Nitroethane → 2-(Heptyloxy)-6-(1-nitroethyl)quinoline

HRID 709909Notes

Reaction equation

HRID 709909 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[N:8]=[C:7]([O:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH3:19])[CH:6]=[CH:5]2.[N+:20]([CH2:23][CH3:24])([O-:22])=[O:21].C(=O)([O-])[O-].[Cs+].[Cs+]>COCCOC.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C(P(C(C)(C)C)C1C=CC=CC=1C1C=CC=CC=1C)(C)(C)C>[CH2:13]([O:12][C:7]1[CH:6]=[CH:5][C:4]2[C:9](=[CH:10][CH:11]=[C:2]([CH:23]([N+:20]([O-:22])=[O:21])[CH3:24])[CH:3]=2)[N:8]=1)[CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH3:19]

Participants

7

Reactant 3

HCID 6587NitroethaneHCID 10796Cesium carbonateHCID 674087426-Bromo-2-(heptyloxy)quinoline

Product 1

HCID 866429352-(Heptyloxy)-6-(1-nitroethyl)quinolineYield 78%

Reagents, catalysts & solvents 3

HCID 27349372-(Di-tert-butylphosphino)-2'-methyl-1,1'-biphenylCatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 80711,2-DimethoxyethaneSolvent

Procedure

6-bromo-2-(heptyloxy)quinoline (2.014 g, 6.27 mmol) and Pd2(dba)3 (172 mg, 0.188 mmol, 0.03 eq.) were dissolved in DME (5 mL) and stirred under nitrogen atmosphere for 10 min. 2-di-tert-butylphosphino-2′-methylbiphenyl (117 mg, 0.36 mmol, 0.06 eq.) was added and the mixture was stirred at r.t. for 10 min. Then nitroethane (0.9 mL, 12.54 mmol, 2.0 eq.) and cesium carbonate (2.5 g, 7.5 mmol, 1.2 eq.) were added. The mixture was stirred at 50° C. under nitrogen atmosphere for 15 h. The mixture was extracted with ethyl acetate and the organic layer was purified by silica gel column chromatography using petroleum/ethyl acetate (5/1) as eluent to give product as a slight red oil (1.5 g, 78%). ESI-MS: 317.1 (M+H)+. 1H NMR (400 MHz, CDCl3) δ 7.98 (d, 1H), 7.86 (d, 1H), 7.79 (s, 1H), 7.69 (q, 1H), 6.93 (d, 1H), 5.77-5.74 is (m, 1H), 4.46 (t, 2H), 1.98 (d, 3H), 1.84-1.80 (m, 2H), 1.48-1.29 (m, 8H), 0.89 (t, 3H).

Workup

  1. stirringthe mixture was stirred at r.t. for 10 min
  2. stirringThe mixture was stirred at 50° C. under nitrogen atmosphere for 15 h
  3. extractionThe mixture was extracted with ethyl acetate
  4. customthe organic layer was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-55feb6a1c6884d7ebb865e18d18ad509
Source dataset
uspto-grants-2015_11
Patent number
US09181191B2

Reaction notes

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