Sodium hydride → O-((2E,6E,10E)-3,7,11,15-tetramethylhexadeca-2,6,10,14-tetraen-1-yl) pyridin-3-ylcarbamothioate

HRID 2167199Notes

Reaction equation

HRID 2167199 reaction equation
[H-].[Na+].[CH2:3]([CH2:13]/[C:14](/[CH3:23])=[CH:15]/[CH2:16][CH2:17]/[C:18](/[CH3:22])=[CH:19]/[CH2:20][OH:21])/[CH:4]=[C:5](/[CH2:7][CH2:8][CH:9]=[C:10]([CH3:12])[CH3:11])\[CH3:6].[N:24]1[CH:29]=[CH:28][CH:27]=[C:26]([N:30]=[C:31]=[S:32])[CH:25]=1>C1COCC1>[N:24]1[CH:29]=[CH:28][CH:27]=[C:26]([NH:30][C:31](=[S:32])[O:21][CH2:20]/[CH:19]=[C:18](\[CH3:22])/[CH2:17][CH2:16]/[CH:15]=[C:14](\[CH3:23])/[CH2:13][CH2:3]/[CH:4]=[C:5](\[CH3:6])/[CH2:7][CH2:8][CH:9]=[C:10]([CH3:12])[CH3:11])[CH:25]=1

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 27372423-Pyridyl isothiocyanateHCID 5281365Geranylgeraniol

Product 1

HCID 86701128O-((2E,6E,10E)-3,7,11,15-tetramethylhexadeca-2,6,10,14-tetraen-1-yl) pyridin-3-ylcarbamothioateYield 70%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

To a solution of NaH (60% dispersed in oil, 32 mg, 0.81 mmo) in THF (4 mL) at 0° C. was added alcohol 1 (180 mg, 0.62 mmol) in THF (1 mL) and the reaction mixture was stirred for 30 min at this temperature. Then 3-pyridyl isothiocyanate (169 mg, 124 mmol) in THF (1 mL) was added and stirred at rt. After stirring for 12 h, the reaction mixture was quenched water and extracted with EtOAc (3×). The organic layer was dried and concentrated to get a residue, which was purified by column chromatography (Hexane/EtOAc) to yield thiocarbamate 38a as a viscous liquid (179 mg, 70%). TLC Rf: 0.23 (20% EtOAc/hexanes); 1H NMR (300 MHz, CDCl3): δ 8.55 (d, 1H), 8.40 (d, 1H), 7.95 (m, 1H), 7.30 (m, 2H), 5.49 (t, 1H), 5.11 (m, 3H), 4.70 (d, 2H), 2.16-1.19 (m, 12H), 1.76 (s, 3H), 1.68 (s, 3H), 1.60 (s, 9H); LCMS: MS (m/z): 427 (M+H).

Workup

  1. stirringstirred at rt
  2. stirringAfter stirring for 12 h
  3. customthe reaction mixture was quenched water
  4. extractionextracted with EtOAc (3×)
  5. customThe organic layer was dried
  6. concentrationconcentrated
  7. customto get a residue, which
  8. customwas purified by column chromatography (Hexane/EtOAc)

Sources & evidence

ORD record
ord-b220dd79f714418dba688c270dc50f78
Source dataset
uspto-grants-2015_06
Patent number
US09045403B2

Reaction notes

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