Dichloromethane → HCID 12774965, compound

HRID 1155485Notes

Reaction equation

HRID 1155485 reaction equation
[C:1]1([CH2:7][C:8]([NH:10][C@H:11]2[C:35](=[O:36])[N:13]3[C:14]([C:19]([O:21][CH:22]([C:29]4[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=4)[C:23]4[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=4)=[O:20])=[C:15]([CH3:18])[CH2:16][S:17][C@H:12]23)=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C(Cl)Cl.ClN1[C:45](=[O:46])CCC1=O>CO>[C:1]1([CH2:7][C:8]([NH:10][C@H:11]2[C:35](=[O:36])[N:13]3[C:14]([C:19]([O:21][CH:22]([C:23]4[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=4)[C:29]4[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=4)=[O:20])=[C:15]([CH3:18])[C@@H:16]([O:46][CH3:45])[S:17][C@H:12]23)=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

5

Reactant 3

HCID 6344DichloromethaneHCID 31398ChlorosuccinimideHCID 70532880HCID 70532880, compound

Product 1

HCID 12774965HCID 12774965, compoundYield 21%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a solution of diphenylmethyl 7α-phenylacetamido-3-methyl-3-cephem-4-carboxylate (2.88 g, 5.8 mmol) in 40 ml of methanol and 60 ml. of methylene chloride, was added N-chlorosuccinimide (882 mg, 6.6 mmol) and the mixture was stirred for 90 minutes at room temperature. The reaction solution was then washed with brine (2×), dried over magnesium sulfate, filtered, and the solvent was evaporated under reduced pressure. The resultant yellow foam (2.84 g) was chromatographed over 100 grams of silica gel employing 10-15% of ethyl acetate in toluene as the eluting solvent. The first fraction to elute from the column was the desired 2α-methoxy cephem compound which was subsequently recrystallized from a mixture of ethyl acetate and cyclohexane to give pure diphenylmethyl 7α-phenylacetamido-2α-methoxy-3-methyl-3-cephem-4-carboxylate. (638 mg, 21% yield) (mp 144°-145° C.) i.r. (CHCl3) 1780, 1725 and 1680 cm-1 ; n.m.r. (CDCl 3) δ 1.95 (s, 3, CH3) 3.35 (s, 3, OCH3), 3.45 (s, 2, CH2Ph), 4.60 (s, 1, C2 -H), 4.70 (d, J=2 and 8 Hz, 1, C7 -H), 4.85 (d, J=2 Hz, 1, C6 -H) 6.95 (s, 1, CH2Ph), 7.3 (m, 16, aromatic and N-H); u.v. (CHCl3) λmax 264 nm (ε=9726).

Workup

  1. washThe reaction solution was then washed with brine (2×)
  2. dry with materialdried over magnesium sulfate
  3. filtrationfiltered
  4. customthe solvent was evaporated under reduced pressure
  5. customThe resultant yellow foam (2.84 g) was chromatographed over 100 grams of silica gel employing 10-15% of ethyl acetate in toluene as the eluting solvent
  6. washThe first fraction to elute from the column
  7. customwas subsequently recrystallized from a mixture of ethyl acetate and cyclohexane

Sources & evidence

ORD record
ord-788c160fcb1644f5bdcca61cc755050a
Source dataset
uspto-grants-1981_11
Patent number
US04302391

Reaction notes

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