(Z)-ethyl 3-(diethoxyphosphoryloxy)but-2-enoate | 2667-51-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (Z)-ethyl 3-(diethoxyphosphoryloxy)but-2-enoate
• 英文别名: 3-diethoxyphosphoryloxy-trans-crotonic acid ethyl ester；(Z)-3-Diaethoxyphosphoryloxy-crotonsaeure-aethylester；3-Diaethoxyphosphoryloxy-trans-crotonsaeure-aethylester；Phosphorsaeure-((Z)-2-aethoxycarbonyl-1-methyl-vinylester)-diaethylester；Diethyl phosphate 3-hydroxycrotonic acid, ethyl ester；ethyl (Z)-3-diethoxyphosphoryloxybut-2-enoate
• CAS: 2667-51-8
• 化学式: C₁₀H₁₉O₆P
• 分子量: 266.231
• InChiKey: JHCCEPMFFLZBLL-HJWRWDBZSA-N

物化性质

• 沸点：
  123-125 °C(Press: 1 Torr)
• 密度：
  1.139±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  17
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (Z)-ethyl 3-(diethoxyphosphoryloxy)but-2-enoate 在 二甲基二环氧乙烷 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 48.0h， 以98%的产率得到(2R,3R)-3-(Diethoxy-phosphoryloxy)-3-methyl-oxirane-2-carboxylic acid ethyl ester
  参考文献：
  名称：

  烯醇磷酸酯的二甲基二环氧乙烷环氧化

  摘要：

  通过在环境温度下用二甲基二环氧乙烷环氧化，可以轻松制备各种烯醇式磷酸酯的新型环氧化物。在室温下，这些不稳定的环氧化物重新排列成相应的α-二烷氧基次膦氧基取代的羰基产物3。

  DOI：

  10.1016/s0040-4039(00)97105-3
• 作为产物：
  描述：

  (E)-ethyl 3-(diethoxyphosphoryloxy)but-2-enoate 生成 (Z)-ethyl 3-(diethoxyphosphoryloxy)but-2-enoate
  参考文献：
  名称：

  异构的取代乙烯基磷酸酯为内吸性杀虫剂。

  摘要：

  DOI：

  10.1126/science.122.3170.597-a

文献信息

• Formation of trisubstituted buta-1,3-dienes and α,β-unsaturated ketones <i>via</i> the reaction of functionalized vinyl phosphates and vinyl phosphordiamidates with organometallic reagents
  作者：Petr Oeser、Jakub Koudelka、Hana Dvořáková、Tomáš Tobrman

  DOI：10.1039/d0ra07472a

  日期：——

  ester functional group with organometallic reagents. We found that the functionalized vinyl phosphates were smoothly converted into tri- and tetrasubstituted buta-1,3-dienes via the reaction with aryllithium reagents. Moreover, the vinyl phosphordiamidates were converted into α,β-unsaturated ketones using Grignard reagents. Based on the performed experiments, we proposed a reaction mechanism, which was

  我们研究了含有酯官能团的磷酸乙烯酯和二氨基磷酸乙烯酯与有机金属试剂的反应。我们发现功能化的磷酸乙烯酯通过与芳基锂试剂的反应顺利转化为三和四取代的 1,3-丁二烯。此外，使用格氏试剂将乙烯基磷二酰胺酯转化为α，β-不饱和酮。基于所进行的实验，我们提出了一种反应机理，并通过关键中间体的分离得到了证实。
• A general method of synthesis of functionalized Z-vinylic tellurides starting from β-dicarbonyl compounds
  作者：Rafael E Barrientos-Astigarraga、Priscila Castelani、Celso Y Sumida、Julio Zukerman-Schpector、João V Comasseto

  DOI：10.1016/s0040-4020(01)01204-2

  日期：2002.2

  Z-Vinylic tellurides are prepared by stereoselective vinylic substitution on Z/E mixtures of enolphosphates, acetates, tosylates and triflates by organotellurolates. The reaction is sensitive to the nature of the organotellurolate; the aromatic derivatives react slower than the aliphatic ones. The reaction time is not influenced by the nature of the leaving group.

  Z- Vinylic碲化物是通过在烯醇磷酸酯，乙酸酯，甲苯磺酸酯和三氟甲磺酸酯的Z / E混合物上通过立体立体乙烯基化合物进行立体选择性乙烯基取代而制得的。该反应对有机碲酸根的性质敏感。芳香族衍生物的反应比脂肪族衍生物慢。反应时间不受离去基团性质的影响。
• Synthesis of functionalized tri- and tetrasubstituted vinylic tellurides from enolphosphates through vinylic substitution by lithium butyltellurolate
  作者：R.E Barrientos-Astigarraga、P Castelani、C.Y Sumida、J.V Comasseto

  DOI：10.1016/s0040-4039(99)01633-0

  日期：1999.10

  Vinylic tellurides are precursors of important highly reactive vinylic organometallics (e.g. vinyl Li and Cu species). Herein we report that tri- and tetrasubstituted functionalized vinylic tellurides can be prepared from enolphosphates through a vinylic substitution by lithium butyltellurolate. Starting from mixtures of Z- and E-enolphosphates, only the Z-vinylic telluride is formed.

  乙烯基碲化物是重要的高反应性乙烯基有机金属（例如乙烯基Li和Cu物质）的前体。在本文中，我们报道可以通过烯丙基磷酸酯通过碲酸丁二酸锂的乙烯基取代来制备三和四取代的官能化的乙烯基碲化物。从Z-和E-烯醇磷酸酯的混合物开始，仅形成Z-乙烯基碲化物。
• Phosphorylation of ethyl acetoacetate and acetylacetone in the conditions of Todd-Atherton reaction
  作者：V. G. Kirakosyan、G. H. Minasyan、V. S. Hakobyan、M. H. Injikyan

  DOI：10.1134/s1070363212120183

  日期：2012.12

  The reaction of diethyl phosphite with ethyl acetoacetate and acetylacetone in the presence of carbon tetrachloride, 20% aqueous alkali, and triethylbutylammonium chloride (TEBAC) at 0–15°C followed by stirring for 3 h without cooling gave ethyl 3-(diethoxyphosphoryloxy)but-2-enoate I and 4-(diethoxyphosphoryloxy)-3-penten-2-one II in 63 and 70% yield, respectively. According to the H NMR data, compounds

  在四氯化碳、2​​0% 碱水溶液和三乙基丁基氯化铵 (TEBAC) 存在下，亚磷酸二乙酯与乙酰乙酸乙酯和乙酰丙酮在 0-15°C 下反应，然后在不冷却的情况下搅拌 3 小时，得到 3-(二乙氧基磷酰氧基)乙酯。 -2-enoate I 和 4-(二乙氧基磷酰氧基)-3-penten-2-one II 的产率分别为 63% 和 70%。根据 H NMR 数据，在化合物 I 的情况下，化合物 I 和 II 以 75:25 的比例和在化合物 II 的情况下以 85:15 的比例形成 Z，E-异构体的混合物。
• Stereochemistry in the Ene Reactions of Singlet Oxygen and Triazolinediones with Allylic Alcohols. A Mechanistic Comparison
  作者：Georgios Vassilikogiannakis、Manolis Stratakis、Michael Orfanopoulos、Christopher S. Foote

  DOI：10.1021/jo990258b

  日期：1999.5.1

  The ene reaction of singlet oxygen with (Z)-4-methylpent-3-en-2-ol-2,5,5,5-d(4) (1-OH-d4) in nonpolar solvents exhibits a 90% three diastereoselectivity in the adduct derived from the major syn perepoxide intermediate, but also a moderate three diastereoselectivity in the adduct derived from the minor anti perepoxide. Photooxygenation of 2,4-dimethylpent-3-en-2-ol (2) exhibits a significant solvent dependence in the syn/anti methyl stereoselectivity, with nonpolar solvents promoting syn methyl reactivity, while polar solvents promote anti methyl reactivity. These results are in agreement with a steering effect between hydroxyl and singlet oxygen in the rate-determining step of the reaction. N-Phenyltriazolinedione addition to the chiral allylic alcohol 4-methylpent-3-en-2-ol (1-OH) is highly three diastereoselective in nonpolar solvents, with a solvent dependent variation in the threo/erythro ene products. On the other hand, the nonfunctionalized chiral alkene 2,4-dimethyl-2-hexene (1-Et) exhibits poor diastereoselectivity. Reaction of PTAD with 1-OH-d4 in nonpolar solvents, exhibits a significant three diastereoselectivity from the syn aziridinium imide intermediate, and a moderate three diastereoselectivity from the anti intermediate. These results are consonant with a steering effect between the hydroxyl and the electrophile, as proposed in the case of singlet oxygen addition to allylic alcohols 1-OH and 2. In contrast to the analogous O-1(2) ene reaction, a solvent independent ratio syn/anti similar to 50/50 was found in the addition of MTAD to 2. The intermolecular kinetic isotope effect in the reaction of 2 with MTAD (k(H)/k(D) = 1.15 +/- 0.02), is consistent with formation of the intermediate in fast step, indicative that the steering effect during the formation of aziridium imide is not important in the reaction kinetics. This energetic profile is in contrast to triazolinedione addition to the secondary allylic alcohol 1-OH, where the high three selectivity and the slight inverse kinetic isotope effect of k(H)/k(D) = 0.98 +/- 0.02 are consonant with the formation of the intermediate in the rate-determining step. An explanation for the increased reactivity of the syn methyl in the addition of MTAD to 2 (similar to 50%) is offered.