Isobutyl nitrite → Triphenylmethyl 3-methyl-7beta-phenoxyacetamidoceph-3-em-4-carboxylate

HRID 1657395Notes

Reaction equation

HRID 1657395 reaction equation
[CH3:1][C:2]1[CH2:3][S:4][C@@H:5]2[C@H:12]([NH:13][C:14](=[O:23])[CH2:15][O:16][C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=3)[C:11](=[O:24])[N:6]2[C:7]=1[C:8]([OH:10])=[O:9].[C:25]1([C:31](N)([C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1.N(OCC(C)C)=O.S([O-])([O-])(=O)=O.[Na+].[Na+]>ClCCl>[CH3:1][C:2]1[CH2:3][S:4][C@@H:5]2[C@H:12]([NH:13][C:14](=[O:23])[CH2:15][O:16][C:17]3[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=3)[C:11](=[O:24])[N:6]2[C:7]=1[C:8]([O:10][C:31]([C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)([C:38]1[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=1)[C:32]1[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=1)=[O:9]

Participants

6

Reactant 4

HCID 10958Isobutyl nitriteHCID 24436Sodium SulfateHCID 138598TritylamineHCID 111318273-Methyl-7beta-phenoxyacetamidoceph-3-em-4-carboxylic acid

Product 1

HCID 68133143Triphenylmethyl 3-methyl-7beta-phenoxyacetamidoceph-3-em-4-carboxylateYield 50%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To 3-methyl-7β-phenoxyacetamidoceph-3-em-4-carboxylic acid (3.43 g., 9.5 m. moles) in dichloromethane (50 ml) was added triphenylmethylamine (4.3 g., 16.6 m. moles), isobutyl nitrite (3.43 g., 33.2 m. moles) and anhydrous sodium sulphate (5 g) and the mixture heated 2 hours at 35°. The cooled solution was washed with 5% sodium bicarbontate (30 ml) and water (30 ml). The organic solution was evaporated to a solid, the solid slurried in toluene (40 ml) cooled, filtered and slurry-washed with cold toluene (15 ml) to yield the previously unreported title compound (2.88 g. 50.0% yield based on the input acid) m.pt. 182°, pure by t.l.c. The compound possessed ν max (1% CHBr3 solution) 3380 (NHCO), 1775 (β-lactam), 1723 (αβ-unsaturated ester) 1686 - 1518 Cm-1 (amide carbonyl); τ (11% CDCl3 solution) 2.2 - 3.2 (complex, phenyl rings + phenoxy ring + --NH), 5.41 (singlet, phenoxy methylene acetamido group, H2), 4.09 (doublet of doublets J 4.5, 9 Hz, C-7, H) 4.95 (doublet, J 4.5 Hz, H), 6.51 + 6.97 (two doublets [branches of a quartet]J 18 Hz, H2), 8.08 (singlet, C-3, H3). Found C, 70.63; H, 5.16 N, 4.52. C35H30N2O5S requires C, 71.18; H, 5.09; N, 4.75%.

Workup

  1. temperaturethe mixture heated 2 hours at 35°
  2. washThe cooled solution was washed with 5% sodium bicarbontate (30 ml) and water (30 ml)
  3. customThe organic solution was evaporated to a solid
  4. temperaturecooled
  5. filtrationfiltered
  6. washslurry-washed with cold toluene (15 ml)

Sources & evidence

ORD record
ord-e602c793f784431890a8615f36162d4d
Source dataset
uspto-grants-1976_06
Patent number
US03960843

Reaction notes

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