2-[3-Cyano-4,5,5-trimethylfuran-2(5H)-ylidene]malononitrile → HCID 72536678, compound

HRID 1618875Notes

Reaction equation

HRID 1618875 reaction equation
[CH:1]12[CH2:8][CH:5]([CH2:6][CH2:7]1)[CH:4]1[CH:2]2[N:3]1[C:9]1[C:16]([F:17])=[C:15]([F:18])[C:12]([CH:13]=O)=[C:11]([F:19])[C:10]=1[F:20].[C:21]([C:23]1[C:24](=[C:31]([C:34]#[N:35])[C:32]#[N:33])[O:25][C:26]([CH3:30])([CH3:29])[C:27]=1[CH3:28])#[N:22]>C(O)(=O)C.N1C=CC=CC=1>[CH:5]12[CH2:8][CH:1]([CH2:7][CH2:6]1)[CH:2]1[CH:4]2[N:3]1[C:9]1[C:16]([F:17])=[C:15]([F:18])[C:12]([CH:13]=[CH:28][C:27]2[C:26]([CH3:29])([CH3:30])[O:25][C:24](=[C:31]([C:32]#[N:33])[C:34]#[N:35])[C:23]=2[C:21]#[N:22])=[C:11]([F:19])[C:10]=1[F:20]

Participants

5

Reactant 2

HCID 99903452-[3-Cyano-4,5,5-trimethylfuran-2(5H)-ylidene]malononitrileHCID 59180866HCID 59180866, compound

Product 1

HCID 72536678HCID 72536678, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidCatalystHCID 1049PyridineSolvent

Procedure

In a 100-mL round bottom flask with stirbar was added 4-(3-aza-tricyclo[3.2.1.02,4]oct-3-yl)-2,3,5,6-tetrafluoro-benzaldehyde (0.35 g, 1.23 mmol), 2-(3-cyano-4,5,5-trimethyl-5H-furan-2-ylidene)-malononitrile (0.39 g, 2 mmol), pyridine (5 mL) and acetic acid (several drops). The mixture was stirred under nitrogen at room temperature for 3 days. TLC showed that one red fluorescent product had formed as the main product. The reaction was stopped. The product mixture was poured into ice-water (500 mL) and vigorously stirred for 4 h. The crude products were extracted with CH2Cl2 (100 mL×5). The combined organic layer was dried over anhydrous MgSO4. After removing solvent, the crude organic product was adsorbed on silica gel, placed at the top of a silica column and eluted (hexane/EtOAc=2/1). Fraction containing only the first red fluorescent product were combined and concentrated to give a red solid, which was recrystallized from 1-propanol to give the final product as red needles. Mp 233° C. IR (neat): 2951, 2228, 1573, 1481, 1390, 1366, 1163, 1107, 983, 962 cm−1. 1H NMR (400 MHz, CDCl3): δ 7.64 (d, J=16.8 Hz, 1H), 7.23 (d, J=16.8 Hz, 1H), 2.70 (br s, 4H), 1.80 (s, 6H), 1.63-1.51 (m, 3H), 1.34-1.27 (m, 2H), 0.98-0.92 (m, 1H); 13C NMR (100 MHz, CDCl3): 176.4, 173.4, 148-139 (m), 132.5, 118.8 (t), 111.4, 110.6, 109.9, 97.6, 95.3 (m).

Workup

  1. customhad formed as the main product
  2. stirringvigorously stirred for 4 h
  3. extractionThe crude products were extracted with CH2Cl2 (100 mL×5)
  4. dry with materialThe combined organic layer was dried over anhydrous MgSO4
  5. customAfter removing solvent
  6. washeluted (hexane/EtOAc=2/1)
  7. additionFraction containing only the first red fluorescent product
  8. concentrationconcentrated
  9. customto give a red solid, which
  10. customwas recrystallized from 1-propanol

Sources & evidence

ORD record
ord-1be4be68871e4541a05f98f52ea92aac
Source dataset
uspto-grants-2014_07
Patent number
US08772048B2

Reaction notes

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