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Coche2 Chuong 2-3
Coche2 Chuong 2-3
Coche2 Chuong 2-3
Bui th su
Chng 2. Phn ng chuyn v phn t
Trong phn ng th, s xut v nhp ca cc nhm xy ra trn cng 1 nguyn t carbon theo
nguyn tc cu trc phn t thay i t nht. Nhng c nhng phn ng hu c s xut v
nhp xy ra khng trn cng mt nguyn t carbon v i khi c s thay i khung sn
carbon. Phn ng hu c km theo s thay i v tr nhm chc hay thay i khung carbon
gi l phn ng chuyn v phn t. Chuyn v ni phn t l s chuyn v m nhm dch
chuyn khng tch hn khi phn t v dch chuyn sang v tr khc trong cng phn t. Khi
trng thi trung gian c c cu vng. Chuyn v lin phn t l s chuyn v m nhm
dch chuyn tch khi phn t v dch chuyn sang v tr khc trong cng phn t hoc ti
phn t khc.Ta xt mt s phn ng chuyn v ni phn t trong h thng thiu in t v
h thng giu in t.
2.1. S chuyn v trong h thng thiu in t
H thng thiu in t l h thng cha nguyn t thiu in t, tc nguyn t ch c 6 in
t tng ha tr. Nguyn t c 6 in t c th l nguyn t trung ha hoc mang in tch
dng. Nguyn t thiu in t c th l carbon, nit, xy. Do thiu in t nn h khng
bn, to tin cho s chuyn v. Chuyn v trong h thiu in t cn gi l chuyn v thn
hch. Ta xt chuyn v ti 2 nguyn t k cn nhau, gi l s chuyn v 1,2, trong nguyn
t mang nhm dch chuyn l nguyn t i, nguyn t nhn nhm dch chuyn l nguyn t
n.
C A
Z
C A
Z
Cation carbonium
Carben
Nitren
Cation oxonium
C
R
C
C
R
C
C
R
N
C
R
O
C C
R
C C
R
C C
R
C N
R
C O
R
C N
R
C O
R
Trong h, A l nguyn t c 6 in t lp ha tr, do thiu in t. Nhm Z v tr s 2
di chuyn sang A cng i in t lin kt. A nhn in t t Z nn d 1 in t v mang
in tch m, ng thi c 8 in t tng ha tr. A c th l C, N, O tng ng vi cation
carbonium, carben, nitren, cation oxonium.
H thiu in t c th c to thnh do nhm L tch ra cng i in t lin kt, li
cation carbonium c nguyn t C thiu in t. Nhm Z tng tc vi C
bng i in t
lin kt, cho trng thi chuyn tip vng 3. Z tip tc dch chuyn sang nguyn t C mi,
48
cho trung gian l cation carbonium mi l h thiu in t. H nhn 1 cht thn hch N
cho sn phm.
C C
Z
L
C C
Z
C C C C
Z
C C
N
Z
Z
- L N
Qu trnh phn ng c trnh by d hiu nh trn. Thc th phn ln chuyn v 1,2 xy ra
trong 1 giai on. Trng thi chuyn tip c biu din bng vng 3 mang in tch dng.
Ngi ta cho rng nhm Z v L tham gia vo trng thi chuyn tip, v c th c nhm N
cng tham gia vo trng thi chuyn tip.
C C C C C C
Z
L
Z
L
Z
L
C C
Z
L
N
C C
Z
L N
C C
Z
N L
S xut nhm L v s dch chuyn nhm Z xy ra cng lc, hoc nhm N cng tham gia
giai on ny. Thc nghim cho thy nhm dch chuyn lu gi cu hnh, nhm xut v
nhm dch chuyn v tr i lch nhau. Nh vy, cu to trng thi chuyn tip ny c
khng nh.
Trng thi chuyn tip thnh lp khi nhm dch chuyn Z ly in t o to lin kt mi vi
C n trong khi lin kt o c vi C i cha t. Ngoi ra gia nguyn t C i v C n c
mt phn lin kt biu din bng on thng ri. Nh vy vng 3 ny c lp bng 2 in
t v c s cng hng vng. Theo quy tc Huckel vng 3 ny c tnh thm v c tnh bn.
Nhm Z tng tc bng i in t lin kt, nh mt baz, hay mt cht thn hch, vi tm
thiu in t nh mt tm acid, hay tm thn in t. Phn ng cho mt h thiu in t mi
l ion carbonium. Ion ny c th nhn mt cht thn hch N
hay tch 1 H
o
linh ng cho
alcen, cng nh c th cho phn ng chuyn v vi cc nhm ti 2 C
o
cho ra nhiu sn
phm khc nhau. Nhng thng ch c 1 phn ng chuyn v xy ra. D hiu rng nhm
dch chuyn l nhm c lc thn hch mnh hn. Khuynh hng di chuyn ca cc nhm
tng dn theo th t:
H < CH
3
< C
2
H
5
< i-C
3
H
7
< t-C
4
H
9
< C
6
H
5
Cc nhm phenil dch chuyn tng dn theo th t:
49
p-NO
2
-Ph < p-Cl-Ph < Ph < p-Ph-Ph < p-CH
3
-Ph < p-CH
3
O-Ph
Ta thy cc nhm alkil bc cng cao cng u tin, nhm phenil u tin hn nhm alkil, cc
nhm th y in t trn vng thm lm tng tnh u tin.
Trng hp nhm H dch chuyn: Vn o 1s ca H tng tc vi vn o 2p ca C mang
in tch dng, lin kt vi vn o sp3 ca C i cha t. Ti trng thi chuyn tip, lai
ha ca 2 carbon l trng thi gia sp3
v p.
H1s
C2p
Csp3
H1s
C2p
Csp3
Trng hp nhm alkil R dch chuyn: Vn o bin HOMO ca R tng tc vi vn o
LUMO ca C carbonium. Ta thy cu hnh ca R c bo ton.
C2p
Csp3
C2p
Csp3
B
C
A
B
C
A
B
C
A
Trng hp nhm aril Ar dch chuyn: aril l h in t t thm nn chuyn v ca aril ging
nh s th ni phn t qua giai on to trung gian cation ciclohexadienil.
2.1.1. S chuyn v n nguyn t carbon
1. Chuyn v pinacol
Nm 1859 Wittig nhn c pinacol, n nm 1860 ng pht hin pinacol trong dung dch
acid bin i thnh pinacolon.
H
3
C C
CH
3
OH
C
CH
3
OH
CH
3
H
3
C C
O
C
CH
3
CH
3
CH
3
H
2
SO
4
Pinacol Pinacolon
Sau nhiu phn ng ng tng t c nghin cu v phn ng ca Wittig tr thnh
phn ng u tin ca nhm phn ng mang tn chuyn v pinacol. Chuyn v pinacol l
phn ng ca 1,2-glicol trong mi trng acid b tch nc thnh hp cht carbonil.
Trong mi trng acid, nhm hidroxil b proton ha thnh nhm xut tt, s mt 1 phn t
nc lm C mang nhm xut tr thnh C thiu in t (carbonium). S dch chuyn nhm
alkil ti C k cn cng s tch 1 ion H
tc kch
thun li hn t hng exo.
1
2
3
4
5
6
7
X
exo
1
2
3
4
5
6
7
endo
X
1
2
3
4
5
6
7
1
2
3
4
5
6
7
1
2
3
4
5
7
6
1
2
3
4
5
6
7
Y
1 2
3
4
5
7
6
Y
Y
1 2
3
4
5
7
6
Y
3. Chuyn v Wolf
Chuyn v Wolf l chuyn v ca carben sinh ra t diazoceton di tc dng nhit hoc nh
sng t ngoi hoc xc tc bc. Carben l hp cht c carbon ha tr 2, c 6 in t tng ha
tri. Do thiu in t nn carben c khuynh hng cho phn ng chuyn v.
O
C C N N
R
CH
2
R'
O
C C N N
R
CH
2
R'
O C C N N
R
CH
2
R'
Ag
2
O
_ N
2
Ag
2
O
_ N
2
O
C C
R
CH
2
R'
O
C CH
R
CH R'
O
C C
H
R
CH R'
O C C CH
2
R'
R
O C C CH
2
R'
R
ceten
ceton khong no
~ H
~ R
carben
Carbocation thng c lm bn bng tng tc vi i in t khng phn chia ca xy
bn cnh (chuyn v pinacol) hoc nhn tc kch cht thn hch t bn ngoi (chuyn v
Wagner Meerwein), trong trng hp ny c tng tc ca i in t t do sinh ra do
dch chuyn ca R, to thnh ceten, hoc dch chuyn H, to thnh ceton khng no. Ceten
cng nhanh nc thnh acid, alcol thnh ester, amin thnh amid.
R CH C O
RCH
2
COOOH
RCH
2
COOR'
RCH
2
CONHR'
H
2
O
R'OH
R'NH
2
T l sn phm ceten v ceton ph thuc vo nhit phn ng: nhit thp ceton khng
no nhiu hn, nhit cao (>50
O
C) cho nhiu sn phm l chuyn ha cht ca acid.
Phn ng c ng dng ko di mch acid thm 1 C. y l phn ng Arndt Eistert.
R C
OH
O
SOCl
2
R C
Cl
O
CH
2
N
2
R C
CH
2
O
N
2
1. Ag
2
O
2. H
2
O
R CH
2
C
O
OH
54
M rng vng ceton.
O
+ CH
2
O
CH
2
N
2
O
N
2
+
O
- N
2
Lm hp vng.
O
N
2
H
EtOH
COOEt
Bi tp:
1. Chuyn v ni phn t trong h thiu in t thng xy ra trong mi trng acid. Phn
ng c th xy ra trong mi trng baz khng, ti sao?
2. Trong phn ng chuyn v trong h thiu in t, cu hnh nhm dch chuyn c bo
ton. iu ny ni ln c im g ca c ch phn ng?
3. Trong chuyn v pinacol, nhm xut v nhm dch chuyn lun v tr i lch nhau. Mt
khc cu hnh carbon mang nhm xut lun b ngch o. iu ny ni ln c im g ca
c ch phn ng?
4. Gii thch c im ca phn ng chuyn v pinacol:
- OH ti C mang nhm phenil d tch ra hn OH ti C mang nhm alkil.
- Nhm phenil d dch chuyn hn nhm alkil.
- Nu 2 yu t trn tc ng khng cng chiu th phn ng xy ra theo chiu no, cho v d.
5. Trong chuyn v pinacol, 1,2-glicol lun c cu trng m ti 2 nhm OH v tr bn
lch do c lin kt hidro ni phn t. Vit c ch cc phn ng sau, lu c im ny ca
phn ng.
treo
eritro
H
CH
3
CH
2
COCH
3
+ CH CHO
H
3
C
H
3
C
CH
3
CH
2
COCH
3
CH
3
CH CHCH
3
OH OH
6. Trong chuyn v Wagner Meerwein ca 3|-fridelanol thnh 13(18)-oleanen ngi ta
cho rng c 7 dch chuyn u xy ra cng lc. iu ny c chng minh bng s kin g?
7. Vit c ch phn ng.
55
OH
OH
CH
3
CH
3
CH
3
C CH
3
O
O
CH
3
CH
3
+
H
OH
CH
3
OH
CH
3
H
CH
3
C CH
3
O
OH
OH
CH
3
Ph
H
Ph
C CH
3
O
OH
CH
3
OH
Ph
H
Ph
C CH
3
O
56
Bui th by
2.1.2. S chuyn v n nguyn t nit
Cc nhm alkil v aril c khuynh hng chuyn v n nguyn t nit thiu in t. Phn
ng ngang qua trng thi chuyn tip vng 3.
R C
O
N X O
C N
R
X O C N R + X
hoc
C
R
N X
C N
R
X C N R
+ X
Trng thi chuyn tip vng 3 thun li nu nhm di chuyn l aril v c cc nhm th y
in t. Cc d kin ph hp c ch ny l: phn ng bc 1; cu hnh R c lu gi,
nghin cu ng v nh du cho thy phn ng xy ra ni phn t; nhm R khng c s
thay i. Theo c ch ny, s tch X
v s dch chuyn R xy ra
cng lc. Khi kho st s chuyn v ca amid c C
o
bt i xng, ngi ta thy cu hnh ca
57
C
o
khng tay i. Nh vy nhm dch chuyn i ngang qua vng 3 v to lin kt mi ngay
ti lin kt c b t.
C C H
Me
Et
O
NH
2
C H
Me
Et
N
O
C N H
Me
Et
C O
Nu phn ng thc hin trong alcol th nhn c sn phm l uretan.
C N O R
R'OH
C HN
O
OR'
R
2. Chuyn v Lossen
Chuyn v Lossen l phn ng xy ra khi un acid hidroxamic O-acil ha vi baz, nhn
c sn phm isocianat. Trong mi trng nc, isocianat b thy phn thnh amin bc 1,
t hn 1 carbon so vi acid ban u.
R
1
C
O
NH OCOR
2
HO
R
1
N C O
H
2
O
R
1
NH
2
+ CO
2
Phn ng theo c ch tng t chuyn v Hofmann. Hidro ti nguyn t nit ca acid
hidroxamic O-acil ha c dng tch ra di dng proton bng baz, cho trung gian anion
y in t, lm nhm carboxil tch ra cng i in t lin kt. Lc ny nit cn 6 in t
tng ha tr nn thiu in t, lm nhm alkil dch chuyn sang nit, cho nitren. Tng t
nh chuyn v Hofmann, nitren khng bn nn thc t khng to ra m cng lc xy ra
chuyn v nhm alkil cng tng tc ca i in t t do trn N, cho sn phm isocianat,
thy phn thnh amin.
R
1
C
N
O
O
R
2
O H
OH
R
1
C
N
O
O
R
2
O
R
1
N C O
H
2
O
-R
2
COO
R
1
NH
2
+ CO
2
Phn ng khng c s dng rng ri trong tng hp hu c v acid hidroxamic khng c
sn.
3. Chuyn v Curtius
Chuyn v Curtius xy ra khi phn hy bng nhit hoc bng quang cc azid acid, to thnh
isocianat.
RCON
3
R N C O + N
2
(hv)
Phn ng xy ra theo c ch tng t phn ng Hofmann. Azid acid b nhit phn thnh
nitren, l h thiu in t ti N. Nhm alkil dch chuyn n N cng i in t lin kt cho
sn phm isocianat.
R' C
O
N N N
- N
2
R C
O
N
~ R
R N C O
- H
2
O
RNH
2
+ CO
2
58
Trong iu kin khan nc v khng c alcol, isocianat nhn c vi hiu sut cao. Cng
nh chuyn v Hofmann, nitren thc t khng tn ti, m s nhit phn tch phn t kh nit
xy ra cng lc vi s dch chuyn nhm alkil.
R C N
O
N N C N R
O
+ N
2
Tuy nhin phn hy quang ha azid acid, nitren to thnh trong qu trnh phn ng nh mt
cht trung gian.
R' C
O
N N N R C
O
N
+ N
2
Khi nhit phn alkilazid, sn phm nhn c l imin. S chuyn v xy ra tng t, nhng
c khc bit l c to thnh trung gian alkilnitren. Trong trung gian ny c th c chuyn v
ca aril, alkil hoc hidro.
R
2
C NR
+ N
2
R
3
C
N N N
Cicloazid v arilazid nhit phn cho chuyn v cng s m rng vng.
N
3
R
N
R
+
NR
N
3
N
NHPh
(Lu : y khng phi l chuyn v Cutius v cht u khng phi l azid acid, do trung
gian isocianat khng to thnh. Phn ng ny c chuyn v tng t chuyn v Cutius).
Azid acid c iu ch t azid Na v clorur acid hoc hidrazid acid v acid nitr .
+ NaN
3
R C
O
N
3
R C
O
Cl
+
NaCl
R C
O
OR'
+ H
2
N NH
2
- R'OH
R C
O
NH NH
2
HONO
R C
O
N
3
+
H
2
O
hidrazid acid
4. Chuyn v Schmidt
Chuyn v Schmidt l phn ng xy ra khi cng acid hidrazoic vo hp cht carbonil nh
aldehid, ceton, acid carboxilic, trong s c mt ca acid mnh. Cng ceton cho amid hoc
tetrazol ty thuc mi trng s dng l nc hoc khan nc.
59
C O
R'
R'
+ H N N N R'
R'
N N N
H
OH
- H
2
O
C N
R'
R' N N
- N
2
C N
R'
R'
~R
R N C R'
H
2
O
R N C R'
OH
R' C NHR
O
HN
3
R' C
N
N
R'
N N
H
N
N
N
N
R'
R
tetrazol
- H
S tch nhm N
2
v s dch chuyn R xy ra cng lc. Nhm dch chuyn l nhm v tr
trans vi nhm ra i. Khi tch loi 1 phn t nc, nhm ln hn s v tr trans vi nhm
diazonium. Do trong ceton khng i xng, th t di chuyn cc nhm nh sau:
t-Bu > Ph ~ i-Pr > Et > Me
Nh vy vi ceton, phn ng trong dung dch nc ging nh thm nguyn t N vo gia
CO v nhm alkil. Acid carboxilic trong mi trng acid mnh hoc acid Lewis chuyn v
thnh amin vi 1 nguyn t carbon t hn.
R C
O
OH R C
OH
OH R C
O
OH
2
H
- H
2
O
R C
O
HN
3
- H
R C N
O
N N
- N
2
R C
O
N C N O R
H
3
O
RNH
2
+ CO
2
5. Chuyn v Beckmann
Chuyn v Beckmann l phn ng chuyn v ca oxim to thnh t aldehid hoc ceton, di
tc dng ca acid mnh hoc c mt PCl
5
, cho sn phm l amid th.
C O
R
R'
H
2
N-NH
2
C N
R
R' OH
H
- H
2
O
C N
R
R'
~R
R' C N R
H
2
O
- H
R C
O
NHR
Phn ng tng t chuyn v Schmidt, s tch OH di dng phn t nc xy ra cng lc
vi s dch chuyn R, trong nhm R v tr trans vi OH s dch chuyn. Khng c
cation nitrenium t do. Khuynh hng cc nhm dch chuyn ging nh trong phn ng
Schmidt.
2.1.3. S chuyn v n nguyn t xi
Khi xi c nhm xut ra i cng i in t lin kt, ta c h cha nguyn t xi thiu in
t. S chuyn v n nguyn t xi lm xi tr v trng thi bnh thng.
C O
R
X
C O
R
+ X
60
Nhm xut X thng l HO
, RCOO
.
2.2.1. Chuyn v Stevens
Chuyn v Stevens l chuyn v ca mui amonium bc 4 hay mui sulfonium di tc dng
ca baz mnh thnh amin bc 3 hay tioeter (mercaptan).
A CH
2
N
R
1
R
3
R
2
NaNH
2
A CH N
R
1
R
2
R
3
A l nhm rt in t (RCO
, ROOC
...). A rt in t, cng vi N
rt in t lm H ca
nhm metilen linh ng, di tc dng ca baz mnh b tch ra di dng proton, li i
in t lin kt trn C, to ilur, l h giu in t. S dch chuyn R
3
lm trit tiu in tch,
cho c cu bn. Nhm di chuyn thng l nhm allil, benzil.
A CH
2
N
R
1
R
3
R
2
NaNH
2
A CH N
R
1
R
2
R
3
ilur
A CH N
R
1
R
2
R
3
~R
3
Th d:
(CH
3
)
2
NCH
2
COPh
CH
2
Ph
OH
(CH
3
)
2
N
PhCH
2
CHCOPh (CH
3
)
2
NCHCH
2
OPh
CH
2
Ph
PhCOCH
2
SCH
3
CH
2
Ph
OH
PhCOCHSCH
3
CH
2
Ph
PhCOCHSCH
3
CH
2
Ph
2.2.2. Chuyn v Wittig
Chuyn v Wittig l chuyn v ca eter di tc dng ca baz rt mnh l alkil hay arillitium,
thnh alcol. H trong eter c tnh acid yu hn trong mui amonium hay sulfonium nn baz
dng mnh hn.
R
1
CH
2
O R
2
R
3
Li
R
1
CH OLi
R
2
+ R
3
H
64
Di tc dng ca baz rt mnh, eter b tch proton thnh carbanion. Nhm metil tng tc
vi i in t p trn carbanion, chuyn v thnh alcol.
CH
3
O CH
2
Ph
PhLi
- PhH
CH
3
O CHPh Li O CHPh
CH
3
Li OH CHPh
CH
3
H
3
O
2.2.3. C ch chuyn v Stevens v Wittig
Chuyn v Stevens v Wittig c im chung l tch proton trong mi trng baz to ra
carbanion, l h giu in t. Nhm dch chuyn tng tc bng vn o LUMO vi vn
o HOMO ca carbanion. n gin, ta xem R tch ra nh R
v nm trong s tng tc
vi 2 tm mang in tch m l C v A (A l N, S hoc O). Vn o trng ca R
c th l
sp
2
hoc sp
3
, tng tc c th theo trc vung gc hay song song (theo Mebins). Trong
trng hp u cu hnh ca nhm di chuyn b nghch o, trong trng hp sau cu hnh
c bo ton.
C A
R
C A
C
LUMO
HOMO
hay
Nhm s thy r l c 2 trng hp u khng th thc hin c do tr ngi lp th qu
ln. Do c th ngh phn ng phi xy ra trong 2 giai on: R
c tch ra v gn vo
C
. Trong trng hp phi nhn c sn phm tiu trin. Thc t cho thy sn phm
nhn c ch yu c lu gi cu hnh.
Xut hin mu thun: phn tch tng tc vn o cho thy trng thi chuyn tip khng c
cu to vng 3, nhng thc nghim ng h trng thi chuyn tip vng 3. T gi thit
rng t dng ilur tch ra 1 trung gian c hot tnh rt mnh, mnh n ni phn ng rt
Cht Nhm dch chuyn % SP lu gi cu hnh
Chuyn v Stevens
PhCOC
H
_
N Me
2
CH(Me)Ph
CH(Me)Ph 97
CH
2
=CHC
H
_
N Me
2
CH(Me)Ph
CH(Me)Ph 90
Chuyn v Wittig
PhC
H-OC(Me)(Et)Ph
C(Me)(Et)Ph 80 90
PhC
H-OCH(Me)Ph
CH(Me)Et 62
CH
2
=CHC
H-OCH(Me)Et
CH(Me)Et 74
65
nhanh v cu hnh cha kp thay i. Trung gian c hot tnh mnh nht l gc t do. Thc
t cho thy trong cc phn ng chuyn v trn c s t ni ng li.
(CH
3
)
2
NCH
2
COPh
CH
2
Ph
OH
(CH
3
)
2
N
PhCH
2
CHCOPh (CH
3
)
2
N
PhCH
2
CHCOPh (CH
3
)
2
N
PhCH
2
CHCOPh
(CH
3
)
2
NCHCH
2
OPh
CH
2
Ph
C ch phn ng qua giai on to cp gc t do trn N v nhm benzil. C
cho N 1 in t
t do v tr thnh gc t do. Gc t do benzil tng tc nhanh vi gc t do mi to thnh
cho sn phm chuyn v. Gc t do sinh ra trong cc phn ng ny c chng minh bng
ph cng hng t ht nhn.
Lin kt n k tm anion d dng t ni ng li. Cc phn ng chuyn v ny xy ra
nhit thp, chuyn v Wittig thc hin -60
O
C. Bnh thng c th ngh rng cc tng
tc in t xy ra nh sau.
ArCH O
R
ArCH O
R
ArCH O
R
Nhng thc t phn ng thng khng xy ra nh vy. y c dch chuyn 1 in t. Nu
thay cc mi tn bng mi tn 1 cnh biu din tng tc ca 1 in t, ta c bc tranh ca
phn ng. Gc t do R v ArCH c to thnh.
ArCH O R
ArCH O R
Gc R dch chuyn n gc ArCH t c ly gn trong thi gian ngn, gc R cha kp sp xp
li. Cu hnh c bo ton.
2.2.4 Chuyn v Favorsky
Trong khi nghin cu o,o-diclorceton, Favorski d nh iu ch o-diceton bng phn ng
thy phn o,o-diclorceton trong dung dch kim. Nhng thay v nhn c diceton, ng
nhn c acid metacrilic t cht u l metil-o,o-dicloretilceton.
Sau nhm ca Favorski p dng phn ng cho nhiu hp cht o-haloceton khc v m ra
phn ng chuyn v mang tn ng. Chuyn v c cng b ln u vo nm 1895. Chuyn
v Favorski l phn ng ca baz thn hch vi o-haloceton qua trung gian l ciclopropanon,
ty thuc baz thn hch cho sn phm l chuyn ha cht ca acid carboxilic. Vi baz l
hidroxid kim loi kim, alcoxid, amin, sn phm l mui ca acid carboxilic, ester, amid.
66
R C
O
Cl
Cl
C
O
C
R
O C
O
C
R
C
O
C
R
R'O
R'NH
+ CO
2
R'O
HO
R'NH
2
H
2
O
2
C ch phn ng l ti tranh lun thi gian di. Ban u ngi ta cho rng phn ng bt
u bng s cng thn hch ca baz thn hch vo nhm carbonil.
R C
O
C
X
+ OR'
C
O
C
X
R
C
O
C
R
R'O R'O
Nu phn ng xy ra theo c ch ny th t o-clorbenzilmetilceton ch bin kim phi nhn
c acid o-phenilpropionic. Thc t phn ng cho sn phm l acid |-phenilpropionic.
Nh vy phn ng khng xy ra theo c ch ny.
PhCHCOCH
3
Cl
HO PhCH(CH
3
)COOH
(khong xay ra)
PhCH
2
CH
2
COOH
+
Favorski xut c ch ngang qua trung gian ciclopropanon, nhng khi iu kin thc
nghim v l thuyt cha cho php chng minh. n nm 1951 Loftfield dng phng php
nguyn t C nh du chng minh c ch phn ng i qua trung gian vng 3.
O
Cl
i-C
5
H
11
ONa
COOC
5
H
11
COOC
5
H
11
*
*
*
+
O
Cl
COOH
COOH
*
*
*
+
HO
*
*
*
Phn ng bt u bng s tch proton v tr o pha bn kia carbon mang clor, tip theo l th
thn hch ni phn t cng s ra i nhm xut clor, to thnh vng ciclopropanon. Baz thn
hch cng vo nhm carbonil, O
, H
2
OBr
, RSO
2
, HSO
3
- Cht thn in t va gm cc phc halogenur alkil v acil vi acid Lewis (RCl.AlCl
3
,
RBr.GaBr
3
, RCOCl.AlCl
3
...), phc ca alcol vi acid Lewis v Bronsted mnh (ROH.BF
3
,
ROH.H
3
PO
4
, ROH.HF...).
- Cht thn in t yu gm cation diazonium ArN
2
, iminium CH
2
=N
H
2
, nitrosonium
NO
, dioxid carbon CO
2
.
71
Cht thn in t mnh: tc dng c vi cc dn xut benzen c nhm th rt v y in
t. Cht thn in t va: tc dng c vi benzen v dn xut cha nhm th cho in
t (-NO
2
, -SO
3
H, -COR, -CN...) v halogen. Cht thn in t yu: ch tc dng c vi
dn xut benzen cha nhm th y in t mnh (-OH, OR, -NH
2
, -NR
2
, -O
...). Bng di
y cho thy s to thnh mt s cht thn hch mnh, va v yu trch t ti liu: Carey F.
A., Sundberg R. J. (2007), Advanced Organic Chemistry, Part A: Structure and
Mechanisms, 5th Edition, Prenum Press, New York, trang 743.
3.2.2. C ch phn ng
S th thn in t trn h thm xy ra theo kiu cng tch. Cht thn in t ban u
tng tc vi cc vn o t ca h thm, to thnh phc t. Tip tc phn ng, cht thn
in t tin gn li 1 trong cc C v xc lp lin kt o vi C ny. Carbon chuyn t lai ha
sp
2
sang sp
3
, h thm b ph v, do nng lng h rt cao, h khng bn. a h v
trng thi bn, 1 proton c tch ra ngang qua phc t v cho sn phm th.
72
+ X
X
X
H
X
H
X
+ H
phuc
Khi cho lung kh DCl i qua dung dch benzen trong n-hexan -78
o
C, ngi ta nhn c
phc phn t vi t l l 1:1. Phc ny khng mu, khng dn in. Nh vy trong dung
dch khng c ion v mnh phn t mang in tch. Bng phn tch nhiu x tia X cc tinh
th phc benzen v cc hidrocarbon thm khc vi cc cht thn in t khc nhau, xc
lp cu to cho nhn qua vn o t ca cc phc ny. y l phc t. Cc aren l baz t, c
th to phc t kiu cho nhn vi cc acid Lewis cng nh DCl khng phn ly. Khi nhit
tng, phc t nhanh chng b phn hy.
Khi cho AlCl
3
vo dung dch DCl trong benzen hay benzen th, dung dch dn in v c
mu. S dn in chng t trong dung dch c ion hoc phn t mang in tch. Phn tch
ph cng hng proton v
13
C cho thy c to thnh phc ion.
C
6
H
6
+ DCl + AlCl
3
C
6
H
6
D AlCl
4
y l phc o. Phc o to thnh nhit thp, khi tng nhit phc o b phn hy. Phc
o c th phn hy thnh sn phm hay cht u, ty thuc s tch cht thn in t hay tch
proton, mnh no tch d hn. Thng thng tch proton d hn nhiu, v trong nhiu
trng hp phc o to thnh khng thun nghch. Vi cc aren v cht thn in t khc
nhau bn phc o khc nhau.
Me
Me
Me
+ C
2
H
5
F
BF
3
- 80
O
C
Me
Me
Me
H
C
2
H
5
BF
4
0
O
C
Me
Me
Me
C
2
H
5
90%
Me
Me
Me
+ C
2
H
5
COF
AgBF
4
CH
3
NO
2
- 60
O
C
Me
Me
Me
H
COC
2
H
5
BF
4 Me
Cl
Me
COC
2
H
5
Giai on chm ca nhiu phn ng th thn in t h thm l giai on to phc o. Gin
nng lng tng qut cho thy c 2 phc t trc v sau phc o.
+ E
H E
Z
Z
Z
E
H
Z
TC1
TC2
TC3
TC4
Z
E
E
+ H
73
Thc t ng hc phn ng th thn in t trn h thm ty thuc trng hp c th. Cht
thn in t mnh c mc nng lng cao, trng thi chuyn tip mc gn cht u. Khi
ta c trng thi chuyn tip sm. Trng hp ny c trng cho cc phn ng ta nhit.
in tch dng phn b trong vng t, do t c s khc bit v tr phn ng trn vng
benzen c sn nhm th.Vi cht thn in t yu, trng thi chuyn tip mc gn phc o,
ta c trng thi chuyn tip tr. Lin kt o to hon chnh, in tch dng phn b trong
vng v tp trung nhiu hn v tr orto v para i vi nhm th c sn trong vng
benzen. Phn ng thu nhit. Hnh biu din di y trch t ti liu: Carey F. A., Sundberg
R. J. (2007), Advanced Organic Chemistry, Part A: Structure and Mechanisms, 5th Edition,
Prenum Press, New York, trang 789.
Kho st hiu ng ng v gip lm sng t c ch phn ng. Vi tng phn ng c th,
hiu ng ng v khc nhau. Hiu ng ng v k
H
/k
D
hoc k
H
/k
T
ca mt s phn ng c
trch t ti liu: Carey F. A., Sundberg R. J. (2007), Advanced Organic Chemistry, Part A:
Structure and Mechanisms, 5th Edition, Prenum Press, New York, trang 790. Phn ng c
hiu ng ng v k
H
/k
D
hoc k
H
/k
T
khi giai on tch proton khi phc o cho sn phm l
giai on chm.
74
Hiu ng ng v khng r rng trong phn ng nitro ha, halogen ha, trong khi phn ng
acil ha, sulfon ha, nitroso ha v ghp cp diazo c giai on chm l deproton ha. Hiu
ng ng v cho thy vi cc cht thn in t yu nh trong phn ng nitroso ha v ghp
cp diazo, vn tc phn ng ph thuc hon ton vo vn tc tch proton. Nhng trong 2
trng hp ca phn ng ghp cp diazo, nhm sulfon v tr 8 cho hiu ng ng v, trong
khi v tr 4 khng c hiu ng ng v. Chung quy c 4 loi c ch cho phn ng th thn
in t h thm, biu in bng gin nng lng trch t ti liu: Carey F. A., Sundberg
R. J. (2007), Advanced Organic Chemistry, Part A: Structure and Mechanisms, 5th Edition,
Prenum Press, New York, trang 791.
Trng hp (a), giai on xc nh vn tc phn ng l giai on hot ha cht thn in t.
c trng cho loi c ch ny l vn tc phn ng khng ph thuc vo nng hp cht
thm. Trong trng hp (b), giai on chm l giai on to thnh phc o, trng thi chuyn
75
tip sm, vn tc phn ng ph thuc vo nng c cht thn in t v hp cht thm.
Trng hp (c) cng c giai on chm l to phc o, nhng trng thi chuyn tr. Trong
trng hp (d) giai on chm l giai on tch proton v thm ha thnh sn phm, c
trng l hiu ng ng v ti v tr th.
Trong trnh by c ch phn ng th thn in t trn h thm ta nn lu s to thnh v
c cu cht thn in t v c cu phc o.
3.2.3. Phn ng th thn in t trn benzen c 1 nhm th
Ti trng thi chuyn tip trc phc o, gia benzen th v cht thn in t c phn b
in tch dng. Nu trng thi chuyn tip sm, in tch dng ch yu phn b trn cht
thn in t, nu trng thi chuyn tip tr, in tch dng ch yu trn vng thm. Nu
trn vng benzen c 1 nhm th, c th c 4 trng hp phc o.
H
E
H
E
E H
X E
X X
X
orto meta para ipso
T cc phc ca v tr tc kch orto, meta v para, 1 proton c tch ra, nhng t phc ca
v tr ipso nhm tch ra l X di dng X
, , NR
3
, P
R
3
, S
R
2
, S
Ar, CH
2
N
R
3
, POR
2
,
B(OH)
2
Mt s nhm th khng nh hng r rng nh CF
3
, CHCl
2
, CH
2
NO
2
, CH
2
CH
2
NO
2
,
CH
2
CH
2
N
R
3
, CH
2
P
R
3
, CH
2
S
R
2
...
Nhm th loi 1, tr halogen, u tng hot vng benzen. Nhm tng hot mnh nht l O
trong ion phenolat. Nhm tng hot mnh l R
2
N, NHR, NH
2
, OH, OR, OAC,v SR. Nhm
tng hot yu l cc nhm alkil. cc halogen u lm gim hot h thm. Nhm th loi 2
u gim hot vng benzen, vn tc phn ng chm hn benzen, v thng ch cho th 1
ln.
Tnh nh hng cc nhm th c gii thch bng tnh bn ion arenonium (phc o) trung
gian. Nhm th c th lm bn hoc lm km bn cation ny, do s chn lc v tr phi
ph hp phc bn hn c. Ta xt cc phc o trung gian c th c trong phn ng th thn
in t ca anisol, clorobenzen v nitrobenzen.
76
OCH
3
E
H
OCH
3
E
H
OCH
3
E
H
OCH
3
E
H
OCH
3
H E
OCH
3
H E
OCH
3
H E
OCH
3
H E
OCH
3
E
H
OCH
3
E
H
OCH
3
E
H
Cc phc o ca s th para v orto ca anisol c bn ha do c tng tc y in t ca
nhm MeO v trong 1 cng thc gii hn c tng tc trc tip ca C
v nhm OMe, do
s th vo v tr para v orto trn anisol xy ra nhanh hn th trn benzen. Phc o ca
th meta khng c s bn ha do trong cc cng thc gii hn khng c tng tc trc
tip ca C
BF
4
. Ion nitronium to
thnh trong hn hp acid nitric v acid sulfuric hoc khng c acid sulfuric.
2H
2
SO
4
+ HNO
3
NO
2
+ 2HSO
4
+ H
3
O
3HNO
3
H
3
O
+ NO
2
2NO
3
Nitro ha c th coi nh trn 2 giai on.
80
NO
2
+
Z
H NO
2
NO
2
Z
-H
Giai on chm ca phn ng c th l giai on to thnh cht thn in t hoc giai on
to phc o, ty thuc hot tnh cht nn.
Phn ng nitro ha t nhy vi nhm alkil trong vng benzen. Toluen b brom ha nhanh
gp 600 ln so vi benzen, nhng b nitro ha ch nhanh hn 27 ln. Chng t trng thi
chuyn tip ca nitro ha l chuyn tip sm, ngha l gn ging cht u hn phc o.
Trong hn hp HNO
3
H
2
SO
4
tnh chn lc phn ng v chn lc v tr rt thp. Vi cc
hn hp nitro ho c nng ion nitronium thp nh HNO
3
CH
3
NO
2
hay HNO
3
(CH
3
CO)
2
O, tnh chn lc tng dn, khc bit trong vn tc phn ng ca cc cht nn khc
nhau tng ln. Nu cht nn c nhm th gim hot, nng lng hot ha tng ln, trng thi
chuyn tip dch chuyn ra xa. Khi y tnh chn lc vi cht nn tng ln. p-Nitrotoluen
khong 200 ln hot tnh hn nitrobenzen. Nh vy nh hng ca nhm metil trong trng
thi chuyn tip tng ln 10 ln (xem bng trang trc trch t ti liu: Carey F. A.,
Sundberg R. J. (2007) Advanced Organic Chemistry, Part A: Structure and Mechanisms, 5th
Edition, Prenum Press, New York, trang 798)
2. Halogen ha
Trong phn ng halogen ha aren, hot tnh halogen gim dn theo dy: Cl
2
> Br
2
> I
2
. Cht
thn in t c th l halogen phn t, phc halogen vi acid Lews. Cc acid hipohalogen
(ClOH, BrOH, IOH) l tc nhn halogen ha yu, nhng trong mi trng acid l cc tc
nhn hologen ha mnh. Thng dng dung dch Cl
2
v Br
2
trong acid acetic. Halogen phn
81
t dng cho cht nn hot tnh cao, vi cht nn hot tnh thp cn c xc tc acid Lewis
hoc acid Bronsted.
+
Cl Cl + FeCl
3
H
Cl.....Cl.....FeCl
3
H
Cl
FeCl
4
Clor v brom trong acid acetic phn ng vi trng thi chuyn tip tr, gn phc o. Tnh
chn lc phn ng halogen ha cao. Vn tc ring f
p
ca brom ha toluen khong 2400,
trong khi ca nitro ha toluen khong 50. Khi c mt Cl hoc Br trong vng benzen, vn tc
halogen ha tip theo gim xung 7 8 ln, khc vi phn ng nitro ha, vn tc a nhm
nitro th 2 gim 10
7
ln. Do phn ng clor ha v brom ha thng cho sn phm di- v
trihalogen. Vi cc aren c nhm th gim hot, halogen ha c tnh chn lc vi cht nn
cao. Brom ha benzen, toluen, anisol khng cho thy c hiu ng ng v. Nhng brom ha
dn xut cng knh ca anisol nh dn xut N,N-dimetilanilin hay 1,3,5-trialkil cho thy c
hiu ng ng v. Hiu ng ng v trong h cng knh thng do cc yu t lp th. C th
brom kch thc ln kh chim v tr phng do cn tr ca nhm th ln. Cng c th nhm
th ln cn tr dung mi hay baz tch proton.
82
Bui th mi
3. Alkil ha Fiedel Crafts
Alkil ha aren trong s c mt xc tc l acid Lewis hoc acid proton gi l alkil ha theo
Friedel Crafts. Aren c th c alkil ha bng cc tc nhn halogenur alkil, alcol v alcen
trong s xc tc ca acid Lewis. Hot tnh xc tc ca acid Lewis th t trong dy: AlBr
3
>
GaBr
3
> AlCl
3
> GaCl
3
> FeCl
3
> SbCl
5
> TiCl
4
> BF
3
> BCl
3
> SnCl
4
> SbCl
3
. Tc nhn
thng dng l halogenur alkil v xc tc thng dng l AlCl
3
.
Acid Lewis tng tc vi halogenur alkil, to phc phn cc trong C mang 1 phn in
tch dng. Phc to thnh tng tc nh cht thn in t vi aren. C th c s to thnh
ion carbenium nu gc alkil c cu trc thun li, th d cation t-butil.
R X
AlCl
3
R X AlCl
3
R + AlCl
4
+ R AlCl
4
R
H
AlCl
4
R
+ AlCl
3
+ HCl
o o
Alkil ha theo Friedel Crafts c tnh chn lc phn ng v tc cht thp, trng thi chuyn
tip sm. phn ng ca halogenur alkil gim dn theo dy: Ph
3
CX > Ph
2
CHX >
PhCH
2
CX > CH
2
=CHCH
2
X > R
3
CX > R
2
CHX > RCH
2
X > CH
3
X. Kh nng to phc ca
halogenur vi acid Lewis gim mnh t flourur, clorur, bromur n iodur, v y cng l
th t hot tnh ca halogenur. Do iodur alkil khng c dng lm tc nhn alkil ha.
S khc bit trong hot tnh ln n ni c th alikl ha chn lc u alikl c F trong s c
mt Br trong cng phn t.
C
6
H
6
+ FCH
2
CH
2
Br
BF
3
20
O
C
4h
C
6
H
5
CH
2
CH
2
Br
(94%)
Alkil ha theo Friedel Crafts c 3 hn ch.
- Sn phm alkil ha c hot tnh vi cht thn in t cao hn cht u nn thng xy ra
s a alkil ha. gim a alkil ha ngi ta dng lng d aren nh dung mi.
- Trong qu trnh phn ng tc nhn alkil ha thng b ng phn ha, do cho nhiu sn
phm.
+ CH
3
CH
2
CH
2
Cl
AlCl
3
, C
6
H
6
50
O
C
CH
2
CH
2
CH
3 CH
3
CHCH
3
+
(35%) (65%)
Clorur isopropil sinh ra trong phn ng do clorur n-propil ng phn ha. Clorur alkil bc 2
hot tnh hn alkil bc 1 nn sn phm isopropil nhiu hn sn phm n-propil.
- Trong sn phm alkil ha thng c chuyn v. Metil ha toluen cho hn hp cc ng
phn para, meta v orto. Trong mi trng phn ng c HCl v acid Lewis, sau mt thi
gian ch c mt sn phm l ng phn meta. Cc phn ng chuyn v l qu trnh thun
nghch, ng phn meta l ng phn bn hn nn sau mt thi gian trong hn hp phn
ng ch c ng phn meta.
83
CH
3
CH
3
H
H CH
3
CH
3
~ CH
3
CH
3
H
CH
3
CH
3
CH
3
CH
3
H
CH
3
CH
3
CH
3
- H
- H
Alcol v alcen trong s c mt acid mnh c th lm cht thn in t cho phn ng alkil
ha.
R
3
COH + H R
3
CH
2
OH
2
R
3
C
R
2
C=CHR' + H R
2
CCH
2
R'
S to thnh cation carbenium c chng minh bng ph NMR.
Cc aren c nhm th rt in t nh NO
2
, NO, CN, COOR... khng cho phn ng alkil ha
theo Friedel Crafts. Amin thm, phenol cng khng cho phn ng alkil ha theo Friedel
Crafts v acid Lewis to phc cho nhn vi N v O lm gim hot aren.
4. Acil ha Friedel Crafts
a nhm acil vo h thm bng tc nhn acil ha di tc dng xc tc ca acid Lewis gi
l acil ha theo Friedel Craft. Tc nhn acil ha l halogenur acil v anhidrid acid. Cc
cht ny tc dng vi acid Lewis to phc kiu cho nhn vi t l 1:1 v 1:2. Tc nhn thn
in t c th l phc cho nhn hoc ion acilium.
R C X
O
+ MX
n
C O R +
MX
n-1
R C X
O
+ MX
n
R C X
O
MX
n
Giai on chm ca phn ng l tc kch ca 1 trong cc cht thn in t (RCO
,
RCOCl.AlCl
3
) vi aren. Tc cht ph thuc vo iu kin c th ca phn ng. Khi acil ha
aren bng clorur acid, xc tc AlCl
3
, trong dung mi phn cc khng proton (nitrobenzen,
nitrometan), cht thn in t l ion acilium. Trong dung mi phn cc nh (clorur metilen,
diclorometan, tretachorur carbon) cht thn in t l phc. Halogenur acid thm to thnh
mui acilium d hn halogenur acid dy bo. Vi phc cho nhn, c ch phn ng m t
nh sau.
Z
Ceton thm baz hn halogenur acid, do to phc bn hn vi acid Lewis. Do acil ha
bng halogenur acid cn nhiu hn 1 ng lng xc tc, cn acil ha bng anhidrid acid
cn 2 mol acid Lewis, v c 2 O carbonil.
chn lc trong phn ng acil ha khng cao (xem bng trch t ti liu: Carey F. A.,
Sundberg R. J. (2007) Advanced Organic Chemistry, Part A: Structure and Mechanisms, 5th
84
Edition, Prenum Press, New York, trang 812). Theo s liu trong bng, ion alkilacilium
(acetil, propionil) c t l o/p thp hn cc ion thm. Nu chn lc ph thuc vo cc yu
t lp th, kt qu phi ngc li. C th cho rng i vi cc ion acilium thm, cht thn
in t l ion acilium, cn trong trng hp dy bo c phn ng ca phc cng knh ca
alkil halogenur vi acid Lewis.
i khi phn ng acil ha theo Friedel Crafts c hiu ng ng v yu. Hiu ng ng v
chng t giai on tch proton khng hon ton nhanh hn s to thnh phc o, v c
trng hp phc o to thnh thun nghch.
Acil ha theo Friedel Crafts khng c 3 hn ch nh trong phn ng aklil ha. Phn ng
th 1 ln v ceton thm khng th phn ng tip v b gim hot. Phn ng khng km ng
ha v chuyn v. Tc nhn acil ha mnh nht l anhidrid acid hn tp ca acid carboxilic
v acid trifluorometansulfonic thng c iu ch trc tip trong hn hp phn ng. Tc
nhn ny acil ha benzen v cc aren khng cn xc tc.
5. Ghp cp diazo
Ion diazonium l cht thn in t yu, ch phn ng c vi aren c nhm y in t
mnh.
ArN N
O
O
N
NAr
+
Ion arildiazonium to thnh khi diazo ha amin thm, bn nhit thp. Ion nitrosonium
tng tc nhm amin cng s tch 1 phn t nc.
+
HONO ArN N
H
O
H
+ H
2
O
ArN N
H
O ArN N OH
ArN N
ArNH
2
H
+ H
2
O
85
Aril vi nhm th rt in t lm tng tnh thn in t, nhm y in t lm gm tnh thn
in t. c im c ch phn ng ghp cp diazo l trong iu kin xc nh giai on xc
nh vn tc phn ng l giai on tch proton. iu ny c xc nh bng hiu ng ng
v. Mt khc phn ng c xc tc bng baz. Do cc hp cht c th phn ng ghp cp
diazo khng nhiu nn khng c s liu v tnh chn lc ca phn ng. D sao c th d
on rng phn ng c tnh chn lc cao.
3.3. Phn ng th thn hch
Phn ng th thn hch trn h thm c th biu din nh sau.
N
Nu h thm c nhm th X rt in t, h thm tr nn ngho in t v c th cho phn
ng th thn hch. ta ni h thm c tng hot i vi tc kch thn hch. Trong iu kin
khc nghit (nhit cao, baz mnh) v vi cht thn hch mnh, h thm c th cho phn
ng th thn hch m khng cn c nhm th tng hot (rt in t).
3.3.1. Phn ng th thn hch trong h thm hot ng
H thm hot ng l h thm c 1 hoc nhiu nhm rt in t nh NO
2
, NO, RSO
2
, N
2
,
CN... C nhiu cht thn hch c th cho phn ng nh HO
, RO
, RS
, RNH
2
, NH
2
NH
2
...
Ging nh trong phn ng th thn in t, ban u c tng tc lin phn t cho cht trung
gian c c cu ging phc o (phc ipso). Tuy nhin phc o ny khng mang in tch
dng m mang in tch m. Ta gi phc o anion. Nm 1902 Meisenheimer phn lp c
phc o anion t 2,4,6-trinitrophenetol vi ion metilat.
OC
2
H
5
O
2
N NO
2
NO
2
CH
3
O
O
2
N
NO
2
NO
2
C
2
H
5
O OCH
3
- C
2
H
5
O
OCH
3
O
2
N NO
2
NO
2
Ph nhiu v tia X cho thy phc phng c cc nhm nitro nm trong mt phng vng
benzen, 2 nguyn t O ca 2 nhm metoxil nm trong mt phng vung gc. Gc o bng
gc t din, gc | bng 100
O
.
Phc anion c tnh bn ph thuc vo tnh khng c nh (chuyn ng t do ca in t)
ca 1 hoc mt s nhm rt in t.
Nu trn vng benzen ti v tr para v orto c 2 nhm th rt in t mnh (NO
2
, SO
2
R,
CN...) v nhm xut km (Z l H, OR, OAr...) th phc o anion c th c lp hay nhn
dng. Nu nhm xut l halogen hay nhm OSO
2
R, cng nh nu ch c 1 nhm rt in t
mnh, phc o khng nhn bit c do b nhanh chng chuyn thnh sn phm.
86
N
Z Nu
NO
2
NO
2
Z Nu
N
NO
2
Z Nu
NO
2
NO
2
Z Nu
NO
2
NO
2
Z Nu
NO
2
N
Z Nu
N
O O
O
O
O O
O
O
o
o o
o
o
o
o
Nh vy c ch phn ng th thn in t trn h thm hot ng c th biu din trn 2
giai on: cng thn hch to thnh trung gian phc ipso v tch nhm xut cho ra sn
phm. Giai on chm ca phn ng trong phn ln trng hp l giai on cng thn hch.
Nu nhm xut l halogen, khc vi phn ng S
N
2, vn tc phn ng gim dn theo chiu: F
> Cl > Br ~I. Ta bit nng lng ct d li lin kt C F l ln nht nn giai on tch nhm
xut khng phi l giai on chm ca phn ng.
Nu phn ng th thn hch xy ra trn h thm c nhiu nhm xut, ta c nh hng phn
ng. Ta xt trng hp phn ng ca cc pentafluorophenil do F xut nhanh hn cc
halogen khc v bn thn 5 nhm F lm tng hot mnh vng benzen. C th ngh rng,
phn ng th thn hch hon ton ngc vi phn ng th thn in t, ngha l nhm nh
hng orto v para trong phn ng th thn in t th nh hng meta trong phn ng th
thn hch. Pentafluoronitrobenzen phn ng vi amoniac cho hiu sut 95% vi hn hp sn
phm gm 95% 2-nitro-3,4,5,6- v 4-nitro-2,3,5,6-tetrafluoroanilin.
NO
2
F
F
F
F
F
NO
2
F
F
F
F
NH
2
F
F
NH
2
F
F
NO
2
NH
3
+
Cc nhm NH
2
, OCH
3
, O
, cng nh CH
3
nh hng meta. Fluor v halogen nh hng
meta.
F
F F
F
F
F OMe
F
+ MeO
F
F
F
+ MeO
F
OMe
F
87
nh hng i khi b nh hng bi yu t lp th. Khi un trong ng nghim kn hn hp
2,5-dinitro-meta-xilen vi dung dch amoniac c s thay th nhm nitro ti v tr 2 "cht
chi" ch khng phn ng ti v tr 5 trng tri.
NO
2
Me Me
NO
2
NH
2
Me Me
NO
2
+ NH
2
+ HNO
2
Nhm nitro ti v tr 2 do yu t lp th vi 2 nhm metil bn cnh nn khng cng phng
vi vng benzen, do khng lm bn phc o anion nu s th xy ra ti v tr 5. Phn ng
tng t xy ra vi 2,3-dinitrotoluen.
Me
NO
2
+ NH
2
NO
2
Me
NH
2
NO
2
+ HNO
2
3.3.2. Phn ng th thn hch trong h thm khng tng hot
Halogenur aril c trng t nht 1 v tr orto cho phn ng th thn hch vi cht thn hch
mnh. Cht thn hch mnh ng thi l baz mnh, tch H linh ng nht l ti v tr orto
vi halogen. Carbanion to thnh nhanh chng tch halogen cho ra trung gian khng mang
in tch c hot tnh rt cao. Trung gian ny gi l aryn, c ch c tham gia trung gian ny
gi l c ch aryn, thng l benzyn.
X
Z
+ Nu
H
X
Z
- HNu
Z
- X
Cc h thm khng tng hot khi c mt cht thn hch mnh hoc trong iu kin nhit
cao cho phn ng th thn hch theo c ch benzyn. Di y mt s th d.
Me
Cl
+ NaOH
Me
OH
Me
OH
+
350 -400
O
C
ap suat
Cl
Me
NH
2
Me
+ KNH
2
NH
3
long
Me
NH
2
- 33
O
C
+
88
Cl
NaOH
340
O
C
OH
OH
*
*
(58%) (42%)
*
Hn hp sn phm to thnh cho thy trung gian benzyn cho phn ng vi cht thn hch ti
2 v tr ca lin kt 3.
Carbon trong c cu benzyn c lai ha sp, ngha l c gc 180
O
. Nhng trong vng 6 khng
th c gc ha tr 180
O
. C th ngh rng lin kt t th 2 ca benzyn nm trn mt phng
ca vng benzen c th c to thnh bng xen ph ca vn o sp
2
. S xen ph ny yu
hn nhiu lin kt t thng thng.
Benzyn c hot tnh rt cao nn khng th tch v c lp c. S tn ti ca benzyn ch xc
nh c bng phng php ph. Benzyn nhanh chng cng cht thn hch k c cht thn
hch yu, v chn lc thp. phn ng ca benzyn gim dn trong cc cht thn hch:
RS
> Ph3C
> PhCC
~I
> Br
> Cl
> ROH ~H
2
O.
Khi cho hn hp bromobenzen v o-deuteribromobenzen lng bng nhau phn ng vi
lng thiu amidur, ngi ta thy trong aren khng phn ng lng deuteribromobenzen
nhiu hn bromobenzen. Nh vy deuteribromobenzen c phn ng km hn
bromobenzen, ngha l H
hay D
c tch ra bng NH
2
85 90 10 15 100 0
F l nhm th I mnh, cho hu nh sn phm meta (qua I) v nhiu para (qua II). CN c I
ngang vi F nhng ng thi c R mnh. Cng hng ca nhm NH
2
vi CN lm tng tnh
bn anion VI m khng lm tng tnh bn anion V. Nh vy c hiu ng cm v cng hng
u thun li cho s to thnh sn phm meta t II. T I, cng hng ca CN vi NH
2
trong
III m khng c trong IV, nhng trong trng hp ny hiu ng cm quan trng hn. Nh
vy, vi nhm th CN, sn phm para t II nhiu hn sn phm meta t I. Nhm metoxil
tng t F, nhng hiu ng yu hn. Nhm metil c hiu ng +I yu, O
c +I mnh v +R
mnh nn c nh hng ngc vi CN.
-----------HT----------