tridec-2-yn-1-ol

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

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

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

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

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

Procedure: Z-2-Tridecen-1-ol was prepared according to the method of Example 6 using 2-tridecyn-1-ol (98 mg, 0.5 mmol), rhodium(III) chloride trihydrate (1.3 mg, 0.005 mmol), copper(II) nitrate hemipentahydrate (5.8 mg, 0.025 mmol), triethoxysilane (0.21 g, 0.23 mL, 1.25 mmol), THF (2.5 mL) and water (0.5 mL) at room temperature for 8 hours to afford 96 mg (0.48 mmol, 97%) of 2-tridecene-1-ol which was a 6:1 Z:E mixture by spectroscopic analysis. Spectral analysis of the Z-isomer: IR (neat) 3337.2, 2924.8, 2854.6, 1462.6, 1016.2 cm-1 : 1H NMR (300 MHz, CDCl3) δ 5.56 (m, 2 H), 4.17 (d, J=5.9 Hz, 2H), 2.04 (br p, 2 H), 1.24 (m, 17 H), 0.86 (t, J=6.7 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 1133.22, 58.58, 31.91, 29.62, 29.49, 29.34, 29.23, 27.44, 22.69, 15.24, 14.11.

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

Procedure: Z-2-Tridecen-1-ol was prepared according to the method of Example 6 using 2-tridecyn-1-ol (98 mg, 0.5 mmol), rhodium(III) chloride trihydrate (1.3 mg, 0.005 mmol), copper(II) nitrate hemipentahydrate (5.8 mg, 0.025 mmol), triethoxysilane (0.21 g, 0.23 mL, 1.25 mmol), THF (2.5 mL) and water (0.5 mL) at room temperature for 8 hours to afford 96 mg (0.48 mmol, 97%) of 2-tridecene-1-ol which was a 6:1 Z:E mixture by spectroscopic analysis. Spectral analysis of the Z-isomer: IR (neat) 3337.2, 2924.8, 2854.6, 1462.6, 1016.2 cm-1 : 1H NMR (300 MHz, CDCl3) δ 5.56 (m, 2 H), 4.17 (d, J=5.9 Hz, 2H), 2.04 (br p, 2 H), 1.24 (m, 17 H), 0.86 (t, J=6.7 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 1133.22, 58.58, 31.91, 29.62, 29.49, 29.34, 29.23, 27.44, 22.69, 15.24, 14.11.

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 2-tridecyn-1-ol (2 g, 10 mmol) in Et2O (50 mL) was added LiAlH4 (1 g, 26 mmol, 2.6 equiv). The resulting mixture was refluxed for 12 hours and allowed to cool to 25° C. A saturated solution of sodium-potassium tartrate was then added and the resulting mixture was stirred for an additional 3 hours. The organic layer was separated, dried (MgSO2) and concentrated by rotary evaporation to yield trans-2-tridecen-1-ol (50) as a colorless oil: 1H NMR (CDCl3) δ 5.62 (dt, J1 =15.3 Hz, J2 =5.1 Hz, 1 H), 5.70 (dt, J1 =15.3 Hz, J2 =5.7 Hz, 1 H), 4.08 (t, J=4.2 Hz, 2 H), 2.04 (q, J=6 Hz, 2 H), 1 30 (m, 16 H), 0.88 (t, J=6.9 Hz, 3 H); 13C NMR (CDCl3) δ 133.72, 128.92, 63.96, 32.31, 32.01, 29.72, 29.60, 29.43, 29.28, 29.24, 22.78, 14.20. ##STR24## The resulting mixture was refluxed for 12 hours The organic layer was separated dried (MgSO2) concentrated by rotary evaporation

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 2-tridecyn-1-ol (2 g, 10 mmol) in Et2O (50 mL) was added LiAlH4 (1 g, 26 mmol, 2.6 equiv). The resulting mixture was refluxed for 12 hours and allowed to cool to 25° C. A saturated solution of sodium-potassium tartrate was then added and the resulting mixture was stirred for an additional 3 hours. The organic layer was separated, dried (MgSO2) and concentrated by rotary evaporation to yield trans-2-tridecen-1-ol (50) as a colorless oil: 1H NMR (CDCl3) δ 5.62 (dt, J1 =15.3 Hz, J2 =5.1 Hz, 1 H), 5.70 (dt, J1 =15.3 Hz, J2 =5.7 Hz, 1 H), 4.08 (t, J=4.2 Hz, 2 H), 2.04 (q, J=6 Hz, 2 H), 1 30 (m, 16 H), 0.88 (t, J=6.9 Hz, 3 H); 13C NMR (CDCl3) δ 133.72, 128.92, 63.96, 32.31, 32.01, 29.72, 29.60, 29.43, 29.28, 29.24, 22.78, 14.20. ##STR24## The resulting mixture was refluxed for 12 hours The organic layer was separated dried (MgSO2) concentrated by rotary evaporation

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

Procedure: 1-Bromo-2-tridecyne (colorless oil) was prepared from 2-tridecyn-1-ol using the CBr4/triphenylphosphine mixture in dichloromethane to carry out the halogenation. 1-Bromo-2-tridecyne (colorless oil) was thus formed with a yield of 91%.

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

Procedure: A process for preparing the sex pheromone of Lymantria dispar L. effectively which comprises the steps of reacting 1-bromodecane and propargyl alcohol tetrahydropyranylether in the presence of sodium hydroxide to give 1-tetrahydropyranyloxy-2-tridecyne, treating the tetrahydropyranyloxy-2-tridecyne with p-toluenesulfonic acid to give 2-tridecyn-1-ol, catalystic-hydrogenating the 2-tridecyn-1-ol in the presence of Lindlar catalyst to give (Z)-2-tridecen-1-ol, oxidizing the (Z)-2-tridecen-1-ol with peroxide to give (±)-cis-2,3-epoxy-1-tridecanol, reacting the (±)-cis-2,3-epoxy-1-tridecanol with acid anhydride in the presence of hydrolase in an organic solvent for a stereoselective acylation and recovering unreacted optically active (2R, 3S)-cis-2,3-epoxy-1-tridecanol after the acylation, reacting the optically active (2R, 3S)-cis-2,3-epoxy-1-tridecanol with toluenesulfonylchloride to give (2R, 3S)-cis-1-p-toluenesulfoxy-2,3-epoxytridecane, and reacting the (2R, 3S)-cis-1-p-toluenesulfoxy-2,3-epoxytridecane with di(4-methylpentyl) lithium copper reagent to yield (7R, 8S)-cis-2-methyl-7,8-epoxyoctadecane which is the sex pheromone of Lymantria dispar L.