2-Bromo-1-(3-nitrophenyl)ethan-1-one → 2-Amino-4-(3-nitrophenyl)thiazole

HRID 2375877Notes

Reaction equation

HRID 2375877 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([CH:11]=[CH:12][CH:13]=1)[C:7](=O)[CH2:8]Br)([O-:3])=[O:2].[NH2:14][C:15]([NH2:17])=[S:16]>CN(C=O)C>[N+:1]([C:4]1[CH:5]=[C:6]([C:7]2[N:14]=[C:15]([NH2:17])[S:16][CH:8]=2)[CH:11]=[CH:12][CH:13]=1)([O-:3])=[O:2]

Participants

4

Reactant 2

HCID 752132-Bromo-1-(3-nitrophenyl)ethan-1-oneHCID 2723790Thiourea

Product 1

HCID 6135042-Amino-4-(3-nitrophenyl)thiazoleYield 93.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of 3-nitrophenacyl bromide (244 mg, 1.00 mmol) and thiourea (76.1 mg, 1.00 mmol) in DMF (2 mL) was stirred at 60° C. for 16 h. The mixture was concentrated in vacuo to obtain a yellow solid that was then washed with H2O and dried to yield a yellow solid (206 mg). The solid was dissolved in DMSO and purified by SCX column (4×6 mL capacity), eluted with CH2Cl2 (4×6 mL), MeOH (4×12 mL) and then released by NH3 (7 N in MeOH, 4×6 mL) to give a light-yellow solid of 4-(3-aminophenyl)-thiazol-2-ylamine. 1H NMR (DMSO-d6, 400 MHz): δ=7.24 (brs, 2H), 7.35 (s, 1H), 7.65-7.69 (m, 1H), 8.10-8.13 (m, 1H), 8.23-8.26 (m, 1H), 8.62 (t, 1H, J=1.8 Hz). MS (ES+): m/z 223.12 (45) [M}+]. HPLC: tR=2.82 min (ZQ2000, polar—5 min). The combined CH2Cl2 and MeOH solution was concentrated in vacuo to give a yellow solid of 4-(3-aminophenyl)-1H-imidazole-2-thiol. 1H NMR (DMSO-d6, 400 MHz): δ=7.75 (t, 1H, J=8.0 Hz), 8.01 (d, 1H, J=0.8 Hz), 8.17-8.20 (m, 1H), 8.35-8.37 (m, 1H), 8.56 (d, 1H, J=1.6 Hz), 8.72 (t, 1H, J=1.8 Hz), 12.56 (s, 1H). MS (ES+): m/z 222.12 (15) [MH+]. HPLC: tR=2.97 min (ZQ2000, polar 5 min).

Workup

  1. concentrationThe mixture was concentrated in vacuo
  2. customto obtain a yellow solid
  3. washthat was then washed with H2O
  4. customdried

Sources & evidence

ORD record
ord-c5917b4ea2f94579b0b65dad81e8b280
Source dataset
uspto-grants-2008_12
Patent number
US07465726B2

Reaction notes

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