NH HNG CA HIU NG CU TRC N TNH AXIT, BAZ I.

Cc loi hiu ng STT HIU NG CM NG (I) CH3 CH2 CH3 ( = 0) CH3 CH2 CH2 Cl ( = 1,8D) HIU NG LIN HP (C) CH2 = CH2 ( = 0)

V d

CH2 = CH - CH = O

( - )

Bn cht

(p - ) S phn cc lan truyn dc theo trc lin S phn cc ca lin kt do 1 nguyn t hoc 1 nhm nguyn t trong h lin hp kt C 2 loi: + C; C C 2 loi ( y e : + I; ht e: I)

CH2 = CH - Cl

R
3 Phn loi

C
(R: gc ankyl)

X - C = C

+I

+C

(X: Cl, F, OH, NH2: c cp e t do)

X
- I (X: Hal, NO2,)

C = C - C = Z
-C
C=Z c th l C=O, NO2, COOH, COOR...

c im

Quy lut

Hiu ng I gim nhanh theo mch C CH3 CH2 CH2 COOH Ka = 1,5.10-5 CH3 CH2 CHCl COOH K a = 139.10-5 CH3 CHCl CH2 COOH K a = 8,9.10-5 CH2Cl CH2 CH2 COOH Ka = 3,0.10-5 Hiu ng I ca X tng theo m in F > Cl > Br F > OH > NH2 C CH > C6H5 > CH = CH2 Hiu ng + I ca R tng theo bc ca R C(CH3)3 > CH(CH3)2 > C2H5 > CH3

Hiu ng C t thay i khi mch C ko di.

Hiu ng C ca Z tng theo phn cc O N C NH C O C CH2 O Hiu ng +C ca X gim theo chiu tng ca kch thc ca nguyn t v gim theo chiu tng ca m in nu kch thc nguyn t nh nhau: F > Cl > Br > I

>

>

>

Ch : - Nhm c C thng i vi I. V d CH=O, NO2, CH=O, COOH, COOR, NO2, SO3H... - Nguyn t c cp e t do c hiu ng +C thng c I thi ty trng hp m hiu ng no mnh hn V d: X l Halogen

X l OH, NH2, OCH3 th + C > -I

II. nh hng ca cu trc n tnh axit, baz 1. Tnh axit. - Axit l cht cho proton. - c im: C nguyn t H linh ng (c lin kt A-H phn cc, A c A ln)

- Mi yu t lm tng s phn cc ca lin kt O H v lm tng bn ca anion sinh ra u lm tng tnh axit, tc l lm tng Ka hay lm gim pKa (pKa = lg Ka ) 1.1. Vi cc hp cht c cha chc phenol - Nhm c kh nng ht e (-I hoc -C): lm tng s phn cc ca lin kt O-H s lm tng tnh axit. - Nhm c kh nng y e (+ I hoc + C): lm gim s phn cc ca lin kt O-H s lm tng tnh axit. Ch : - Nhm v tr octo to c lin kt Hidro vi nhm OH c th lm gim tnh axit do lm H kh phn ly ra. - Nhm v tr meta khng c hiu ng C do khng phi h lin hp (lin kt n, i khng xen k).

OH

CH=O
Nu trng thi tnh khng kt lun c tnh axit th bt buc phi xt trng thi ng tc l xt bn ca anion sinh ra.

V d 1. Sp xp theo trnh t gim dn tnh axit ca cc cht sau. Gii thch.

OH O O OH O OH

; (C)

(B)

(D)

Gii. Tnh axit th t gim dn: (C) > (D) > (B). - Cht (C): nhm CH3CO- v tr para, gy ra hiu ng C v I lm tng tnh phn cc ca - OH.
O OH

-Cht (D): nhm CH3CO- v tr meta, gy ra hiu ng I, khng c C nn OH ca D phn cc km OH ca C.

-Cht (B): nhm CH3CO- v tr octo to lin kt H vi H trong nhm OH nn H kh phn ly ra H+ hn, tnh axit s gim.
O H O

V d 2. Cho pKa ca phenol l 9,98 v bng gi tr pKa ca cc cht sau y Trng hp Cht O m p 1 NO2 C6H4 OH 7,23 8,4 7,15 2 Cl C6H4 OH 8,48 9,02 9,38 3 CH3 C6H4 OH 10,28 10,08 10,14 Gii thch cc gi tr pKa. a. Trng hp 1. nhm NO2 c c C v I. - nhm NO2 v tr para, gy ra hiu ng C v I , phn cc ca OH ln nht tnh axit ln nht. - nhm NO2 v tr meta , ch c I tnh axit yu nht. - nhm NO2 v tr octo : xut hin lin kt Hidro ni phn t nn lm cho tnh axit b hn ng phn para nhng trng thi ng , aninon sinh ra li bn do NO2 c hiu ng C v I c bit l I rt mnh do gn hn. (Cng nhiu nhm ht e, in tch m cng c gii ta, anion cng bn). Nn tnh axit ca ng phn octo vn ln hn ng phn meta.

b.Trng hp 2. Halogen c I > +C - I gim dn theo mch C nn tnh axit gim dn theo th t: ng phn octo>meta>para. .Trng hp 3. CH3 c hiu ng +I ,v l nhm nh hng octo para trong phn ng th SE y e vo v tr octo v para mnh hn meta tnh axit ca ng phn meta l ln nht. CH3 . (Hoc chnh xc hn CH3 v tr o,p c hiu ng +I, +H cn v tr m ch c +I) 1.2. Vi cc hp cht c cha chc COOH - Nhm c kh nng ht e lm tng s phn cc ca lin kt O-H s lm tng tnh axit. - Nhm c kh nng y e lm gim s phn cc ca lin kt O-H s lm tng tnh axit. a. Vi dy axit bo no R-COOH Bc ca R cng ln, + I cng mnh, tnh axit cng gim HCOOH > CH3-COOH> CH3CH2-COOH>CH3CH2CH2-COOH> (CH3)2CH-COOH > (CH3)3C-COOH + I =O Gc bc 0 Gc bc 1 Gc bc 1 Gc bc 2 Gc bc 3 Nu c nhm th c I, tnh axit s tng STT Axit Pka 1 CH3-CH2-COOH 4,87 2 CH3-COOH 4,76 3 CH3O-CH2-COOH 3,53 4 Cl-CH2-COOH 2,87 5 F-CH2-COOH 2,57 +I1 > +I2 tnh axit ca 2>1. A ca F> O>Cl -I5 > -I4 > -I3 tnh axit ca 5>4>3 STT Axit Pka

1 2 3

Cl-CH2-COOH Cl2CH-COOH CCl3-COOH

2,87 1,25 0,66

STT Axit Pka 1 CF3-CH2-CH2-COOH 4,16 2 CF3-CH2-COOH 3,02 3 CF3-COOH 0,23 b. Vi dy axit bo khng no R-COOH Axit khng no thng c tnh axit mnh hn axit no (v A ca Csp>Csp2>Csp3), nht l axit , do v tr ny ch c I, khng +C (v tr va I v +C). STT Axit Pka 1 CH3-CH2-COOH 4,87 2 CH2=CH-COOH 4,26 3 1,84 C- COOH H-C Gia 2 ng phn cis v trans ca axit khng no, ng phn cis c tnh axit mnh hn (do hiu ng khng gian lm gim nh hng +C ca ni i.). V d. STT Axit Pka 1 Cis- CH3-CH=CH-COOH 4,38 2 Trans - CH3-CH=CH-COOH 4,68 c. Vi axit thm: STT Axit Pka 1 H-COOH 3,75 2 C6H5-COOH 4,18 3 CH3-COOH 4,76 1< 2 do H khng c hiu ng cn C6H5 c I <+C (do COOH l nhm phn hot ha). 2> 3 do trng thi ng th CH3-COOCH3 c +I lm mt in tch m tng ln, anion khng bn. C6H5 c I,-C lm mt in tch c gii ta , anion bn

Vi dn xut ca axit Benzoic X-C6H4-COOH, th y thuc vo bn cht X v v tr ca X m tnh axit c th tng hay gim. Quy lut: D X y e hay ht e nhng X v tr octo th lun lm tng tnh axit (ng phn octo lun c tnh axit ln hn axit Benzoic v ln hn cc ng phn cn li), do hiu ng octo ( tng hp ca nhiu yu t nh I, hiu ng khng gian, lin kt Hidro ni phn t.....). C6H5-COOH c Pka = 4,18 v bng sau y: STT X p m o 1 NO2 3,43 3,49 2,17 2 F 4,14 3,87 3,27 3 OH 4,54 4,08 2,98 4 CH3 4,37 4.27 3,91 2. Tnh baz - Baz l cht nhn proton H+. - c im: C nguyn t Z c cp e t do

Thng gp: - Nhm 1: Anion ca cc axit yu nh C2H5O-, OH-, C6H5COO-, CH3COO-... - Nhm 2: Amin, ancol, phenol. 2.1. Nhm 1. Anion ca cc axit yu c coi la baz lin hp ca axit HA HA H+ + AAxit Baz lin hp Axit cng yu th Baz lin hp c tnh baz cng mnh. Tnh axit: C2H5OH < H-OH < C6H5OH < CH3COOH Tnh baz: C2H5ONa> NaOH > C6H5ONa > CH3COONa 2.2. Nhm 2 Amin c tnh baz mnh hn ancol v phenol, nhng li yu hn cc ancolat v phenolat: CH3O() > HO() > C6H5O() > CH3NH2 > CH3OH > C6H5OH Xt ring trng hp amin - Tnh baz ca cc amin dy bo > NH3 > Amin thm

NH3 <

Amin bc 2 c tnh baz mnh hn amin bc 1 (v c 2 nhm gy hiu ng +I) v hn c amin bc 3 (v amin bc 3 c 3 gc R lm cation sinh ra c hirat ha khng bn do n ng khng gian). a thm nhm ht e vo gc R (-I,-C) s lm cho tnh baz gim i STT Cht Pkb 1 13,5

2 3

8,7 6,3

4 NH3 4,76 - Amin thm : Nhm th ht e gn vo nhn thm lm gim tnh baz v ngc li. Cho Pkb ca C6H5NH2 l 9,42 ; xt X-C6H4-NH2 STT X Pkb ca ng phn para Pkb ca ng phn meta 1 CH3 8,88 9,31 2 NO2 12,98 11,5 III. CC BI TP MINH HA Bi tp 1. Sp xp (c gii thch) theo trnh t tng dn tnh baz ca cc cht sau: -NH-CH3 , -CH2-NH2 , C6H5-CH2-NH2, p-O2N-C6H4-NH2.

Gii O2N- C6H4-NH2 < C6H5-CH2-NH2 < Nhm p-O2N-C6H4- Nhm -C6H4-CH2ht electron mnh do ht e yu theo c nhm -NO2 (-I -C) hiu ng -I

-CH2-NH2< Nhm -CH2-C6H11 y e, lm tng mt e trn

-NH-CH3 Nhm C6H11 v -CH3 y e, - Amin bc II

lm gim nhiu mt nhm NH2 e trn nhm NH2 Bi tp 2. Sp xp (c gii thch) theo trnh t tng dn tnh baz ca cc cht sau: CH3-CH(NH2)-COOH, CH2=CH-CH2-NH2, CH3-CH2-CH2-NH2, CH C-CH2-NH2 . Gii Trt t tng dn tnh baz : CH3-CH-COOH < CH C-CH2-NH2 < CH2=CH-CH2-NH2 < CH3-CH2-CH2-NH2 NH2 Tn ti dng -I1 > -I2 + I3 ion lng cc - I1 > - I2 do m in ca Csp > Csp2 Bi tp 3. So snh tnh axit ca cc cht trong cc dy sau (c gii thch): a. CH3COOH, CH2=CH-COOH; C6H5-OH, p-CH3-C6H4-OH , p-CH3-CO-C6H4-OH b. Axit: benzoic, phenyletanoic, 3-phenylpropanoic, xiclohexyletanoic, 1-metylxiclohexan-cacboxylic Gii a. Tnh axit tng dn theo th t: p-CH3-C6H4-OH < C6H5-OH < p-CH3-CO-C6H4-OH < CH3COOH < CH2=CH-CH2-COOH +I, -I,-C +I -I - Nhm OH ca phenol c tnh axit yu hn nhm OH ca nhm caboxylic.

H3C COOH
+ I1

+ I2

CH2COOH

CH2CH2COOH -I1

-I 2

CH2COOH

-I 3

COOH

<
b.

<
+ I2
Cho:

<
-I 1 < -I 2

<
< -I 3

Cc gc hirocacbon c hiu ng +I ln th Ka gim v -I ln th Ka tng Bi tp 4 .

Hy gii thch. Bi gii. Do s to lin kt hiro lm cho mt electron oxi lin kt i gim lm cho s ht electron tng.

Axit maleic(dng cis) c pKa(1) nh hn(tnh axit mnh hn) pKa(1) ca axit fumaric(dng trans).

<

+ I1

pK a(1) CH COOH COOH CH CH 3,02 1,85

pK a(2) 4,32 6,07

HOOC CH HOOC

H C O C O H...O C

H C O H

Do dng cis c s lin kt hiro ni phn t nn c s rng buc H nn dng cis c pKa(2) ln hn(tnh axit yu hn) pKa(2) ca dng trans.

O H C O C O
Bi tp 4 . Cho 4 axit:

C H...O

H C O

C C H C

H C O H

Tch H+kh h n

O Tch H+dh n

CH3CH2COOH (A) CH3COCOOH (B) CH3COCH2COOH (C) CH3CH(+NH3)COOH (D). Sp xp A, B, C, D theo trnh t tng dn tnh axit. Gii thch. Gii: Axit CTCT Trt t sp xp

O
A

CH3CH2 + I

C O H
O

(4)

CH3

C O -I

CH2

C O H

(2)

(3)

O
D

CH3 CH NH3 -I m nh

C O H

(1)