物理有机化学作业——109宿舍（阐述下列反应并描述其反应机理：）Baylis-Hillman Reaction Beckmann Rearrangement Benzoin CondensationBirch Reduction Bischler-Napieralski Reaction Claisen CondensationClaisen Rearrangement Curtius Rearrangement (Reaction)Cannizzaro Oxidation ReductionDarzens Reaction Dieckmann Condensation Favorskii Reaction Fries Rearrangement Heck Reaction Henry Reaction Mannich Reaction Michael AdditionNef Reaction Pinacol Rearrangement Reformatsky ReactionRitter Reaction Schmidt Reaction Suzuki Coupling Swern Oxidation Tsuji-Trost Reaction Ullmann ReactionVilsmeier Reaction Wittig ReactionBeckmann重排肟在酸如硫酸、多聚磷酸以及能产生强酸的五氯化磷、三氯化磷、苯磺酰氯、亚硫酰氯等作用下发生重排，生成相应的取代酰胺，如环己酮肟在硫酸作用下重排生成己内酰胺：反应机理在酸作用下，肟首先发生质子化，然后脱去一分子水，同时与羟基处于反位的基团迁移到缺电子的氮原子上，所形成的碳正离子与水反应得到酰胺。
迁移基团如果是手性碳原子，则在迁移前后其构型不变，例如：反应实例Baylis-Hillman Reaction Baylis-Hillman反应反应机理：A key step is the addition of the amine catalyst to the activated alkene to form a stabilized nucleophilic anion. This in situ-generated nucleophile then adds to the aldehyde. Subsequent elimination of the catalyst leads to the observed products.一个关键的一步是加入胺活化的催化剂烯烃形成一个稳定的亲核性负离子。
这situ-generated nucleophile 然后增加醛。
随后导致消灭催化剂观测到的产品。
Other activating nitrogen nucleophiles may be suitable too and DMAP and DBU are superior to DABCO in some cases:其他激活氮nucleophiles也可以推广深度DMAP和DBU是我们的优势,DABCO在某些情况下:product of the addition of DBU and methylacrylateFor aryl aldehydes under polar, nonpolar, and protic conditions, it has been determined that therate-determining step is second-order in aldehyde and first-order in DABCO and acrylate. On the basis of this reaction rate data, Tyler McQuade recently proposed (J. Org. Chem.2005, 70, 3980. DOI) the following mechanism involving the formation of a hemiacetal intermediate:为芳香醛在极性的,非极性,protic条件,已经定断出限速步骤是二阶在醛和一阶在DABCO、丙烯酸酯。
在此基础上,对反应速率数据,泰勒McQuade最近提出(J。
有机2005年12月,70,化学3980。
往)以下的形成机理有关hemiacetal中级:Benzoin Condensation 安息香缩合The Benzoin Condensation is a coupling reaction between two aldehydes that allows the preparation of α-hydroxyketones. The first methods were only suitable for the conversion of aromatic aldehydes.这是一种偶联反应安息香凝结在两个醛,允许准备α-hydroxyketones。
第一个方法只适用于转换的芳香醛类。
Mechanism of Benzoin CondensationAddition of the cyanide ion to create a cyanohydrin effects an umpolung of the normal carbonyl charge affinity, and the electrophilic aldehyde carbon becomes nucleophilic after deprotonation: A thiazolium salt may also be used as the catalyst in this reaction (see Stetter Reaction).增加了氰化物离子创建一个cyanohydrin的影响正常的umpolung羰基费用的亲和力,又electrophilic醛碳离子后成为一个thiazolium亲盐也可以用作该反应的催化剂(见Stetter反应)。
A strong base is now able to deprotonate at the former carbonyl C-atom:强碱deprotonate现在已经能够在前羰基C-atom:A second equivalent of aldehyde reacts with this carbanion; elimination of the catalyst regenerates the carbonyl compound at the end of the reaction:第二个相当于醛与本carbanion;消除反应催化剂的羰基化合物一度结束的反应:Birch还原反应机理反应实例Bischler-Napieralski合成法反应机理反应实例Claisen Condensation克莱森缩合反应羧酸酯在强碱作用下发生缩合，生成β－酮酯。
例如,乙酸乙酯在乙醇钠作用下生成乙酰乙酸乙酯：Claisen Rearrangement 克莱森重排反应重新排列的脂肪克来森是[3,[3],-sigmatropic重排烯丙乙烯基醚热转化为一个不饱和羰基化合物。
克来森重排香气的陪同下rearomatization:对醇醚化的或酚类化合物和后续的克来森重排就有可能在热条件的延伸的碳链分子。
Curtius Rearrangement（Curtius重排）The Curtius Rearrangement is the thermal decomposition of carboxylic azides to produce an isocyanate. These intermediates may be isolated, or their corresponding reaction or hydrolysis products may be obtained.Curtius重排的是azides羧基的热分解产生一个异氰酸酯。
这些中间体可能隔离或相应的反应或水解产品可以被获得。
The reaction sequence - including subsequent reaction with water which leads to amines - is named the Curtius Reaction. This reaction is similar to the Schmidt Reaction with acids, differing in that the acyl azide in the present case is prepared from the acyl halide and an azide salt.反应序列与水反应,包括随后导致,叫做"美国Curtius胺反应。
这个反应施密特是相似的,只是在与酸反应的酰azide准备在本案从酰基卤素和一个azide盐。
Mechanism of the Curtius RearrangementPreparation of azides:（准备azides:）Decomposition:分解:Reaction with water to the unstable carbamic acid derivative which will undergo spontaneous decarboxylation:与水反应carbamic酸衍生物稳定的,将接受自发脱羧:Isocyanates are versatile starting materials:异氰酸酯是多才多艺的原料:Isocyanates are also of high interest as monomers for polymerization work and in the derivatisation of biomacromolecules.异氰酸酯的利息高的单体聚合的derivatisation工作好,biomacromolecules。
Cannizzaro Oxidation ReductionCannizzaro（坎尼扎罗）氧化还原反应砍尼扎罗反应（Cannizzaro反应）也译作康尼查罗反应、康尼扎罗反应、卡尼扎罗反应。
意大利化学家斯塔尼斯奥拉.坎尼扎罗通过用草木灰处理苯甲醛，得到了苯甲酸和苯甲醇，首先发现了这个反应，反应名称也由此得来。
是无α活泼氢的醛在强碱作用下发生分子间氧化还原反应，生成一分子羧酸和一分子醇的有机歧化反应.坎尼扎罗反应中常用的醛有芳香醛（如苯甲醛）和甲醛。