Water → HCID 178419294, compound

HRID 1873199Notes

Reaction equation

HRID 1873199 reaction equation
C[Al](C)C.[Br:5][C:6]1[CH:23]=[C:22]([C:24]2[C:33]3[C:34]4[CH:40]=[CH:39][CH:38]=[CH:37][C:35]=4[S:36][C:32]=3[C:31]([Br:41])=[C:30]3[C:25]=2[CH:26]=[CH:27][CH:28]=[CH:29]3)[CH:21]=[C:20]([Br:42])[C:7]=1[O:8][C@H:9]([CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)[C:10]([NH2:12])=O.C[Si]([N:47]=[N+:48]=[N-:49])(C)C.O>CCOCC>[Br:42][C:20]1[CH:21]=[C:22]([C:24]2[C:33]3[C:34]4[CH:40]=[CH:39][CH:38]=[CH:37][C:35]=4[S:36][C:32]=3[C:31]([Br:41])=[C:30]3[C:25]=2[CH:26]=[CH:27][CH:28]=[CH:29]3)[CH:23]=[C:6]([Br:5])[C:7]=1[O:8][C@@H:9]([C:10]1[NH:49][N:48]=[N:47][N:12]=1)[CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

Participants

6

Reactant 4

HCID 962WaterHCID 78378AzidotrimethylsilaneHCID 16682925TrimethylaluminumHCID 21970376HCID 21970376, compound

Product 1

HCID 178419294HCID 178419294, compoundYield 57%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
85 °C

Procedure

Trimethylaluminum (7.24 mL, 14.4 mmol, 2.0 M solution in toluene) was added to (R)-2-[2,6-dibromo-4-(6-bromo-benzo[b]naphtho[2,3-d]thiophen-11-yl)-phenoxy ]-3-phenyl-propionamide (1.33 g, 1.93 mmol) under a dry nitrogen atmosphere. Trimethylsilyl azide (1.92 mL, 14.4 mmol) was then added and the solution was heated in a 85° C. oil bath. After 7 h the reaction mixture was cooled to room temperature and diluted with ether. Water was cautiously added and after bubbling subsided, the mixture was partitioned between dilute aqueous HCl and ether. The ether phase was concentrated and triturated with petroleum ether, a small amount of methanol, a small amount of ether and finally petroleum ether to provide the title compound as a white solid (0.802 g, 57%): mp 238-239° C.: NMR (DMSO-d6); δ8.28 (d, J=8 Hz, 1 H), 8.07 (d, J=8 Hz, 1 H), 7.81-7.74 (m, 3 H), 7.62 (ddd, 8, 7, 1 Hz, 1 H), 7.57-7.53 (m, 2 H), 7.44 (ddd, 8, 7, 1 Hz, 1 H), 7.38-7.22 (m, 5 H), 6.60 (d, J=8 Hz, 1 H), 5.87 (dd, J=9, 7 Hz, 1 H), 3.90 (dd, J=13, 7, 1H), 3.80 (dd, J=13, 8, 1H); MS (-ESI): [M-H], 3 bromine isotope pattern, 731 (60%), 733 (90%) 735 (100%) 737 (60%); Anal. Calc. for C31H19Br3N40S: C, 50.64, H, 2.61, N, 7.62. Found: C, 49.65, H, 2.434, N, 7.16.

Workup

  1. temperatureAfter 7 h the reaction mixture was cooled to room temperature
  2. customafter bubbling
  3. customthe mixture was partitioned between dilute aqueous HCl and ether
  4. concentrationThe ether phase was concentrated
  5. customtriturated with petroleum ether

Sources & evidence

ORD record
ord-96f238529b0e468998cf5024ebfff0b3
Source dataset
uspto-grants-2000_08
Patent number
US06110962

Reaction notes

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