ti: phn ng th (S)

gio vin hng dn:Ng Th Thun sinh vin thc hin:

1) Nguyn Hng Hi 2) Trn Quc t 3) L nh Thng 4) L c Anh 5) Trnh Thnh Cng 6) Nguyn vn Tng 7) Nguyn Trng Hong

I) Khi nim chung v phn ng th trong ha hc hu c

1) Khi nim Phn ng th k hiu l ch S (Substitution),trong mt nguyn t hay mt nhm nguyn t trong phn t c thay th bng mt nguyn t hay nhm nguyn t khc.

Phn ng th l mt phn ng ph bin trong ha hc hu c.Phn ng c biu din tng qut nh sau:
A+B-C Trong : AB + C

A l tc nhn th (Hay nhm th)

B l trung tm b th C l nhm b th

2) Phn loi -Nu trung tm B giu in t th l phn ng th i in t S E , A l nhm ngho in t (A l cation.) n c phn thnh 2 loi nh +Th i in t n phn t S E 1 : +Th i in t lng phn t S E 2 -Nu trung tm B ngho in t th l phn ng th i nhn, SN v A l nhm giu in t ( l anion). N cn c phn ra thnh: +Th i nhn n phn t S N 1 +Th i nhn lng phn t S N 2

-nu tc nhn A l gc th y l phn ng th gc SR

II) C ch phn ng
1) c ch phn ng SN
a) c ch phn ng th SN 1 L phn ng xy ra theo c ch 2 giai on ion ha v kt hp cation: Giai on 1: ion ha, chm R-X R(+) + X(-) Giai on 2: kt hp cation, nhanh R(+) +Y(-) Y-R v R-Y ( bin th raxemic) Nh vy tc phn ng ch ph thuc vo [RX]. Phn ng bc 1. v=k[RX]. N lm quay mt phn cu hnh

V d:

CH 3 + NaOH

CH3 CH3 - C - OH CH 3 tert-butanol + NaCl

CH3 - C - Cl CH 3 tert-butyllorua

CH3 CH3 - C - Cl CH3

CH3 CH3 - C CH 3 + Cl

CH3 CH3 - C CH 3 + OH

CH3 CH3 - C - OH CH3

Nh ta bit, cacbocation hnh thnh c cu trc phng nn tc nhn nucleophin c th tn cng t pha trn hoc pha di mt phng cacbocation vi xc sut nh nhau nn nu cht u l mt cht quang hot th sn phm hnh thnh s l bin th raxemic:

Gii thch tnh lp th

Ngoi ra cn do hin tng chuyn v nn cn c thm nhng sn phm khc, nh: CH3CH2CH2CH2(*) => CH3CH2CH(*)CH3 (bn hn) nn s c thm nhng sn phm khc nh 2-X Butan

b) phn ng th SN2

V Y- v X- cng du nn Y- s i vo pha i din vi X, iu ny lm cho cu hnh ca RY s ngc vi RX:

Nhn xt: Nu y- khng d nhiu th Phn ng bc 2 Th t tham gia phn ng SN2 nh sau: metyl > dn xut bc 1 > dn xut bc 2 > dn xut bc 3

V d

c) Cc yu t nh hng n c ch phn ng +nh hng bi gc R R nh hng chnh n c ch th Nu gc R la ankyl bc thp SN 2 xy ra d dng Nu gc R la anlkyl , ankyl bc cao SN1 xy ra d dng Nu gc R la allyl, aryl metyl xy ra ng thi SN1 va SN2 Nu gc R la vinyl hay phenyl kh xy ra SN1 ln SN2

Cacbocation cng bn th phn ng xy ra theo c ch SN1 cng thun li, c th ta ch tng gc:

Gc ankyl: bc ca cacbon mang X cng cao th kh nng tham gia SN2 cng gim, trong khi kh nng tham gia SN1 cng tng Gc hidrocacbon c nh hng ti tc phn ng th nucleophin. i vi cc gc no, tc cc phn ng th nucleophin nh sau: SN2 : CH3- > CH3CH2- > (CH3)2CH- > (CH3)3CSN1 : CH3- < CH3CH2- < (CH3)2CH- < (CH3)3C-

nh hng ca nhm b th ( nhm i ra X- ) Kh nng phn ng ca cc dn xut RX trong cc phn ng SN1 cng nh SN2 khng nhng ph thuc vo gc hidrocacbon m mt phn cn c quyt nh bi bn cht ca nhm b thay th X.
+

Kh nng phn ng: i vi R-X th: I > Br > Cl >> F , nguyn nhn l do di lin kt C-I l ln nht v s phn cc ha I l ln nht. Cc nhm -OH phn ng km nht, do bnh thng khng tch ra ion -OH c, chnh v th ancol ch c este ha trong mi trng axit v ete chi c phn ct trong mi trng axit.

-tc phn ng SN2 tng theo nng l lc Nu ca Y-. Lc Nu tun theo quy tc sau: Anion c lc Nu cao hn phn t trung ha tng ng: RO- > ROH; OH- >H2O; NH2- >NH3 Lc Nu tng khi m in gim: I- >Br- > Cl- >FNH2- >RO- >HO- >R2 NH>NH3 >F- > H2O HS->HOC2 H5 S- >C2 H5 O-

+ nh hng ca dung mi
oDung mi c vai tr rt quan trng. Nu khng c tng tc vi dung mi th phn ng th hu nh khng xy ra.
oKhi chuyn t dung mi ny sang dung mi khc th tc phn ng s thay i, ng thi cn c th thay i c c ch phn ng.

2) C ch phn ng th electrophin Tc nhn phn ng l nhm thiu ht e, chng tn cng vo trung tm giu e. Nhm b thay th e tch ra khng mang theo cp e lin kt.
*c ch phn ng SE thng gp cc phn ng th vng thm, nn nn trong ti ny ch trnh by phn ng th electron vo nhn thm. (SEAr)

a) C ch chung Tt c cc phn ng SEAr u din ra theo mt con ng , v bt u bng s tn cng ca cc tc nhn electronphin vo h thng thm to thnh phc khng thm, sau to ra hp cht c mt nhm mi tn cng vo (to li h thng electron ca vng thm c cha nhm th E) C ch gm 2 giai on:

giai on 1:
H

Tn cng ca tc nhn

electronphin

Giai on 2:
H E
+

Ti to hp cht thm

Giai on 1 din ra chm, giai on 2 din ra nhanh chng, nn giai on 1 quyt nh tc phn ng. S ny mi ch l n gin ha qu trnh, thc cht cn nhiu qu trnh c th to phc trc khi to phc

Halogen ha
Br
Br2/FeBr3

C ch:

Br2

FeBr3
Br H

Br

+ [FeBr4]
Br

+
Brom benzen

HBr

Br

Br

H+

Benzen

phc

phc

Nitro ha
NO2
HNO3/H2SO4

C ch:
O

HNO3 + H2SO4

NO2 +
H NO NO 2 2H

2HSO4 + H2O
NO NO 2 2
HSO HSO 4 4
-

O O N N ++

+
Nitro benzen

H 2O

+ N + N O

Benzen

phc

phc

phc

phc

Sunfo ha
SO3H
H2SO4

C ch:
O: -

H2SO4

SO3 +
SO3 H

H3O + HSO4
SO3 SO3H H+

: :

+
Axit benzen sunfonic

H2O

+ :S O:

HSO4

Benzen

phc

Ankyl ha theo Friedel-Crafts

R
AlX3 khan

C ch:

Dng ankyl halogenua lm tc nhn ankyl ho di s c mt ca cht xc tc Liuyt:

R - X + AlX3
H + R ..... X..... AlX3 + R AlX4

+ ..... ..... R X AlX3

R

+
Benzen

R-X

(R : gc ankyl X : halogen)

H - X + AlX3

Alkyl benzen

Axyl ha theo Friedel-Crafts

O +
Benzen

C ch:

+ ..... AlX3 ..... R X Tc nhn axyl

+ H - halogenua X + AlX3 AlX4 dng l cc axyl ha +thng RCOX hoc cc anhydrit axit (RCO)2O:

R - C - X + AlX3 O
AlX3 khan

X
O H C R + AlX4 + H - X + AlX3 R C O

X-C-R
(R : gc ankyl X : halogen)

C O
Aryl alkyl xeton

R + HX
R + C O ..... AlX3 X

: :

: :

+ C O ..... AlX3

b) Cc yu t nh hng n c ch b.1. nh hng ca nhm th n s th SEAr: Mt nhm th R c sn nhn thm c nh hng n v tr ca cc nhm vo sau gi l nhm R nh hng. R
+ E xc t c E

Nguyn nhn: + Khi benzen cha b th, mt electron 6 nguyn t C trong vng l nh nhau vo ch thu c mt sn phm khi th ln u.

+ Khi th ln th hai, nhm th mi c th nh hng vo cc v tr ortho, meta v para so vi nhm nh hng, s thu c mt hn hp 3 sn phm ng phn c t l phn trm khc nhau.
Khi nhn thm c sn mt nhm th: Da trn c s tc dng nh hng ngi ta chia lm 2 loi nhm th: Nhm th loi I: Tc dng nh hng nhm th vo sau u tin vo v tr ortho v para so vi nhm th nh sn: gm cc nhm th hot ha nhn thm (O-, NR2, NH2, -OH, -OR, -NHCOCH3, -CH3, C(CH3), C6H5-) v mt s nhm th phn hot ha nhn thm (halogen, -CH Cl,)
I ortho para

Nhm th loi II: Tc dng nh hng nhm th vo sau u tin vo v tr meta so vi nhm th nh sn; ng thi cc nhm th ny th ng ha s th: gm cc nhm th phn hot ha nhn thm (-NO2, -NR3, CF3, -CN, -COOH, -COOR, -SO3H, SO2R, -CHO, -COR.) V d nh:
Lo i I CH3 ortho ortho para ortho Lo i I OCH3 ortho

II

meta

Lo i I I NO2

meta para

Khi nhn thm c sn nhiu nhm th: Trng hp nhn thm c sn nhiu nhm th th v tr nhm th vo sau c quyt nh bi nhm th c tc dng nh hng mnh hn. Trng hp nhm th nh sn cng loi: Da vo thc nghim lp c trt t nh hng cc nhm th nh sn cng loi theo dy sau: Nhm th loi I: O- > -NR2 > -NHR > NH2 > -OH > -OR > NHCOR > halogen (F > Cl > Br > I) > > - OCOR > - R > -ankenyl Nhm th loi II: -NO2 > -NR3 > -CN > -COOH > -COOR > SO H > -CHO> -COR

V d
Lo i I OCH3 ortho Cl Lo i I para ortho Lo i I OCH3 CH3 Lo i I para Lo i II NO2 Lo i II COOH meta

Trng hp nhm th nh sn khc loi: Nhm th loi I ng vai tr nh hng nhm th vo sau. V d:
Lo i I NHCOCH3 ortho para NO2 Lo i I I ortho para SO3H Lo i I I Lo i I OH Lo i I CH3 NO2 Lo i I I para

Lo i I CH3 ortho para NO2 Lo i I I

Lo i I CH3 ortho

Lo i I I COOH Cl Lo i I para

NO2 Lo i I I

Gii thch quy lut th SEAr

Quy lut th c xy dng trn c s thc nghim. Tuy nhin c th gii thch quy lut th da trn c s yu t in t v ng hc *Tu thuc vo bn cht nhm th m mt electron vng tng ln hoc gim i, do kh nng phn ng th SEAr s d dng hn hoc kh hn khi khng c nhm th

Phn loi nhm th nh vng: Nhm th hot ha nhn thm: gm cc nhm th th hin cc hiu ng dng (+C, +I, +H) y electron vo vng lm tng kh nng tham gia phn ng SE ca vng benzen thun li cho phn ng SEAr. V d: cc nhm th O-, -NR2, NH2, -OH, -OR > NHCOR

I ortho para

 Nhm th phn hot ha nhn thm: gm cc nhm th th hin cc hiu ng m (-C, -I) ht electron vo vng lm gim kh nng tham gia phn ng SE ca vng benzen kh khn cho phn ng SEAr. V d: cc nhm th NO2, COOR, -CN
II meta II II II II

b.2) nh hng ca cht xc tc Cc phn ng th SEAr u cn s c mt ca cc cht xc tc. Vai tr ca cht xc tc l lm tng qu trnh to tc nhn electrophin b3 )nh hng ca tc nhn electrophin Tc nhn electrophin nh hng n kh nng phn ng ch khng nh hng ti con ng phn ng. V n ch c mt con ng i ra sn phm.

3) C ch phn ng SR
Thng gp hydrocacbon no hoc nhnh no ca

hydrocacbon thm -Cc gc t do l tiu phn trung gian, khng bn, c thi gian sng ngn -Vi tc nhn l cc gc t do tn cng vo S phn ng theo c ch gc t do:

R -H + X -Y

RX + HY X - Y : Hal2 , SO2Cl2 , R3C- O- Cl , CCl3Br, CF3I,

Phn ng xy ra c chiu sng hoc c cht khi

mu

Phn ng xy ra c chiu sng hoc c cht khi mu c im: phn ng dy chuyn to ra sn phm trung gian l gc cacbo t do R, Bc quyt nh to thnh sn phm l bc pht trin mch, trong bc pht trin l giai on chm, n quyt nh tc phn ng

. phn ng C 3 bc chnh

V d: phn ng halogen ho Bc khi mu: Bc pht trin: Tt mch: XX h

. 2X
. R + HX (*)

. X + RH . R + . R . X . R + + + XX . R . X . X

. RX + X R-R

X2
R-X

3.2) cc yu t nh hng
a) nh hng ca halogen
Bn cht halogen c nh hng trc tip ti

phn ng. Ni chung, F2 phn ng mnh, I2 phn ng kh khn nn dng Cl2 v Br2. Kh nng phn ng nh sau: F2 > Cl2 > Br2 > I2

b) nh hng ca ankan:
Cc nguyn t H c kh nng th khc

nhau, kh nng th gim dn theo th t: Hbc 3 > Hbc 2 > Hbc 1

Ngoi ra cn ph thuc vo c halogen, nh

Brom c tnh chn lc cao hn so vi Clo v Brom hot ng yu hn Clo.

c) 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).

d) nh hng ca tnh 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 v d: 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

trong qu trnh lm khng trnh nhng thiu st, hy vng cc bn v c gio b sung bi c hon thin hn