KHOA CNG NGH HO HC ----o0o---TIU LUN MN HC : HA HU C

TI

Ngi thc hin: Hng Hong MSSV: 09113901 Lp: 210405002 GV hng dn: TS. Nguyn Vn Bi

Thnh ph H Ch Minh, thng 10 nm 2010

MC LC
M BI..........................................................................................................................3

M BI
Ha hc hu c l ngnh khoa hc v nhng cu trc, tnh cht, thnh phn, phn ng, v cch tng hp ca nhng hp cht hu c. Nhim v c bn ca ha hu c l: nghin cu tng hp cc hp cht hu c v tch bit cc sn phm hu c; nghin cu xc nh cu trc cc hp cht hu c; nghin cu tnh cht v c ch phn ng ca cc hp cht hu c. Trong nghin cu v c ch phn ng l mt trong nhng mng quan trng trong ha hu c. C ch phn ng m t mt tin trnh phn ng din ra t cht u ti cht cui i qua cc trng thi chuyn tip v hp cht trung gian. C nhiu loi phn ng khc nhau nh: phn ng th, phn ng cng, phn ng tch Song mi loi u c mt c ch phn ng ring. Trong phn ng th theo c ch gc l mt phn ng ph bin ca hydrocacbon no nh ankan. T vic nghin cu phn ng th theo c ch gc ca hydrocacbon no, ta s hiu r hn v cc dn xut th ca hydrocacbon v trnh c sai st khi iu ch dn xut th ca hydrocacbon trong thc nghim. Do ti chn ti: phn ng theo c ch gc ca hydrocacbon no gip cc bn hiu r vn trn.

NI DUNG
1. Gc t do Gc t do l tiu phn electrophin c electron t do trn obitan, c kh nng phn ng cao. C ch chung ca phn ng gc t do gm hai giai on. Giai on u l s hnh thnh gc t do, thng bng s phn ct ng lin kt: X X + Y Y gi l giai on kch thch. Qu trnh phn ly ca nhng cht c lin kt yu nh cc hydropeoxit, ankyl, axyl, iankyl peoxit, cc peaxit, hp cht azo c th t xy ra hay khi c nhit, hay mt s cht sinh gc khi c nh sng nh clo, brom, mt s xeton hoc bng cch chuyn mt electron Me + e Me thng t kim loi hoc bng con ng in ha. Giai on th hai l s chuyn ha gc t do, l qu trnh t hp ca cc gc t do ging nhau hay khc nhau cho san phm: X + Y X Y Qu trnh ny gi l qu trnh tt mch. Qu trnh ny thng khng trc tip gia hai gc v gc l tiu phn rt hot ng, lng gc sinh ra cn rt thp nn gc c th va chm vi cc phn t khc sinh ra mt tiu phn c s electron l ti to ra mt gc mi. Chng hn nh: X + R XH + R H Qu trnh sinh ra mt phn t v mt gc mi nh mt gc mi ti to gi l giai on chuyn mch. Gc mi ny li tip tc tng tc vi cc phn t sinh ra gc mi cho n khi tt mch nh trn gi l qu trnh chui, gm hng trm hay hng ngn qu trnh chuyn mch cho ti khi kt thc. Ngoi ra c th c qu trnh chuyn mch bng phn ct gc t do hay phn t phn ng hoc bng chuyn v.[3] 2. Phn ng th gc t do ca hydrocacbon no 2.1 C ch chung C ch chung ca phn ng l: R R X Y 4

Phn ng c th xy ra bng s phn ct cht ban u: R R + X X bng cch t xy ra hay khi c nh sng hay nhit, nhng qu trnh ny t thc t, nn thng gy ra bng tc dng ca mt gc t do a thm vo phn ng gi l cht kch thch hay khi mo sinh ra gc t do ca cht ban u R : R + W X Gc ny sinh ra c th thc hin phn ng tch: R + Y R + W W Y hay t hp: R + Y R Y 2.2 Phn ng th hydro ca hydrocacbon no R + X R + H H Y X Y XY= Halogen(x2), SO2Cl2, CCl3Br, CF3I, R3COCl, C6H5ICl2, [R2NHCl]+ Phn ng c xc tin khi c nh sng hay nhit hay vi cht sinh gc t do kch thch phn ng. Phn ng th hydro bng nhm th X trong phn ng gc khng th xy ra s phn ct trc tip lin kt C thnh C v H v DH = 104kcal/mol. H Phn ng c th xy ra theo s tn cng ng b lng phn t tng t S N2 t pha sau ca C (gi l SR2C). C ch ny rt him. Trng hp cht mch h ch c mt thng bo v c ch ny gia trimetylmetan vi gc triflometyl to thnh CH3CF3 ng thi vi sn phm khc.
[3]

2.3 Phn ng halogen ha Ankan thng clo ha hay brom ha bng clo hay brom khi c nh sng kh kin hay UV. Phn ng cho nhiu ng phn v v tr, ng phn mono-, i- v polyhalogen nn nu dng tng hp mt cht tinh khit th rt hn ch. Phn ng thng dng cho loi hydrocacbon ch c mt loi hydro nh etan, xyclohexan, neopentan. Clo ha c th dng tc nhn khc nh SO2Cl2, Cl2O, PCl5, photgen, tert-butyl hypoclorua, N-halogenamit v axit sunfuric. 5

Brom c tnh chn lc hn, dng ch yu cho dn xut bc ba v loi benzyl, tnh chn lc v tr rt cao khi c nhm k. C th dng tc nhn Br 2 voi HgO hot ng hn, Br2O, BaCCl4, tert-butyl bromua, N-bromsuxinimic. Flo t dng v hot tnh cao, thng phn ct mch, cho nhiu sn phm ph, thng dng ClF3 -75C. F2 -70C pha long trong N2 v brom triflooxit 25C c tnh chn lc cao cacbon bc ba nhng l c ch electrophin, khng phi c ch gc. Iot c th dng khi c nh sng c chiu di sng 184,9 nm nhng iot ha cng chm v HI hnh thnh kh RI. C ch halogen ha theo c ch gc: Kch thch: X2 2X

Pht trin mch (hay ln mch): X + R HX + R H R + X R + X X H Tt mch: R + X RX

Gc R l mt tiu phn trung gian c hnh thnh qua mt trng thi chuyn tip ca X vi R Qu trnh ng hc nh sau: H.

Hnh 2.1 Gin th nng ca phn ng halogen ha ankan Giai on quyt nh tc phn ng l giai on hnh thnh gc R i hi mt nng lng hot ha cao hnh thnh mt trng thi chuyn tip: 6

[R H X]# Trng thi chuyn tip ny c th chuyn v pha cht ban u hay v pha sn phm, do , giai on ny l thun nghch, thng theo hng c nng lng hot ha nh. giai on ny, obitan cha mt electron cua X tn cng vo H, xen ph vi obitan 1s ca H gy ra s y electron lm gim s xen ph ca obitan 1s ca H vi obitan Csp, lin kt C bt u dn ra v yu i. Khi lin kt C yu i, khng i H H hi nhiu bn cht s ca obitan nn lm tng bn cht s ca cc lin kt C khc. Qu H trnh ti lai ha cacbon bt u chuyn Csp sang Csp. Cacbon dn dn phng ra ngoi, lin kt C cn tr thnh ngn hn v bn hn. H Trng thi chuyn c th hnh dung bng tng tc obitan nh sau:
H H C H b a H Cl #

Hnh 2.2 Tng tc obitan: a- obitan c bn cht trung gian gia Csp3-H v Csp2-H b- obitan c bn cht trung gian gia sp3 v p Trng thi chuyn ny s to thnh gc vi cacbon lai ha sp2 hay tr v cht ban u vi cacbon lai ha sp3. Do , giai on ny l thun nghch. Giai on th hai, gc R tng tc vi X2 qua trng thi chuyn tip: [R X X] S hnh thnh trng thi chuyn ny i hi nng lng hot ha nh, thng khong 2 kcal/mol. Trng thi chuyn ny s chuyn thnh sn phm. 4 Giai on chuyn R ti trng thi chuyn tip trn l thu nhit v t trng thi chuyn tip ti sn phm l pht nhit mnh, do , c hai giai on ny l khng cn bng v pht nhit. C ch Halogen ha ankan nh trn l c ch chui, trong qu trnh c s tham gia v ti to gc kch thch ban u tip tc phn ng. Song c tnh chung ca phn ng chui l ng cong ng hc c thi k cm ng, sau giai on cm ng , tc 7

 phn ng xy ra rt nhanh, hu nh tc thi. Thng ng cong ng hc ca phn ng gc c bn cht ca hnh ch S.[2] Giai on tt mch l t hp cc gc t do nn cng l giai on pht nhit. Nu dng tc nhn khc cng c s phn ct tng t xc tc nh sng v ln mch tip theo nhng khng cn tch hydro bng halogen. Vi tert- buoxyclorua (tert- C4H9OCl): RH + tert-C4H9O R + tert-C4H9OH R + tert-C4H9Ocl RCl + tert-C4H9O Xiclohexan, xiclopentan, tc dng vi halogen tng t ankan, ngha l cho phn ng th. Th d:
Br + Br2
hv

HBr

Tuy nhin xiclopropan li tham gia phn ng cng vng, v vng ny km bn. m Th d:
+ Br2 CCl4 Br-CH 2-CH2-CH2-Br

2.4 Phn ng nitro ha Nitro ha ankan c thc hin ln u tin ngay t nm 1888 bi M.I. Konovalop bng cch un nng ankan vi dung dch axit nitric 10 - 20% trong bnh kn nhit 150C. T n-hexan thu c 2-nitrohexan vi hiu sut 63%. CH3(CH2)4CH3 + HNO3 CH3CH(NO2)(CH2)3CH3 + H2O Ngy nay, ngi ta thc hin phn ng nitro ha ankan 420 - 450C (pha kh) bng axit nitric m c hoc nit ioxit. Trong iu kin , ngoi phn ng lm t lin kt C cn xy ra phn ng b gy lin kt C v th thng to ra hn hp cc H C, nitro ankan vi s nguyn t C bng hoc nh hn ankan ban u. Th d:

420oC

CH3CH2CH3 + HNO3

CH3CH(NO2)CH3 + CH3CH2CH2NO2 + 33% 26% 9% 32% + CH3CH2NO2 + CH3NO2 + H2O

Phn ng nitro ha ankan cng xy ra theo c ch gc nhng khng hon ton ging vi phn ng clo ha. Nit ioxit sinh ra trong hn hp phn ng vn l mt phn t l electron (O=N=O) ng vai tr gc t do (nh Cl ) m u cho s ph trin mch:
RH HNO2 R + + + NO2 NO2

HNO2 H 2O + RNO2

R 2NO 2

HNO3

O2 l gc tng i bn, thi gian sng di hn nhiu so vi Cl, n c mt trong hn hp phn ng vi lng p o so vi gc R.[1] 2.5 Phn ng sunfo ha Axit sunfuric dng oleum khi un nng vi ankan s sunfo ha chm ankan, u tin cacbon bc ba:
CH 3 CH3 CH CH 3 CH 2 CH3 + H2SO4 CH 3 C CH 2CH 3

SO3H

2.6 Phn ng sunfo clo ha Ankan tc dng vi clo v lu hunh ioxit khi chiu nh sng to thanh2ankyl sunfoclorua:
O RH + SO 2 + Cl 2 hv RSCl O + HCl

l phn ng dy chuyn theo c ch gc m giai on pht trin mch c s tham gia ng thi ca Cl2 v SO2:

O RH +Cl HCl R SO 2 RS O Cl 2

O RSCl O + Cl

C th d dng thy rng, ngoi ankyl sunfoclorua ra, phn ng cn to ra ankyl clorua. trnh phn ng clo ha, ngi ta ly SO2 vi lng d ln. Khi xc sut va chm gia R va Cl2 s tr nn khng ng k so vi gia R v SO2. T l cc sn phm th hidro cc bc cng ging nh phn ng clo ha. Trong cng nghip, ngi ta sunfoclo ha cc ankan phn on C8 16 t du m C ri cho sn phm tc dng vi xt sn xut cht hot ng b mt dng lm cht git ra tng hp.[1]
CnH 2n+2 SO 2, Cl2, hv HCl CnH2n+1SO 2Cl 2NaOH + CnH 2n+1SO 3 Na + NaCl + H 2O

(cht hot ng b mt) 3. Nhng nhn t nh hng ca phn ng th gc (SR) Khc vi phn ng ion, trong phn ng gc, trung tm phn ng l H. Trong trng thi chuyn nguyn t H dng mt AO tham gia lin kt vi gc tn cng Y v nhm i ra R bng 3 electron: [Y H R]. thy c nh hng ca cc nhn t, c th hnh dung trng thi chuyn c tnh ng hnh gn nh gc allyl:

H 2C

CH2

S phn ct H xy ra cng d nu nng lng phn ly lin kt cng nh, gc i ra cng bn, do cng chu nh hng ca nhm th trung tm phn ng v gc ankyl i ra. Nhng nhn t nh hng ti qu trnh chuyn l tnh bn ca lin kt phn ct v to thnh, hiu ng lp th, hiu ng phn cc v nh hng ca dung mi. Trong phn ng chui, giai on hnh thnh ra sn phm l giai on phn ct bi gc t do. Gc t do lun phn ct ly nguyn t n ha tr nh hydro v halogen, ri n hai ha tr, khng bao gi phn ct nguyn t ba hay bn ha tr. 10

Nhn t quyt nh l lp th. Cc nguyn t n ha tr bn ngoi d cho gc tip cn hn l cc nguyn t ha tr cao. Mt khc, phn ng thun li khi phn ng pht nhit hn l thu nhit tnh t nng lng lin kt phn ct v to thnh. Trong trng hp s khc nhau v nng lng khng ln th nhn t lp th quan trong hn v trong hai kh nng th nguyn t n ha tr c chn lc hn. Nhiu nghin cu v hat tnh ca hp cht aliphatic (cht bo) th hydro l nhm i ra v nguyn t clo l tiu phn tn cng, bt k nguyn t hydro no cng c kh nng i ra, v th thng tm thy hn hp sn phm, tuy nhin cc gc khng phi hon ton khng chn lc m d phn ng mt vi v tr trong phn t d mt hydro hn cc v tr khc.[3] 3.1 nh hng ca halogen

Bn cht halogen c nh hng trc tip ti phn ng. Ni chung, F 2 phn ng mnh, I2 phn ng kh khn nn dng Cl2 v Br2. Kh nng phn ng nh sau: F2 > Cl2 > Br2 > I2 i vi F2, s phn tch F2 2F rt thu nhit, i hi nng lng hot ha cao, song khi c mt s nh phn t F2 phn ly c th bt u phn ng ln mch. C hai giai on ln mch c nng lng hot ha nh, phn ng d xy ra v pht nhit ln. Nhit ny m bo cho s phn ly tip F2. S d dng flo ha c gii thch bng nng lng hot ha thp ca giai on ln mch v gi tr H ln mch cao. S pht nhit mnh c th gy ra hin tng n v ph hy nhiu lin kt trong phn t. Do , ni chung khng dng phn ng flo ha trc tip bng F2 v phn ng ny khng c dng trong phng th nghim. Ngi ta c th dng tc nhn yu hn flo ha, chng hn CoF 3 (do tc dng ca CoF2 + F2): 2CoF2 + F2 2CoF3 CH4 + 8CoF3 CF4 + 8CoF2 + 4HF i vi Cl2, nng lng phn ly Cl2 l 58kcal/mol, thu nhit do hp thu nng lng t ngoi. Giai on ln mch l pht nhit mnh. Do , phn ng xy ra do giai on pht nhit, gi tr H ln. Chng hn vi metan: 11

CH4 + Cl CH3 + HCl CH3 + Cl2 CH3Cl + Cl

H = +2 kcal/mol H = 26,7 kcal/mol

--------------------------------------------------------------CH4 + Cl2 CH3Cl + HCl H = 24,7 kcal/mol i vi Br2, phn ng c H kch thch trung gian gia flo v clo ha, song nng lng hot ha giai on ln mch cao (18 kcal/mol) do ch c nhng nguyn t Brom hot ng mnh mi phn ng c v mi khc phc c hng ro nng lng cao ny. Nh vy, brom phn ng km hn clo, phn ng t pht nhit hn. i vi I2, phn ng vi ankan rt chm, c th coi nh khng c kh nng phn ng, tuy giai on kch thch xy ra d dng nhng giai on ln mch li thu nhit, nng lng hot ha cao. Ngay 300C, s nguyn t iot c nng lng cao phn ng cng rt t. Do , ngi ta iu ch dn xut iot bng cch gin tip, nh phn ng th cc nhm chc khc bng iot. Thc t, nguyn t iot rt km hot ng, thng ime ha cho tr li I2 v gc R phn ng voi HI ti to RH v I2. Giai on Phn ng Ln mch Tt mch Kch thch X2 2X

H , kcal/mol F Cl +37 -33 -37 +58 -1 -23 -58

Br +46 +15 -21 -46

I +35 +31 -17 -36 +14

X + CH4 CH3 + HX

CH3 + X2 CH3X + X -71 2X X2

-104 -24 -6 Bng 3 S thay i H phn ng halogen ha vi CH4

Phn ng halogen ha xy ra da vo hiu ng nhit ca phn ng, song ch yu da vo hiu ng nhit ca giai on ln mch. Giai on ny xc nh di mch ng hc. Chng hn nh clo ha, chiu di mch ng hc c th t ti 104, ngha l phn ng chui clo ha c mt vng phn ng l 104 ln phn ng t khi bt u ln mch cho n khi tt mch phn ng. Phn ng halogen ha thc t ch dng hai halogen: clo v brom, trong clo phn ng mnh hn, cn Br2 c tnh chn lc hn. S khc nhau v kh nng phn ng ca hai halogen ny c so snh bng gin sau:[2] 12

Hnh 3.1 Gin so snh phn ng ca Cl2 v Br2 vi CH4. 3.2 nh hng ca cu trc ankan Cu trc ca ankan nh hng ti s hnh thnh sn phm v nng lng phn ng giai on ln mch. y c s khc nhau v kh nng phn ng ca hydro c bc khc nhau. Phn ng phn ct ly H bng X xy ra vi nng lng hot ha khc nhau: Nng lng hot ha H#, kcal/mol R + X R + HX H

R= X= Cl X= Br

CH3 4 18

R bc 1 1 13

R bc 2 0,5 10

R bc 3 0,1 7,9

Chng hn phn ng clo ho propan trong dung dch CCl4 25C: CH3CH2CH3 + Cl2 CH3CH2CH2Cl + CH3CHClCH3 43% 57% T l hai sn phm to thnh cho thy H ca phn ng vi H bc hai thp hn bc nht l 3 kcal/mol, ngha l H bc hai tng tc vi clo d hn H bc nht. V trong propan c 2H bc hai v 6H bc nht cho nn hot tnh tng i gia chng l: = =

13

Phn ng phn nh trn gin nng lng ca phn ng:

Hnh 3.2 Gin th nng ca phn ng ca Cl vi propan Tng t vi 2 metylpropan: (CH3)3CH + Cl2 (CH3)3CCl + (CH3)2CHCH2Cl 36% v hot tnh tng i l: = = Trong phn ng gc cn ch ti tnh chn lc H. linh ng ca H ph thuc vo nh hng ca gc ankyl, chng hn s thay i tc d phn ng tng i trong cc hp cht sau: CH3 H CH3CH2 H (CH3)2CH H -4 kt 7,10 1 220 S khc nhau chng t H ca H cc bc khc nhau l: Hbc 3 > Hbc 2 > Hbc 1 ng thi t cc H ca cc trng thi cho thy s, khc nhau v H ca trng thi chuyn chng t tnh bn ca gc bc ba > bc hai > bc nht v bn cht trng thi chuyn khng c bn cht gc hon ton. Brom cng phn ng tng t: CH3CH2CH3 + Br2 CH3CH2CH2Br + CH3CHBrCH3 14 (CH3)3C H 4 1,9.10 64%

8% 300C trong tng kh. T l tc tng i l: = = Cn tc ca hai phn ng l: vH bc 1 = k1[CH3CH2CH3][Br] vH bc 2 = k2[CH3CH2CH3][Br]

92%

v t l sn phm cng l t l ca hai hng s tc : = So snh hai phn ng trn, hai phn ng ging nhau, phn ng c nng lng hot ha cao hn s c hng s tc d nh hn. So vi clo ha, H# trong clo ha ch 1 kcal/mol, cn brom ha l 3 kcal/mol, cng nh t l tc tng i, cho thy, clo c tnh chn lc km hn, brom c tc phn ng vi H bc hai ln hn hn H bc mt nhiu, c tnh chn lc cao hn. Khi phn ng vi 2, 2, 3 trimetylbutan, brom ch cho mt sn phm:
(CH3)CCH(CH3)2 + Br2 hv, CCl4 (CH3)3CCBr(CH3)2

Nh vy, brom c tnh chn lc cao hn clo, nguyn t brom km hot ng hn, trng thi chuyn trong qu trnh phn ng hnh thnh chm hn, ngha l trng thi chuyn c bn cht gc kh y hn. Cn clo hot ng hn, trng thi chuyn nhanh hn v trng thi chuyn c bn cht gc km hn. R + Br [RHBr] R + HBr H R + Br [RHBr] R + HBr H Kh nng ph ng cng cao nu nng lng phn ly ca H to thnh cng ln. X Nng lng phn ly ca H to thnh gim th nng lng hot ha tng, lm gim X phn ng nhng ng thi lm tng tnh chn lc ca qu trnh gia bc 1, 2, 3. Khi gim nng lng H to thnh, phn ng tr thnh km pht nhit hn, trng X thi chuyn chuyn gn v pha sn phm hn, lin kt C trong trng thi chuyn b H ko di hn v electron khng cp i nh ch trn cacbon trong trng thi chuyn

15

cng ln, s khc nhau v tnh n nh ca gc to thnh cng ln, do lm tng tnh chn lc ca qu trnh. S khc nhau v tc phn ng ph thuc vo s gii ta electron t do lm cho gc n nh hn th ng thi cng lm n nh trng thi chuyn bng tng tc electron vi bn cht gc chm n trong trng thi chuyn. Bn cht gc cng ln trong trng thi chuyn c n nh bng gii ta electron t do th lm tng tc phn ng.[2] 3.3 nh hng ca dung mi Khc vi phn ng ion, phn ng gc t nhy vi tnh phn cc ca dung mi. Chng hn, khi chuyn t dung mi hydrocacbon ( = 2) ti dung mi nitrometan ( = 39) tc ca phn ng gc ch tng 10 ln, (trong phn ng ion tng 102 104 ln). Mt khc, phn ng gc cng t nhy vi lc ion. iu gy ra bi s phn chia in tch nh trong phn ng gc so vi ion. Gc t do l tiu phn khng cha in tch nn tnh phn cc khng solvat cc tc nhn, khng lm thay i tc . Song trong nhiu phn ng to thnh trng thi chuyn c s phn chia in tch, ngha l trng thi chuyn phn cc hn cht ban u nn dung mi cng cao th trng thi chuyn cng c n nh hn, lm tng tc phn ng, ng thi cng nh hng n tnh chn lc ca phn ng. Tnh chn lc ca phn ng ln khi dng dung mi c kh nng to phc vi gc t do, nht l tnh chn lc tng khi dng dung mi thm. Chng hn, clo ha 2,3- imetylbutan trong cc dung mi khc nhau:
CH3CHCHCH 3 H 3C CH3 Cl CH3CHCCH 3 H 3C CH3 CH3CHCClCH3 H3C CH3 + Cl CH3CHCHCH2 H3C CH3 CH3CHCHCH2Cl H3C CH3

kbc 3/ kbc 1 Tetraclorua cacbon 3,5 Nitrobenzen 16

kbc 3/ kbc 1 4,9

Tricloetylen Propionitrin Sunfua cacbon Benzen

3,6 4,0 33,0 14,6

Clobenzen Flobenzen Toluen Anizol

17,1 10,3 15,4 18,4

Tnh chn lc do nh hng ca dung mi thm trn c th gii thch c da vo s thay i trng thi chuyn khi gc c solvat ha. Khi c dung mi phn cc, s solvat cht ban u tng, gim tnh pht nhit ca giai on phn ct H, trng thi chuyn chuyn v pha hnh thnh sn phm trn trc ta (tin Hammond) tng mc ko dn lin kt C Do s khc nhau v H. phn ly lin kt C bc nht bc ba c nh hng ln n tc phn ng lm tng H tnh chn lc.[3] 3.4 Ha hc lp th Phn ng th gc ca H t chu nh hng khng gian ca nhm th, ngay vi H bc ba, phn ng cng xy ra vi tc ln. nh hng lp th ch c nhng trng hp ring, chng hn nh clo ha vo cc v tr khc nhau ca hydrocacbon: (CH3)2C 2 2 2 3 CH CH CH CH 1 2 3 4 5 kt = C2 2,9 C3 3,7 C4 5,3 C5 1

Khi clo ha H bc ba trong 2,4- imetylpentan hay 2,2,4- trimetylpentan, tc phn th gim do kh khn lp th v tc th cng gim khi dng tc nhn gc c th tch ln, thng th tch gc ln th th t th thay i: C bc 3 < C bc 1 < C bc 2 H H H Chng hn nh phn ng: R= R3+H + (CH3)2CHCH2CH3 kkt = C bc 1 H C bc 2 H C bc 3 H (CH3)3C 1,7 6,0 1,0 CH3 0,32 0,93 1,0

Ha hc lp th ca phn ng gc ph thuc vo cu trc cht ban u. i vi dy ankan, phn ng raxemic ha hon ton v to gc trung gian d nhch o: 17

X C H

R' R''

R' R''

C
R' R''

Tc d nghch o nhanh hn phn ng tip theo. Chng hn nh phn ng:

C2H2 Cl + C H 3C ClCH2 quang hoat

HCl

H3C C

C2H5 +Cl 2 C 2H 5

CH3 C Cl + Cl

CH2Cl

CH2Cl raxemic

Cng c vi trng hp bo ton cu hnh. l trng hp c hiu ng anchime trong gc to thnh do c nguyn t hay nhm nguyn t v tr c cp electron n:
H C 2H 5 C* CH3 CH 2Br Br Br C 2H 5 C CH 3 CH 2 Br Br2 C 2H 5 C* CH3 CH 2Br

Phn ng c xc tin khi c nhm k gy ra tnh chn lc v tr, nh phn ng trn cho hiu ng 90% sn phm th cacbon bn cnh cacbon c brom. y brom mt hot tnh do hiu ng cm ng m to nn gc t do cu nh l cht trung gian vng giai on sau l phn ct m vng.[3]

3.5 nh hng ca oxi Oxi c nh hng ln trong cc phn ng gc t do. Chng hn, clo ha metan c cha mt lng nh oxi, phn ng khng xy ra ngay m ch bt u sau khi chi ph ht oxi. Thi gian t lc u cho n khi phn ng bt u gi l chu k cm ng. Trong thi gian ny, gc t do sinh ra tham gia phn ng vi O2 theo phn ng: R + O2 R O O lm tt mch phn ng ca gc R.

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Oxi c kh nng tng tc ln vi gc t do xut pht t cu trc electron ca oxi, trong , oxi cn c hai electron c thn trn hai obitan *. Phn ng ca oxi lm km hm phn ng gc, nn gi oxi l cht km hm cc qu trnh gc t do.[2]

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KT BI
Ni tm li, c nhiu yu t nh hng n phn ng th theo c ch gc ca hydrocacbon no, lm tng, cn tr hoc to ra cc dn xut khc ngoi mun. Chng ta c th li dng nhng yu t tng hp cc dn xut hydrocacbon theo mong mun. Nhn chung cc phn ng hu c u ch n giai on c bn, trong nhng n v phn t tng tc vi nhau v lin kt vi nhau to sn phm mi. Tng tc ny c th xy ra gia ton b phn t hay mt phn t b phn tch ra chu s chuyn ha.

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Ti liu tham kho [1]. PGS.TS. Nguyn Hu nh, [Ha hc hu c 1], (2003), NXB Gio Dc, H Ni. [2]. PGS.TS. Thi Don Tnh, [C s ha hc hu c tp 1], (2006), NXB Khoa Hc v K Thut, H Ni. [3]. PGS.TS. Thi Don Tnh, [C ch v phn ng ha hc hu c tp 3], (2008), NXB Khoa Hc v K Thut, H Ni. [4]. ThS. T Minh Thnh, [Ha hc hu c tp 1], (1999), NXB i Hc Quc Gia TP.HCM, TP.HCM.

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