Propionitrile → HCID 178449192, compound

HRID 236711Notes

Reaction equation

HRID 236711 reaction equation
[C:1]([NH:3][C:4](=[N:7][CH2:8][CH2:9][S:10][CH2:11][C:12]1[NH:16][CH:15]=[N:14][C:13]=1[CH3:17])SC)#[N:2].[CH2:18]([NH2:22])[C:19]#[C:20][CH3:21].C(#N)CC.NC(=N)S>>[C:1]([NH:3][C:4]([NH:7][CH2:8][CH2:9][S:10][CH2:11][C:12]1[NH:16][CH:15]=[N:14][C:13]=1[CH3:17])=[N:22][CH2:18][C:19]#[C:20][CH3:21])#[N:2]

Participants

5

Reactant 4

HCID 7854PropionitrileHCID 12599998But-2-yn-1-amineHCID 178503877HCID 178503877, compoundHCID 178513445HCID 178513445, compound

Product 1

HCID 178449192HCID 178449192, compound

Procedure

A mixture of N-cyano-N'-{2-[(4-methyl-5-imidazolyl)methylthio]ethyl}-S-methylisothiourea (3.00 g. 0.0111 mole) and 2-butyne-1-amine (3.07 g., 0.0445 mole) in 60 ml. of propionitrile was stirred at reflux for 40 hours. TLC assay of an aliquot of the reaction mixture showed a trace of the isothiourea starting material, so the mixture was refluxed for an additional 6 hours and then stirred at room temperature for 64 hours. The solvent (along with excess amine) was removed at reduced pressure and the residual gum was placed on silica gel (100-200 mesh) and eluted with a mixture of methylene chloride (97 parts) and methanol (3 parts). The middle fractions were combined and evaporated to give 1.81 g. of yellow gum. The gum was dissolved in 20 ml. of ethyl acetate and crystallized at -15° C. The resulting pale yellow solid (1.2 g.) was dissolved in 11 ml. of hot acetonitrile and recrystallized at -15° C.; yield 1.072 g., m.p. 128°-130° C.

Workup

  1. temperatureat reflux for 40 hours
  2. temperatureso the mixture was refluxed for an additional 6 hours
  3. customThe solvent (along with excess amine) was removed at reduced pressure
  4. washeluted with a mixture of methylene chloride (97 parts) and methanol (3 parts)
  5. customevaporated
  6. customto give 1.81 g
  7. dissolutionThe gum was dissolved in 20 ml
  8. customof ethyl acetate and crystallized at -15° C
  9. dissolutionThe resulting pale yellow solid (1.2 g.) was dissolved in 11 ml
  10. customof hot acetonitrile and recrystallized at -15° C.

Sources & evidence

ORD record
ord-1cfe63293357432baaaa5e42b0061178
Source dataset
uspto-grants-1979_06
Patent number
US04157347

Reaction notes

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