Hydrochloric Acid → HCID 13094356, compound

HRID 1287893Notes

Reaction equation

HRID 1287893 reaction equation
Cl.N[C:3]1[CH:4]=[CH:5][C:6]2[CH2:7][CH2:8][CH:9]([CH3:20])[N:10]3[C:15]=2[C:14]=1[C:13](=[O:16])[C:12]([C:17]([OH:19])=[O:18])=[CH:11]3.N([O-])=O.[Na+].C(=O)([O-])[O-].[Na+].[Na+].[C-:31]#[N:32].[Na+]>C(O)(=O)C.O>[C:31]([C:3]1[CH:4]=[CH:5][C:6]2[CH2:7][CH2:8][CH:9]([CH3:20])[N:10]3[C:15]=2[C:14]=1[C:13](=[O:16])[C:12]([C:17]([OH:19])=[O:18])=[CH:11]3)#[N:32]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 8929Sodium CyanideHCID 10340Sodium CarbonateHCID 13094348HCID 13094348, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 13094356HCID 13094356, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent3×

Conditions

Temperature
50 °C

Procedure

A mixture of 70 ml. of 6N hydrochloric acid and 10-amino-6,7-dihydro-5-methyl-1-oxo-benzo[ij]quinolizine-2-carboxylic acid (10 g., 0.039 mole) is treated at 0° to 5° C. with sodium nitrite (2.7 g., 0.39 mole) in 10 ml. of water. The solution is stirred for about ten minutes, then neutralized by the addition of solid sodium carbonate. A solution of cuprous chloride (4.7 g., 0.048 mole) in 20 ml. of water and sodium cyanide (4.75 g., 0.097 mole) in 10 ml. of water is cooled to 0° C., then the diazonium solution is added dropwise with vigorous stirring. After the stirring for 30 minutes at 0° C. the mixture is heated at 50° C. for 15 minutes, then stirred at about 25° C. for about 65 hours. The solution is acidified to pH 6 with glacial acetic acid to provide a brown solid which is collected by filtration, washed with water, then extracted into two 200 ml. portions of boiling dichloroethane. The hot dichloroethane extracts are filtered, then the filtrate is concentrated to provide an orange solid. The solid is washed thoroughly with hexane, recrystallized from N,N-dimethyl formamide, dissolved in dilute reprecipitated with glacial acetic acid and recrystallized dilute base, from N,N-dimethyl formamide to provide 10-cyano-6,7-dihydro-5-methyl-1-oxo-1H,5H-benzo[ij]quinolizine-2-carboxylic acid, m.p. >300° C.

Workup

  1. additionA mixture of 70 ml
  2. stirringstirred at about 25° C. for about 65 hours
  3. customto provide a brown solid which
  4. filtrationis collected by filtration
  5. washwashed with water
  6. extractionextracted into two 200 ml
  7. filtrationThe hot dichloroethane extracts are filtered
  8. concentrationthe filtrate is concentrated
  9. customto provide an orange solid
  10. washThe solid is washed thoroughly with hexane
  11. customrecrystallized from N,N-dimethyl formamide
  12. dissolutiondissolved
  13. additionin dilute
  14. customreprecipitated with glacial acetic acid
  15. customrecrystallized
  16. additiondilute base

Sources & evidence

ORD record
ord-40cc8ca2a51246339d6055018f14d8ad
Source dataset
uspto-grants-1976_10
Patent number
US03985882

Reaction notes

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