1-Pentanethiol → HCID 19800174, compound

HRID 1646928Notes

Reaction equation

HRID 1646928 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:27])[CH2:23][CH2:24][CH2:25][CH3:26]>C1COCC1>[ClH:1].[CH2:22]([S:27][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][CH3:26]

Participants

6

Reactant 4

HCID 80671-PentanethiolHCID 24386Thionyl ChlorideHCID 24758Sodium hydrideHCID 10331340HCID 10331340, compound

Product 1

HCID 19800174HCID 19800174, compoundYield 19%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A mixture of 1 g (0.0044 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 0.18 g (0.0078 mol) NaH, 2 ml (0.016 mol) pentanethiol, 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 (36), 0.26 g, 19% yield crystallized from ethyl acetate as colorless crystals, mp 123°-124° C. NMR ppm (CDCl3) 0.9 (3H, t), 1.38 (4H, m), 1.7 (2H, m), 2.58-2.7 (1H, m), 3.0 (3H, d), 3 05-3.2 (4H, m), 3.5-3.6 (1H, m), 3.7-3.82 (1H, m), 4.4-4.47 (1H, d), 6.8 (1H, m), 8.15 (1H, d), 8.28 (1H, d). Anal. C15H23N3S-HCl requires C: 57.40; H: 7.71; N: 13.37%. Found C: 57.43; H: 7.63; N: 13.45%.

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 (36), 0.26 g, 19% yield crystallized from ethyl acetate as colorless crystals, mp 123°-124° C

Sources & evidence

ORD record
ord-6ca88d4497c3467a838df49c05832f30
Source dataset
uspto-grants-1993_01
Patent number
US05182283

Reaction notes

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