Hydrochloric Acid → HCID 12764424, compound

HRID 1155093Notes

Reaction equation

HRID 1155093 reaction equation
[CH:1]1([C:4]([N:6]2[CH:13]3[CH2:14][N:9]([C:10]4[CH:18]=[C:17]([N+:19]([O-])=O)[CH:16]=[CH:15][C:11]=4[CH2:12]3)[CH2:8][CH2:7]2)=[O:5])[CH2:3][CH2:2]1.Cl.C(=O)(O)[O-].[Na+]>C(O)C.O.[Fe]>[CH:1]1([C:4]([N:6]2[CH:13]3[CH2:14][N:9]([C:10]4[CH:18]=[C:17]([NH2:19])[CH:16]=[CH:15][C:11]=4[CH2:12]3)[CH2:8][CH2:7]2)=[O:5])[CH2:2][CH2:3]1

Participants

7

Reactant 3

HCID 313Hydrochloric AcidHCID 516892Sodium BicarbonateHCID 12764423HCID 12764423, compound

Product 1

HCID 12764424HCID 12764424, compoundYield 64%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 702EthanolSolvent2×HCID 962WaterSolvent2×

Procedure

Iron powder (104 g.) was added to a warm (50° C.) solution of 4-cyclopropanecarbonyl-9-nitro-3,4,5,6-tetrahydro-2H-1,5-methano-1,4-benzodiazocine (75 g.) in ethanol (600 ml.) and water (300 ml.). The mixture was heated to reflux, then a solution of concentrated hydrochloric acid (45 ml.), ethanol (90 ml.) and water (90 ml.) was added dropwise. Stirring was continued for four hours after the addition was complete. The mixture was allowed to cool somewhat, then sodium bicarbonate (75 g.) was cautiously added, and the mixture was filtered. The filtrate was concentrated nearly to dryness, and the residue was partitioned between water and chloroform. The chloroform layer was washed with brine, dried, treated with charcoal and stripped of chloroform. Two recrystallizations of the tan foam residue from methanol afforded 4-cyclopropanecarbonyl-9-amino-3,4,5,6-tetrahydro-2H-1,5-methano-1,4-benzodiazocine (43 g., m.r. 105°-107° C.), the compound of Formula II wherein Q' is cyclopropanecarbonyl. The product appeared to be a methanol solvate. Recrystallization of part of a similarly prepared product from ethyl acetate afforded product free of solvent (m.r. 142°-144° C.).

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux
  3. additionafter the addition
  4. temperatureto cool somewhat
  5. filtrationthe mixture was filtered
  6. concentrationThe filtrate was concentrated nearly to dryness
  7. customthe residue was partitioned between water and chloroform
  8. washThe chloroform layer was washed with brine
  9. customdried
  10. additiontreated with charcoal
  11. customTwo recrystallizations of the tan foam residue from methanol

Sources & evidence

ORD record
ord-3cdfbb854eca4f29b7addee27ca09150
Source dataset
uspto-grants-1981_11
Patent number
US04299830

Reaction notes

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