化學(xué)汪小蘭有機(jī)四

1、2021-12-30官能團(tuán)： ，通式：CnH2n. 第一節(jié) 烯烴的結(jié)構(gòu)乙烯的鍵參數(shù)第三章 單烯烴C CCHHCHH 0.108nm0.133nm121.7 117C=C 鍵能610kJ/mol2021-12-30Carbon sp2 (trigonal, 3 + 1 bonds)sp2sp2sp22pz2py2px2s2pzhybridised C atom in C2X4 isolated C atom120ppsp2sp2 sp2sp2CC Planar154pm134pm2021-12-30 -Bonding(Bonding molecular orbital) 2021-12-30烯烴

2、的反應(yīng)CCCH加成、氧化、還原、聚合H上的反應(yīng)（氧化、鹵代）乙烯分子的形成乙烯模型2021-12-30第二節(jié) 烯烴的同分異構(gòu)和命名 一、烯烴的同分異構(gòu) 烯烴的異構(gòu)包括碳干異構(gòu)、位置異構(gòu)、順?lè)串悩?gòu)。例：丁烯同分異構(gòu)體： CH3CH2CH CHCH3 CH CH2 CH3CH3C CH2CH3(1) 1-丁烯 （2）2-丁烯（3）異丁烯位置異構(gòu) 碳干異構(gòu)位置異構(gòu)(1)、(3)碳干異構(gòu)2021-12-30CCH3CHCH3HCCH3CHHCH3(4) 順-2-丁烯 （5）反-2-丁烯順?lè)串悩?gòu)順（cis）：兩個(gè)雙鍵上的氫原子處于雙鍵的同一側(cè)；反（trans）：處于異側(cè)。順?lè)串悩?gòu)也叫幾何異構(gòu)，屬于立體異

3、構(gòu)CCacdbab, c d時(shí)存在順?lè)串悩?gòu)體2021-12-30cis-trans Isomerismv思考v構(gòu)型與構(gòu)象的差異？vDifferent spatial arrangementsvThe arrangements cannot be converted into one another by rotationvSubstituents are defined as being up or down (or left or right) with respect to a plane2021-12-30Z，E標(biāo)記 較優(yōu)基團(tuán)處于同側(cè)為Z型 反之為E型2021-12-30cis-tran

4、s IsomerismvCompounds are different because it is not possible to rotate 360 degrees around any given bond.順?lè)串悩?gòu)不能通過(guò)鍵旋轉(zhuǎn)而相互轉(zhuǎn)化Isomers cannot be interconverted by rotationSubstituents can always be classified with respect to a plane in the molecule as being on one side or the other取代基在平面的兩側(cè)vcis both sub

5、stituents on same side of planevtrans substituents on opposite sides of plane2021-12-30二、烯烴的命名 1. 選擇含雙鍵最長(zhǎng)的碳鏈作為主鏈（母體），根據(jù)主鏈碳原子數(shù)命名為某烯。 2. 從靠近雙鍵最近的一端開(kāi)始編號(hào)。 3. 命名時(shí)雙鍵的位次必須表明，以雙鍵碳原子中編號(hào)小的表示。 5,5-二甲基-1-己烯2021-12-30CH2CH2CH3CHCH2CH3CH2CHCH2CH3CHCHCH3EthenePropene1-Butene2-Butene“Ethylene”“Propylene”2021-12-30C

6、CHCH3CH3CH32-Methyl-2-butene2021-12-30CH3CHCH2CH2CHCHCH3CH36-Methyl-2-heptene2021-12-30烯基 Ethyl CH2=CH- Vinyl 1-Propenyl 2-Butenyl 2-PentenylIsopropenyl(for 1-methylvinyl) Allyl 2021-12-30 Z-E構(gòu)型命名E-Z NomenclatureCC*CC*(Z)(E)2021-12-30 命名規(guī)則E-Z Nomenclature RulesvSEQUENCE RULE 1: 連接在雙鍵碳上的四個(gè)基團(tuán)都不相同時(shí)，原子序

7、數(shù)大的原子為較優(yōu)基團(tuán)。v 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.vCOROLLARY: 如兩個(gè)原子是同位素較重的一個(gè)較優(yōu)v If two atoms are isotopes of the same element, the heavier isotope receives the

8、higher priority.2021-12-30 E-Z命名規(guī)則 Nomenclature RulesvSEQUENCE RULE 2: 第一規(guī)則無(wú)法確定優(yōu)勢(shì)基團(tuán)，接下來(lái)比較基團(tuán)中下一個(gè)原子。vIf 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 fr

9、om the double bond.2021-12-30 E-Z Nomenclature Rulesv在名稱前標(biāo)記（E）或（Z），用短線隔開(kāi)。vTo 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 hyph

10、en.2021-12-30ExamplesCCH3CHCH3CH2CH3CH3(C)CH3HC2H5(第二原子：C,H,H)CH3(第二原子：H,H,H)C2H5CH3(E)-3-甲基-2-戊烯Question: (CH3)3C-與-CH2Cl哪個(gè)為優(yōu)先基團(tuán)？2021-12-30CCCH3HCH2CH2CH2CH3CH2CHCH2CH3CH3 （E)-6-甲基-3-丙基-2-辛烯 （E)-6-Methyl-3-propyl-2-octene2021-12-30IntentionIntentionZ、E和順（Cis）、反（Trans）并不總是一一對(duì)應(yīng)的。思考題：舉例說(shuō)明以上結(jié)論2021-12-3

11、0第三節(jié) 烯烴的化學(xué)性質(zhì) 典型反應(yīng)：加成反應(yīng)在反應(yīng)中， 鍵斷開(kāi)，兩個(gè)不飽和原子和其它原子或原子團(tuán)結(jié)合，形成兩個(gè)鍵，這種反應(yīng)稱為加成反應(yīng)。2021-12-30Addition Reactions+CCXYCCXY2021-12-30一、催化氫化RCH CH2 + H2 RCH2CH3 + 氫化熱催化劑2021-12-30乙烯氫化反應(yīng)機(jī)制催化氫化機(jī)制： H2 H HC CHH HHH HC CHH HHH-CH2CH2-H乙烯加氫2021-12-30Hydrogenation of Alkenes+H2Pt, Pd,or NiRCH CH RRCH CH RHH syn-addition(ster

12、eospecific)Also PtO2 - sometimes Ru, Rh, or Re2021-12-30n H2 + Pt Pt(H )2nHHH.Hydrogen Adsorbed onCatalyst Surface.finely-dividedparticlesdispersed insolutionPtPtPtPtPt.H.HPt.HPtPtPtPtPt.2021-12-30.H.H.H.H.H.H.H.HRRRR.HALKENEAPPROACHES2021-12-30.H.H.H.H.H.H.H.H.HRRRR.ALKENE PICKS UPTWO HYDROGENS2021

13、-12-30.H.H.H.H.H.H.HRRRR.H.HALKANE ISFORMED2021-12-30氫化熱：1 1molmol不飽和化合物氫化時(shí)放出的熱量。不飽和化合物氫化時(shí)放出的熱量。（氫化熱較小較穩(wěn)定）（氫化熱較小較穩(wěn)定）氫化熱的大小反應(yīng)烯烴的相對(duì)穩(wěn)定性。雙鍵碳原子上的烷基越多，烯烴越穩(wěn)定。R2C=CR2R2C=CHRRCH=CHRRCH=CH2CH2=CH2.2-甲基丙烯反-2-丁烯順-2-丁烯1-丁烯。2021-12-30Alkene Stability CCCCCH3HH3CHCH3 HCH3Hacidcatalyst76% 24%Steric Strain2021-12-30

14、二、親電加成Electrophilic Addition to a Double Bond+CH2CH2XYXCH2CH2Y親電試劑（E）：本身缺電子又有能力從反應(yīng)中得到電子形成共價(jià)鍵的試劑2021-12-301. 與酸的加成強(qiáng)酸如硫酸、氫鹵酸可以直接作用；弱有機(jī)酸（如乙酸）、醇、水等要在強(qiáng)酸催化下進(jìn)行。1）與鹵化氫加成（Addition of Hydrogen Halides）+CH CHRRHXR CH CH RHX2021-12-30不對(duì)稱烯烴加成取向Markovnikov Addition to an Alkene+majorproductminorproductCH3CH CH2HB

15、rCH3CH CH2HBrCH3CH CH2BrH2021-12-30 Markovnikov Addition to an Alkene+major product minor productX = Cl, Br, ICCH2CH3CH3HXCH3CCH2CH3XHCH3CCH2CH3HX2021-12-30 CC H3C H3C H2CC H3C H3C H3C l+C HC H3C H2C lC H3HClmajorminorone of the possible products is formedin larger amounts than the other oneCompareo

16、nly one of the possible products isonly one of the possible products isformed (100%).formed (100%).區(qū)位選擇性反應(yīng)2021-12-30 CH2+ HClCH3Cl. conversely, the anion X adds to the mosthighly substituted carbon ( the carbon withmost alkyl groups attached).2021-12-30 KARASCH效應(yīng)（過(guò)氧化物效應(yīng)在過(guò)氧化物存在下，氫溴酸與不對(duì)稱烯烴加成時(shí)，反應(yīng)取向是Ant

17、i-Markovnikov rule.CH3CH CH2 + HBr CH3CH2CH2Br過(guò)氧化物2021-12-302）與硫酸加成H2C CH2 + H2SO4 CH3CH2OSO2OH0-15C硫酸氫乙酯98H2SO4CH2CH2H2O90CCH3CH2OH與不對(duì)稱烯烴加成同樣遵循Markovnikov rule.用上法制備醇叫間接水合，設(shè)備腐蝕嚴(yán)重。2021-12-30Addition of Sulfuric Acid to an Alkene+H2SO4(cold, concentrated)an alkyl hydrogen sulfateCH CH2RRCH CH2HOSOHOO

18、2021-12-30Addition of Water to an Alkene+H2OH2SO4an alcoholRCH CH2RCH CH2HOH2021-12-30直接水合：直接水合：CH3CH CH2 CH3CHCH3OHH2O/H3PO4或硅藻土300C,7MPa2. 與鹵素加成CC + X2CCX X Br2/CCl4溶液用來(lái)檢驗(yàn)烯烴鹵素對(duì)烯烴加成的活性次序：F2Cl2Br2I2(不反應(yīng)）ICl 、 IBr次鹵酸（X2+H2O)與不對(duì)稱烯烴加成的主要產(chǎn)物為何？2021-12-30Halohydrin Formation鹵代醇Br2H2ORCH CHRRCH CHROH Bra b

19、romohydrinHOBr鹵代醇的形成2021-12-303. 3. 與乙硼烷加成( (硼氫化反應(yīng)：由B BH H鍵對(duì)烯烴雙鍵進(jìn)行的加成反應(yīng)）由C C. . H H. . B Brownrown建立CC + B2H6CCHBH22BH3 B2H62021-12-30乙基硼 二乙基硼三乙基硼CH3CH CH2 CH3CH2CH2BH2B2H62B2H6(CH3CH2CH2)3B絕大多數(shù)烯烴與二硼烷的加成產(chǎn)物是三烷基硼，少數(shù)立體障礙大的烯烴則停留在一烷基硼或二烷基硼階段。2021-12-30 (CH3)2C CHCH3B2H6THF(CH3)2CHCH CH3 2BH二（1,2-二甲基丙基）硼烷

20、DIsiamylborane(Sia2BH)(CH3)2C C(CH3)2B2H6THF(CH3)2CHC CH3BH2CH31,1,2-三甲基丙基硼烷thexylborane（thBH2，or HBH2）B2H6THFBH9-硼二環(huán)3.3.1壬烷9-borabicyclo3.3.1nonane（9-BBN)硼氫化反應(yīng)2021-12-30特點(diǎn)： 特點(diǎn)：1.氫加到含氫較少的雙鍵碳原子上；2.順式加成，選擇性好；3.產(chǎn)率高；4.反應(yīng)條件溫和。C C+ B2H6硼氫化C CH3B氧化C C OH硼氫化氧化反應(yīng)：2021-12-30例1CH3OHHCH3OHH解：CH3OHH2SO4 CH3B2H6H

21、CH3BH2H順式加成H2O2, OHHCH3OHH2021-12-30三、氧化反應(yīng) 1. 用KMnO4或OsO4 （四氧化鋨）氧化3RCH CH2 + 2KMnO4 + 4H2O 3RCHOHCH2 +OH2MnO2 + 2KOH堿性或中性介質(zhì)順-1，2-二醇由于二元醇的進(jìn)一步氧化，反由于二元醇的進(jìn)一步氧化，反應(yīng)條件不易控制，收率低。如應(yīng)條件不易控制，收率低。如用四氧化鋨代替高錳酸鉀，則用四氧化鋨代替高錳酸鉀，則收率大大提高，但毒性大。收率大大提高，但毒性大。在酸性介質(zhì)中，氧化更易進(jìn)行，且發(fā)生雙鍵斷裂。CH2= CO2 , RCH= RCOOHRRC= RRC=O2021-12-302. 2

22、. 臭氧化 另外，有H2O2產(chǎn)生，能使醛進(jìn)一步氧化成羧酸。H2O 鋅（還原劑）鋅（還原劑）2021-12-30還原水解可以避免產(chǎn)物的進(jìn)一步氧化有種常用的還原劑： 1）Zn/H2O 2）H2,Pd 臭氧化還原水解產(chǎn)物：CH2= CH2O , RCH= RCHORRC= RRC=O推測(cè)烯烴的結(jié)構(gòu)2021-12-30ALKENE OXIDATION - OZONOLYSISNO OVEROXIDATION (ii) Zn, H2O(i) O3CCCOOCOverall useful diagnostic tool for thedetermination of double bond placeme

23、nt.Very useful synthetic reaction for the creationof carbonyl compounds with absolutecontrol over over the placement of the carbonyl.2021-12-30臭氧化反應(yīng)烯烴的臭氧化反可用于推測(cè)烯烴的結(jié)構(gòu)。生成的羰基化合物中的氧是分別邊在原烯烴中以雙鍵相連的兩個(gè)碳上。2021-12-303 3催化氧化CH2 CH2 + O2 OCH2H2CAg200-300 COrganic ReactionRO2021-12-30四、聚合反應(yīng) 聚合反應(yīng)：由單體分子相互作用生成高分子化

24、合物的反應(yīng)叫聚合反應(yīng)。nH2C=CH2 TiCl4Al(C2H5)30.11MPa6075 C乙烯（單體）聚乙烯（高分子） CH2 CH2()n2021-12-30Polymerization of Propene1)+H2SO4+HSO4_+CH3CH CH2CH3CH CH2H+CH3CH CH32)+slow+CH3CH CH2CH3CH CH2CH CH3CH33)+CH3CH CH2CH CH3CH3+HSO4_CH3CH CH CH CH3CH3+HSO2OH2021-12-30五、 H 上的反應(yīng)1. 鹵代CH3CHCH2 + Cl2 ClCH2CHCH2300 CCH3CH CH

25、2 + Br2 BrCH2CHCH2500 CC C C CX官 能 團(tuán)H2021-12-302. 氧化 CH3CH CH2 + NH3 + O2 CH2催化劑 CHCN + H2O丙烯腈2021-12-30第五節(jié) 烯烴的制備一、消除反應(yīng) 1. 一鹵代烴脫HX 2. 鄰二鹵代烴脫X2 3. 醇脫H2OCCHX CC+ HX-消除CCXX CC+ ZnX22021-12-30Saytzeff RuleCH3CH2CH(OH)CH3 CH3CHCHCH3 + CH3CH2CHCH281%19% H2SO4加熱 二、炔烴的還原CH3CHCHCH2CH CHCH3OHH3C CH2CH(CH3)CH

26、CHCH CHCH3Al2O3共軛烯烴2021-12-30反式加成第六節(jié) 烯烴的親電加成反應(yīng)歷程1.烯烴與溴加成+ B rB r-CCB r+ B r-CCB rB r- +CCB rB rCC在極性分子誘導(dǎo)下，非極性的乙烯分子和溴分子發(fā)生極化。溴鎓離子2021-12-301)+slow+RCH CH2BrBrRCHCH2Br_2)+RCHCH2Br+Br:._. anti-addition(stereospecific)CCBrBrHHRH+Br2021-12-30+B rHHnote size ofbromine環(huán)狀溴鎓離子2021-12-30HH-B rHHBrBrBr+bridgingblocks approachfrom this side2021-12-30BrHH+Br-BrHH+Br-BrHH+Br-symmetric ion -bromide ion couldadd