Phosgeniminium chloride → HCID 59770949, compound

HRID 2218960Notes

Reaction equation

HRID 2218960 reaction equation
[C:1]([O:5][C:6](=[O:18])[NH:7][CH2:8][C:9]1[CH:14]=[C:13]([Br:15])[C:12]([OH:16])=[C:11]([NH2:17])[CH:10]=1)([CH3:4])([CH3:3])[CH3:2].[Cl-].Cl[C:21](=[N+:23]([CH3:25])[CH3:24])Cl>C(Cl)Cl>[C:1]([O:5][C:6](=[O:18])[NH:7][CH2:8][C:9]1[CH:14]=[C:13]([Br:15])[C:12]2[O:16][C:21]([N:23]([CH3:25])[CH3:24])=[N:17][C:11]=2[CH:10]=1)([CH3:4])([CH3:2])[CH3:3]

Participants

4

Reactant 2

HCID 2723945Phosgeniminium chlorideHCID 59770951HCID 59770951, compound

Product 1

HCID 59770949HCID 59770949, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A mixture of Tert-butylN—(3-amino-5-bromo-4-hydroxybenzyl)carbamate (300 mg, 0.95 mmol) and dichloromethylenedimethylammonium chloride (phosgene iminium chloride, 240 mg, 1.48 mmol) in 10 mL of dry CH2Cl2 was refluxed for 6 h. After cooling the solution was extracted with EtOAc, washed with NaHCO3, brine and dried (MgSO4). After purification by column chromatography (1% MeOH in CH2Cl2) 192 mg (55%) of the title compound were obtained. 1H NMR (CDCl3) δ 7.14 (s, 1H, H-6); 7.04 (s, 1H, H-4); 5.11 (bs, 1H, NH); 4.31 (d, 2H, J=5.6 Hz, CH2); 3.23, 3.22 (s, 6H, NCH3 2×); 1.48 (s, 9H, (CH3)3C); 13C NMR (CDCl3) δ 163.3 (C-2), 156.2 (CO), 146.6 (C-7a), 145.1 (C-3a), 137.0 (C-5), 122.8 (C-6), 114.3 (C-4), 100.6 (C-7), 79.9 ((CH3)3C), 44.7 (CH2), 38.1 (NCH3×2), 28.8 ((CH3) 3C).

Workup

  1. temperaturewas refluxed for 6 h
  2. temperatureAfter cooling the solution
  3. extractionwas extracted with EtOAc
  4. washwashed with NaHCO3, brine
  5. dry with materialdried (MgSO4)
  6. customAfter purification by column chromatography (1% MeOH in CH2Cl2) 192 mg (55%) of the title compound
  7. customwere obtained

Sources & evidence

ORD record
ord-8a8d6d66a4a0468c9673b9c1c2704b05
Source dataset
uspto-grants-2008_08
Patent number
US07414036B2

Reaction notes

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