Hydrochloric Acid → HCID 15065173, compound

HRID 2255155Notes

Reaction equation

HRID 2255155 reaction equation
N[C:2]1[C:7]([CH2:8][OH:9])=[N:6][C:5]([O:10][CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[C:4]([CH2:18][CH:19]([CH3:21])[CH3:20])[N+:3]=1[O-:22].C(#N)C.N(OCCC(C)C)=O.[ClH:34]>C(OCC)C>[CH2:11]([O:10][C:5]1[C:4]([CH2:18][CH:19]([CH3:21])[CH3:20])=[N+:3]([O-:22])[C:2]([Cl:34])=[C:7]([CH2:8][OH:9])[N:6]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 6342AcetonitrileHCID 8053Isoamyl NitriteHCID 178441366HCID 178441366, compound

Product 1

HCID 15065173HCID 15065173, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

There were mixed 2.17 g of 2-amino-5-benzyloxy-3-hydroxymethyl-6-isobutylpyrazine 1-oxide, 2.89 g of cuprous chloride, 1.42 g of cupric chloride and 22 ml of acetonitrile, and the mixture was stirred for 10 minutes at room temperature. Thereto was added 2.88 ml of isoamyl nitrite at room temperature. The mixture was stirred for 30 minutes, whereby an exothermic reaction of 40°-45° C. was taken place. (No cooling was made.) To the reaction mixture were added 60 ml of 2% hydrochloric acid and 50 ml of diethyl ether to cause phase separation. The aqueous layer was extracted with 50 ml of diethyl ether twice. The extract was combined with the above diethyl ether layer. The combined mixture was dried over magnesium sulfate. The solvent was removed by evaporation. The residue was purified by a silica gel column chromatography (eluting solvent: 50% by volume of ethyl acetate-n-hexane), followed by recrystallization by diethyl ether-n-hexane to obtain 1.73 g of 3-benzyloxy-6-chloro- 5-hydroxymethyl-2-isobutylpyrazine 1-oxide (Compound B-12) as pale yellow plate-like crystals having a melting point of 85.0°-88.0° C.

Workup

  1. stirringThe mixture was stirred for 30 minutes
  2. customwhereby an exothermic reaction of 40°-45° C.
  3. customphase separation
  4. extractionThe aqueous layer was extracted with 50 ml of diethyl ether twice
  5. dry with materialThe combined mixture was dried over magnesium sulfate
  6. customThe solvent was removed by evaporation
  7. customThe residue was purified by a silica gel column chromatography (eluting solvent: 50% by volume of ethyl acetate-n-hexane)
  8. customfollowed by recrystallization by diethyl ether-n-hexane

Sources & evidence

ORD record
ord-b677c72bd5c64f62b17bb2651e43e214
Source dataset
uspto-grants-1993_08
Patent number
US05238938

Reaction notes

Loading…