1-Butanol → Dimethyl 4-cyano-4-(naphthalen-2-yl)heptanedioate

HRID 333283

反応式

HRID 333283 の反応式
[CH:1]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[CH:3][C:2]=1[CH2:11][C:12]#[N:13].[CH3:14][O:15][C:16](=[O:19])[CH:17]=[CH2:18].[CH2:20](O)CCC.C[CH2:26][O:27][C:28]([CH3:30])=[O:29].CCCCCCC>CO.[OH-].C([N+](CCCC)(CCCC)CCCC)CCC>[C:12]([C:11]([C:2]1[CH:3]=[CH:4][C:5]2[C:10](=[CH:9][CH:8]=[CH:7][CH:6]=2)[CH:1]=1)([CH2:20][CH2:30][C:28]([O:27][CH3:26])=[O:29])[CH2:18][CH2:17][C:16]([O:15][CH3:14])=[O:19])#[N:13]

参加物

7

反応物 4

HCID 2631-ButanolHCID 7294Methyl AcrylateHCID 820082-NaphthylacetonitrileHCID 21899848Ethylacetate heptane

生成物 1

HCID 58954823Dimethyl 4-cyano-4-(naphthalen-2-yl)heptanedioate

試薬・触媒・溶媒 2

HCID 2723671Tetrabutylammonium Hydroxide触媒HCID 887Methanol溶媒

反応条件

温度
70 °C

実験手順

A 3-L, three-necked flask equipped with a temperature probe, reflux condenser, addition funnel and overhead stirrer was charged with 2-naphthylacetonitrile (300 g, 1.79 mol), methylacrylate (600 mL, 6.65 mol) and tent-butanol (900 mL). A solution of tetrabutylammonium hydroxide (1 M; 75 mL, 75 mmol) in methanol was added slowly through an addition funnel over a period of 30 min (Note: Highly exothermic). The resulting clear solution was stirred at 70° C. for 2 h and assayed by TLC (3:7 EtOAc/Heptane; stained using Hanessian solution) and GC. The reaction mixture was cooled to room temperature before being concentrated under reduced pressure. The residue was partitioned between 2 M HCl (1 L) and MTBE (4 L). The phases were separated and the aqueous phase was extracted with MTBE (500 mL). The combined organic phases were washed with brine (1 L), dried over MgSO4, filtered and concentrated under reduced pressure at 40-45° C. to give a residue which was passed through a bed of silica (1:4 EtOAc/Heptane) to yield the title compound [569 g, 93%, 100% (AUC) by GC] as an off-white solid. 1H NMR (CDCl3, 300 MHz): δ 7.75 (2 d merged, 2H), 7.45 (dd, 1H), 3.5 (s, 6H), 2.4-2.2 (m, 6H), 2.15-1.98 (m, 2H).

後処理

  1. temperaturereflux
  2. additioncondenser, addition funnel and overhead stirrer
  3. temperatureThe reaction mixture was cooled to room temperature
  4. concentrationbefore being concentrated under reduced pressure
  5. customThe residue was partitioned between 2 M HCl (1 L) and MTBE (4 L)
  6. customThe phases were separated
  7. extractionthe aqueous phase was extracted with MTBE (500 mL)
  8. washThe combined organic phases were washed with brine (1 L)
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure at 40-45° C.
  12. customto give a residue which

出典と根拠

ORDレコード
ord-876dc529fee744e5895a1eaab76bc5ba
出典データセット
uspto-grants-2014_11
特許番号
US08877975B2

関連ノート

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