Formic Acid → HCID 21785499, compound

HRID 866288Notes

Reaction equation

HRID 866288 reaction equation
[NH2:1][CH:2]([CH3:15])[C:3]([N:5]([CH:12]([CH3:14])[CH3:13])[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)=[O:4].[CH:16](O)=O>C1(C)C=CC=CC=1>[N+:1]([CH:2]([CH3:15])[C:3]([N:5]([CH:12]([CH3:14])[CH3:13])[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)=[O:4])#[C-:16]

Participants

4

Reactant 2

HCID 284Formic AcidHCID 12603575HCID 12603575, compound

Product 1

HCID 21785499HCID 21785499, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
-10 °C

Procedure

α-amino-N-isopropylpropionanilide (88.5 g.) was mixed with 80 g. of concentrated formic acid, then heated at 125° C. for 2 hours. The temperature was lowered to 100° C. and toluene added. The mixture was then refluxed. Water and formic acid were removed azeotropically. Upon crystallization, the toluene solvent was removed and the residue, identified as N-isopropyl-2-formamido propionanilide, triturated with ether and filtered. The formamide, (23.4 g.), was dissolved in methylene chloride and 50.5 g. triethylamine added thereto. The clear solution was cooled to -10° C. and 22.8 g. POCl3 added. After stirring at below zero temperature for 15 minutes, excess 10% sodium carbonate solution was added, taking care that temperature did not exceed 20° C. The mixture was allowed to stir at ambient temperature briefly, then the layers were separated. The organic layer was washed with 100 ml 2% salt solution, dried over MgSO4, filtered and stripped. The oily residue was taken up in methylcyclohexane and stirred. The cyclohexane solution was decanted from the insoluble oil and cooled and scratched to produce a solid which was filtered and air-dried. Recrystallization from heptane provided 2-isocyano-N-isopropylpropionanilide melting at 47°-50° C.

Workup

  1. customwas lowered to 100° C.
  2. temperatureThe mixture was then refluxed
  3. customWater and formic acid were removed azeotropically
  4. customUpon crystallization
  5. customthe toluene solvent was removed
  6. customtriturated with ether
  7. filtrationfiltered
  8. dissolutionThe formamide, (23.4 g.), was dissolved in methylene chloride
  9. additiontriethylamine added
  10. additionPOCl3 added
  11. additionexcess 10% sodium carbonate solution was added
  12. customdid not exceed 20° C
  13. stirringto stir at ambient temperature briefly
  14. customthe layers were separated
  15. washThe organic layer was washed with 100 ml 2% salt solution
  16. dry with materialdried over MgSO4
  17. filtrationfiltered
  18. stirringstirred
  19. customThe cyclohexane solution was decanted from the insoluble oil
  20. temperaturecooled
  21. customto produce a solid which
  22. filtrationwas filtered
  23. customair-dried
  24. customRecrystallization from heptane

Sources & evidence

ORD record
ord-95b2db791bf244ee8986cff6ba188b5f
Source dataset
uspto-grants-1978_07
Patent number
US04098600

Reaction notes

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