(2-(1,3-dioxolan-2-yl)ethyl)magnesium bromide | 37610-80-3

• 物质功能分类: 有机原料 - 有机金属盐
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧戊环
• 英文名称: (2-(1,3-dioxolan-2-yl)ethyl)magnesium bromide
• 英文别名: 1,3-dioxolan-2-ylethylmagnesium bromide；[2-(1,3-dioxolan-2-yl)ethyl]magnesium bromide；2-([1,3]dioxolan-2-yl)ethylmagnesium bromide；2-(1,3-dioxolan-2-yl)ethylmagnesium bromide；{[1,3]-dioxolan-2-ylethyl}magnesium bromide；3,3-(ethylenedioxy)propylmagnesium bromide
• CAS: 37610-80-3
• 化学式: C₅H₉BrMgO₂
• 分子量: 205.334
• InChiKey: QCIMSEZOHQGKRH-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.18
• 重原子数：
  9.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

安全信息

• 海关编码：
  2932999099

反应信息

• 作为反应物：
  描述：

  (2-(1,3-dioxolan-2-yl)ethyl)magnesium bromide 在 重铬酸吡啶 、 四丁基氟化铵 、 4-甲基苯磺酸吡啶 、 苯基锂 、 lithium chloride 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 46.67h， 生成 [(1S,3Z,5R)-3-[(2E)-2-[(1R,3aS,7aR)-1-[(E,2R,5S)-5-[2-(1,3-dioxolan-2-yl)ethyl]-6-(methoxymethoxy)-6-methylhept-3-en-2-yl]-7a-methyl-2,3,3a,5,6,7-hexahydro-1H-inden-4-ylidene]ethylidene]-5-[tert-butyl(dimethyl)silyl]oxy-2-methylidenecyclohexyl]oxy-tert-butyl-dimethylsilane
  参考文献：
  名称：

  A Short, Efficient Copper-Mediated Synthesis of 1α,25-Dihydroxyvitamin D₂ (1α,25-Dihydroxyergocalciferol) and C-24 Analogs^1,2

  摘要：

  Two synthetic routes to the nonnatural hormone 1 alpha,25-dihydroxyergocalciferol [2b, 1 alpha,25-(OH)(2)-D-2] and analogs modified at C-24 have been developed both starting from aldehyde 7b. Key steps in route A (eight steps, approximate to 38% overall yield from 7b) are (1) stereoselective addition of (E)-vinyllithium reagent 8c to aldehyde 7b; and (2) S(N)2' anti-displacement of the allylic phosphate of 5e by organocuprates derived from Grignard reagents and CuCN in the presence of LiCl. Key steps in route B (eight steps from 7b, 48% overall yield) are (1) Wittig-Horner type coupling between ketone 22, which bears an allylic phosphate group on the side chain, and the ylide derived from the Lythgoe-Roche phosphine oxide to form the vitamin D triene unit; and (2) efficient S(N)2' anti-displacement of the phosphate group of 23 by the organocuprate derived from MeMgCl, CuCN, and LiCl, without affecting the labile vitamin D triene system, to give, after deprotection, 1 alpha,25-(OH)2-D-2. Route B is particularly attractive as an approach to diverse C-24 vitamin D analogs for biological screening.

  DOI：

  10.1021/jo970604u
• 作为产物：
  描述：

  2-(2-溴乙基)-1,3-二恶烷 在 magnesium 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 (2-(1,3-dioxolan-2-yl)ethyl)magnesium bromide
  参考文献：
  名称：

  Electroactive and luminescent polymers: new fluorene-heterocycle-based hybrids

  摘要：

  描述了从9,9-二烷基-2,7-二溴芴（18a，烷基=C10H21；24，烷基=Et）和吡咯、噻吩、3,4-亚乙基二氧噻吩以及呋喃衍生的共聚物的合成、表征和电致变色性质。两条合成9,9-二乙基-2,7-双（吡咯-2-基）芴（30）的路线分别获得了30%和20%的产率。单体30经电化学聚合生成电活性聚合物薄膜。最低单体氧化电位（Ep,m=0.4 V vs. Ag/Ag+）在四乙基铵对甲苯磺酸盐（TEATOS）-CH3CN中观察到，但薄膜形成缓慢。光谱电化学分析发现聚30的带隙为2.4 eV，聚合物氧化后出现两个低能量吸收峰，峰值为1.2 eV和2.2 eV，这一现象归因于价带和导带之间双极化子带的形成。通过Stille偶联反应，18a分别与2,5-双（三甲基锡基）噻吩（21a）、5,5′-双（三甲基锡基）-2,2′-双噻吩（21b）、2,5-双（三甲基锡基）-3,4-亚乙基二氧噻吩（21c）和2,5-双（三甲基锡基）呋喃（22）反应，合成了可溶性芴-杂环聚合物34a-d，产率较高。NMR光谱与所提出的聚合物34a-d的结构一致，NMR和IR光谱中未观察到34d中呋喃单元的开环证据。34a-d的分子量在8000 g mol–1范围内，多分散性指数（PDI）为2。聚合物34a-c的带隙测得为2.4 eV，而聚合物34d的带隙为2.6 eV。聚合物34a-c通过溶液掺杂SbCl5形成新的低能量双极化子带，以牺牲紫外-可见光吸收为代价。然而，聚合物34d不能通过SbCl5进行氧化掺杂。

  DOI：

  10.1039/a903374b

文献信息

• Tandem Cycloaddition Reactions of Allenyl Diazo Compounds Forming Triquinanes via Trimethylenemethane Diyls
  作者：Taek Kang、Won-Yeob Kim、Yeokwon Yoon、Byung Gyu Kim、Hee-Yoon Lee

  DOI：10.1021/ja207591e

  日期：2011.11.16

  A tandem reaction strategy for forming triquinanes from linear allenyl diazo compounds through an intramolecular 1,3-dipolar cycloaddition reaction of an allenyl diazo group that generates a trimethylenemethane (TMM) diyl followed by an intramolecular [2 + 3] TMM diyl cycloaddition reaction has been developed. The new tandem cycloaddition reaction is readily applicable to the synthesis of complex molecules

  通过分子内 1,3-偶极环加成反应生成三亚甲基甲烷 (TMM) 二基，然后分子内 [2 + 3] TMM 二基环加成反应，通过分子内 1,3-偶极环加成反应从线性丙二烯基重氮化合物形成三喹烷的串联反应策略发达。新的串联环加成反应很容易适用于复杂分子的合成，具有高通用性和效率。
• Asymmetric synthesis from pyridines: use of new chiral 1,4-dihydropyridines in a short synthesis of 5,8-disubstituted indolizidine (+)-209B
  作者：Dino Gnecco、Christian Marazano、Bhupesh C. Das

  DOI：10.1039/c39910000625

  日期：——

  The synthetic potentiality of chiral oxazolidines, prepared from 3-picoline via a 1,4-dihydropyridine intermediate, has been illustrated by an expeditious route to the 5,8-disubstituted indolizidine alkaloid (+)-209B.

  通过由3-皮考啉经1,4-二氢吡啶中间体制备的手性噁唑啉的合成潜力，已经通过一条便捷的途径阐明了合成5,8-双取代吲哚里西定生物碱（+）-209B的方法。
• Diastereocontrol by a Hydroxyl Auxiliary in the Synthesis of Pyrrolidines via Radical Cyclization
  作者：Magnus Besev、Lars Engman

  DOI：10.1021/ol026038t

  日期：2002.9.1

  [reaction: see text] Organoselenium precursors of 3-aza-5-hexenyl radicals carrying a 1-hydroxyalkyl group in the 2-position were prepared by addition of organometallic reagents to N-allyl-2-aziridinecarbonitrile, reduction of the resulting aziridine ketone, and regioselective benzeneselenol ring opening of the aziridine. Reductive radical cyclization was highly selective, affording the corresponding

  [反应：见正文]通过向N-烯丙基-2-氮丙啶腈中添加有机金属试剂，还原得到的氮丙啶酮，制备在2位带有1个羟烷基的3-氮杂-5-己烯基的有机硒前体，和氮丙啶的区域选择性苯硒酚开环。还原性自由基环化是高度选择性的，提供相应的反式2,4-二取代的吡咯烷（顺式/反式约1/10）作为主要的非对映异构体。重结晶得到的物质基本上更富含反式异构体（顺式/反式＜1/25）。
• A Convenient Method for the Regioselective Synthesis of 4-Alkyl(aryl)pyridines Using Pyridinium Salts
  作者：Kin-ya Akiba、Y\={u}ji Iseki、Makoto Wada

  DOI：10.1246/bcsj.57.1994

  日期：1984.7

  (81–94%). The dihydropyridines were oxidized by oxygen to give 4-alkyl(aryl)pyridines (38–68%). Grignard reagents also reacted with 1-t-butyldimethylsilylpyridinium triflate with almost complete regioselectivity (>99%) to afford the corresponding 1,4-dihydropyridines, which were easily oxidized by oxygen to give 4-substituted pyridines in higher yields than above (58–70%).

  RCu·BF3 与1-乙氧基羰基氯化吡啶在4-位反应，几乎完全区域选择性（>99%），以高产率（81-94%）得到相应的1,4-二氢吡啶衍生物。二氢吡啶被氧氧化得到4-烷基（芳基）吡啶（38-68%）。格氏试剂还与 1-叔丁基二甲基甲硅烷基吡啶鎓三氟甲磺酸盐反应，以几乎完全的区域选择性（>99%）得到相应的 1,4-二氢吡啶，它们很容易被氧气氧化得到 4-取代的吡啶，产率高于上述（58- 70%）。
• Synthesis of 2,3-Dihydropyrrolizines from Weinreb 3-(Pyrrolidin-2-ylidene­)propionamides or Weinreb<i>N-</i>Vinylprolinamides
  作者：Alfonso González-Ortega、Luis Calvo、M. Carmen Sañudo

  DOI：10.1055/s-2002-35220

  日期：——

  Weinreb 3-(pyrrolidin-2-ylidene)propionamides and Weinreb N-vinylprolinamides were used for the synthesis of 2,3-dihydropyrrolizines. The selective reaction of the carboxamide group with organometallic compounds allowed us to obtain a great variety of carbonyl intermediates, analogous to the Hantzsch and Knorr pyrrole synthesis, which were thermally cyclized.

  Weinreb 3-(吡咯烷-2-亚基)丙酰胺和Weinreb N-乙烯基脯氨酰胺被用于合成2,3-二氢吡咯嗪。羧酰胺基团与有机金属化合物的选择性反应使我们能够获得多种类似于Hantzsch和Knorr吡咯合成中的羰基中间体，这些中间体在热力作用下环化。