HA I CNG B2

CHNG I : CU TO V KH NNG PHN

NG CA CC HP CHT HU C

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I CNG V HA HC HU C
Danh t cht hu c c Berzlius s dng ln u tin
vo nm 1807 ch nhng cht trch t cc c th sng
(ng vt, thc vt) phn bit vi cc cht v c l nhng
cht xem nh c ly t vt cht khng c s sng nh
:t, , mui,
hin nay ngi ta nh ngha ha hc hu c l ha hc
ca cc hidrocarbon v dn xut.

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B. NG PHN
ng phn l mt hin tng ph bin v quan trng trong
ha hc hu c.
Hin tng mt cng thc phn t ng vi hai hay nhiu
cht khc nhau c gi l hin tng ng phn.

2 loi ng phn
+ ng phn cu to

+ ng phn lp th

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ong phan
ong phan cau tao
(constitutional isomers)

ong phan lap the

(stereoisomers)

ong phan cau dang

(conformational isomers)

ong phan cau hnh

(configurational isomers)

ong phan hnh hoc

(geometric isomers)

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ong phan quang hoc

(enantiomers)

1. ONG PHAN CAU TAO :

Cac ong phan cau tao (ong phan phang ) phan biet nhau ve
cau tao hoa hoc ( trnh t sap xep cua cac nguyen t trong phan
t hoac ve loai lien ket)
+ ong phan mach
+ ong phan v tr
+ ong phan nhom chc
+ ong phan lien ket

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a. ong phan mach : phan biet vi nhau ve cach sap xep mach
carbon.

V du :
CH3 - CH2 - CH2 - CH3

CH3 - CH - CH3

n - butan

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CH3

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i - butan

b. ong phan v tr : cac ong phan v tr phan biet nhau ve v tr

cua nhom chc
V du :

CH3 - CH - CH3

CH3 - CH2 - CH2 - OH

OH
propanol - 2

propanol - 1

CH3 - CH = CH CH3

CH2 = CH- CH2 CH3

Buten - 2

Buten 1

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c. ong phan nhom chc : cac ong phan nay co cung cong thc
phan t nhng co nhom chc khac nhau.
V du :

C2H6O :

CH3 CH2 OH

Ru etylic

CH3 O CH3

dimetyl ete

C3H6O :
CH3 CH2 CH = O
CH3 CO CH3

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andehyt propionic
axeton

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OH

OH

OH
OH

OH

1,2-dihydroxylbenzen
(pyrocatechin)

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1,3-dihydroxylbenzen
(resorcinol)

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OH
1,4-dihydroxylbenzen
(hydroquinon)

d. ong phan lien ket : cac ong phan nay phan biet nhau ve
loai lien ket gia cac nguyen t trong phan t.
V du : C4H8 co 2 ong phan la buten 2 va xiclobutan.
CH3 - CH = CH - CH3

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10

CHU Y : co mot so trng hp ma mot chat hu c co the phan

ng c theo hai cong thc cau tao khac nhau tuy ieu kien th
nghiem.
Hai dang nay lien tuc chuyen hoa lan nhau trong mot can bang,
khien cho hon hp cua chung the hien nh mot hp chat duy
nhat.
Hien tng nay c goi la hien tng ho bien hay hien tng
tautomer

* Tautomer (ho bien) : 2 chat ong phan ton tai dang can bang
vi nhau, ch khac nhau v tr cua 1 proton va dan ti s thay oi
v tr cua 1 lien ket oi.

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11

1 . Ho bien enol xeton :

R - CH = C - R'
OH
dang enol

R - CH 2 - C - R'
O
dang xeton

Dang xeton ben hn dang enol va c tao thanh nhieu hn.

2 . Ho bien imit amit :

R - C = N - R'

R - C - NH - R'

OH
dang imit

O
dang amit

Dang amit ben hn dang imit va c tao thanh nhieu hn

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12

2. ONG PHAN LAP THE :

Cac ong phan lap the (ong phan khong gian) phan biet nhau ve
cau hnh ngha la phan biet nhau ve s phan bo khong gian cua
cac nguyen t hoac nhom nguyen t trong phan t.
Cac chat ong phan phan biet nhau do s phan bo khong gian
cua cac nguyen t, nhom nguyen t xung quanh phan khong
trung vi anh hoac phan cng nhac cua phan t.
Hai loai ong phan lap the :
+ ong phan hnh hoc
+ ong phan quang hoc
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13

2.1. ong phan hnh hoc :

Neu co hai nguyen t noi vi nhau bang mot lien ket cong hoa tr
cng nhac (ngha la khong co s quay cua hai phan phan t quanh
truc noi hai nguyen t nay) th hai nhom the noi vi chung co the
co nhng cach phan bo khong gian khac nhau :
* ong phan kieu cis trans : nhom the giong nhau nam cung
pha oi vi nhau goi la ong phan cis, khac pha oi vi nhau
goi la ong phan trans.
* ong phan kieu E Z : vi Z ch 2 nhom ln cung pha, E ch
2 nhom ln khac pha

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14

Vi cau tao a,b C = C a,b hoac a,b C = C a,c se co hai cach

phan bo khong gian cng nhac sau:

a
b

a
C

va

Cau hnh cis

H
C

HOOC

va

COOH

COOH
C

HOOC

C
H

Axit Fumaric ( trans )

Axit Maleic ( cis )

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Cau hnh trans

V du :
H

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15

a
b

a
C

va

cau hnh cis

c
C

cau hnh trans

V du :

H
C

HOOC

va

CH3

CH3
C

HOOC

Axit izo crotonic ( cis )

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H
C

Axit crotonic ( trans )

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17

Loai ong phan hnh hoc xuat hien cac hp chat vong no la do
s phan bo khong gian khac nhau xung quanh mot lien ket cng
nhac hoac 1 phan cng nhac cua vong.

H
H3C
H

H
CH3

H3C

cis - 1,2 - dimetyl

xiclopropan

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H
CH3

trans - 1,2 - dimetyl

xiclopropan

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18

2. ong phan quang hoc :

2.1 Thuyet carbon t dien va quy c bieu dien c cau phan t
trong khong gian :

a. Thuyet carbon t dien :

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19

Carbon phi oi xng hay carbon bat oi xng, ky hieu la C*.

*
CH3 - CH - CH 2 - CH3
Cl
*
HOCH2 - CH - CHO
OH

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CH3 -*CH - COOH

OH

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20

b. Quy c bieu dien c cau phan t trong khong gian:

+ Cong thc phoi canh :

+ Mo hnh t dien :
a

a
b

+ Cong thc chieu Fischer :

a

a
chieu
b

c
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c
b

d
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21

+ Cong thc chieu Fischer :

a

a
chieu
b

c
b

at t dien sao cho mot canh nam ngang hng ve pha ngi
quan sat roi chieu xuong mat phang giay.
Truc thang ng la mach carbon ong thi bieu dien cac lien
ket hng ra pha sau mat phang giay
Truc nam ngang bieu dien cac lien ket hng ra pha trc
mat phang giay
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22

c. Tnh quang hoat :

- Chat HC co kha nang lam quay mat phang cua anh sang
phan cc sang phai hoac sang trai 1 goc nhat nh co tnh
hoat ong quang hoc hay tnh quang hoat
VD : axit lactic, cac chat ng,
- Chat hoat ong quang hoc chat quang hoat
- o manh cua tnh quang hoat c xac nh bang ai lng
[], la o quay cc rieng

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23

Neu mat phang dao ong lech ve pha phai so vi ngi quan
sat, chat quang hoat c goi la chat quay phai ( co tr so
dng ).

Neu mat phang dao ong lech ve pha trai so vi ngi quan
sat chat quang hoat c goi la chat quay trai ( co tr so am ).
Goc quay cc co the o c bang mot phan cc ke
(Polarimeter).

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24

Nguon sang

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Lang knh
Nicol

602003 - Chuong I

Anh sang phan cc

phang

25

ieu kien can va u e mot hp chat co tnh quang hoat la phai

co s bat oi xng trong phan t.
Phan t bat oi xng la phan t khong the chong kht len anh
cua no cho bi mot gng phang
phan t bat oi xng la phan t khong co mat phang oi xng
hay mot tam oi xng nao trong chnh no

Cl

Cl

CH3

CH3
H

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(a)

CH3

C2H5
H

(b)
602003 - Chuong I

(a). 2 Clo propan

(b). 2 Clo butan
26

d. ong phan quang hoc do phan t co mot carbon phi oi xng

Trong a so cac hp chat hu c co tnh quang hoat phan t
cua chung eu co cha carbon phi oi xng
V du: phan t axit Lactic CH3- CHOH- COOH co 1C*.

Co 2 loai axit Lactic co goc quay cc bang nhau nhng ngc

nhau ve dau: mot axit Lactic quay phai va mot axit Lactic quay
trai
Hai axit nay la hai ong phan quang hoc va c goi la hai
chat oi quang ( hay hai chat oi hnh )
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27

COOH

COOH

CH3

CH3
OH

HO

Axit ( - ) - Lactic

Axit ( + ) - Lactic

COOH

COOH
H

HO

OH

CH3

CH3
Axit ( - ) Lactic
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Axit ( + ) Lactic
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31

Hon hp nhng lng bang nhau cua 2 chat oi quang th

khong co tnh quang hoat va c goi la hon hp raxemic.
ong phan quang hoc la nhng chat ong phan co cau tao
giong nhau nhng s phan bo cua cac nhom the trong khong
gian khac nhau tac dung tren anh sang phan cc khac nhau.

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32

* Hai ong phan oi quang : khong khac nhau nhieu ve tnh

chat hoa hoc va ly hoc
- Lam quay mat phang phan cc cua anh sang mot goc bang
nhau nhng ngc chieu nhau
- Co tnh chat hoa hoc giong nhau nhng khac nhau ve kha
nang tham gia phan ng vi cac tac nhan la nhng chat hoat
ong quang hoc
- Khac nhau ve mot so tnh chat ly hoc nh : v ngot, oc tnh,
cac vi sinh vat co the phan huy chat nay ma khong co tac ong
en chat kia

- Nhng tinh the ong phan (+) va (-) ket tinh nhng dang
bat oi khac nhau.
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33

e. ong phan quang hoc do phan t co n C* khong tng ng.

Qui tac Vant Hoff.

f. Trng hp ac biet : phan t co Cacbon phi oi xng tng

ng . Dang meso.
2 phan nay SV oc tai lieu

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34

Ky hieu cau hnh :

1. Danh phap D L :

K hieu cau hnh cua cac ong phan quang hoc ngi ta lay
Glyxerandehit CH2OH CHOH CH= O lam chuan va quy
c:
CH = O

CH
H

OH

HO

CH2OH

CH2OH
D - Glyxerandehit
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L - Glyxerandehit
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35

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36

Vi cac phan t kieu R CHX - R (X = O, N, S, halogen,)

nhom nao b oxi hoa sau hn th pha tren cua cong thc chieu
Fischer
Neu s phan bo cua X giong vi D- Glyxerandehit : co cau
hnh D
Neu s phan bo cua X giong vi L- Glyxerandehit : co cau hnh
L.
R'
R'
H

Cau hnh D

Cau hnh L

Th t cac nhom b oxi hoa :

RH < RCH2OH < RCH=O < RCOOH
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37

CHNG I : CAU TAO VA KHA NANG PHAN

NG CUA CAC HP CHAT HU C
B - HIEU NG HOA HOC
Trong phan t chat hu c, cac nguyen t co anh hng lan
nhau mot cach trc tiep hoac gian tiep, ma trong a so trng
hp la do s khac biet ve o am ien gia 2 nguyen t lien ket
gay nen.
S tac ong tng ho gia cac nguyen t trong phan t lam thay
oi s phan cc cua phan t c goi la hieu ng hoa hoc.
S tac ong nay khac nhau tuy thuoc vao he c khao sat la he
khong lien hp hay he lien hp.
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38

I. HIEU NG CAM NG :
Xet hai phan t propan va n propylclorua :
CH3 - CH2 - CH3

=0

CH3 - CH2 - CH2

Cl

Lien ket C1- Cl b phan cc manh ve pha Clo la nguyen t

co o am ien ln hn.
nguyen t Cl mang mot phan ien tch am ; nguyen t
carbon mang mot phan ien tch dng.

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39

en lt cac lien ket C1- C2 va C2 C3 cung b phan cc mac

du s phan cc a yeu hn nhieu.
Ket qua la phan t n - propylclorua tr nen phan cc .

CH3 - CH2 - CH2

Cl

S phan cc hay s dch chuyen mat o electron nh vay

goi la anh hng cam ng hay hieu ng cam ng, k hieu
bang I (Inductive effect).
Nguyen t Clo la nguyen t gay anh hng cam ng.

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40

Quy c :
- Nguyen t hidro lien ket vi carbon trong lien ket C-H co
hieu ng I = O.
- Nguyen t hay nhom nguyen t X co kha nang hut electron
manh hn hidro c coi la co hieu ng cam ng am I

- Nguyen t hay nhom nguyen t co kha nang ay electron

manh hn hidro th c coi la nhom co hieu ng cam ng
dng +I

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41

Chieu chuyen dch mat o electron :

Y
+I

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C - H
I=0

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X
-I

42

Hieu ng +I thng thay cac nhom ankyl va cac nhom mang

ien tch am :
Trong day cac nhom ankyl hieu ng +I tang theo o phan
nhanh hay la bac cua nhom :
- CH3

< - CH2 - CH3 < - CH - CH3 <

CH3

CH3
- C - CH3
CH3

Trong day cac nhom mang ien tch am, nhom co o am

ien nho hn la nhom co hieu ng +I ln hn :

- O10/7/2012

<

- S-

<

602003 - Chuong I

- Se43

Hieu ng I thng thay cac nhom khong no, cac nhom mang
ien tch dng, cac nhom co cac nguyen to co o am ien ln
(halogen, cancogen ):
Cacbon sp co hieu ng I ln hn Cacbon sp2 va sp3 :

-C

CH

>

- CH = CR2

>

- CH2 - CR3

-C

CR

>

- C6H5

>

- CH = C(R)2

Nhom mang ien tch dng co hieu ng I ln hn nhom co

cau tao giong the ma khong mang ien:
- +OR2 > - OR
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- + NR3 > - NR2

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44

 Nguyen t hoac nhom nguyen t co o am ien cang ln th

hieu ng I cang manh:
-F > -OR > -NR2 > -CR3

-F > -Cl > -Br > -I

V du :

Ka.10-5

10/7/2012

O
H - CH 2 - C - OH Cl
1,76

O
O
CH2 - C - OH F CH 2 - C - OH
260
136

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45

ac iem cua hieu ng cam ng :

- Hieu ng cam ng gam rat nhanh khi mach cac lien ket
keo dai.
- Cac yeu to khong gian t anh hng en hieu ng cam ng

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46

CH3 - CH2 - CH2 - COOH

Ka = 1,55 . 10-5

CH3 - CH2 - CH - COOH

Ka = 139 . 10-5

Cl

CH3 - CH - CH2 - COOH

Ka = 8,8 . 10-5

Cl

Cl - CH2 - CH2 - CH2 - COOH

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Ka = 3,0 . 10-5
47

II. HIEU NG LIEN HP :

Hieu ng lien hp ch ac trng cho cac he lien hp la he thong
bao gom cac lien ket oi luan phien vi cac lien ket n (lien
hp , ) hoac he thong co nguyen t con cap electron t do noi
vi mot lien ket oi (lien hp p, ):

C=C-C=Y

.. p

C=C - X

Trong cac he lien hp co s chuyen dch electron ac trng cho

cac electron khac vi c che chuyen dch cam ng tren.

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48

He lien hp ,

He lien hp p,
p

C = C - C = Y

C = C - X

CH2 = C - CH = CH2

CH2 = CH - Cl

CH3

CH2 = CH - CH = O

CH2 = CH - O - CH3

CH2 = CH CH = CH2
NH2

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49

V du : phan t butadien- 1,3 trang thai bnh thng khong

phan cc,
CH2 = CH - CH = CH2
neu thay mot hidro nhom CH2 bang nhom CH=O
CH2 = CH - CH = CHO
Nhom - CHO se tham gia lien hp vi cac orbital p cua butadien.
Nh ac tnh phan cc san co cua nhom CH=O, toan bo
orbital mi hnh thanh cua phan t b dch chuyen mot
phan ve pha nguyen t oxi :

CH2 = CH - CH = CH - CH = O
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50

CH2 = CH - CH = CH - CH = O
S phan cc phan t gay nen bi s dch chuyen mat o electron
nh vay c goi la hieu ng lien hp va ky hieu bang ch C
(Conjugate effect ).
Nhom CH = O co hieu ng lien hp theo c che hut electron c
goi la nhom co hieu ng lien hp am C.
Nhng nhom co tac dung ay electron bang cach lien hp tng
t nh tren c goi la nhom co hieu ng lien hp dng +C.

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51

V du cac nhom Cl, -OH, -NH2 trong cac he lien hp p, di

ay la cac nhom co hieu ng +C :
..
Cl - CH = CH2

..
H2N

..
HO

Hieu ng +C thng gap cac he lien hp p, vi cac nhom the X

co cap electron t do va tham gia chuyen dch electron theo hng
i ve pha lien ket :

..
X C

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52

- Nhom mang ien tch am co hieu ng +C ln hn nhom tng t

ma khong mang ien :
_
-O
>
- OR
Vi nguyen t cua nhng nguyen to trong cung mot chu ky nho
hoac trong cung mot phan nhom chnh cua he thong tuan hoan,
hieu ng +C giam t trai sang phai ( trong mot chu ky ) va t tren
xuong di (trong mot phan nhom ) :
- NH2 > - OR > - F
- F > - Cl > - Br > - I

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53

Hieu ng C thng gap cac he lien hp , co cha cac

nhom khong no vi cong thc chung C=Y (co mot so nhom vi
cong thc C Z nh C N ; mot so nhom khac khong cha
carbon nh NO2).
Hng chuyen dch electron c bieu th bang nhng mui ten
cong nh sau :

Nguyen t hoac nhom nguyen t Y co o am ien cang ln th

hieu ng lien hp am C cang manh :

C =O

>

C = NR

>

C =CR2

- NO2 > - CN > = CO > - COOR > - COOH

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* ac iem cua hieu ng lien hp :

- Hieu ng lien hp xuat hien nhanh, lan truyen trong he cung
nhanh va giam hieu lc khong ang ke khi mach lien hp keo dai
(xa trung tam gay hieu ng)
- H lien hp con phu thuoc vao yeu to lap the, khi he giam tnh
chat lien hp (cau tao phang) th h lien hp cung giam theo. No
khong con hieu lc khi he mat tnh chat ong phang.

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55

III. HIEU NG SIEU LIEN HP :

Nghien cu nhng tnh chat vat ly va hoa hoc cua cac phan t
hu c, ngoai s lien hp , va p, a neu tren con co s
lien hp , la s lien hp gia orbital cua nhom ankyl va
orbital cua lien ket oi, lien ket ba hay vong thm.
Ngi ta goi o la s sieu lien hp hay hieu ng sieu lien hp,
k hieu bang ch H (Hyper conjugation) .
Hieu ng sieu lien hp cua cac nhom ankyl luon luon la hieu
ng ay electron; chieu chuyen dch mat o electron cung c
mo ta bang cac mui ten cong :
H

H
H C CH = CH2
H
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CH3
602003 - Chuong I

H
C
56

Hieu ng sieu lien hp t le vi so lien ket C H v tr so vi

lien ket oi :
- CH3 > - CH2 CH3 > - CH( CH3)2 > - C( CH3 )3

cac nhom ankyl khi gan cac lien ket gay hieu ng sieu lien
hp ngc lai vi h cam ng.

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57