Methyl iodide → HCID 20491784, compound

HRID 434708Notes

Reaction equation

HRID 434708 reaction equation
[CH:1]([NH:4][CH:5]([CH3:7])[CH3:6])(C)C.C([Li])CCC.CCCCCC.[N+](C1[C:27]2[CH:28]=[CH:29][CH:30]=[CH:31][C:26]=2[C:25](=[CH2:32])[C:24]2[CH:33]=[CH:34][CH:35]=[CH:36][C:23]=2C1)#[C-].C([N-]C(C)C)(C)C.[Li+].CI>O1CCCC1>[N+:4]([C:5]1([CH3:7])[C:23]2[CH:36]=[CH:35][CH:34]=[CH:33][C:24]=2[C:25](=[CH2:32])[C:26]2[CH:27]=[CH:28][CH:29]=[CH:30][C:31]=2[CH2:6]1)#[C-:1]

Participants

7

Reactant 5

HCID 6328Methyl iodideHCID 7912DiisopropylamineHCID 2724682Lithium diisopropylamideHCID 20491803HCID 20491803, compoundHCID 178418244HCID 178418244, compound

Product 1

HCID 20491784HCID 20491784, compoundYield 86.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Diisoproylamine (1.1 g, 10.9 mmole) in 25 ml of dry tetrahydrofuran was stirred in a dry ice/acetone bath. Under a nitrogen blanket, this solution was treated with n-butyllithium/hexane (5.0 ml of 2.2 M solution) added dropwise over 10 minutes. After 5 minutes, a solution of 10-isocyano-5-methylene-10,11-dihydro-5H-dibenzo[a,d]cycloheptene (2.4 g, 10.4 mmole) in 25 ml of dry tetrahydrofuran was added dropwise (over 45 minutes) to the lithium diisopropylamide solution. The resulting deep red solution was stirred in the cold for 15 minutes then treated with methyliodide (4.56 g, 32 mmole) added all at once. The mixture was stirred 2 hours in the cold and an additional 1 hour at room temperature. The solvent was removed in vacuo and the residue chromatographed on 75 g of silica gel, eluted with methylene chloride. The combined product fractions were evaporated in vacuo to give 2.2 g (86%) solid. Recrystallization from ether gave, m.p. 146°-147.5° C.

Workup

  1. additionadded dropwise over 10 minutes
  2. additionadded all at once
  3. stirringThe mixture was stirred 2 hours in the cold and an additional 1 hour at room temperature
  4. customThe solvent was removed in vacuo
  5. customthe residue chromatographed on 75 g of silica gel
  6. washeluted with methylene chloride
  7. customThe combined product fractions were evaporated in vacuo

Sources & evidence

ORD record
ord-ed3207f535e74482b9a8462237d9ae18
Source dataset
uspto-grants-1983_08
Patent number
US04399141

Reaction notes

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