Acetic Acid → N,N'-Bis(2-ethylphenyl)acetamidine

HRID 1033075Notes

Reaction equation

HRID 1033075 reaction equation
[CH2:1]([C:3]1[CH:9]=[CH:8][CH:7]=[CH:6][C:4]=1[NH2:5])[CH3:2].C(O[CH2:19][CH3:20])(OCC)(OCC)C.[C:21](O)(=O)[CH3:22]>>[CH2:1]([C:3]1[CH:9]=[CH:8][CH:7]=[CH:6][C:4]=1[NH:5][C:4](=[N:5][C:21]1[CH:22]=[CH:9][CH:8]=[CH:7][C:6]=1[CH2:19][CH3:20])[CH3:3])[CH3:2]

Participants

4

Reactant 3

HCID 176Acetic AcidHCID 113572-EthylanilineHCID 66221Triethyl orthoacetate

Product 1

HCID 15379807N,N'-Bis(2-ethylphenyl)acetamidineYield 53.7%

Conditions

Temperature
195 °C

Procedure

Following the procedure for Taylor and Ehrhart ((Taylor, E. C. et al., J. Org. Chem. 28:1108 (1963)), a stirred solution, under Nb 2, of 2-ethylaniline (2.14 g, 17.7 mmol), triethyl orthoacetate (1.37 g, 8.5 mmol) and glacial acetic acid (0.45 ml, 7.9 mmol) was refluxed at 95°-110° for 2.5 hours. The resulting clear light brown solution was heated (oil bath temperature was 195° C.) under vacuum (30 Mm Hg) and the volatile materials were recovered through a short distillation head. The brown oil residue was dissolved in 10 ml of diethyl ether then extracted with 10 ml of 0.6N sodium carbonate. The layers were separated and the aqueous layer was extracted with 2×10 ml of diethyl ether. The combined organic layers were dried (Na2SO4) and the solvent removed at reduced pressure to give 1.15 g of light brown solid. Distillation (bulb to bulb, 190°-200°/0.5 Mm) gave 1.13 g of light brown oil that solidified on standing. Crystallization from 20 ml of boiling petroleum ether gave 595 mg of white crystals, Mp 80°-82° C. Recrystallization of 421 mg from 2 ml of boiling petroleum ether gave 380 mg of white granular crystals Mp 80°-81.5° C.

Workup

  1. distillationthe volatile materials were recovered through a short distillation head
  2. dissolutionThe brown oil residue was dissolved in 10 ml of diethyl ether
  3. extractionthen extracted with 10 ml of 0.6N sodium carbonate
  4. customThe layers were separated
  5. extractionthe aqueous layer was extracted with 2×10 ml of diethyl ether
  6. dry with materialThe combined organic layers were dried (Na2SO4)
  7. customthe solvent removed at reduced pressure
  8. customto give 1.15 g of light brown solid
  9. distillationDistillation (bulb to bulb, 190°-200°/0.5 Mm)

Sources & evidence

ORD record
ord-4c1029427f004827a470568cb7edc1a0
Source dataset
uspto-grants-1994_05
Patent number
US05308869

Reaction notes

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