Methane → HCID 22807221, compound

HRID 1649171Notes

Reaction equation

HRID 1649171 reaction equation
[CH2:1]1[C:4](=[O:5])[N:3]2[C@@H:6](C(O)=O)/[C:7](/[O:11][C@H:2]12)=[CH:8]/[CH2:9]O.COC(OC)N(C)C.C>O1CCCC1.C1(C=CC(O)=CC=1)O>[CH:8]([C:7]1[O:11][C@H:2]2[N:3]([C:4](=[O:5])[CH2:1]2)[CH:6]=1)=[CH2:9]

Participants

6

Reactant 3

HCID 297MethaneHCID 78373Dimethylformamide dimethyl acetalHCID 5280980Clavulanic Acid

Product 1

HCID 22807221HCID 22807221, compoundYield 83.3%

Reagents, catalysts & solvents 2

HCID 785HydroquinoneCatalystHCID 8028TetrahydrofuranSolvent3×

Procedure

Clavulanic acid (3.0 mmole) in dry tetrahydrofuran (10 ml) and N,N-dimethylformamide dimethylacetal (0.4 g., 3.35 mmole) in dry tetrahydrofuran (10 ml) were added simultaneously to a rapidly stirred solution of hydroquinone (20 mg) in tetrahydrofuran (20 ml) at room temperature. After addition was complete (5 minutes), the mixture was decolourised using charcoal and filtered, the filter being washed well with more tetrahydrofuran. The solvent was evaporated from the filtrate under reduced pressure to yield (5R)-3-vinyl-7-oxo-4-oxa-1-azabicyclo[3.2.0]-hept-2-ene (340 mg., 2.5 mmole) as a colourless oil, which was immediately dissolved in methyl acrylate (15 ml). The resulting solution was heated at 80° (bath temperature) for 2 hours, then the methyl acrylate was evaporated under reduced pressure and the resulting residue was chromatographed on silica gel using ethyl acetate/protroleum ether (b.p. 60°-80°). Isomer I of the title compound was thus obtained as a colourless gum (84 mg), [α]D 25 =+308.5° (c 1.0, CHCl3). (Found: M+, 223.0839; C11H13NO4 requires 223.0844). νmax (CHCl3): 1795 (β-lactam C=O), 1735 (ester C=O), 1710 (sh)(C=C) cm-1. δ(CDCl3): 1.56 (1, J 12 Hz, 1H, C(11)H), 2.0-2.8 (complex, 4H), 2.93 (d, J 16 Hz, 1H C(4)H), 3.29 (dd, J 16, 2 Hz, 1H, C(4)H), 3.65 (s, 3H, CO2CH3), 4.10 (ddd, J 12, 4, 2 Hz, 1H C(1)H), 5.11 (m, 2H, C(5)H and C(8)H). m/e: 223 (M+, 20%), 195 (33), 192(25), 182(3), 167(10), 164(17), 154(40), 122(30), 121(15), 95(100), 94(24). Isomer II of the title compound was also obtained as a colourless gum (45 mg), [α]D25 =+181.9° (c 1.0, CHCl3). Found: M, 223.0849; C11H13NO4 requires 223.0844). νmax (CHCl3): 1792 (β-lactam C=O), 1735 (ester C=O), 1710 (sh)(C=C) cm-1. δ(CDCl3): 1.55 (dt, J 6, 12 Hz, 1H C(11)H), 2.0-3.0 (complex, 4H) 2.92 (d, J 16 Hz, 1H, C(4)H), 3.28 (dd, J 16, 2 Hz, 1H C(4)H), 3.69 (s, 3H, CO2CH3), 4.05 (ddd, J 12, 5, 2 Hz, 1H, C(1)H), 5.10 (m, 2H, C(5)H, C(8)H). m/e: 223 (M+ , 6%), 195(22), 192(17), 182(14), 167(8), 164(10), 154(3), 122(37), 121(95), 95(52), 94(20), 55(100).

Workup

  1. additionAfter addition
  2. custom(5 minutes)
  3. filtrationfiltered
  4. washthe filter being washed well with more tetrahydrofuran
  5. customThe solvent was evaporated from the filtrate under reduced pressure

Sources & evidence

ORD record
ord-f4f60287606446af8034022b48fe1b5e
Source dataset
uspto-grants-1983_11
Patent number
US04415584

Reaction notes

Loading…