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

HRID 509149Notes

Reaction equation

HRID 509149 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, 52, (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-8e113e86ac8b4e8aa862bc31bee37617
Source dataset
uspto-grants-2015_08
Patent number
US09096555B2

Reaction notes

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