Ammonia → 1-[2-(4,5,10,11-tetrahydro-1H-dibenzo[a,d]cyclohepten-5-yl)ethyl]pyrrolidine

HRID 1981189Notes

Reaction equation

HRID 1981189 reaction equation
[Li].N.[CH:3]1[C:13]2[CH2:12][CH2:11][C:10]3[CH:14]=[CH:15][CH:16]=[CH:17][C:9]=3[CH:8]([CH2:18][CH2:19][N:20]3[CH2:24][CH2:23][CH2:22][CH2:21]3)[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[CH:8]([CH2:18][CH2:19][N:20]3[CH2:21][CH2:22][CH2:23][CH2:24]3)[C:9]=2[CH2:17][CH:16]=[CH:15]1

Participants

7

Reactant 4

HCID 222AmmoniaHCID 517055Sodium BenzoateHCID 3028194LithiumHCID 201879311-[2-(10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-yl)ethyl]pyrrolidine

Product 1

HCID 201879291-[2-(4,5,10,11-tetrahydro-1H-dibenzo[a,d]cyclohepten-5-yl)ethyl]pyrrolidine

Reagents, catalysts & solvents 2

HCID 6386tert-ButanolSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

10.4 g of lithium are added to a mixture of 2.6 l of dry ammonia and 1.6 l of dry tetrahydrofuran at -50° under an argon atmosphere. After 2.5 minutes, the deep blue solution is treated while stirring well at -50° to -43° over a period of 6 minutes with a solution, pre-cooled to -50°, of 150 g of 1-[2-(10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-yl)ethyl]pyrrolidine and 351 g of t-butanol in 1.8 l of dry tetrahydrofuran. After completion of the addition, the dark blue mixture is stirred at -43° to -39° until decolorization has occurred (about 10 minutes). After an additional 2 minutes, the mixture is treated with 12.0 g of sodium benzoate and subsequently the ammonia is removed. The residue is subsequently washed six times with 500 ml of saturated sodium chloride solution each time, dried over magnesium sulfate and evaporated in vacuo. The light brown oil obtained is purified by column chromatography on 500 g of aluminium oxide (activity grade II, neutral) using benzene for the elution, there being obtained crude 1-[2-(4,5,10,11-tetrahydro-1H-dibenzo[a,d]cyclohepten-5-yl)ethyl]pyrrolidine as a light yellow oil which crystallizes slowly upon standing.

Workup

  1. additionthe deep blue solution is treated
  2. additionAfter completion of the addition
  3. stirringthe dark blue mixture is stirred at -43° to -39° until decolorization
  4. custom(about 10 minutes)
  5. waitAfter an additional 2 minutes
  6. customsubsequently the ammonia is removed
  7. washThe residue is subsequently washed six times with 500 ml of saturated sodium chloride solution each time
  8. dry with materialdried over magnesium sulfate
  9. customevaporated in vacuo
  10. customThe light brown oil obtained
  11. customis purified by column chromatography on 500 g of aluminium oxide (activity grade II, neutral)
  12. washfor the elution, there

Sources & evidence

ORD record
ord-f419a22bc24a4590924aa1ff1f005452
Source dataset
uspto-grants-1985_04
Patent number
US04513002

Reaction notes

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