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

HRID 335030Notes

Reaction equation

HRID 335030 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(Cl)(Cl)(Cl)Cl.[C:35](Cl)(Cl)=[S:36]>O.C(Cl)Cl>[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:35]=[S:36]

Participants

7

Reactant 4

HCID 5943Carbon TetrachlorideHCID 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 73%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6344DichloromethaneSolvent

Procedure

To a solution of (S)-2-(4-nitrophenyl)-1-(2-phenylthiazol-4-yl)ethanamine hydrobromide salt, 42, (726 mg, 1.79 mmol) and CaCO3 (716 mg, 7.16 mmol) in H2O (2 mL) is added CCl4 (3 mL) followed by thiophosgene (0.28 mL, 3.58 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 which is purified over silica (CH2Cl2) to afford 480 mg (73%) of the desired product as a yellow solid. 1H NMR (300 MHz, CDCl3) δ 8.15 (d, J=8.7 Hz, 2H), 7.97-7.99 (m, 2H), 7.43-7.50 (m, 3H), 7.34 (d, J=8.7 Hz, 2H), 7.15 (d, J=0.9 Hz, 1H), 5.40-5.95 (m, 1H), 3.60 (dd, J=13.8 and 6.0 Hz, 1H), 3.46 (dd, J=13.8 and 6.0 Hz).

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 which
  6. customis purified over silica (CH2Cl2)

Sources & evidence

ORD record
ord-b2207c91acb64311a523244328781bf6
Source dataset
uspto-grants-2014_11
Patent number
US08883832B2

Reaction notes

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