(3,3-二乙氧基-1-丙烯-2-基)苯 | 80234-04-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: (3,3-二乙氧基-1-丙烯-2-基)苯
• 中文别名: 4-[(1E,3Z)-3-氨基-3-亚氨基丙-1-烯-1-基]苯基4-[(二氨基甲亚基)氨基]苯酸酯二甲磺酸酯
• 英文名称: atropaldehyde diethyl acetal
• 英文别名: (3,3-diethoxyprop-1-en-2-yl)benzene；3,3-diethoxyprop-1-en-2-ylbenzene
• CAS: 80234-04-4
• 化学式: C₁₃H₁₈O₂
• 分子量: 206.285
• InChiKey: PGRGWTSTROMQAI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 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：

  (3,3-二乙氧基-1-丙烯-2-基)苯 在 Amberlyst 15 、 硼烷 、 氨 作用下， 以 四氢呋喃 、 丙酮 为溶剂， 反应 8.0h， 生成 3-carbamoyl-2-phenylpropionaldehyde
  参考文献：
  名称：

  Synthesis and in Vitro Reactivity of 3-Carbamoyl-2-phenylpropionaldehyde and 2-Phenylpropenal:  Putative Reactive Metabolites of Felbamate

  摘要：

  We propose that 3-carbamoyl-2-phenylpropionaldehyde is an intermediate in the metabolism of felbamate, an anti-epileptic drug with a unique profile of therapeutic activity, and undergoes a cascade of chemical reactions responsible for the toxic properties of the parent drug. To test this hypothesis, we have synthesized 3-carbamoyl-2-phenylpropionaldehyde and evaluated its in vitro reactivity. This molecule was found to be highly unstable at physiological pH (t(1/2) less than or equal to 30 s) and to undergo facile elimination to 2-phenylpropenal, an a,P-unsaturated aldehyde commonly termed atropaldehyde. However, the predominant reaction pathway for 3-carbamoyl-2-phenylpropionaldehyde was reversible cyclization to generate 4-hydroxy-5-phenyltetrahydro-1,3-oxazin-2-one, a urethane that has a considerably longer half-life at physiological pH (t(1/2) greater than or equal to 5 h) and may serve as a stable reservoir of the reactive aldehyde both in, vitro and in vivo. Atropaldehyde is a potent electrophile and was found to exhibit cytotoxicity to cultured fibroblasts (50% growth inhibition (GI(50)) = 4.1 +/- 1.1 mu M) comparable to the known unsaturated aldehyde toxins, 4-hydroxy-2-nonenal and acrolein. 3-Carbamoyl-2-phenylpropionaldehyde also exhibited significant cytotoxicity (GI(50) = 53 +/- 8 mu M), whereas 2-phenyl-1,3-propanediol monocarbamate (GI(50) > 500 mu M) and 3-carbamoyl-2-phenylpropionic acid (GI(50) > 500 mu M) were nontoxic. We have additionally demonstrated the formation of a glutathione-atropaldehyde conjugate from the in vitro incubation of 3-carbamoyl-2-phenylpropionaldehyde with glutathione. Thus, the potent cytotoxicity and potential allergenicity of atropaldehyde implicate this unsaturated aldehyde as a possible causative agent in the toxicities observed with felbamate treatment.

  DOI：

  10.1021/tx9601566
• 作为产物：
  描述：

  丙烯醛缩二乙醇 在 溴 、 palladium diacetate 、 caesium carbonate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 2-二环己基磷-2,4,6-三异丙基联苯 作用下， 以 1,4-二氧六环 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 (3,3-二乙氧基-1-丙烯-2-基)苯
  参考文献：
  名称：

  钯催化α-卤代烯基缩醛与有机硼烷的铃木反应模块化合成α-取代的烯基缩醛

  摘要：

  已经开发了用于制备α-取代的链烯基缩醛的模块化且直接的合成策略。α-卤代烯基乙缩醛在温和的条件下，通过钯催化的Suzuki交叉偶合，可与（杂）芳基硼酸，硼酸芳基酯或B-烷基-9-硼环[3.3.1]壬烷平稳反应，并具有良好或高收率。该协议具有广泛的基板范围和良好的功能组兼容性，并且易于扩展。

  DOI：

  10.1055/a-1322-3916

文献信息

• Thermal rearrangement of N-arylmethyl- and N-alkyl-2,2-dihalogenocyclopropyl imines
  作者：Shinto Kagabu、Chihaya Ando、Junko Ando

  DOI：10.1039/p19940000739

  日期：——

  temperatures. An ionic mechanism triggered by the halide ion dissociation is proposed for the thermal rearrangement on the basis of a study using deuteriated imine 15m, and the effects of additives and solvents. On the other hand, difluorocyclopropyl imine undergoes a homolytic cleavage of cyclopropane 1,3-bond with lower activation energy than the dichlorocyclopropyl imine, and afforded the N-alkyl-3-fluoropyrrole

  据报道，对1-取代的2，2-二卤代环丙基亚胺进行热异构化的扩展研究。的热解Ñ -arylmethyl -2,2- dichlorocyclopropanecarbaldimines 15A - ħ产生2-芳基- 16A - ħ和2-芳基-4-氯-吡啶衍生物17A - ħ，而Ñ -alkylcyclopropyl亚胺15I，Ĵ收率Ñ -alkylchloropyrroles 。2，2-二溴环丙烷类似物在较低温度下进行热解。在使用氘化亚胺的研究的基础上，提出了由卤化物离子解离引发的离子机理用于热重排。15m，以及添加剂和溶剂的影响。另一方面，二氟环丙基亚胺以比二氯环丙基亚胺低的活化能进行环丙烷1，3-键的均相裂解，优先得到N-烷基-3-氟吡咯衍生物。
• Acid-catalyzed cleavage of C–C bonds enables atropaldehyde acetals as masked C2 electrophiles for organic synthesis
  作者：Shaomin Chen、Minghao Li、Yanlong Gu

  DOI：10.1039/d1cc04000f

  日期：——

  Acid-catalyzed tandem reactions of atropaldehyde acetals were established for the synthesis of three important molecules, 2,2-disubstituted indolin-3-ones, naphthofurans and stilbenes. The synthesis was realized using novel reaction cascades, which involved the same two initial steps: (i) SN2′ substitution, in which the atropaldehyde acted as an electrophile; and (ii) oxidative cleavage of the carbon–carbon

  阿托醛缩醛的酸催化串联反应被建立用于合成三个重要分子，2,2-二取代 indolin-3-ones、萘并呋喃和芪。该合成是使用新的反应级联反应实现的，其中涉及相同的两个初始步骤：(i) S N 2' 取代，其中阿托醛充当亲电子试剂；(ii) 生成的苯乙醛类产物的碳-碳键的氧化裂解。与文献方法相比，本协议不仅避免使用昂贵的贵金属催化剂，而且操作简单。
• PEG400-enhanced synthesis of gem-dichloroaziridines and gem-dichlorocyclopropanes via in situ generated dichlorocarbene
  作者：Qing-Wen Song、Bing Yu、An-Hua Liu、Ying He、Zhen-Zhen Yang、Zhen-Feng Diao、Qing-Chuan Song、Xue-Dong Li、Liang-Nian He

  DOI：10.1039/c3ra43307b

  日期：——

  efficient phase transfer catalyst for the cycloaddition reaction of imines with dichlorocarbene, which is generated in situ from chloroform and sodium hydroxide, to give gem-dichloroaziridines in moderate to excellent yields at ambient temperature. This protocol is also extended to the synthesis of cyclopropanes from a variety of alkenes. In this study, PEG400 behaves as a phase transfer reagent thanks to

  PEG 400用作亚胺与二氯卡宾的环加成反应的有效相转移催化剂，该反应是由亚胺从原位生成的氯仿 和 氢氧化钠在室温下以中等至极好的收率得到宝石-二氯氮丙啶。该方案还扩展到由多种烯烃合成环丙烷的过程。在这项研究中，由于PEG 400具有与碱金属阳离子配位的能力，因此它可以作为相转移试剂。值得注意的是，一锅法合成的宝石-二氯氮丙啶苯甲醛芳香胺也已成功进行。该原位生成的酸，从CO衍生的2和高氧2也可有效地应用于促进酰胺合成经由所述宝石-dichloroaziridine通路。还简要说明了宝石-二氯环丙烷作为平台化学品的应用，以通过开环反应得到2-苯基丙烯醛衍生物。
• Bromomethyl Silicate: A Robust Methylene Transfer Reagent for Radical-Polar Crossover Cyclopropanation of Alkenes
  作者：Wenping Luo、Yewen Fang、Li Zhang、Tianhang Xu、Yongjun Liu、Yan Li、Xiaoping Jin、Jiakan Bao、Xiaodong Wu、Zongyong Zhang

  DOI：10.1002/ejoc.202000134

  日期：2020.3.22

  new bifunctional C1 synthon: With bromomethyl silicate as a CH2 source, visible‐light‐induced cyclopropanation has been demonstrated to be amenable to the alkenes including Michael acceptors, styrene derivatives, and unactivated 1,1‐dialkyl ethylenes. In addition to the broad substrate scope, this radical‐polar crossover process is also characterized by its redox‐neutral process, mild conditions, and

  一种新的双功能C1合成子：以溴代甲基硅酸盐为CH 2来源，可见光诱导的环丙烷化反应适用于烯烃，包括Michael受体，苯乙烯衍生物和未活化的1,1-二烷基乙烯。除了广泛的底物范围外，这种自由基-极性交叉过程还具有氧化还原中性过程，温和条件和良好的官能团相容性的特点。
• Grignard Reactions of 4-Substituted-2-keto-1,3-dioxanes:  Highly Diastereoselective Additions Controlled by a Remote Alkyl Group
  作者：William F. Bailey、David P. Reed、Daniel R. Clark、Gabriel N. Kapur

  DOI：10.1021/ol015914k

  日期：2001.6.1

  [see reaction]. The reactions of Grignard reagents with a representative series of simple cis-2-keto-4-substituted-1,3-dioxanes have been investigated. The stereochemical outcome of these highly diastereoselective additions (dr > 90:10) is consonant with Cram's chelate model on the assumption that RMgX coordinates preferentially with the ring oxygen remote from the C(4) substituent.

  [请参阅反应]。研究了格氏试剂与代表性的一系列简单的顺式-2-酮-4-取代的1,3-二恶烷的反应。这些高度非对映选择性添加物（dr> 90:10）的立体化学结果与Cram螯合物模型一致，其前提是RMgX优先与远离C（4）取代基的环氧协调。