Hydrochloric Acid → 5-Methyl-3-Methoxy-5,6,7,8,9,10,11,12-Octahydro-5,11-Methano-Benzocyclodecen-13-One

HRID 1076809Notes

Reaction equation

HRID 1076809 reaction equation
[H-].[Na+].Br[CH2:4][CH2:5][CH2:6][CH2:7][CH2:8]Br.[CH3:10][CH:11]1[C:20]2[C:15](=[CH:16][CH:17]=[C:18]([O:21][CH3:22])[CH:19]=2)[CH2:14][CH2:13][C:12]1=[O:23].Cl>C1C=CC=CC=1>[CH3:10][C:11]12[C:12](=[O:23])[CH:13]([CH2:14][C:15]3[CH:16]=[CH:17][C:18]([O:21][CH3:22])=[CH:19][C:20]=31)[CH2:8][CH2:7][CH2:6][CH2:5][CH2:4]2

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 81001,5-DibromopentaneHCID 24758Sodium hydride2×HCID 107977551-Methyl-7-methoxy-2-tetralone

Product 1

HCID 214100925-Methyl-3-Methoxy-5,6,7,8,9,10,11,12-Octahydro-5,11-Methano-Benzocyclodecen-13-OneYield 27%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent3×

Procedure

Oil-free sodium hydride (5.28 g.) in benzene (50 ml.) is added to a stirred mixture of 1,5-dibromopentane (184 g.) and 1-methyl- 7-methoxy-2-tetralone (32 g.) in dry benzene (300 ml.). Stirring is continued for 12 hours at 25° and at reflux for an additional 15 hours. The mixture is cooled, sodium hydride (5.8 g.) in 50 ml. benzene added, stirring continued at 25° /10 hours, and at reflux for 12 additional hours. After cooling excess base is neutralized with concentrated hydrochloric acid and the inorganic solids which precipitate are removed by filtration. Washing and filtrate with saline, drying over sodium sulfate, concentrating and vacuum distilling gives an oil (21 g.), b.p. 160°-190° C. (0.5 mm.) containing 6.5 g. (27%) of the title product by vapor phase chromotography (3% OVI, C200-225-250).

Workup

  1. temperatureat reflux for an additional 15 hours
  2. temperatureThe mixture is cooled
  3. stirringstirring
  4. customcontinued at 25°
  5. custom10 hours
  6. temperatureat reflux for 12 additional hours
  7. temperatureAfter cooling excess base
  8. customthe inorganic solids which precipitate are removed by filtration
  9. washWashing
  10. dry with materialfiltrate with saline, drying over sodium sulfate
  11. concentrationconcentrating
  12. distillationvacuum distilling
  13. customgives an oil (21 g.), b.p. 160°-190° C. (0.5 mm.)
  14. additioncontaining 6.5 g

Sources & evidence

ORD record
ord-6903bc2b21644b35a2f608ef52f2461c
Source dataset
uspto-grants-1976_05
Patent number
US03957872

Reaction notes

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