Triethylamine → HCID 86746599, compound

HRID 1613095Notes

Reaction equation

HRID 1613095 reaction equation
[O:1]=[C:2]([CH2:29][C:30](=[O:34])[CH:31]([CH3:33])[CH3:32])[O:3][CH2:4][CH2:5][N:6]1[C:13](=[O:14])[N:12]([CH2:15][CH2:16][OH:17])[C:10](=[O:11])[N:9]([CH2:18][CH2:19][O:20][C:21](=[O:28])[CH2:22][C:23](=[O:27])[CH:24]([CH3:26])[CH3:25])[C:7]1=[O:8].S(N=[N+:46]=[N-:47])(C1C=CC(C)=CC=1)(=O)=O.C(N(CC)CC)C.C(C1C=CC(S([N:67]=[N+:68]=[N-])(=O)=O)=CC=1)(O)=O>C(#N)C.ClCCl.C(OCC)(=O)C.ClCCl>[N+:67](=[C:29]([C:30](=[O:34])[CH:31]([CH3:33])[CH3:32])[C:2](=[O:1])[O:3][CH2:4][CH2:5][N:6]1[C:13](=[O:14])[N:12]([CH2:15][CH2:16][OH:17])[C:10](=[O:11])[N:9]([CH2:18][CH2:19][O:20][C:21](=[O:28])[C:22](=[N+:46]=[N-:47])[C:23](=[O:27])[CH:24]([CH3:26])[CH3:25])[C:7]1=[O:8])=[N-:68]

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 13661p-Toluenesulfonyl azide2×HCID 86999Benzoic acid, 4-(azidosulfonyl)-HCID 67856376HCID 67856376, compound

Product 1

HCID 86746599HCID 86746599, compound

Reagents, catalysts & solvents 3

HCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolventHCID 21226138Dichloromethane ethylacetateSolvent

Conditions

Temperature
0 °C

Procedure

The above-described compound 26, in the amount produced, is dissolved in 50 ml of acetonitrile, and the solution is cooled to 0° C. 2.37 g (12 mmol) of tosyl azide are added to the cooled solution with stirring, and 2.5 g (25 mmol) of triethylamine are subsequently added dropwise at such a rate that the temperature does not exceed 5° C. The mixture is stirred at this temperature for 60 minutes, and subsequently warmed to room temperature. After 2 hours, tosyl azide is no longer detectable in the mixture by thin-layer chromatography (silica gel, dichloromethane as eluent). 1.70 g (7.5 mmol) of 4-carboxyphenylsulfonyl azide are added to the mixture at 0° C., and the mixture is stirred for 30 minutes. After a further 2 hours at room temperature, the solvent is removed by distillation in vacuo. The residue is taken up in dichloromethane, and the solution is washed three times with 200 ml of 10% aqueous potassium hydroxide solution in each case. The mixture is subsequently washed with water until neutral, and the organic phase is dried using sodium sulfate. Evaporation leaves a red oil, which is substantially freed from solvent residues by applying a high vacuum. Column chromatography on silica gel using dichloromethane/ethyl acetate as eluent gives 5.4 g of colorless α-diazo-β-keto ester/sulfonate 27, which has the following composition.

Workup

  1. customdoes not exceed 5° C
  2. stirringThe mixture is stirred at this temperature for 60 minutes
  3. temperaturesubsequently warmed to room temperature
  4. stirringthe mixture is stirred for 30 minutes
  5. waitAfter a further 2 hours at room temperature
  6. customthe solvent is removed by distillation in vacuo
  7. washthe solution is washed three times with 200 ml of 10% aqueous potassium hydroxide solution in each case
  8. washThe mixture is subsequently washed with water until neutral, and the organic phase
  9. customis dried
  10. customEvaporation
  11. customleaves a red oil, which

Sources & evidence

ORD record
ord-b4a03ec955b94097943f32318e4569dc
Source dataset
uspto-grants-1993_03
Patent number
US05191069

Reaction notes

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