Bromomethylcyclopropane → HCID 19097378, compound

HRID 486047Notes

Reaction equation

HRID 486047 reaction equation
[H-].[K+].[CH3:3][N:4]1[CH2:9][CH2:8][CH:7]([CH3:10])[C:6]([CH3:15])([CH2:11][CH2:12][CH2:13][OH:14])[CH:5]1[CH3:16].[CH:17]1([CH2:20]Br)[CH2:19][CH2:18]1>CCCCCC.C1COCC1.[I-].C([N+](CCCC)(CCCC)CCCC)CCC.CCOCC>[CH:17]1([CH2:20][O:14][CH2:13][CH2:12][CH2:11][C:6]2([CH3:15])[CH:7]([CH3:10])[CH2:8][CH2:9][N:4]([CH3:3])[CH:5]2[CH3:16])[CH2:19][CH2:18]1

Participants

8

Reactant 3

HCID 81503BromomethylcyclopropaneHCID 82127Potassium hydrideHCID 19097395HCID 19097395, compound2×

Product 1

HCID 19097378HCID 19097378, compoundYield 50%

Reagents, catalysts & solvents 4

HCID 67553Tetrabutylammonium IodideCatalystHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Procedure

Potassium hydride (3.8 g, 33 mmol) was washed with dry hexane (2×10 mL) and suspended in THF (60 mL) under a nitrogen atmosphere and 1,2,3,4-tetramethyl-3-piperidinepropanol (6.0 g, 30 mole) in THF (50 mL) was added dropwise over 10 minutes. The mixture was stirred at room temperature for 45 minutes then approximately 5 mole percent of tetrabutylammonium iodide, followed by cyclopropylmethyl bromide (4.5 g, 33 mmol) in THF (20 mL) was added. The mixture was stirred for 24 hours, diluted with ether and washed with brine (3×50 mL]. The organic layer was separated, dried over Na2SO4 and concentrated in vacuo. The residue was combined with additional crude 3-[3-(cyclopropylmethoxy)propyl)1,2,3,4-tetramethylpiperidine which was obtained from a similar experimental run but starting with 1.0 g of 1,2,3,4-tetramethyl-3-piperidinepropanol, and the mixture was purified by column chromatography on silica eluting with 10% ether/hexanes to 1% isopropylamine/10% ether/hexanes to afford 3.8 g(50%) of 3-[3-(cyclopropylmethoxy)propyl]1,2,3,4-tetramethylpiperidine. The product was dissolved in ethanol, treated with 7.2 U ethereal·HCl and diluted with ether to afford 3.2 g of the hydrochloride salt as a cream colored solid. The salt was recrystallized from ethanol/ether and had a melting point of 127-128° C.

Workup

  1. additionwas added
  2. stirringThe mixture was stirred for 24 hours
  3. washwashed with brine (3×50 mL]
  4. customThe organic layer was separated
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated in vacuo
  7. customwas obtained from a similar experimental run
  8. customthe mixture was purified by column chromatography on silica eluting with 10% ether/hexanes to 1% isopropylamine/10% ether/hexanes

Sources & evidence

ORD record
ord-a646e86aae1a4804b021dc5685f664f9
Source dataset
uspto-grants-1994_03
Patent number
US05290789

Reaction notes

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