一溴二氯甲烷 | 75-27-4

• 物质功能分类: 化学试剂 - 有机试剂 - 卤代脂肪烃
• 分子结构分类: 有机化合物 - 有机卤素化合物 - 卤代烷
• 中文名称: 一溴二氯甲烷
• 中文别名: 溴二氯代甲烷；二氯溴甲烷；二氯一溴甲烷
• 英文名称: bromodichloromethane
• 英文别名: dichlorobromomethane；bromodichoromethane；BDCM；bromo(dichloro)methane
• CAS: 75-27-4
• 化学式: CHBrCl₂
• 分子量: 163.829
• InChiKey: FMWLUWPQPKEARP-UHFFFAOYSA-N

物化性质

• 熔点：
  −55 °C(lit.)
• 沸点：
  87 °C(lit.)
• 密度：
  1.98 g/mL at 25 °C(lit.)
• 闪点：
  87-89°C
• 溶解度：
  水：不溶
• 物理描述：
  Dichlorobromomethane is a clear colorless liquid. (NTP, 1992)
• 颜色/状态：
  Liquid
• 蒸汽密度：
  Relative vapor density (air = 1): 5.6
• 蒸汽压力：
  50 mm Hg at 20 °C
• 亨利常数：
  0.00 atm-m3/mole
• 分解：
  When heated to decomp it emits very toxic fumes of /hydrogen bromide and hydrogen chloride/.
• 气味阈值：
  Odor threshold low: 1680 mg/cu m odor high 1680 mg/cu m. /Bromochloromethane/
• 折光率：
  Index of refraction: 1.4964 at 20 °C/D
• 保留指数：
  698;686;690;695;702;687.4;688;697;680.1;685.8;690;699;690;715;691;693;694;704;715
• 稳定性/保质期：
  对机体存在不可逆损伤的风险，请在使用时穿着防护服并佩戴手套。

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  4
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

ADMET

代谢

当给予啮齿类动物时，卤代乙酸盐已被证明能增加肝脏中硫代巴比妥酸反应物和8-羟基脱氧鸟苷酸水平的形成。这些反应似乎会受到先前处理的影响。为了探讨可能导致这些氧化应激修饰的潜在机制，研究了三氯乙酸盐（TCA）或二氯乙酸盐（DCA）预处理对改变溴二氯乙酸盐（BDCA）的代谢及其代谢物处置的能力，在雄性B6C3F1小鼠中进行研究。在饮水中给予小鼠1 g/L DCA和TCA的两周预处理改变了BDCA的初始肝脏代谢及其代谢物DCA的进一步代谢。DCA预处理可抑制细胞质中1 mM DCA或BDCA的代谢高达70%。相比之下，DCA预处理使肝脏微粒体BDCA代谢增加了1.3倍，但对DCA的微粒体代谢几乎没有影响。增加的微粒体BDCA代谢似乎可归因于诱导了一种产生CO2和溴二氯甲烷（BDCM）作为代谢物的代谢途径。TCA预处理在细胞质中抑制BDCA代谢高达70%，在微粒体中抑制30%，但对DCA代谢几乎没有影响。这些结果表明，在高剂量卤代乙酸盐的癌症生物测试中，肝脏的代谢变得相当复杂。BDCA是一个很好的例子，因为它被代谢为至少两种具有不同作用模式的致癌代谢物，即BDCM和DCA。当剂量接近于诱导小鼠癌症的剂量时，这些代谢物占给药剂量的比例和数量将会有显著变化。这篇文章证明了当卤代乙酸盐混合处理时，这些相互作用将会发生。

... When administered to rodents, haloacetates have been shown to increase formation of thiobarbituric acid-reactive substances and 8-hydroxydeoxyguanosine levels in the liver. These responses appear to be modified by prior treatment. To examine potential mechanisms that account for these modifications in oxidative stress, the ability of trichloroacetate (TCA) or dichloroacetate (DCA) pretreatment to alter the metabolism of bromodichloroacetate (BDCA) and the disposition of its metabolites was examined in male B6C3F1 mice. Two-week pretreatment with 1 g/L DCA and TCA in the drinking water of mice alters the initial hepatic metabolism of BDCA and the further metabolism of its metabolite DCA. DCA pretreatment inhibits cytosolic metabolism of both 1 mM DCA or BDCA up to 70%. In contrast, DCA pretreatment stimulates hepatic microsomal BDCA metabolism 1.3-fold but has little effect on microsomal metabolism of DCA. Increased microsomal metabolism of BDCA appears to be attributable to the induction of a metabolic pathway that produces CO2 and bromodichloromethane (BDCM) as metabolites. TCA pretreatment inhibits BDCA metabolism up to 70% in the cytosol and 30% in microsomes but has little effect on DCA metabolism. These results indicate that the hepatic metabolism of the haloacetate becomes quite complex at the high doses that have been employed in cancer bioassays. BDCA serves as a good example, because it is metabolized to at least two carcinogenic metabolites that have different modes of action, BDCM and DCA. As doses approach those that induce cancer in mice, the proportion of and amounts of these metabolites as a fraction of the dose administered will change substantially. This article demonstrates that those interactions will occur from mixed treatment with haloacetates as well.

来源:Hazardous Substances Data Bank (HSDB)

代谢

饮用水消毒副产品溴二氯甲烷（CHBrCl(2)）之前已被证明在过度表达大鼠谷胱甘肽转移酶theta 1-1（GSTT1-1）的沙门氏菌中具有诱变性。在这项研究中，采取了多种实验方法来调查由GSTT1-1介导的CHBrCl(2)代谢产生的反应中间体与DNA共价结合的潜力。首先，将含有(14)CHBrCl(2)，补充谷胱甘肽（GSH）和牛胸腺DNA的鼠类肝细胞质培养物与对照（无鼠类细胞质）相比，在分离DNA的液闪计数（LSC）后，与纯化DNA相关的总放射性（RAD）量大约增加了3倍（大鼠肝细胞质）和7倍（小鼠肝细胞质）。DNA标记的相对增加与这些鼠类细胞质对CHBrCl(2)的共轭活性一致。其次，将表达GSTT1-1的S. typhimurium暴露于(14)CHBrCl(2)导致细菌DNA相关的总放射性随浓度依赖性增加。在DNA的酶促水解和随后的HPLC分析后，无法将DNA相关的放射性分配给特定的脱氧核苷加合物。这种观察结果的可能解释是在DNA分离和水解过程中，形成了一种短暂的加合物，这种加合物不稳定。为了规避加合物不稳定性的问题，将(14)CHBrCl(2)与GSH的反应在重组大鼠GSTT1-1的催化下，在存在牛胸腺DNA或替代的模型亲核试剂脱氧鸟苷的情况下进行。用(14)C标记的DNA的羟基磷灰石色谱或(14)C标记的脱氧鸟苷衍生物的HPLC色谱显示了(14)CHBrCl(2)-派生的代谢物与DNA和脱氧鸟苷的低产共价结合（大约0.02%的(14)CHBrCl(2)通过GSTT1-1转化为DNA加合物）。与大鼠肝脏（非靶组织）相比，大鼠肾脏和大肠（在慢性CHBrCl(2)暴露后发展肿瘤的组织）中细胞色素P450（CYP）和GST催化的CHBrCl(2)生物转化进行了比较。与肾脏和大肠相比，肝脏具有显著的解毒CHBrCl(2)（到二氧化碳）的能力，这是因为CYP催化的氧化作用，肝脏的内在清除率（V(max)/K(m)）大约是肾脏和大肠的16倍。相比之下，GST介导的GSH与CHBrCl(2)共轭在大肠和肾脏的效率仅略低于肝脏（大约低2到4倍），因此，与非肝脏组织相比，这些外肝脏组织中产生的具有共价修饰DNA能力的反应中间体的相对量可能增加。这些发现的意义在于，CHBrCl(2)与GSH的共轭可以导致DNA的共价修饰，而大鼠的癌症靶组织与肝脏（大鼠的非靶组织）相比，解毒能力大幅降低，但生物活化能力仅略有下降。

The drinking water disinfection byproduct bromodichloromethane (CHBrCl(2)) was previously shown to be mutagenic in Salmonella typhimurium that overexpress rat glutathione transferase theta 1-1 (GSTT1-1). Several experimental approaches were undertaken in this study to investigate the DNA covalent binding potential of reactive intermediates generated by GSTT1-1-mediated metabolism of CHBrCl(2). First, rodent hepatic cytosol incubations containing (14)CHBrCl(2), supplemented glutathione (GSH), and calf thymus DNA resulted in approximately 3-fold (rat liver cytosol) and 7-fold (mouse liver cytosol) greater amounts of total radioactivity (RAD) associated with the purified DNA as compared to a control (absence of rodent cytosol) following liquid scintillation counting (LSC) of isolated DNA. The relative increase in DNA labeling is consistent with the conjugation activity of these rodent cytosols toward CHBrCl(2). Second, exposure of GSTT1-1-expressing S. typhimurium to (14)CHBrCl(2) resulted in a concentration-dependent increase of bacterial DNA-associated total radioactivity. Characterization of DNA-associated radioactivity could not be assigned to a specific deoxynucleoside adduct(s) following enzymatic hydrolysis of DNA and subsequent HPLC analysis. A possible explanation for this observation was formation of a transient adduct that was unstable in the DNA isolation and hydrolysis procedures employed. To circumvent problems of adduct instability, reactions of (14)CHBrCl(2) with GSH catalyzed by recombinant rat GSTT1-1 were performed in the presence of calf thymus DNA or, alternatively, the model nucleophile deoxyguanosine. Hydroxyapatite chromatography of (14)C-labeled DNA or HPLC chromatography of (14)C-labeled deoxyguanosine derivatives demonstrated the covalent binding of (14)CHBrCl(2)-derived metabolites to DNA and deoxyguanosine in low yield (approximately 0.02% of (14)CHBrCl(2) biotransformed by GSTT1-1 resulted in DNA adducts). Cytochrome P450 (CYP)- and GST-catalyzed biotransformation of CHBrCl(2) in rat tissues (kidney and large intestine) that develop tumors following chronic CHBrCl(2) exposure were compared with rat liver (a nontarget tissue). Rat liver had a significant capacity to detoxify CHBrCl(2) (to carbon dioxide) compared with kidney and large intestine as a result of CYP-catalyzed oxidation, liver was approximately 16-fold more efficient than kidney and large intestine when intrinsic clearance values (V(max)/K(m)) were compared. In contrast, the efficiency of GST-mediated GSH conjugation of CHBrCl(2) in kidney and large intestine was only slightly lower than liver (approximately 2- to 4-fold lower), thus, the relative amounts of reactive intermediates that are produced with the capacity to covalently modify DNA may be enhanced in these extrahepatic tissues. The significance of these findings is that conjugation of CHBrCl(2) with GSH can result in the covalent modification of DNA and that cancer target tissues in rats have a much reduced detoxification capacity, but only a modest decrease in bioactivation capacity, as compared to the liver (a nontarget tissue in rats).

来源:Hazardous Substances Data Bank (HSDB)

代谢

Haloforms are metabolized to carbon monoxide by hepatic mixed function oxidases & this reaction is markedly stimulated by sulfhydryl cmpd. Max stimulation occurred at 0.5 mmolar glutathione. A mechanism for conversion of haloforms to carbon monoxide is proposed. /Haloforms/ 卤代甲烷通过肝脏混合功能氧化酶代谢为一氧化碳，这种反应被巯基化合物显著刺激。最大刺激发生在0.5毫摩尔谷胱甘肽时。提出了一种将卤代甲烷转化为一氧化碳的机制。/卤代甲烷/

Haloforms are metabolized to carbon monoxide by hepatic mixed function oxidases & this reaction is markedly stimulated by sulfhydryl cmpd. Max stimulation occurred at 0.5 mmolar glutathione. A mechanism for conversion of haloforms to carbon monoxide is proposed. /Haloforms/

来源:Hazardous Substances Data Bank (HSDB)

代谢

三卤甲烷（卤仿）通过大鼠肝脏微粒体组分代谢为一种碳一氧化物，此过程需要NADPH和分子氧以实现最大活性。结果表明，三卤甲烷是通过细胞色素P450依赖的混合功能氧化酶系统代谢为碳一氧化物的。

Trihalomethanes (haloforms) were metabolized to carbon monoxide by a rat liver microsomal fraction requiring NADPH & molecular oxygen for max activity. Results suggest haloforms are metab to carbon monoxide by a cytochrome P450 dependent mixed-function oxidase system. /Trihalomethanes/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

评估：没有关于溴二氯甲烷致癌性的相关流行病学数据。在实验动物中有足够的证据表明溴二氯甲烷具有致癌性。总体评估：溴二氯甲烷可能对人类具有致癌性（2B组）。

Evaluation: No epidemiological data relevant to the carcinogenicity of bromodichloromethane were available. There is sufficient evidence in experimental animals for the carcinogenicity of bromodichloromethane. Overall evaluation: Bromodichloromethane is possibly carcinogenic to humans (Group 2B).

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

二氯溴甲烷：合理预期为人类致癌物。

Bromodichloromethane: reasonably anticipated to be a human carcinogen.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

分类 B2；可能的人类致癌物。基于不充分的人类数据和两个动物物种（小鼠和大鼠）的充分致癌性证据，表现为大鼠中肾脏肿瘤和大肠肿瘤的发生率增加，雄性小鼠中肾脏肿瘤，以及雌性小鼠中肝脏肿瘤。//根据前美国环保署指南的分类/

Classification B2; probable human carcinogen. Based on inadequate human data and sufficient evidence of carcinogenicity in two animal species (mice and rats) as shown by increased incidence of kidney tumors and tumors of the large intestine in male and female rats, kidney tumors in male mice, and liver tumors in female mice. //Classification based on former EPA guidelines/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌物分类

国际癌症研究机构致癌物：溴二氯甲烷

IARC Carcinogenic Agent:Bromodichloromethane

来源:International Agency for Research on Cancer (IARC)

毒理性

• 致癌物分类

国际癌症研究机构（IARC）致癌物分类：2B组：可能对人类致癌

IARC Carcinogenic Classes:Group 2B: Possibly carcinogenic to humans

来源:International Agency for Research on Cancer (IARC)

吸收、分配和排泄

单次口服剂量为20毫克/千克的大鼠中，(14)C-溴二氯甲烷的清除非常迅速。3小时后在胃肠道和尸体中仅回收了32%，6小时后回收了41%。大部分化合物是从胃中回收的。脂肪含量比任何其他组织都要多。尿液中出现的不到1%。其余的...可能是通过呼吸排出的...

A single oral dose of 20 mg/kg ... /as (14)C-bromodichloromethane/ in rats is cleared very rapidly. Only 32% is recovered from GI tract & carcass after 3 hr, & 41% after 6 hr. Most of cmpd was recovered from stomach. Fat contained more than any other tissue. Less than 1% appeared in urine. Balance ... probably exhaled ...

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

一个31天的老鼠给药序列被用来研究溴氯甲烷在大鼠脂肪和血液血清中的一些生理分布、代谢、储存和消除速率方面。对于这种挥发性化合物，组织水平波动，但并未表明随着时间增加储存。脂肪组织与血液血清的水平从未相差超过3倍。在停止给药后的3-6天内，大多数卤代化合物已经离开了被检查的组织。

A 31-day rat-dosing sequence was used to study some aspects of physiological distribution, metabolism, storage & rate of elimination of bromodichloromethane from rat adipose & blood serum. For the volatile cmpd, tissue levels fluctuated but did not indicate incr storage with time. Adipose tissue to blood serum levels never differed by more than a factor of 3. Within 3-6 days after dosing was terminated, most of the halogenated cmpd had left the examined tissues.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

溴氯甲烷可能通过吸入或摄入轻易被吸收，广泛分布，优先到达高脂肪含量的组织，并部分通过呼出气体排出。

Bromodichloromethane may be absorbed readily by inhalation or ingestion, be distributed widely, preferentially to tissues with high lipid content, and be eliminated in part via expired breath.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

溴二氯甲烷在大鼠和猴子体内的药代动力学和组织分布进行了研究。该化合物主要通过肺部以原形或代谢物的形式排出。

Pharmacokinetics and tissue distribution of bromodichloromethane was examined in rats and monkeys. The compound was excreted primarily via the lung either unchanged or as metabolites.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 危险等级：
  6.1
• 危险品标志：
  Xn
• 安全说明：
  S16,S26,S36/37,S36/37/39,S36/39,S45
• 危险类别码：
  R22,R40
• WGK Germany：
  3
• 海关编码：
  29037990
• 危险品运输编号：
  2810
• RTECS号：
  PA5310000
• 包装等级：
  III
• 危险类别：
  6.1
• 储存条件：
  本品应密封保存在阴凉避光的地方。

SDS

国标编号:
ＣＡＳ:	75-27-4
中文名称:	一溴二氯甲烷
英文名称:	Monobromo-dichloro-methane；Bro
别 名:	二氯溴甲烷
分子式:	CHBrCl 2 ；BrCHCl 2
分子量:	163.8
熔 点:	-56.9℃
密 度:	2.006
蒸汽压:
溶解性:	难溶于水，溶于醇、苯、醚等有机溶剂
稳定性:
外观与性状:	无色液体
危险标记:
用 途:	来源：饮用水消毒产物

2.对环境的影响

一、健康危害
一溴二氯甲烷的毒性比三氯甲烷稍大，具有卤代烃化合物的共性，即对皮肤及粘膜有强烈的刺激性。能够经皮肤吸收后，侵蚀中枢神经，也作用于肺、心、肝、肾上腺和胃肠等内脏器管而引起中毒。
二、毒理学资料及环境行为
亚急性和慢性毒性：小鼠经口50mg/kg/日×14日肝肿大，体液免疫功能抑制；小鼠经口125mg/kg/日×14日肝肿大，血液葡萄糖含量下降，体液免疫功能抑制；小鼠经口250mg/kg/日×14日肝脾肿大，肝肾功能异常。
一溴二氯甲烷存在于水环境和底质环境中。环境监测结果表明，在饮用水中已被检出含有一溴二氯甲烷。尤其是经过加氯处理后的饮用水，该卤代烃污染物的含量，最高可达100μg/L左右。美国安全饮水委员会饮水调查结果表明，在饮用水源水中，一溴二氯甲烷的最高浓度为11μg/L，而在经过处理的水中最高浓度达到116μg/L。一般认为饮用水中这些卤化物是因为加氯过程中，消毒灭菌的同时，氯化了水体中天然存在的有机物质所生成的。

3.现场应急监测方法

直接进水样气相色谱法

4.实验室监测方法

吹扫捕集-气相色谱法(中国环境监测总站，水质)
气相色谱法《常见有毒化学品环境事故应急处置技术与监测方法》胡望钧主编
气相色谱法《固体废弃物试验与分析评价手册》中国环境监测总站等译

5.环境标准

美国(1981)饮用水(瓶装水)0.1mg/ L

6.应急处理处置方法

防止沾污扩散：为降低饮用水中一溴二氯甲烷，研究氯化前破坏或去除可被卤化的有机母体的方法，将可导致降低自来水中氯化产物及其对人类健康的危害。当饮用水水源中含有较高有机物质(微粒态或吸附在矿物微粒上的溶质)时，先混凝和过滤去除大量的有机物质，然后氯化处理，能直接减少包括一溴二氯甲烷在内的三卤甲烷的产生。

制备方法与用途

类别：有毒物质

毒性分级：中毒

急性毒性：口服-大鼠 LD50: 916 毫克/公斤

可燃性危险特性：热分解产生有毒溴化物和氯化物烟雾

储运特性：库房通风、低温干燥

灭火剂：干粉、干砂、二氧化碳、泡沫、1211 灭火剂

反应信息

• 作为反应物：
  描述：

  一溴二氯甲烷 在 氨 作用下， 以 甲醇 为溶剂， 生成
  参考文献：
  名称：

  卤代甲基铵基3D卤化物钙钛矿。

  摘要：

  具有ABX3典型结构的3D钙钛矿正在成为实现高性能光电器件的关键材料。A位阳离子的变化有望获得增强的性能。但是，仅限于甲胺，甲am和铯的几种可用选择。在这项工作中，卤代甲基铵被开发为A阳离子，以扩大杂化钙钛矿的家族。卤代甲基铵基钙钛矿的单晶和胶体纳米晶体已成功合成，显示出广阔的前景，可作为设备探索的替代方法。特别地，证明了来自单晶测量的改进的热稳定性和低激子结合能，并且对于胶体纳米晶体实现了从蓝色到绿色的明亮可调发射。

  DOI：

  10.1002/adma.201903830
• 作为产物：
  描述：

  氯仿 在 氢溴酸 、 氢化铝 作用下， 生成 一溴二氯甲烷
  参考文献：
  名称：

  Production of organic bromides

  摘要：

  公开号：

  US02553518A1
• 作为试剂：
  描述：

  亚磷酸二苄酯 在 一溴二氯甲烷 、 氨 作用下， 生成 Phosphorsaeure-dibenzylester-amid
  参考文献：
  名称：

  Atherton; Todd, Journal of the Chemical Society, 1947, p. 677

  摘要：

  DOI：

文献信息

• Compositions for Treatment of Cystic Fibrosis and Other Chronic Diseases
  申请人：Vertex Pharmaceuticals Incorporated

  公开号：US20150231142A1

  公开（公告）日：2015-08-20

  The present invention relates to pharmaceutical compositions comprising an inhibitor of epithelial sodium channel activity in combination with at least one ABC Transporter modulator compound of Formula A, Formula B, Formula C, or Formula D. The invention also relates to pharmaceutical formulations thereof, and to methods of using such compositions in the treatment of CFTR mediated diseases, particularly cystic fibrosis using the pharmaceutical combination compositions.

  本发明涉及含有上皮钠通道活性抑制剂与至少一种ABC转运蛋白调节剂化合物（A式、B式、C式或D式）的药物组合物。该发明还涉及这些药物配方，以及使用这些组合物治疗CFTR介导的疾病，特别是囊性纤维化的方法。
• Kinetics of the R+Cl2 (R=CH2Cl, CHBrCl, CCl3 and CH3CCl2) reactions. An ab initio study of the transition states
  作者：Jorma A. Seetula

  DOI：10.1039/a804223c

  日期：——

  The kinetics of the reactions of CH2Cl, CHBrCl, CCl3 and CH3CCl2 radicals with molecular chlorine were investigated in a heatable tubular reactor coupled to a photoionization mass spectrometer. The reactions were studied under pseudo-first-order conditions. The radicals were photogenerated at 248 nm. The pressure-independent rate constants determined were fitted to the following Kooij and Arrhenius expressions (units in cm3 molecule-1 s-1): k(CH2Cl)=7.56×10-17(T)1.45 exp(-350 J mol-1/RT), k(CHBrCl)=5.83×10-20(T)2.3 exp(-300 J mol-1/RT), k(CCl3)=(8.4±2.9)×10-13 exp[-(25±9) kJ mol-1/RT] and k(CH3CCl2)=1.10×10-26(T)4.3 exp(+15000 J mol-1/RT). The Arrhenius rate expression for the Cl+CCl4 reaction was determined to be k(Cl+CCl4)=(3.9±3.2)×10-13 exp[-(71±9) kJ mol-1/RT] using the kinetics measured and the thermochemistry of the CCl3 radical. Errors for the Kooij expressions were estimated to be 25% overall, and for the Arrhenius expressions they were calculated to be 1σ+Student's t values. The transition states of the measured R+Cl2 and four other similar reactions were localized and fully optimized at the MP2/6-31G(d,p) level of theory by abinitio methods. The energetics of the reactions were considered by determining thermochemical and activation parameters of the reactions. The reactivity differences of the radicals studied were explained by a free-energy correlation using an electronegativity difference scale.

  在可加热的管式反应器中，结合光电离质谱仪，研究了CH₂Cl、CHBrCl、CCl₃和CH₃CCl₂自由基与分子氯的反应动力学。这些反应在准一级条件下进行了研究，自由基在248 nm下光生。测得的与压力无关的速率常数拟合为以下Kooij和Arrhenius表达式（单位为cm³ molecule⁻¹ s⁻¹）： k(CH₂Cl) = 7.56×10⁻¹⁷(T)¹.⁴⁵ exp(-350 J mol⁻¹/RT) k(CHBrCl) = 5.83×10⁻²⁰(T)².³ exp(-300 J mol⁻¹/RT) k(CCl₃) = (8.4±2.9)×10⁻¹³ exp[-(25±9) kJ mol⁻¹/RT] k(CH₃CCl₂) = 1.10×10⁻²⁶(T)⁴.³ exp(+15000 J mol⁻¹/RT) 利用测得的反应动力学和CCl₃自由基的热化学数据，确定了Cl+CCl₄反应的Arrhenius速率表达式为： k(Cl+CCl₄) = (3.9±3.2)×10⁻¹³ exp[-(71±9) kJ mol⁻¹/RT] Kooij表达式的误差估计为总体25%，而Arrhenius表达式的误差计算为1σ加上学生的t值。通过从头计算方法，在MP2/6-31G(d,p)理论水平上，定域并完全优化了所测量的R+Cl₂反应和其他四个类似反应的过渡态。通过确定反应的热化学和活化参数，考虑了反应的能量学。通过使用电负性差异尺度进行自由能相关，解释了所研究自由基的反应性差异。
• Fe₃O₄-Catalyzed Halogen-Exchange Reactions of Polyhalomethanes
  作者：Masahiro Nakada、Sei-ichi Tokumoto、Minoru Hirota

  DOI：10.1246/bcsj.60.3979

  日期：1987.11

  Triiron tetraoxide pretreated by polyhalomethane was shown to catalyze the halgen-exchange reactions of polyhalomethanes CHlBrmCln(l=1 or 2). The exchange proceeds consecutively giving, for example, CHBrCl2, CHBr2Cl, and CHBr3 as the main products from CHCl3. The mechanism of the reaction is discussed briefly.

  经多卤甲烷预处理的四氧化三铁被证明可催化多卤甲烷 CHlBrmCln(l=1 或 2) 的卤素交换反应。交换继续进行，例如 CHBrCl2、CHBr2Cl 和 CHBr3 作为 CHCl3 的主要产品。简要讨论了反应机理。
• Generation of Halomethyl Radicals by Halogen Atom Abstraction and Their Addition Reactions with Alkenes
  作者：Robynne K. Neff、Yong-Liang Su、Siqi Liu、Melina Rosado、Xinhao Zhang、Michael P. Doyle

  DOI：10.1021/jacs.9b05921

  日期：2019.10.23

  α-Aminoradicals undergo halogen atom abstraction to form halomethyl radicals in reactions initiated by the combination of tert-butyl hydroperoxide, aliphatic trialkylamine, halocarbon, and copper(I) iodide. The formation of the α-aminoradical circumvents preferential hydrogen atom transfer in favor of halogen atom transfer, thereby releasing the halomethyl radical for addition to alkenes. The resulting

  α-氨基在由叔丁基过氧化氢、脂肪族三烷基胺、卤代烃和碘化铜（I）的组合引发的反应中经历卤素原子抽吸形成卤甲基自由基。α-氨基自由基的形成避免了有利于卤素原子转移的优先氢原子转移，从而释放卤代甲基自由基以加成到烯烃中。所得自由基加成产物与叔丁基过氧基团相加形成 α-过氧-β,β-二氯丙苯产物，该产物可转化为其相应的 β,β-二氯醇和新型吡啶衍生物。计算分析清楚地解释了氯仿与传统 HAT 的偏差，并建立了正式的氧化加成/还原消除作为最低能量途径。
• Mn-Mediated Coupling of Alkyl Iodides and Chiral <i>N</i>-Acylhydrazones:  Optimization, Scope, and Evidence for a Radical Mechanism
  作者：Gregory K. Friestad、Jean-Charles Marié、Suh、Jun Qin

  DOI：10.1021/jo061158q

  日期：2006.9.1

  of the use of photolysis with manganese carbonyl to mediate stereoselective intermolecular radical addition to N-acylhydrazones. Photolysis (300 nm) of alkyl halides and hydrazones in the presence of Mn2(CO)10 and InCl3 as a Lewis acid led to reductive radical addition; diastereomer ratios ranged from 93:7 to 98:2 at ca. 35 °C. The reaction tolerates additional functionality in either reactant, enabling

  立体选择性自由基加成物具有优异的潜力，可用于直接不对称胺合成的温和，非碱性碳-碳键结构。具有无环立体控制的向C N键的有效分子间自由基加成以前主要限于仲和叔自由基，这从合成应用的角度来看是一个严重的局限。在这里，我们提供了使用光解与羰基锰介导N-酰基hydr的立体选择性分子间自由基加成的完整细节。Mn 2（CO）10和InCl 3存在下卤代烷和的光解（300 nm）由于路易斯酸导致还原性自由基的添加；非对映体比在约93∶7至98∶2的范围内。35°C。该反应可耐受任一反应物的附加功能，从而可以进行后续的转化，如有效的不对称甜氨酸合成所示。比较了一系列在恶唑烷酮助剂上带有不同取代基的；始终如一的高非对映控制表明，取代基的身份对非对映选择性几乎没有实际影响。进一步的机械控制实验证实了自由基的中介性，并表明独立制备的烷基或酰基锰五羰基化合物没有有效地添加到氮中-酰基hydr在热或光解（300 n

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