Sodium hydride → HCID 11387750, compound

HRID 1466710Notes

Reaction equation

HRID 1466710 reaction equation
Br[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][C:8]([CH3:15])([CH3:14])[C:9]([O:11][CH2:12][CH3:13])=[O:10].[C:16]1([CH3:28])[CH:21]=[CH:20][C:19]([S:22]([CH2:25][N+:26]#[C-:27])(=[O:24])=[O:23])=[CH:18][CH:17]=1.[H-].[Na+]>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.CS(C)=O>[CH2:12]([O:11][C:9](=[O:10])[C:8]([CH3:15])([CH3:14])[CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][CH2:2][C:25]([N+:26]#[C-:27])([S:22]([C:19]1[CH:18]=[CH:17][C:16]([CH3:28])=[CH:21][CH:20]=1)(=[O:23])=[O:24])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][C:8]([CH3:14])([CH3:15])[C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH3:13]

Participants

6

Reactant 3

HCID 24758Sodium hydrideHCID 161915Tosylmethyl isocyanideHCID 11482859HCID 11482859, compound

Product 1

HCID 11387750HCID 11387750, compoundYield 100%

Reagents, catalysts & solvents 2

HCID 67553Tetrabutylammonium IodideCatalystHCID 679Dimethyl SulfoxideSolvent

Procedure

To a solution of ethyl 8-bromo-2,2-dimethyloctanoate (35.0 g, 125.4 mmol), tetrabutylammonium iodide (4.6 g, 12.5 mmol), and p-toluenesulphonylmethyl isocyanide (TosMIC, 12.2 g, 62.7 mmol) in anhydrous DMSO (450 mL) was added sodium hydride (60% dispersion in mineral oil, 6.3 g, 158 mmol) under cooling with an ice-water bath and under N2 atmosphere. The reaction mixture was stirred for 23 h at room temperature, then carefully hydrolyzed with ice-water (500 mL) and extracted with MTBE (3×200 mL). The organic layers were washed with water (300 mL) and brine (150 mL), dried over MgSO4, and concentrated in vacuo to give crude 9-isocyano-2,2,16,16-tetramethyl-9-(toluene-4-sulfonyl)-heptadecanedioic acid diethyl ester (37.0 g, 100%). 1H NMR (300 MHz, CDCl3/TMS): δ (ppm): 7.88 (d, J=7.9 Hz, 2H), 7.42 (d, J=7.9 Hz, 2H), 4.10 (q, J=7.5 Hz, 4H), 2.48 (s, 3H), 2.05-1.75 (m, 3H), 1.65-1.20 (m, 21H), 1.15 (t, J=7.5 Hz, 6H), 1.10 (s, 12H). 13C NMR (75 MHz, CDCl3/TMS): δ (ppm): 177.89, 163.75, 146.23, 131.35, 130.28, 129.82, 81.79, 60.17, 42.09, 40.57, 33.09, 29.68, 25.17, 24.78, 23.66, 14.31. HRMS (LSIMS, gly): Calcd for C37H54NO6S (MH+): 592.3672. found: 592.3667.

Workup

  1. temperatureunder cooling with an ice-water bath and under N2 atmosphere
  2. extractionextracted with MTBE (3×200 mL)
  3. washThe organic layers were washed with water (300 mL) and brine (150 mL)
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-fb3d329380e840b78e20aa3300661640
Source dataset
uspto-grants-2015_04
Patent number
US09000041B2

Reaction notes

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