二苯并[b,f][1,4]噁唑频 | 257-07-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并恶嗪类
• 中文名称: 二苯并[b,f][1,4]噁唑频
• 中文别名: 二苯-(b,f)-1,4-氧杂吖庚因；二苯并[B,F][1,4]噁唑频
• 英文名称: dibenz[b,f][1,4]oxazepine
• 英文别名: dibenzo[b,f][1,4]oxazepine；Dibenz<1,4>oxazepin；Dibenzo<1,4>oxazepin；Dibenz[b,f][1,4loxazepine；benzo[b][1,4]benzoxazepine
• CAS: 257-07-8
• 化学式: C₁₃H₉NO
• mdl: MFCD00449255
• 分子量: 195.221
• InChiKey: NPUACKRELIJTFM-UHFFFAOYSA-N

物化性质

• 熔点：
  68-69 °C
• 沸点：
  331.88°C (rough estimate)
• 密度：
  1.1266 (rough estimate)
• 物理描述：
  Dibenz(b,f)(1,4)oxazepine is a colorless liquid, odorless to fruity.
• 颜色/状态：
  Pale yellow crystalline solid
• 气味：
  Pepper-like odor
• 溶解度：
  In water, 124 mg/L at 25 °C (est)
• 蒸汽压力：
  2.2X10-4 mm Hg at 25 °C (est)
• 分解：
  When heated to decomposition it emits toxic vapors of /Nitrogen oxides/.
• 保留指数：
  1811;1800;1803.5

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

ADMET

代谢

二苯并[b,f]-1,4-[11(14)-C]恶嗪（CR）在大鼠、恒河猴和豚鼠以及离体灌注的大鼠肝脏中的命运已经得到了研究。以1.56至3470微摩尔/千克的剂量给大鼠注射14C-CR，无论剂量或给药途径如何，大部分（59-93%）以7-、4-和9-羟基化10,11-二氢二苯并[b,f]-1,4-恶嗪-11(10H)-酮的硫酸盐形式在尿液中排出。在血液中，无论是在体内还是在肝脏灌注液中，CR的浓度都呈双相下降，最初被CR-内酰胺（二氢二苯并[b,f]-1,4-恶嗪-11(10H)-酮）取代，随后是7-、4-和9-羟基内酰胺的硫酸盐。CR在肝脏灌注液中的消失速率比在体内慢。胆汁中只含有少量的硫酸盐共轭物和大量的共轭2-氨基-2'-羟甲基二苯基醚（氨基醇）。在鼠尿或血液中未发现此物质。对恒河猴和豚鼠的初步研究表明，它们的排泄模式和代谢物相似。然而，只有自由的羟基内酰胺从猴尿中分离出来，豚鼠尿液中检测到氨基醇的痕迹。小鼠的全身体部放射自显影证实了CR从血液迅速进入心脏、肝脏、肾脏和小肠，并有胆汁排出的证据。这与大鼠的研究一致，表明高度亲脂性化合物被迅速吸收，经过肝脏代谢、胆汁分泌、肠肝循环和肾脏排泄。

The fate of dibenz[b,f]-1,4-[11(14)-C]oxazepine (CR) in rats, rhesus monkey and guinea-pig and in isolated perfused rat livers has been examined. 14C-CR was administered to rats at doses from 1.56 to 3470 umol/kg and irrespective of dose or route of administration most (59-93%) was eliminated in the urine as primarily the sulfates of the 7-, 4- and 9-hydroxylated 10,11-dihydrodibenz[b,f]-1,4-oxazepine-11(10H)-one. In blood, both in vivo and in liver perfusates, CR concentrations decreased biphasically to be replaced initially with CR-lactam (dihydrodibenz[b,f]-1,4-oxazepine-11(10H)-one), followed by the sulfates of the 7-, 4- and 9-hydroxylactams. The rate of disappearance of CR in liver perfusates was slower than in vivo. Bile contained only small amounts of sulphate conjugates and significant amounts of conjugated 2-amino-2'-hydroxymethyldiphenyl ether (amino alcohol). This was not identified in the urine or blood of rats. Preliminary studies in rhesus monkey and the guinea-pig show similar excretory patterns and metabolites. However, only free hydroxylactams were isolated from monkey urine and traces of the amino alcohol were detected in guinea-pig urine. Whole-body autoradiography of mice confirm the rapid disappearance of CR from blood into heart, liver, kidneys and small intestine with evidence of biliary excretion. It is consistent with the rat studies showing the rapid absorption of a highly lipophilic compound undergoing hepatic metabolism, biliary secretion, enterohepatic recirculation and renal excretion. /Dibenz[b,f]-1,4-[11(14)-C]oxazepine (CR)/

来源:Hazardous Substances Data Bank (HSDB)

代谢

CR（二苯并[b,f]-1,4-噁嗪）通过大鼠肝脏105,000 g超滤液组分代谢，包括（a）环开和还原为2-氨基-2'-羟甲基二苯基醚，以及（b）在C11位的氧化生成环状内酰胺。反应（a）是NADPH依赖性的，透析和亚甲基蓝会使其降低，而反应（b）对热稳定，透析会使其失活，氰化物、对氯汞苯甲酸、戊巴比妥和甲萘醌会抑制它，亚甲基蓝、甲磺酸吩噻嗪和2,6-二氯酚靛酚会刺激它。反应（a）类似于醛还原酶（E.C.1.1.1.2）的反应，反应（b）类似于钼羟基酶（E.C.1.2.3.1）的反应。反应（a）也可以由肝微粒体中的NADH依赖性酶催化，并且在该细胞组分中也会发生内酰胺的后续羟基化。CR在一些额外肝脏组织中也通过相同的途径进行代谢，包括肾脏、小肠和肺，尽管产量有限。蜗牛（Helix pomatia）的消化腺提取物能将CR转化为其内酰胺，并且量显著。CR的体外代谢与体内观察预测的相似。

CR (dibenz[b,f]-1,4-oxazepine) is metabolized by rat liver 105,000 g supernatant fractions by (a) ring opening and reduction to 2-amino-2'-hydroxymethyldiphenyl ether and (b) oxidation at C11 to give a cyclic lactam. Reaction (a) is NADPH-dependent, decreased by dialysis and methylene blue, whereas reaction (b) is heat-resistant, inactivated by dialysis, inhibited by CN-, p-chloromercuribenzoate, amytal and menadione, and stimulated by methylene blue, phenazine methosulphate and 2,6-dichlorophenol indophenol. Reaction (a) is similar to that of aldehyde reductases (E.C.1.1.1.2) and reaction (b) to that of molybdenum hydroxylases (E.C.1.2.3.1). Reaction (a) is also catalysed by an NADH-dependent enzyme in liver microsomes and subsequent hydroxylation of the lactam also occurs in this cell fraction. Some extrahepatic metabolism of CR occurs via the same routes in kidney, small intestine and lung, though the yield is limited. Digestive gland extract of Helix pomatia converts CR to its lactam in significant amounts. The metabolism of CR in vitro is similar to that predicted from observations in vivo. /CR (dibenz[b,f]-1,4-oxazepine)/

来源:Hazardous Substances Data Bank (HSDB)

代谢

以下是大二苯[b,f]-1,4-氧氮杂环庚烷（CR）的几种中间体在大鼠体内和体外代谢命运的考察，以建立CR的代谢和排泄顺序。在孤立灌注的大鼠肝脏中加入开环的2-氨基-2'-羟甲基二苯醚（氨基酸醇）后，迅速以高度极性的结合物混合物形式在胆汁中清除，而在体内主要的排泄途径是在尿液中以4-、7-和9-羟基内酰胺硫酸盐的形式。CR的内酰胺仅在尿液中排出，给出与CR相同的产物，但C10-C11二氢衍生物的代谢物分布与母体化合物不同，表明它在体内CR的命运中仅扮演一个外围角色。来自尿硫酸酶的7-、4-和9-羟基内酰胺的混合物在血液中迅速清除，无论是在体内还是孤立灌注肝脏中，都以硫酸盐的形式硫酸化和分泌到血液中。很少有胆汁排泄。当羟基内酰胺的尿硫酸盐静脉注射给大鼠时，1小时内70%通过尿液排出；然而，如果结扎肾脏，硫酸盐的胆汁排泄会更高（5小时内58%）。在大鼠十二指肠内给予CR代谢的胆汁结合物后，全部剂量被重新吸收，再次分泌到胆汁中或以硫酸盐的形式在尿液中排出。这些研究证实，大鼠体内CR的主要代谢命运是氧化成内酰胺，随后是环羟基化、硫酸化和尿液排泄。/大二苯[b,f]-1,4-氧氮杂环庚烷（CR）/

The fates of several intermediates of dibenz[b,f]-1,4-oxazepine (CR) metabolism in vivo and in vitro in rats have been examined to establish the metabolism and excretory sequence of CR. The ring-opened 2-amino 2'-hydroxymethyldiphenyl ether (amino alcohol) added to isolated perfused rat liver was rapidly cleared in bile as a mixture of highly polar conjugates, whereas the major route of excretion in vivo was as the 4-, 7- and 9-hydroxylactam sulfates in urine. The lactam of CR was eliminated exclusively in urine giving the same products as obtained for CR, but the distribution of metabolites of the C10-C11 dihydro derivative of CR was unlike that of the parent compound indicating that it occupies only a peripheral role in the fate of CR in vivo. A mixture of 7-, 4- and 9-hydroxylactams derived from the enzymic hydrolysis of urinary sulphates was rapidly removed from blood, sulphated and secreted as sulphates into blood both in vivo and in isolated perfused liver. Little biliary excretion occurred. When the urinary sulfates of the hydroxy lactams were administered i.v. to rats, 70% was eliminated in urine within 1 hr; however, if the kidneys were ligated biliary excretion of sulphate was higher (58% in 5 h). After intraduodenal administration of the biliary conjugates of CR metabolism, all of the dose was resorbed to be re-secreted in bile or excreted as sulphates in urine. These studies confirm that the major metabolic fate of CR in the rat is oxidation to lactam, followed by ring hydroxylation, sulfation and urinary excretion. /Dibenz[b,f]-1,4-oxazepine (CR)/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌物分类

未列入国际癌症研究机构(IARC)的清单。

Not listed by IARC.

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 相互作用

二苯并(b,f)-1,4-氧氮杂环庚烷（CR）是一种强效的外周感官刺激物，通过静脉注射、腹腔注射、口服、经皮和吸入途径对多种实验室哺乳动物进行的实验表明，其急性致死和亚致死毒性非常低。没有发现特定器官的病理变化。将CR的急性毒性与其两种其他外周感官刺激物——氯乙酰苯（CN）和氯代苯甲酰亚甲基马来酰亚胺（CS）进行比较，结果显示CR的毒性显著低于这两种物质。由烟火技术产生的CR烟雾比纯CR（热力产生）气溶胶的毒性要大；这是由于燃烧烟雾生成混合物时，大气中存在烟火分解产物。然而，由烟火技术产生的CR烟雾的半数致死毒性显著低于由烟火技术产生的CN或CS烟雾。在多次口服CR后，并未发生短期累积毒性。研究了从1-氯-2-硝基苯和钠苯酚合成CR过程中遇到的三个醚中间体的急性毒理学；发现这三种醚的急性毒性都比CR本身要低。 /二苯并(b,f)-1,4-氧氮杂环庚烷/

Dibenz(b,f)-1,4-oxazepine (CR), a potent peripheral sensory irritant material, has been shown to have a very low acute lethal and sub-lethal toxicity by intravenous, intraperitoneal, oral, percutaneous and inhalation routes to several species of laboratory mammal. There was no organ-specific pathology. Comparison of the acute toxicity of CR with that of two other peripheral sensory irritants, 1-chloroacetophenone (CN) and 2-chlorobenzyl-lidene malononitrile (CS), shows CR to be significantly less toxic than either of them. Pyrotechnically generated CR smoke was more toxic than pure (thermally generated) aerosols of CR; this was due to the presence of pyrotechnic decomposition products in the atmosphere from the burning of the smoke generating composition. However, the median lethal toxicity of pyrotechnically generated CR smoke was very significantly less than that of either pyrotechnically generated CN or CS smokes. Short-term cumulative toxicity did not occur following multiple oral dosing with CR. The acute toxicology of three ether intermediates encountered in the synthesis of CR from 1-chloro-2-nitrobenzene and sodium phenoxide (2-nitrodiphenyl ether, 2-aminodiphenyl ether and 2-formamidodiphenyl ether) was investigated; all three ethers were found to be less acutely toxic than CR itself. /Dibenz(b,f)-1,4-oxazepine/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 解毒与急救

治疗包括帮助受影响的人在他的血液中获得更多氧气，并阻止因催泪瓦斯引起的化学烧伤进一步恶化。用于治疗哮喘的药物（如支气管扩张剂和类固醇）也可能被用来帮助患者呼吸。眼睛接触的处理方法是用清水冲洗眼睛，直到眼睛中没有催泪瓦斯的迹象。对于催泪瓦斯中毒没有解毒剂。皮肤烧伤的处理采用标准的烧伤管理技术，包括使用药物敷料。/催泪瓦斯/

Treatment consists of helping the affected person get more oxygen in his or her blood and of stopping agent-caused chemical burns from getting worse. Medications that are used to treat asthma (such as bronchodilators and steroids) may also be used to help the person breathe. Eye exposures are treated by rinsing the eyes with water until there is no evidence of riot control agents in the eyes. No antidote exists for poisoning from riot control agents. Burn injuries to the skin are treated with standard burn management techniques, including use of medicated bandages. /Riot control agents/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 人类毒性摘录

人类暴露研究/ 化学刺激物o-氯代苄基亚硝基甲烷（CS），n-壬酸香草酰胺（VAN）和二苯并氧氮杂（CR）及其衍生物使用人类水泡基底进行了检测。通过这种方法发现的相对效力，CR大于VAN大于CS，与非人类测试系统发现的效力相冲突，但CS和CR的效力等级反映了在人类眼睛和舌头测试中报告的等级。因此，从人类获得的数据在评估刺激物效力时似乎很重要。研究了CS、CR、VAN、辣椒素和缓激肽之间的相互作用，以发现任何共同的刺激活动途径。在重复将所有刺激物应用于水泡基底时，自我脱敏发展，并且也发生了选择性交叉脱敏。

/HUMAN EXPOSURE STUDIES/ The chemical irritants o-chlorobenzylidene malononitrile (CS), n-nonanoylvanillylamine (VAN) and dibenzoxazepine (CR) and several of its derivatives have been assayed using the human blister base. The relative potencies found by this method, CR greater than VAN greater than CS, conflicted with those found in non-human test systems but the rank order of potency of CS and CR reflected that reported in tests on the human eye and tongue. Data derived from humans thus appear to be of importance when assessing irritant potency. Interactions between CS, CR, VAN, capsaicin and bradykinin were investigated to discover any common pathways of irritant activity. Self-desensitization developed on repeated application of all agents to the blister base and selective cross-desensitization also occurred.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 人类毒性摘录

/症状和体征/ 刺激性失能剂，也称为防暴剂、催泪剂和催泪瓦斯，是通过气溶胶分散的化学物质，能引起眼睛、鼻子、嘴巴、皮肤和呼吸道的刺激。催泪瓦斯是常见名称，指的是在低浓度下会在眼睛中引起疼痛、流泪和难以保持眼睛睁开的物质。可能部署的只有三种药剂：（一）氯乙酰苯（CN）；（二）2-氯苯亚甲基甲酸（CS）；或（三）二苯[b,f]-1,4-氧氮杂（CR）。CN是最有毒的催泪剂，在高浓度下已导致角膜上皮损伤和结膜水肿。它至少导致了五人死亡，这些死亡是由于肺部损伤和/或窒息造成的。CS是比CN强10倍的催泪剂，但系统毒性较低。CR是最强的催泪剂，系统毒性最小，且高度稳定。CN、CS和CR几乎能立即在眼睛中引起疼痛、大量流泪和眼睑闭合，使暴露者失去能力。除了对眼睛的影响外，这些药剂还会引起鼻子和嘴巴、喉咙和气道的刺激，有时甚至刺激皮肤，特别是在湿润和温暖区域。在大量暴露的情况下，吞下的催泪瓦斯可能会引起呕吐。严重的系统毒性很少见，最常发生在CN上；当这些药剂在封闭非通风空间内以非常高的浓度使用时，最有可能发生。根据现有的毒理学和医学证据，CS和CR在威胁生命或不可逆转的毒性效果方面有很大的安全边际。没有证据表明，健康个体会在露天暴露于CS或CR后经历长期健康影响，尽管CR的污染更难以去除。/二苯[b,f]-1,4-氧氮杂（CR）/

/SIGNS AND SYMPTOMS/ Irritant incapacitants, also called riot control agents, lacrimators and tear gases, are aerosol-dispersed chemicals that produce eye, nose, mouth, skin and respiratory tract irritation. Tear gas is the common name for substances that, in low concentrations, cause pain in the eyes, flow of tears and difficulty in keeping the eyes open. Only three agents are likely to be deployed: (i) 1-chloroacetophenone (CN); (ii) 2-chlorobenzylidene malononitrile (CS); or (iii) dibenz[b,f]-1,4-oxazepine (CR). CN is the most toxic lacrimator and at high concentrations has caused corneal epithelial damage and chemosis. It has accounted for at least five deaths, which have resulted from pulmonary injury and/or asphyxia. CS is a 10-times more potent lacrimator than CN but is less systemically toxic. CR is the most potent lacrimator with the least systemic toxicity and is highly stable. CN, CS and CR cause almost instant pain in the eyes, excessive flow of tears and closure of the eyelids, and incapacitation of exposed individuals. Apart from the effects on the eyes, these agents also cause irritation in the nose and mouth, throat and airways and sometimes to the skin, particularly in moist and warm areas. In situations of massive exposure, tear gas, which is swallowed, may cause vomiting. Serious systemic toxicity is rare and occurs most frequently with CN; it is most likely to occur when these agents are used in very high concentrations within confined non-ventilated spaces. Based on the available toxicological and medical evidence, CS and CR have a large safety margin for life-threatening or irreversible toxic effects. There is no evidence that a healthy individual will experience long-term health effects from open-air exposures to CS or CR, although contamination with CR is less easy to remove. /Dibenz[b,f]-1,4-oxazepine (CR)/

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 海关编码：
  2934999090
• 储存条件：
  库房应低温、通风、干燥，并保持密闭状态，同时要与食品原料分开存放。

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 为 563 毫克/公斤；口服-小鼠 LD50 为 770 毫克/公斤
刺激数据：眼-兔子 5 海氏单位 轻度
可燃性危险特性：可燃；火场分解生成有毒的氮氧化物气体
储运特性：库房低温、通风干燥保存；密闭容器储存；与食品原料分开存放
灭火剂：水、二氧化碳、干粉、砂土

反应信息

• 作为反应物：
  描述：

  二苯并[b,f][1,4]噁唑频 在 盐酸 、 copper(l) chloride 、 sodium nitrite 作用下， 以 水 为溶剂， 反应 0.25h， 以67%的产率得到占吨酮
  参考文献：
  名称：

  Dibenz[b,e]azepines. Part 3. Acid hydrolysis

  摘要：

  DOI：

  10.1007/bf02464284
• 作为产物：
  描述：

  2-苯氧基苯甲酰胺 在 PPA 作用下， 生成 二苯并[b,f][1,4]噁唑频
  参考文献：
  名称：

  Dibenz[b,e]azepines. Part 3. Acid hydrolysis

  摘要：

  DOI：

  10.1007/bf02464284
• 作为试剂：
  描述：

  2-diazo-N-methyl-3-oxo-butamide-N-phenyl 在 sodium methylate 、 二苯并[b,f][1,4]噁唑频 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 9.0h， 生成 N-甲基吲哚酮
  参考文献：
  名称：

  在光辐射下以重氮乙酸酯为酮的前体合成3-烷氧基/芳氧基-β-内酰胺

  摘要：

  由亚胺与烷基/芳基重氮乙酸酯在光辐射条件下的反应以令人满意的至良好的产率合成3-烷氧基/芳氧基-β-内酰胺。通常，使用当前方法从线性亚胺获得反式-β-内酰胺作为主要产物。相反，在三乙胺的存在下，亚胺和烷氧基/芳氧基乙酰氯或它们的等价物的相应的热反应提供了作为主要或专有产物的顺式-β-内酰胺。由线性亚胺形成反式-β-内酰胺的原因是亚胺由其反式异构体异构化为顺式-在UV辐射下的异构体。报道的方法代表了用于合成3-烷氧基/芳氧基-β-内酰胺的无金属和中性方法。 重氮乙酸酯-亚胺-乙烯酮-β-内酰胺-光辐射-施陶丁格反应

  DOI：

  10.1055/s-0030-1259485

文献信息

• Highly enantioselective direct Mannich reaction of seven-membered cyclic imines dibenzo[b,f][1,4]oxazepines with acetone via organocatalysis
  作者：You-Qing Wang、Yuan-Yuan Ren

  DOI：10.1016/s1872-2067(14)60225-4

  日期：2015.1

  dibenzo[ b,f ][ 1,4 ]oxazepines as seven-membered cyclic imines underwent a highly enantioselective direct Mannich reaction with acetone when catalyzed by proline. These reactions gave a range of optically active β-carbonyl seven-membered N -heterocycles with excellent enantioselectivity (93%–98% ee). With 2-butanone as a Mannich donor, the single regioselective product was obtained with 96%–97% ee. The absolute

  摘要 各种取代的二苯并[ b, f ][ 1,4 ]氧氮杂作为七元环亚胺，在脯氨酸催化下与丙酮发生高度对映选择性的直接曼尼希反应。这些反应产生了一系列具有优异对映选择性 (93%–98% ee) 的光学活性 β-羰基七元 N-杂环。以 2-丁酮作为曼尼希供体，获得了具有 96%–97% ee 的单一区域选择性产物。通过对其衍生物的 X 射线单晶分析，产物的绝对构型被指定为 R。
• Enantioselective addition of Et2Zn to seven‐membered cyclic imines catalyzed by a (R)-VAPOL-Zn(II) complex
  作者：Lode De Munck、Verena Sukowski、Carlos Vila、José R. Pedro

  DOI：10.1016/j.tetlet.2017.07.042

  日期：2017.8

  substituted dibenzo[b,f][1,4]oxazepines underwent an enantioselective alkylation with Et2Zn catalyzed by a (R)-VAPOL-Zn(II) complex. The corresponding chiral 11-ethyl-10,11-dihydrodibenzo[b,f][1,4]oxazepine derivatives were obtained with good yields and moderate enantioselectivities. This represents the first example of enantioselective addition of Et2Zn to cyclic aldimines.

  （R）-VAPOL-Zn（II）配合物催化的各种取代的二苯并[ b，f ] [1,4]氮杂ze庚因与Et 2 Zn进行对映选择性烷基化。以良好的产率和中等的对映选择性获得了相应的手性11-乙基-10，11-二氢二苯并[ b，f ] [1，4]奥氮平衍生物。这代表了将Et 2 Zn对映选择性加成到环状亚胺上的第一个例子。
• [EN] INHIBITORS OF HISTONE DEACETYLASE<br/>[FR] INHIBITEURS DE L'HISTONE DÉACÉTYLASE
  申请人：METHYLGENE INC

  公开号：WO2009055917A1

  公开（公告）日：2009-05-07

  This invention relates to compounds and methods for the inhibition of HDAC enzymatic activity. More particularly, the invention provides for compounds of formula (I), (I) and N-oxides, hydrates, solvates, pharmaceutically acceptable salts, prodrugs and complexes thereof, and racemic and scalemic mixtures, diastereomers and enantiomers thereof, wherein L, M, n, R, W, X and Y are as defined in the specification.

  这项发明涉及化合物和用于抑制HDAC酶活性的方法。更具体地，该发明提供了符合式(I)、(I)和N-氧化物、水合物、溶剂合物、药用可接受盐、前药和其复合物、外消旋和手性混合物、非对映异构体和对映体的化合物，其中L、M、n、R、W、X和Y如规范中定义的。
• Stereoselective control in the Staudinger reactions involving monosubstituted ketenes with electron acceptor substituents: experimental investigation and theoretical rationalization
  作者：Hengzhen Qi、Xinyao Li、Jiaxi Xu

  DOI：10.1039/c0ob00783h

  日期：——

  The stereoselectivity of the Staudinger reactions involving monosubstituted ketenes with electron acceptor substituents was investigated experimentally by determination of the product stereochemistry and theoretically via DFT calculations. The results indicate that imines preferentially attack the less sterically hindered exo-side of the ketenes to generate zwitterionic intermediates. Subsequently, for cyclic imines, the intermediates undergo a conrotatory ring closure directly to produce β-lactams, while for linear imines, the imine moiety of the intermediates isomerizes to more stable intermediates, which further undergo a conrotatory ring closure to afford trans-β-lactams. The steric hindrance and the isomerization, rather than the torquoelectronic effect, play crucial roles in controlling the stereoselectivity in the practical Staudinger reactions involving monosubstituted ketenes with electron acceptor substituents, although the unaccessible borylketene with a powerful electron acceptor group controls the stereoselectivity torquoelectronically, in theory.

  通过确定产物立体化学和基于密度泛函理论（DFT）的计算，实验上研究了涉及带有电子受体取代基的单取代乙烯酮的斯陶丁格反应的立体选择性。结果表明，亚胺优先攻击乙烯酮上立体障碍较小的外侧，生成内鎓离子中间体。随后，对于环状亚胺，中间体直接进行协同环合反应生成β-内酰胺；而对于线性亚胺，中间体的亚胺部分异构化为更稳定的中间体，后者进一步进行协同环合反应，产生反式β-内酰胺。在实际涉及带有电子受体取代基的单取代乙烯酮的斯陶丁格反应中，立体障碍和异构化而不是扭曲电子效应在控制立体选择性中起着关键作用，尽管在理论上，具有强电子受体基团的不可获得的硼乙烯酮通过扭曲电子效应控制立体选择性。
• N-Heterocyclic Carbene (NHC)-Catalyzed One-Pot Aerobic Oxidative Synthesis of 2-Substituted Benzo[d]oxazoles, Benzo[d]thiazoles and 1,2-Disubstituted Benzo[d]imidazoles
  作者：Xiu-Feng Hou、Quan Zhou、Shu Liu、Ming Ma、He-Zhen Cui、Xi Hong、Shuang Huang、Jing-Fan Zhang

  DOI：10.1055/s-0036-1591524

  日期：2018.3

  aerobic oxidative synthesis of 2-arylbenzo[d]oxazoles, 2-substituted benzo[d]thiazoles, and 1,2-disubstituted benzo[d]imidazoles. N-Heterocyclic carbene (NHC), generated in situ from easily available N-heterocyclic imidazolium salt with air as terminal oxidant, has successfully been utilized as a cheap and efficient catalyst for one-pot aerobic oxidative synthesis of 2-arylbenzo[d]oxazoles, 2-substituted

  摘要 N-杂环卡宾（NHC）是由易获得的N-杂环咪唑盐以空气为末端氧化剂原位生成的，已成功地用作便宜且有效的一锅好氧氧化合成2-芳基苯并[ d ]恶唑的催化剂，2-取代的苯并[ d ]噻唑和1,2-二取代的苯并[ d ]咪唑。 N-杂环卡宾（NHC）是由易获得的N-杂环咪唑盐以空气为末端氧化剂原位生成的，已成功地用作便宜且有效的一锅好氧氧化合成2-芳基苯并[ d ]恶唑的催化剂，2-取代的苯并[ d ]噻唑和1,2-二取代的苯并[ d ]咪唑。

表征谱图