1,4-Dimethyl-3,6-dimethylenepiperazine-2,5-dione | 50501-00-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: 1,4-Dimethyl-3,6-dimethylenepiperazine-2,5-dione
• 英文别名: 1,4-dimethyl-3,6-dimethylene-2,5-dioxopiperazine；1,4-dimethyl-3,6-dimethylene-2,5-piperazinedione；1,4-dimethyl-3,6-dimethylene-piperazine-2,5-dione；1,4-Dimethyl-3,6-dimethylen-2,5-piperazindion；1,4-Dimethyl-3,6-dimethylidenepiperazine-2,5-dione
• CAS: 50501-00-3
• 化学式: C₈H₁₀N₂O₂
• 分子量: 166.18
• InChiKey: WLYWOEHSOIAOTQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  40.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,4-Dimethyl-3,6-dimethylenepiperazine-2,5-dione 生成 1,6-Dihydroxy-7,9-dimethyl-8,10-dioxo-3,4-dithia-7,9-diaza-bicyclo<4,2,2>decan
  参考文献：
  名称：

  Addition of Methanesulfenyl Chloride and Sulfur Chloride to 1,4-Dimethyl-3,6-dimethylene-2,5-piperazinedione and Substitution of the Adducts

  摘要：

  向 3,6-二亚甲基-(1a) 和 3,6-二苄基-1,4-二甲基-2,5-哌嗪二酮 (1b) 中加入甲磺酰氯或硫酰氯可得到 Markownikoff 产物。在 1a 中加入甲磺酰氯的过程在 1 小时内逐步进行，并产生了相应的 3,6-双（甲硫基亚甲基）衍生物的 (Z,Z)-、(Z,E)- 和 (E,E) - 异构体的混合物，同时氯化氢逐渐被消除。加合物中的 3,6- 二氯基团被水、乙硫醇和乙醇取代后，分别得到相应的羟基、乙硫基和乙氧基衍生物。用乙硫醇和硫化氢进行类似的取代，然后通气，分别得到 7,9 二甲基-1,6-双（甲硫基甲基）-8,10-二氧代-2,5-二硫杂-7,9-二氮杂双环[4,2,2]-癸烷和相应的 3,6-epitetrathio 衍生物。氯化硫与 1a 和 1b 以同样的方式反应，得到了一些 1,6-二取代-7,9-二甲基-8,10-二氧代-3,4-二硫杂-7,9-二氮杂双环[4,2,2]-癸烷。还描述了新化合物的质量碎片。

  DOI：

  10.1246/bcsj.47.1215
• 作为产物：
  描述：

  N-Methylalanin 在 溴 作用下， 生成 1,4-Dimethyl-3,6-dimethylenepiperazine-2,5-dione
  参考文献：
  名称：

  Herscheid, Jacobus D. M.; Scholten, Henk P. H.; Tijhuis, Marian W., Recueil des Travaux Chimiques des Pays-Bas, 1981, vol. 100, # 2, p. 73 - 78

  摘要：

  DOI：

文献信息

• The reaction of α- and ω-methylenelactams with nitrones. Influence of electronic and geometric factors on the stereoselectivity of their 1,3-dipolar cycloaddition
  作者：Séverinne Rigolet、Jean Marie Mélot、Joel Vébrel、Angèle Chiaroni、Claude Riche

  DOI：10.1039/b000129p

  日期：——

  Various four to six-membered ring α- and ω-methylenelactams 1–5 were reacted with nitrones 6 and afforded good yields of spiroadducts 7–12 through a regiospecific [3 + 2] cycloaddition. Owing to the creation of at least two new asymmetric centres, mixtures of diastereoisomers were usually obtained whose structures were established by two-dimensional NOESY experiments or X-ray crystallography. Among the dipolarophiles, 3-methyleneazetidin-2-ones 1 yielded adducts with a very high stereoselectivity. A similar behaviour was also observed with α-benzoylnitrone 6a as a 1,3-dipole. Electronic and geometric interactions of the reagents 1–5 and 6 in the course of the cycloaddition process were discussed in order to account for the experimental stereochemical outcomes.

  各种四到六元环的α-和ω-亚甲基内酰胺1–5与硝醇6反应，通过区域特异性[3 + 2]环加成反应获得了良好产率的螺环加成物7–12。由于形成了至少两个新的不对称中心，通常会得到包括邻异构体在内的混合物，其结构通过二维NOESY实验或X射线晶体学确定。在极性体中，3-亚甲基氮杂环丁烯-2-酮1产生的加成物具有非常高的立体选择性。用α-苯甲酰硝醇6a作为1,3-偶极体时，也观察到类似的行为。在环加成过程中，还讨论了试剂1–5和6的电子与几何相互作用，以解释实验的立体化学结果。
• Synthesis of sulfur-bridged piperazinediones by reaction of 3,6-dibromo-1,4-dimethyl-2,5-piperazinedione with<i>geminal</i>dithiols
  作者：Ananthachari Srinivasan、Aldean J. Kolar、Richard K. Olsen

  DOI：10.1002/jhet.5570180811

  日期：1981.12

  the 3,6-position with a geminal dithiol-bridging group. These sulfur-bridged piperazinediones formally represent derivatives of the 2,4-dithia-6,8-diaza-7,9-dioxobicyclo[3.2.2]nonane ring system. Attempts to transform these sulfur-bridged piperazinediones to 3,6-epidithiopiperazinediones by removal of the bridging group common to the sulfur functionality were unsuccessful. Studies also are reported of

  几个反应偕二硫醇与3,6-二溴-1,4-二甲基-2,5-哌嗪二酮在3,6-位被取代的良好的产率哌嗪衍生物，得到偕二硫醇桥接基团。这些硫桥联哌嗪二酮正式代表2,4-二硫-6,8-二氮杂-7,9-二氧代双环[3.2.2]壬烷环系统的衍生物。通过除去硫官能团共有的桥连基团，尝试将这些硫桥连的哌嗪二酮转化为3，6-表二硫代哌嗪二酮是不成功的。还报道了将硫代乙酸加到3，6-二亚甲基-2，5-哌嗪二酮中得到3，6-二乙酰硫基-3，6-二甲基-2，5-哌嗪二酮的研究。将3，6-二乙酰硫基衍生物转化为表硫基哌嗪二酮环系统，得到表二硫代哌嗪和表二硫代哌嗪二酮的混合物。
• SRINIVASAN, A.;KOLAR, A. J.;OLSEN, R. K., J. HETEROCYCL. CHEM., 1981, 18, N 8, 1545-1548
  作者：SRINIVASAN, A.、KOLAR, A. J.、OLSEN, R. K.

  DOI：——

  日期：——
• Herscheid, Jacobus D. M.; Scholten, Henk P. H.; Tijhuis, Marian W., Recueil des Travaux Chimiques des Pays-Bas, 1981, vol. 100, # 2, p. 73 - 78
  作者：Herscheid, Jacobus D. M.、Scholten, Henk P. H.、Tijhuis, Marian W.、Ottenheim, Harry C. J.

  DOI：——

  日期：——
• Addition of Methanesulfenyl Chloride and Sulfur Chloride to 1,4-Dimethyl-3,6-dimethylene-2,5-piperazinedione and Substitution of the Adducts
  作者：Juji Yoshimura、Yuichi Sugiyama、Kenji Matsunari、Hiroshi Nakamura

  DOI：10.1246/bcsj.47.1215

  日期：1974.5

  Addition of methanesulfenyl chloride or sulfur chloride to 3,6-dimethylene-(1a) and 3,6-dibenzylidene-1,4-dimethyl-2,5-piperazinediones (1b) gave the Markownikoff products. The addition of methanesulfenyl chloride to 1a proceeded stepwise within 1 hr, and gave a mixture of (Z,Z)-, (Z,E)-, and (E,E)-isomers of the corresponding 3,6-bis(methylthiomethylene) derivative, accompanied by gradual elimination of hydrogen chloride. 3,6-Di-chloro groups of the adduct were substituted with water, ethanethiol and ethanol to give the corresponding hydroxy, ethylthio, and ethoxy derivatives, respectively. A similar substitution with ethanedithiol and hydrogen sulfide followed by aeration gave 7,9-dimethyl-1,6-bis(methylthiomethyl)-8,10-dioxo-2,5-dithia-7,9-diazabicyclo[4,2,2]-decane and the corresponding 3,6-epitetrathio derivative, respectively. The same mode of reaction of sulfur chloride with 1a and 1b gave a few 1,6-disubstituted-7,9-dimethyl-8,10-dioxo-3,4-dithia-7,9-diazabicyclo[4,2,2]-decanes. Mass fragmentations of new compounds were also described.

  向 3,6-二亚甲基-(1a) 和 3,6-二苄基-1,4-二甲基-2,5-哌嗪二酮 (1b) 中加入甲磺酰氯或硫酰氯可得到 Markownikoff 产物。在 1a 中加入甲磺酰氯的过程在 1 小时内逐步进行，并产生了相应的 3,6-双（甲硫基亚甲基）衍生物的 (Z,Z)-、(Z,E)- 和 (E,E) - 异构体的混合物，同时氯化氢逐渐被消除。加合物中的 3,6- 二氯基团被水、乙硫醇和乙醇取代后，分别得到相应的羟基、乙硫基和乙氧基衍生物。用乙硫醇和硫化氢进行类似的取代，然后通气，分别得到 7,9 二甲基-1,6-双（甲硫基甲基）-8,10-二氧代-2,5-二硫杂-7,9-二氮杂双环[4,2,2]-癸烷和相应的 3,6-epitetrathio 衍生物。氯化硫与 1a 和 1b 以同样的方式反应，得到了一些 1,6-二取代-7,9-二甲基-8,10-二氧代-3,4-二硫杂-7,9-二氮杂双环[4,2,2]-癸烷。还描述了新化合物的质量碎片。