Methyl 4-ethoxy-2-(isocyanatosulfonyl)benzoate → Methyl 2-[[[4-(difluoromethoxy)-6-methoxypyrimidin-2-yl]aminocarbonyl]aminosulfonyl]-4-ethoxybenzoate

HRID 2352460

反応式

HRID 2352460 の反応式
[F:1][CH:2]([F:13])[O:3][C:4]1[CH:9]=[C:8]([O:10][CH3:11])[N:7]=[C:6]([NH2:12])[N:5]=1.[CH2:14]([O:16][C:17]1[CH:26]=[CH:25][C:20]([C:21]([O:23][CH3:24])=[O:22])=[C:19]([S:27]([N:30]=[C:31]=[O:32])(=[O:29])=[O:28])[CH:18]=1)[CH3:15]>ClCCl>[F:13][CH:2]([F:1])[O:3][C:4]1[CH:9]=[C:8]([O:10][CH3:11])[N:7]=[C:6]([NH:12][C:31]([NH:30][S:27]([C:19]2[CH:18]=[C:17]([O:16][CH2:14][CH3:15])[CH:26]=[CH:25][C:20]=2[C:21]([O:23][CH3:24])=[O:22])(=[O:29])=[O:28])=[O:32])[N:5]=1

参加物

4

反応物 2

HCID 13987873Methyl 4-ethoxy-2-(isocyanatosulfonyl)benzoateHCID 146956544-Difluoromethoxy-6-methoxypyrimidin-2-amine

生成物 1

HCID 14695655Methyl 2-[[[4-(difluoromethoxy)-6-methoxypyrimidin-2-yl]aminocarbonyl]aminosulfonyl]-4-ethoxybenzoate

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

実験手順

To a slurry of 4-difluoromethoxy-6-methoxypyrimidin-2-amine (0.56 g, 2.92 mmol) in dry dichloromethane (5 mL) was added a solution of methyl 4-ethoxy-2-(isocyanatosulfonyl)benzoate (crude, ca. 5.6 mL) in dichloromethane (5 mL). The reaction mixture was heated at reflux for 3 hours, during which time the solid dissolved. On stirring at room temperature for 12 hours a new solid formed. The crude reaction mixture was chromatographed directly on a column of silica gel using as eluant 40:1, 20:1, and finally 10:1 dichloromethane-ether, all containing 2 mL/L acetic acid. The appropriate fractions were diluted with toluene and rotary evaporated to give a solid. The solid was slurried in hexanes, collected, washed with butyl chloride, 1:1 butyl chloride-hexanes, hexanes and air dried. The product was a white crystalline solid melting at 195°-196° C. PMR (CDCl3, 200 MHz): δ 12.02 (bs, 1H); 7.91 (d, 1H); 7.78 (d, 1H); 7.52 (t, 1H); 7.34 (bs, 1H); 7.09 (dd, 1H); 5.97 (s, 1H); 4.17 (q, 2H); 4.12 (s, 3H); 3.87 (s, 3H); 1.46 (t, 3H). IR (Nujol): 1722 (vs, C=O) cm-1.

後処理

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux for 3 hours, during which time the solid
  3. dissolutiondissolved
  4. customformed
  5. customThe crude reaction mixture
  6. customwas chromatographed directly on a column of silica gel using as eluant 40:1, 20:1, and finally 10:1 dichloromethane-ether
  7. additionThe appropriate fractions were diluted with toluene
  8. customrotary evaporated
  9. customto give a solid
  10. customcollected
  11. washwashed with butyl chloride, 1:1 butyl chloride-hexanes, hexanes and air
  12. customdried

出典と根拠

ORDレコード
ord-751080ef335f47a0adacf464ed0300de
出典データセット
uspto-grants-1989_10
特許番号
US04877442

関連ノート

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