allyloxyacetyl chloride | 56680-79-6

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 酰卤
• 英文名称: allyloxyacetyl chloride
• 英文别名: allyloxyacetic acid chloride；2-prop-2-enoxyacetyl chloride
• CAS: 56680-79-6
• 化学式: C₅H₇ClO₂
• 分子量: 134.562
• InChiKey: JYHQQVUADRVUPA-UHFFFAOYSA-N

物化性质

• 沸点：
  48-50 °C(Press: 12 Torr)
• 密度：
  1.111±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  8
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  allyloxyacetyl chloride 在 sodium hydroxide 、 N-碘代丁二酰亚胺 作用下， 以 1,4-二氧六环 、 甲醇 、 N,N-二甲基乙酰胺 为溶剂， 反应 20.5h， 生成 Dimethyl 2,4,6-triiodo-5-<3-(iodomethyl)-5-oxo-4-morpholinyl>-1,3-benzenedicarboxylate
  参考文献：
  名称：

  Heterocyclic Nonionic X-ray Contrast Agents. 4. The Synthesis of Dihydro-2(3H)-furanylidenamino, 5-oxo-1-pyrrolidinyl, and 5-oxo-4-morpholinyl Derivatives by an Intramolecular Iodocyclization Approach

  摘要：

  Intramolecular iodocyclization of omega-alkenylanilides 6 and [omega-(alkenyloxy)alkyl]anilides 7 resulted in the formation of dihydro-2(3H)-furanylidenamines 8 and 1,4-dioxan-2-ylideneamines 9, respectively, by an amide-oxygen participative nucleophilic attack on the expected iodonium intermediate. The latter heterocyclic ring system is new. If a strong base is present, the mode of ring closure was mainly diverted to an amide-nitrogen participative nucleophilic attack, leading to (iodomethyl)-pyrrolidinones 10 and (iodomethyl)morpholinones 11, from 6 and 7, respectively. Unique interconvertible syn-anti isomerism in the imino-ether 8a was demonstrated by variable temperature NMR studies. The major component in this mixture was the 8a anti-isomer. Acetolysis of the iodocyclized products, followed by deacetylation, provided the heterocyclically substituted polyhydroxytriiodoisophthalamides 16-18. Hydrolytic studies on the imidate 16d revealed an interesting pH dependence. As expected the amine 3d and the amide 22 resulted in pH values of 2 and 6. At pH 12, however, the Chapman rearrangement product 17d was the major product. The compounds obtained in this investigation are of interest as X-ray contrast agents.

  DOI：

  10.1021/jo00119a020
• 作为产物：
  描述：

  2-烯丙氧基-乙酸 在 草酰氯 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 allyloxyacetyl chloride
  参考文献：
  名称：

  5-己烯基从硝酰基自由基加成到 4-戊烯基烯酮和来自丙烯酰基反应的环化

  摘要：

  光化学沃尔夫重排用于形成 5-取代-4-戊烯基烯酮 1a??1d (RCH=CHCH2XCH2CH=C=O: 1a R = H, X = CH2; 1b R = Ph, X = CH2; 1c R = c- Pr, X = CH2; 1d R = H, X = O), 其中...

  DOI：

  10.1139/v03-076

文献信息

• Pyrolysis of azetidinone derivatives: a versatile route towards electron-rich alkenes, C-1 allylation and/or homologation of aldehydes
  作者：Nouf S. Al-Hamdan、Osama M. Habib、Yehia A. Ibrahim、Nouria A. Al-Awadi、Osman M. E. El-Dusouqui

  DOI：10.1039/c4ra01024h

  日期：——

  β-thiolactams led essentially to stereoselective synthesis of the high energy electron-rich Z-alkenes. Extension of this methodology to the pyrolysis of 3-allyloxy derivatives gave a simple direct route to the synthetically important 4-pentenal. These pyrolytic transformations convert aldehydes to aryloxyalkenes (a protected homologation) and 4-pentenal (a C-1 allylation and homologation). The starting

  β-内酰胺和β-硫代内酰胺的热解基本上导致了高能富电子的Z-烯烃的立体选择性合成。将该方法扩展至3-烯丙氧基衍生物的热解，给出了一条通往合成重要的4-戊烯醛的简单直接途径。这些热解转化将醛转化为芳氧基烯烃（受保护的同系物）和4-戊烯醛（C-1烯丙基化和同系物）。起始的3-芳氧基和3-烯丙氧基-β-内酰胺是通过标准的Staudinger乙烯酮-亚胺[2 + 2]环加成反应合成的。通过用Lawesson试剂对β-内酰胺进行硫杂化，可以容易地以高收率获得相应的β-硫内酰胺。
• Intramolecular transamidation of β-lactams as a means for the enzymatic control of ring opening: Effect of substituents on the rate of reaction
  作者：Luca Banfi、Giuseppe Guanti、Marcello Rasparini

  DOI：10.1016/s0040-4039(98)02118-2

  日期：1998.12

  A series of simple monocyclic β-lactams bearing side-chains, containing amino groups, have been synthesized, and the rate of their intramolecular transamidation studied. Protection of the amino group with an enzymatically cleavable group, allows us to selectively control the ring enlargement process.

  已经合成了一系列带有氨基的带有侧链的简单单环β-内酰胺，并研究了它们的分子内酰胺化率。用酶可裂解基团保护氨基，使我们能够选择性地控制环的扩大过程。
• Formation of pyridazino[6,1-c][1,4]oxazin-8(7H)-ones by intramolecular cycloaddition of azoalkenes
  作者：Thomas L. Gilchrist、Robert C. Wasson、Frank D. King、Gordon Wootton

  DOI：10.1039/p19870002517

  日期：——

  of 2-allyloxyalkanoic acids (1) and of prop-2-ynyloxyacetic acid have been prepared. These hydrazides have then been converted into the hydrazones (6) and (7), respectively, by reaction with phenacyl chloride. The azoalkenes have been generated from the hydrazones by reaction with sodium carbonate. The products isolated were the pyridazino-oxazinones (8)[from (6)] and (9)[from (7)], formed by spontaneous

  已经制备了2-烯丙氧基链烷酸（1）和丙-2-炔氧基乙酸的酰肼（3）和（4）。然后，通过与苯甲酰氯反应，将这些酰肼分别转化为the（6）和（7）。通过与碳酸钠反应，由生成了偶氮烯烃。分离的产物是由偶氮烯烃的自发分子内环加成反应形成的哒嗪-恶嗪酮（8）[来自（6）]和（9）[来自（7）]。（6b）和（6c）具有不相邻于羰基的不对称碳中心的化合物各自产生非对映异构的恶嗪的混合物，但是在每种情况下具有相当大的选择性（6：1）。这归因于过渡态中的空间效应。用衍生自酰肼（3）和（4）的和溴代丙酮酸乙酯进行了一系列类似的转化。还已经制备了N-乙酰基-N-烯丙基甘氨酸酰肼（11）。通过与碳酸钠反应，将由该酰肼和苯甲酰氯形成的hydr （13）转化为偶氮烯，将其环化，得到吡嗪并[1,2 - b ]哒嗪-8-一（14a）。）。
• Nonionic radiographic contrast agents
  申请人：Bracco International B.V.

  公开号：US05614638A1

  公开（公告）日：1997-03-25

  New nonionic radiographic contrast agents having the formula ##STR1## wherein Y is a single bond, --CH.sub.2 CH.sub.2 --, --CH.sub.2 O--, --OCH.sub.2 --, ##STR2## --CH.sub.2 --, --CH.sub.2 --CH.sub.2 --CH.sub.2 --, --O-- or ##STR3## R.sub.1, R.sub.1 ' and R.sub.2 are the same or different and are hydrogen, alkyl or hydroxyalkyl. Hydroxyalkyl refers to such alkyl groups having 1 or more hydroxy groups. Preferred hydroxyalkyl groups include: ##STR4## R.sub.3 and R.sub.4 are the same or different and are hydrogen, methyl or --CH.sub.2 CH.sub.2 OH; R.sub.5 is hydrogen, alkyl, --CH.sub.2 CH.sub.2 OH, CH.sub.2 OH or OH and R.sub.6 is alkyl, --CH.sub.2 CH.sub.2 OH, CH.sub.2 OH, OH or hydrogen and may be the same or different than R.sub.5 and m is zero or one, with the proviso that no methylene or methine carbon atom of the heterocyclic ring is attached to both a nitrogen and an oxygen atom with the additional proviso that when Y is a single bond, m is not zero. These new contrast agents are water soluble and have desirable low osmolality and anticoagulant properties.

  新的非离子X线造影剂具有以下结构式：##STR1## 其中Y是单键，--CH.sub.2 CH.sub.2 --，--CH.sub.2 O--，--OCH.sub.2 --，##STR2## --CH.sub.2 --，--CH.sub.2 --CH.sub.2 --CH.sub.2 --，--O--或##STR3## R.sub.1，R.sub.1'和R.sub.2相同或不同，可以是氢，烷基或羟基烷基。羟基烷基指的是具有1个或更多羟基的烷基基团。首选的羟基烷基基团包括：##STR4## R.sub.3和R.sub.4相同或不同，可以是氢，甲基或--CH.sub.2 CH.sub.2 OH；R.sub.5是氢，烷基，--CH.sub.2 CH.sub.2 OH，CH.sub.2 OH或OH，R.sub.6是烷基，--CH.sub.2 CH.sub.2 OH，CH.sub.2 OH，OH或氢，可能与R.sub.5不同，m为零或一，但条件是杂环环的亚甲基或亚甲烷碳原子不同时连接到氮和氧原子，另外条件是当Y是单键时，m不为零。这些新的造影剂可溶于水，具有理想的低渗透压和抗凝血性能。
• Intramolecular Opening of β-Lactams with Amines as a Strategy Toward Enzymatically or Photochemically Triggered Activation of Lactenediyne Prodrugs
  作者：Luca Banfi、Giuseppe Guanti、Marcello Rasparini

  DOI：10.1002/ejoc.200390188

  日期：2003.3

  to develop a general strategy for selective activation of designed enediyne prodrugs belonging to the “lactenediyne” family, we studied the scope of intramolecular transamidation of simple monocyclic β-lactams bearing a tethered amine. The effect of substituents, of reaction media, and of the type of tether, on the rate of transamidation is disclosed. The possibility of triggering the transamidation

  为了开发选择性激活属于“lactenediyne”家族的设计的烯二炔前药的一般策略，我们研究了带有束缚胺的简单单环 β-内酰胺的分子内转酰胺化的范围。公开了取代基、反应介质和系链类型对转酰胺化速率的影响。在模型单环 β-内酰胺上证明了在温和条件下通过合适的酶或紫外线的作用触发转酰胺事件的可能性。最后，β-内酰胺分子内打开导致更大的七元环的策略被用于乳糖二炔，证明环扩大可以释放烯二炔部分的反应性。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)