Ammonium Chloride → HCID 60111299, compound

HRID 1008247Notes

Reaction equation

HRID 1008247 reaction equation
[CH2:1]([O:4][C:5]([N:7]([CH2:35][C:36]1[CH:41]=[C:40]([O:42][CH2:43][CH:44]=[CH2:45])[C:39]([Br:46])=[C:38]([O:47][CH2:48][CH:49]=[CH2:50])[CH:37]=1)[C@H:8]([CH2:23][O:24][Si](C(C)C)(C(C)C)C(C)C)[CH2:9][C:10]1[CH:15]=[CH:14][C:13]([O:16][C:17](=[O:22])[O:18][CH2:19][CH:20]=[CH2:21])=[CH:12][CH:11]=1)=[O:6])[CH:2]=[CH2:3].N1C=CC=CC=1.F.[Cl-].[NH4+]>C1COCC1>[CH2:1]([O:4][C:5]([N:7]([CH2:35][C:36]1[CH:37]=[C:38]([O:47][CH2:48][CH:49]=[CH2:50])[C:39]([Br:46])=[C:40]([O:42][CH2:43][CH:44]=[CH2:45])[CH:41]=1)[C@H:8]([CH2:23][OH:24])[CH2:9][C:10]1[CH:15]=[CH:14][C:13]([O:16][C:17](=[O:22])[O:18][CH2:19][CH:20]=[CH2:21])=[CH:12][CH:11]=1)=[O:6])[CH:2]=[CH2:3]

Participants

5

Reactant 3

HCID 25517Ammonium ChlorideHCID 64774Pyridine, hydrofluoride (1:1)HCID 60111270HCID 60111270, compound

Product 1

HCID 60111299HCID 60111299, compoundYield 94%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To 24 (1.15 g, 1.49 mmol, 1.0 equiv) in THF (20 mL) in a high density polyethylene vial was added hydrogen fluoride-pyridine (1 mL) once an hour for 4 hours (4 mL total), after which time saturated aqueous ammonium chloride was added and the THF was removed under reduced pressure. The remaining solution was extracted with CH2Cl2. The organics were combined, washed with brine, dried over Na2SO4, and concentrated. Purification by flash chromatography (20→60% EtOAc/hexane) afforded 25 (0.86 g, 94%) as a colorless oil. Rf=0.23 (50% EtOAc/hexane); [α]28D=−29.24° (c=1, CH2Cl2); FTIR (neat, cm−1) 3447, 2932, 1761, 1695, 1588, 1435, 1421, 1242; 1H NMR (400 MHz, DMSO, 80° C.) δ7.18-7.12 (m, 2H), 7.10-7.04 (m, 2H), 6.63 (s, 2H), 6.07-5.94 (m, 3H), 5.90-5.78 (m, 1H), 5.42 (dd, J=15.2, 2.0 Hz, 2H), 5.39 (dd, J=14.0, 1.6 Hz, 1H), 5.30 (dd, J=10.4, 1.6 Hz, 1H), 5.25 (dd, J=10.6, 1.8 Hz, 2H) 5.18 (d, J=16.8 Hz, 1H), 5.13 (d, J=10.4 Hz), 4.73-4.71 (m, 2H), 4.55-4.54 (m, 4H), 4.72 (d, J=4.0 Hz, 2H), 4.36 (d, J=16.0 Hz, 1H), 4.24 (d, J=16.4 Hz, 1H), 4.21-4.12 (m, 1H), 3.62-3.57 (m, 1H), 3.53-3.49 (m, 1H), 2.90-2.77 (m, 2H); 13C NMR (100 MHz, DMSO, 80° C.) δ155.3, 155.1, 152.2, 148.8, 140.1, 136.3, 132.9, 132.8, 131.5, 129.3, 120.1, 116.8, 116.6, 116.3, 105.8, 105.6, 99.1, 69.2, 69.0, 68.1, 64.7, 61.3, 60.5, 48.1, 34.3; HRMS (ES+) calculated for C30H34BrNO8 (M+H)+: 616.1468, found: 616.1570.

Workup

  1. customthe THF was removed under reduced pressure
  2. extractionThe remaining solution was extracted with CH2Cl2
  3. washwashed with brine
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated
  6. customPurification by flash chromatography (20→60% EtOAc/hexane)

Sources & evidence

ORD record
ord-d75bafe63f0f4644a29ad57b4dfda56e
Source dataset
uspto-grants-2004_09
Patent number
US06797819B1

Reaction notes

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