Iodine → HCID 18707051, compound

HRID 1422103Notes

Reaction equation

HRID 1422103 reaction equation
[Mg].II.Br[CH2:5][CH2:6][CH3:7].[CH2:8]([O:15][C:16]1[C:17](Br)=[N:18][CH:19]=[CH:20][CH:21]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1>C(OCC)C.BrCCC.C1C=CC(P(C2C=CC=CC=2)CCP(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Ni]Cl.O>[CH2:8]([O:15][C:16]1[C:17]([CH2:5][CH2:6][CH3:7])=[N:18][CH:19]=[CH:20][CH:21]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1

Participants

9

Reactant 4

HCID 807IodineHCID 78401-BromopropaneHCID 5462224MagnesiumHCID 107780003-(Benzyloxy)-2-bromopyridine

Product 1

HCID 18707051HCID 18707051, compoundYield 71.7%

Reagents, catalysts & solvents 4

HCID 78401-BromopropaneCatalystHCID 2734542[1,2-Bis(diphenylphosphino)ethane]dichloronickel(II)CatalystHCID 962WaterSolventHCID 3283Diethyl EtherSolvent2×

Procedure

Solid magnesium (0.7 g, 30 mmol) was stirred in 15 ml of dry diethyl ether under a nitrogen atmosphere. An iodine crystal and 1 drop of 1-bromopropane was added and the mixture was heated to reflux. The heating source was removed and the remaining 1-bromopropane (2.46 g, 20 mmol) was added in portions. The Grignard reagent was stirred for 1/2 hour at room temperature. 3-Benzyloxy-2-bromopyridine (3.66 g, 13.8 mmol) and a catalytic amount of [1,2-bis(diphenylphosphino)ethane]dichloronickel(II) was dissolved in 200 ml of dry diethyl ether under a nitrogen atmosphere, and the Grignard reagent was added dropwise. The reaction mixture was stirred for 3 hours, and carefully poured into 200 ml of water. The aqueous layer was extracted with 2×100 ml of diethyl ether. The combined organic layers were dried overmagnesium sulfate and the solvent was evaporated. The crude product was purified by column chromatography over silica gel 60, using 50% of diethyl ether in petroleum ether as the eluent to afford 2.25 g (71%) of 3-benzyloxy-2-propylpyridine. 1H--NMR (CDCl3, 200 MHz) δ: 0.98 (t,3 H); 1.77 (sextet, 2 H); 1.86 (t, 2 H); 5.07 (s, 2 H); 7.02-7.16 (m, 2 H); 7.27-7.45 (m, 5 H); 8.12 (dd, 1 H).

Workup

  1. temperaturethe mixture was heated to reflux
  2. customThe heating source was removed
  3. extractionThe aqueous layer was extracted with 2×100 ml of diethyl ether
  4. dry with materialThe combined organic layers were dried overmagnesium sulfate
  5. customthe solvent was evaporated
  6. customThe crude product was purified by column chromatography over silica gel 60

Sources & evidence

ORD record
ord-c4b495bf33ee412391d97ea700d73dc5
Source dataset
uspto-grants-2000_06
Patent number
US06080754

Reaction notes

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