6-sulfanylhexan-1-ol

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

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

Procedure: 6-Mercapto-1-hexanol (1.4 mL, 10.2 mmol) was added to a suspension of NaH (60% in mineral oil, 0.42 g, 10.5 mmol) in THF (20 mL) and stirred at room temperature for 10 min then cooled down to −78° C. in dry ice bath. A suspension of the product Example 46a (1.74 g, 9.03 mmol) was added to the above mixture and stirred at −78° C. for 2.5 hours. The reaction was quenched with water (20 mL) and extracted with Et2O (100 mL). The extract was washed with water (2×100 mL) and brine (100 mL), dried over Na2SO4, filtered, and concentrated under reduced pressure. The product was purified by silica gel colurnn chromatography eluting with 1:2 EtOAc:Hex to obtained the title compound as a viscous oil, 1.8 g (81%). 1H NMR (300 MHz, CDCl3) δ 8.67 (d, J=5.3 Hz, 1H), 7.00 (d, J=5.3 Hz, 1H), 3.63 (t, J=6.6 Hz, 2H), 3.14 (t, J=7.4 Hz, 2H), 2.60 (s, 1H), 1.8-1.4(mult, 8H); 13C NMR (75 MHz, CDCl3) δ 173.4, 160.7, 157.8, 116.2, 62.3, 32.3, 30.8, 28.6, 28.3, 25.1; mass spectrum (API-TIS) m/z 247 (M+H). was added to the above mixture stirred at −78° C. for 2.5 hours The reaction was quenched with water (20 mL) extracted with Et2O (100 mL) The extract was washed with water (2×100 mL) and brine (100 mL) dried over Na2SO4 filtered concentrated under reduced pressure The product was purified by silica gel colurnn chromatography eluting with 1:2 EtOAc

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

Procedure: To 14 ml of a methanol solution of sodium methoxide (1M solution) are added 2.04 g of 6-mercaptohexanol and 0.24 g of sodium borohydride, to which a THF (20 ml) solution containing 2.18 g of 2-methoxy-3-octadecyloxypropyl methanesulfonate is added dropwise under nitrogen streams with stirring. The mixture is stirred at room temperature for 20 hours and then at 40° C. for 1 hour. After the addition of water, the mixture is extracted with ethyl acetate. The extracted layer is washed with water, dried and concentrated under reduced pressures to obtain an oily product. Purification of the oily product by silica gel column chromatography gives 2.31 g of the captioned compound. is added dropwise under nitrogen streams The mixture is stirred at room temperature for 20 hours the mixture is extracted with ethyl acetate The extracted layer is washed with water dried concentrated under reduced pressures to obtain an oily product Purification of the oily product by silica gel column chromatography

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

Procedure: To a solution of 6-mercapto-hexan-1-ol (2.5 mL) in MeCN (30 mL) at 0° C. was added sodium hydride (60% suspension in mineral oil, 0.81 g). The mixture was stirred at 0° C. for 1 h then 2-bromo-1,1-dimethoxy-ethane (2.4 mL) was added. The resulting mixture was stirred at RT for 20 h, then was quenched by addition of saturated sodium bicarbonate solution. The mixture was extracted with ethyl acetate (×3), then the combined organics were washed with saturated sodium bicarbonate solution, then with brine, dried over sodium sulfate, filtered and evaporated in vacuo. Purification was by silica gel chromatography eluting with 25% ethyl acetate in cyclohexane to give the subtitled compound as a colourless liquid. Yield 1.85 g. The resulting mixture was stirred at RT for 20 h was quenched by addition of saturated sodium bicarbonate solution The mixture was extracted with ethyl acetate (×3) the combined organics were washed with saturated sodium bicarbonate solution with brine, dried over sodium sulfate filtered evaporated in vacuo Purification eluting with 25% ethyl acetate in cyclohexane

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

Procedure: 6-Mercapto-1-hexanol (1.4 mL, 10.2 mmol) was added to a suspension of NaH (60% in mineral oil, 0.42 g, 10.5 mmol) in THF (20 mL) and stirred at room temperature for 10 min then cooled down to −78° C. in dry ice bath. A suspension of the product Example 46a (1.74 g, 9.03 mmol) was added to the above mixture and stirred at −78° C. for 2.5 hours. The reaction was quenched with water (20 mL) and extracted with Et2O (100 mL). The extract was washed with water (2×100 mL) and brine (100 mL), dried over Na2SO4, filtered, and concentrated under reduced pressure. The product was purified by silica gel colurnn chromatography eluting with 1:2 EtOAc:Hex to obtained the title compound as a viscous oil, 1.8 g (81%). 1H NMR (300 MHz, CDCl3) δ 8.67 (d, J=5.3 Hz, 1H), 7.00 (d, J=5.3 Hz, 1H), 3.63 (t, J=6.6 Hz, 2H), 3.14 (t, J=7.4 Hz, 2H), 2.60 (s, 1H), 1.8-1.4(mult, 8H); 13C NMR (75 MHz, CDCl3) δ 173.4, 160.7, 157.8, 116.2, 62.3, 32.3, 30.8, 28.6, 28.3, 25.1; mass spectrum (API-TIS) m/z 247 (M+H). was added to the above mixture stirred at −78° C. for 2.5 hours The reaction was quenched with water (20 mL) extracted with Et2O (100 mL) The extract was washed with water (2×100 mL) and brine (100 mL) dried over Na2SO4 filtered concentrated under reduced pressure The product was purified by silica gel colurnn chromatography eluting with 1:2 EtOAc

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

Procedure: 6-Mercapto-1-hexanol (1.4 mL, 10.2 mmol) was added to a suspension of NaH (60% in mineral oil, 0.42 g, 10.5 mmol) in THF (20 mL) and stirred at room temperature for 10 min then cooled down to −78° C. in dry ice bath. A suspension of the product Example 46a (1.74 g, 9.03 mmol) was added to the above mixture and stirred at −78° C. for 2.5 hours. The reaction was quenched with water (20 mL) and extracted with Et2O (100 mL). The extract was washed with water (2×100 mL) and brine (100 mL), dried over Na2SO4, filtered, and concentrated under reduced pressure. The product was purified by silica gel colurnn chromatography eluting with 1:2 EtOAc:Hex to obtained the title compound as a viscous oil, 1.8 g (81%). 1H NMR (300 MHz, CDCl3) δ 8.67 (d, J=5.3 Hz, 1H), 7.00 (d, J=5.3 Hz, 1H), 3.63 (t, J=6.6 Hz, 2H), 3.14 (t, J=7.4 Hz, 2H), 2.60 (s, 1H), 1.8-1.4(mult, 8H); 13C NMR (75 MHz, CDCl3) δ 173.4, 160.7, 157.8, 116.2, 62.3, 32.3, 30.8, 28.6, 28.3, 25.1; mass spectrum (API-TIS) m/z 247 (M+H). was added to the above mixture stirred at −78° C. for 2.5 hours The reaction was quenched with water (20 mL) extracted with Et2O (100 mL) The extract was washed with water (2×100 mL) and brine (100 mL) dried over Na2SO4 filtered concentrated under reduced pressure The product was purified by silica gel colurnn chromatography eluting with 1:2 EtOAc

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

Procedure: To 14 ml of a methanol solution of sodium methoxide (1M solution) are added 2.04 g of 6-mercaptohexanol and 0.24 g of sodium borohydride, to which a THF (20 ml) solution containing 2.18 g of 2-methoxy-3-octadecyloxypropyl methanesulfonate is added dropwise under nitrogen streams with stirring. The mixture is stirred at room temperature for 20 hours and then at 40° C. for 1 hour. After the addition of water, the mixture is extracted with ethyl acetate. The extracted layer is washed with water, dried and concentrated under reduced pressures to obtain an oily product. Purification of the oily product by silica gel column chromatography gives 2.31 g of the captioned compound. is added dropwise under nitrogen streams The mixture is stirred at room temperature for 20 hours the mixture is extracted with ethyl acetate The extracted layer is washed with water dried concentrated under reduced pressures to obtain an oily product Purification of the oily product by silica gel column chromatography

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

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

Procedure: The general procedure in example 39 was followed. 5-Iodo-m-xylene (144 μL, 1.0 mmol), 6-mercaptohexanol (137 μL, 1.0 mmol), CuI (10 mg, 0.05 mmol), K2CO3 (276 mg, 2.0 mmol), ethylene glycol (111 μL, 2.0 mmol) and 2-Propanol (1.0 mL) were used to obtain the 6-(3,5-dimethylphenyl)mercaptohexanol (212 mg, 92% yield) as colorless oil. Column chromatographic solvent (hexane/ethyl acetate=3/1). Rf=0.4 (hexane/ethyl acetate=2/1). 1H NMR (CDCl3, 300 MHz) δ 6.92 (s, 2 H), 6.78 (s, 1 H), 3.62 (q, 2 H, J=4.8 Hz), 2.90 (t, 2 H, J=7.2 Hz), 2.27 (s, 6 H), 1.30-1.68 (m, 9 H). 13C NMR (CDCl3, 75 MHz)δ 138.6, 136.5, 127.8, 126.7, 63.2, 33.8, 33.0, 29.5, 28.9, 25.7, 21.7. IR (neat, cm−1) 3320 (broad), 3060, 3022, 2972, 2847. MS (EI) m/z (relative intensity) 238 (40), 138 (100). Anal Cald for C14H22OS, Cald. C: 70.54, H: 9.30; Found C: 70.29, H: 9.33.

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

Procedure: The general procedure in example 39 was followed. 5-Iodo-m-xylene (144 μL, 1.0 mmol), 6-mercaptohexanol (137 μL, 1.0 mmol), CuI (10 mg, 0.05 mmol), K2CO3 (276 mg, 2.0 mmol), ethylene glycol (111 μL, 2.0 mmol) and 2-Propanol (1.0 mL) were used to obtain the 6-(3,5-dimethylphenyl)mercaptohexanol (212 mg, 92% yield) as colorless oil. Column chromatographic solvent (hexane/ethyl acetate=3/1). Rf=0.4 (hexane/ethyl acetate=2/1). 1H NMR (CDCl3, 300 MHz) δ 6.92 (s, 2 H), 6.78 (s, 1 H), 3.62 (q, 2 H, J=4.8 Hz), 2.90 (t, 2 H, J=7.2 Hz), 2.27 (s, 6 H), 1.30-1.68 (m, 9 H). 13C NMR (CDCl3, 75 MHz)δ 138.6, 136.5, 127.8, 126.7, 63.2, 33.8, 33.0, 29.5, 28.9, 25.7, 21.7. IR (neat, cm−1) 3320 (broad), 3060, 3022, 2972, 2847. MS (EI) m/z (relative intensity) 238 (40), 138 (100). Anal Cald for C14H22OS, Cald. C: 70.54, H: 9.30; Found C: 70.29, H: 9.33.

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

Procedure: The general procedure in example 39 was followed. 5-Iodo-m-xylene (144 μL, 1.0 mmol), 6-mercaptohexanol (137 μL, 1.0 mmol), CuI (10 mg, 0.05 mmol), K2CO3 (276 mg, 2.0 mmol), ethylene glycol (111 μL, 2.0 mmol) and 2-propanol (1.0 mL) were used to obtain the 6-(3,5-dimethylphenyl)mercaptohexanol (212 mg, 92% yield) as colorless oil. Column chromatographic solvent (hexane/ethyl acetate=3/1). Rf=0.4 (hexane/ethyl acetate=2/1). 1H NMR (CDCl3, 300 MHz) δ 6.92 (s, 2 H), 6.78 (s, 1 H), 3.62 (q, 2 H, J=4.8 Hz), 2.90 (t, 2 H, J=7.2 Hz), 2.27 (s, 6 H), 1.30-1.68 (m, 9 H). 13C NMR (CDCl3, 75 MHz) δ 138.6, 136.5, 127.8, 126.7, 63.2, 33.8, 33.0, 29.5, 28.9, 25.7, 21.7. IR (neat, cm−1) 3320 (broad), 3060, 3022, 2972, 2847. MS (EI) m/z (relative intensity) 238 (40), 138 (100). Anal Cald for C14H22OS, Cald. C, 70.54; H, 9.30. Found C, 70.29; H, 9.33.

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

Procedure: 6-Mercapto-1-hexanol (1.4 mL, 10.2 mmol) was added to a suspension of NaH (60% in mineral oil, 0.42 g, 10.5 mmol) in THF (20 mL) and stirred at room temperature for 10 min then cooled down to −78° C. in dry ice bath. A suspension of the product Example 46a (1.74 g, 9.03 mmol) was added to the above mixture and stirred at −78° C. for 2.5 hours. The reaction was quenched with water (20 mL) and extracted with Et2O (100 mL). The extract was washed with water (2×100 mL) and brine (100 mL), dried over Na2SO4, filtered, and concentrated under reduced pressure. The product was purified by silica gel column chromatography eluting with 1:2 EtOAc:Hex to obtained the title compound as a viscous oil, 1.8 g (81%). 1H NMR (300 MHz, CDCl3) δ 8.67 (d, J=5.3 Hz, 1H), 7.00 (d, J=5.3 Hz, 1H), 3.63 (t, J=6.6 Hz, 2H), 3.14 (t, J=7.4 Hz, 2H), 2.60 (S, 1H), 1.8-1.4(mult, 8H); 13C NMR (75 MHz, CDCl3) δ 173.4, 160.7, 157.8, 116.2, 62.3, 32.3, 30.8, 28.6, 28.3, 25.1; mass spectrum (API-TIS) m/z 247 (M+H). was added to the above mixture stirred at −78° C. for 2.5 hours The reaction was quenched with water (20 mL) extracted with Et2O (100 mL) The extract was washed with water (2×100 mL) and brine (100 mL) dried over Na2SO4 filtered concentrated under reduced pressure The product was purified by silica gel column chromatography eluting with 1:2 EtOAc