1,4-Dioxane → (2R,3S,5R,6R) 2-Carbamoyloxymethyl-2-methyl-6-(2-phenoxyacetamido)penam-3-carboxylic Acid p-Nitrobenzyl Ester

HRID 2295923Notes

Reaction equation

HRID 2295923 reaction equation
[N+:1]([C:4]1[CH:35]=[CH:34][C:7]([CH2:8][O:9][C:10]([C@@H:12]2[N:16]3[C:17](=[O:30])[C@@H:18]([NH:19][C:20](=[O:29])[CH2:21][O:22][C:23]4[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=4)[C@H:15]3[S@@:14](=O)[C:13]2([CH3:33])[CH3:32])=[O:11])=[CH:6][CH:5]=1)([O-:3])=[O:2].ClC(Cl)(Cl)C([N:40]=[C:41]=[O:42])=O.[O:45]1CCOCC1>>[N+:1]([C:4]1[CH:35]=[CH:34][C:7]([CH2:8][O:9][C:10]([C@@H:12]2[N:16]3[C:17](=[O:30])[C@@H:18]([NH:19][C:20](=[O:29])[CH2:21][O:22][C:23]4[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=4)[C@H:15]3[S:14][C@:13]2([CH2:33][O:45][C:41](=[O:42])[NH2:40])[CH3:32])=[O:11])=[CH:6][CH:5]=1)([O-:3])=[O:2]

Participants

4

Reactant 3

HCID 312751,4-DioxaneHCID 76400Trichloroacetyl isocyanateHCID 11145535(1S,3S,5R,6R) 2,2-dimethyl-6-phenoxyacetamidopenam-3-carboxylic acid-1-oxide p-nitrobenzyl ester

Product 1

HCID 12817536(2R,3S,5R,6R) 2-Carbamoyloxymethyl-2-methyl-6-(2-phenoxyacetamido)penam-3-carboxylic Acid p-Nitrobenzyl Ester

Procedure

A solution of (1S,3S,5R,6R) 2,2-dimethyl-6-phenoxyacetamidopenam-3-carboxylic acid-1-oxide p-nitrobenzyl ester (7.52 g, 15.0 mmol) and trichloroacetyl isocyanate (5.0 ml, 7.9 g, 42 mmol) in dioxane (75 ml) was refluxed under nitrogen for 3.5 hours and concentrated in vacuo. The concentrate was stirred with methanol (100 ml) and the solution was decanted from a black tar with methanol rinses (2×10 ml). The solution was diluted with water (5 ml), adjusted to pH 7.4 with 5% sodium bicarbonate, and held at pH 7.4-7.5 with 3% H2SO4 for 2.5 hours. The mixture was distributed between methylene chloride (100 ml) and water (50 ml). The organic phase was washed with water (50 ml), combined with a CH2Cl2 back extract (50 ml), dried (4A molecular sieve), polish filtered with CH2Cl2 washes (2×20 ml), and concentrated in vacuo to a light brown oil.

Workup

  1. concentrationconcentrated in vacuo
  2. customthe solution was decanted from a black tar with methanol rinses (2×10 ml)
  3. additionThe solution was diluted with water (5 ml)
  4. washThe organic phase was washed with water (50 ml)
  5. extractionback extract (50 ml)
  6. dry with materialdried (4A molecular sieve)
  7. filtrationpolish filtered with CH2Cl2 washes (2×20 ml)
  8. concentrationconcentrated in vacuo to a light brown oil

Sources & evidence

ORD record
ord-823454ab3d644c0f964c98a814017cb6
Source dataset
uspto-grants-1984_01
Patent number
US04426520

Reaction notes

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