Azidotrimethylsilane → HCID 178419293, compound

HRID 1873198Notes

Reaction equation

HRID 1873198 reaction equation
C[Al](C)C.[Br:5][C:6]1[CH:15]=[C:14]([C:16]2[C:25]3[C:26]4[CH:32]=[CH:31][CH:30]=[CH:29][C:27]=4[S:28][C:24]=3[C:23]([Br:33])=[C:22]3[C:17]=2[CH:18]=[CH:19][CH:20]=[CH:21]3)[CH:13]=[C:12]([Br:34])[C:7]=1[O:8][CH2:9][C:10]#[N:11].C[Si]([N:39]=[N+:40]=[N-:41])(C)C>O>[Br:5][C:6]1[CH:15]=[C:14]([C:16]2[C:25]3[C:26]4[CH:32]=[CH:31][CH:30]=[CH:29][C:27]=4[S:28][C:24]=3[C:23]([Br:33])=[C:22]3[C:17]=2[CH:18]=[CH:19][CH:20]=[CH:21]3)[CH:13]=[C:12]([Br:34])[C:7]=1[O:8][CH2:9][C:10]1[NH:41][N:40]=[N:39][N:11]=1

Participants

5

Reactant 3

HCID 78378AzidotrimethylsilaneHCID 16682925TrimethylaluminumHCID 18687827HCID 18687827, compound

Product 1

HCID 178419293HCID 178419293, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
80 °C

Procedure

Trimethylaluminum (2.55 mL, 3.84mmol, 2.0 M solution in toluene) was added to [2,6-dibromo-4-(6-bromo-benzo[b]naphtho[2,3-d]thiophen-11-yl)-phenoxy]-acetonitrile (0.615 g, 1.02 mmol) under a dry nitrogen atmosphere. Trimethylsilyl azide (0.510 mL, 3.84 mmol) was then added and the solution was heated in a 80° C. oil bath. After 16.5 h the reaction mixture was cooled to room temperature and water was cautiously added. The mixture was partitioned between dilute aqueous HCl and ethyl acetate. The layers were separated and the 2% phosphoric acid in methanol washed silica gel was added to the organic phase. The solvent was removed and the adsorbate was flashed using 2% phosphoric acid in methanol washed silica gel (eluent:gradient: 4:1 to 7:3 petroleum ether:ethyl acetate) to provide the title compound as a white solid, which was recrystallized from cyclohexane (0.365 g, 55%): mp 243-245° C.: NMR (DMSO-d6); δ8.29 (d, J=8 Hz, 1H), 8.09 (d, J=8 Hz, 1 H), 7.89 (s, 2 H), 7.80 (ddd, J =8, 7, 1 Hz, 1 H), 7.66-7.57 (m, 2 H), 7.55 (ddd, J=8, 7, 1 Hz, 1 H), 7.40 (ddd, J=8, 7, 1 Hz, 1 H), 6.71 (d, J=8 Hz, 1 H), 5.64 (s, 2 H), 1.34 (cyclohexane, 0.3 mole eq); MS (EI): [M+], 3 bromine isotope pattern, 642, 644, 646, 648; Anal. Calc. for C24H13Br3N40S.0.33 C6 H12: C, 46.39, H, 2.55, N, 8.32. Found: C, 46.28, H, 2.43, N, 7.90.

Workup

  1. temperatureAfter 16.5 h the reaction mixture was cooled to room temperature
  2. customThe mixture was partitioned between dilute aqueous HCl and ethyl acetate
  3. customThe layers were separated
  4. washthe 2% phosphoric acid in methanol washed silica gel
  5. additionwas added to the organic phase
  6. customThe solvent was removed
  7. washwashed silica gel (eluent:gradient: 4:1 to 7:3 petroleum ether:ethyl acetate)

Sources & evidence

ORD record
ord-f99de85409584f75b13a2c13f853bfcd
Source dataset
uspto-grants-2000_08
Patent number
US06110962

Reaction notes

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