Acetic Acid → 1-Cyano-1-isopropylsulphonyl-4-dimethylamino-1,3-butadiene

HRID 1591279Notes

Reaction equation

HRID 1591279 reaction equation
[CH3:1][N:2]([CH3:7])[CH:3]=[CH:4][CH:5]=O.[CH:8]([S:11]([CH2:14][C:15]#[N:16])(=[O:13])=[O:12])([CH3:10])[CH3:9].N1CCCCC1.C(O)(=O)C>C1(C)C=CC=CC=1.O>[C:15]([C:14]([S:11]([CH:8]([CH3:10])[CH3:9])(=[O:13])=[O:12])=[CH:5][CH:4]=[CH:3][N:2]([CH3:7])[CH3:1])#[N:16]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 8082PiperidineHCID 791253-(Dimethylamino)-2-propenalHCID 27785302-(Isopropylsulfonyl)acetonitrile

Product 1

HCID 545474291-Cyano-1-isopropylsulphonyl-4-dimethylamino-1,3-butadieneYield 67%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 1140TolueneSolvent

Procedure

3-Dimethylaminoacrolein (17 ml, 0.17 mol) and isopropylsulphonylacetonitrile (25 g, 0.17 mol) were dissolved in toluene (250 ml) and piperidine (1 ml) and acetic acid (2.5 ml) were then added. The solution was heated under reflux in a water separator until no more water was formed (about 3 hours). On cooling, crystals formed which were filtered off under suction and dried to give 26 g 1-cyano-1-isopropylsulphonyl-4-dimethylamino-1,3-butadiene as yellow-brown crystals, m.pt. 102°-104° C. The remaining toluene was then extracted with water (2×50 ml), dried over sodium sulphate and evaporated under vacuum to give about 15 g of a brown syrup. This was then purified over silica using ethyl acetate as eluant to give a further 8.8 g 1-cyano-1-isopropylsulphonyl-4-dimethylamino-1,3-butadiene crystals. Yield: 90.2% of the theoretical.

Workup

  1. temperatureThe solution was heated
  2. customwas formed (about 3 hours)
  3. temperatureOn cooling
  4. customcrystals formed which
  5. filtrationwere filtered off under suction
  6. customdried

Sources & evidence

ORD record
ord-62435d69f3964309a4b70612c050e545
Source dataset
uspto-grants-1993_04
Patent number
US05206372

Reaction notes

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