2-(1,1-dimethylethyl)-5-methylene-1,3-dioxolan-4-one | 163921-31-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧戊环
• 英文名称: 2-(1,1-dimethylethyl)-5-methylene-1,3-dioxolan-4-one
• 英文别名: 2-tert-Butyl-5-methylene-1,3-dioxolane-4-one；2-tert-butyl-5-methylidene-1,3-dioxolan-4-one
• CAS: 163921-31-1
• 化学式: C₈H₁₂O₃
• 分子量: 156.181
• InChiKey: WSNGKBUHQKTUIH-UHFFFAOYSA-N

物化性质

• 沸点：
  269.4±29.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(1,1-dimethylethyl)-5-methylene-1,3-dioxolan-4-one 在 溴 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 5-(bromomethylidene)-2-tert-butyl-1,3-dioxolan-4-one
  参考文献：
  名称：

  Ag 2 CO 3促进的Pd催化的无环仲酰胺的烯基化反应合成叔酰胺

  摘要：

  使用[Pd 2（dba）3 ]，XantPhos和Ag 2 CO 3作为碱，开发了在温和的反应条件下由无环仲酰胺和溴丙烯酸酯制备叔烯酰胺的Pd催化方法。该反应通过立体定向金属介导的氧化插入机制发生。

  DOI：

  10.1021/acs.orglett.6b02305
• 作为产物：
  描述：

  (2S,5R)-2-tert-Butyl-5-phenylsulfanylmethyl-[1,3]dioxolan-4-one 在 间氯过氧苯甲酸 、 亚磷酸三乙酯 作用下， 以 二氯甲烷 、 苯 为溶剂， 生成 2-(1,1-dimethylethyl)-5-methylene-1,3-dioxolan-4-one
  参考文献：
  名称：

  2-烷基-5-亚甲基-1,3-二氧戊环-4-酮和2-烷基-3-酰基-5-亚甲基-1,3-恶唑烷-4-酮的合成及Diels-Alder反应：高度exo和非对映体选择性手性乙烯酮当量

  摘要：

  手性亲双烯体1-3发生高度exo和非对映体选择性Diels-Alder反应。的狄尔斯-阿尔德反应3也路易斯酸催化条件下是高度选择性的外型。

  DOI：

  10.1016/s0040-4039(00)70683-6

文献信息

• Process for producing optically active 2-norbornanone
  申请人：Kuraray Co., Ltd.

  公开号：US05498799A1

  公开（公告）日：1996-03-12

  An optically active 5-methylenedioxolan-4-one derivative is subjected to Diels-Alder reaction with cyclopentadiene, and the resulting Diels-Alder reaction product is hydrolyzed to convert it into an optically active 2-hydroxynorbornene-2-carboxylic acid, which is then subjected to catalytic hydrogenation to form an optically active 2-hydroxynorbornane-2-carboxylic acid. The hydroxycarboxylic acid is subjected to oxidative decarboxylation to obtain an optically active 2-norbornanone.

  一个具有光学活性的5-亚甲基二氧兰-4-酮衍生物被用于与环戊二烯进行Diels-Alder反应，产生的Diels-Alder反应产物被水解以转化为一个具有光学活性的2-羟基去氢莰烯-2-羧酸，然后经过催化加氢反应形成一个具有光学活性的2-羟基去氢莰烷-2-羧酸。羟基羧酸经过氧化脱羧反应得到一个具有光学活性的2-去氢莰酮。
• Direct Stereoselective β-Arylation of Enol Ethers by a Decarboxylative Heck-Type Reaction
  作者：Mahmoud Hachem、Cédric Schneider、Christophe Hoarau

  DOI：10.1002/ejoc.201901877

  日期：2020.4.16

  PdII‐catalyzed decarboxylative Heck coupling of α‐alkoxyacrylates with (hetero)aryl carboxylic acids for the stereocontrolled production of (Z)‐β‐heteroarylated vinyl ethers is reported. This methodology offers a rational and step‐economical route to the family of attractive β‐arylated α‐alkoxy α,β‐unsaturated carboxylates, which is a relevant class of building blocks with different applications.

  报道了Pd II催化的α-烷氧基丙烯酸酯与（杂）芳基羧酸的Heck偶联，用于立体控制（Z）-β-杂芳基化乙烯基醚的生产。这种方法为吸引人的β-芳基化α-烷氧基α，β-不饱和羧酸盐家族提供了一条合理，分步经济的途径，这是一类具有不同应用的重要组成部分。
• Some diastereoselective radical reactions of substituted 1,3-dioxolan-4-ones
  作者：Athelstan L.J. Beckwith、Christina L.L. Chai

  DOI：10.1016/s0040-4020(01)88012-1

  日期：1993.9

  The radical 3, generated (i) from reactions of 5-substituted 2-tert-butyl-1,3-dioxolan-4-ones with N-bromosuccinimide, (ii) from related bromo compounds by reaction with tributylstannane or with allyltributyltin, and (iii) by radical addition to 5-methylene-1,3-dioxolan-4-one, undergoes carbon-bromine, carbon-hydrogen, and carbon-carbon bond formation trans to the tert-butyl group with moderate to

  基团3，（i）由5-取代的2-叔丁基-1,3-二氧戊环-4-酮与N-溴代琥珀酰亚胺反应生成，（ii）由相关的溴化合物与三丁基锡烷或烯丙基三丁基锡反应生成，和（iii）通过自由基加成至5-亚甲基-1,3-二氧戊环-4-酮，进行碳-溴，碳-氢和碳-碳键的形成，以中等至高的非对映选择性转化为叔丁基。
• Enantioselective Syntheses of (−)- and (+)-Homocitric Acid Lactones
  作者：Gastón H. Rodríguez R、Jean-François Biellmann

  DOI：10.1021/jo951063g

  日期：1996.1.1

  Highly enantioselective syntheses of enantiomers of homocitric acid lactones (R)-5a and (S)-5b are described. Thermal Diels-Alder cycloadditions of 2a and 2b to 1,3-butadiene produced adducts 3a and 3b, respectively. Oxidative ozonolysis of latter adducts gave products 4a and 4b which after acid treatment afforded a mixture with 5a and 5b as major component. Acid lactones 5a and 5b were converted into

  描述了高柠檬酸内酯（R）-5a和（S）-5b的对映异构体的高度对映选择性的合成。2a和2b的热Diels-Alder环加成到1，3-丁二烯分别产生加合物3a和3b。后一种加合物的氧化臭氧分解得到产物4a和4b，其在酸处理后得到以5a和5b为主要成分的混合物。将酸性内酯5a和5b转化为其二甲基酯6a和6b，将其通过色谱法纯化。皂化后，将获得的产物结晶以产生（-）-和（+）-高纯酸内酯（（R）-5a和（S）-5b）。Diels-Alder加合物3a和3b的非对映体过量（de）通过乙二醇8a，8b和外消旋8的Mosher酯测定。内酯2a和2b的Diels-Alder环加成产物与1,3-丁二烯的非对映选择性为96％。
• 5-Methylene-1,3-dioxolan-4-one derivatives, process for their production, polymers of the derivatives, resist compositions, and pattern formation process
  申请人：——

  公开号：US20040248031A1

  公开（公告）日：2004-12-09

  The 5-methylene-1,3-dioxolan-4-one derivative of the present invention is represented by the formula (1) indicated below, and it is a novel monomer from which a homopolymer and a copolymer excellent in light transparency and heat stability are obtained. Moreover, the polymer obtained by (co)polymerizing a monomer composition comprising the derivative represented by the formula (1) indicated below is excellent in the resist performance such as sensitivity, resolution and dry etching resistance, and solubility in an organic solvent, also having little line edge roughness, and thus it is preferably used as a resin for a resist composition. 1 wherein R 1 represents a bridged cyclic hydrocarbon group containing 4 to 16 carbon atoms, or a linear or branched alkyl group containing 1 to 6 carbon atoms which has a bridged cyclic hydrocarbon group containing 4 to 16 carbon atoms as a substituent; R 2 represents a hydrogen atom, or a linear or branched alkyl group containing 1 to 6 carbon atoms; or R 1 and R 2 represent a bridged cyclic hydrocarbon group containing 4 to 16 carbon atoms together with the carbon atom to which they are bound, provided that the alkyl group and the bridged cyclic hydrocarbon group may have at least one substituent selected from a group consisting of a linear or branched alkyl group containing 1 to 6 carbon atoms which may be optionally substituted, a hydroxy group, a carboxy group, an acyl group containing 2 to 6 carbon atoms, an alkoxy group containing 1 to 6 carbon atoms, and a carboxy group esterified with an alcohol containing 1 to 6 carbon atoms.

  本发明的5-亚甲基-1,3-二氧杂环戊酮衍生物的化学式如下所示，是一种新型单体，可制备出具有优异光透明度和热稳定性的均聚物和共聚物。此外，通过聚合由下式表示的衍生物组成的单体混合物得到的聚合物具有优异的感光性、分辨率、干法蚀刻抗性和有机溶剂溶解性，同时具有较小的线边粗糙度，因此它可作为光刻胶组分的树脂。其中，R1代表含有4到16个碳原子的桥环烃基，或含有4到16个碳原子的桥环烃基作为取代基的线性或支链烷基，R2代表氢原子，或含有1到6个碳原子的线性或支链烷基，或R1和R2与它们所连接的碳原子一起代表含有4到16个碳原子的桥环烃基，前提是烷基和桥环烃基可以具有至少一个选自以下一组的取代基：含有1到6个碳原子的线性或支链烷基（可以选择性地被取代）、羟基、羧基、含有2到6个碳原子的酰基、含有1到6个碳原子的烷氧基和含有1到6个碳原子的醇酯化的羧基。