Acetic Acid → 2-[1-(4-Nitrophenyl)ethylidene]malononitrile

HRID 32468

反応式

HRID 32468 の反応式
[CH3:1][C:2]([C:4]1[CH:9]=[CH:8][C:7]([N+:10]([O-:12])=[O:11])=[CH:6][CH:5]=1)=O.[CH2:13]([C:16]#[N:17])[C:14]#[N:15].C(O)(=O)C.C([O-])(=O)C.[NH4+]>C1(C)C=CC=CC=1.[Cl-].[Na+].O.C(OCC)(=O)C>[C:14]([C:13]([C:16]#[N:17])=[C:2]([C:4]1[CH:5]=[CH:6][C:7]([N+:10]([O-:12])=[O:11])=[CH:8][CH:9]=1)[CH3:1])#[N:15]

参加物

8

反応物 4

HCID 176Acetic AcidHCID 7487p-NitroacetophenoneHCID 8010MalononitrileHCID 517165Ammonium Acetate

生成物 1

HCID 110420862-[1-(4-Nitrophenyl)ethylidene]malononitrile

試薬・触媒・溶媒 3

HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒HCID 57417360Sodium chloride; water溶媒

実験手順

4Nitro acetophenone (2.0 g, 12.1 mmoles, 1 eq) and malonodinitrile (2.4 g, 36.3 mmoles, 3 eq) were dissolved in 20 mL of anhydrous toluene. To the solution were added glacial acetic acid (0.40 mL, 7.0 mmoles, 0.19 eq) and ammonium acetate (0.26 g, 3.3 mmoles, 0.09 eq). The system was heated to reflux using a Dean-Stark trap and a condenser. After 1 hour, the reaction mixture was cooled to room temperature and poured into brine (50 mL) and ethyl acetate (100 mL). The aqueous layer was washed with 3×10 mL ethyl acetate. The combined organic layers were washed with 50 mL brine, dried over anhydrous sodium sulfate and concentrated to dryness. The dark residue was partially purified using a silica plug (40% ethyl acetate-hexane) affording crude 1,1-dicyano-2-(4-nitrophenyl)-propene. The product was used as such in the next step. TLC (40% ethyl acetate-hexane)=0.61. LC-MS (m/e)=214.2 (MH+).

後処理

  1. temperatureThe system was heated
  2. temperatureto reflux
  3. washThe aqueous layer was washed with 3×10 mL ethyl acetate
  4. washThe combined organic layers were washed with 50 mL brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated to dryness
  7. customThe dark residue was partially purified

出典と根拠

ORDレコード
ord-6d008957c3f242c8bb72a9cb85c950bb
出典データセット
uspto-grants-2008_09
特許番号
US07427623B2

関連ノート

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