6-chlorohex-1-ynyl(trimethyl)silane

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

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

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

Procedure: To a solution of diisopropylamine (153 g, 1.52 mol) in anhydrous THF (1.0 L) at 0° C., n-butyllithium (2.5 M in hexane, 608 mL, 1.52 mol) was added dropwise. The mixture was stirred for 20 minutes at 0° C. and then cooled to −78° C. To this mixture, a solution of (6-chlorohex-1-yn-1-yl)trimethylsilane (144 g, 0.76 mol) in anhydrous THF (200 mL) was added dropwise. The resulting mixture was allowed to warm to room temperature and stirred for 16 h. The reaction mixture was carefully quenched at room temperature with saturated aqueous NH4Cl (500 mL), and then extracted with pentane (2×200 mL). The combined organic layers were washed with brine (500 mL) and dried over anhydrous Na2SO4. The solvent was evaporated on a rotary evaporator. The residue was distilled at 160-162° C./760 Torr to afford the title compound as a colorless liquid (81 g, yield 70%). 1H NMR (CDCl3, 400 MHz): δ 3.05-3.01 (m, 1H), 2.26-2.20 (m, 2H), 2.17-2.10 (m, 2H), 1.93-1.84 (m, 2H), 0.11 (s, 9H). cooled to −78° C to warm to room temperature stirred for 16 h The reaction mixture was carefully quenched at room temperature with saturated aqueous NH4Cl (500 mL) extracted with pentane (2×200 mL) The combined organic layers were washed with brine (500 mL) dried over anhydrous Na2SO4 The solvent was evaporated on a rotary evaporator The residue was distilled at 160-162° C./760 Torr

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 6-chlorohex-1-yne (100 mL, 94.6 g, 0.82 mol) in anhydrous Et2O (500 mL) at −78° C., n-butyllithium (2.5 M in hexane, 360 mL, 0.90 mol) was added over 40 minutes. The resulting mixture was stirred for 30 minutes at −78° C. Chlorotrimethylsilane (125 mL, 1.0 mol) was then added. The mixture was allowed to warm to room temperature and stirred for 16 h. The reaction mixture was carefully quenched with saturated aqueous NH4Cl (300 mL) at room temperature and extracted with Et2O (2×200 mL). The combined organic layers were washed with brine (200 mL), dried over anhydrous Na2SO4, and concentrated in vacuo to afford the title compound (144 g, yield 93%). 1H NMR (DMSO-d6, 400 MHz): δ 3.65 (t, 2H), 2.25 (t, 2H), 1.82-1.75 (m, 2H), 1.58-1.51 (m, 2H), 0.12 (s, 9H). to warm to room temperature stirred for 16 h The reaction mixture was carefully quenched with saturated aqueous NH4Cl (300 mL) at room temperature extracted with Et2O (2×200 mL) The combined organic layers were washed with brine (200 mL) dried over anhydrous Na2SO4 concentrated in vacuo

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 6-chlorohex-1-yne (100 mL, 94.6 g, 0.82 mol) in anhydrous Et2O (500 mL) at −78° C., n-butyllithium (2.5 M in hexane, 360 mL, 0.90 mol) was added over 40 minutes. The resulting mixture was stirred for 30 minutes at −78° C. Chlorotrimethylsilane (125 mL, 1.0 mol) was then added. The mixture was allowed to warm to room temperature and stirred for 16 h. The reaction mixture was carefully quenched with saturated aqueous NH4Cl (300 mL) at room temperature and extracted with Et2O (2×200 mL). The combined organic layers were washed with brine (200 mL), dried over anhydrous Na2SO4, and concentrated in vacuo to afford the title compound (144 g, yield 93%). 1H NMR (DMSO-d6, 400 MHz): δ 3.65 (t, 2H), 2.25 (t, 2H), 1.82-1.75 (m, 2H), 1.58-1.51 (m, 2H), 0.12 (s, 9H). to warm to room temperature stirred for 16 h The reaction mixture was carefully quenched with saturated aqueous NH4Cl (300 mL) at room temperature extracted with Et2O (2×200 mL) The combined organic layers were washed with brine (200 mL) dried over anhydrous Na2SO4 concentrated in vacuo

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

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

Procedure: To a solution of diisopropylamine (153 g, 1.52 mol) in anhydrous THF (1.0 L) at 0° C., n-butyllithium (2.5 M in hexane, 608 mL, 1.52 mol) was added dropwise. The mixture was stirred for 20 minutes at 0° C. and then cooled to −78° C. To this mixture, a solution of (6-chlorohex-1-yn-1-yl)trimethylsilane (144 g, 0.76 mol) in anhydrous THF (200 mL) was added dropwise. The resulting mixture was allowed to warm to room temperature and stirred for 16 h. The reaction mixture was carefully quenched at room temperature with saturated aqueous NH4Cl (500 mL), and then extracted with pentane (2×200 mL). The combined organic layers were washed with brine (500 mL) and dried over anhydrous Na2SO4. The solvent was evaporated on a rotary evaporator. The residue was distilled at 160-162° C./760 Torr to afford the title compound as a colorless liquid (81 g, yield 70%). 1H NMR (CDCl3, 400 MHz): δ 3.05-3.01 (m, 1H), 2.26-2.20 (m, 2H), 2.17-2.10 (m, 2H), 1.93-1.84 (m, 2H), 0.11 (s, 9H). cooled to −78° C to warm to room temperature stirred for 16 h The reaction mixture was carefully quenched at room temperature with saturated aqueous NH4Cl (500 mL) extracted with pentane (2×200 mL) The combined organic layers were washed with brine (500 mL) dried over anhydrous Na2SO4 The solvent was evaporated on a rotary evaporator The residue was distilled at 160-162° C./760 Torr

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 6-chlorohex-1-yne (100 mL, 94.6 g, 0.82 mol) in anhydrous Et2O (500 mL) at −78° C., n-butyllithium (2.5 M in hexane, 360 mL, 0.90 mol) was added over 40 minutes. The resulting mixture was stirred for 30 minutes at −78° C. Chlorotrimethylsilane (125 mL, 1.0 mol) was then added. The mixture was allowed to warm to room temperature and stirred for 16 h. The reaction mixture was carefully quenched with saturated aqueous NH4Cl (300 mL) at room temperature and extracted with Et2O (2×200 mL). The combined organic layers were washed with brine (200 mL), dried over anhydrous Na2SO4, and concentrated in vacuo to afford the title compound (144 g, yield 93%). 1H NMR (DMSO-d6, 400 MHz): δ 3.65 (t, 2H), 2.25 (t, 2H), 1.82-1.75 (m, 2H), 1.58-1.51 (m, 2H), 0.12 (s, 9H). to warm to room temperature stirred for 16 h The reaction mixture was carefully quenched with saturated aqueous NH4Cl (300 mL) at room temperature extracted with Et2O (2×200 mL) The combined organic layers were washed with brine (200 mL) dried over anhydrous Na2SO4 concentrated in vacuo

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

Procedure: A mixture of 6-chloro-1-trimethylsilylhex-1-yne (14.0 g.) and sodium iodide (30 g) in butanone (100 ml) was heated at reflux, with stirring, for 10 hours. After this time the solvent was removed in vacuo and the residue partitioned between diethyl ether and water. The organic phase was separated, washed with water and brine before drying over anhydrous magnesium sulphate. The solvent was removed under reduced pressure to leave 6-iodo-1-trimethylsilylhex-1-yne as a yellow oil (20.0 g). was heated at reflux After this time the solvent was removed in vacuo the residue partitioned between diethyl ether and water The organic phase was separated washed with water and brine before drying over anhydrous magnesium sulphate The solvent was removed under reduced pressure

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

Procedure: A solution of trimethylsilylacetylene (4.9 g., Aldrich) in dry tetrahydrofuran (40 ml.) was stirred at 0° under a current of nitrogen and n-butyllithium (31.25 ml. of 1.6M solution in hexane) was added dropwise. The solution was stirred for 30 minutes and a solution of 1-chloro-4-iodobutane (10.9 g.) in dry tetrahydrofuran (30 ml.) was added. The reaction mixture was allowed to warm to 20° and stirred for 18 hours. The mixture was poured into water and the aqueous mixture was extracted with diethyl ether. The ethereal extracts were washed with water and dried over anhydrous magnesium sulphate. The solvent was removed in vacuo. 6-Chloro-1-trimethylsilylhex-1-yne was obtained as a yellow liquid and was used without further purification. was added dropwise to warm to 20° stirred for 18 hours the aqueous mixture was extracted with diethyl ether The ethereal extracts were washed with water dried over anhydrous magnesium sulphate The solvent was removed in vacuo

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

Procedure: To a solution of diisopropylamine (153 g, 1.52 mol) in anhydrous THF (1.0 L) at 0° C., n-butyllithium (2.5 M in hexane, 608 mL, 1.52 mol) was added dropwise. The mixture was stirred for 20 minutes at 0° C. and then cooled to −78° C. To this mixture, a solution of (6-chlorohex-1-yn-1-yl)trimethylsilane (144 g, 0.76 mol) in anhydrous THF (200 mL) was added dropwise. The resulting mixture was allowed to warm to room temperature and stirred for 16 h. The reaction mixture was carefully quenched at room temperature with saturated aqueous NH4Cl (500 mL), and then extracted with pentane (2×200 mL). The combined organic layers were washed with brine (500 mL) and dried over anhydrous Na2SO4. The solvent was evaporated on a rotary evaporator. The residue was distilled at 160-162° C./760 Torr to afford the title compound as a colorless liquid (81 g, yield 70%). 1H NMR (CDCl3, 400 MHz): δ 3.05-3.01 (m, 1H), 2.26-2.20 (m, 2H), 2.17-2.10 (m, 2H), 1.93-1.84 (m, 2H), 0.11 (s, 9H). cooled to −78° C to warm to room temperature stirred for 16 h The reaction mixture was carefully quenched at room temperature with saturated aqueous NH4Cl (500 mL) extracted with pentane (2×200 mL) The combined organic layers were washed with brine (500 mL) dried over anhydrous Na2SO4 The solvent was evaporated on a rotary evaporator The residue was distilled at 160-162° C./760 Torr

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 6-chlorohex-1-yne (100 mL, 94.6 g, 0.82 mol) in anhydrous Et2O (500 mL) at −78° C., n-butyllithium (2.5 M in hexane, 360 mL, 0.90 mol) was added over 40 minutes. The resulting mixture was stirred for 30 minutes at −78° C. Chlorotrimethylsilane (125 mL, 1.0 mol) was then added. The mixture was allowed to warm to room temperature and stirred for 16 h. The reaction mixture was carefully quenched with saturated aqueous NH4Cl (300 mL) at room temperature and extracted with Et2O (2×200 mL). The combined organic layers were washed with brine (200 mL), dried over anhydrous Na2SO4, and concentrated in vacuo to afford the title compound (144 g, yield 93%). 1H NMR (DMSO-d6, 400 MHz): δ 3.65 (t, 2H), 2.25 (t, 2H), 1.82-1.75 (m, 2H), 1.58-1.51 (m, 2H), 0.12 (s, 9H). to warm to room temperature stirred for 16 h The reaction mixture was carefully quenched with saturated aqueous NH4Cl (300 mL) at room temperature extracted with Et2O (2×200 mL) The combined organic layers were washed with brine (200 mL) dried over anhydrous Na2SO4 concentrated in vacuo