1-Hexanethiol → HCID 19800167, compound

HRID 1646927Notes

Reaction equation

HRID 1646927 reaction equation
[Cl:1][C:2]1[C:3]([C:8]2(O)[CH2:13][CH2:12][CH2:11][N:10]([CH3:14])[CH2:9]2)=[N:4][CH:5]=[CH:6][N:7]=1.S(Cl)(Cl)=O.[H-].[Na+].[CH2:22]([SH:28])[CH2:23][CH2:24][CH2:25][CH2:26][CH3:27]>C1COCC1>[ClH:1].[CH2:22]([S:28][C:2]1[C:3]([C:8]2[CH2:9][N:10]([CH3:14])[CH2:11][CH2:12][CH:13]=2)=[N:4][CH:5]=[CH:6][N:7]=1)[CH2:23][CH2:24][CH2:25][CH2:26][CH3:27]

Participants

6

Reactant 4

HCID 81061-HexanethiolHCID 24386Thionyl ChlorideHCID 24758Sodium hydrideHCID 10331340HCID 10331340, compound

Product 1

HCID 19800167HCID 19800167, compoundYield 21%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A mixture of 1.1 g (0.0048 mol) of (1) and 7 ml of thionyl chloride was stirred 1 h, the excess thionyl chloride was evaporated, and the residue was treated with ice-water. The solution was made basic with 5 N NaOH and the mixture extracted 3× with 25 ml of CH2Cl2. The solvent was evaporated from the dried extracts, the residue was dissolved in 10 ml of THF, and the solution was added to a suspension of sodium hexylthiolate in THF prepared from 0.21 g (0.0091 mol) NaH, 2 ml (0.014 mol) hexanethiol, and 30 ml of THF. The reaction was heated to reflux for 20 min followed by distillation of most of the THF from the reaction mixture. The solvents were evaporated, the residue treated with water, and the mixture extracted 3× with 25 ml of CH2Cl2. The solvent was evaporated from the dried extracts and the residue purified by radial chromatography eluting with 5% ethanol/0.5% NH4OH/CHCl3. The hydrochloride salt (35), 0.33 g, 21% yield crystallized from ethyl acetate as a white solid, mp 120.5°-122° C. NMR ppm(CDCl3) 0.9 (3H,t), 1.31 (4H, m), 1.44 (2H, m), 1.67 (2H, m), 2.6-2.7 (1H, m), 2.96 (3H, d), 3.05-3.22 (4H, m), 3.54-3.64 (1H, m), 3.72-3.8 (1H, m), 4.4-4.45 (1H, d), 6.8 (1H, m), 8.15 (1H, d), 8.28 (1H, d). Anal. C16H25N3S-HCl requires C: 58.61; H: 7.99; N: 12.81%. Found C: 58.48; H: 7.93; N: 12.84%.

Workup

  1. customthe excess thionyl chloride was evaporated
  2. additionthe residue was treated with ice-water
  3. extractionthe mixture extracted 3× with 25 ml of CH2Cl2
  4. customThe solvent was evaporated from the dried extracts
  5. dissolutionthe residue was dissolved in 10 ml of THF
  6. additionthe solution was added to a suspension of sodium hexylthiolate in THF
  7. temperatureThe reaction was heated
  8. temperatureto reflux for 20 min
  9. distillationfollowed by distillation of most of the THF from the reaction mixture
  10. customThe solvents were evaporated
  11. additionthe residue treated with water
  12. extractionthe mixture extracted 3× with 25 ml of CH2Cl2
  13. customThe solvent was evaporated from the dried extracts
  14. customthe residue purified by radial chromatography
  15. washeluting with 5% ethanol/0.5% NH4OH/CHCl3
  16. customThe hydrochloride salt (35), 0.33 g, 21% yield crystallized from ethyl acetate as a white solid, mp 120.5°-122° C

Sources & evidence

ORD record
ord-4482c58f7d3f4460896f2b31c11a42af
Source dataset
uspto-grants-1993_01
Patent number
US05182283

Reaction notes

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