Chloroform → HCID 19800635, compound

HRID 1646438Notes

Reaction equation

HRID 1646438 reaction equation
[CH:1]([C:3]1[CH:7]=[CH:6][S:5][CH:4]=1)=[CH2:2].[CH:8]([C:11]([CH3:21])([N:14]1[C:18](=[O:19])[CH:17]=[CH:16][C:15]1=[O:20])[C:12]#[N:13])([CH3:10])[CH3:9].C(Cl)(Cl)Cl.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>O1CCOCC1>[CH:8]([C:11]([CH3:21])([N:14]1[C:18](=[O:19])[C:17]2[C:16](=[CH:2][CH:1]=[C:3]3[CH:7]=[CH:6][S:5][C:4]3=2)[C:15]1=[O:20])[C:12]#[N:13])([CH3:10])[CH3:9]

Participants

6

Reactant 4

HCID 6212ChloroformHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 108878533-VINYLTHIOPHENEHCID 13730721HCID 13730721, compound

Product 1

HCID 19800635HCID 19800635, compound

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Conditions

Temperature
50 °C

Procedure

A mixture of 3-vinylthiophene (10.0 g, 0.0908 mol), α-isopropyl-α-methyl-2,5-dioxo-3-pyrroline-1- acetonitrile (18.3 g, 0.0953 mol) and chloroform is stirred at 50° C. for 20 hours and at room temperature for one week. The mixture is concentrated in vacuo to give a yellow oil residue, which is column chromatographed on silica gel using methylene chloride as an eluent to afford a yellow oil. The oil is taken up in dioxane and treated with dichlorodicyano-p-benzoquinone, (17.2 g, 0.0760 mol), stirred for 21 hours at 100° C., cooled to 25° C. and filtered (the filter cake is washed once with benzene). The filtrate is concentrated in vacuo to give an orange semisolid residue. The residue is washed through neutral alumina with methylene chloride:hexanes (1:1) and flash chromatographed on silica gel using hexane:ethyl acetate (4:1) as an eluent to afford the title product as a pale yellow solid, 4.21 g (15.6%), mp 99°-107° C.

Workup

  1. concentrationThe mixture is concentrated in vacuo
  2. customto give a yellow oil residue, which
  3. customchromatographed on silica gel
  4. customto afford a yellow oil
  5. stirringstirred for 21 hours at 100° C.
  6. temperaturecooled to 25° C.
  7. filtrationfiltered (the filter cake
  8. washis washed once with benzene)
  9. concentrationThe filtrate is concentrated in vacuo
  10. customto give an orange semisolid residue
  11. washThe residue is washed through neutral alumina with methylene chloride:hexanes (1:1) and flash
  12. customchromatographed on silica gel

Sources & evidence

ORD record
ord-c6a0e982524841f99b497ffbb27e96d3
Source dataset
uspto-grants-1993_01
Patent number
US05180419

Reaction notes

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