Diethyl Ether → HCID 49855159, compound

HRID 1503133Notes

Reaction equation

HRID 1503133 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]2[C:10](=[CH:11][CH:12]=1)[NH:9][CH:8]=[C:7]2/[C:13](=[CH:16]/[C:17]1[CH:18]=[N:19][CH:20]=[CH:21][CH:22]=1)/[C:14]#[N:15])([O-])=O.[Cl-].[NH4+].C(OCC)C.CCCCCCC>C(O)C.[Zn]>[NH2:1][C:4]1[CH:5]=[C:6]2[C:10](=[CH:11][CH:12]=1)[NH:9][CH:8]=[C:7]2/[C:13](=[CH:16]/[C:17]1[CH:18]=[N:19][CH:20]=[CH:21][CH:22]=1)/[C:14]#[N:15]

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 8900HeptaneHCID 25517Ammonium ChlorideHCID 67514262HCID 67514262, compound

Product 1

HCID 49855159HCID 49855159, compound

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 702EthanolSolvent

Procedure

To a mixture of (Z)-2-(5-nitro-1H-indol-3-yl)-3-pyridin-3-yl-acrylonitrile (370 mg, 1.27 mmol, 1.0 eq.) in ethanol (40 mL) were added zinc powder (667 mg, 10.2 mmol, 8.0 eq.) and then, ammonium chloride (679 mg, 12.7 mmol, 10.0 eq.). The reaction mixture was stirred at room temperature for 30 minutes and filtered through a celite pad. The filtrate was concentrated under reduced pressure and partitioned between water and ethyl acetate. The organic layer was washed with brine, dried over MgSO4 and evaporated. The residue was purified by silica gel flash-column chromatography (eluent: CH2Cl2/EtOH, 96/4 to 94/6) to afford, after trituration with diethyl ether, the compound (40) as a orange solid (80 mg, 24%). IR νmax (cm−1): 2216 (νCN), 3340 (νN—H); 1H NMR (DMSO, 500 MHz) δ (ppm): 4.72 (2H, s, aniline H), 6.63 (1H, dd, J6′-7′=8.9 Hz, J6′-4′=2.4 Hz, H6′), 7.19 (1H, d, J7′-6′=8.9 Hz, H7′), 7.22 (1H, d, J4′-6′=2.4 Hz, H4′), 7.54 (1H, dd, J5″-4″=7.9 Hz, J5″-6″=4.8 Hz, H5″), 7.59 (1H, s, H3), 7.61 (1H, s, H2′), 8.29 (1H, d, J4″-5″=7.9 Hz, H4″), 8.57 (1H, d, J6″-5″=4.8 Hz, H6″), 8.93 (1H, s, H2″), 11.37 (1H, s, indolic H); 13C NMR (DMSO, 75.5 MHz) δ (ppm): 103.0 (C4′), 109.3 (C2), 109.9 (C3′), 113.2 (C6′), 113.4 (C7′), 118.5 (C1), 124.2 (C5″), 125.1 (C3a′), 127.1 (C2′), 130.9 (C3), 131.1 (C3″), 131.5 (C7a′), 134.7 (C4″), 143.7 (C5′), 149.8 (C6″), 150.2 (C2″); ESI-MS: m/z 261.1 ([M+H]+); HRESI-MS: m/z 261.1153 (calcd for C16H13N4+, 261.1140).

Workup

  1. filtrationfiltered through a celite pad
  2. concentrationThe filtrate was concentrated under reduced pressure
  3. custompartitioned between water and ethyl acetate
  4. washThe organic layer was washed with brine
  5. dry with materialdried over MgSO4
  6. customevaporated
  7. customThe residue was purified by silica gel flash-column chromatography (eluent: CH2Cl2/EtOH, 96/4 to 94/6)
  8. customto afford

Sources & evidence

ORD record
ord-8e8191afce94486a8774b01552a321bc
Source dataset
uspto-grants-2015_12
Patent number
US09212138B2

Reaction notes

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