Diethyl (cyanomethyl)phosphonate → tert-Butyl {3-[2-cyanovinyl]cyclohexyl}carbamate

HRID 712037ノート

反応式

HRID 712037 の反応式
CC(C)([O-])C.[K+].[C:7]([CH2:9]P(=O)(OCC)OCC)#[N:8].[CH:18]([CH:20]1[CH2:25][CH2:24][CH2:23][CH:22]([NH:26][C:27](=[O:33])[O:28][C:29]([CH3:32])([CH3:31])[CH3:30])[CH2:21]1)=O>O1CCCC1>[C:7]([CH:9]=[CH:18][CH:20]1[CH2:25][CH2:24][CH2:23][CH:22]([NH:26][C:27](=[O:33])[O:28][C:29]([CH3:32])([CH3:31])[CH3:30])[CH2:21]1)#[N:8]

参加物

5

反応物 3

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 23665647Potassium tert-butoxideHCID 86717490tert-Butyl N-(3-formylcyclohexyl)carbamate

生成物 1

HCID 86717491tert-Butyl {3-[2-cyanovinyl]cyclohexyl}carbamate

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
0 °C

実験手順

To 1.0 M potassium tert-butoxide in THF (2.0 mL, 2.0 mmol) was added diethyl cyanomethylphosphonate (0.30 mL, 1.8 mmol) dropwise at 0° C. and the mixture was stirred at 0° C. for 1 h. A solution of tert-butyl (3-formylcyclohexyl)carbamate (0.30 g, 1.3 mmol) in tetrahydrofuran (9.3 mL) was added dropwise, then cooling bath was removed, and the mixture was stirred at room temperature overnight. The mixture was diluted with EtOAc, washed with water, concentrated and purified on silica gel column (eluting with 0-30% EtOAc in hexanes) to give the desired product as a mixture of cis- and trans-isomer mixtures (0.12 g, 36%). LCMS calculated for C14H22N2O2Na (M+Na)+: m/z=273.2. Found: 273.1.

後処理

  1. temperaturecooling bath
  2. customwas removed
  3. stirringthe mixture was stirred at room temperature overnight
  4. additionThe mixture was diluted with EtOAc
  5. washwashed with water
  6. concentrationconcentrated
  7. custompurified on silica gel column (eluting with 0-30% EtOAc in hexanes)

出典と根拠

ORDレコード
ord-a7ef6578c94145b298ec38ddc04e0045
出典データセット
uspto-grants-2015_11
特許番号
US09181271B2

反応ノート

読み込み中…