tert-Butyl cyanoacetate → HCID 69767014, compound

HRID 585771Notes

Reaction equation

HRID 585771 reaction equation
[CH3:1][O:2][C:3](=[O:17])[C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[C:7]([O:13][CH2:14][CH3:15])=[CH:6][C:5]=1[NH2:16].[CH3:18]OC(OC)N(C)C.[C:26]([O:30][C:31](=[O:35])[CH2:32][C:33]#[N:34])([CH3:29])([CH3:28])[CH3:27]>C(O)(C)(C)C>[C:26]([O:30][C:31](=[O:35])[C:32]([C:33]#[N:34])=[CH:18][NH:16][C:5]1[CH:6]=[C:7]([O:13][CH2:14][CH3:15])[C:8]([N+:10]([O-:12])=[O:11])=[CH:9][C:4]=1[C:3]([O:2][CH3:1])=[O:17])([CH3:29])([CH3:28])[CH3:27]

Participants

5

Reactant 3

HCID 70693tert-Butyl cyanoacetateHCID 78373Dimethylformamide dimethyl acetalHCID 69623052HCID 69623052, compound

Product 1

HCID 69767014HCID 69767014, compoundYield 100.1%

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Conditions

Temperature
28.5 °C

Procedure

A 3-L round-bottomed flask under N2 equipped with an overhead stirrer, a condenser and a thermocouple is charged with 2-amino-4-ethoxy-5-nitrobenzoic acid methyl ester (100 g, 0.416 mol) and N,N-dimethylformamide dimethyl acetal (59.5 g, 0.499 mol) and t-butanol (800 mL). The reaction mixture is heated to reflux for 1.5 h. The reaction mixture is cooled to 22 to 35° C. and the t-butylcyanoacetate (117 g, 0.832 mol) added. The reaction mixture is stirred at 20 to 30° C. for 2 h. The precipitate is collected by suction filtration, washed with heptane (500 mL), then dried to constant weight under reduced pressure (50 mm Hg)) at 45° C. overnight to provide the title compound as a off-white solid (162.9 g, 95% yield, >95% purity by HPLC). 1H NMR (300 MHz, DMSO-d6): 12.7 (d, J=12.9 Hz, 1H), 8.77 (d, J=12.9 Hz, 1H), 8.50 (s, 1H), 7.47 (s, 1H), 4.37 (q, J=7 Hz, 2H), 3.91 (s, 3H), 1.52 (s, 9H), 1.40 (t, J=7 Hz, 3H).

Workup

  1. customA 3-L round-bottomed flask under N2 equipped with an overhead stirrer, a condenser
  2. temperatureThe reaction mixture is heated
  3. temperatureto reflux for 1.5 h
  4. filtrationThe precipitate is collected by suction filtration
  5. washwashed with heptane (500 mL)
  6. customdried to constant weight under reduced pressure (50 mm Hg)) at 45° C. overnight

Sources & evidence

ORD record
ord-953f0c6b507f423cbc8d78f7f6606deb
Source dataset
uspto-grants-2005_08
Patent number
US06933388B2

Reaction notes

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