3-methyl-3-sulfanylhexan-1-ol

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 5.0 g (34 mmol) of (rac)-3-mercapto-3-methyl-hexan-1-ol in 20 ml of CCl4 was added in portions 8.6 g (37 mmol) of 3,5-dinitrobenzoyl chloride. The mixture was stirred for 72 h, then 10 ml of a saturated NaHCO3 solution was added, the organic layer was separated, washed with 15 ml of brine, dried over MgSO4 and concentrated in vacuo. The residue was purified by flash-chromatography (silicagel, hexane/EtOAc 4:1) and gave 9.8 g (84%) of (rac)-3,5-dinitro-benzoic acid 3-mercapto-3-methyl-hexyl ester. the organic layer was separated washed with 15 ml of brine dried over MgSO4 concentrated in vacuo The residue was purified by flash-chromatography (silicagel, hexane/EtOAc 4:1)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: At a temperature of −78° C. to a solution of 16.0 g (67.1 mmol) of (rac)-3-benzylsulfanyl-3-methyl-hexan-1-ol of step (c) in 200 ml of Et2O was added from a cylinder about 200 ml of NH3 Then pieces of Na (ca. 4.0 g) were added until the reaction mixture remained blue for more than 20 min. The blue colored mixture was allowed to warm up to room temperature overnight and EtOH was added until the blue color disappeared. The mixture was then acidified with about 2.7 M of HCl, and extracted three times with 150 ml of Et2O. The combined organic layers were dried over Na2SO4 and concentrated in vacuo. Distillation of the crude product at reduced pressure (40 mbar/130° C.) gave 11.2 g (73%) of (rac)-3-mercapto-3-methyl-hexan-1-ol in form of a colorless oil. remained blue for more than 20 min extracted three times with 150 ml of Et2O The combined organic layers were dried over Na2SO4 concentrated in vacuo Distillation of the crude product at reduced pressure (40 mbar/130° C.)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: At a temperature of −78° C. to a solution of 16.0 g (67.1 mmol) of (rac)-3-benzylsulfanyl-3-methyl-hexan-1-ol of step (c) in 200 ml of Et2O was added from a cylinder about 200 ml of NH3. Then pieces of Na (ca. 4.0 g) were added until the reaction mixture remained blue for more than 20 min. The blue colored mixture was allowed to warm up to room temperature overnight and EtOH was added until the blue color disappeared. The mixture was then acidified with about 2.7 M of HCl, and extracted three times with 150 ml of Et2O. The combined organic layers were dried over Na2SO4 and concentrated in vacuo. Distillation of the crude product at reduced pressure (40 mbar/130° C.) gave 11.2 g (73%) of (rac)-3-mercapto-3-methyl-hexan-1-ol in form of a colorless oil. remained blue for more than 20 min extracted three times with 150 ml of Et2O The combined organic layers were dried over Na2SO4 concentrated in vacuo Distillation of the crude product at reduced pressure (40 mbar/130° C.)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 5.0 g (34 mmol) of (rac)-3-mercapto-3-methyl-hexan-1-ol in 20 ml of CCl4 was added in portions 8.6 g (37 mmol) of 3,5-dinitrobenzoyl chloride. The mixture was stirred for 72 h, then 10 ml of a saturated NaHCO3 solution was added, the organic layer was separated, washed with 15 ml of brine, dried over MgSO4 and concentrated in vacuo. The residue was purified by flash-chromatography (silicagel, hexane/EtOAc 4:1) and gave 9.8 g (84%) of (rac)-3,5-dinitro-benzoic acid 3-mercapto-3-methyl-hexyl ester. the organic layer was separated washed with 15 ml of brine dried over MgSO4 concentrated in vacuo The residue was purified by flash-chromatography (silicagel, hexane/EtOAc 4:1)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: At a temperature of −78° C. to a solution of 16.0 g (67.1 mmol) of (rac)-3-benzylsulfanyl-3-methyl-hexan-1-ol of step (c) in 200 ml of Et2O was added from a cylinder about 200 ml of NH3 Then pieces of Na (ca. 4.0 g) were added until the reaction mixture remained blue for more than 20 min. The blue colored mixture was allowed to warm up to room temperature overnight and EtOH was added until the blue color disappeared. The mixture was then acidified with about 2.7 M of HCl, and extracted three times with 150 ml of Et2O. The combined organic layers were dried over Na2SO4 and concentrated in vacuo. Distillation of the crude product at reduced pressure (40 mbar/130° C.) gave 11.2 g (73%) of (rac)-3-mercapto-3-methyl-hexan-1-ol in form of a colorless oil. remained blue for more than 20 min extracted three times with 150 ml of Et2O The combined organic layers were dried over Na2SO4 concentrated in vacuo Distillation of the crude product at reduced pressure (40 mbar/130° C.)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: At a temperature of −78° C. to a solution of 16.0 g (67.1 mmol) of (rac)-3-benzylsulfanyl-3-methyl-hexan-1-ol of step (c) in 200 ml of Et2O was added from a cylinder about 200 ml of NH3 Then pieces of Na (ca. 4.0 g) were added until the reaction mixture remained blue for more than 20 min. The blue colored mixture was allowed to warm up to room temperature overnight and EtOH was added until the blue color disappeared. The mixture was then acidified with about 2.7 M of HCl, and extracted three times with 150 ml of Et2O. The combined organic layers were dried over Na2SO4 and concentrated in vacuo. Distillation of the crude product at reduced pressure (40 mbar/130° C.) gave 11.2 g (73%) of (rac)-3-mercapto-3-methyl-hexan-1-ol in form of a colorless oil. remained blue for more than 20 min extracted three times with 150 ml of Et2O The combined organic layers were dried over Na2SO4 concentrated in vacuo Distillation of the crude product at reduced pressure (40 mbar/130° C.)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: At a temperature of −78° C. to a solution of 16.0 g (67.1 mmol) of (rac)-3-benzylsulfanyl-3-methyl-hexan-1-ol of step (c) in 200 ml of Et2O was added from a cylinder about 200 ml of NH3. Then pieces of Na (ca. 4.0 g) were added until the reaction mixture remained blue for more than 20 min. The blue colored mixture was allowed to warm up to room temperature overnight and EtOH was added until the blue color disappeared. The mixture was then acidified with about 2.7 M of HCl, and extracted three times with 150 ml of Et2O. The combined organic layers were dried over Na2SO4 and concentrated in vacuo. Distillation of the crude product at reduced pressure (40 mbar/130° C.) gave 11.2 g (73%) of (rac)-3-mercapto-3-methyl-hexan-1-ol in form of a colorless oil. remained blue for more than 20 min extracted three times with 150 ml of Et2O The combined organic layers were dried over Na2SO4 concentrated in vacuo Distillation of the crude product at reduced pressure (40 mbar/130° C.)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 5.0 g (34 mmol) of (rac)-3-mercapto-3-methyl-hexan-1-ol in 20 ml of CCl4 was added in portions 8.6 g (37 mmol) of 3,5-dinitrobenzoyl chloride. The mixture was stirred for 72 h, then 10 ml of a saturated NaHCO3 solution was added, the organic layer was separated, washed with 15 ml of brine, dried over MgSO4 and concentrated in vacuo. The residue was purified by flash-chromatography (silicagel, hexane/EtOAc 4:1) and gave 9.8 g (84%) of (rac)-3,5-dinitro-benzoic acid 3-mercapto-3-methyl-hexyl ester. the organic layer was separated washed with 15 ml of brine dried over MgSO4 concentrated in vacuo The residue was purified by flash-chromatography (silicagel, hexane/EtOAc 4:1)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: At a temperature of −78° C. to a solution of 16.0 g (67.1 mmol) of (rac)-3-benzylsulfanyl-3-methyl-hexan-1-ol of step (c) in 200 ml of Et2O was added from a cylinder about 200 ml of NH3 Then pieces of Na (ca. 4.0 g) were added until the reaction mixture remained blue for more than 20 min. The blue colored mixture was allowed to warm up to room temperature overnight and EtOH was added until the blue color disappeared. The mixture was then acidified with about 2.7 M of HCl, and extracted three times with 150 ml of Et2O. The combined organic layers were dried over Na2SO4 and concentrated in vacuo. Distillation of the crude product at reduced pressure (40 mbar/130° C.) gave 11.2 g (73%) of (rac)-3-mercapto-3-methyl-hexan-1-ol in form of a colorless oil. remained blue for more than 20 min extracted three times with 150 ml of Et2O The combined organic layers were dried over Na2SO4 concentrated in vacuo Distillation of the crude product at reduced pressure (40 mbar/130° C.)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: At a temperature of −78° C. to a solution of 16.0 g (67.1 mmol) of (rac)-3-benzylsulfanyl-3-methyl-hexan-1-ol of step (c) in 200 ml of Et2O was added from a cylinder about 200 ml of NH3. Then pieces of Na (ca. 4.0 g) were added until the reaction mixture remained blue for more than 20 min. The blue colored mixture was allowed to warm up to room temperature overnight and EtOH was added until the blue color disappeared. The mixture was then acidified with about 2.7 M of HCl, and extracted three times with 150 ml of Et2O. The combined organic layers were dried over Na2SO4 and concentrated in vacuo. Distillation of the crude product at reduced pressure (40 mbar/130° C.) gave 11.2 g (73%) of (rac)-3-mercapto-3-methyl-hexan-1-ol in form of a colorless oil. remained blue for more than 20 min extracted three times with 150 ml of Et2O The combined organic layers were dried over Na2SO4 concentrated in vacuo Distillation of the crude product at reduced pressure (40 mbar/130° C.)