Stannous chloride dihydrate → 1,3-Naphthalenediamine

HRID 1768088Notes

Reaction equation

HRID 1768088 reaction equation
I[C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5]([N+:12]([O-])=O)=[CH:4][C:3]=1[N+:15]([O-])=O.O.O.Cl[Sn]Cl.C([O-])(O)=O.[Na+].O(C(OC(C)(C)C)=O)C(OC(C)(C)C)=O>CCOC(C)=O.C1COCC1>[NH2:12][C:5]1[C:6]2[C:11](=[CH:10][CH:9]=[CH:8][CH:7]=2)[CH:2]=[C:3]([NH2:15])[CH:4]=1

Participants

7

Reactant 4

HCID 61436Stannous chloride dihydrateHCID 90495Di-tert-butyl dicarbonateHCID 516892Sodium BicarbonateHCID 10969971HCID 10969971, compound

Product 1

HCID 1899431,3-NaphthalenediamineYield 199.7%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A suspension of (3) (1.0 g, 2.9 mmol) and SnCl2.2H2O (9.8 g, 436 mmol) in EtOAc (100 mL) was heated at reflux for 30 min. The white suspension was poured onto ice (ca. 100 g), and sat. aq. NaHCO3 was added until the aqueous layer was basic as shown by litmus paper inspection. The mixture was extracted with ethyl acetate, the organic layer was washed with water, dried and the solvent was removed under reduced pressure to give crude 1,3-naphthalenediamine. This material was dissolved in THF (30 mL) and treated with BOC2O (3.0 g). The mixture was heated under reflux for 5 hrs. The solvent was removed and the residue was purified by column chromatography on silica gel. Elution with CH2Cl2 gave naphthalene-1,3-(bis-tertbutoxycarbamate) (4) (0.916 g, 88%) as a brown solid: mp (petroleum ether) 129–131° C.; 1H NMR (CDCl3) δ 7.94 (s, 1H), 7.78 (s, 1H), 7.74 (m, 2H), 7.41 (m, 2H), 6.94 (s, 1H), 6.69 (s, 1H), 1.55 (s, 9H), 1.54 (s, 9H); 13C NMR δ 153.11, 152.75, 135.75, 134.75, 133.69, 128.47, 126.46, 124.36, 122.28, 119.67, 110.57, 110.47, 80.88, 80.57, 28.33. Anal (C20H26N2O4) C, H, N.

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 30 min
  3. additionwas added until the aqueous layer
  4. extractionThe mixture was extracted with ethyl acetate
  5. washthe organic layer was washed with water
  6. customdried
  7. customthe solvent was removed under reduced pressure
  8. customto give crude 1,3-naphthalenediamine
  9. temperatureThe mixture was heated
  10. temperatureunder reflux for 5 hrs
  11. customThe solvent was removed
  12. customthe residue was purified by column chromatography on silica gel
  13. washElution with CH2Cl2

Sources & evidence

ORD record
ord-8c4250d87a774da19328a24d2845d8fd
Source dataset
uspto-grants-2007_06
Patent number
US07235578B2

Reaction notes

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