pentadec-2-yn-1-ol

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

Procedure: The same procedure for 8-nonyn-1-ol was followed with 2- pentadecyn-1-ol (4.51 g, 20.1 mmol), KH (2.38 g, 59.4 mmol), and 1,3-diaminopropane (65 mL). This produced 3.18 g of white solid (70%): mp 42-44° C. IR (thin film( ν 3430, 2926, 2252 cm−1: 1H—NMR δ4.30 (t, 1H, J=5.0 Hz), 3.64 (t, 2H, J=6.6 Hz), 2.18 (td, 2H, J=2.6 Hz, 6.6 Hz), 1.94 (t, 1H, J=2.6 Hz), 1.49-1.26 (bm, 22H); 13C—NMR δ 84.8, 68.0, 63.1, 32.8, 29.6, (2C), 29.5 (2C), 29.4, 28.9, 28.5, 28.7, 28.0, 25.7, 18.4; MS m/z 231.53 (M++Li). Anal. Calcd for C15H28O: C, 80.29; H, 12.58. Found: C, 18.20; H, 12.50.

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

Procedure: Isomerization of pentadec-2-yn-1-ol (12.5 g, 54.95 mmol) using NaH/ethylenediamine as described above furnished pentadec-14-yn-1-ol (9.4 g, 76%) as a white solid. M.P.: 54.2-54.8° C. TLC: 30% EtOAc/hexanes, Rf≈0.45; 1H NMR (400 MHz, CDCl3) δ 3.60-3.65 (m, 2H), 2.16 (dt, 2H, J=7.1 Hz, 2.4 Hz), 1.92 (t, 1H, J=2.4 Hz), 1.47-1.60 (m, 4H), 1.22-1.35 (m, 18H).

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

Procedure: Cleavage of the THP ether from crude 2-(pentadec-2-ynyloxy)tetrahydro-2H-pyran (30 g) using PTSA as described above gave pentadec-2-yn-1-ol (18.6 g, 85%) as a colorless oil. TLC: 30% EtOAc/hexanes, Rf≈0.40; 1H NMR (CDCl3, 300 MHz) δ 4.25 (s, 2H), 2.17-2.23 (m, 2H), 1.70 (br s, 1H), 1.40-1.53 (m, 2H), 1.20-1.48 (m, 18H), 0.87 (t, 3H, J=7.3 Hz).

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

Procedure: Cleavage of the THP ether from crude 2-(pentadec-2-ynyloxy)tetrahydro-2H-pyran (30 g) using PTSA as described above gave pentadec-2-yn-1-ol (18.6 g, 85%) as a colorless oil. TLC: 30% EtOAc/hexanes, Rf≈0.40; 1H NMR (CDCl3, 300 MHz) δ 4.25 (s, 2H), 2.17-2.23 (m, 2H), 1.70 (br s, 1H), 1.40-1.53 (m, 2H), 1.20-1.48 (m, 18H), 0.87 (t, 3H, J=7.3 Hz).

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The compound (12,374 g) of (1) above was dissolved in a N solution (230 ml) of hydrochloric acid in methanol and the mixture was heated at 65° C. for 1.5 hours. The reaction mixture was concentrated under reduced pressure and the residue was purified by silica gel column chromatography to give 8.465 g of 2-pentadecynyl alcohol. The reaction mixture was concentrated under reduced pressure the residue was purified by silica gel column chromatography

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The compound (12.374 g) of (1) above was dissolved in a 1N solution (230 ml) of hydrochloric acid in methanol and the mixture was heated at 65° C. for 1.5 hours. The reaction mixture was concentrated under reduced pressure and the residue was purified by silica gel column chromatography to give 8.465 g of 2-pentadecynyl alcohol. The reaction mixture was concentrated under reduced pressure the residue was purified by silica gel column chromatography

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The compound (12.374 g) of (1) above was dissolved in a 1N solution (230 ml) of hydrochloric acid in methanol and the mixture was heated at 65° C. for 1.5 hours. The reaction mixture was concentrated under reduced pressure and the residue was purified by silica gel column chromatography to give 8.465 g of 2-pentadecynyl alcohol. The reaction mixture was concentrated under reduced pressure the residue was purified by silica gel column chromatography

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

Procedure: The same procedure for 8-nonyn-1-ol was followed with 2- pentadecyn-1-ol (4.51 g, 20.1 mmol), KH (2.38 g, 59.4 mmol), and 1,3-diaminopropane (65 mL). This produced 3.18 g of white solid (70%): mp 42-44° C. IR (thin film( ν 3430, 2926, 2252 cm−1: 1H—NMR δ4.30 (t, 1H, J=5.0 Hz), 3.64 (t, 2H, J=6.6 Hz), 2.18 (td, 2H, J=2.6 Hz, 6.6 Hz), 1.94 (t, 1H, J=2.6 Hz), 1.49-1.26 (bm, 22H); 13C—NMR δ 84.8, 68.0, 63.1, 32.8, 29.6, (2C), 29.5 (2C), 29.4, 28.9, 28.5, 28.7, 28.0, 25.7, 18.4; MS m/z 231.53 (M++Li). Anal. Calcd for C15H28O: C, 80.29; H, 12.58. Found: C, 18.20; H, 12.50.

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

Procedure: The same procedure for 8-nonyn-1-ol was followed with 2- pentadecyn-1-ol (4.51 g, 20.1 mmol), KH (2.38 g, 59.4 mmol), and 1,3-diaminopropane (65 mL). This produced 3.18 g of white solid (70%): mp 42-44° C. IR (thin film( ν 3430, 2926, 2252 cm−1: 1H—NMR δ4.30 (t, 1H, J=5.0 Hz), 3.64 (t, 2H, J=6.6 Hz), 2.18 (td, 2H, J=2.6 Hz, 6.6 Hz), 1.94 (t, 1H, J=2.6 Hz), 1.49-1.26 (bm, 22H); 13C—NMR δ 84.8, 68.0, 63.1, 32.8, 29.6, (2C), 29.5 (2C), 29.4, 28.9, 28.5, 28.7, 28.0, 25.7, 18.4; MS m/z 231.53 (M++Li). Anal. Calcd for C15H28O: C, 80.29; H, 12.58. Found: C, 18.20; H, 12.50.

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The compound (12.374 g) of (1) above was dissolved in a 1N solution (230 ml) of hydrochloric acid in methanol and the mixture was heated at 65° C. for 1.5 hours. The reaction mixture was concentrated under reduced pressure and the residue was purified by silica gel column chromatography to give 8.465 g of 2-pentadecynyl alcohol. The reaction mixture was concentrated under reduced pressure the residue was purified by silica gel column chromatography

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The compound (12.374 g) of (1) above was dissolved in a 1N solution (230 ml) of hydrochloric acid in methanol and the mixture was heated at 65° C. for 1.5 hours. The reaction mixture was concentrated under reduced pressure and the residue was purified by silica gel column chromatography to give 8.465 g of 2-pentadecynyl alcohol. The reaction mixture was concentrated under reduced pressure the residue was purified by silica gel column chromatography

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

Procedure: Isomerization of pentadec-2-yn-1-ol (12.5 g, 54.95 mmol) using NaH/ethylenediamine as described above furnished pentadec-14-yn-1-ol (9.4 g, 76%) as a white solid. M.P.: 54.2-54.8° C. TLC: 30% EtOAc/hexanes, Rf≈0.45; 1H NMR (400 MHz, CDCl3) δ 3.60-3.65 (m, 2H), 2.16 (dt, 2H, J=7.1 Hz, 2.4 Hz), 1.92 (t, 1H, J=2.4 Hz), 1.47-1.60 (m, 4H), 1.22-1.35 (m, 18H).