Sodium sulfide nonahydrate → 2H-Pyran, 2,2'-[thiobis[(2,2-dimethyl-6,1-hexanediyl)oxy]]bis[tetrahydro-

HRID 48310

Reaction equation

HRID 48310 reaction equation
Br[CH2:2][CH2:3][CH2:4][CH2:5][C:6]([CH3:16])([CH3:15])[CH2:7][O:8][CH:9]1[CH2:14][CH2:13][CH2:12][CH2:11][O:10]1.[OH2:17].[OH2:18].O.O.O.O.O.O.O.[S-2:26].[Na+].[Na+]>C(O)C.O>[CH3:15][C:6]([CH3:16])([CH2:7][O:8][CH:9]1[CH2:14][CH2:13][CH2:12][CH2:11][O:10]1)[CH2:5][CH2:4][CH2:3][CH2:2][S:26][CH2:2][CH2:3][CH2:4][CH2:5][C:6]([CH3:16])([CH3:15])[CH2:7][O:17][CH:11]1[CH2:12][CH2:13][CH2:14][CH2:9][O:18]1

Participants

5

Reactant 2

HCID 73972Sodium sulfide nonahydrateHCID 103796142-(6-Bromo-2,2-dimethylhexyloxy)-tetrahydropyran

Product 1

HCID 100728862H-Pyran, 2,2'-[thiobis[(2,2-dimethyl-6,1-hexanediyl)oxy]]bis[tetrahydro-Yield 78.7%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent

Procedure

A solution of 2-(6-bromo-2,2-dimethyl-hexyloxy)-tetrahydro-pyran (14.9 g, 50.8 mmol) in ethanol (100 ml) was added dropwise over 30 min to a solution of sodium sulfide nonahydrate (6.10 g, 25.41 mmol) in water (10 ml) at rt under N2 atmosphere. The reaction mixture was stirred at rt for 18 h and then heated to reflux for 3.5 h. The solution was concentrated in vacuo, 5% NaOH (100 ml) was added, and the reaction mixture was extracted with CH2Cl2 (200 ml). The organic layer was dried over MgSO4, concentrated in vacuo, and dried in high vacuo to give bis-(5,5-dimethyl-6-tetrahydropyranyloxy-hexyl)-sulfide (9.17 g, 78%) as a slightly yellowish oil. 1H NMR (300 MHz, CDCl3), d (ppm): 4.54 (t, 2H, J=2.9); 3.83 (m, 2H); 3.48 (m, 2H); 3.45 (d, 2H, J=9.2); 2.98 (d, 2H, J=9.2); 2.50 (t, 4H, J=7.3); 1.82 (m, 2H); 1.75-1.44 (m, 16H); 1.42-1.18 (m, 10H); 0.894 (s, 6H); 0.887 (s, 6H). 13C NMR (75 MHz, CDCl3), d (ppm): 98.90; 76.26; 61.68; 38.77; 34.04; 32.00; 30.51; 25.44; 24.42; 24.36; 23.20; 19.28. Calcd. for C26H51SO4: 459.3508, found 459.3504.

Workup

  1. temperatureheated
  2. temperatureto reflux for 3.5 h
  3. concentrationThe solution was concentrated in vacuo, 5% NaOH (100 ml)
  4. additionwas added
  5. extractionthe reaction mixture was extracted with CH2Cl2 (200 ml)
  6. dry with materialThe organic layer was dried over MgSO4
  7. concentrationconcentrated in vacuo
  8. customdried in high vacuo

Sources & evidence

ORD record
ord-707fde9d978a41ff9d7d7eb21bd1c594
Source dataset
uspto-grants-2004_03
Patent number
US06703422B2

Linked notes

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