4-Chloro-3-nitropyridine → 4-Cyclohexenyl-3-nitropyridine

HRID 69874Notes

Reaction equation

HRID 69874 reaction equation
Cl[C:2]1[CH:7]=[CH:6][N:5]=[CH:4][C:3]=1[N+:8]([O-:10])=[O:9].[C:11]1(B(O)O)[CH2:16][CH2:15][CH2:14][CH2:13][CH:12]=1>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl.COCCOC>[C:11]1([C:2]2[CH:7]=[CH:6][N:5]=[CH:4][C:3]=2[N+:8]([O-:10])=[O:9])[CH2:16][CH2:15][CH2:14][CH2:13][CH:12]=1

Participants

5

Reactant 2

HCID 27357814-Chloro-3-nitropyridineHCID 38629021-Cyclohexenylboronic acid

Product 1

HCID 690448894-Cyclohexenyl-3-nitropyridineYield 82%

Reagents, catalysts & solvents 2

HCID 178418807HCID 178418807, compoundCatalystHCID 80711,2-DimethoxyethaneSolvent

Procedure

A solution of 4-chloro-3-nitro pyridine (1 eq.), cyclohexenyl boronic acid (1.7 eq.), and Pd(dppf)Cl2—CH2Cl2 (0.05 eq) in 3:1 DME/2M Na2CO3, at a concentration of 0.1 M was heated at 95° C. for 16 hours. Upon cooling the reaction was partitioned between EtOAc and H2O, was washed with NaCl(sat.), dried over MgSO4, was filtered and the volatiles were removed in vacuo. The material was purified by SiO2 chromatography (20% EtOAc/hexanes eluant) to yield 4-cyclohexenyl-3-nitropyridine (82%). LCMS (m/z): 205.0 (MH+); LC Rt=3.84 min.

Workup

  1. temperatureUpon cooling the reaction
  2. customwas partitioned between EtOAc and H2O
  3. washwas washed with NaCl(sat.)
  4. dry with materialdried over MgSO4
  5. filtrationwas filtered
  6. customthe volatiles were removed in vacuo
  7. customThe material was purified by SiO2 chromatography (20% EtOAc/hexanes eluant)

Sources & evidence

ORD record
ord-e9a23e06244e4836baba6265ef0bfc7a
Source dataset
uspto-grants-2014_09
Patent number
US08822497B2

Reaction notes

Loading…