1,3-Dibromopropane → HCID 18599317, compound

HRID 1719526Notes

Reaction equation

HRID 1719526 reaction equation
Br[CH2:2][CH2:3][CH2:4]Br.C(=O)([O-])[O-].[K+].[K+].[CH3:12][C:13]1[CH:18]=[CH:17][C:16]([CH:19]=[C:20]2[CH2:25][CH2:24][CH2:23][CH2:22][CH:21]2[NH2:26])=[CH:15][CH:14]=1>C(O)C>[CH3:12][C:13]1[CH:14]=[CH:15][C:16](/[CH:19]=[C:20]2/[CH:21]([N:26]3[CH2:4][CH2:3][CH2:2]3)[CH2:22][CH2:23][CH2:24][CH2:25]/2)=[CH:17][CH:18]=1

Participants

5

Reactant 3

HCID 80011,3-DibromopropaneHCID 11430Potassium CarbonateHCID 53709014HCID 53709014, compound

Product 1

HCID 18599317HCID 18599317, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A mixture of N-[2-[4-methylphenyl)methylene]cyclohexyl]amine, from step C above, 0.64 g (3.2 mmol) with 1.28 g (6.4 mmol) of 1,3-dibromopropane and 0.88 g (6.4 mmol) of potassium carbonate in 20 ml of ethanol as refluxed 18 hr, evaporated and the residue was taken up in a water/diethyl ether mixture. The aqueous layer was separated and saturated with solid potassium hydroxide and extracted with diethyl ether. The ether extract was washed with saturated sodium chloride solution, dried with magnesium sulfate and evaporated. The residue, 0.67 g, was chromatographed using a HPLC Merck C silica gel column using a 3% methanol in chloroform solution containing 0.5% ammonium hydroxide mixture as eluent. Elution with 620 ml of this eluting mixture gave mixtures of products containing the N-allyl derivative of the starting N-[2-[(4-methylphenyl)methylene]cyclohexyl]amine. Elution of the column contents with 5% methanol in chloroform containing 0.5% ammonium hydroxide (240 ml) gave no product. The next 540 ml gave 180 mg of (±)-(E)-1-[2-[(4-methylphenyl)methylene]cyclohexyl]-azetidine. GC analyses (3% SE 30) 100% at 4.99 min, UV λmax(ε)247(15,300). HR mass spectrum Found 241.1844, Calcd. for C17H23N 241.1830. The NMR spectrum was also consistent for this named product.

Workup

  1. customevaporated
  2. customThe aqueous layer was separated and saturated with solid potassium hydroxide
  3. extractionextracted with diethyl ether
  4. extractionThe ether extract
  5. washwas washed with saturated sodium chloride solution
  6. dry with materialdried with magnesium sulfate
  7. customevaporated
  8. customThe residue, 0.67 g, was chromatographed
  9. additioncontaining 0.5% ammonium hydroxide mixture as eluent
  10. washElution with 620 ml of this eluting mixture
  11. customgave mixtures of products
  12. washElution of the column contents with 5% methanol in chloroform containing 0.5% ammonium hydroxide (240 ml)
  13. customgave no product

Sources & evidence

ORD record
ord-6de2fc2abd7541e2b1f1a1f9f17885e7
Source dataset
uspto-grants-1985_09
Patent number
US04540690

Reaction notes

Loading…