Dabco → HCID 20087903、化合物

HRID 483357ノート

反応式

HRID 483357 の反応式
S(Cl)(Cl)(=O)=O.[Cl:6][C:7]1[CH:8]=[C:9]2[C:14](=[CH:15][CH:16]=1)[NH:13][C:12]([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[S:23]CC1C=CC=CC=1)=[CH:11][C:10]2=[O:31].N12CCN(CC1)CC2>>[Cl:6][C:7]1[CH:16]=[CH:15][C:14]2[N:13]3[S:23][C:18]4[CH:19]=[CH:20][CH:21]=[CH:22][C:17]=4[C:12]3=[CH:11][C:10](=[O:31])[C:9]=2[CH:8]=1

参加物

4

反応物 3

HCID 9237DabcoHCID 24648Sulfuryl chlorideHCID 20087902HCID 20087902、化合物

生成物 1

HCID 20087903HCID 20087903、化合物収率 26%

反応条件

温度
25 °C

実験手順

Sulfuryl chloride (0.305 ml, 3.78 mmole, 1.0 equiv.) was added dropwise over 3 min to a suspension of 6-chloro-2-[2-[(phenylmethyl)thio]phenyl]-4(1H)-quinolinone (1.43 g, 3,78 mmole, 1 equiv.) in dry, EtOH-free CHCl3 (190 ml) at -15° C. The mixture was stirred for 0.5 hr, then was heated to reflux. After 20 min, the reaction was cooled to 25° C, and 1,4-diazabicyclo[2.2.2]octane (636 mg, 5.67 mmole, 1.5 equiv.) was added. The nearly homogeneous solution was stirred at 25° C. for an additional 5 min, then was washed with H2O (3×50 ml). The combined aqueous layers, which contained suspended product, were back - extracted with CHCl3, and the combined organic layers were diluted with CHCl3 (200 ml) and MeOH (50 ml) to dissolve suspended solids. Drying (MgSO4), concentration, and silica gel chromatography (CHCl3, then 10% MeOH in 50% EtOAc/CHCl3, then 10% MeOH/CHCl3) gave 3-chloro-5H-[1,2]benzisothiazolo[2,3-a]quinoline-5-one (0.28 g, 26%) as a yellow solid. Two recrystallizations from CHCl3 /EtOAc gave yellow, very fine needles: mp>350° C.; TLC (5% MeOH in 50% EtOAc/CHCl3) Rf 0.32; 1H NMR (CDCl3) δ8.52 (d, J=2.2 Hz, 1 H), 8.00 (app d, 1 H), 7.62-7.74 (m, 3 H), 7.50-7.60 (m, 1H), 7.44 (d, J=8.8 Hz, 1 H), 7.08 (s, 1 H); IR (KBr) 1613, 1587, 1567, 1554, 1539, 1461, 1450 cm-1 ; MS (NH3), m/e (%) 288 (41, (37Cl M+H)+), 286 (100, (35Cl M+H)+). Anal. Calcd for C15H8ClNOS: C, 63.05; H, 2.82; N, 4.90. Found: C, 62.83; H, 2.51; N, 4.75.

後処理

  1. customin dry
  2. customat -15° C
  3. temperaturewas heated to reflux
  4. waitAfter 20 min
  5. stirringThe nearly homogeneous solution was stirred at 25° C. for an additional 5 min
  6. washwas washed with H2O (3×50 ml)
  7. extractionwere back - extracted with CHCl3
  8. additionthe combined organic layers were diluted with CHCl3 (200 ml) and MeOH (50 ml)
  9. dissolutionto dissolve
  10. customDrying
  11. concentration(MgSO4), concentration, and silica gel chromatography (CHCl3

出典と根拠

ORDレコード
ord-9bd539e62dfd4819b3f653750c8289bf
出典データセット
uspto-grants-1993_07
特許番号
US05225418

反応ノート

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