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

HRID 1651050Notes

Reaction equation

HRID 1651050 reaction equation
[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]

Participants

6

Reactant 4

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

Product 1

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

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

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 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 (q, 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 cm-1.

Workup

  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. washbenzene, while the title compound was eluted with benzene
  12. customEvaporation of the benzene eluate

Sources & evidence

ORD record
ord-5df4a988d30d4f00b99dd08ed667d5a2
Source dataset
uspto-grants-1990_05
Patent number
US04927828

Reaction notes

Loading…