Thiophosgene → (S)-2-phenyl-4-(1-isothiocyanato-2-(4-nitrophenyl)ethyl)thiazole

HRID 2193889Notes

Reaction equation

HRID 2193889 reaction equation
Br.[N+:2]([C:5]1[CH:10]=[CH:9][C:8]([CH2:11][C@@H:12]([C:14]2[N:15]=[C:16]([C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)[S:17][CH:18]=2)[NH2:13])=[CH:7][CH:6]=1)([O-:4])=[O:3].C([O-])([O-])=O.[Ca+2].[C:30](Cl)(Cl)=[S:31]>C(Cl)(Cl)(Cl)Cl.O.C(Cl)Cl.O>[N:13]([C@H:12]([C:14]1[N:15]=[C:16]([C:19]2[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=2)[S:17][CH:18]=1)[CH2:11][C:8]1[CH:7]=[CH:6][C:5]([N+:2]([O-:4])=[O:3])=[CH:10][CH:9]=1)=[C:30]=[S:31]

Participants

7

Reactant 3

HCID 10040ThiophosgeneHCID 10112Calcium CarbonateHCID 66704795(s)-2-(4-Nitrophenyl)-1-(2-phenylthiazol-4-yl)ethanamine hydrobromide salt

Product 1

HCID 57841130(S)-2-phenyl-4-(1-isothiocyanato-2-(4-nitrophenyl)ethyl)thiazoleYield 93%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 17768942Tetrachloromethane--water (1/1)Solvent

Procedure

To a solution of (S)-2-(4-nitrophenyl)-1-(2-phenylthiazol-4-yl)ethanamine hydrobromide salt, 38, (2.03 g, 5 mmol) and CaCO3 (1 g, 10 mmol) in CCl4/water (10:7.5 mL) is added thiophosgene (0.46 mL, 6 mmol). The reaction is stirred at room temperature for 18 hours then diluted with CH2Cl2 and water. The layers are separated and the aqueous layer extracted with CH2Cl2. The combined organic layers are washed with brine, dried (Na2SO4) and concentrated in vacuo to a residue that is purified over silica (CH2Cl2) to afford 1.71 g (93% yield) of the desired product. ESI+MS 368 (M+1).

Workup

  1. customThe layers are separated
  2. extractionthe aqueous layer extracted with CH2Cl2
  3. washThe combined organic layers are washed with brine
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated in vacuo to a residue that
  6. customis purified over silica (CH2Cl2)

Sources & evidence

ORD record
ord-432863cacd7348ea89be5d7fe2cf194c
Source dataset
uspto-grants-2012_12
Patent number
US08329916B2

Reaction notes

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