3,3-dimethoxyprop-1-yne | 22537-06-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,3-dimethoxyprop-1-yne
• 英文别名: 3,3-dimethoxypropyne；propargylaldehyde dimethyl acetal；3,3-Dimethoxy-1-propyne
• CAS: 22537-06-0
• 化学式: C₅H₈O₂
• 分子量: 100.117
• InChiKey: OYSKRUJJSNSHLV-UHFFFAOYSA-N

物化性质

• 沸点：
  111 °C
• 密度：
  0.927±0.06 g/cm3(Predicted)
• 保留指数：
  722

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  7
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,3-dimethoxyprop-1-yne 在 对甲苯磺酸 正丁基锂 作用下， 以 甲醇 为溶剂， 反应 10.5h， 生成 tert-butyl N-[(2R,3S)-1,3-dihydroxy-6,6-dimethoxyhex-4-yn-2-yl]carbamate
  参考文献：
  名称：

  Glycosyl .alpha.-amino acids via stereocontrolled buildup of a penaldic acid equivalent. A novel synthetic approach to the nucleosidic component of the polyoxins and related substances

  摘要：

  DOI：

  10.1021/jo00299a017
• 作为产物：
  描述：

  丙烯醛二甲缩醛 在 氢氧化钾 、 溴 作用下， 生成 3,3-dimethoxyprop-1-yne
  参考文献：
  名称：

  Metabolic depropargylation and its relationship to aldehyde dehydrogenase inhibition in vivo

  摘要：

  The relationship between metabolic depropargylation in vitro to inhibition of the low Km aldehyde dehydrogenase (AIDH) of rat liver mitochondria in vivo was determined for a number of compounds bearing a propargyl substituent on nitrogen or oxygen. Only those compounds which enzymatically released the highly reactive alpha, beta-acetylenic aldehyde, propioladehyde, when incubated in vitro with phenobarbital-induced rat liver microsomes, e.g., tripropargylamine (4), pargyline (1a), and N-propargylbenzylamine (1b), significantly elevated blood acetaldehyde levels when administered in vivo. Mitochondrial AIDH activity in these animals was corresponding reduced to less than or equal to 20% that of control animals. Compounds that did not inhibit mitochondrial AlDH activity to this degree did not produce significant levels of propiolaldehyde when incubated with microsomes. Thus, for this series of compounds, metabolic depropargylation is a requirement for AlDH inhibitory activity in vivo.

  DOI：

  10.1021/jm00180a018

文献信息

• Method for the Production of N-Substituted (3-Dihalomethyl-1-Methyl-Pyrazole-4-yl) Carboxamides
  申请人：Zierke Thomas

  公开号：US20100174094A1

  公开（公告）日：2010-07-08

  The present invention relates to a process for preparing N-substituted (3-dihalomethylpyrazol-4-yl)carboxamides of the formula (I) in which R 1 is optionally substituted phenyl or C 3 -C 7 -cycloalkyl, R 1a is hydrogen or fluorine, or R 1a together with R 1 is optionally substituted C 3 -C 5 -alkanediyl or C 5 -C 7 -cycloalkanediyl, R 2 is C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl or C 1 -C 4 -alkoxy-C 1 -C 2 -alkyl, X is F or Cl and n is 0, 1, 2 or 3; which comprises A) providing a compound of the formula (II) in which X is F or Cl, Y is Cl or Br and R 2 has one of the meanings given above and B) reacting a compound of the formula (II) with carbon monoxide and a compound of the formula (III) in which R 1 , R 1a and n have one of the meanings given above; in the presence of a palladium catalyst; to intermediates used for the preparation according to the process according to the invention, and also to processes for their preparation.

  本发明涉及一种制备式(I)的N-取代(3-二卤甲基吡唑-4-基)羧酰胺的方法 其中R1是可选的取代苯基或C3-C7环烷基，R1a是氢或氟，或者R1a与R1一起是可选的取代C3-C5-烷二基或C5-C7-环烷二基，R2是C1-C6-烷基，C2-C6-烯基，C2-C6-炔基或C1-C4-烷氧基-C1-C2-烷基，X是F或Cl，n为0、1、2或3；包括 A)提供式(II)的化合物 其中X是F或Cl，Y是Cl或Br，R2具有上述给定的含义之一 B)将式(II)的化合物与一氧化碳和式(III)的化合物反应 其中R1、R1a和n具有上述给定的含义之一；在钯催化剂的存在下； 用于根据本发明的方法制备的中间体，以及用于它们的制备的方法。
• Enantioselective Synthetic Methodology to Prepare trans-Fused Bicyclo[5.3.0]decane Systems: an Approach to the Synthesis of the Pseudoguaiane Carbon Framework
  作者：Ángel M. Montaña、David Fernández、Roger Pagès、Alexander C. Filippou、Gabriele Kociok-Köhn

  DOI：10.1016/s0040-4020(99)01009-1

  日期：2000.1

  An enantioselective method to prepare trans-fused bicyclo[5.3.0]decane systems is described. This methodology is based on two key reactions: a [4+3] cycloaddition reaction (to generate the seven-membered ring) and the Nicholas reaction (to insert the five-membered ring). The application of this methodology to the enantioselective synthesis of the pseudoguaiane carbon skeleton is presented. This enantioselective

  描述了制备反式稠合双环[5.3.0]癸烷体系的对映选择性方法。该方法基于两个关键反应：[4 + 3]环加成反应（生成七元环）和尼古拉斯反应（插入五元环）。介绍了该方法在拟愈创木碳骨架对映选择性合成中的应用。用于构建反式双环[5.3.0]癸烷体系的这种对映选择性策略是通用的，可用于制备包含该碳骨架的多种生物活性天然产物。
• Synthesis of the 10-oxabicyclo[5.2.1]decane framework present in bioactive natural products
  作者：Ángel M. Montaña、Stefano Ponzano、Maria-Filomena Sanasi、Gabriele Kociok-Köhn

  DOI：10.1039/c8ob00194d

  日期：——

  multigram level with good overall yield. Further biological, biochemical and biophysical studies are being carried out in our laboratory on these 1,7-epoxycyclononane derivatives to determine the potential of this kind of oxabicyclic compound as future hits and/or leads for the development of new anticancer drugs. The preliminary evaluation of the anticancer activity of the representative synthesized compounds

  本工作涉及存在于生物活性天然产物（如海藻磷脂）中的10-氧杂双环[5.2.1]癸烷骨架的合成，具有潜在的抗肿瘤作用。这种合成方法涉及几个关键反应：（a）通过呋喃前体与氧基烯丙基阳离子的[4 + 3]环加成反应合成多官能化环庚烯；（b）尼古拉斯与炔丙基阳离子的反应，以炔丙基六羰基二羰基配合物稳定；（c）所得乙炔的脱金属和水合；（d）立体收敛的羟醛环化反应生成关键的氧三环中间体，以及（e）β片段化过程，该过程在次碘酸盐光解作用下可提供所需的产物，产率中等至良好。通过对C4上的羰基进行自由基加成。合成方法已按比例放大到数克水平，并具有良好的整体收率。我们的实验室正在对这些1,7-环氧环壬烷衍生物进行进一步的生物学，生化和生物物理研究，以确定此类草酸双环化合物作为未来抗击和/或开发新抗癌药物的先导的潜力。对代表性合成化合物针对白血病癌细胞系K-562和SR的抗癌活性的初步评估显示，对于功能方便的10-氧杂双环，GI
• Design and synthesis of new antitumor agents with the 1,7-epoxycyclononane framework. Study of their anticancer action mechanism by a model compound
  作者：Ángel M. Montaña、Julia Lorenzo、Stefano Ponzano、Maria-Filomena Sanasi

  DOI：10.1016/j.bmc.2018.05.009

  日期：2018.7

  This article describes the design, synthesis and biological evaluation of a new family of antitumor agents having the 1,7-epoxycyclononane framework. We have developed a versatile synthetic methodology that allows the preparation of a chemical library with structural diversity and in good yield. The synthetic methodology has been scaled up to the multigram level and can be developed in an enantioselective

  本文介绍了具有1,7-环氧环壬烷骨架的新型抗肿瘤药物家族的设计，合成和生物学评估。我们已经开发了一种通用的合成方法，可以制备具有结构多样性和高收率的化学文库。合成方法已扩展到多克级，可以以对映选择性的方式开发。研究体外在癌细胞系HL-60和MCF-7之前，模型化合物的抑制作用显示出比顺铂更好的生长抑制作用。通过荧光显微镜对癌细胞的观察表明凋亡小体的存在和微管的降解。通过流式细胞术对癌细胞的细胞周期和死亡机理的研究表明，细胞周期停滞在G 0 / G 1期，并且细胞优选通过细胞凋亡而死于坏死。在subG 0 / G 1水平观察到高百分比的凋亡细胞。这表明我们的模型化合物不能像诺考达唑那样用作抗有丝分裂剂，作为参考，它可以阻止G 2的细胞周期/ M阶段。通过原子力显微镜，圆二色性和琼脂糖凝胶电泳评估抗癌剂与DNA分子的相互作用。结果表明该模型化合物没有DNA作为靶分子。将在硅片模型化合物的研究表明，一个潜在的良好口服生物利用度。
• Versatile Methodology to Synthesize Oxygen-Bridged Nine- and Ten-Membered Cycloalkanes by the Hypoiodite Reaction
  作者：Ángel M. Montaña、Stefano Ponzano、Gabriele Kociok-Köhn、Mercè Font-Bardia、Xavier Solans

  DOI：10.1002/ejoc.200700172

  日期：2007.9

  to the tertiary hydroxy group on C-6. This β-fragmentation is followed by a ring contraction from a ten- to a nine-membered ring system, by a free-radical addition to the carbonyl group on C-4. The reaction of precursors (not functionalized on C-3) with LTA and iodine produced a β-fragmentation without any further structural rearrangement, affording 1,8-epoxycyclodecanes. The transformation of the carbonyl

  6-羟基-2,7-二甲基-11-oxatricyclo[6.2.1.02,6]undecan-4-one 的 C-3 衍生物与四乙酸铅 (LTA) 和碘反应，以良好的收率得到 1,7-环氧环壬烷是与 C-6 上的叔羟基相邻的 C2-C6 键发生 β 断裂的结果。这种 β 断裂之后是从十元环系统到九元环系统的环收缩，通过自由基加成到 C-4 上的羰基。前体（未在 C-3 上官能化）与 LTA 和碘的反应产生了 β-断裂，没有任何进一步的结构重排，得到 1,8-环氧环癸烷。C-4 上的羰基向乙酸酯的转化避免了自由基加成和重排，以高产率提供了相应的环癸烷。通过这种方法，1,7-环氧环壬烷或 1,

表征谱图