Ammonium formate → HCID 75968173, compound

HRID 2199361Notes

Reaction equation

HRID 2199361 reaction equation
[CH:1]([O-])=[O:2].[NH4+].[F:5][C:6]1[CH:27]=[CH:26][CH:25]=[CH:24][C:7]=1[CH:8]=[C:9]1[C:14](=[O:15])[C:13](=[CH:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=2[F:23])[CH2:12][NH:11][CH2:10]1>C(#N)C>[CH:1]([N:11]1[CH2:10][C:9](=[CH:8][C:7]2[CH:24]=[CH:25][CH:26]=[CH:27][C:6]=2[F:5])[C:14](=[O:15])[C:13](=[CH:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=2[F:23])[CH2:12]1)=[O:2]

Participants

4

Reactant 2

HCID 2723923Ammonium formateHCID 66993057HCID 66993057, compound

Product 1

HCID 75968173HCID 75968173, compoundYield 58.3%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

Compound 18 was synthesized by two methods. In the first method, acetic anhydride (3 ml) was added drop-wise to an ice-cold solution of compound 1 (300 mg, 0.96 mmol) in formic acid (6 ml), and the reaction mixture was stirred at room temperature for 16 h. The solvent was distilled-off under vacuum. The solid obtained was recrystallized from chloroform and hexanes to obtain 18 as a yellow solid (148 mg, 45% yield). In the second method, ammonium formate (121 mg, 1.92 mmol) was added to a solution of compound 1 (300 mg, 0.96 mmol) in dry acetonitrile. The mixture was refluxed for 24 h, before evaporating to dryness. The solid was recrystallized from methylene chloride and hexanes to obtain pure 18 as a yellow solid (190 mg, 57% yield). Rf (60:40 ethyl acetate:hexanes)=0.60. 1H NMR (400 MHz, CDCl3): δ 8.16 (s, 1H, CHO), 8.09, 8.06 (2s, 2H, C═CH), 7.60-7.22 (m, 8H, Ar—H), 4.87, 4.66 (2s, 4H). 13C NMR (100 MHz, CDCl3): δ 185.34, 162.14 (d, J=45.6), 160.95, 159.87 (d, J=45.9), 132.85, 132.19 (d, J=25.7), 131.12 (d, J=25.4), 130.78, 124.46 (d, J=3.1), 116.49 (d, J=22.1), 116.18 (d, J=22.3), 46.38 (d, J=5.4), 41.11 (d, J=5.2). ESI Mass calculated for C20H15F2NNaO2 (M+Na)+362.10. found 362.07.

Workup

  1. temperatureThe mixture was refluxed for 24 h
  2. custombefore evaporating to dryness
  3. customThe solid was recrystallized from methylene chloride and hexanes

Sources & evidence

ORD record
ord-c2eca7dc8b6f4a36be69a358b7fa27ee
Source dataset
uspto-grants-2016_06
Patent number
US09359196B2

Reaction notes

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