Ammonia → HCID 54431794, compound

HRID 372815Notes

Reaction equation

HRID 372815 reaction equation
C1C2CCC(=O)CCC=2C=CC=1.[Br-].C(CCCC[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)#N.[H-].[Na+].[NH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH:47]1[CH2:53][CH2:52][C:51]2[CH:54]=[CH:55][CH:56]=[CH:57][C:50]=2[CH2:49][CH2:48]1.N.[Li]>C(O)C.CCOCC.C(COC)OC>[NH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH:47]1[CH2:53][CH2:52][C:51]2[CH2:54][CH:55]=[CH:56][CH2:57][C:50]=2[CH2:49][CH2:48]1

Participants

10

Reactant 6

HCID 222AmmoniaHCID 24758Sodium hydrideHCID 3028194LithiumHCID 11418829(4-Cyanobutyl)(triphenyl)phosphanium bromideHCID 122344855,6,8,9-Tetrahydro-7H-benzo[7]annulen-7-oneHCID 53726431HCID 53726431, compound

Product 1

HCID 54431794HCID 54431794, compound

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 3283Diethyl EtherSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

A mixture of 16.0 g. (0.1 mole) of 5,6,8,9-tetrahydro-7H-cycloheptabenzen-7-one and 42.4 g. (0.1 mole) of cyanobutyltriphenylphosphonium bromide in 500 ml. of dimethoxyethane is stirred under nitrogen and treated portionwise with 0.11 mole of 50% NaH dispersed in mineral oil. After several hours, the mixture is freed of solvent and the product extracted into ether. The crude product is dissolved in ethanol, treated with NH3 and 10 g. of Raney nickel and hydrogenated at 1500 psi of hydrogen at 100°-120°. After uptake is complete, the mixture is cooled, freed of catalyst and the product isolated from solvent. The crude 7-aminopentyl-6,7,8,9-tetrahydro-5H-benzocycloheptene is taken up in 100 ml. of ether and added to 500 ml. of liq. NH3. The solution is treated with 20 g. of lithium in small pieces over 1 hour. Then absolute ethanol is added slowly dropwise to discharge the color. After removal of NH3, the mixture is cooled, treated with water, and extracted with ether. Removal of solvents leaves crude 7-aminopentyl-1,4,6,7,8,9-hexahydro-5H-benzocycloheptene which is converted to its N-benzoyl derivative and thence to the tetrol as described previously.

Workup

  1. additionA mixture of 16.0 g
  2. additiondispersed in mineral oil
  3. waitAfter several hours
  4. extractionthe product extracted into ether
  5. dissolutionThe crude product is dissolved in ethanol
  6. additiontreated with NH3 and 10 g
  7. customat 100°-120°
  8. temperaturethe mixture is cooled
  9. customthe product isolated from solvent
  10. additionThe solution is treated with 20 g
  11. customAfter removal of NH3
  12. temperaturethe mixture is cooled
  13. additiontreated with water
  14. extractionextracted with ether
  15. customRemoval of solvents

Sources & evidence

ORD record
ord-af11587b24ee43ae9999148cdb1397df
Source dataset
uspto-grants-1978_05
Patent number
US04092318

Reaction notes

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