(+-)-alpha-Pinene → Tetraethyl-para-menthane-2,6-diyldiphosphonate

HRID 2052227笔记

反应方程式

HRID 2052227 反应方程式
[P:1]([OH:8])([O:5][CH2:6][CH3:7])[O:2][CH2:3][CH3:4].C(O[O:14][C:15]([CH3:18])(C)C)(C)(C)C.[CH3:19][C:20]1[CH:25]2[C:26]([CH3:28])([CH3:27])[CH:23]([CH2:24]2)[CH2:22][CH:21]=1>>[CH2:3]([O:2][P:1]([CH:21]1[CH2:22][CH:23]([CH:26]([CH3:27])[CH3:28])[CH2:24][CH:25]([P:1](=[O:5])([O:14][CH2:15][CH3:18])[O:2][CH2:3][CH3:4])[CH:20]1[CH3:19])(=[O:8])[O:5][CH2:6][CH3:7])[CH3:4]

参与物

4

反应物 3

HCID 6654(+-)-alpha-PineneHCID 8033二叔丁基过氧化物HCID 12977Ethyl phosphite, (C2H5O)2(OH)P2 次

产物 1

HCID 131711680Tetraethyl-para-menthane-2,6-diyldiphosphonate收率 70%

实验过程

To a 5-liter vessel equipped with a mechanical stirrer was added 863 ml (6.7 mol) of diethyl hydrogen phosphite (DEHP). The stirred DEHP was heated to 140° and then 12.3 ml (0.067 mol) of di-tertiary-butyl peroxide was added. Finally, α-pinene, 211 ml (1.3 mol), was added dropwise over a period of 10-30 minutes while the reaction temperture was maintained at 140°-150°. This mixture was heated for 5 hours at 140°, cooled at room temperature, and then distilled in vacuo to yield 54.2 g (0.2 mol; 15.4%) of diethyl para-menth-6-en-2-ylphosphonate, bp=180°-185° (1.2 mm), and 376.5 g (0.91 mol, 70.0%) of tetraethyl-para-menthane-2,6-diyldiphosphonate), bp=198° (0.4 mm). The NMR spectrum showed an A2B3 pattern corresponding to the ethyl groups at 4.12δ and 1.35δ along with the remainder of the proton signals between 2.5δ and 0.8δ.

后处理

  1. customTo a 5-liter vessel equipped with a mechanical stirrer
  2. temperaturewas maintained at 140°-150°
  3. temperatureThis mixture was heated for 5 hours at 140°
  4. distillationdistilled in vacuo

来源与证据

ORD记录
ord-3ae75d1f74d24e68972b2a3d1e0d8f74
来源数据集
uspto-grants-1980_01
专利号
US04183879

反应笔记

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