Stannous Chloride → HCID 66916317, compound

HRID 227166Notes

Reaction equation

HRID 227166 reaction equation
[CH2:1]([O:8][C:9]1[C:10]([O:27][CH3:28])=[CH:11][C:12]([N+:24]([O-])=O)=[C:13]([CH:23]=1)[C:14]([N:16]1[CH2:20][CH2:19][CH2:18][CH:17]1[CH2:21][OH:22])=[O:15])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Sn](Cl)Cl>CO>[NH2:24][C:12]1[CH:11]=[C:10]([O:27][CH3:28])[C:9]([O:8][CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)=[CH:23][C:13]=1[C:14]([N:16]1[CH2:20][CH2:19][CH2:18][CH:17]1[CH2:21][OH:22])=[O:15]

Participants

4

Reactant 2

HCID 24479Stannous ChlorideHCID 66916207HCID 66916207, compound

Product 1

HCID 66916317HCID 66916317, compound

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A solution of the nitro compound 2 (15.49 g, 40.12 mmol, 1.0 equiv) and tin (II) chloride (45.27 g, 200.64 mol, 5.0 equiv) in methanol (300 mL) was heated at reflux for 4 h. Excess solvent was removed by rotary evaporation under reduced pressure. The residue was treated carefully with a saturated aqueous sodium bicarbonate solution to basify the mixture to pH 9. The resulting suspension was allowed to stir overnight with ethyl acetate (100 mL), and filtrated through Celite to remove precipitated tin salts. The aqueous phase was extracted with EtOAc (2×50 mL), and the combined organic phase washed with brine (50 mL), dried (MgSO4), and evaporated in vavuo to provide 3 as a pink oil, which was used in the subsequent reaction without further purification: [α]20D=−97° (c=0.18, CHCl3); 1H NMR (CDCl3, 400 MHz): δ 1.50-1.81 (m, 3H, 1-H, 2-H), 2.05-2.15 (m, 1H, 1-H), 3.03-3.16 (m, 1H, 3-H), 3.23-3.36 (m, 1H, 3-H), 3.56-3.78 (m, 2H, 11-H), 3.88 (s, 3H, 7-OMe), 4.21-4.38 (m, 1H, 11a-H), 4.47-4.75 (m, 1H, 3-H), 5.03 (d, 1H, J=12.4 Hz, OBn), 5.10 (d, 1H, J=12.4 Hz, OBn), 6.26 (s, 1H, 9-H), 6.66 (s, 1H, 6-H), 7.28-7.41 (m, 5H, Ph); 13C NMR (CDCl3, 400 MHz): δ 24.8, 28.5, 51.1, 55.7, 61.1, 67.5, 72.5, 100.8, 116.9, 127.5, 127.7, 128.4, 137.4, 138.8, 142.6, 153.0, 171.1, 171.7; IR (neat): 3436, 33.52, 29.67, 28.73, 1621, 1589, 1513, 1448, 1402, 1264, 1216, 1172, 1110, 1025 cm−1; MS (FAB) m/z (relative intensity) 379 ([M+Na]+., 5), 357 (M+., 100), 255 (58).

Workup

  1. temperatureat reflux for 4 h
  2. customExcess solvent was removed by rotary evaporation under reduced pressure
  3. additionThe residue was treated carefully with a saturated aqueous sodium bicarbonate solution
  4. filtrationfiltrated through Celite
  5. customto remove
  6. customprecipitated tin salts
  7. extractionThe aqueous phase was extracted with EtOAc (2×50 mL)
  8. washthe combined organic phase washed with brine (50 mL)
  9. dry with materialdried (MgSO4)
  10. customevaporated in vavuo

Sources & evidence

ORD record
ord-b9b9cc93e21f4c45863ab7df58c2730a
Source dataset
uspto-grants-2009_07
Patent number
US07557099B2

Reaction notes

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