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1、11 芳卤化合物和芳磺酸（Halogen compounds and aromatic sulfonate）Ppt documents may experience poor browsing on the WAP side. It is recommended that you first select TXT, or download the source file to the local view.The eleventh chapter, aromatic halogen compounds and aromatic sulfonic acidSection 1 aromatic h
2、alogen compounds second quarter aromatic sulfonic acidHalogen compounds(1) nomenclature of aromatic compounds (two) preparation of aromatic halogen compounds (three) physical properties of halogen compounds (four) chemical properties of aryl halidesThe eleventh chapter, aromatic halogen compounds an
3、d aromatic sulfonic acidHalogen compoundsThe aromatic compounds in the aromatic molecule are replaced by halogen compounds, which are called aryl halides, or halogenated aromatic hydrocarbons. According to the relative positions of halogen atoms and aromatic rings, halogenated aromatic hydrocarbons
4、can be divided into three categories:Br, Cl, halogenated benzene, CH2Cl, benzyl type, CH2CH2Br, isolated type(1) nomenclature of aryl halidesHalogen atoms are regarded as substituents. Cases:CH3, C2H5, Cl, Br, 2-, chlorine, -4-, bromine, ethylbenzene, CHCH2CH2Cl4 CH 321CH2ClCHCl2Cl, 4-, chloro tolue
5、ne, or chlorinated tolueneBenzyl chloride or benzyl chlorideCH3 methylene dichlorideAlphaCH=CHBrBetaThree3- phenyl -1- butaneBeta brominated styrene(two) the preparation of aromatic halogen compounds(1) direct halogenation (2) chloride (3) was prepared by diazonium salt(two) the preparation of aroma
6、tic halogen compounds(1) direct halogenationCH3 CH3Cl2 Fe, Cl2 h v?Cl CH3 + Cl CH2Cl CH3CH2CH3Br2 h VCHCH3 Br(bromine selectivity is greater than chlorine)CH2CH3Cl2 h VCHCH3 + Cl 56%CH2CH2Cl44%When electrophilic substitution takes place, the benzene ring on the upper side of the benzene ring is repl
7、aced by the upper benzene ring; the upper chain is replaced by an alpha electrophilic substitution; the benzene ring on the X-; when the radical is substituted, the upper side of the X- chain is alpha.(2) methylation;+ HCHO + HClGlacial acetic acid, H3PO4 56%CH2Cl + H2O(3) prepared by diazonium salt
8、NH2(1) NaNO2, HClN2+BF4CH3(2) HBF4FCH3(76%-84%) (89%)CH3(three) the physical properties of aryl halidesHalogenated aromatic hydrocarbons are insoluble in water and soluble in organic solvents; halogenated halogenated aromatic hydrocarbons are slightly aromatic; halogenated benzyl halides generally h
9、ave irritating and tear effects. The melting point and boiling point M.P: molecular symmetry = = b.p:, melting point of intermolecular forces; increase boiling up. The two highest melting point star halobenzene, two adjacent halobenzene highest boiling point. Spectroscopic properties, nuclear magnet
10、ic resonance spectra. (291) examples: NMR spectra and nuclear magnetic resonance(four) the chemical properties of aryl halides(1) the influence of the position of benzene ring on the activity of halogen atom(1) the special stability of halogenated halogenated benzene (II), the special activity of be
11、nzyl halide (a), additive elimination mechanism (b), mechanism of elimination addition (mechanism of alkyne)(4) the role of metals(a) the formation of Grignard reagent (b) the formation of aryl lithium reagent (c), Wurtz-Fittig reaction (Ding), Ulmann reaction(2) nucleophilic substitution reaction o
12、n aromatic ring(a) hydrolysis (b) ammonia hydrolysis(3) the mechanism of nucleophilic substitution reaction on aromatic ring(5) electrophilic substitution reaction on aromatic ring(four) the chemical properties of aryl halidesTwo types of reactions: reaction of halogen atoms; electrophilic substitut
13、ion reactions on aromatic rings.(1) the influence of the position of benzene ring on the activity of halogen atomThe activity sequence of three halogenated aromatic hydrocarbons: Benzyl type, isolation type C6H5CH2Cl, C6H5CH2CH2Cl, halogenated benzene type. C6H5Cl(1) the special stability of halogen
14、ated halogenated benzene compoundsUnder general conditions,ArX? The halogen atom was not easy in the halogen atom is not easy to be OH, RO, CN - and NH3 - in the nucleus is not easy to be replaced by a halogen atom reagent; reagents substituted;? Not with no alcohol solution and AgNO3 reaction; alco
15、hol solution reaction;? Do alkylation the use of reagents for Friedel Crafts reaction can do for alkylation reagent reaction using fourier. Cases:ClNaOH/H2OHard！The -X bonds in Why ArX have partial double bond properties, it is difficult to break the C- bonds with partial double bonds, the propertie
16、s are difficult to break, and the bonds have partial double bond properties in the middleExplanation of the hybrid orbital theory: Interpretation of the hybrid orbital theory:C C CC C C ClThat is:Cl multi electron p- pion conjugation makes the C X bond double bondThe explanation of resonance theory:
17、 the explanation of resonance theory:Cl Cl+ Cl + Cl + ClThe C-X bond has the properties of double bonds(b) benzyl halide, a specific activity, BThis kind of halogen halogen atom in the active N1 and SN2? S reaction occurs easily; and the reaction occurs easily; reaction? Alcohol solution and easy ea
18、sy and AgNO3 reaction; alcohol solution reaction;? Can also be used as alkylation reagent for the use of Fourier reaction can be used as the alkylation Friedel Crafts reaction test agent. Example 1:CH2ClNaOH/H 2OCH2OH (faster than saturated halogenated hydrocarbons)CH2Cl CH2ClNaCN/H2OCH2CN (faster t
19、han saturated halogenated hydrocarbons) CH2NH2 (faster than saturated halogenated hydrocarbons)NH3/ROHExample 2:Cl, CH2Cl, CH2CH2Cl + AgNO3alcoholDo not react with AgCl (fast) + PhCH2ONO2 AgCl (slow)(distinguishing three different halogenated hydrocarbons) 3:AlCl3CH2Cl +CH2-Why benzyl halides have s
20、pecial activity, and why benzyl halides have special activity?The -X key in ArCH2X has a special activity, easy to break in the C- key, with special liveliness, easy to disconnect. The key has a special activity in the SN1:C, C, C, C, C, C+CH H+: + deltaDelta+Delta+The positive charge in CH2 is disp
21、ersed,The stability of PhCH2+ increases+SN2:C, C, C, C, C, CCl ClCH HTransition state C6H5 CNuH HIncreased stabilityNu(2) nucleophilic substitution reaction on aromatic ring(I) hydrolytic armourClNaOH/Cu 350-370, C, 20MPa harsh conditionsONa.H+OHPrepared by cumene oxidation methodChlorobenzene was o
22、nce an important chemical raw material. It was used in large quantities to produce phenol, but it was eliminated because of high energy consumption and serious pollution. However, the hydrolysis reaction is easy if the neighboring atoms of the halogen atom and the nitro group attract strong electron
23、 groups:O2NClNa2CO3/H2O 130, C.O2NOHO2NCl NO2NO2Na2CO3/H2O 100, C.O2NOH NO2NO2O2NCl NO2Na2CO3/H2O 35, C.O2NOH NO2Cases:O2NCl ClNaOH/H2OO2N ClOHEthylene glycol (b)ClNH3/Cu2O 200, C, 6MPa harsh conditionsNH2.Preparation of nitrobenzene by hydrogenation reduction(3) the mechanism of nucleophilic substi
24、tution reaction on aromatic ring(I) addition elimination mechanism; additive elimination mechanismDelta Cl Delta+?ClNucleophilic addition of OH is slow-OHElimination of -ClOH(I) Cl-fastCl- - - - - - -ohohcloh- - - - - - -(ii)(iii)(iv)显然, 当芳环上有吸电子基时, 将会使负电荷得到 有效分散, 有利于碳负离子中间体的稳定, 从而使反 应速度加快:所以, 卤素原子的
25、邻、对位有硝基等强吸电子基时, 水解及亲核取代反应容易进行:cl- - - - - - -ohclohclohcloh- - - - - - -n + ono- - - - - - -n + ono- - - - - - - - - - - - -non +no- - - - - - -n + ono -氮上正电荷直接分散负电荷 最稳定, 对真实结构贡献最大- - - - - - -no nocln +oh- - - - - - -o + n ocloh- - - - - - -no nocln+oh- - - - - - -no nocln+oh- - - - - - -氮上正电荷直接分散负
26、电荷 最稳定, 对真实结构贡献最大反之, 当芳环上连有r - 、ro - 等供电子基时, 将会使碳 负离子趋于更不稳定, 水解及亲核取代反应更难进行.(乙) 消除 加成机理 苯炔机理 乙 消除 - 加成机理 苯炔机理) 加成机理 (苯炔机理当苯环上没有较强的吸电子基存在时, 卤原子被取代的 反应是按照消除 - 加成机理进行的:非正常三键 - hcl cl h nanh / 液nh 2 3 条件苛刻 苯炔 nh2nh2 -nh2 nh3nh2+ nh2 -nh2nh3+ nh2nh2例: ch3clknh2 - 液nh3ch3nh2 + ch3 nh2(4) 与金属的作用(甲) grignard
27、试剂的生成 甲 试剂的生成ch2cl + mg cl cl cl纯醚clch2mgcl mgcl+ mgthf 回流 纯醚br + mgclmgbrarmgx型格氏试剂以及在合成上的应用与rmgx相 似, 都可用来制备醇.(乙) 芳基锂试剂的生成 乙cl + 2li键能大于ar - br 醚li + licl活性大于镁br + ch3ch2ch2ch2lili + ch3ch2ch2ch2br与烷基锂的化学性质相似, 芳基锂的亲核性和碱性 均比相应的格氏试剂强, 在合成应用中, 有机锂一般充 作中间体, 不须分离即可直接使用.(丙) wurtz - fittig反应 丙 反应br+ ch3ch
28、2ch2ch2br + 2na (ch2) 3ch3 + ch3 (ch2) 3 - (ch2) 3ch3 + 2nabr. b.p 126 c b.p 183 c可蒸馏除去. 20 c醚此反应可以用来制备直链烷烃取代的芳烃.但它仅 适用于不含有羟基、羰基、硝基等官能团的化合物.(丁) ulmann反应 丁 反应2 icu230 c.联苯+ cui2氯苯和溴苯亦可发生此反应, 但要困难一些. 但卤素原子的邻、对位有吸电子基时, 可以促进反应的 进行.例如:2clo2 ncuthe no2no2 225 c.2,2 - 二硝基联苯(5) 芳环上的亲电取代反应卤原子是使芳环钝化的第一类定位基. 例
29、如, 氯苯比苯难硝化, 新引入的硝基进入氯的邻、 对位:cl混酸 110 ccl, no2 +.clno2.(benzene nitration at a reaction temperature of 60 C)Second quarter aromatic sulfonic acid(a) named aromatic sulfonic acids (two) preparation of aromatic sulfonic acid (three) physical properties of aromatic sulfonic acid (four) chemical properti
30、es of aromatic sulfonic acid (five) sulfonyl chlorides and aryl sulfonamide (six) benzene sulfonate and surfactant (seven) ion exchange resinSecond quarter aromatic sulfonic acid(1) nomenclature of aromatic sulfonic acidSulfonic acid is the mother substance. Such as:CH3, CH2SO3H, SO3H, SO3H, p-tolue
31、ne sulfonic acid, benzyl sulfonic acid, SO3H, naphthalene sulfonic acidSO3H SO3H benzene two sulfonic acidOH, 5- hydroxy -1- naphthalene sulfonic acid(two) the method of making aromatic sulfonic acid(1) direct sulfonationClean process, reduce waste acid, conducive to environmental protection SO3?SO3
32、HCH3CH3SO3H +CH3C12H25SO3?C12H25SO3H(2) indirect sulfonationCH2Cl +H2O, H+190-220, C, Na2SO3, -NaCl nucleophilic substitution. CH2SO3NaSodium benzyl sulfonateCH2SO3HBenzyl sulfonic acidCl NO2 NO2Na2SO3SO3Na NO2 NO2H2O, H+Nucleophilic substitution of 2,4- two nitrobenzene sulfonic acid sodiumSO3H NO2
33、 NO2 (98%)2,4- two nitrobenzene sulfonic acid(three) physical properties of aromatic sulfonic acidAromatic sulfonic acid is a volatile colorless crystal, soluble in water, insoluble or slightly soluble in non-polar organic solvents. ? and aromatic sulfonic acid potassium and sodium, calcium, barium
34、and lead salts are soluble in water, so the introduction of sulfonic acid in organic matter can greatly improve the water solubility.(four) the chemical properties of aromatic sulfonic acid(1) reaction of hydroxyl radical in acidic (2) sulfo group (3) reaction of sulfo group(1) hydrolysis (II) of al
35、kali fusion with other nucleophilic substitution reactions(4) electrophilic substitution reaction on aromatic ring(four) the chemical properties of aromatic sulfonic acidThe reaction on the sulfo group: 1. Acidity; the hydroxyl radical in the sulfonyl group is replaced; and sulfonic acid group is su
36、bstituted. Reaction on the aromatic ring: aromatic sulfonic acid is more difficult to electrophilic substitution than benzene.(1) acidity;Sulfonic acid belongs to organic strong acid, whose acidity is equivalent to that of sulfuric acid, and can be made into salt with alkali, and can also be balance
37、d with NaCl to form salt:SO3H + NaOH, SO3H + NaClAcid-baseSO3Na + H2O, SO3Na + HClAlkali acidThe use of the acidity of aromatic sulfonic acid can be used instead of sulfuric acid as a catalyst, with less side reaction and less pollution.(2) the reaction of hydroxyl groups in sulfo groupThe hydroxyl
38、radical in the sulfonyl group can also be substituted by chlorine atoms to form sulfonyl chloride:SO3H + ClSO3H, 32 SO3Na + PCl3, SO3Na + POCl320-25 C CCl4. SO2Cl 32 + H2SO4. SO2Cl +, 2NaCl + NaPO3, SO2Cl +, NaCl + NaPO3.170-180 C170-180 CSulfonyl chloride is also prepared by the reaction of aromati
39、c hydrocarbons with excess sulphonic acid:+ 2ClSO3H20-25 C CCl4 75%-77%. SO2Cl + H2SO4 + HCl(3) the reaction of sulfo group(I) hydrolytic armourHydrolysis reaction is the reverse reaction of sulfonation reaction. Under acidic catalysis, the sulfonyl group or its sodium salt is co heated with water t
40、o remove the sulfonyl group. The essence of the reaction is the electrophilic substitution reaction of H+ as a electrophilic reagent attacking the aromatic ring.SO3HH2O, HCl 180, C.+ H2SO4By using the hydrolysis reaction of sulfo group, occupying in organic synthesis can be carried out. Such as:CH3H
41、2SO4CH3 SO3HCl2 FeCH3ClH2O/H+CH3ClSO3HBr2 Fe180 C.OH H2SO4 HO3SOH SO3HBr OH HO3S SO3HH2 OBr OH?(b) alkali fusion and other nucleophilic substitution reactions; bCH3 SO3Na NaOH (S). 320 C浓H2SO4 160 CCH3在水，氢+CH3竹红菌素衍生物哦。含NaOH（溶液）H +NaOH（固体）熔融在哦这是工业上制酚的方法之一。但反应物分子中不宜含有硝基和卤原子，因为硝基化合物易与碱反应，卤原子可被羟基取代。其它亲核
42、试剂也可与芳磺酸盐发生亲核取代反应：$NaCN 300 Ccn。so3k O ONH3（过量）？，加压NH2 O O（4）芳环上的亲电取代反应磺基是吸电子基，它使苯环致钝，亲电取代反应活性降低，新引入基上间位。例如：$+硫酸SO3发烟硫酸200-230 C。$ $间苯二磺酸+ H2O注意：芳磺酸一般不进行酰基化反应、注意芳磺酸一般不进行酰基化反应、烷基化反应及氯芳磺酸一般不进行酰基化反应甲基化反应！甲基化反应因为这些反应的进攻试剂的亲电性太弱。（五）芳磺酰氯和芳磺酰胺芳磺酰氯中的氯原子不如羧酸酰氯中的氯原子活泼，只发生微弱的水解。但在碱存在下，仍可顺利地水解、醇解和氨解：（1）H2O，哦（2）
43、H2O，H卢武铉吡啶+H3C$对甲苯磺酸H3Cso3rH3Cso2cl2nh3对甲苯磺酸酯H3C H3Cso2nh2 +氯化铵+ + so2nhr RNH3Cl对甲苯磺酰胺2rnh2N取代对甲苯磺酰胺芳磺酰氯可作为磺酰化试剂，在芳环上引入磺酰基生成砜：CL so2cl + ClAlCl3亲电取代氯所以氯4,4-二氯二苯砜（制备聚砜的原料）芳基磺酰氯亦可被还原：H3C so2clZn-H2O？H3CSO22锌（1）碳酸钠（2）H2O，H+H3Cso2h对甲苯亚磺酸so2clzn-h2so40 C，91%SH苯硫酚芳磺酰氯在某些有机物的合成、胺的鉴别、分离以及反应机理的研究中具有一定的重要性A.取代醇羟基：取代醇羟基：CH3 H3C chch2-oharso2clchch2cn chch2-oso2ar H3C CH3 CH3好的离去基团有利于SN1和SN2差的离去基团氰化钠（CH3）2s = O，80%H3C基（1）眼（2）溴化锂，丙酮，94%CH2Br TS = H3C SO2B.亲核取代反应的立体化学R H H + Cl TS C-O R不涉