(+/-)-(1S*,2R*,6S*,7R*)-4-Oxatricyclo<5.2.1.0^2,6>dec-8-en-3-one | 85718-44-1

• 物质功能分类: 有机原料 - 烃类化合物及其衍生物 - 环烃
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (+/-)-(1S*,2R*,6S*,7R*)-4-Oxatricyclo<5.2.1.0^2,6>dec-8-en-3-one
• 英文别名: 4-oxatricyclo[5.2.1.0^2,6]-8-decen-5-one；4-oxatricyclo[5.2.1.0 ^2,6]-8-decen-3-one；cis-4-Oxa-tricyclo[5.2.1.02.6]dec-8-en-3-one；4-oxatricylo[5.2.1.0^2,6]-8-decen-3-one；3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1(3H)-one；4-oxatricyclo[5.2.1.02,6]dec-8-en-3-one
• CAS: 85718-44-1
• 化学式: C₉H₁₀O₂
• 分子量: 150.177
• InChiKey: WOJWXGGCIZZKFQ-UHFFFAOYSA-N

物化性质

• 熔点：
  97-99 °C(Solv: ethyl acetate (141-78-6); cyclohexane (110-82-7))
• 沸点：
  301.3±41.0 °C(Predicted)
• 密度：
  1.248±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+/-)-(1S*,2R*,6S*,7R*)-4-Oxatricyclo<5.2.1.0^2,6>dec-8-en-3-one 在 sodium hydroxide 、 碘 、 碳酸氢钠 、 对甲苯磺酸 、 溶剂黄146 、 potassium iodide 、 锌 作用下， 以 甲醇 为溶剂， 反应 201.75h， 生成 (1SR,2RS,6SR,7RS)-4-oxatricyclo[5.2.1.0^2,6]dec-8-en-3-one
  参考文献：
  名称：

  Enzymatic resolution of norbor(NE)nylmethanols in organic media and an application to the synthesis of (+)- and (−)-endo-Norbornene lactone.

  摘要：

  The enzymatic resolution of some norbornene carboxylic acids, norbornenylmethanols and -methylamines was evaluated. The kinetic resolution of norbornyl- and norbornenylmethanols by Porcine Pancreatic Lipase (PPL)-catalyzed transesterification in methyl acetate as the solvent leads to corresponding acetates and remaining methanols both of high enantiomeric purity. A useful application is the synthesis of both enantiomers of endo-norbornene lactone 8n via transesterification of iodolactone 18. The influence of structural variations on the efficiency of the PPL-catalyzed resolution of lactone methanols 21, 23, 25 and 28, at the optimal reaction conditions established for iodolactone 18, was investigated.

  DOI：

  10.1016/s0040-4020(01)80984-4
• 作为产物：
  描述：

  3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride 在 sodium tetrahydroborate 作用下， 以66%的产率得到(+/-)-(1S*,2R*,6S*,7R*)-4-Oxatricyclo<5.2.1.0^2,6>dec-8-en-3-one
  参考文献：
  名称：

  Enzymatic resolution of norbor(NE)nylmethanols in organic media and an application to the synthesis of (+)- and (−)-endo-Norbornene lactone.

  摘要：

  The enzymatic resolution of some norbornene carboxylic acids, norbornenylmethanols and -methylamines was evaluated. The kinetic resolution of norbornyl- and norbornenylmethanols by Porcine Pancreatic Lipase (PPL)-catalyzed transesterification in methyl acetate as the solvent leads to corresponding acetates and remaining methanols both of high enantiomeric purity. A useful application is the synthesis of both enantiomers of endo-norbornene lactone 8n via transesterification of iodolactone 18. The influence of structural variations on the efficiency of the PPL-catalyzed resolution of lactone methanols 21, 23, 25 and 28, at the optimal reaction conditions established for iodolactone 18, was investigated.

  DOI：

  10.1016/s0040-4020(01)80984-4

文献信息

• Cationic Chiral Fluorinated Oxazaborolidines. More Potent, Second-Generation Catalysts for Highly Enantioselective Cycloaddition Reactions
  作者：Karla Mahender Reddy、Eswar Bhimireddy、Barla Thirupathi、Simon Breitler、Shunming Yu、E. J. Corey

  DOI：10.1021/jacs.6b00100

  日期：2016.2.24

  placement of fluorine substituents in the chiral ligand. This approach has led to a new, second-generation family of chiral oxazaborolidinium cationic species which can be used to effect many Diels-Alder reactions in >95% yield and >95% ee using catalyst loadings at the 1-2 mol % level. The easy recovery of the chiral ligand makes the application of these new catalysts especially attractive for large-scale

  手性配体与路易斯酸金属衍生物的配位是对映选择性亲电催化的一种有用策略，通常导致催化活性水平低于原始未络合化合物的催化活性水平。通过进一步将质子或强路易斯酸连接到复合物上进行活化提供了一种克服手性配体失活作用的方法。本文所述的研究表明，通过在手性配体中明智地放置氟取代基，可以进一步提高催化活性。这种方法产生了一个新的第二代手性 oxazaborolidinium 阳离子物种家族，使用 1-2 mol% 水平的催化剂负载量，该物种可用于以 >95% 的产率和 >95% 的 ee 进行许多 Diels-Alder 反应。
• Efficient and Selective Cu/Nitroxyl-Catalyzed Methods for Aerobic Oxidative Lactonization of Diols
  作者：Xiaomin Xie、Shannon S. Stahl

  DOI：10.1021/jacs.5b01036

  日期：2015.3.25

  unsymmetrical diols, whereas a Cu/TEMPO catalyst system (TEMPO = 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl) displays excellent chemo- and regioselectivity for the oxidation of less hindered unsymmetrical diols. These catalyst systems are compatible with all classes of alcohols (benzylic, allylic, aliphatic), mediate efficient lactonization of 1,4-, 1,5-, and some 1,6-diols, and tolerate diverse functional groups

  Cu/硝酰基催化剂已被鉴定为在使用环境空气作为氧化剂的温和反应条件下促进二醇的高效和选择性有氧氧化内酯化。反应的化学选择性和区域选择性可以通过改变硝酰基助催化剂的特性来调节。Cu/ABNO 催化剂体系 (ABNO = 9-氮杂双环 [3.3.1]nonan-N-oxyl) 与对称二醇和受阻不对称二醇表现出优异的反应性，而 Cu/TEMPO 催化剂体系 (TEMPO = 2,2,6, 6-四甲基-1-哌啶基-N-氧基）对受阻较小的不对称二醇的氧化显示出优异的化学和区域选择性。这些催化剂体系与所有类型的醇（苄醇、烯丙基、脂肪醇）相容，介导 1,4-、1,5- 和一些 1,6-二醇的有效内酯化，并耐受不同的官能团，
• Novel multicomponent oxidation catalyst and process for producing epoxy compound therewith
  申请人：Hori Yoji

  公开号：US20070117993A1

  公开（公告）日：2007-05-24

  A novel multicomponent oxidation catalyst that can be effectively used in, for example, an epoxidation reaction of olefins, etc., being inexpensive and high in versatility and that exhibits high catalytic activity; and a process for producing an epoxy compound through hydrogen peroxide oxidation of an olefin with the use of the multicomponent oxidation catalyst. There is provided a multicomponent oxidation catalyst comprising a tungsten compound, a quaternary ammonium salt, any of phosphoric acids and/or boric acids and a hydrogen sulfate salt. Further, there is provided a process for producing an epoxy compound, characterized in that an olefin is oxidized with hydrogen peroxide in the presence of the above multicomponent oxidation catalyst. The epoxy compound obtained by this process is useful as an intermediate of agricultural chemicals, medicines or the like, a raw material of various polymers, etc.

  提供一种新型多组分氧化催化剂，可有效用于烯烃的环氧化反应等，成本低廉、通用性高且具有高催化活性；以及通过使用多组分氧化催化剂进行烯烃的过氧化氢氧化反应制备环氧化合物的方法。提供一种多组分氧化催化剂，包括钨化合物、季铵盐、磷酸和/或硼酸中的任何一种以及氢硫酸盐。此外，提供一种制备环氧化合物的方法，其特征在于在上述多组分氧化催化剂的存在下，将烯烃与过氧化氢氧化。通过该方法获得的环氧化合物可用作农药、药品或其他中间体、各种聚合物等的原材料。
• ラクトン化合物の精製方法
  申请人：三菱ケミカル株式会社

  公开号：JP2021147374A

  公开（公告）日：2021-09-27

  【課題】環状酸無水物を還元反応させて得られる反応生成物からラクトン化合物を抽出した後、固体として回収する場合は容易に粉末化でき、固体として回収しない場合は次工程での反応温度を高くできるラクトン化合物の精製方法を提供する。【解決手段】下記式（１）で表される環状酸無水物を還元反応させて得られる反応生成物から下記式（２）で表されるラクトン化合物を、抽出溶媒により抽出して抽出液を得、前記抽出液に、沸点が１２０℃以上かつ前記抽出溶媒よりも高沸点の炭化水素系溶剤を添加し濃縮して前記抽出溶媒を前記炭化水素系溶剤に置換する、ラクトン化合物の精製方法。［化１］【選択図】なし

  【问题】提供从还原环状酸无水物得到的反应产物中提取内酯化合物的精制方法，该内酯化合物可以容易地收集为固体并粉末化，如果不作为固体收集，则可以提高内酯化合物在下一步反应中的反应温度。 【解决方案】从通过下式（1）表示的环状酸无水物还原反应产物中，提取通过下式（2）表示的内酯化合物，通过萃取剂进行萃取，得到萃取液。将沸点高于120℃并且比萃取剂更高的沸点的烷基溶剂添加到萃取液中，浓缩并置换萃取剂为烷基溶剂，从而精制内酯化合物。
• (Meth)acrylate esters, starting alcohols for the preparation thereof, processes for preparing both, polymers of the esters, chemically amplifiable resist compositions, and method for forming patterns
  申请人：——

  公开号：US20040063882A1

  公开（公告）日：2004-04-01

  The (meth)acrylate of the present invention is represented by the following formula (1). The (meth)acrylate can be produced by first producing a lactone by reducing an addition product obtained by the Diels-Alder reaction between 1,3-diene and maleic anhydride, and then hydrating the lactone to produce an alcohol followed by (meth)acrylation of the alcohol. A polymer produced by (co)polymerizing a monomer composition comprising the (meth)acrylate of the present invention is excellent in transparency, dry etching resistance, and solubility in organic solvents, and so it is preferably used as a resin for a chemically amplified resist composition. 1 wherein each of R 1 , R 2 , R 3 and R 4 represents a hydrogen atom, a methyl group or an ethyl group; either one of X 1 or X 2 represents a (meth)acryloyloxy group and the other represents a hydrogen atom; both A 1 and A 2 represent hydrogen atoms, or A 1 and A 2 form —O—, —CH 2 — or —CH 2 CH 2 —.

  本发明的（甲基）丙烯酸酯由以下公式（1）表示。可以通过首先通过还原1,3-二烯和马来酸酐之间的Diels-Alder反应得到的加成产物来制备内酯，然后水解内酯以产生醇，随后对醇进行（甲基）丙烯化来生产（甲基）丙烯酸酯。通过共聚合包含本发明的（甲基）丙烯酸酯的单体组成物制备的聚合物在透明度，干法蚀刻抗性和有机溶剂溶解性方面表现出色，因此最好将其用作化学放大抗蚀剂组合物的树脂。其中R1、R2、R3和R4中的每一个代表氢原子、甲基基团或乙基基团；X1或X2中的任意一个代表（甲基）丙烯酰氧基，另一个代表氢原子；A1和A2均表示氢原子，或A1和A2形成-O-，-CH2-或-CH2CH2-。