Phenylhydrazine → HCID 58403372, compound

HRID 2369229Notes

Reaction equation

HRID 2369229 reaction equation
[C:1]1([NH:7]N)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[F:9][C:10]1[CH:18]=[C:17]2[C:13]([CH2:14][CH2:15][C:16]2=O)=[CH:12][CH:11]=1>C(O)C.C(O)(=O)C>[F:9][C:10]1[CH:18]=[C:17]2[C:13]([CH2:14][C:15]3[C:2]4[CH:3]=[CH:4][CH:5]=[CH:6][C:1]=4[NH:7][C:16]=32)=[CH:12][CH:11]=1

Participants

5

Reactant 2

HCID 7516PhenylhydrazineHCID 15194646-Fluoro-1-indanone

Product 1

HCID 58403372HCID 58403372, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidCatalystHCID 702EthanolSolvent

Conditions

Temperature
85 °C

Procedure

To a solution of phenyl hydrazine (1.32 mL, 13.32 mmol) and 6-fluoro-1-indanone (2.02 g, 13.46 mmol) in ethanol (7.6 mL) was added glacial acetic acid (3 drops). The solution was stirred at reflux (85° C.) for 17 minutes and cooled to room temperature. Upon cooling, white crystals precipitated out of solution. These crystals were collected by vacuum filtration and dissolved in isopropanol (23 mL). Sulfuric acid (36N, 1.51 mL) was added via syringe and the resulting solution was stirred at reflux (90° C.) for 18 hours and subsequently cooled to room temperature. The solution was then basified to pH 10 via addition of aqueous sodium hydroxide (2% by mass) resulting in the formation of precipitate. The solid was collected by vacuum filtration to yield 37b as a brown solid in 46% crude yield (1.38 g, 6.17 mmol). Crude product was brought on to the next step without further purification. For purposes of characterization, the product was purified by flash column chromatography (20:1 to 20:1.5 hexanes-ethyl acetate). 1H NMR (600 MHz, CDCl3): δ 8.26 (s, 1H), 7.64-7.65 (d, 1H, J=7.8 Hz), 7.42-7.44 (m, 2H), 7.20-7.23 (td, 1H, J=7.2, 1.2 Hz), 7.16-7.19 (td, J=7.2, 1.2 Hz) 7.12-7.14 (dd, 1H, J=8.4, 2.4 Hz), 6.88-6.91 (m, 1H), 3.68 (s, 1H); 13C NMR (150 MHz, CDCl3): δ 161.5-163.1 (d, J=242 Hz), 142.9 (d, J=2.4 Hz), 142.3 (d, J=2.9 Hz), 140.7, 136.5 (d, J=9.6 Hz), 126.0 (d, J=9.0 Hz), 124.5, 123.9, 122.3, 120.4, 119.2, 112.2, 111.0 (d, J=22.7 Hz), 104.8 (d, J=24.3 Hz), 29.8; FTIR: cm−1 3398, 1589, 1528, 1462, 1268, 1187, 744, 665. ESI-HRMS: Calcd. for C15H10FN+ [M]+: 223.0792. found 223.0792.

Workup

  1. temperaturecooled to room temperature
  2. temperatureUpon cooling
  3. customwhite crystals precipitated out of solution
  4. filtrationThese crystals were collected by vacuum filtration
  5. dissolutiondissolved in isopropanol (23 mL)
  6. additionSulfuric acid (36N, 1.51 mL) was added via syringe
  7. stirringthe resulting solution was stirred
  8. temperatureat reflux (90° C.) for 18 hours
  9. temperaturesubsequently cooled to room temperature
  10. additionThe solution was then basified to pH 10 via addition of aqueous sodium hydroxide (2% by mass)
  11. customresulting in the formation of precipitate
  12. filtrationThe solid was collected by vacuum filtration

Sources & evidence

ORD record
ord-83c9faa2e3b3449886155d20bdb8966e
Source dataset
uspto-grants-2014_04
Patent number
US08703936B2

Reaction notes

Loading…