Chlorosulfonyl isocyanate → HCID 70581038, compound

HRID 2049731Notes

Reaction equation

HRID 2049731 reaction equation
[OH:1][CH2:2][C:3]1[CH2:4][S:5][C@@H:6]2[CH:13]([NH:14][C:15]([O:17][CH2:18][C:19]3[CH:24]=[CH:23][C:22]([N+:25]([O-:27])=[O:26])=[CH:21][CH:20]=3)=[O:16])[C:12](=[O:28])[N:7]2[C:8]=1[C:9]([OH:11])=[O:10].ClS([N:33]=[C:34]=[O:35])(=O)=O>C(#N)C>[C:34]([O:1][CH2:2][C:3]1[CH2:4][S:5][C@@H:6]2[CH:13]([NH:14][C:15]([O:17][CH2:18][C:19]3[CH:24]=[CH:23][C:22]([N+:25]([O-:27])=[O:26])=[CH:21][CH:20]=3)=[O:16])[C:12](=[O:28])[N:7]2[C:8]=1[C:9]([OH:11])=[O:10])(=[O:35])[NH2:33]

Participants

4

Reactant 2

HCID 70918Chlorosulfonyl isocyanateHCID 70581202HCID 70581202, compound

Product 1

HCID 70581038HCID 70581038, compound

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

3-Hydroxymethyl-7-(p-nitrobenzyloxycarbonylamino) 3-cephem-4-carboxylic acid (2.0 g.; 5 m. mole) was suspended in dry acetonitrile (100 ml) and with stirring was cooled to 0°-5° C. under nitrogen. Chlorosulphonylisocyanate (1.1 ml.; 12.5 m. mole) was added dripwise under nitrogen giving a clear solution almost immediately after the addition. The solution was stirred for 1 hour at 0°-5° C. and evaporated to dryness. The resulting gum was dissolved in aqueous sodium bicarbonate such that the final solution was at pH 1.5. This aqueous solution (150 ml) was layered with ethyl acetate (200 ml) and the mixture was stirred at 20° C. for 18 hours. The ethyl acetate layer was separated, washed with brine, dried over magnesium sulphate and evaporated to dryness to give 3-carbamoyloxymethyl-7-(p-nitrobenzyloxycarbonylamino)-3-cephem-4-carboxylic acid as a cream powder (1.73 g.; 77% of theory). Thin layer chromatography in chloroform, acetone, acetic acid (50:50:7) revealed a single spot at Rf =0.11. δ (DMSO) 8.64 (1H, d, CONH), AA'BB' 8.3 and ##STR13## 6.54 (2H, S, --CONH2 exchanges D2O), 5.55 (2H, m, H7 and α-protons), 5.28 (2H, s, benzylic CH2), 5.12 (1H, d, H6), AB quartet 4.9 and 4.6 (2H, 3-CH2), and 3.55 (2H, s, S-CH2 --), γ max (nujol) 1780 (β-lactam C=O) 1710 (broad), 1520 (NO2)cm-1 ; λ max (EtOH) 266 nm (εm 16220).

Workup

  1. temperaturewas cooled to 0°-5° C. under nitrogen
  2. additionafter the addition
  3. stirringThe solution was stirred for 1 hour at 0°-5° C.
  4. customevaporated to dryness
  5. dissolutionThe resulting gum was dissolved in aqueous sodium bicarbonate such that the final solution
  6. stirringthe mixture was stirred at 20° C. for 18 hours
  7. customThe ethyl acetate layer was separated
  8. washwashed with brine
  9. dry with materialdried over magnesium sulphate
  10. customevaporated to dryness

Sources & evidence

ORD record
ord-00d8d28f056944308a80a9470e85eaf7
Source dataset
uspto-grants-1980_04
Patent number
US04198503

Reaction notes

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