Methanesulfonic acid, trifluoro-, 6-chloro-2-pyridinyl ester → HCID 22218087、化合物

HRID 1795380ノート

反応式

HRID 1795380 の反応式
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]

参加物

6

反応物 3

HCID 11357467Methanesulfonic acid, trifluoro-, 6-chloro-2-pyridinyl esterHCID 178418816HCID 178418816、化合物HCID 178443146HCID 178443146、化合物2 回

生成物 1

HCID 22218087HCID 22218087、化合物収率 71%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒HCID 13387N-methyl-2-pyrrolidone溶媒

実験手順

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).

後処理

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

出典と根拠

ORDレコード
ord-658e69690931413d94444035c6f17706
出典データセット
uspto-grants-2006_04
特許番号
US07026478B2

反応ノート

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