Reaction #1869147

ord-817cd11527084050ab0e75f85e5e8e0a

Reaction equation

Cc1ccccc1C(C#N)=C1SC=CC1=NO
(3-(hydroxy)imino-3H-thiophen-2-ylidene)-(2-methylphenyl)-acetonitrile
CCCS(=O)(=O)Cl
propanesulfonyl chloride
O
water
CCN(CC)CC
triethylamine
CCCS(=O)(=O)ON=C1C=CSC1=C(C#N)c1ccccc1C
yellow crystals
Yield 70.0%
CCCS(=O)(=O)ON=C1C=CSC1=C(C#N)c1ccccc1C
(3-(propanesulfonyloxy)imino-3H-thiophen-2-ylidene)-(2-methylphenyl)-acetonitrile
Yield 70.0%

Conditions

Detailed conditions
See reaction.notes.procedure_details.

Workup

  1. 1
    TemperatureTo the solution cooled
  2. 2
    Otherexceed 10° C
  3. 3
    OtherThe organic layer was separated
  4. 4
    Washwashed with 150 g of water three times
  5. 5
    ConcentrationThe organic layer was concentrated in vacuum
  6. 6
    workup.ADDITIONMethanol was added to the
  7. 7
    Concentrationconcentrate for recrystallization
  8. 8
    Filtrationfollowed by filtration
  9. 9
    Otherdrying
  10. 10
    OtherThere were obtained crude yellow crystals
  11. 11
    OtherThe crude yellow crystals were purified by silica gel column chromatography (eluent, dichloromethane)
  12. 12
    ConcentrationThe elute was concentrated
  13. 13
    Otherfollowed by recrystallization from methanol, filtration
  14. 14
    Otherdrying

Procedure

In 490 g of tetrahydrofuran were dissolved 45 g (0.19 mol) of (3-(hydroxy)imino-3H-thiophen-2-ylidene)-(2-methylphenyl)-acetonitrile in Synthesis Example 1 and 27.0 g (0.19 mol) of commercially available propanesulfonyl chloride. To the solution cooled, 20.6 g (0.20 mol) of triethylamine was added dropwise such that the temperature might not exceed 10° C. The solution was allowed to ripen for 1 hour at room temperature, after which 150 g of water and 500 g of dichloromethane were added. The organic layer was separated, and washed with 150 g of water three times. The organic layer was concentrated in vacuum. Methanol was added to the concentrate for recrystallization, followed by filtration and drying. There were obtained crude yellow crystals. The crude yellow crystals were purified by silica gel column chromatography (eluent, dichloromethane). The elute was concentrated, followed by recrystallization from methanol, filtration and drying. There was obtained 77 g of yellow crystals (yield 70%).

Source

DOI: 10.6084/m9.figshare.5104873.v1Patent: US07498126B2uspto-grants-2009_03