Acetonitrile → Benzyl 4,5-dichloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)picolinate

HRID 1913940ノート

反応式

HRID 1913940 の反応式
[Cl:1][C:2]1[C:7]([Cl:8])=[C:6](Cl)[N:5]=[C:4]([C:10]([O:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[O:11])[CH:3]=1.[Cl:20][C:21]1[CH:26]=[CH:25][C:24](B2OCCCO2)=[C:23]([F:33])[C:22]=1[O:34][CH3:35].[F-].[Cs+].C(#N)C>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O>[Cl:1][C:2]1[C:7]([Cl:8])=[C:6]([C:24]2[CH:25]=[CH:26][C:21]([Cl:20])=[C:22]([O:34][CH3:35])[C:23]=2[F:33])[N:5]=[C:4]([C:10]([O:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[O:11])[CH:3]=1

参加物

7

反応物 4

HCID 6342AcetonitrileHCID 25953Cesium fluorideHCID 577824192-(4-Chloro-2-fluoro-3-methoxyphenyl)-1,3,2-dioxaborinaneHCID 86668437Benzyl 4,5,6-trichloropicolinate

生成物 1

HCID 70495430Benzyl 4,5-dichloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)picolinate

試薬・触媒・溶媒 2

HCID 178418476HCID 178418476、化合物触媒HCID 962Water溶媒

実験手順

A 250 mL three-neck flask equipped with a reflux condenser and nitrogen inlet was charged with benzyl 4,5,6-trichloropicolinate (17.77 g, 56.10 mmol), 2-(4-chloro-2-fluoro-3-methoxyphenyl)-1,3,2-dioxaborinane (19.20 g, 79.0 mmol) and CsF (17.04 g, 112.0 mmol). Acetonitrile (100 mL) and water (30 mL) were added. The reaction mixture was evacuated/backfilled with nitrogen (5×). Solid Pd(PPh3)2Cl2 (1.724 g, 2.456 mmol) was added. The solution was evacuated/backfilled with nitrogen (5×) and then stirred at reflux for 90 min. A white solid precipitated upon cooling to room temperature. The solid was filtered, washed with water and dried in air (18.66 g, 75%): 1H NMR (400 MHz, CDCl3) δ 8.23 (s, 1H, pyridine H), 7.52-7.32 (m, 5H, phenyl), 7.27 (dd, JH-H=8.4 Hz, JF-H=1.7 Hz, 1H, aromatic), 7.10 (dd, JH-H=8.4 Hz, JF-H=6.8 Hz, 1H, aromatic), 5.44 (s, 2H, CH2Ph), 3.98 (d, J JF-H=1.3 Hz, 3H, OMe); 13C{1H} NMR (101 MHz, CDCl3) δ 163.0, 153.7, 153.5 (d, JF-C=253 Hz, C2′), 146.0, 144.5 (d, JF-C=13 Hz), 144.1, 135.0, 134.2, 129.9 (d, JF-C=3 Hz), 128.5, 126.1, 125.8 (d, JF-C=14 Hz), 125.3 (d, JF-C=3 Hz), 124.9 (d, JF-C=2 Hz), 67.9 (CH2), 61.5 (d, JF-C=4 Hz, OMe). Anal. Calcd for C20H13Cl3FNO3: C, 54.51; H, 2.97; N, 3.18. Found: C, 54.60; H, 3.08; N, 3.16.

後処理

  1. customA 250 mL three-neck flask equipped with a reflux condenser and nitrogen inlet
  2. temperatureat reflux for 90 min
  3. customA white solid precipitated
  4. filtrationThe solid was filtered
  5. washwashed with water
  6. customdried in air (18.66 g, 75%)

出典と根拠

ORDレコード
ord-f3c73a33f46249c198f5baac1058d7f6
出典データセット
uspto-grants-2013_12
特許番号
US08609855B2

反応ノート

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