Isopropanol → HCID 131715517, compound

HRID 1252258Notes

Reaction equation

HRID 1252258 reaction equation
[C:1]1([C@@H:7]([O:9][C:10](=[O:25])[CH2:11][C:12]([CH:14]=[CH:15][C:16]2C=C[CH:19]=[C:18]([N+:22]([O-:24])=[O:23])[CH:17]=2)=O)[CH3:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[NH2:26][C:27]([CH3:39])=[CH:28][C:29](=[O:38])[CH2:30][S:31]([NH:34][CH:35]([CH3:37])[CH3:36])(=[O:33])=[O:32].[CH:40](O)(C)[CH3:41]>CN(C)C=O.CCOCC>[C:1]1([C@@H:7]([O:9][C:10](=[O:25])[C:11]2[C@H:12]([C:14]3[CH:15]=[CH:16][CH:17]=[C:18]([N+:22]([O-:24])=[O:23])[CH:19]=3)[C:28]([C:29](=[O:38])[CH2:30][S:31](=[O:32])(=[O:33])[NH:34][CH:35]([CH3:36])[CH3:37])=[C:27]([CH3:39])[NH:26][C:40]=2[CH3:41])[CH3:8])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

6

Reactant 3

HCID 3776IsopropanolHCID 53648819HCID 53648819, compoundHCID 86742150HCID 86742150, compound

Product 1

HCID 131715517HCID 131715517, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent

Procedure

A solution of 6.8 g of (S)-3-nitrobenzylideneacetoacetic acid 1-phenylethyl ester in a mixture of 20 ml of isopropanol and 10 ml of dimethylformamide was treated under argon with 4.40 g of 4-amino-N-isopropyl-2-oxo-3-pentenesulfonamide and the mixture was thereupon heated to reflux for 8 hours. After concentration under reduced pressure the oily residue was chromatographed on 800 g of silica gel with methylene chloride/ethyl acetate (4:1) as the elution agent, whereby the two expected epimers were eluted as a mixture. The homogeneous fractions yielded an oil which was taken up in 300 ml of ether and left to stand at room temperature overnight. The crystallized-out product was filtered off, washed with a small amount of ether and recrystallized from ethanol. There were obtained 2.3 g of (R)-1,4-dihydro-5-[(isopropylsulfamoyl)acetyl]-2,6-dimethyl-4-(3-nitrophenyl)nicotinic acid (S)-1-phenylethyl ester in the form of yellow crystals, m.p. 151°-153°, specific rotation: [α]54620 =+518° (c=1.0% w/v, ethanol). On the basis of the NMR spectrum this was the (+)-enantiomer of the racemate A described in Example 14.

Workup

  1. temperaturethe mixture was thereupon heated
  2. temperatureto reflux for 8 hours
  3. concentrationAfter concentration under reduced pressure the oily residue
  4. customwas chromatographed on 800 g of silica gel with methylene chloride/ethyl acetate (4:1) as the elution agent, whereby the two expected epimers
  5. washwere eluted as a mixture
  6. customThe homogeneous fractions yielded an oil which
  7. waitleft
  8. filtrationThe crystallized-out product was filtered off
  9. washwashed with a small amount of ether
  10. customrecrystallized from ethanol

Sources & evidence

ORD record
ord-e0b43a1f76f74d69938acc879b707f7b
Source dataset
uspto-grants-1988_05
Patent number
US04742069

Reaction notes

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