Hydrochloric Acid → HCID 19079046, compound

HRID 1735849Notes

Reaction equation

HRID 1735849 reaction equation
[CH:1](NC(C)C)([CH3:3])[CH3:2].C([Li])CCC.[CH:13]1[C:23]2[CH2:22][CH2:21][C:20]3[CH:24]=[CH:25][CH:26]=[CH:27][C:19]=3[CH:18]([C:28]#[N:29])[C:17]=2[CH:16]=[CH:15][CH:14]=1.C(Br)C=C.Cl>C1COCC1.CCCCCC>[CH2:3]([C:18]1([C:28]#[N:29])[C:19]2[CH:27]=[CH:26][CH:25]=[CH:24][C:20]=2[CH2:21][CH2:22][C:23]2[CH:13]=[CH:14][CH:15]=[CH:16][C:17]1=2)[CH:1]=[CH2:2]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 7841Allyl bromideHCID 7912DiisopropylamineHCID 1409111110,11-dihydro-5H-dibenzo[a,d]cycloheptene-5-carbonitrileHCID 178418339Butyllithium

Product 1

HCID 19079046HCID 19079046, compoundYield 100%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

Dissolved diisopropylamine (11.07 g, 0.109 mol) in 150 mL of dry THF and cooled to 0° C. under a nitrogen atmosphere. Added 40.1 mL (0.100 mol) of 2.5M n-butyl lithium in hexane dropwise via addition funnel. Stirred at 0° C. for 10 mins then cooled to -78° C. Added 10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-nitrile (20.00 g, 0.0912 mol) dissolved in 100 mL of dry THF dropwise via addition funnel. Stirred at -78° C. for 45 mins. Added allyl bromide (14.34 g, 0.119 mol) via syringe, and allowed reaction mixture to warm slowly to room temperature. Stirred at room temperature for 90 mins. Added 250 mL of 0.5N HCl, and separated layers. Extracted aqueous solution with ethyl acetate. Washed combined organic extracts with saturated NaCl, dried with MgSO4, filtered, and evaporated. Purified crude product by flash chromatography on silica gel eluting with 5% ethyl acetate-hexane then 10% ethyl acetate-hexane. Combined appropriate fractions and evaporated to give 23.65 g (100% yield) of 10,11-dihydro-5-(2-propenyl)-5H-dibenzo[a,d]cyclohepten-5-nitrile.

Workup

  1. additiondropwise via addition funnel
  2. temperaturethen cooled to -78° C
  3. stirringStirred at -78° C. for 45 mins
  4. customreaction mixture
  5. temperatureto warm slowly to room temperature
  6. stirringStirred at room temperature for 90 mins
  7. customseparated layers
  8. washWashed
  9. dry with materialdried with MgSO4
  10. filtrationfiltered
  11. customevaporated
  12. customPurified crude product by flash chromatography on silica gel eluting with 5% ethyl acetate-hexane
  13. customevaporated

Sources & evidence

ORD record
ord-30208886545a4826985120116d021614
Source dataset
uspto-grants-1996_07
Patent number
US05538986

Reaction notes

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