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CHUONG X https://websrv1.ctu.edu.vn/coursewares/supham/donghoahoc/ch10.

htm

CHNG X

NH HNG CA HIU NG TH LN TC PHN NG

I. M U

II. PHNG TRNH HAMMETT

III. S M RNG PHNG TRNH HAMMETT

1. i vi hp cht thm nhiu ln th, nhiu vng

2. Hp cht d vng, cng c th m rng p dng cho (VII) v (VIII)

3. Hp cht bo

4. Phng trnh Hammett dng ci tin

IV. PHNG TRNH YUKAVA - TSUNO

V. PHNG TRNH TAFT

1. Hiu ng lp th v hiu ng trng trong phn ng ca hp cht bo

2. Hiu ng lp th v hiu ng trng ca hp cht th trong phn ng ca dn


xut benzen th octo

Bi tp chng X

CHNG X

NH HNG CA HIU NG TH LN TC PHN NG

I M U

S thay i cu to phn t (s phn b electron, cu hnh khng gian) gy ra do s a thm nhm


th vo, c nh hng r rt ln hot tnh ca hp cht, do ln tc phn ng. Nghin cu nh hng
ca s th ln tc phn ng c th rt ra kt lun v bn cht ca sn phm trung gian v trng thi
chuyn tip ca phn ng nghin cu.

Vn ny c ngha cho ta hiu bit v cu trc v kh nng phn ng ca hp cht hu c. S


m t nh lng l thuyt vn ny thuc nhim v ca ha lng t v nhit ng hc thng k. Tuy
nhin, vic nghin cu nh lng, mi lin h gia cu trc v hot tnh ca cht phn ng cng c th
tin hnh bng thc nghim.

Nhiu cng trnh thc nghim thit lp mi lin h gia logarit hng s tc phn ng ca hp
cht hu c trong phn ng (A) vi logarit hng s tc trong phn ng khc (B), thu c s ph

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thuc tuyn tnh sau:

S ph thuc tuyn tnh ca bin thin entanpi t do khng nhng i vi trng hp thay i cu
trc, m cn i vi s thay i mi trng phn ng. V d qui tc xc tc Bronsted trong xc tc axit -
baz v s ph thuc ca tc phn ng vo phn cc ca dung mi.

II. PHNG TRNH HAMMETT

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III. S M RNG PHNG TRNH HAMMETT

1 i vi hp cht thm nhiu ln th, nhiu vng TOP

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2 Hp cht d vng, cng c th m rng p dng cho (VII) v (VIII) TOP

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3 Hp cht bo TOP

S ph thuc Hammett lc u ch p dng i vi dn xut th ca benzen, trong hiu ng


electron ca cht th R c chuyn n trung tm phn ng Y qua nhm phnyl meta v para, vi gi
thit khng tn ti hiu ng lp th gia R v Y.

C th ngh rng ngoi hiu ng trn, cn tn ti hiu ng khc - l tng tc ht qua nhng
phn cu trc cng, n s lm trung gian trong s chuyn dch ca hiu ng electron.

4 Phng trnh Hammett dng ci tin TOP

IV. PHNG TRNH YUKAVA - TSUNO

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V. PHNG TRNH TAFT

Nh trnh by trn, theo Hammett i vi phn ng ca dn xut benzen th v tr meta v


para mi tn ti hiu ng trng (cm ng) ln trung tm phn ng, cn trong phn ng ca dn xut th
v tr octo, hiu ng lp th c vai tr nht nh. Do khng th s dng dng Hammett cho loi phn
ng ny. Bi v, khng quan st thy c s ph thuc tuyn tnh gia logarit hng s tc phn ng thy
phn kim, th v tr octo ca axit benzoic v logarit hng s in ly ca axit ny.

Ngi ta c gng xem xt hiu ng trng v hiu ng lp th trong phn ng ca hp cht bo


v dn xut th benzen v tr octe v xc nh cc tham s ring cho tng loi phn ng.

1 Hiu ng lp th v hiu ng trng trong phn ng ca hp cht bo TOP

Nh nghin cu thc nghim, Taft i n kt lun rng trong phn ng m hot tnh ca cht phn
ng ch ph thuc vo hiu ng cm ng ca cht th (khng ph thuc vo hiu ng cm ng lp th,
ng phn ha) th nh hng ca hiu ng th cm ng (hay hiu ng trng) c th m t phng trnh
Taft.

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2 Hiu ng lp th v hiu ng trng ca hp cht th trong phn ng ca dn xut


TOP
benzen th octo

Trong trng hp ch c hiu ng trng c ngha cn tng tc lp th v cc tng tc khc (v


d tng tc cu hydro) i vi phn ng dn xut th v tr octo ca benzen khng c vai tr cng c
th s dng s ph thuc nh phng trnh Hammett.

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Bi tp chng X

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