 hours and then cooled, and the solvent was removed by distillation. The residue was fractionated under reduced pressure. Approximately 19.4 g of 4-[4-(dimethylethylsilyl)butyl]-1-bromobenzene (67.9 percent yield) were obtained at a pressure of 0.05 hPa and at a temperature of 110° to 112° C. A mixture containing 18 g (0.06 Mol) of this derivative, 6.3 g (0.07 Mol) of CuCN and 10 ml of dimethylformamide was heated at 160° C. for 8 hours. The mixture, still hot at 80° C., was poured into a mixture containing 30 g of iron(III) chloride, 7.5 ml of concentrated hydrochloric acid and 90 ml of water, and the full mixture was stirred at 70° C. for 75 minutes. The product was then extracted with tert-butyl methyl ether, the extract was washed, dried and evaporated, and the residue was fractionated. About 9.9 g of 4-[4-(dimethylethylsilyl)butyl]benzonitrile were obtained at 0.02 hPa and at 114° to 116° C. (66.6 percent yield). the mixture was added dropwise to a stirred solution cooled the solvent was removed by distillation

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a sample of sodium acetate (2.50 g, 30.48 mmol, 0.63 equiv) under a N2 atmosphere was added a 32% solution (in dilute aqueous acetic acid) of peracetic acid (50 mL, 18.08 g, 237.74 mmol, 4.92 equiv). The mixture was stirred at rt for 10 min to completely dissolve the NaOAc. This peroxide solution was then added dropwise over a period of 5 min to a solution of alkene 11a (10.20 g, 4832 mmol, 1 equiv) in dichloromethane (100 mL) at rt. The mixture was heated at reflux temperature with stirring for 3 h. Monitoring by TLC (silica gel, hexanes) confirmed the completion of the reaction. Water (100 mL) was added and the organic phase separated. The aqueous phase was extracted with CH2Cl2 (3×100 mL), and the combined organic extracts were washed sequentially with a saturated solution of sodium hydrogencarbonate (2×), and brine, dried over anhydrous Na2SO4, and then concentrated. High-vacuum drying afforded the epoxide 12a (10.80 g, 47.56 mmol, 98%) as a clear oil: Rf˜0.2 (hexanes); 1H NMR (400 MHz, CDCl3): δ 1.73-1.92 (m, 2H), 2.45-2.49 (4-tet, 1H), 2.66-2.82 (m, 3H), 2.90-2.96 (m, 1H), 7.08 (d, J=8.4 Hz, 2H), 7.41 (d, J=8.4 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 31.8, 34.2, 47.3, 51.7, 119.9, 130.3, 131.6, 140.3; HRMS (EI) Calcd. for C10H11BrO: 225.9993 (M+). Found: 225.9996. The mixture was heated at reflux temperature with stirring for 3 h the completion of the reaction the organic phase separated The aqueous phase was extracted with CH2Cl2 (3×100 mL) the combined organic extracts were washed sequentially with a saturated solution of sodium hydrogencarbonate (2×), and brine dried over anhydrous Na2SO4 concentrated High-vacuum drying