Acrylonitrile → HCID 86709314, compound

HRID 529392Notes

Reaction equation

HRID 529392 reaction equation
[NH2:1][C:2]1([CH2:18][OH:19])[C:15]2[CH:14]=[C:13]([Cl:16])[N:12]=[CH:11][C:10]=2[O:9][C:8]2[C:3]1=[CH:4][C:5]([Br:17])=[CH:6][CH:7]=2.C1COCC1.[C:25](#[N:28])[CH:26]=[CH2:27].[OH-].[Na+]>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.O>[NH2:1][C:2]1([CH2:18][O:19][CH2:27][CH2:26][C:25]#[N:28])[C:15]2[CH:14]=[C:13]([Cl:16])[N:12]=[CH:11][C:10]=2[O:9][C:8]2[C:3]1=[CH:4][C:5]([Br:17])=[CH:6][CH:7]=2

Participants

7

Reactant 4

HCID 7855AcrylonitrileHCID 8028TetrahydrofuranHCID 14798Sodium HydroxideHCID 58465926HCID 58465926, compound

Product 1

HCID 86709314HCID 86709314, compound

Reagents, catalysts & solvents 2

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 962WaterSolvent

Procedure

A 200-mL RBF was charged with (5-amino-7-bromo-3-chloro-5H-chromeno[2,3-c]pyridin-5-yl)methanol (5.416 g, 15.86 mmol), tetrabutylammonium hydrogen sulfate (0.269 g, 0.793 mmol), THF (79 mL), and acrylonitrile (5.22 mL, 79 mmol) to give a clear, brown solution. NaOH (2N aq.) (19.82 mL, 39.6 mmol) was added, and the resulting biphasic mixture was stirred for 4 h. The mixture was diluted with water (110 mL) and extracted with EtOAc (3×50 mL). The combined organic extracts were washed with water (100 mL), washed with brine, dried over sodium sulfate, filtered, and concentrated. The crude product was purified by chromatography on silica gel (0-100% EtOAc/Hexane) to afford 3-((5-amino-7-bromo-3-chloro-5H-chromeno[2,3-c]pyridin-5-yl)methoxy)propanenitrile. 1H NMR (400 MHz, DMSO-d6) δ=8.28 (d, J=0.4 Hz, 7 H), 7.98 (s, 7 H), 7.88 (d, J=0.4 Hz, 7 H), 7.50 (dd, J=2.5, 8.7 Hz, 8 H), 7.13 (d, J=8.7 Hz, 7 H), 3.61-3.48 (m, 2 H), 3.34 (t, J=6.0 Hz, 2 H), 2.95 (s, 2 H); MS m/z=394.0. Calc'd for C16H14BrClN3O2: 394.0.

Workup

  1. customto give a clear, brown solution
  2. extractionextracted with EtOAc (3×50 mL)
  3. washThe combined organic extracts were washed with water (100 mL)
  4. washwashed with brine
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe crude product was purified by chromatography on silica gel (0-100% EtOAc/Hexane)

Sources & evidence

ORD record
ord-0679e27f278a40deb4b9341cc63c6716
Source dataset
uspto-grants-2016_05
Patent number
US09346827B2

Reaction notes

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