Tin tetrachloride → HCID 67385624, compound

HRID 1410284Notes

Reaction equation

HRID 1410284 reaction equation
[CH2:1]([N:3]([CH2:22][CH3:23])[CH2:4][CH2:5][S:6][C:7]1[CH:12]=[CH:11][C:10](/[CH:13]=[CH:14]/[C:15]([O:17][CH3:18])=[O:16])=[CH:9][C:8]=1[N+:19]([O-])=O)[CH3:2].[Sn](Cl)(Cl)(Cl)Cl>C(O)(=O)C.CO>[NH2:19][C:8]1[CH:9]=[C:10](/[CH:13]=[CH:14]/[C:15]([O:17][CH3:18])=[O:16])[CH:11]=[CH:12][C:7]=1[S:6][CH2:5][CH2:4][N:3]([CH2:1][CH3:2])[CH2:22][CH3:23]

Participants

4

Reactant 2

HCID 24287Tin tetrachlorideHCID 67385454HCID 67385454, compound

Product 1

HCID 67385624HCID 67385624, compoundYield 73.9%

Reagents, catalysts & solvents 1

HCID 10129899Acetic acid methanolSolvent

Conditions

Temperature
50 °C

Procedure

(E)-Methyl 3-(4-(2-(diethylamino)ethylthio)-3-nitrophenyl)acrylate (736 mg, 2.2 mmol) was suspended in 15 mL solution of glacial acetic acid-Methanol. Under stirring, Tin Chloride (4.9 g, 21.7 mmol) was added and the resulted solution was heated to 0-100° C. for 0.5-5.0 hours. Cooling it then to room temperature. Removing the solvent under reduced pressure. Slowly add saturated sodium carbonate (20 mL) and dichloromethane (20 mL) to the residue with thoroughly stirring for 10-120 min. The organic layer was separated and dried with MgSO4. Removing off MgSO4 and the filtrate was concentrated into an oil. The product was purified through chromatography. 496.3 mg of (E)-methyl 3-(3-amino-4-(2-(diethylamino)ethylthio)-phenyl)acrylate was obtained. Yield: 73.9%. TLC: 0.31 (DCM:MeOH=9:1). MP: 153.2° C.-154.6° C. HPLC: 98.5%; tR=7.82 min (LC/PDA: Diamonsil C18 5μ 150×4.6 mm, flow rate 1.0 mL/min, grade: 10-100% B, 12 minutes; mobile phase A: H2O; mobile phase B: acetonitrile; UV254). 1HNMR (400 MHz, CDCl3) δ: 7.56 (1H, d, J=16 Hz), 7.39 (1H, d, J=8 Hz), 7.28 (1H, s), 6.87 (1H, dd, J=8 Hz and 16 Hz), 6.39 (1H, d, J=16 Hz), 4.51 (2H, s), 3.81 (3H, s), 3.05 (6H, m), 1.29 (6H, t, J=7.2 Hz); MS (m/z): 309 (MH)+.

Workup

  1. temperatureCooling it
  2. customto room temperature
  3. customRemoving the solvent under reduced pressure
  4. stirringSlowly add saturated sodium carbonate (20 mL) and dichloromethane (20 mL) to the residue with thoroughly stirring for 10-120 min
  5. customThe organic layer was separated
  6. dry with materialdried with MgSO4
  7. customRemoving off MgSO4
  8. concentrationthe filtrate was concentrated into an oil
  9. customThe product was purified through chromatography

Sources & evidence

ORD record
ord-1ce9a48d3cd84344ad4261334b6c44be
Source dataset
uspto-grants-2014_12
Patent number
US08921424B2

Reaction notes

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