Hydrogen Sulfide → 3-Amino-2-cyano-3-ethoxypropenethioamide

HRID 1439319Notes

Reaction equation

HRID 1439319 reaction equation
[NH2:1][C:2]([O:8][CH2:9][CH3:10])=[C:3]([C:6]#[N:7])[C:4]#[N:5].C(N(CC)CC)C.[SH2:18]>N1C=CC=CC=1>[NH2:1][C:2]([O:8][CH2:9][CH3:10])=[C:3]([C:6]#[N:7])[C:4](=[S:18])[NH2:5]

Participants

5

Reactant 3

HCID 402Hydrogen SulfideHCID 8471TriethylamineHCID 263761[Amino(ethoxy)methylidene]propanedinitrile

Product 1

HCID 859268953-Amino-2-cyano-3-ethoxypropenethioamideYield 43.8%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

A mixture of 51.2 g of 3-amino-3-ethoxy-2-cyano-2-propenenitrile (above) and 37.8 g of triethylamine in 200 ml of pyridine was continuously stirred and heated to 70° while 60 g of gaseous hydrogen sulfide was bubbled in during 1.5 hours. Heating was continued at 65°-70° for 0.5 hour. Thin-layer chromatographic analysis indicated that no reaction had occurred. The mixture was heated overnight at 55° but still no reaction had occurred. An additional 150 ml of pyridine was added and the mixture was heated to 75°-80° while 17 g of hydrogen sulfide was bubbled in during 0.5 hour. Thin-layer chromatographic analysis indicated that a reaction had occurred, but was incomplete. An additional 18 g of hydrogen sulfide was added during 1 hour at 75°-80°; thin-layer chromatography indicated that the reaction was completed. The reaction mixture was evaporated to dryness under reduced pressure. The residue was recrystallized from ethanol to give a first crop of 28 g of 3-amino-2-cyano-3-ethoxypropenethioamide; m.p. 170°-171°. A second crop of 15 g of this product (m.p. 169°-171°) was obtained by diluting the mother liquor with ice-water. A small sample of crop I was recrystallized again from ethanol (charcoal) to give an analytical sample; m.p. 180°-181°. A total of 43.0 g of 3-amino-2-cyano-3-ethoxypropenethioamide was obtained. The nmr spectrum was consistent with the assigned structure.

Workup

  1. customwas bubbled in during 1.5 hours
  2. temperatureHeating
  3. temperatureThe mixture was heated overnight at 55°
  4. additionAn additional 150 ml of pyridine was added
  5. temperaturethe mixture was heated to 75°-80° while 17 g of hydrogen sulfide
  6. customwas bubbled in during 0.5 hour
  7. additionAn additional 18 g of hydrogen sulfide was added during 1 hour at 75°-80°
  8. customThe reaction mixture was evaporated to dryness under reduced pressure
  9. customThe residue was recrystallized from ethanol

Sources & evidence

ORD record
ord-53c5d1ccb8d34a71b40d746c41caed77
Source dataset
uspto-grants-1977_11
Patent number
US04059433

Reaction notes

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