10烯,炔,二烯烃的化学性质

1、ch3c=ch2ch3+ hbrch3cch3brch3+ ch3cch2brch3h90% 10% ch2=ch2 + br2nacl-h2och2ch2brbr+ ch2ch2broh+ ch2ch2brclch3ch=ch2 + hoso2ohch3chch3ohch3chch3oso2ohh2oh_clch3ch=ch2 + hoso2ohch3chch3ohch3chch3oso2ohh2oclcce nuslow+ccenu-fastccenu亲电试剂亲核试剂+加成取向加成取向markovnikov马氏规则马氏规则ch3c=ch2ch3hbrch3cch3ch3+ch3chch3c

2、h2+3oc+1oc+(a)(b)(c)在不对称烯烃的加成中在不对称烯烃的加成中, 氢总是加到含氢较多的双键碳原子上。氢总是加到含氢较多的双键碳原子上。ch3ch3hbrbr ch3hch3( )+-ch3cch=ch2ch3ch3hclch3cchch3clch3h3c+ ch3cchch3ch3clch317% 83%ch3cch=ch2ch3ch3hclch3cchch3clch3h3c ch3cchch3ch3clch317% ch3cchch3ch3ch3+cl-ch3迁移ch3cchch3ch3ch3+cl-83%ch3chch=ch2ch3hclch3cchhch3ch3+cl-

3、ch3chchch3ch3cl-h-迁移ch3cch2ch3ch3+cl-ch3cch2ch3clch3(40%)(60%)硫酸、磷酸等催化，烯烃与水直接加成生成醇。硫酸、磷酸等催化，烯烃与水直接加成生成醇。ch3ch=ch2 + h2oh3po4195oc,2mpach3chch3ohch3ch=ch2 + hoso2ohch3chch3ohch3chch3oso2ohh2o间接水合法制备烯烃，条件缓和，实验室常用间接水合法制备烯烃，条件缓和，实验室常用+ br2brbrch3ch3+ br2ch3brbrch3速率控制步骤反式加成产物ccbr2slowccbr+ br-+step 1ste

4、p 2ccbr+ br-fastccbrbrcchch3hch3br2cchhh3cch3br+br-cbrcbrch3hhh3ccbrcbrhch3hch3ch3ch3brch3ch3hbrbrhhbrh(r)(r)(s)(s)dl-ch3ch=ch2 + cl2(h2o)ch3chch2clohhobrch3ho h h3c br br h h3c ho+c ch h3 3c ch h2 2c ch h= =c ch h2 2r ro oo or r p pe er ro ox xi id de es sn no oc ch h3 3c ch h2 2c ch h2 2c ch h2 2b

5、 br rc ch h3 3c ch h2 2c ch hc ch h3 3b br rh hb br r 反马氏加成反马氏加成羟汞化羟汞化脱汞反应脱汞反应催化加氢反应催化加氢反应ch3ch3+ h2pth hch3h3cch3+ d2ptddch3ch3ch3+ h2pth hch3h3cch3+ d2ptddch3ch3cch2ch360%h2so470occh3cch3ch3+ch3cch2ch3ch3cch2cch3ch3ch3ch3+ch3cch2cch3ch3ch3ch3+-h+ch3cchcch3ch3ch3ch3ch3cch2cch2ch3ch3ch3+nch2=chr催化剂或

6、引发剂 ch2chrnkmno4(冷)顺加hhoo mnoo-k+h2ohhohohch3c=chch2ch3ch3oh-，kmno4ch3cch3o + ch3ch2coohcc + o3加成ccooo重排oococznh2oco+ occh3ch=cch3ch3 1) o32) zn/h2och3cho + ch3coch3cchch3ch2ch3h+ ch3co3hccoch3ch2hch3h+ ccohhch3ch3ch2h3ch+ c6h5co3hoh3choh3ch+76% 24%ch3ch3+ clco3hch3ch3o( 控制mol 1:1 )ch3ch=ch2 + cl250

7、0occcl4r.t.clch2ch=ch2ch3chch2cl clcl2高温2clch3ch=ch2 + clch2ch=ch2cl2clch2ch=ch2 + clch3chch2clcl2ch3chch2cl + clclnoobrch3ch2ch2ch=ch2nbs(c6h5coo)2ch3ch2chch=ch2 + ch3ch2ch=chch2brbrch3ch2chch=ch2ch3ch2chchch2ch3ch2chch=ch2brch3ch2ch=chch2brch3ch=ch2 + cl2500occcl4r.t.clch2ch=ch2ch3chch2cl clch3ch=

8、ch2 + cl2500occcl4r.t.clch2ch=ch2ch3chch2cl clcce nuslow+ccenu-fastccenu亲电试剂亲核试剂+c ch h3 3c ch hc ch hh h+ + h hb bh hh hc cc ch hb bh hh hh h3 3c ch hh hh hc cc ch hb bh hh hh h3 3c ch hh hh hh hh hh hh h3 3c ch hc cc cb b3 3顺式加成产物cc(sp3) 25 154 347cc(sp2) 33 134 611cc(sp) 50 120 837s%键长 键能ch2chch2

9、cchbr2-20oc,ccl4ch2chch2cchbrbr(90%)chch +chclcl2fecl3chclcl2chcl2chcl2chch + hclhgcl2150-160occh2chclhgcl2hclch3chcl2chch+h+ch2ch+ch2ch2+h+ch3ch2+chchnc4h9+ hbrroornc4h9ch chbr+ nc4h9chbrch2brhcch + h2ohgso4h2so4 hchchoh 乙烯醇ch3cho异构化ccohccoh烯醇式 酮式hgso4h2so4ch3(ch2)5cch + h2och3(ch2)5cch3o(95%)6 rcc

10、h + b2h6ccrhh3b2h2o2oh-6rch2choch3coohrch=ch26 rccr + b2h6cchrr3b2ch3coohccrrhhcis-hcch + ch3ohch2choch3亲核试剂chch + ch3coohch2chocch3o亲核试剂rccr + h2ccrrhhh2rch2ch2rpdpdc2h5ccc2h5 + h2pd/caco3喹啉ccc2h5c2h5hhrccr + h2lindlar cat.ccrhhr (顺式烯烃)ch3ch2ccch2ch2ch3nalig. nh3ccch3ch2hhch2ch2ch398%hcch + nh2-hcc

11、-+ nh3(pka=25)碳氢化合物中h的酸性顺序：ch ch chspsp2sp3rcch + nanh2lig.nh3rcc-na+ nh3hcch + 2ag(nh3)2+agccaghcch + 2cu(nh3)2+cucccuhcch + nanh2hcc-na+n-c4h9brch3(ch2)3cch双烯烃聚集双烯 ch2=c=ch2共轭双烯 ch2=ch-ch=ch2隔离双烯ch2=ch-ch2-ch=ch2cccc133.7pm146pmcc 134pmcc 154pmch2=ch-ch=ch2 + br2ch2chch=ch2 + ch2brbrch=chch2brbr 1

12、,2-加成 1，4-加成ch2chchch3+ch2=chchch3+ch2ch=chch3+br-br-ch2=chchbrch3ch2ch=chch3br1,2-加成产物1,4-加成产物ch2chchch2+ hch2chchch3+brch2chchch3br-ch2=chchch3 + ch2ch=chch3brbr弯箭头表示电子弯箭头表示电子离域，可以从双离域，可以从双键到与该双键直键到与该双键直接相连的原子上接相连的原子上或单键上或单键上ch2=chch=ch2 + hbrch3ch=chch2br + ch3chch=ch2br-80oc 20% 80%40oc 80% 20%

13、1,4- 1,2-1,2-加成：加成：低温有利低温有利1,4-加成：加成：高温有利高温有利ch2=chch=ch2 + hbrch3ch=chch2br + ch3chch=ch2br-80oc 20% 80%40oc 80% 20% 1,4- 1,2-ch2=cch=ch2 + hbrch3ch3cch=ch2ch3+ch3cchch3ch2+-br-brch3cch3ch=ch2brch3c=chch3ch2brch2=cch=ch2 + hbrch3?+ cho苯100occho100%+ooo苯ooo+ +ooochocoorch2ccch2hhch2ccch2hhs-顺-1，3-丁二

14、烯s-反-1，3-丁二烯双烯体 亲双烯体 相对反应速率ch2=chcoc2h5occncnccncn112.64.6*106+ +6 61 1% %3 39 9% %ch3+ cooch3ch3cooch3ch3cooch3+ + +c ch ho oh h3 3c cc ch ho oh h3 3c cc ch ho o 7 70 0% % 3 30 0% %+ +h hc co oo oh hh ho oo oc ch hc co oo oh hh hh hc co oo oh hc co oo oh hh hh hc co oo oh h+ +oa b cohcohccooch3cooch3ohohochocho+ooo苯oooooochocoorooochocoorohcohccooch3cooch3ohohochochooa b cohcohccooch3cooch3ohohochochoohcohccooch3cooch3ohohochochokmno4(冷)顺