Phenylhydrazine → HCID 11183936, compound

HRID 2369227Notes

Reaction equation

HRID 2369227 reaction equation
[C:1]1([NH:7]N)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH3:9][O:10][C:11]1[CH:19]=[C:18]2[C:14]([CH2:15][CH2:16][C:17]2=O)=[CH:13][CH:12]=1.[OH-].[Na+]>C(O)C.C(O)(=O)C.C(OCC)(=O)C.O>[CH3:9][O:10][C:11]1[CH:19]=[C:18]2[C:14]([CH2:15][C:16]3[C:2]4[CH:3]=[CH:4][CH:5]=[CH:6][C:1]=4[NH:7][C:17]=32)=[CH:13][CH:12]=1

Participants

8

Reactant 3

HCID 7516PhenylhydrazineHCID 14798Sodium HydroxideHCID 3340366-Methoxy-1-Indanone

Product 1

HCID 11183936HCID 11183936, compound

Reagents, catalysts & solvents 4

HCID 176Acetic AcidCatalystHCID 702EthanolSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
85 °C

Procedure

To a solution of phenyl hydrazine (1.21 mL, 1.33 g, 12.3 mmol) and 6-methoxy-1-indanone (2.01 g, 12.4 mmol) in ethanol (20 mL) was added glacial acetic acid (4 drops). The solution was stirred at reflux (85° C.) for 15 minutes and cooled to room temperature. Upon cooling, pale yellow crystals precipitated out of solution. Crystals were collected via vacuum filtration and dissolved in isopropanol (41 mL). Sulfuric acid (36 N, 1.39 mL) was added via syringe and the resulting solution was stirred at reflux (90° C.) for 18 hours—some precipitate formed over the course of the reaction. Upon cooling to room temperature, the solution was basified to pH 10 with aqueous sodium hydroxide (2% by mass) resulting in the formation of additional precipitate. The solid was collected by vacuum filtration to yield a brown solid which was subsequently dissolved in ethyl acetate (10 mL), diluted with H2O (10 mL), and extracted 1×15 mL dichloromethane to remove excess water. The organic layers were combined, dried over anhydrous magnesium sulfate and concentrated to yield a brown solid in 61% crude yield (1.76 g, 7.50 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 hexanes—ethyl acetate). 1H NMR (600 MHz, CDCl3): δ 8.28 (s, 1H), 7.64-7.65 (d, 1H, J=7.2 Hz), 7.42-7.44 (m, 2H), 7.16-7.21 (qd, 2H, J=7.2, 1.2 Hz), 7.03-7.04 (d, 1H, J=2.4 Hz), 6.77-6.78 (dd, 1H, J=7.8, 2.4 Hz), 3.89 (s, 3H), 3.68 (s, 2H); 13C NMR (150 MHz, CDCl3): δ 159.0, 143.1, 140.6, 139.8, 136.1, 125.7, 124.8, 123.2, 121.8, 120.2, 119.0, 112.0, 109.9, 103.8, 55.6, 29.5. FTIR: cm−1 3390, 2934, 1609, 1577, 1528, 1467, 1274, 1251, 1037, 837, 745.: Calcd. for C16H14ON+ [M+H]+: 236.1070. found 263.1071.

Workup

  1. temperaturecooled to room temperature
  2. temperatureUpon cooling
  3. custompale yellow crystals precipitated out of solution
  4. filtrationCrystals were collected via vacuum filtration
  5. dissolutiondissolved in isopropanol (41 mL)
  6. additionSulfuric acid (36 N, 1.39 mL) was added via syringe
  7. stirringthe resulting solution was stirred
  8. temperatureat reflux (90° C.) for 18 hours—some precipitate
  9. customformed over the course of the reaction
  10. temperatureUpon cooling to room temperature
  11. customresulting in the formation of additional precipitate
  12. filtrationThe solid was collected by vacuum filtration
  13. customto yield a brown solid which
  14. extractionextracted 1×15 mL dichloromethane
  15. customto remove excess water
  16. dry with materialdried over anhydrous magnesium sulfate
  17. concentrationconcentrated
  18. customto yield a brown solid in 61% crude yield (1.76 g, 7.50 mmol)
  19. customCrude product was brought on to the next step without further purification
  20. customFor purposes of characterization, the product was purified by flash column chromatography (20:1 hexanes—ethyl acetate)

Sources & evidence

ORD record
ord-efde713f80c04e98b14466101168c016
Source dataset
uspto-grants-2014_04
Patent number
US08703936B2

Reaction notes

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