Tin tetrachloride → HCID 69122097, compound

HRID 476404Notes

Reaction equation

HRID 476404 reaction equation
[CH2:1]([O:8][C:9](=[O:33])[CH2:10][CH2:11][O:12][C:13]1[CH:18]=[C:17]([N+:19]([O-])=O)[C:16]([C:22]([N:24]2[CH2:28][CH2:27][CH2:26][CH:25]2[CH2:29][OH:30])=[O:23])=[CH:15][C:14]=1[O:31][CH3:32])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Sn](Cl)(Cl)(Cl)Cl>CO.C(OCC)(=O)C>[CH2:1]([O:8][C:9](=[O:33])[CH2:10][CH2:11][O:12][C:13]1[CH:18]=[C:17]([NH2:19])[C:16]([C:22]([N:24]2[CH2:28][CH2:27][CH2:26][CH:25]2[CH2:29][OH:30])=[O:23])=[CH:15][C:14]=1[O:31][CH3:32])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 2

HCID 24287Tin tetrachlorideHCID 69272690HCID 69272690, compound

Product 1

HCID 69122097HCID 69122097, compound

Reagents, catalysts & solvents 2

HCID 887MethanolSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

The nitro compound C5 (59 g, 0.128 mol) was dissolved in methanol (650 mL). Tin chloride (130 g, 0.577 mol, 4.5 eq) was added and the mixture was heated under reflux for 6 hours until completion of the reaction (TLC, 5% methanol in ethyl acetate). The methanol was removed under vacuum and the residue was dissolved in ethyl acetate (1 L) in a 5 L flask and 2 L of saturated sodium hydrogen carbonate aqueous solution was carefully added. The mixture was mechanically stirred for 2 hours and the resulting emulsion was then left to settle overnight. The pH was 8. It was filtered through celite. The residue was washed twice with ethyl acetate and the aqueous layer was extracted with ethyl acetate. The organic layers were combined, dried with magnesium sulfate, and concentrated in vacuo to leave the crude product as a black tar (50 g). TLC analysis showed presence of small quantities of impurities but the product was use in the next step with no further purification. 1H NMR (CDCl3) δ 7.36 (m, 5H), 6.74 (s, 1H), 6.28 (s, 1H), 5.19 (s, 2H), 4.28 (t, J=6.2 Hz, 2H), 3.73 (s, 3H), 3.77-3.50 (m, 2H), 2.91 (t, J=6.2 Hz, 2H), 2.15 (m, 1H), 1.88-1.60 (m, 2H).

Workup

  1. temperaturethe mixture was heated
  2. customThe methanol was removed under vacuum
  3. dissolutionthe residue was dissolved in ethyl acetate (1 L) in a 5 L flask
  4. addition2 L of saturated sodium hydrogen carbonate aqueous solution was carefully added
  5. waitthe resulting emulsion was then left
  6. waitto settle overnight
  7. filtrationIt was filtered through celite
  8. washThe residue was washed twice with ethyl acetate
  9. extractionthe aqueous layer was extracted with ethyl acetate
  10. dry with materialdried with magnesium sulfate
  11. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-55a044d62fe749818eed2c2f47c44026
Source dataset
uspto-grants-2014_01
Patent number
US08637664B2

Reaction notes

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