Methanesulfonic acid, trifluoro-, 6-chloro-2-pyridinyl ester → HCID 22218087, compound

HRID 1795380Notes

Reaction equation

HRID 1795380 reaction equation
Cl[C:2]1[N:7]=[C:6](OS(C(F)(F)F)(=O)=O)[CH:5]=[CH:4][CH:3]=1.[CH2:16]([Mg]Br)[CH:17]([CH3:19])[CH3:18].[CH2:22]([Mg]Cl)[CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH3:35]>C1COCC1.CN1C(=O)CCC1>[CH2:16]([C:6]1[CH:5]=[CH:4][CH:3]=[C:2]([CH2:35][CH2:34][CH2:33][CH2:32][CH2:31][CH2:30][CH2:29][CH2:28][CH2:27][CH2:26][CH2:25][CH2:24][CH2:23][CH3:22])[N:7]=1)[CH:17]([CH3:19])[CH3:18]

Participants

6

Reactant 3

HCID 11357467Methanesulfonic acid, trifluoro-, 6-chloro-2-pyridinyl esterHCID 178418816HCID 178418816, compoundHCID 178443146HCID 178443146, compound2×

Product 1

HCID 22218087HCID 22218087, compoundYield 71%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 13387N-methyl-2-pyrrolidoneSolvent

Procedure

To a solution of 6-chloro-2-(trifluoromethanesulfonyloxy)pyridine (508 mg, 1.94 mmol) and Fe(acac)3 (34 mg, 0.096 mmol) in THF (8 mL) and NMP (2.3 mL) at 0° C. is slowly added a solution of isobutylmagnesium bromide (2M in Et2O, 1.1 mL, 2.2 mmol) causing a color change to yellow-brown. After stirring for 3 min at that temperature, a solution of C14H29MgCl (1M in THF, 2.3 mL, 2.3 mmol) is introduced via syringe causing an immediate color change to black-violet. After stirring for 5 min, an additional portion of Fe(acac)3 (20 mg, 0.057 mmol) and C14H29MgCl (1M in THF, 0.5 mL, 0.5 mmol) are added consecutively and the resulting mixture is stirred for another 15 min. Quenching of the reaction with brine followed by a standard extractive work up and flash chromatography (hexanes/ethyl acetate, 20/1) affords 2-(isobutyl)-6-(tetradecyl)pyridine as a colorless liquid (449 mg, 71%). 1H NMR (300 MHz, CDCl3): δ 7.47 (t, J=8.3 Hz, 1H), 6.94 (d, J=7.6 Hz, 1H), 6.90 (d, J=7.6 Hz, 1H), 2.71 (t, J=7.7 Hz, 2H), 2.58 (d, J=7.2 Hz, 2H), 2.07 (m, J=6.8 Hz, 1H), 1.68 (m, 2H), 1.20–1.35 (m, 22H), 0.87–0.92 (m, 9H). 13C NMR (75 MHz, CDCl3): 161.9, 160.9, 136.0, 120.4, 119.6, 47.6, 38.5, 32.0, 30.1, 29.80, 29.78, 29.75, 29.71, 29.6, 29.48, 29.47, 29.2, 22.8, 22.3, 13.9. MS m/z (rel. intensity) 331 (11, [M+], 316 (9), 289 (31), 176 (11), 162 (16), 149 (100), 120 (24), 107 (23).

Workup

  1. stirringAfter stirring for 5 min
  2. stirringthe resulting mixture is stirred for another 15 min
  3. customQuenching of the reaction with brine

Sources & evidence

ORD record
ord-658e69690931413d94444035c6f17706
Source dataset
uspto-grants-2006_04
Patent number
US07026478B2

Reaction notes

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