Tin tetrachloride dihydrate → 5-Amino-2-[2-(4-amino-phenyl)-vinyl]-benzenesulfonic Acid, 2,2-Dimethylpropyl Ester

HRID 277588Notes

Reaction equation

HRID 277588 reaction equation
[CH3:1][C:2]([CH3:29])([CH3:28])[CH2:3][O:4][S:5]([C:8]1[CH:13]=[C:12]([N+:14]([O-])=O)[CH:11]=[CH:10][C:9]=1[CH:17]=[CH:18][C:19]1[CH:24]=[CH:23][C:22]([N+:25]([O-])=O)=[CH:21][CH:20]=1)(=[O:7])=[O:6].O.O.[Sn](Cl)(Cl)(Cl)Cl>C(OCC)(=O)C>[NH2:14][C:12]1[CH:11]=[CH:10][C:9]([CH:17]=[CH:18][C:19]2[CH:20]=[CH:21][C:22]([NH2:25])=[CH:23][CH:24]=2)=[C:8]([S:5]([O:4][CH2:3][C:2]([CH3:29])([CH3:1])[CH3:28])(=[O:7])=[O:6])[CH:13]=1

Participants

4

Reactant 2

HCID 85782573Tin tetrachloride dihydrateHCID 867578655-Nitro-2-[2-(4-nitro-phenyl)-vinyl]-benzenesulfonic Acid 2,2-Dimethylpropyl Ester

Product 1

HCID 571227015-Amino-2-[2-(4-amino-phenyl)-vinyl]-benzenesulfonic Acid, 2,2-Dimethylpropyl EsterYield 35%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent2×

Procedure

5-Nitro-2-[2-(4-nitro-phenyl)-vinyl]-benzenesulfonic acid 2,2-dimethylpropyl ester (Example 56, 1.10 g, 2.62 mmol) was dissolved in 52 mL of ethyl acetate. Tin chloride dihydrate (2.95 g, 13.1 mmol) was added and a reflux condenser attached. The solution was heated to reflux and stirred overnight. After cooling to room temperature the solution was diluted with ethyl acetate (300 mL) and washed with saturated sodium bicarbonate. The whole mixture was filtered thru Celite and the aqueous layer discarded. The organic layer was then washed with brine and dried over MgSO4. After concentration on a rotovap the crude material was purified by a gradient flash column using 3 to 10% ethyl acetate in dichloromethane as the eluant to afford 0.33 g of the title compound as a oily red solid (35%): 1HNMR (CDCl3): δ7.63 (d, J=9 Hz, 1H), 7.58 (d, J=16 Hz, 1H), 7.33 (d, J=9 Hz, 2H), 7.31 (d, J=3 Hz, 1H), 6.89 (dd, J=9 Hz, 3 Hz, 1H), 6.86 (d, J=16 Hz, 1H), 6.68 (d, J=9 Hz, 2H), 3.89 (br s, 4H), 3.61 (s, 2H), 0.86 (s, 9H); MS (ES-POS): [M+H]+ 361; Analytical HPLC determined that this compound was 90% pure by C-18 reverse phase.

Workup

  1. customa reflux condenser attached
  2. temperatureThe solution was heated
  3. temperatureto reflux
  4. washwashed with saturated sodium bicarbonate
  5. filtrationThe whole mixture was filtered thru Celite
  6. washThe organic layer was then washed with brine
  7. dry with materialdried over MgSO4
  8. concentrationAfter concentration on a rotovap the crude material
  9. customwas purified by a gradient flash column

Sources & evidence

ORD record
ord-23a9b67d96e9418a95b9bf4493e5d40c
Source dataset
uspto-grants-2002_03
Patent number
US06355633B1

Reaction notes

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