Methanesulfonic Acid → 3-Amino-2-cyano-3-(ethylmethylamino)propenenitrile

HRID 616512Notes

Reaction equation

HRID 616512 reaction equation
[C:1]([C-:3]([C:6]#[N:7])[C:4]#[N:5])#[N:2].[K+].[CH2:9]([NH:11][CH3:12])[CH3:10].CS(O)(=O)=O>C(COC)OC>[NH2:2][C:1]([N:11]([CH2:9][CH3:10])[CH3:12])=[C:3]([C:6]#[N:7])[C:4]#[N:5]

Participants

5

Reactant 3

HCID 6395Methanesulfonic Acid2×HCID 12219N-MethylethylamineHCID 10964525Potassium Tricyanomethanide

Product 1

HCID 859420403-Amino-2-cyano-3-(ethylmethylamino)propenenitrileYield 57.4%

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent

Procedure

An attempted preparation by the method of Example VI, part C, was unsuccessful. Thus, a mixture of 129 g of potassium tricyanomethanide, 59 g of ethylmethylamine, and 2000 ml of dimethoxyethane was treated with 65 ml (96 g) of methanesulfonic acid added dropwise during 30 min. The reaction was mildly exothermic and solid formation was noted during addition of the methanesulfonic acid. The reaction mixture was heated under reflux for one hour and was allowed to stand two days at ambient temperature. The solids were removed by filtration and the filter cake was washed with toluene. The combined filtrate and washings were evaporated under reduced pressure. The residue was heated to 200° in an oven. The residue was removed from the oven and water was added immediately. The near boiling aqueous suspension was treated with charcoal and filtered through a mat of Filter-Aid® diatomaceous earth in a large, steam heated, Buchner funnel. The aqueous filtrate was allowed to cool, producing crystals. The crystals were collected by filtration, dried, and recrystallized from acetonitrile to yield 86 g of 3-amino-2-cyano-3-(ethylmethylamino)propenenitrile, mp 140°-141°. The ir spectrum was consistent with the assigned structure.

Workup

  1. customAn attempted preparation by the method of Example VI, part C
  2. additionadded dropwise during 30 min
  3. temperatureThe reaction mixture was heated
  4. temperatureunder reflux for one hour
  5. customThe solids were removed by filtration
  6. washthe filter cake was washed with toluene
  7. customThe combined filtrate and washings were evaporated under reduced pressure
  8. temperatureThe residue was heated to 200° in an oven
  9. customThe residue was removed from the oven and water
  10. additionwas added immediately
  11. additionwas treated with charcoal
  12. filtrationfiltered through a mat of Filter-Aid® diatomaceous earth in a large, steam
  13. temperatureheated
  14. temperatureto cool
  15. customproducing crystals
  16. filtrationThe crystals were collected by filtration
  17. customdried
  18. customrecrystallized from acetonitrile

Sources & evidence

ORD record
ord-d5259f22aff44ef592049366ea268342
Source dataset
uspto-grants-1978_02
Patent number
US04075001

Reaction notes

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