Acetonitrile → HCID 178465845, compound

HRID 585772Notes

Reaction equation

HRID 585772 reaction equation
C(OC(=O)/[C:7](/[C:26]#[N:27])=[CH:8]\[NH:9][C:10]1[CH:15]=[C:14]([O:16][CH2:17][CH3:18])[C:13]([N+:19]([O-:21])=[O:20])=[CH:12][C:11]=1[C:22]([O:24]C)=O)(C)(C)C.C(#N)C.C1CCN2C(=NCCC2)CC1>OS(C(F)(F)F)(=O)=O.CCOC(C)=O.CCCCCC>[CH2:17]([O:16][C:14]1[CH:15]=[C:10]2[C:11]([C:22]([OH:24])=[C:7]([C:26]#[N:27])[CH:8]=[N:9]2)=[CH:12][C:13]=1[N+:19]([O-:21])=[O:20])[CH3:18]

Participants

6

Reactant 3

HCID 6342AcetonitrileHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 69623041HCID 69623041, compound

Product 1

HCID 178465845HCID 178465845, compoundYield 70.4%

Reagents, catalysts & solvents 2

HCID 62406Trifluoromethanesulfonic acidCatalystHCID 21226206Ethyl acetate hexaneSolvent

Procedure

A 100-mL round-bottomed flask equipped with an overhead stirrer, a condenser and a thermocouple is charged with (Z)-2-Cyano-3-(5′-ethoxy-2′-methoxycarbonyl-4′-nitrophenyl)amino-2-propenoic acid t-butyl ester (2.5 g, 6.3 mmol) and acetonitrile (50 mL). The triflic acid (0.12 mL, 0.21 mmol) is added to the heterogeneous reaction medium. Upon disappearance of the starting material as evidenced by TLC (20% EtOAc/hexane), the DBU (4.0 mL, 4.25 mmol) is added to the reaction mixture. The reaction is then heated to reflux and monitored for completion (>95% by HPLC—Phenomenex 3 micron Phenyl-hexyl column (150×4.6 mm)). The reaction is then quenched with 10% HCl (100 mL) and diluted with water (400 mL). After stirring for 15 minutes at room temperature the suspension is filtered and the collected solid allowed to “air” dry. The collected solid is suspended in ethyl acetate (25 mL) at room temperature and filtered again and allowed to “air” dry. This procedure provides 1.15 g (70%) of the title compound as a beige solid that is >95% product by NMR integration. 1H NMR (300 MHz, DMSO-d6): 12.9 (s, 1H), 8.79 (s, 1H), 8.51 (s, 1H), 7.24 (s, 1H), 4.27 (q, J=7 Hz, 2H), 1.41 (t, J=7 Hz, 3H).

Workup

  1. customA 100-mL round-bottomed flask equipped with an overhead stirrer, a condenser
  2. temperatureThe reaction is then heated
  3. temperatureto reflux
  4. customThe reaction is then quenched with 10% HCl (100 mL)
  5. additiondiluted with water (400 mL)
  6. filtrationis filtered
  7. customdry
  8. customis suspended in ethyl acetate (25 mL) at room temperature
  9. filtrationfiltered again
  10. customdry

Sources & evidence

ORD record
ord-f226fe8f0ae14d279bb8682574fabb73
Source dataset
uspto-grants-2005_08
Patent number
US06933388B2

Reaction notes

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