2-Vinylpyridine → HCID 66837013, compound

HRID 2175396Notes

Reaction equation

HRID 2175396 reaction equation
[CH:1]([C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][N:4]=1)=[CH2:2].[N+](=[CH:11][C:12]([O:14][CH2:15][CH3:16])=[O:13])=[N-]>C1(C)C=CC=CC=1>[N:4]1[CH:5]=[CH:6][CH:7]=[CH:8][C:3]=1[C@@H:1]1[CH2:2][C@H:11]1[C:12]([O:14][CH2:15][CH3:16])=[O:13]

Participants

4

Reactant 2

HCID 75212-VinylpyridineHCID 12192Ethyl diazoacetate

Product 1

HCID 66837013HCID 66837013, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A solution of 2-vinylpyridine (2 g, 19.02 mmol) in toluene (40 mL) was treated with ethyl diazoacetate (1.973 ml, 19.02 mmol) and stirred at reflux overnight. The mixture was concentrated in vacuo and the residue was purified by gradient elution on silica gel (0 to 50% EtOAc in hexanes) to elute peak 1 (A-1-trans) (1.6 g, 44%), then the solvent gradient was increased to 100% EtOAc to elute peak 2 (A-2-cis). (914 mg, 25%), both as yellow oils. Enantiomers of A-1-trans can be resolved by chiral preparative supercritical fluid chromatography (SFC) (3.0 cm i.d.×25 cm ChiralTech IC, 7% EtOH/CO2, 70 mL/min) and analyzed by chiral analytical SFC (4.6 mm i.d.×25 cm ChiralTech IC, 7% EtOH/CO2, 2.4 mL/min) ent1=3.6 min, ent2=4.1 min to give the title compound. 1H NMR δ (500 MHz, CDCl3): 8.44 (m, 1H), 7.56 (td, J=7.6, 1.7 Hz, 1H), 7.22 (dd, J=7.8, 1.0 Hz, 1H), 7.08 (ddd, J=7.6, 4.9, 1.2 Hz, 1H), 4.17 (q, J=7.3 Hz, 2H), 2.58 (ddd, J=10.0, 6.1, 3.9 Hz, 1H), 2.25 (ddd, J=9.5, 5.6, 3.9 Hz, 1H), 1.61, (m, 2H), 1.28 (t, J=7.1 Hz, 3H). LRMS (ES) calculated M+H for C11H13NO2S: 192.2. Found: 192.1.

Workup

  1. temperatureat reflux overnight
  2. concentrationThe mixture was concentrated in vacuo
  3. customthe residue was purified by gradient elution on silica gel (0 to 50% EtOAc in hexanes)
  4. washto elute peak 1 (A-1-trans) (1.6 g, 44%)
  5. temperaturethe solvent gradient was increased to 100% EtOAc
  6. washto elute peak 2 (A-2-cis)
  7. customanalyzed by chiral analytical SFC (4.6 mm i.d.×25 cm ChiralTech IC, 7% EtOH/CO2, 2.4 mL/min) ent1=3.6 min, ent2=4.1 min

Sources & evidence

ORD record
ord-22fd941b58234a2b864406cbccccb733
Source dataset
uspto-grants-2015_06
Patent number
US09062059B2

Reaction notes

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