Ammonia → Ethyl imino(2-bromopyridin-5-yl)acetate

HRID 2288795Notes

Reaction equation

HRID 2288795 reaction equation
[C:1](Cl)(=[O:3])[CH3:2].[CH2:5]([OH:7])[CH3:6].[Br:8][C:9]1[CH:14]=[CH:13][C:12](CC#N)=[CH:11][N:10]=1.[NH3:18]>C(Cl)(Cl)Cl.CCOCC>[NH:18]=[C:6]([C:12]1[CH:13]=[CH:14][C:9]([Br:8])=[N:10][CH:11]=1)[C:5]([O:3][CH2:1][CH3:2])=[O:7]

Participants

7

Reactant 4

HCID 222AmmoniaHCID 702EthanolHCID 6367Acetyl chlorideHCID 177499762-(6-Bromopyridin-3-yl)acetonitrile

Product 1

HCID 53879744Ethyl imino(2-bromopyridin-5-yl)acetateYield 89%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6212ChloroformSolvent2×

Procedure

Under nitrogen, 299 mL (4.20 mol) of acetyl chloride was added dropwise to a solution of 299 mL (5.11 mol) of absolute ethanol and 400 mL of chloroform at 0° C. A solution of 72.0 g (370 mmol) of 2-bromo-5-cyanomethylpyridine from step 5 in 1100 mL of chloroform was added dropwise with stirring. Stirring was continued at 0° C. for 4 h and the reaction was allowed to come to ambient temperature overnight. The reaction was diluted with 2500 mL of anhydrous ether and stirring was continued for an additional 2 h. The precipitated imidate hydrochloride salt was collected by filtration in a glove bag under nitrogen and washed with anhydrous ether. Under nitrogen, a mechanically stirred suspension of this material in 3500 mL of anhydrous ether at -78° C. was treated with 36 g (2.1 mol) of anhydrous ammonia. The reaction was allowed to slowly warm to ambient temperature overnight and the ammonium chloride removed by filtration. The filtrate was concentrated in vacuo giving 78.7 g (89%) of crude ethyl imino(2-bromopyridin-5-yl)acetate as a brown oil: NMR (CDCl3) δ 1.29 (t, J=7 Hz, 3H), 3.51 (s, 2H), 4.13 (q, J=7 Hz, 2H), 7.43 (dd, J=8 and 2 Hz, 1H), 7.48 (d, J=8 Hz, 1H), 8.26 (d, J=2 Hz, 1H); MS (FAB) m/e (rel intensity) 245 (100), 243 (90), 217 (35), 215 (38), 200 (5), 198 (5).

Workup

  1. stirringStirring
  2. waitto come to ambient temperature overnight
  3. stirringstirring
  4. waitwas continued for an additional 2 h
  5. filtrationThe precipitated imidate hydrochloride salt was collected by filtration in a glove bag under nitrogen
  6. washwashed with anhydrous ether
  7. additionUnder nitrogen, a mechanically stirred suspension of this material in 3500 mL of anhydrous ether at -78° C.
  8. customthe ammonium chloride removed by filtration
  9. concentrationThe filtrate was concentrated in vacuo

Sources & evidence

ORD record
ord-32f124971e6f49c1ab20f1b28e4e7942
Source dataset
uspto-grants-2000_07
Patent number
US06090828

Reaction notes

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