Sodium hydride → 2-[7-Isocyano-2,2,12,12-tetramethyl-13-(tetrahydro-pyran-2-yloxy)-7-(toluene-4-sulfonyl)-tridecyloxy]-tetrahydro-pyran

HRID 47975Notes

Reaction equation

HRID 47975 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.[C:17]1([CH3:29])[CH:22]=[CH:21][C:20]([S:23]([CH2:26][N+:27]#[C-:28])(=[O:25])=[O:24])=[CH:19][CH:18]=1.[H-].[Na+]>CS(C)=O.C(OCC)C.[I-].C([N+](CCCC)(CCCC)CCCC)CCC.O>[N+:27]([C:26]([S:23]([C:20]1[CH:19]=[CH:18][C:17]([CH3:29])=[CH:22][CH:21]=1)(=[O:24])=[O:25])([CH2:2][CH2:3][CH2:4][CH2:5][C:6]([CH3:15])([CH3:16])[CH2:7][O:8][CH:9]1[CH2:14][CH2:13][CH2:12][CH2:11][O:10]1)[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)#[C-:28]

Participants

8

Reactant 3

HCID 24758Sodium hydrideHCID 161915Tosylmethyl isocyanideHCID 103796142-(6-Bromo-2,2-dimethylhexyloxy)-tetrahydropyran

Product 1

HCID 113310192-[7-Isocyano-2,2,12,12-tetramethyl-13-(tetrahydro-pyran-2-yloxy)-7-(toluene-4-sulfonyl)-tridecyloxy]-tetrahydro-pyranYield 112.8%

Reagents, catalysts & solvents 4

HCID 67553Tetrabutylammonium IodideCatalystHCID 679Dimethyl SulfoxideSolvent2×HCID 962WaterSolvent2×HCID 3283Diethyl EtherSolvent

Procedure

To a solution of 2-(6-bromo-2,2-dimethyl-hexyloxy)-tetrahydro-pyran (13.0 g, 44.33 mmol) and p-toluenesulphonylmethyl isocyanide (4.33 g, 22.17 mmol) in anhydrous DMSO (50 ml) and anhydrous diethyl ether (50 ml) was added sodium hydride (60% dispersion in mineral oil, 2.13 g, 53.20 mmol) at rt under N2 atmosphere. After solidification of the reaction mixture, additional anhydrous DMSO (50 ml) was added. After stirring for 5.5 h at room temperature, tetrabutylammonium iodide (1.64 g, 4.43 mmol) was added and the mixture stirred for additional 22.5 h at rt. The reaction mixture was carefully hydrolyzed with water (10 ml), diluted with water (200 ml), and extracted with diethyl ether (200 ml). The organic layer was washed with saturated NaCl solution (100 ml), dried over MgSO4, and concentrated in vacuo to give crude 2-[7-isocyano-2,2,12,12-tetramethyl-13-(tetrahydro-pyran-2-yloxy)-7-(toluene-4-sulfonyl)- tridecyloxy]-tetrahydro-pyran (15.5 g) as an oil.

Workup

  1. stirringthe mixture stirred for additional 22.5 h at rt
  2. extractionextracted with diethyl ether (200 ml)
  3. washThe organic layer was washed with saturated NaCl solution (100 ml)
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-55e30725d5f7496b975ca7e0da0cda61
Source dataset
uspto-grants-2004_03
Patent number
US06699910B2

Reaction notes

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