N-benzyl-2-(bromomethyl)aziridine | 25662-24-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-benzyl-2-(bromomethyl)aziridine
• 英文别名: 1-benzyl-2-(bromomethyl)aziridine
• CAS: 25662-24-2
• 化学式: C₁₀H₁₂BrN
• 分子量: 226.116
• InChiKey: HDWSXVXUSOFXPM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-benzyl-2-(bromomethyl)aziridine 在 potassium carbonate 作用下， 以 乙腈 为溶剂， 反应 50.0h， 生成 3-diethylamino-2-(phenylmethyl)amino-1-(1,2,4-triazol-1-yl)propane
  参考文献：
  名称：

  Synthesis of 2-(aminomethyl)aziridines and their microwave-assisted ring opening to 1,2,3-triaminopropanes as novel antimalarial pharmacophores

  摘要：

  A variety of 2-(aminomethyl)aziridines was prepared and converted into the corresponding 1,2,3-triaminopropanes through a novel, microwave-assisted and regioselective ring opening by diethylamine in acetonitrile. Antiplasmodial assays revealed antimalarial activity for 2-[(1,2,4-triazol-1-yl)methyl]aziridines and 2-(N,N-diethylaminomethyl)aziridines, as well as for the corresponding 1-(diethylamino) propanes obtained through ring opening, pointing to the relevance of both the 2-(aminomethyl)aziridine and the 1,2,3-triaminopropane unit as novel antimalarial pharmacophores. (C) 2010 Elsevier Masson SAS. All rights reserved.

  DOI：

  10.1016/j.ejmech.2010.11.037
• 作为产物：
  描述：

  (E)-N-烯丙基-1-苯基甲亚胺 在 sodium tetrahydroborate 、 溴 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 2.5h， 生成 N-benzyl-2-(bromomethyl)aziridine
  参考文献：
  名称：

  2-亚甲基氮丙啶的新合成。

  摘要：

  通过碱诱导的2-（溴甲基）氮丙啶的1，2-脱氢溴化反应，已经开发出了一种新的合成方法，可以产生2-亚甲基氮丙啶。几对碱-溶剂对没有产生2-亚甲基氮丙啶。在四氢呋喃中仅叔丁醇钾提供与取代产物竞争的2-亚甲基氮丙啶，即2-（叔丁氧基甲基）氮丙啶。1-（芳基甲基）-2-亚甲基氮杂环丁烷的各种尝试的官能化均未成功，但它们被证明是合成β-内酰胺衍生物（即1-（芳基甲基）-2-亚氨基氮杂环丁烷）的极好底物，通过叠氮化物携带电子-取代基。

  DOI：

  10.1021/jo962351v

文献信息

• Opposite Regioselectivity in the Sequential Ring-Opening of 2-(Alkanoyloxymethyl)aziridinium Salts by Bromide and Fluoride in the Synthesis of Functionalized β-Fluoro Amines
  作者：Norbert De Kimpe、Matthias D’hooghe

  DOI：10.1055/s-2006-947359

  日期：2006.8

  1-Arylmethyl-2-(bromomethyl)aziridines were converted into the corresponding 2-(alkanoyloxymethyl)aziridines upon treatment with potassium 2-methylpropanoate or potassium 2-­methylbutyrate in DMSO in excellent yields, following regio­selective ring-opening towards N-(2-bromo-3-alkanoyloxy­propyl)amines ­using allyl bromide or an arylmethyl bromide in acetonitrile. Treatment of the latter β-bromo amines with tetrabutyl­ammonium fluoride in acetonitrile afforded 2-amino-1-fluoro­propanes as the major compounds (72-86%) besides the isomeric 1-amino-2-fluoropropanes in minor quantities (14-28%). The ring-opening of the intermediate aziridinium salts by bromide and ­fluoride in acetonitrile resulted in a different regioselectivity with a preferential attack of bromide at the more hindered carbon atom and of fluoride at the less hindered carbon atom of the aziridinium ion.

  1-芳甲基-2-(溴甲基)氮杂环丁烷在二甲基亚砜中与钾2-甲基丙酸酯或钾2-甲基丁酸酯反应，经过区域选择性的环打开生成N-(2-溴-3-烷酰氧基丙基)胺，使用烯丙基溴或芳甲基溴在乙腈中进行反应，可以高效地转化为相应的2-(烷酰氧甲基)氮杂环丁烷。后者的β-溴胺类在乙腈中与四丁基氟化铵反应，主要生成2-氨基-1-氟丙烷（72-86%），同时也有少量异构的1-氨基-2-氟丙烷（14-28%）。中间体氮杂环丁烷盐通过在乙腈中的溴和氟进行环打开，导致不同的区域选择性，其中溴优先攻击更受阻的碳原子，而氟优先攻击较少受阻的碳原子。
• A Novel Entry toward 2-Imino-1,3-thiazolidines and 2-Imino-1,3-thiazolines by Ring Transformation of 2-(Thiocyanomethyl)aziridines
  作者：Matthias D'hooghe、Alex Waterinckx、Norbert De Kimpe

  DOI：10.1021/jo048486f

  日期：2005.1.1

  2-(N-acylimino)-3-arylmethyl-4-chloromethyl-1,3-thiazolidines has been developed by ring transformation of 1-arylmethyl-2-(thiocyanomethyl)aziridines upon treatment with a catalytic amount of titanium(IV) chloride in dichloromethane. The latter 2-(thiocyanomethyl)aziridines were prepared in high yields from 1-arylmethyl-2-(bromomethyl)aziridines by reaction with potassium thiocyanate in DMF. The 2-imino-1,3-thiazolidines

  一种3-芳基甲基-4-氯甲基-2-亚氨基-1,3-噻唑烷和2-（N-酰基亚氨基）-3-芳基甲基-4-氯甲基-1,3-噻唑烷的新的，有效的和直接的合成方法通过在催化量的二氯甲烷中用催化量的氯化钛（IV）处理，通过1-芳基甲基-2-（硫氰基甲基）氮丙啶环的环化反应制得的化合物。通过在DMF中与硫氰酸钾反应，由1-芳基甲基-2-（溴甲基）氮丙啶高产率地制备后一种2-（硫氰基甲基）氮丙啶。如此获得的2-亚氨基-1,3-噻唑烷和2-（N-酰基酰亚胺）-1,3-噻唑烷可以通过用酰氯和乙醚中的碱处理而容易地相互转化成2-（N-酰基亚氨基）噻唑烷或通过在甲醇中用碳酸钾处理成N-去保护的2-亚氨基噻唑烷。通过叔丁醇钾在DMSO中将2-（N-酰基亚氨基）-3-芳基甲基-4-氯甲基-1,3-噻唑烷脱卤化氢得到2-（N-酰基亚氨基）-4-甲基-2,3-二氢-1,3-噻唑啉产量高。
• Synthesis and antiplasmodial evaluation of aziridine–(iso)quinoline hybrids and their ring-opening products
  作者：Stéphanie Vandekerckhove、Sofie De Moor、Dries Segers、Carmen de Kock、Peter J. Smith、Kelly Chibale、Norbert De Kimpe、Matthias D'hooghe

  DOI：10.1039/c3md20377h

  日期：——

  Aziridine–(iso)quinoline hybrid systems were prepared as novel synthetic intermediates en route to functionalized (iso)quinolines with potential antimalarial activity. Various quinolinecarboxaldehydes were converted into quinoline–aziridine–pyrazole, –pyridazinone or –pyrimidinone hybrids, and the three-membered azaheterocyclic moiety in these compounds was finally subjected to ring opening by either methanol or water to provide the corresponding functionalized quinolines. In addition, 5-hydroxyisoquinoline was used for the preparation of isoquinoline–aziridine chimeras, which were further transformed into a variety of functionalized isoquinolines via regioselective aziridine ring opening by various nucleophiles. Antiplasmodial evaluation of these new aziridine–(iso)quinoline hybrids and their ring-opening products revealed micromolar potency (0.22–30 μM) for all representatives against a chloroquine-sensitive strain of the malaria parasite Plasmodium falciparum. The six most potent compounds also showed micromolar activity against a chloroquine-resistant strain of P. falciparum with IC50-values ranging between 1.02 and 17.58 μM.

  氮杂环丙烷–（异）喹啉杂化体系被制备为合成中间体，旨在产出具有潜在抗疟疾活性的功能化（异）喹啉。各种喹啉羧醛被转化为喹啉–氮杂环丙烷–吡唑、–吡嗪酮或–嘧啶酮杂化物，这些化合物中的三元氮杂环部分最终通过甲醇或水开环，得到相应的功能化喹啉。此外，5-羟基异喹啉被用于制备异喹啉–氮杂环丙烷嵌合体，这些嵌合体又通过各种亲核试剂的区域选择性氮杂环丙烷开环转化为多种功能化异喹啉。对这些新型氮杂环丙烷–（异）喹啉杂化物及其开环产物的抗疟评估显示，所有代表对疟原虫Plasmodium falciparum的氯喹敏感株具有微摩尔级的活性（0.22–30 μM）。六种最具活性的化合物对氯喹耐药株P. falciparum也表现出微摩尔级的活性，IC50值在1.02到17.58 μM之间。
• Synthesis of 2-[(Arylmethylene)amino]cyclopropanecarbonitriles via a Two-Step Ring Transformation of 2-(Cyanomethyl)aziridines
  作者：Norbert De Kimpe、Sven Mangelinckx、Matthias D’hooghe、Sietske Peeters

  DOI：10.1055/s-0028-1088000

  日期：2009.4

  Reaction of 2-(cyanomethyl)aziridines with N-bromosuccinimide in dichloromethane results in the formation of 3-[(arylmethylene)amino]-4-bromobutanenitriles in high yield. The latter β-amino-γ-bromobutanenitriles were converted into separable trans- and cis-2-[(arylmethylene)amino]cyclopropanecarbonitriles through a 1,3-cyclization by reaction with potassium tert-butoxide, thus culminating in a two-step ring transformation of 2-(cyano­methyl)aziridines into 2-[(arylmethylene)amino]cyclopropanecarbonitriles.

  2-(氰基甲基)氮杂环丁烯与N-溴琥珀酰亚胺在二氯甲烷中的反应生成高收率的3-[(芳烯基)氨基]-4-溴丁腈。后者的β-氨基-γ-溴丁腈通过与醋酸钾的反应进行1,3-环化，转化为可分离的反式和顺式2-[(芳烯基)氨基]环丙烷碳腈，从而完成了2-(氰基甲基)氮杂环丁烯到2-[(芳烯基)氨基]环丙烷碳腈的两步环转化。
• Cobalt carbonyl-catalyzed carbonylation of functionalized aziridines to versatile β-lactam building blocks
  作者：Nicola Piens、Kristof Van Hecke、Dieter Vogt、Matthias D'hooghe

  DOI：10.1039/c7ob00832e

  日期：——

  carbonylation of different classes of non-activated aziridines with diverse substitution patterns was investigated. Special attention was devoted to selectivity issues and reaction optimization. This study resulted in the regio- and stereospecific synthesis of 24 novel β-lactam target structures in high yields on a multigram scale. The synthetic potential of the newly obtained azetidin-2-ones was illustrated

  研究了具有不同取代模式的不同类别的未活化氮丙啶的Co 2（CO）8催化的羰基化作用。特别关注选择性问题和反应优化。这项研究导致了24克新型β-内酰胺靶标结构的立体定位和立体定向合成，高产达数克。通过扩环，闭环和/或侧链官能化方案说明了新获得的氮杂环丁烷-2-酮的合成潜力，从而可以直接进入新型吡咯烷，C稠合的双环和三环β-内酰胺类化合物。和单环碳青霉烯类似物。