Thiophosgene → N-(2-tert-butyldimethysilyloxy-4-nitrophenyl)-N'-phenyl-thiourea

HRID 323024Notes

Reaction equation

HRID 323024 reaction equation
[Si:1]([O:8][C:9]1[CH:15]=[C:14]([N+:16]([O-:18])=[O:17])[CH:13]=[CH:12][C:10]=1[NH2:11])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].C([O-])(O)=O.[Na+].[C:24](Cl)(Cl)=[S:25]>C(Cl)(Cl)Cl.O>[Si:1]([O:8][C:9]1[CH:15]=[C:14]([N+:16]([O-:18])=[O:17])[CH:13]=[CH:12][C:10]=1[NH:11][C:24]([NH:11][C:10]1[CH:12]=[CH:13][CH:14]=[CH:15][CH:9]=1)=[S:25])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 10040ThiophosgeneHCID 516892Sodium BicarbonateHCID 154857102-[(Tert-butyldimethylsilyl)oxy]-4-nitroaniline

Product 1

HCID 15524278N-(2-tert-butyldimethysilyloxy-4-nitrophenyl)-N'-phenyl-thioureaYield 98%

Reagents, catalysts & solvents 1

HCID 22418719Chloroform waterSolvent

Conditions

Temperature
23 °C

Procedure

N-(2-tert-Butyldimethysilyloxy-4-nitrophenyl)-N′-phenyl-thiourea was prepared by treating a biphasic solution of 2-tert-butyldimethysilyloxy-4-nitroaniline (80 mg, 0.308 mmol) and NaHCO3 in CHCl3:H2O (2.5:1, 7 mL) with thiophosgene at 0° C. The solution was allowed to warm to 23° C. and the reaction was continued overnight. The CHCl3 layer was separated and dried over sodium sulfate. The solution was concentrated in vacuo and the residue was dissolved in toluene and treated with aniline (100 uL) at 23° C. for 12 h. The reaction mixture was concentrated and the residue was purified by flash chromatography (10% EtOAc/hexanes) to afford the titled compound as a yellow solid (120.8 mg, 98%) mp: 144-145° C.; 1H NMR (CD3OD/CDCl3): d 8.65 (d, 1H, J=10.0 Hz), 7.58 (d, 1H, J=10.0 Hz), 7.47 (d, 1H, J=1.25 Hz), 7.26 (m, 4H), 7.10(m, 1H).

Workup

  1. customN-(2-tert-Butyldimethysilyloxy-4-nitrophenyl)-N′-phenyl-thiourea was prepared
  2. customThe CHCl3 layer was separated
  3. dry with materialdried over sodium sulfate
  4. concentrationThe solution was concentrated in vacuo
  5. dissolutionthe residue was dissolved in toluene
  6. additiontreated with aniline (100 uL) at 23° C. for 12 h
  7. concentrationThe reaction mixture was concentrated
  8. customthe residue was purified by flash chromatography (10% EtOAc/hexanes)

Sources & evidence

ORD record
ord-b6e95a1e098c4b8e828cd72ebb7b0f8e
Source dataset
uspto-grants-2001_04
Patent number
US06211373B1

Reaction notes

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