Ammonia → 1,4,10,11-tetrahydro-5H-dibenzo[a,d]cycloheptene

HRID 1981192Notes

Reaction equation

HRID 1981192 reaction equation
N.[Li].[CH:3]1[C:13]2[CH2:12][CH2:11][C:10]3[CH:14]=[CH:15][CH:16]=[CH:17][C:9]=3[CH2:8][C:7]=2[CH:6]=[CH:5][CH:4]=1.C([O-])(=O)C1C=CC=CC=1.[Na+]>O1CCCC1.C(O)(C)(C)C>[CH2:14]1[C:10]2[CH2:11][CH2:12][C:13]3[CH:3]=[CH:4][CH:5]=[CH:6][C:7]=3[CH2:8][C:9]=2[CH2:17][CH:16]=[CH:15]1

Participants

7

Reactant 4

HCID 222AmmoniaHCID 7002910,11-dihydro-5H-dibenzo(a,d)cyclohepteneHCID 517055Sodium BenzoateHCID 3028194Lithium

Product 1

HCID 201879321,4,10,11-tetrahydro-5H-dibenzo[a,d]cycloheptene

Reagents, catalysts & solvents 2

HCID 6386tert-ButanolSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A mixture, stirred at -40°, of 1.28 l of dry tetrahydrofuran and 2.1 l of dry liquid ammonia is treated with 8.6 g of lithium wire. The mixture is stirred for 2 minutes and subsequently there is added thereto over a period of 6 minutes a solution, pre-cooled to -40°, of 80.0 g of 10,11-dihydro-5H-dibenzo[a,d]cycloheptene in 1.44 l of dry tetrahydrofuran and 280 g of t-butanol. After a color change from blue to colorless, the mixture is treated with 6.0 g of sodium benzoate and the ammonia is evaporated. The mixture is washed three times with 500 ml of water each time. The combined aqueous washings are extracted twice with 1.0 l of ether each time. The organic phases are combined, washed with saturated sodium chloride solution, dried over magnesium sulfate and evaporated. The oily residue is purified by fractional crystallization from petroleum ether (low-boiling) at -25°. There is obtained 1,4,10,11-tetrahydro-5H-dibenzo[a,d]cycloheptene as white crystals of melting point 42.5°-43°.

Workup

  1. additionsubsequently there is added
  2. waitover a period of 6 minutes a solution
  3. customthe ammonia is evaporated
  4. washThe mixture is washed three times with 500 ml of water each time
  5. extractionThe combined aqueous washings are extracted twice with 1.0 l of ether each time
  6. washwashed with saturated sodium chloride solution
  7. dry with materialdried over magnesium sulfate
  8. customevaporated
  9. customThe oily residue is purified by fractional crystallization from petroleum ether (low-boiling) at -25°

Sources & evidence

ORD record
ord-92d27c4b3df4473e97832e3cbc42a9ce
Source dataset
uspto-grants-1985_04
Patent number
US04513002

Reaction notes

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