(4S)-1-methyl-4-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]-heptane | 96-08-2

• 物质功能分类: 有机原料 - 烃类化合物及其衍生物
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: (4S)-1-methyl-4-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]-heptane
• 英文别名: 1,2:8,9-diepoxy-p-menthane；S(–)-limonene diepoxide；(1Ξ,4S,8Ξ)-1,2;8,9-diepoxy-p-menthane；(1Ξ,4S,8Ξ)-1,2;8,9-Diepoxy-p-menthan；(4S)-1-methyl-4-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane
• CAS: 96-08-2
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: RBHIUNHSNSQJNG-KJTVYLTBSA-N

物化性质

• 沸点：
  237.18°C (rough estimate)
• 密度：
  0.9607 (rough estimate)
• LogP：
  0.663 (est)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  25.1
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 危险品标志：
  Xi
• 海关编码：
  2932999099
• 包装等级：
  Z01
• 安全说明：
  S26,S36/37/39
• 危险类别码：
  R36/37/38

制备方法与用途

用途：

• 环氧树脂中间体
• 食品包装材料涂层
• 光造型，用于制作医学模型
• 电子材料中间体
• 汽车底漆
• 高压电缆

反应信息

• 作为反应物：
  描述：

  (4S)-1-methyl-4-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]-heptane 在 1,2-二氯乙烷 sodium tetrahydroborate 、 copper(l) iodide 、 magnesium 作用下， 以 乙醇 为溶剂， 反应 4.75h， 生成
  参考文献：
  名称：

  Synthesis of (6s,1's)-(+)-hernandulcin, a sweetner, and its stereoisomers

  摘要：

  DOI：

  10.1016/s0040-4020(01)96071-5
• 作为产物：
  描述：

  (S)-(-)-柠檬烯 在 过氧化氢苯甲酰 、 氯仿 作用下， 生成 (4S)-1-methyl-4-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]-heptane
  参考文献：
  名称：

  Transport of Sewage-Contaminated Sediment in Northeastern Hamilton Harbour

  摘要：

  Dispersal patterns associated with sewage discharges from an STP outfall in northeastern Hamilton Harbour were obtained in 1992 and 1996 using coprostanol as a tracer. Both surveys revealed a distinctive shore-parallel pattern, characterized by a south-eastward trend and a second transport direction toward the northwest and southwest. As physical support for the tracer patterns, vertical profiles of currents near the outfall were monitored during four time periods from 1991 to 2000. Current data indicated the flow at the outfall was complicated; there was flow in all directions at all depths. However, the cumulative surface flow followed the prevailing wind (toward the east and northeast), while the bottom flow was approximately in opposition to the surface flow (to the west-northwest). Combining this circulation structure with the seasonal variation in buoyancy of the effluent discharge, the bi-directional transport pattern interpreted from the tracer distribution could be explained using a model in which the STP effluent plume was advected by local current at a position in the water column where the plume was stable. During January through August when the effluent was denser than ambient harbour water, it tended to be advected by flows lower in the water column moving the plume toward the north to west and into the central basin. During the rest of the year, it was lighter and more influenced by surface currents, which advected the plume onshore (toward the east and northeast) where it was deflected by shoreline geometry in a shore-parallel direction toward the southeast.

  DOI：

  10.1016/s0380-1330(02)70564-9

文献信息

• Substrate-Induced Diastereoselectivity in the Dimethyldioxirane Epoxidation of Simple Alkenes and Dienes
  作者：Amalia Asouti、Lazaros P. Hadjiarapoglou

  DOI：10.1055/s-2001-18751

  日期：——

  Various alkenes and dienes, such as (R)- or (S)-limonene 2, 2-carene 6, 3-carene 8, (R)-α-pinene 10, (S)-α-pinene 12, and endo-dicyclopentadiene 14 were transformed into the corresponding mono- and bis-epoxides by epoxidation with dimethyldioxirane (as an acetone solution). The selectivity observed in these epoxidations is explained by the assumption of hydrogen bonding between bridge protons and the dioxirane.

  各种烯烃和二烯烃，例如（R）-或（S）-柠檬烯2、2-蒈烯6、3-蒈烯8、（R）-α-蒎烯10、（S）-α-蒎烯12以及endo-二环戊二烯14，通过二甲基二氧杂环丙烷（以丙酮溶液形式）的环氧化反应，被转化为相应的单环氧和双环氧化合物。在这些环氧化过程中观察到的选择性可以通过桥连质子与二氧杂环丙烷之间氢键的假设来解释。
• Development of a lipase-mediated epoxidation process for monoterpenes in choline chloride-based deep eutectic solvents
  作者：Sumanth Ranganathan、Sandra Zeitlhofer、Volker Sieber

  DOI：10.1039/c7gc01127j

  日期：——

  Chemical syntheses in contemporary process industries today are predominantly conducted using organic solvents, which are potentially hazardous to humans and the environment alike.

  当代工业过程中的化学合成主要使用有机溶剂进行，这些溶剂对人类和环境都具有潜在危险。
• Catalytic Activity of Molybdenum(II) Complexes in Homogeneous and Heterogeneous Conditions
  作者：Maria Vasconcellos Dias、Marta S. Saraiva、Paula Ferreira、Maria José Calhorda

  DOI：10.1021/om501068q

  日期：2015.4.27

  significantly depend on the complex and the nature of the substrate. The general conclusions are (i) complex C1 has the highest activity; (ii) tungsten complexes C4 and C5 are more active than the molybdenum analogues; (iii) the immobilization of the catalysts improves the performance; and (iv) silica gel and the polyhedral oligomeric silsesquioxane supports modify the selectivity, leading to products

  新的配合物[MoBr（η 3 -C 3 H ^ 5）（CO）2（大号）2 ]（C1）和[MX 2（CO）3（大号）2 ]（M =钼（II），X = I （C2）； M ＝ Mo（II），X ＝ Br（C3）； M ＝ W（II），X ＝ I（C4）； M ＝ W（II），X ＝ Br（C5））通过反应合成2-氨基-1,3,4-噻二唑（的大号带）[MoBr（η 3 -C 3 H ^ 5）（CO）2（NCCH 3）2 ]（1），[MoI 2（CO）3（CH 3 CN）2 ]（M = Mo（2）; M = W（4））或[MoBr 2（CO）3（CH 3 CN）2 ]（M = Mo（3）; M = W（5））以2：1的比例。五个复合物固定在MCM-41，得到的材料MCM-CN（Ñ = 1 - 5），和C1也被固定化在硅胶（二氧化硅-C1）和在多面体低聚倍半硅氧烷（立方-C1）。配合物和材料已通过光
• Alumina-Catalyzed Epoxidation with Hydrogen Peroxide: Recycling Experiments and Activity of Sol-Gel Alumina
  作者：Renato G. Cesquini、Juliana M. de S. e Silva、Camile B. Woitiski、Dalmo Mandelli、Roberto Rinaldi、Ulf Schuchardt

  DOI：10.1002/1615-4169(200209)344:8<911::aid-adsc911>3.0.co;2-t

  日期：2002.9

  Commercial alumina looses some activity after the first epoxidation reaction of (S)-limonene with hydrogen peroxide, but maintains a good activity and a very high selectivity in the subsequent three reactions. After this its activity is strongly reduced, probably due to structural modifications. Aluminas obtained by sol-gel methods are normally less active than the commercial alumina. However, the use of monomeric

  在（S）-柠檬烯与过氧化氢的第一次环氧化反应后，商用氧化铝失去了一些活性，但在随后的三个反应中却保持了良好的活性和很高的选择性。此后，可能由于结构修饰而使其活性大大降低。通过溶胶-凝胶法获得的氧化铝通常比市售氧化铝活性低。然而，使用单体仲丁醇铝和草酸形成稳定的氧化铝中间相可以得到非常活泼的氧化铝，其以过氧化氢催化反应性较低的环己烯的环氧化，收率为98％。接近50％的活性氧被用在分子氧的形成中。
• A Cyclodextrin-Modified Ketoester for Stereoselective Epoxidation of Alkenes
  作者：Wing-Kei Chan、Wing-Yiu Yu、Chi-Ming Che、Man-Kin Wong

  DOI：10.1021/jo034296d

  日期：2003.8.1

  CD-substituted dioxirane, which can effect stereoselective alkene epoxidation. The 2-mediated (S)-alpha-terpineol epoxidations proceeded to give terpineol oxides in high yields, and the stereoselectivities (i.e., cis-/trans-epoxide ratio) decreased from 2.5:1 to 1:1.2 with increasing steric bulkiness of the terpenes. This steric-dependent stereoselectivity can be understood based on different binding

  通过将反应性酮部分共价连接到β-环糊精上来制备β-环糊精修饰的酮酸酯2。用Oxone作为末端氧化剂处理2会产生CD取代的二环氧乙烷，这可能会影响立体选择性烯烃环氧化。2介导的（S）-α-萜品醇环氧化反应继续以高收率提供萜品醇氧化物，并且随着其空间体积的增加，立体选择性（即顺式/反式环氧比）从2.5：1降低至1：1.2。萜烯。根据（1）H NMR滴定和2D ROESY实验，可以基于2 /萜烯包合物的不同结合几何形状来理解这种空间依赖性立体选择性。在乙腈水溶液中使用2作为催化剂（20-50 mol％），也可以实现苯乙烯的对映选择性环氧化，