Ammonia → (S)-1-[1-(thiophen-2-ylthiazol-4-yl)-2-(4-nitrophenyl)ethyl]-thiourea

HRID 60056Notes

Reaction equation

HRID 60056 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[S:20][CH:21]=[CH:22][CH:23]=3)[S:17][CH:18]=2)[NH2:13])=[CH:7][CH:6]=1)([O-:4])=[O:3].C([O-])([O-])=O.[Ca+2].[C:29](Cl)(Cl)=[S:30].[NH3:33]>C(Cl)(Cl)(Cl)Cl.O.C(Cl)Cl.O>[S:20]1[CH:21]=[CH:22][CH:23]=[C:19]1[C:16]1[S:17][CH:18]=[C:14]([C@@H:12]([NH:13][C:29]([NH2:33])=[S:30])[CH2:11][C:8]2[CH:7]=[CH:6][C:5]([N+:2]([O-:4])=[O:3])=[CH:10][CH:9]=2)[N:15]=1

Participants

8

Reactant 4

HCID 222AmmoniaHCID 10040ThiophosgeneHCID 10112Calcium CarbonateHCID 66704718(S)-2-(4-nitrophenyl)-1-(thiophen-2-ylthiazol-4-yl)ethanamine hydrobromide salt

Product 1

HCID 59464673(S)-1-[1-(thiophen-2-ylthiazol-4-yl)-2-(4-nitrophenyl)ethyl]-thiourea

Reagents, catalysts & solvents 3

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

Procedure

To a solution of (S)-2-(4-nitrophenyl)-1-(thiophen-2-ylthiazol-4-yl)ethanamine hydrobromide salt, 8, (1.23 g, 2.98 mmol) and CaCO3 (0.597 g, 5.96 mmol) in CCl4/water (10 mL/5 mL) is added thiophosgene (0.412 g, 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 subsequently treated with ammonia (0.5M in 1,4-dioxane, 29.4 mL, 14.7 mmol) which is purified over silica to afford 0.490 g of the desired product as a red-brown solid. ESI+ MS 399 (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 which
  6. customis purified over silica

Sources & evidence

ORD record
ord-2dc39f40fd964af2a9ef9a0dd5016d9f
Source dataset
uspto-grants-2016_09
Patent number
US09440963B2

Reaction notes

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