第四章烯烃和环烷烃 (Alkenes and Cyclic Hydrocarbons)

第四章烯烃和环烷烃 (Alkenes and Cyclic Hydrocarbons)
烯烃官能团：，通式：CnH2n. 第一节烯烃的结构 C=C 键能610kJ/mol 2018/11/23

2018/11/23 2018/11/23

p-Bonding (Bonding molecular orbital)
2018/11/23 p-Bonding (Bonding molecular orbital) 2018/11/23

2018/11/23 乙烯分子的形成乙烯模型烯烃的反应 2018/11/23

第二节烯烃的同分异构和命名一、烯烃的同分异构碳干异构、位置异构、顺反异构例：丁烯有5种同分异构体：碳干异构 2018/11/23
第二节烯烃的同分异构和命名一、烯烃的同分异构碳干异构、位置异构、顺反异构例：丁烯有5种同分异构体：碳干异构 2018/11/23

2018/11/23 顺（cis）反（trans） 2018/11/23

cis-trans Isomerism Different spatial arrangements
2018/11/23 cis-trans Isomerism Different spatial arrangements Arrangements cannot be converted into one another by rotation Substituents are defined as being up or down (or left or right) with respect to a plane 2018/11/23

2018/11/23 cis-trans Isomerism Compounds are different because it is not possible to rotate 360 degrees around any given bond. Isomers cannot be interconverted by rotation Substituents can always be classified with respect to a plane in the molecule as being on one side or the other cis both substituents on same side of plane trans substituents on opposite sides of plane 2018/11/23

二、烯烃的命名 5,5-二甲基-1-己烯 1. 选择含双键最长的碳链作为主链（母体），根据主链碳原子数命名为某烯。
2018/11/23 二、烯烃的命名 1. 选择含双键最长的碳链作为主链（母体），根据主链碳原子数命名为某烯。 2. 从靠近双键最近的一端开始编号。 3. 命名时双键的位次必须表明，以双键碳原子中编号小的表示。 5,5-二甲基-1-己烯 2018/11/23

Ethene Propene “Ethylene” “Propylene” 1-Butene 2-Butene 2018/11/23

2-Methyl-2-butene 2018/11/23

6-Methyl-2-heptene 2018/11/23

烯基 Ethyl CH2=CH- Vinyl 1-Propenyl 2-Butenyl 2-Pentenyl Allyl
2018/11/23 烯基 Ethyl CH2=CH- Vinyl 1-Propenyl 2-Butenyl 2-Pentenyl Allyl Isopropenyl(for 1-methylvinyl) 2018/11/23

2018/11/23 E-Z Nomenclature 2018/11/23

E-Z Nomenclature Rules
2018/11/23 E-Z Nomenclature Rules SEQUENCE RULE 1: If the four atoms directly attached to the double bond are all different, priority depends on atomic number, with the atom of higher atomic number receiving the higher priority. COROLLARY: If two atoms are isotopes of the same element, the heavier isotope receives the higher priority. 2018/11/23

2018/11/23 E-Z Nomenclature Rules SEQUENCE RULE 2: If the relative priority of two groups cannot be decided by Rule 1, it shall be determined by a similar comparison of the next atoms in the groups (and so on, if necessary), working outward in ranks from the double bond. 2018/11/23

2018/11/23 E-Z Nomenclature Rules To complete the IUPAC name of a particular isomer, enclose the (E) or (Z) symbol in parentheses and place it at the front of the entire name of the compound. Separate the (E) or (Z) symbol from the rest of the name with a hyphen. 2018/11/23

2018/11/23 Question: (CH3)3C-与 -CH2Cl哪个为优先基团？ 2018/11/23

trans-6-Methyl-3-propyl-2-octene
2018/11/23

Intention 1 Z、E和顺（Cis）、反（Trans）并不总是一一对应的。 2018/11/23

第三节烯烃的化学性质 Remember it!
2018/11/23 第三节烯烃的化学性质典型反应：加成反应－－在反应中，  键断开，两个不饱和原子和其它原子或原子团结合，形成两个键。 Remember it! 2018/11/23

2018/11/23 Addition Reactions 2018/11/23

催化剂异相催化剂：铂黑、钯粉、Raney Ni; Fe、Cr、Cu. 均相催化剂：主要为过渡金
2018/11/23 一、催化氢化催化剂异相催化剂：铂黑、钯粉、Raney Ni; Fe、Cr、Cu. 均相催化剂：主要为过渡金属配合物乙烯加氢 2018/11/23

Hydrogenation of Alkenes
2018/11/23 Hydrogenation of Alkenes Also PtO2 -- sometimes Ru, Rh, or Re 2018/11/23

2018/11/23 HYDROGEN ADSORBS ON THE SURFACE OF THE CATALYST . n H Pt Pt(H )2n H . Hydrogen Adsorbed on Catalyst Surface finely-divided particles dispersed in solution Pt . H 2018/11/23

. . . . . . . MECHANISM OF HYDROGENATION H H H H H H H H CATALYST
2018/11/23 MECHANISM OF HYDROGENATION H . H . H . H . H . H CATALYST . H . H 2018/11/23

. . . MECHANISM OF HYDROGENATION H H H HYDROGEN ADSORBS 2018/11/23

. . . . MECHANISM OF HYDROGENATION H H H R ALKENE APPROACHES
2018/11/23 MECHANISM OF HYDROGENATION R . . H . H . H ALKENE APPROACHES 2018/11/23

. . . . MECHANISM OF HYDROGENATION H H H R ALKENE PICKS UP
2018/11/23 MECHANISM OF HYDROGENATION R . . H . H . H ALKENE PICKS UP TWO HYDROGENS 2018/11/23

. . . . . MECHANISM OF HYDROGENATION H H H R R R R ALKANE IS FORMED
2018/11/23 MECHANISM OF HYDROGENATION R R R R . . ALKANE IS FORMED . H . H . H 2018/11/23

氢化热：1mol不饱和化合物氢化时放出的热量。
2018/11/23 氢化热：1mol不饱和化合物氢化时放出的热量。氢化热的大小反应烯烃的相对稳定性。双键碳原子上的烷基越多，烯烃越稳定。 R2C=CR2>R2C=CHR>RCH=CHR> RCH=CH2>CH2=CH2. 2-甲基丙烯>反-2-丁烯>顺-2-丁烯>1-丁烯。 2018/11/23

Alkene Stability 2018/11/23

亲电试剂（E＋）：凡缺电子物种，如正离子等。
2018/11/23 二、亲电加成 Electrophilic Addition to a Double Bond 亲电试剂（E＋）：凡缺电子物种，如正离子等。 2018/11/23

2018/11/23 2018/11/23

（Addition of Hydrogen Halides）
2018/11/23 1. 与酸的加成强酸如硫酸、氢卤酸可以直接作用；弱有机酸（如乙酸）、醇、水等要在强酸催化下进行。 1）与卤化氢加成（Addition of Hydrogen Halides） 2018/11/23

Markovnikov Addition to an Alkene
2018/11/23 卤化氢对烯烃加成的活性次序：HI>HBr>HCl Markovnikov Addition to an Alkene 2018/11/23

Markovnikov Addition to an Alkene
2018/11/23 Markovnikov Addition to an Alkene 2018/11/23

2018/11/23 Markovnikov Rule In the ionic addition of an acid to the carbon-carbon double bond of an alkene, the hydrogen of the acid attaches itself to the carbon atom which already holds the greater number of hydrogens. “Them that has, gets!” “The richer get richer!” (V. W. Markovnikov ) 2018/11/23

REGIOSELECTIVE REACTION REGIOSPECIFIC 区位选择性反应 C H C H C H C H C C H C
2018/11/23 REGIOSELECTIVE REACTION 区位选择性反应 C H C H C H 3 3 3 HCl C H C C H C H C C H + C H C H C H 3 2 3 3 3 2 C l C l major minor one of the possible products is formed in larger amounts than the other one REGIOSPECIFIC Compare only one of the possible products is formed (100%). 2018/11/23

MARKOVNIKOV RULE C H C H C l + HCl When adding HX to a double bond the
2018/11/23 MARKOVNIKOV RULE When adding HX to a double bond the hydrogen of HX goes to the carbon which already has the most hydrogens C H C H 3 2 C l + HCl ..... conversely, the anion X adds to the most highly substituted carbon ( the carbon with most alkyl groups attached). 2018/11/23

在过氧化物存在下，氢溴酸与不对称烯烃加成时，反应取向是Anti-Markovnikov rule.
2018/11/23 KARASCH效应（过氧化物效应在过氧化物存在下，氢溴酸与不对称烯烃加成时，反应取向是Anti-Markovnikov rule. 2018/11/23

与不对称烯烃加成同样遵循Markovnikov rule.
2018/11/23 2）与硫酸加成与不对称烯烃加成同样遵循Markovnikov rule. 2018/11/23

Addition of Sulfuric Acid to an Alkene
2018/11/23 Addition of Sulfuric Acid to an Alkene 2018/11/23

Addition of Water to an Alkene
2018/11/23 Addition of Water to an Alkene 2018/11/23

2. 与卤素加成 Br/CCl4溶液用来检验烯烃直接水合：
2018/11/23 直接水合： 2. 与卤素加成卤素对烯烃加成的活性次序：F2>Cl2>Br2>I2(不反应） Br/CCl4溶液用来检验烯烃 ICl 、 IBr次卤酸（X2+H2O)与不对称烯烃加成的主要产物为何？ 2018/11/23

2018/11/23 Halohydrin Formation 卤代醇的形成 HOBr 2018/11/23

3. 与乙硼烷加成 (硼氢化反应：由B－H键对烯烃双键进行的加成反应）由C. H. Brown建立
2018/11/23 3. 与乙硼烷加成 (硼氢化反应：由B－H键对烯烃双键进行的加成反应）由C. H. Brown建立 2018/11/23

绝大多数烯烃与二硼烷的加成产物是三烷基硼，少数立体障碍大的烯烃则停留在一烷基硼或二烷基硼阶段。
2018/11/23

Sia2BH，thBH2(HBH2）, 9-BBN 2018/11/23

特点：特点：1.氢加到含氢较少的双键碳原子上；2.顺式加成，选择性好；3.产率高；4.反应条件温和。合成应用： 2018/11/23

例1 2018/11/23

三、氧化反应 1. 用KMnO4或OsO4 （四氧化锇）氧化在酸性介质中，氧化更易进行，且发生双键断裂。用KMnO4溶液来鉴定不饱和烃。
2018/11/23 三、氧化反应顺-1，2-二醇 1. 用KMnO4或OsO4 （四氧化锇）氧化在酸性介质中，氧化更易进行，且发生双键断裂。用KMnO4溶液来鉴定不饱和烃。 2018/11/23

2018/11/23 2. 臭氧化另外，有H2O2产生，能使醛进一步氧化成羧酸。 H2O 2018/11/23

还原水解可以避免产物的进一步氧化有种常用的还原剂： 1）Zn/H2O 2）H2,Pd 臭氧化还原水解产物：推测烯烃的结构
2018/11/23 还原水解可以避免产物的进一步氧化有种常用的还原剂： 1）Zn/H2O 2）H2,Pd 臭氧化还原水解产物：推测烯烃的结构 2018/11/23

2018/11/23

2018/11/23 3．催化氧化 Organic Reaction 2018/11/23

2018/11/23 四、聚合反应聚合反应：由单体分子相互作用生成高分子化合物的反应。 2018/11/23

Polymerization of Propene
2018/11/23 Polymerization of Propene 2018/11/23

2018/11/23 五、－H 上的反应 1. 卤代 2018/11/23

－H卤代历程(自由基取代) 2018/11/23

2. 氧化丙烯腈 2018/11/23

第五节烯烃的制备一、消除反应 1. 一卤代烃脱HX -消除 2. 邻二卤代烃脱X2 3. 醇脱H2O 2018/11/23
第五节烯烃的制备一、消除反应 1. 一卤代烃脱HX 2. 邻二卤代烃脱X2 3. 醇脱H2O -消除 2018/11/23

2018/11/23 Saytzeff Rule 二、炔烃的还原共轭烯烃 2018/11/23

第六节烯烃的亲电加成反应历程烯烃与溴加成反式加成在极性分子诱导下，非极性的乙烯分子和溴分子发生极化。溴鎓离子 2018/11/23
第六节烯烃的亲电加成反应历程烯烃与溴加成溴鎓离子反式加成在极性分子诱导下，非极性的乙烯分子和溴分子发生极化。 2018/11/23

Mechanism of Bromination of an Alkene
2018/11/23 Mechanism of Bromination of an Alkene 2018/11/23

WHAT WOULD EXPLAIN FORMATION OF ONLY THE trans PRODUCT ?
2018/11/23 WHAT WOULD EXPLAIN FORMATION OF ONLY THE trans PRODUCT ? ..... A BRIDGED OR CYCLIC INTERMEDIATE 2018/11/23

2018/11/23 CYCLIC BROMONIUM ION 环状溴鎓离子 note size of bromine 2018/11/23

Br + Br BRIDGED BROMONIUM ION Br bridging blocks approach
2018/11/23 BRIDGED BROMONIUM ION Br + Br Br bridging blocks approach from this side 2018/11/23

BRIDGED BROMONIUM ION resonance contributing structures - - - B r H H
2018/11/23 BRIDGED BROMONIUM ION - symmetric ion - bromide ion could add to either side left or right B r H H + B r - - B r B r H H + H + H B r B r resonance contributing structures 2018/11/23

FORMATION OF ENANTIOMERS
2018/11/23 FORMATION OF ENANTIOMERS symmetric intermediate Addition could also start from the top with bromide attacking the bottom. + ENANTIOMERS 2018/11/23

2. 烯烃与HX加成 E+ = Electrophile Nu: = Nucleophile
2018/11/23 2. 烯烃与HX加成 E+ = Electrophile Nu: = Nucleophile General Mechanism: The first step requires a powerful electrophile to attract the pi bond electrons, which then forms a carbocation. A nucleophile quickly adds to the carbocation to form the monosubstituted product. 2018/11/23

3. Markovnikov Rule and Stability of Carbocation
2018/11/23 3. Markovnikov Rule and Stability of Carbocation -超共轭 1）极化 2）碳正离子稳定性叔（3。）>仲（2 。）>伯（1 。）>CH3+ -p超共轭效应 2018/11/23

COMPETING PATHWAYS 决速步骤 rate-determining step slower higher energy
2018/11/23 rate-determining step 决速步骤 slower higher energy intermediate lower energy intermediate faster rate-determininng (slow) step 2018/11/23

2018/11/23 Hyperconjugation 超共轭 H H C C H H H 2018/11/23

CARBOCATION STABILITY
2018/11/23 HYPERCONJUGATION 碳正离子的稳定性 H electrons in an adjacent C-H s bond help to stabilize the positive charge of the carbocation by proximity (overlap) .. + R C C H R H lowest energy tertiary < secondary < highest energy primary 2018/11/23

2018/11/23 4. 自由基加成过氧化物效应 Anti－Markovnikov Rule 2018/11/23

Problem Assignment 乙烯与溴的氯化钠水溶液反应产物除了1,2-二溴乙烷外，还有2-溴乙醇和1-氯-2-溴乙烷，为什么？
完成以下反应 2018/11/23

第七节亲电加成反应的立体化学一、实验结果外消旋体内消旋体 2018/11/23

二、加成反应立体化学解释 (1) (2) 2018/11/23

如何写烯烃加成产物的构型？ 2018/11/23

内消旋体 2018/11/23

外消旋体 2018/11/23

三、光学纯度与对映体过量百分率 2018/11/23

Question Assignment 丁烷一氯代时的产物2-氯丁烷为外消旋体，如何用反应历程来解释？ 2018/11/23

Reading Assignment 外消旋体的拆分昆虫信息素蚕素醇 2018/11/23

手性与气味 * * 香芹酮薄荷油 2018/11/23

环烷烃（脂环烃）脂环烃：碳干为环状而性质与开链烃相似的烃类。第一节脂环烃的分类和命名一、分类 2018/11/23

环数：使环状化合物变成开链化合物所需打破的碳碳键的数目。
2018/11/23

Nomenclature of The Monocycloalkanes
2. 命名环丙烷环戊烷环丁烷环己烷 2018/11/23

Structural formulas of cyclic molecules -- Cyclohexane
Expanded formula 2018/11/23

Condensed formula 2018/11/23

Polygon formula 2018/11/23

Examples of Cyclic Molecules
2018/11/23

More examples 2018/11/23

Nomenclature of the Substituted Monocycloalkanes
If there is only one substituent, do not use the “1”. If there is more than one substituent, you must use all numbers, including “1”! Number around the ring in a direction to get from the first substituent to the second substituent by the shorter path. For equivalent degrees of substitution, number in a direction that follows the alphabetical sequence. A carbon with greater substitution has precedence in numbering. 2018/11/23

1,1-Dimethylcyclohexane
2018/11/23

4-Ethyl-1,1-dimethylcyclohexane
2018/11/23

Two Ways of Naming This 1-Isopropyl-2-methylcyclohexane
1-Methyl-2-(1-methylethyl)cyclohexane 2018/11/23

3-Cyclobutyl-3-methylpentane
2018/11/23

Cycloalkyl Groups 2018/11/23

Nomenclature of Monocyclkenes
从双键碳原子开始编号使取代基位次尽可能小 2018/11/23

螺环烃的命名从小环中与共有碳原子相连的碳原子开始编号，经过共有碳原子，在由较大环回到共有碳原子。尽可能使取代基处在最小的位次。
母体名称前冠以“螺”，后接[ ],方括内注明环中除共有碳原子以外的碳原子数，由小到大，之间用圆点隔开。 2018/11/23

桥环的命名从桥头碳开始编号，经过最大环到达另一桥头，在经次大环回到第一个桥头，最短的桥最后编号。
母体名称前冠以“环数”，后接[ ],方括中表明环内除桥头碳原子外的碳原子数目，从大到小排列，之间用圆点分开。 2018/11/23

2018/11/23

第二节脂环烃的性质一、与开链烃相似的反应 1. 环烷烃的卤代 2. 环烯烃的加成 3. 环烯烃的氧化 2018/11/23

二、小环烷烃特有的反应加氢开环加卤素、加卤化氢开环 2018/11/23

区别：环丙烷对氧化剂（如高锰酸钾）稳定，而烯烃易被氧化
环丁烷在常温下不发生类似反应！环丙烷衍生物与卤化氢的加成，符合Markovnikov Rule. 区别：环丙烷对氧化剂（如高锰酸钾）稳定，而烯烃易被氧化 2018/11/23

第三节脂环烃的结构一、Baeyer张力学说（1885年）
第三节脂环烃的结构一、Baeyer张力学说（1885年） sp3 碳原子键角应为109。28’, 任何与此正常键角的偏差，都会引起分子的张力，这种张力具有力图恢复正常键角的趋势。我们把这种张力叫角张力。 2018/11/23

角张力（Angle Strain） Extra potential energy that a cyclic molecule may possess because bond angles are distorted in order to form a ring. 2018/11/23

角张力示意图 Baeyer张力学说建立在错误假设（认为环烷烃都是平面结构）的基础上，只对小环适用。 2018/11/23

环丙烷环丙烷为张力环，采取重叠式构象。环丙烷C－C键为弯曲键，类似于烯烃的键， 2018/11/23

二、环丁烷和环戊烷的构象平面式 2018/11/23

Cyclobutane (puckered form)
蝴蝶式 2018/11/23

Cyclopentane 信封式 2018/11/23

三、燃烧热和非平面结构环丙烷：平面结构其它环烷烃：非平面结构
燃烧热：用每个CH2单元的平均燃烧热，与开链烷烃每个CH2单元平均燃烧热的差值×n来表示分子的张力能。 2018/11/23

Estimate of Angle Strain
2018/11/23

环己烷（六元环）最稳定，其次是环戊烷（五元环）；大环都是稳定的；小环中的环丙烷最不稳定，其次是环丁烷。
2018/11/23

四、环己烷的构象二种典型构象 1 1 5 4 6 5 3 6 2 4 3 2 船式椅式 1 3 3 6 5 2 6 2 5 1 4 4 全叠式邻位交叉式 2018/11/23

Cyclohexane 椅式构象球棒模型 2018/11/23

Cyclohexane (top view)
no contact 斯陶特模型 2018/11/23

Cyclohexane (boat form)
bowsprit-flagpole interaction 船式构象球棒模型 2018/11/23

Cyclohexane (top view -- steric strain)
船式斯陶特模型 Notice! 2018/11/23

Chair-chair Inversion in Cyclohexane
转环作用中的能量变化 2018/11/23

环己烷的椅式构象最稳定 Reasons：角张力为0 采取邻位交叉式构象，扭转张力最小
1，3-二a键相互作用小。因为H原子范德华半径小，所以范德华张力为0 2018/11/23

Cyclohexane (axial bonds)
与通过分子中心的假象垂直轴平行的C—H键 2018/11/23

Cyclohexane (equatorial bonds)
与垂直轴成109。28’的C－H键 2018/11/23

Cyclohexane (showing both axial and equatorial bonds
直立键平伏键 2018/11/23

转环作用 2018/11/23

Chair-chair Inversion in Methylcyclohexane
甲基环己烷 2018/11/23

环己烷衍生物优势构象的判定环己烷一取代物以取代基处于e-键上的最稳定
含相同取代基的环己烷多元取代物最稳定的构象是e-取代基最多的构象－Hassel规则环上又不同取代基时，大的取代基在e-键上的最稳定－Baton规则 2018/11/23

tert-Butylcyclohexane (equatorial)
叔丁基环己烷 2018/11/23

tert-Butylcyclohexane (space-filling model)
叔丁基环己烷 2018/11/23

tert-Butylcyclohexane (axial group)
叔丁基环己烷 HUGE steric strain 2018/11/23

五、脂环化合物的顺反异构 2018/11/23

反式十氢萘比顺式十氢萘稳定 2018/11/23

Form the Complete IUPAC Name:
反-1-（1,1-二甲基乙基）-4-氯环己烷 trans-1-tert-Butyl-4-chlorocyclohexane 2018/11/23

第四节脂环烃的制法分子内Wurtz反应一、分子内偶联反应 2018/11/23

二、Diels-Alder Reaction
内型（endo) 2018/11/23

三、卡宾合成法四、芳烃还原 2018/11/23

五、脂环烃之间的转化催化重整 2018/11/23

Question Assignment Unsaturation/saturation Implies the presence or absence of multiple (double or triple) bonds. Refer to addition/elimination and the related reduction/oxidation. How to calculate unsaturation? 2018/11/23

问题： 2018/11/23

2018/11/23

第四章烯烃和环烷烃 (Alkenes and Cyclic Hydrocarbons)

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第四章 烯烃和环烷烃 (Alkenes and Cyclic Hydrocarbons)

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Presentation on theme: "第四章 烯烃和环烷烃 (Alkenes and Cyclic Hydrocarbons)"— Presentation transcript:

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第四章烯烃和环烷烃 (Alkenes and Cyclic Hydrocarbons)

Presentation on theme: "第四章烯烃和环烷烃 (Alkenes and Cyclic Hydrocarbons)"— Presentation transcript: