Bicyclo[2.2.1]heptane-1-methanesulfonic acid, 7,7-dimethyl-2-oxo-, (1S)- → HCID 135992966, compound

HRID 968840Notes

Reaction equation

HRID 968840 reaction equation
[CH2:1]([O:3][C:4]([C:6]([CH3:34])([O:8][C:9]1[CH:14]=[CH:13][C:12]([CH2:15][CH2:16][CH2:17][C:18]([NH:20][N:21]([CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[C:28]([O:32][CH3:33])[CH:27]=2)[C:22]([NH2:24])=[O:23])=O)=[CH:11][CH:10]=1)[CH3:7])=[O:5])[CH3:2].C12(CS(O)(=O)=O)C(C)(C)C(CC1)CC2=O>C(OCC)(=O)C>[CH2:1]([O:3][C:4](=[O:5])[C:6]([O:8][C:9]1[CH:14]=[CH:13][C:12]([CH2:15][CH2:16][CH2:17][C:18]2[NH:24][C:22](=[O:23])[N:21]([CH2:25][C:26]3[CH:31]=[CH:30][CH:29]=[C:28]([O:32][CH3:33])[CH:27]=3)[N:20]=2)=[CH:11][CH:10]=1)([CH3:34])[CH3:7])[CH3:2]

Participants

4

Reactant 2

HCID 18462Bicyclo[2.2.1]heptane-1-methanesulfonic acid, 7,7-dimethyl-2-oxo-, (1S)-HCID 59015846HCID 59015846, compound

Product 1

HCID 135992966HCID 135992966, compoundYield 49.2%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

1-[4-[4-(1-Ethoxycarbonyl-1-methyl-ethoxy)phenyl]butyryl]-2-(3-methoxyphenylmethyl)semicarbazide (4.08 g, 8.65 mmol) was dissolved in ethyl acetate (7.5 mL). Camphorsulfonic acid (2.21 g, 9.51 mmol) was added in one portion and the solution was heated to reflux overnight. The solution was cooled to rt and washed with sat'd aq. NaHCO3 (2×40 mL) followed by 1N HCl (2×40 mL). The organic was concentrated to an oil, which was redissolved in ethyl acetate (40 mL). Amberlyst-15 resin (4.41 g) was added and the mixture was heated to 50° C. and stirred for 4 h. The mixture was then cooled to rt, filtered, concentrated, and purified by column chromatography (SiO2, 9:1 ethyl acetate:hexanes) to afford the title compound as an oil (1.93 g, 49.2%). 1H NMR (DMSO-d6) δ 11.47 (s, 1 H), 7.22 (t, 1 H, J=8 Hz), 7.04 (d, 2 H, J=8 Hz), 6.82 (d, 1 H, J=2 Hz), 6.76 (m, 2 H), 6.68 (d, 2 H, J=2 Hz), 4.73 (s, 2 H), 4.13 (q, 2 H, J=7 Hz), 3.69 (s, 3 H), 2.48 (t, 2 H,. J=8 Hz), 2.36 (t, 2 H, J=8 Hz), 1.80 (quint, 2 H, J=7 Hz), 1.47 (s, 6 H), 1.14 (t, 3 H, J=7 Hz); 13C NMR (DMSO-d6) δ 174.0, 160.0, 155.0, 153.8, 146.7, 139.8, 135.5, 130.2, 129.8, 120.1, 119.5, 113.8, 113.2, 79.2, 61.6, 55.6, 47.8, 34.0, 28.4, 26.2, 25.7, 14.6; IR (CHCl3) 2940, 1692, 1508, 1467 cm−1; Anal. Calcd. for C25H31N3O5: C, 66.21.; H, 6.89; N, 9.26. Found: C, 66.29; H, 6.75; N, 9.19.

Workup

  1. temperaturethe solution was heated
  2. temperatureto reflux overnight
  3. washwashed with sat'd aq. NaHCO3 (2×40 mL)
  4. concentrationThe organic was concentrated to an oil, which
  5. dissolutionwas redissolved in ethyl acetate (40 mL)
  6. additionAmberlyst-15 resin (4.41 g) was added
  7. temperaturethe mixture was heated to 50° C.
  8. temperatureThe mixture was then cooled to rt
  9. filtrationfiltered
  10. concentrationconcentrated
  11. custompurified by column chromatography (SiO2, 9:1 ethyl acetate:hexanes)

Sources & evidence

ORD record
ord-2563c7bb56ba4e69bed42b37dbc7d78d
Source dataset
uspto-grants-2007_12
Patent number
US07304062B2

Reaction notes

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