β-carbomethoxy-γ,γ-dimethyl-γ-butyrolactone | 6934-77-6

• 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: β-carbomethoxy-γ,γ-dimethyl-γ-butyrolactone
• 英文别名: methyl 2,2-dimethyl-5-oxotetrahydro-3-furancarboxylate；methyl 2,2-dimethyl-5-oxotetrahydrofuran-3-carboxylate；methyl terebate；Terebinsaeure-methylester；2,2-dimethyl-5-oxo-tetrahydro-furan-3-carboxylic acid methyl ester；2,2-Dimethyl-5-oxo-tetrahydro-furan-3-carbonsaeure-methylester；Methyl 2,2-dimethyl-5-oxooxolane-3-carboxylate
• CAS: 6934-77-6
• 化学式: C₈H₁₂O₄
• 分子量: 172.181
• InChiKey: GOMCUGUMABBDRH-UHFFFAOYSA-N

物化性质

• 沸点：
  148-149 °C(Press: 17 Torr)
• 密度：
  1.130±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  β-carbomethoxy-γ,γ-dimethyl-γ-butyrolactone 在 horse liver acetone 作用下， 以 phosphate buffer 为溶剂， 生成 methyl (+)-(R)-2,2-dimethyl-5-oxotetrahydro-3-furancarboxylate 、 (-)-(S)-2,2-dimethyl-5-oxotetrahydro-3-furancarboxylic acid 、 (3R)-2,2-二甲基-5-氧代四氢-3-呋喃羧酸 、 methyl (-)-(S)-2,2-dimethyl-5-oxotetrahydro-3-furancarboxylate
  参考文献：
  名称：

  化学酶促合成对映体富集的5-氧代-四氢-3-呋喃羧酸衍生物

  摘要：

  通过消旋的外消旋物，获得（ee）范围为60％至92％的（R）-（+）-对ac酸4，（S）-（-）-对苯二甲酸6及其相应的甲酯和乙酯。外消旋的γ-甲基对羟基苯甲酸乙酯14a和14b的酶解可分离未反应的酯（2 R，3 R）-（+）- 14a和内酯酸（2 S，3 R）-（-）- 5b的ee分别为80％和93％ee，前者使用马肝丙酮粉（HLAP），后者使用α-胰凝乳蛋白酶（α-CT）。对映体乙基（2通过面包酵母的乙酰丁二酸二乙酯的还原反应，获得了ee> 99％的S，3 S）-（-）- 14a和（2 S，3 R）-（-）- 14b。

  DOI：

  10.1016/j.tetasy.2004.01.001
• 作为产物：
  描述：

  methyl 5-hydroxy-5-(methoxymethyl)-2,2-dimethyltetrahydrofuran-3-carboxylate 在 ammonium cerium (IV) nitrate 作用下， 以 水 、 乙腈 为溶剂， 反应 1.0h， 生成 β-carbomethoxy-γ,γ-dimethyl-γ-butyrolactone
  参考文献：
  名称：

  通过CAN介导的半胱氨酸的氧化裂解形成γ-内酯。

  摘要：

  取代的γ-内酯的产生可通过应用串联扩链​​-醛醇缩合反应，然后通过CAN介导的醛醇缩合产物的氧化裂解来完成。氧化裂解需要中间分子和α-杂原子的存在。通过氧化裂解形成γ-内酯可用于指定醛醇缩合反应的立体化学，并用作天然产物菜豆酸家族成员的短合成的最后一步。

  DOI：

  10.1021/jo801258h

文献信息

• Sunlight-induced C C bond formation reaction: Radical addition of alcohols/ethers/acetals to olefins
  作者：Mamiko Hayakawa、Hisashi Shirota、Souta Hirayama、Ryuusei Yamada、Tadashi Aoyama、Akihiko Ouchi

  DOI：10.1016/j.jphotochem.2021.113263

  日期：2021.5

  sunlight-induced CC bond formation reactions upon the addition of alcohols/ethers/acetals to olefins proceeded efficiently using di-tert-butyl peroxide (DTBP). The reactions proceeded faster than many of the previously reported sunlight and many conventional lamp photolyses, typically in 3–4 h under irradiation with sunlight, in excellent yield using olefins bearing two electron withdrawing groups (EWGs)

  使用过氧化二叔丁基（DTBP），在将醇/醚/缩醛添加至烯烃后，由阳光引起的C C键形成反应得以有效进行。该反应比许多以前报道的日光和许多常规灯的光解反应进行得更快，通常在日光照射下3-4小时内，使用带有两个吸电子基团（EWG）的烯烃（产品收率> 95％）和带有一个EWG的烯烃的收率好到中等。与使用传统的Xe灯作为光源所获得的产品相比，某些产品的观察到的产率高出约20％，这被证实是由于光强度效应所致。克级实验显示的收率与其相应的小规模实验中观察到的收率相似。
• Photoorganocatalytic synthesis of lactones via a selective C–H activation–alkylation of alcohols
  作者：Nikolaos Kaplaneris、Aikaterini Bisticha、Giorgos N. Papadopoulos、Dimitris Limnios、Christoforos G. Kokotos

  DOI：10.1039/c7gc01903c

  日期：——

  Selective C–H activation is an area of growing importance in modern organic chemistry. Herein, we report our efforts in combining organocatalysis and photocatalysis for the development of a highly efficient and selective visible-light mediated protocol for the C–H activation and addition of various alcohols to a plethora of Michael acceptors, followed by a cyclization reaction leading to lactones,

  选择性C–H活化是现代有机化学中日益重要的一个领域。在此，我们报告了我们在有机催化和光催化相结合方面的努力，以开发高效且选择性的可见光介导的C–H活化方案，并向大量Michael受体添加各种醇，然后进行环化反应，内酯，自然界中反复出现的基序。我们使用苯乙醛酸作为光催化剂，并用普通的家用灯泡作为光源，我们描述了醇与α，β-不饱和酯的多用途α-烷基化/内酯化，可产生高收率的产品。反应机理得到了广泛的研究。
• NEW ZINC PROMOTED SYNTHETIC REACTION OF γ-BUTYROLACTONE DERIVATIVES
  作者：Tatsuya Shono、Hiroshi Hamaguchi、Ikuzo Nishiguchi、Manji Sasaki、Tetsuya Miyamoto、Masatoshi Miyamoto、Shumei Fujita

  DOI：10.1246/cl.1981.1217

  日期：1981.9.5

  Some γ-butyrolactone derivatives have been synthesized by the reaction of dimethyl maleate with carbonyl compounds in the presence of active zinc compound.

  一些γ-丁内酯衍生物通过在活性锌化合物存在下，将二甲基马来酸酯与碳基化合物反应合成。
• The Potential Influence of Climate Change on Offshore Primary Production in Lake Michigan
  作者：Arthur S. Brooks、John C. Zastrow

  DOI：10.1016/s0380-1330(02)70608-4

  日期：2002.1

  This paper examines the potential influence of climate change on the primary productivity of Lake Michigan. Two general circulation models (GCMs) provided physical information on projected regional climate for the years 2030, 2050, and 2090. A 30-year record of meteorological data and limnological observations, from 1961 to through,1990, was used to define present, baseline conditions for the lake. GCM output was used to develop scenarios of future thermal characteristics, mixing patterns, and surface irradiance, which were then used to drive primary production calculations. Mean annual primary production for the base period was 116 g C/m(2). Under base conditions thermal stratification of the lake occurred on 13 June and extended 135 days until 26 October. Conditions projected for 2090 showed the mean date of stratification beginning as early as 5 April and remaining for 225 days until 20 November. Estimated mean annual primary production under these conditions totaled 113 g C/m(2), a decrease of 3% from the mean base value. Under the most extreme conditions of maximum projected cloud cover for 2090, primary production in that year could fall to 101 g C/m(2), a decrease of 13% from the base mean, or down 22% from maximum base production calculated under minimum base cloud cover conditions. The projected decrease may be attributed to physical/chemical constraints imposed on spring primary production by altered climate conditions. Early stratification would shorten the period of winter-spring mixing, during which time nutrients from the sediment are transported to the productive euphotic zone. The spring bloom was projected to diminish if early stratification capped the nutrient supply, and increased cloud cover reduced light input for photosynthesis. To a lesser extent fall production could also be reduced by the extension of the stratified period. Altered physical/chemical conditions influenced by a changing climate will be an important factor to consider in assessing future water quality conditions, primary production and the food web dynamics of the Great Lakes.
• Barbier; Locquin, Bulletin de la Societe Chimique de France, 1913, vol. <4> 13, p. 226
  作者：Barbier、Locquin

  DOI：——

  日期：——