Chloroform → 3-Cyano-2-(4-nitrophenylthio)-5-[2-(4-ethoxycarbonylphenyl)ethenyl]pyridine

HRID 231291

反応式

HRID 231291 の反応式
[Br-].[C:2]([C:4]1[C:5]([S:30][C:31]2[CH:36]=[CH:35][C:34]([N+:37]([O-:39])=[O:38])=[CH:33][CH:32]=2)=[N:6][CH:7]=[C:8]([CH2:10][P+](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[CH:9]=1)#[N:3].C(N(CC)CC)C.C(Cl)(Cl)Cl.[CH2:51]([O:53][C:54]([C:56]1[CH:63]=[CH:62][C:59]([CH:60]=O)=[CH:58][CH:57]=1)=[O:55])[CH3:52]>O>[C:2]([C:4]1[C:5]([S:30][C:31]2[CH:32]=[CH:33][C:34]([N+:37]([O-:39])=[O:38])=[CH:35][CH:36]=2)=[N:6][CH:7]=[C:8]([CH:10]=[CH:60][C:59]2[CH:58]=[CH:57][C:56]([C:54]([O:53][CH2:51][CH3:52])=[O:55])=[CH:63][CH:62]=2)[CH:9]=1)#[N:3]

参加物

6

反応物 4

HCID 6212ChloroformHCID 8471TriethylamineHCID 80498Ethyl 4-formylbenzoateHCID 19754088[3-Cyano-2-(4-nitrophenylthio)-5-pyridinylmethyl]triphenylphosphonium bromide

生成物 1

HCID 542227863-Cyano-2-(4-nitrophenylthio)-5-[2-(4-ethoxycarbonylphenyl)ethenyl]pyridine収率 88.1%

試薬・触媒・溶媒 1

HCID 962Water溶媒

実験手順

A mixture of 4.544 g (7.42 mmol) of [3-cyano-2-(4-nitrophenylthio)-5-pyridinylmethyl]triphenylphosphonium bromide, 0.751 g (7.42 mmol) of triethylamine and 50 mL of chloroform was stirred at room temperature for 15 minutes and 1.322 g (7.42 mmol) of 4-ethoxycarbonylbenzaldehyde then were added. After stirring at room temperature for 96 hours, 100 mL of water were added, the mixture was filtered, and the organic layer was separated and washed twice with 100 mL portions of water, dried and filtered. Evaporation of the filtrate under reduced pressure gave a residue which was chromatographed on silica gel. Unreacted aldehyde was eluted with 2:1 petroleum ether:benzene, while the title compound, alternatively named as 2-(4-nitrophenylthio)-3-cyano-5-(4-ethoxycarbonylstyryl)pyridine, was eluted with benzene. Evaporation of the benzene eluate gave 2.82 g (88%) of 3-cyano-2-(4-nitrophenylthio)-5-[2-(4-ethoxycarbonylphenyl)ethenyl]pyridine as a light yellow solid. The product turns from a solid to a gum below 100° C. and then to a clear liquid between 180 and 220° C.; NMR (Me2SO-d6) delta 1.34 (t, 3H, J=6.3 Hz), 4.32 (g, 2H, J=6.3 Hz), 6.73 (d, 1H, J=13 Hz), 6.99 (d, 1H, J=13 Hz), 7.27 (d, 2H, J=9 Hz), 7.74, 7.85, 7.94 (dd, 2H, 2H), 8.26, 8.31 (dd, 2H, 1H), 8.38 (d, 1H, J=1.8 Hz); IR (KBr) 2220, 1707, 1605, 1597, 1575, 1512, 1344, 1295-1277, 1174 cm31 1.

後処理

  1. stirringAfter stirring at room temperature for 96 hours
  2. filtrationthe mixture was filtered
  3. customthe organic layer was separated
  4. washwashed twice with 100 mL portions of water
  5. customdried
  6. filtrationfiltered
  7. customEvaporation of the filtrate under reduced pressure
  8. customgave a residue which
  9. customwas chromatographed on silica gel
  10. washwas eluted with 2:1 petroleum ether
  11. washwas eluted with benzene
  12. customEvaporation of the benzene eluate

出典と根拠

ORDレコード
ord-9a769e3fbced4e07aa8fa18117929cc1
出典データセット
uspto-grants-1989_07
特許番号
US04845216

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