HCID 10375434, compound → HCID 178464608, compound

HRID 744744Notes

Reaction equation

HRID 744744 reaction equation
[CH2:1]([N:3]([C:6]1[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[CH:9]=[CH:8][CH:7]=1)[C:4]#[N:5])[CH3:2].[ClH:16].[NH2:17][C:18]1[CH:19]=[CH:20][CH:21]=[C:22]2[C:27]=1[O:26][C:25](=[O:28])[CH:24]=[CH:23]2>>[ClH:16].[O:26]1[C:27]2[C:22](=[CH:21][CH:20]=[CH:19][C:18]=2[NH:17][C:4]([N:3]([CH2:1][CH3:2])[C:6]2[C:15]3[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=3)[CH:9]=[CH:8][CH:7]=2)=[NH:5])[CH:23]=[CH:24][C:25]1=[O:28]

Participants

3

Reactant 2

HCID 10375434HCID 10375434, compoundHCID 21191516HCID 21191516, compound

Product 1

HCID 178464608HCID 178464608, compound

Procedure

In a 5 ml round bottom flask was placed N-ethyl-N-1-naphthylcyanamide (766 mg, 3.91 mmol), 8-aminocoumarin hydrochloride (818 mg, 4.15 mmol; Clayton, J., Chem. Soc. 97:1350 (1910)) and a stir bar. The flask was evacuated via aspirator and flushed with N2. This was immediately placed in a preheated 160° C. oil bath where it was allowed to stir under N2 for 9 h. The resulting greenish brown melt was dissolved in methanol (5 ml) and diluted with hot distilled water (20 ml). This solution was basified with 0.1N NaOH (10 ml) and extracted with CHCl3 (4×15 ml) to yield a yellowish brown oil upon drying (910 mg). A TLC of this oil showed a mixture of reactants and product. Reactants were eluted by column chromatography with benzene. The product was eluted with benzene/ethanol 8:1 (TLC Rf=0.44, CHCl3 :EtOH, 1:1), 0.64 g (46%). This pale yellow oil was dissolved in methanol (5 ml), then methanol (5 ml) saturated with HCl gas was added dropwise to yield a light tan foam of the HCl salt after drying. This tan foam was dissolved into ethanol (1 ml) and placed in an ether diffusion chamber for 5 days to afford white prisms, 0.28 g (29%), m.p. 193°-194° C. IR (KBr) 3343, 3303 (--NH), 1712 (carbonyl), 1653 (--C=NH). 1H-NMR (CD3OD) δ1.12 (t, 3H, J=7.2), 3.55 (q, 2H, J=7.2), 6.47 (d, 1H, J=9.3), 7.30-8.12 (m, 11H, H-aromat and one olefinic). 13C-NMR (CD3OD) CO, 161.4; CN3, 157.6; Ar, 145.7, 136.6, 136.1, 132.5, 131.7, 131.5, 131.16, 130.12, 130.0, 129.5, 129.4, 129.4, 127.3, 126.2, 124.1,123.2, 121.9, 117.8; CH2, 58.4; CH3, 18.5. Mass Spec. m/e calcd for C22H19N3O2, 357.1477; Found, 357.1453.

Workup

  1. customIn a 5 ml round bottom flask was placed
  2. customThe flask was evacuated via aspirator
  3. customflushed with N2
  4. customThis was immediately placed in a preheated 160° C.
  5. dissolutionThe resulting greenish brown melt was dissolved in methanol (5 ml)
  6. additiondiluted
  7. distillationwith hot distilled water (20 ml)
  8. extractionextracted with CHCl3 (4×15 ml)
  9. customto yield a yellowish brown oil
  10. customupon drying (910 mg)
  11. additiona mixture of reactants and product
  12. washReactants were eluted by column chromatography with benzene
  13. washThe product was eluted with benzene/ethanol 8:1 (TLC Rf=0.44, CHCl3 :EtOH, 1:1), 0.64 g (46%)
  14. dissolutionThis pale yellow oil was dissolved in methanol (5 ml)
  15. additionmethanol (5 ml) saturated with HCl gas was added dropwise

Sources & evidence

ORD record
ord-f729b406173641068f16c298367b12cd
Source dataset
uspto-grants-1996_09
Patent number
US05559154

Reaction notes

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