(Dimethyl sulfide)trihydroboron → HCID 9911426, compound

HRID 1057637Notes

Reaction equation

HRID 1057637 reaction equation
B.CSC.[CH2:5]([N:12]1[C:24]2[CH:23]=[CH:22][CH:21]=[C:20]([O:25][CH2:26][C:27]#[N:28])[C:19]=2[C:18]2[C:13]1=[CH:14][CH:15]=[C:16]([CH3:29])[CH:17]=2)[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1>C1COCC1>[CH2:5]([N:12]1[C:24]2[CH:23]=[CH:22][CH:21]=[C:20]([O:25][CH2:26][CH2:27][NH2:28])[C:19]=2[C:18]2[C:13]1=[CH:14][CH:15]=[C:16]([CH3:29])[CH:17]=2)[C:6]1[CH:7]=[CH:8][CH:9]=[CH:10][CH:11]=1

Participants

4

Reactant 2

HCID 12423031(Dimethyl sulfide)trihydroboronHCID 18671679HCID 18671679, compound

Product 1

HCID 9911426HCID 9911426, compoundYield 66%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Borane-methyl sulfide (1.2 mL, 0.013 mol) is added to a mixture of 2-[(9-benzyl-6-methyl-9H-carbazol-4-yl)oxy]acetonitrile (1.3337 g, 0.0041 mol) in dry THF (35 mL) and the mixture is allowed to stir at room temperature for 5.5 h. The excess borane then is cautiously quenched with methanol and the mixture is concentrated under reduced pressure. Methanol and dichloromethane are added to the residue and the solution is again concentrated under reduced pressure (repeated twice). The solids are then dissolved in methanol/dichloromethane with heating and 4N HCl (10 mL) is added. The mixture is stirred for 15 min while being warmed slightly. The solvent is then removed under reduced pressure and the residue is partitioned between dichloromethane and aq. sodium bicarbonate. The combined organic layers are dried over sodium sulfate and concentrated to dryness. The residue is chromatographed on silica gel (300 mL) using methanol/dichloromethane (2/98 and 6/94) to give 0.89 g (66%) of the title compound. The salt of 2-[(9-benzyl-6-methyl-9H-carbazol-4-yl)oxy]ethylamine (0.2310 g, 0.70 mmol) is formed with maleic acid in dichloromethane and recrystallized from methanol/dichloromethane/hexane to give 0.2051 g (66%) of the maleic acid salt; mp 187.5-188° C.; MS (ESI+) for C22H22N2O m/z 331.3 (M+H)+; IR (drift) 3027, 2984, 2926, 2887, 1601, 1579, 1497, 1483, 1465, 1364, 1344, 1267, 1150, 865, 747 cm−1; 1H NMR (CD3OD) δ2.52, 3.59, 4.52, 5.54, 6.23, 6.77, 7.09, 7.22, 7.33, 8.16, NH2 not seen. Anal. Calcd for C22H22N2O.C4H4O4: C, 69.94; H, 5.87; N, 6.27. Found: C, 69.93; H, 5.90; N, 6.29.

Workup

  1. customThe excess borane then is cautiously quenched with methanol
  2. concentrationthe mixture is concentrated under reduced pressure
  3. additionMethanol and dichloromethane are added to the residue
  4. concentrationthe solution is again concentrated under reduced pressure (
  5. dissolutionThe solids are then dissolved in methanol/dichloromethane
  6. temperaturewith heating
  7. addition4N HCl (10 mL) is added
  8. stirringThe mixture is stirred for 15 min
  9. temperaturewhile being warmed slightly
  10. customThe solvent is then removed under reduced pressure
  11. customthe residue is partitioned between dichloromethane and aq. sodium bicarbonate
  12. dry with materialThe combined organic layers are dried over sodium sulfate
  13. concentrationconcentrated to dryness
  14. customThe residue is chromatographed on silica gel (300 mL)

Sources & evidence

ORD record
ord-9d0c7576e73746c083f3e4dcccda0eee
Source dataset
uspto-grants-2003_02
Patent number
US06514968B1

Reaction notes

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