Dimethylformamide → 2-Chlorocyclohex-1-ene-1-carbonitrile

HRID 215743

反応式

HRID 215743 の反応式
O=P(Cl)(Cl)Cl.C[N:7]([CH:9]=O)C.[C:11]1(=O)[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12]1.[ClH:18].NO>O>[Cl:18][C:11]1[CH2:16][CH2:15][CH2:14][CH2:13][C:12]=1[C:9]#[N:7]

参加物

6

反応物 4

HCID 6228DimethylformamideHCID 7967CyclohexanoneHCID 24813Phosphorus oxychlorideHCID 443297Hydroxyamine hydrochloride

生成物 1

HCID 498409392-Chlorocyclohex-1-ene-1-carbonitrile収率 60.9%

試薬・触媒・溶媒 1

HCID 962Water溶媒

反応条件

温度
50 °C

実験手順

To a stirring solution of POCl3 (15.20 mL, 163 mmol) at 0° C. was added DMF (13.40 mL, 173 mmol) drop-wise. Monitoring internal temperature, cyclohexanone (10.60 mL, 102 mmol) was slowly added, keeping the temperature between 35 and 40° C. Upon complete addition, the reaction was heated to 50° C. and hydroxylamine hydrochloride (40 g, 576 mmol) was added in eight portions, cooling when necessary to control the exothermic reaction. Upon completing this addition, ice was added to the reaction, followed by water (400 mL), and the mixture resumed stirring for 1 h. Filtration afforded the desired product as a brown solid (8.8 g). Some substrates may require an aqueous work-up/extraction procedure if water solubility is too high. EtOAc is generally a good solvent for this extraction. MS: No signal. 1H NMR (400 MHz, CDCl3 δ ppm 2.47-2.36 (m, 2H), 2.34-2.25 (m, 2H), 1.78-1.67 (m, 1H), 1.67-1.58 (m, 1H).

後処理

  1. customthe temperature between 35 and 40° C
  2. additionUpon complete addition
  3. temperaturecooling when necessary
  4. customthe exothermic reaction
  5. additionthis addition, ice
  6. additionwas added to the reaction
  7. filtrationFiltration

出典と根拠

ORDレコード
ord-3ed87f4794ce40e882f23c7064c7d2c7
出典データセット
uspto-grants-2012_06
特許番号
US08193178B2

関連ノート

読み込み中…