Iodine → HCID 21267369, compound

HRID 265211Notes

Reaction equation

HRID 265211 reaction equation
[CH2:1]([O:7][C:8]1[CH:13]=[CH:12][CH:11]=[C:10]([CH:14]=[CH:15][C:16]2[N:21]=[C:20]([O:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28])[CH:19]=[CH:18][CH:17]=2)[N:9]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH3:6].II>C1COCC1.[Pd].CC([O-])=O.CC([O-])=O.[Pb+2].C1CCCCC1>[CH2:1]([O:7][C:8]1[CH:13]=[CH:12][C:11]2[C:17]3[C:16](=[N:21][C:20]([O:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28])=[CH:19][CH:18]=3)[CH:15]=[CH:14][C:10]=2[N:9]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH3:6]

Participants

6

Reactant 2

HCID 807IodineHCID 54232105HCID 54232105, compound

Product 1

HCID 21267369HCID 21267369, compound

Reagents, catalysts & solvents 3

HCID 131709914Lindlars catalystCatalystHCID 8028TetrahydrofuranSolventHCID 8078CyclohexaneSolvent

Procedure

A mixture of 7.7 g of 2-bromo-6-hexyloxypyridine (prepared by reacting 2,6-dibromopyridine with sodium hexoxide in DMF), 3.9 g of trimethylsilylacetylene, 0.4 g of bis(triphenylphosphine)palladium(II) chloride and 0.05 g of copper (I) iodide in 100 ml of diethylamine is stirred at 20° C. for 12 hours. After the volatile constituents have been removed in a rotary evaporator, the mixture is filtered through SiO2 using dichloromethane; the crude 1-(2-bromopyridin-6-yl)-2-trimethylsilylethtne (7.5 g of melting point 24° to 27° C.) obtained is stirred for 1 hour at 20° C. in 100 ml of methanol with 25 ml of 1N aqueous NaOH solution. The solvent is evaporated, and the residue is chromatographed over SiO2 using dichloromethane/heptane 9:1, giving 4.3 g of 2-bromo-6-ethynylpyridine (brownish oil). A solution of 2 g of 2-bromo-6-ethynylpyridine in 50 ml of benzene to which 2.6 g of 2-bromo-6-hexyloxypyridine, 0.2 g of tetrakis(triphenylphisphine)palladium(0) and 30 ml of n-propylamine have been added is stirred at 20° C. for 10 hours. The volatile constituents are removed by distillation, and the residue is chromatographed over SiO2 using dichloromethane, giving 1.9 g of 1,2-bis(2-hexyloxypyridin-6-yl)ethyne. The latter is hydrogenated quantitatively in 50 ml of THF using Lindlar catalyst [Org. Synth. 46, 89 (1966)] to 1,2-bis(2-hexyloxypyridin-6-yl)ethene. The latter is dissolved in 500 ml of cyclohexane, 4 mol % of iodine are added, and the mixture is exposed to UV light for 10 hours at 25° C. in a quartz apparatus. Chromatography on SiO2 using dichloromethane and recrystallization from acetonitrile give 0.9 g of 2,7-bis(hexyloxy)-1,8-diazaphenanthrene as colorless crystals of melting point 91° C.

Workup

  1. customdichloromethane and recrystallization from acetonitrile

Sources & evidence

ORD record
ord-5a8b241a21654991b1fc1d8869ab5bbc
Source dataset
uspto-grants-1997_07
Patent number
US05648021

Reaction notes

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