Hydrochloric Acid → HCID 53885633, compound

HRID 224356Notes

Reaction equation

HRID 224356 reaction equation
[C:1]([C:3]12[CH:12]3[CH:13]=[C:14]([C:15]#N)[CH:9]([CH2:10][N:11]3[CH3:17])[CH:8]1[CH2:7][N:6]([CH3:18])[CH2:5][CH2:4]2)#[N:2].[C:19]1([Li])[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.Cl.C1C[O:30]CC1>C(=O)=O.CC(C)=O.C1C=CC=CC=1>[C:15]([C:14]1[CH:9]2[CH2:10][N:11]([CH3:17])[CH:12]([CH:13]=1)[C:3]1([C:1]#[N:2])[CH:8]2[CH2:7][N:6]([CH3:18])[CH2:5][CH2:4]1)(=[O:30])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 8028TetrahydrofuranHCID 12340334HCID 12340334, compoundHCID 178506676HCID 178506676, compound

Product 1

HCID 53885633HCID 53885633, compoundYield 16%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 18522661Acetone cardiceSolvent

Procedure

A solution of 12.12 g (50 mM) of 7,11-dicyano-4,9-dimethyl-4,9-diazatricyclo[6.2.2.02,7 ]dodec-11-ene in 150 ml of dried THF is cooled in dry ice-acetone and treated with 26 ml of 1.67 molar (43.5 mM) phenyl lithium in benzene over a 15 minute period. The reaction mixture is allowed to stir at room temperature overnight and then treated with 50 ml of 2.5 N hydrochloric acid. The layers are separated and the tetrahydrofuranbenzene layer is extracted with 20 ml of 1 N hydrochloric acid. The combined product-containing hydrochloric acid layers are washed with methylene chloride and allowed to sit at room temperature for 2 hours. After making alkaline with 5 ml of 50% sodium hydroxide solution the product is extracted into a total of 125 ml of methylene chloride which after drying over MgSO4, and concentration yields 11.35 g of a crude product. By chromatography over silica gel 11-benzoyl-7-cyano-4,9-dimethyl-4,9 -diazatricyclo[6.2.2.02,7 ]dodec-11-ene is isolated analytically pure in an overall yield of 16%, m.p. 120°-139° C., NMR and IR spectrum are in accord with the structure.

Workup

  1. customThe layers are separated
  2. extractionthe tetrahydrofuranbenzene layer is extracted with 20 ml of 1 N hydrochloric acid
  3. additionThe combined product-containing hydrochloric acid layers
  4. washare washed with methylene chloride
  5. waitto sit at room temperature for 2 hours
  6. extractionis extracted into a total of 125 ml of methylene chloride which
  7. dry with materialafter drying over MgSO4, and concentration
  8. customyields 11.35 g of a crude product
  9. customBy chromatography over silica gel 11-benzoyl-7-cyano-4,9-dimethyl-4,9 -diazatricyclo[6.2.2.02,7 ]dodec-11-ene is isolated analytically pure in an overall yield of 16%, m.p. 120°-139° C., NMR and IR spectrum

Sources & evidence

ORD record
ord-9e78c83fc2fb40b1975412c329bfc354
Source dataset
uspto-grants-1980_11
Patent number
US04232026

Reaction notes

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