Carbon Dioxide → 2-(biphenyl-2-yl-hydrazono)-2-cyano-N-cyclopropylmethylacetamide

HRID 31091

Reaktionsgleichung

Reaktionsgleichung von HRID 31091
[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1.Cl.[N:15]([O-])=O.[Na+].[C:19]([CH2:21][C:22]([NH:24][CH2:25][CH:26]1[CH2:28][CH2:27]1)=[O:23])#[N:20].C([O-])(=O)C.[Na+].C(=O)([O-])[O-].[Na+].[Na+].C(=O)=O>C(O)(=O)C.O.C(O)C>[C:3]1([C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=2)[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=1[NH:1][N:15]=[C:21]([C:19]#[N:20])[C:22]([NH:24][CH2:25][CH:26]1[CH2:28][CH2:27]1)=[O:23]

Komponenten

11

Edukt 7

HCID 280Carbon DioxideHCID 313Hydrochloric AcidHCID 70152-AminobiphenylHCID 10340Sodium CarbonateHCID 517045Sodium AcetateHCID 27745962-cyano-N-(cyclopropylmethyl)acetamideHCID 23668193Sodium Nitrite

Produkt 1

HCID 866130972-(biphenyl-2-yl-hydrazono)-2-cyano-N-cyclopropylmethylacetamideAusbeute 36,1 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 176Acetic AcidLösungsmittelHCID 702EthanolLösungsmittelHCID 962WaterLösungsmittel5×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

To a stirred solution of 2-amino biphenyl (2.95 g, 17.4 mmol) in glacial acetic acid (16 mL) and water (14 mL) with cooling was added drop wise concentrated hydrochloric acid (10 mL). Additional water (10 mL) was added to maintain stirring. The mixture was cooled to 0° C. and a solution of sodium nitrite (1.44 g, 20.7 mmol) in water (10 mL) was added drop wise maintaining an internal temperature of <5° C. Upon complete addition, the reaction was stirred at 0° C. for 30 minutes, poured portion wise into a mechanically stirred 3-necked round bottomed flask charged with a predissolved solution of 2-cyano-N-cyclopropylmethylacetamide (2.8 g, 20.3 mmol), sodium acetate (12.0 g, 146 mmol), and sodium carbonate (12.8 g, 121 mmol) in 2:1 water: ethanol (180 mL). Vigorous CO2(g) evolution was observed. After 1 hour at 0° C., the reaction was diluted with water (200 mL) and extracted with ethyl acetate (400 mL). The organic layer was washed with water (200 mL) and brine (200 mL) and dried over sodium sulfate. The mixture was filtered, concentrated, and purified by recrystallization from ethyl acetate/hexanes to afford the title compound as a yellow solid (2.0 g, 36%). 1H NMR (500.133 MHz, CDCl3) δ 9.23 (t, J=5.3 Hz, 1H), 9.13 (bs, 1H), 8.43 (d, J=8.3 Hz, 1H), 8.17 (bs, 1H), 7.86 (d, J=7.2 Hz, 1H), 7.81 (t, J=7.6 Hz, 1H), 7.71 (d, J=7.5 Hz, 2H), 7.49 (t, J=7.2 Hz, 2H), 7.43 (t, J=7.2 Hz, 1H), 3.30 (s, 0H), 3.23 (t, J=6.1 Hz, 2H), 1.12 (septet, J=6.4 Hz, 1H), 0.45 (d, J=8.0 Hz, 2H), 0.29 (d, J=4.1 Hz, 2H). MS APCI, m/z=319 (M+H). HPLC 1.84 min.

Aufarbeitung

  1. temperatureto maintain
  2. temperaturewise maintaining an internal temperature of <5° C
  3. additionUpon complete addition
  4. stirringthe reaction was stirred at 0° C. for 30 minutes
  5. additionpoured portion wise into a mechanically stirred 3-necked round bottomed flask
  6. extractionextracted with ethyl acetate (400 mL)
  7. washThe organic layer was washed with water (200 mL) and brine (200 mL)
  8. dry with materialdried over sodium sulfate
  9. filtrationThe mixture was filtered
  10. concentrationconcentrated
  11. custompurified by recrystallization from ethyl acetate/hexanes

Quellen und Nachweise

ORD-Eintrag
ord-766d06147bcf4372b4e841009bf4f0c9
Quelldatensatz
uspto-grants-2008_09
Patentnummer
US07425556B2

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