三溴乙酸甲酯 | 3222-05-7

• 物质功能分类: 分析化学 - 标准品 - 挥发性有机化合物(VOCs)
• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 中文名称: 三溴乙酸甲酯
• 中文别名: 溴乙酸甲酯
• 英文名称: methyl tribromoacetate
• 英文别名: Tribrom-essigsaeure-methylester；methyl 2,2,2-tribromoacetate
• CAS: 3222-05-7
• 化学式: C₃H₃Br₃O₂
• mdl: MFCD00192327
• 分子量: 310.768
• InChiKey: QQHSHLKOWBDOFC-UHFFFAOYSA-N

物化性质

• 沸点：
  103 °C/15 mmHg(lit.)
• 密度：
  2.33 g/mL at 25 °C(lit.)
• 闪点：
  113 °C
• 保留指数：
  1174;1170.5

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.666
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 危险品标志：
  F,Xi
• 安全说明：
  S16,S26,S36
• 危险类别码：
  R40,R36/37/38
• 海关编码：
  2915900090
• 危险品运输编号：
  UN 2398 3/PG 2
• 储存条件：
  2-8°C

反应信息

• 作为反应物：
  描述：

  三溴乙酸甲酯 在 ammonium hydroxide 作用下， 生成 三溴乙酰胺
  参考文献：
  名称：

  Occurrence, Synthesis, and Mammalian Cell Cytotoxicity and Genotoxicity of Haloacetamides: An Emerging Class of Nitrogenous Drinking Water Disinfection Byproducts

  摘要：

  The haloacetamides, a class of emerging nitrogenous drinking water disinfection byproduct (DBPs), were analyzed for their chronic cytotoxicity and for the induction of genomic DNA damage in Chinese hamster ovary cells. The rank order for cytotoxicity of 13 haloacetamides was DIAcAm > IAcAm > BAcAm > TBAcAm > BIAcAm > DBCAcAm > CIAcAm > BDCAcAm > DBAcAm > BCAcAm > CAcAm > DCAcAm > TCAcAm. The rank order of their genotoxicity was TBAcAm > DIAcAm IAcAm > BAcAm > DBCAcAm > BIAcAm > BDCAcAm > CIAcAm > BCAcAm > DBAcAm > CAcAm > TCAcAm. DCAcAm was not genotoxic. Cytotoxicity and genotoxicity were primarily determined by the leaving tendency of the halogens and followed the order I > Br > > CI. With the exception of brominated trihaloacetamides, most of the toxicity rank order was consistent with structure-activity relationship expectations. For di- and trihaloacetamides, the presence of at least one good leaving halogen group (I or Br but not CI) appears to be critical for significant toxic activity. Log P was not a factor for monohaloacetamides but may play a role in the genotoxicity of trihaloacetamides and possible activation of dihaloacetamides by intracellular GSH and -SH compounds. With the advent of the U.S. EPA Stage 2 DBP regulations, water utilities are considering the use of disinfectants that are alternatives to chlorine. The use of these alternative disinfectants will shift the distribution of DBP chemical classes. The emergence of new, highly toxic iodinated, nitrogenous DBPs, as illustrated by the discovery of bromoiodoacetamide as a new DBP, underscores the importance of comparative toxicity studies to assist in the overall goal of safer drinking water practice.

  DOI：

  10.1021/es071754h
• 作为产物：
  描述：

  甲醇 、 三溴乙酰氯 以95%的产率得到三溴乙酸甲酯
  参考文献：
  名称：

  合成微管稳定海绵生物碱ceratamine A的抗有丝分裂类似物。

  摘要：

  从三溴咪唑开始合成了微管稳定海绵生物碱ceratamine A（1）的抗有丝分裂类似物。合成中的关键步骤是通过乙烯基溴化物和N-甲基酰胺之间的分子内布赫瓦尔德偶联形成氮杂环。这代表了完全不饱和咪唑并[4,5，d]氮杂的首次合成。从合成的ceratamine类似物获得的NMR数据为归属于天然产物的结构提供了支持。

  DOI：

  10.1021/ol7030284

文献信息

• Fe(0)-Mediated Synthesis of Tri- and Tetra-Substituted Olefins from Carbonyls:  An Environmentally Friendly Alternative to Cr(II)
  作者：J. R. Falck、Romain Bejot、Deb K. Barma、Anish Bandyopadhyay、Suju Joseph、Charles Mioskowski

  DOI：10.1021/jo061445u

  日期：2006.10.1

  carbonyls by activated polyhalides. In many instances, Fe(0) was equivalent or superior to Cr(II). Notably, Fe(0), but not Cr(II), proved compatible with a wide range of functionality, inter alia, unprotected phenol, aryl nitro, carboxylic acid, and alkyl nitrile. A surprising reversal of stereoselectivity for aldehydes versus ketones was observed using both metals. The resultant α-halo-α,β-unsaturated or α

  研究了Fe（0）作为Cr（II）的一种经济高效，环保的替代品，用于活化多卤化物对羰基进行烯化。在许多情况下，Fe（0）等于或优于Cr（II）。值得注意的是，事实证明，Fe（0）而不是Cr（II）与广泛的官能度兼容，尤其是与未保护的苯酚，芳基硝基，羧酸和烷基腈。使用两种金属均观察到醛相对于酮的立体选择性出乎意料的逆转。所得的α-卤代-α，β-不饱和或α，β-不饱和的羧酸，酯和腈是许多目标化合物中常见的结构元素，也是制备其他官能团的关键中间体。
• (NHC)AgCl catalyzed bromofluorocyclopropanation of alkenes with CFBr2CO2Na
  作者：Anastasia A. Andrianova、Yulia D. Maslova、Maxim A. Novikov、Sergei E. Semenov、Oleg M. Nefedov

  DOI：10.1016/j.jfluchem.2018.02.001

  日期：2018.5

  (monoalkyl substituted), electron-poor (haloalkenes, allylic esters, α,β-unsaturated esters) and acid/base sensitive silyl- and boronyl substituted alkenes with CFBr2CO2Na and catalytic (IPr)AgCl or (SIPr)AgCl was developed.

  有效的富氟（芳基取代），电子中性（单烷基取代），贫电子（卤代烯烃，烯丙基酯，α，β-不饱和酯）和酸/碱敏感的甲硅烷基和硼烷基取代的烯烃溴氟环丙烷化的有效方法开发了CFBr 2 CO 2 Na和催化（IPr）AgCl或（SIPr）AgCl。
• In Situ Derivatization/Solid-Phase Microextraction for the Determination of Haloacetic Acids in Water
  作者：M. N. Sarrión、F. J. Santos、M. T. Galceran

  DOI：10.1021/ac000479d

  日期：2000.10.1

  An in situ derivatization solid-phase microextraction method has been developed for the determination of haloacetic acids (HAAs) in water. The analytical procedure involves derivatization of HAAs to their methyl esters with dimethyl sulfate, headspace sampling using solid-phase microextraction (SPME), and gas chromatography-ion trap mass spectrometry (GC/ITMS) determination. Parameters affecting both derivatization efficiency and headspace SPME procedure, such as the selection of the SPME coating, derivatization−extraction time and temperature, and ionic strength, were optimized. The commercially available Carboxen-poly(dimethylsiloxane) (CAR-PDMS) fiber appears to be the most suitable for the determination of HAAs. Moreover, the formation of HAA methyl esters was dramatically improved (up to 90-fold) by the addition of tetrabutylammonium hydrogen sulfate (4.7 μmol) to the sample as ion-pairing agent in the derivatization step. The precision of the in situ derivatization/HS-SPME/GC/ITMS method evaluated using an internal standard gave relative standard deviations (RSDs) between 6.3 and 11.4%. The method was linear over 2 orders of magnitude, and detection limits were compound-dependent, but ranged from 10 to 450 ng/L. The method was compared with the EPA method 552.2 for the analysis of HAAs in various water samples, and good agreement was obtained. Consequently, in situ derivatization/HS-SPME/GC/ITMS is proposed for the analysis of HAAs in water.

  开发了一种原位衍生化固相微萃取方法，用于水中卤乙酸（HAAs）的测定。分析过程涉及HAAs与二甲基硫酸酯衍生化为甲酯，使用固相微萃取（SPME）进行顶空采样，以及采用气相色谱-离子阱质谱（GC/ITMS）进行测定。优化了影响衍生化效率和顶空SPME过程的参数，如SPME涂层的选择、衍生化-萃取时间与温度以及离子强度等。市售的Carboxen-聚（二甲基硅氧烷）（CAR-PDMS）纤维似乎最适合于HAAs的测定。此外，在衍生化步骤中，向样品中添加四丁基硫酸氢铵（4.7 μmol）作为离子配对剂，显著提高了HAA甲酯的形成（高达90倍）。使用内标法评估的原位衍生化/HS-SPME/GC/ITMS方法的精密度给出了相对标准偏差（RSDs）在6.3%至11.4%之间。该方法在线性范围超过2个数量级，检出限因化合物而异，但范围在10至450 ng/L之间。该方法与EPA方法552.2针对各种水样中HAAs的分析进行了比较，得到了良好的一致性。因此，提出原位衍生化/HS-SPME/GC/ITMS用于水中HAAs的分析。
• Hexabromoacetone as tribromoacetylating agent of alcohols and amines and as mediator in the conversion of carboxylic acids into amides in the presence of triphenylphosphine
  作者：Fabrício G. Menezes、Rosane Kolling、Adaílton J. Bortoluzzi、Hugo Gallardo、César Zucco

  DOI：10.1016/j.tetlet.2009.03.093

  日期：2009.5

  Hexabromoacetone has been used as an alternative tribromoacetylating agent of primary alcohols and amines and as mediator in the conversion of carboxylic acids into amides in the presence of triphenylphosphine. The reactions have been performed under mild conditions with moderate to good yields. All the products have been adequately characterized by their physical and spectroscopic properties.

  六溴丙酮已用作伯醇和胺的替代三溴乙酰化剂，并在三苯膦存在下将羧酸转化为酰胺时用作介体。反应已在温和的条件下以中等至良好的产率进行。所有产品均已通过其物理和光谱特性充分表征。
• Synthetic Approaches to the Microtubule-Stabilizing Sponge Alkaloid Ceratamine A and Desbromo Analogues
  作者：Matt Nodwell、Alban Pereira、Jenna L. Riffell、Carla Zimmerman、Brian O. Patrick、Michel Roberge、Raymond J. Andersen

  DOI：10.1021/jo802322s

  日期：2009.2.6

  Buchwald/Hartwig amination reaction on a 2-chloroimidazole precursor. Deprotection and aromatization resulted in the first synthesis of desbromoceratamine A (55) and desmethyldesbromoceratamine A (60). An unanticipated addition of atmospheric oxygen was encountered during deprotection of the imidazole ring in the last step of the synthesis leading to C-11 oxygenated ceratamine analogues as byproducts. Evaluation

  描述了微管稳定的西拉敏胺生物碱的两种合成方法。第一种方法涉及尝试将氨基咪唑部分接枝到氮杂环庚烷环上以形成部分氢化形式的ceratamines前所未有的芳香族咪唑并[4,5- d ]氮杂环庚烷核心。该路线最终失败，因为不可能将部分氢化的鲸蜡胺中间体芳香化。第二种方法是先将三溴咪唑进行金属化和官能化，以有效地生成含有乙烯基溴化物和酰胺官能团的关键咪唑中间体。分子内布赫瓦尔德乙烯基酰胺化反应将该关键中间体转化为双环咪唑并[4,5- d氮杂氮杂萘，其氧化态与ceratamines的芳族核相同。使用在2-氯咪唑前体上的布赫瓦尔德/哈特维格胺胺化反应，将存在于ceratamines咪唑环上的2-氨基官能团进行安装。脱保护和芳构化导致去溴代角神经酰胺A（55）和去甲基去溴代角神经酰胺A（60）的首次合成。在合成的最后步骤中，在咪唑环脱保护过程中遇到了意外的大气氧添加，导致副产物C-11氧化的麦角胺类似物

表征谱图