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

HRID 1795380노트

반응식

HRID 1795380 반응식
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]

참가 물질

6

반응물 3

HCID 11357467Methanesulfonic acid, trifluoro-, 6-chloro-2-pyridinyl esterHCID 178418816HCID 178418816, 화합물HCID 178443146HCID 178443146, 화합물2회

생성물 1

HCID 22218087HCID 22218087, 화합물수율 71%

시약·촉매·용매 2

HCID 8028Tetrahydrofuran용매HCID 13387N-methyl-2-pyrrolidone용매

실험 절차

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).

후처리

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

출처 및 근거

ORD 기록
ord-658e69690931413d94444035c6f17706
출처 데이터셋
uspto-grants-2006_04
특허 번호
US07026478B2

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