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

HRID 1578563Notes

Reaction equation

HRID 1578563 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° for 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 chromatography (3% OVI, C200-225-250).

Workup

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

Sources & evidence

ORD record
ord-12a886546fc443a7850c8e5904974d69
Source dataset
uspto-grants-1976_02
Patent number
US03937736

Reaction notes

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