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

HRID 2375583

反応式

HRID 2375583 の反応式
[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]

参加物

11

反応物 7

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

生成物 1

HCID 866130972-(biphenyl-2-yl-hydrazono)-2-cyano-N-cyclopropylmethylacetamide収率 36.1%

試薬・触媒・溶媒 3

HCID 176Acetic Acid溶媒HCID 702Ethanol溶媒HCID 962Water溶媒5 回

反応条件

温度
0 °C

実験手順

To a stirred solution of 2-aminobiphenyl (2.95 g, 17.4 mmol) in glacial acetic acid (16 mL) and water (14 mL) with cooling was added dropwise concentrated hydrochloric acid (10mL). Additional water (10mL) 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 (10mL) was added dropwise maintaining an internal temperature of <5° C. Upon complete addition, the reaction was stirred at 0° C. for 30 minutes, poured portionwise 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.

後処理

  1. temperatureto maintain
  2. temperaturemaintaining an internal temperature of <5° C
  3. additionUpon complete addition
  4. stirringthe reaction was stirred at 0° C. for 30 minutes
  5. additionpoured portionwise 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

出典と根拠

ORDレコード
ord-7ece3439a995436e802bc318331ebe94
出典データセット
uspto-grants-2008_12
特許番号
US07465795B2

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