Benzene → Heptopargil

HRID 1389409Notes

Reaction equation

HRID 1389409 reaction equation
[H-].[Na+].[CH:3]1[CH:8]=CC=C[CH:4]=1.[CH3:9][C:10]12[C:16]([CH3:18])([CH3:17])[CH:13]([CH2:14][CH2:15]1)[CH2:12][C:11]2=[N:19][OH:20].C(Br)C#C>CN(C)C=O.O>[CH2:8]([O:20][N:19]=[C:11]1[CH2:12][CH:13]2[C:16]([CH3:17])([CH3:18])[C:10]1([CH3:9])[CH2:15][CH2:14]2)[C:3]#[CH:4]

Participants

7

Reactant 4

HCID 241BenzeneHCID 7842Propargyl bromideHCID 24758Sodium hydrideHCID 26110Camphor oxime

Product 1

HCID 52692HeptopargilYield 90.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
25 °C

Procedure

4.8 g (0.2 moles) of sodium hydride are added to 150 ml of dry benzene, and a solution of 33.4 g (0.2 moles) of (±)-1,7,7-trimethyl-bicyclo[2,2,1]heptane-2-one-oxime in 50 ml of dimethyl formamide is introduced into the mixture at 50° C. within 0.5 hours. When gas evolution ceases, the mixture is cooled to 25° C., and 23.8 g (0.2 moles) of propargyl bromide are added. The reaction is continued for additional 2 hours. Thereafter the reaction mixture is shaken with water, the phases are separated, the benzene phase is evaporated, and the residue is subjected to fractional distillation in vacuo. 37.0 g (90.5%) of (±)-2-(propargyloxyimino)-1,7,7-trimethyl-bicyclo[2,2,1]heptane are obtained as a light yellow oil; b.p.: 94°-96° C./1.5 mm Hg, nD20 =1.4953.

Workup

  1. customthe phases are separated
  2. customthe benzene phase is evaporated
  3. distillationthe residue is subjected to fractional distillation in vacuo

Sources & evidence

ORD record
ord-01cd2f3dc34b4f9ab1ffb8d53b41acbb
Source dataset
uspto-grants-1981_01
Patent number
US04244888

Reaction notes

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