6-chloromethyl-2,2-dimethyl-4H-1,3-dioxin-4-one | 81956-31-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-chloromethyl-2,2-dimethyl-4H-1,3-dioxin-4-one
• 英文别名: 6-chloromethyl-2,2-dimethyl-1,3-dioxen-4-one；2,2-dimethyl-6-chloromethyl-1,3-dioxin-4-one；6-(chloromethyl)-2,2-dimethyl-1,3-dioxin-4-one
• CAS: 81956-31-2
• 化学式: C₇H₉ClO₃
• 分子量: 176.6
• InChiKey: ZQCKMGFVRPFEFP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  6-chloromethyl-2,2-dimethyl-4H-1,3-dioxin-4-one 在 sodium hydride 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 9.0h， 生成 (R)-3-((S)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-2-(2,2-dimethyl-6-oxo-6H-[1,3]dioxin-4-ylmethyl)-5-oxo-pyrazolidine-1-carboxylic acid methyl ester
  参考文献：
  名称：

  Synthesis of enantiopure aza-analogues of cocaine

  摘要：

  An enantiopure aza-analogue of pseudo-cocaine was synthesized starting from a 5-substituted 3-pyrazolidinone by using an N-acylhydrazonium ion cyclization with a dioxenone nucleophile as the key step. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/s0040-4039(96)02242-3
• 作为产物：
  描述：

  2,2,6-三甲基-4H-1,3-二英-4-酮 在 lithium diisopropyl amide 、 六氯乙烷 作用下， 以 四氢呋喃 为溶剂， 以66%的产率得到6-chloromethyl-2,2-dimethyl-4H-1,3-dioxin-4-one
  参考文献：
  名称：

  A Cautionary Tale in Decanolide Synthesis

  摘要：

  本文介绍了一种合成新型二氧戊烯酮醇 3 的高效聚合方法，在热分解 3 的过程中，通过中间体δ-乙酰酮烯获得了大环内酯 12。通过热分解已知的二氧杂环戊烯醇 2 而不是癸内酯--二茂烷基二内酯 A，得到了大环内酯 16。

  DOI：

  10.1055/s-2008-1078031

文献信息

• Synthesis of bridged bicyclic hydrazines via endocyclic N-acylhydrazonium intermediates: A novel route to the 1-Azatropane skeleton
  作者：Floris P.J.T Rutjes、Henk Hiemstra、Frank O.H Pirrung、W.Nico Speckamp

  DOI：10.1016/s0040-4020(01)80199-x

  日期：1993.1

  Bicyclic molecules with the 1,7-diaza-6,6-dimethylbicyclo[2.2.1]heptane and 1,8-diaza-7,7-dimethylbicyclo[3.2.1]octane (1-aza-7,7-dimethyltropane) skeleton are shown to be efficiently synthesized via cyclization reactions of endocyclic N-acylhydrazonium intermediates. By using a protected β-ketoester as the internal nucleophile, azacocaine analogues are also accessible via this methodology.

  具有1,7-二氮杂-6,6-二甲基双环[2.2.1]庚烷和1,8-二氮杂-7,7-二甲基双环[3.2.1]辛烷（1-氮杂-7,7-二甲基托烷）的双环分子骨架是通过内环N-酰基hydr中间体的环化反应有效合成的。通过使用受保护的β-酮酸酯作为内部亲核试剂，也可以通过这种方法获得氮杂可卡因类似物。
• Synthesis and evaluation of a putative acyl tetramic acid intermediate in tenellin biosynthesis in Beauveria bassiana. A new role for tyrosine
  作者：M.Caragh Moore、Russell J Cox、Gordon R Duffin、David O'Hagan

  DOI：10.1016/s0040-4020(98)00557-2

  日期：1998.7

  The acyltetramic acid 6 previously proposed as a putative intermediate in tenellin biosynthesis in Beauveria bassiana has been synthesised in two isotopically labelled forms. This compound was not incorporated into tenellin and was not identifiable in extracts of B. bassiana and is unlikely to be involved in tenellin biosynthesis. On the other hand a re-evaluation of the role of tyrosine reveals that

  先前被提议作为球孢白僵菌中tenellin生物合成的推定中间体的酰基四酸6已经以两种同位素标记的形式合成。该化合物没有并入tenellin和在提取物是不可识别白僵菌并且不可能参与tenellin生物合成。另一方面，对酪氨酸作用的重新评估表明它是Tenellin的良好前体，可能是在体内直接由L-苯丙氨酸产生的苯丙氨酸羟化酶的作用下生成的。因此，长期以来一直存在的争论认为，酰基四酸6经历氧化环扩环成吡啶酮不再是tenellin生物合成的有效假设。
• Method for the Rapid Synthesis of Highly Functionalized 2-Hydroxy-1-naphthoates. Syntheses of the Naphthoic Acid Components of Neocarzinostatin Chromophore and N1999A2
  作者：Nan Ji、Brad M. Rosen、Andrew G. Myers

  DOI：10.1021/ol048075l

  日期：2004.11.1

  describe a four-step sequence for the synthesis of complex 2-hydroxy-1-naphthoic acids involving Z-selective olefination of benzaldehyde derivatives with a novel dioxolenone-containing phenyl phosphonate reagent, followed by dioxolenone cleavage with alkaline trifluoroethanol and oxidative cyclization (Mn(OAc)(3)) of the resultant trifluoroethyl beta-keto esters. [reaction: see text]

  我们描述了一个复杂的2-羟基-1-萘甲酸的合成的四步骤序列，涉及苯甲醛衍生物与新型含二氧戊烯酮的苯基膦酸酯试剂的Z-选择性烯化反应，然后用碱性三氟乙醇裂解二氧烯酮和氧化环化反应（Mn （OAc）（3））生成的三氟乙基β-酮酯。[反应：看文字]
• Amido compounds and process for producing the same
  申请人：——

  公开号：US20010023297A1

  公开（公告）日：2001-09-20

  A 6-aminocarbonylmethyl-4H-2,3-dioxin-4-one compounds can be produced by reacting a 6-halomethyl-4H-2,3-dioxin-4-one compound with a primary or secondary amine and carbon monoxide. The reaction may be carried out in the presence of a catalyst comprising a platinum group metal. 3-oxopentanedicarboxylic acid monoamides and 3-oxopentanedicarboxylic acid amide esters can be are produced by reacting 6-aminocarbonylmethyl-4H-2,3-dioxin-4-one compound with an alcohol or water. Using such intermediates, 6-aminocarbonylmethyl-4H-2,3-dioxin-4-one compound, 3-oxopentanedicarboxylic acid amide esters can provide in an easy and simple and efficient manner.

  6-氨基甲酰基-4H-2,3-二氧杂环戊酮化合物可以通过将6-卤甲基-4H-2,3-二氧杂环戊酮化合物与一次或二次胺和一氧化碳反应来制备。反应可以在铂族金属催化剂的存在下进行。通过将6-氨基甲酰基-4H-2,3-二氧杂环戊酮化合物与醇或水反应，可以生产3-氧代戊二酸单酰胺和3-氧代戊二酸酰胺酯。使用这些中间体，可以以简单高效的方式提供6-氨基甲酰基-4H-2,3-二氧杂环戊酮化合物和3-氧代戊二酸酰胺酯。
• Ester and process for producing the same
  申请人：Daicel Chemical Industries, Ltd.

  公开号：US20010020103A1

  公开（公告）日：2001-09-06

  6-Alkoxycarbonylmethyl-4H-1,3-dioxin-4-one derivatives are produced by reacting a 6-halomethyl-4H-1,3-dioxin-4-one derivative with carbon monoxide and an alcohol or water, and 3-oxopentanedicarboxylic acid esters are further produced by reacting the above derivatives with an alcohol or water. Such a process can produce 3-oxopentanedicarboxylic acid esters in an easy and simple and efficient manner.

  6-烷氧羰基甲基-4H-1,3-二噁烷-4-酮衍生物是通过将6-卤代甲基-4H-1,3-二噁烷-4-酮衍生物与一氧化碳和醇或水反应而制得的，而3-氧代戊二酸酯则是通过将上述衍生物与醇或水反应而进一步制得的。这种方法可以以简单、高效的方式制得3-氧代戊二酸酯。