Thioanisole → HCID 22666164, compound

HRID 279085Notes

Reaction equation

HRID 279085 reaction equation
C([O:8][C:9]1[CH:10]=[CH:11][C:12]2[O:16][C:15]([S:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][C:23]([NH:25][C:26]3[C:31]([CH:32]([CH3:34])[CH3:33])=[CH:30][CH:29]=[CH:28][C:27]=3[CH:35]([CH3:37])[CH3:36])=[O:24])=[N:14][C:13]=2[CH:38]=1)C1C=CC=CC=1.C1(SC)C=CC=CC=1>FC(F)(F)C(O)=O>[OH:8][C:9]1[CH:10]=[CH:11][C:12]2[O:16][C:15]([S:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][C:23]([NH:25][C:26]3[C:31]([CH:32]([CH3:33])[CH3:34])=[CH:30][CH:29]=[CH:28][C:27]=3[CH:35]([CH3:37])[CH3:36])=[O:24])=[N:14][C:13]=2[CH:38]=1

Participants

4

Reactant 2

HCID 7520ThioanisoleHCID 22666100HCID 22666100, compound

Product 1

HCID 22666164HCID 22666164, compoundYield 97%

Reagents, catalysts & solvents 1

HCID 6422Trifluoroacetic acidSolvent

Procedure

Under cooling in ice bath, 6-(5-benzyloxybenzoxazol-2-ylthio)-N-(2,6-diisopropylphenyl)hexanamide (514 mg, 2.0 mmol) was dissolved in trifluoroacetic acid (20 ml), followed by addition of thioanisole (1.24 g, 10 mmol), with stirring at ambient temperature for 12 hours. The solvent was distilled off from the reaction solution; the resulting residue was diluted with water, and extracted with ethyl acetate. The organic layer was washed sequentially with a saturated sodium hydrogen carbonate solution and saturated sodium chloride solution, and was dried over anhydrous magnesium sulfate, from which the solvents were distilled off. The residue was purified by silica gel column chromatography (30 g of silica gel; elution solvents: hexane:acetone=5:1 to 5:2), to recover the objective compound (459 mg at a yield of 97%) as a pale red amorphous. IR (KBr) cm−1: 3247, 2963, 1649, 1445, 1153. 1H-NMR (d6-DMSO) δ: 1.12 (12H, d, J=6.8 Hz), 1.48-1.91 (6H, m), 2.35 (2H, m), 3.08 (2H, sept, J=6.8 Hz), 3.31 (2H, t, J=7.1 Hz), 6.70 (1H, dd, J=8.8, 2.4 Hz), 6.92 (1H, d, J=2.4 Hz), 7.09 (1H, d, J=8.3 Hz), 7.10 (1H, d, J=7.1 Hz), 7.19 (1H, dd, J=8.3, 7.1 Hz), 7.31 (1H, d, J=8.8 Hz), 8.68 (1H, br s), 8.92 (1H, s). EIMS m/z (relative intensity): 440 (M+, 100). Elementary Analysis: C25H32N2O3S Required: C, 68.15; H, 7.32; N, 6.36; S, 7.28. Found: C, 68.16; H, 7.45; N, 6.26; S, 6.86.

Workup

  1. temperatureUnder cooling in ice bath
  2. distillationThe solvent was distilled off from the reaction solution
  3. additionthe resulting residue was diluted with water
  4. extractionextracted with ethyl acetate
  5. washThe organic layer was washed sequentially with a saturated sodium hydrogen carbonate solution and saturated sodium chloride solution
  6. dry with materialwas dried over anhydrous magnesium sulfate, from which the solvents
  7. distillationwere distilled off
  8. customThe residue was purified by silica gel column chromatography (30 g of silica gel; elution solvents: hexane:acetone=5:1 to 5:2)
  9. customto recover the objective compound (459 mg at a yield of 97%) as a pale red amorphous

Sources & evidence

ORD record
ord-46b7f31d35c84ed59529303e9349ad61
Source dataset
uspto-grants-2002_03
Patent number
US06362208B1

Reaction notes

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