Chuyn 1: DONG PHN HNH HC

1. D|nh nghia
Dng phn hnh hoc (dng phn cis-trans) l loai dng phn lp th sinh ra do su phn b khc nhau cua cc
nguyn tu hoc nhm nguyn tu o hai bn mt b phn cung nhc cua phn tu nhu lin kt di -C = C-, -C = N-, -N =
N- hoc h thng vng no
2. Nguyn nhn xut hin dng phn hnh hc
Do b phn cung nhc cua phn tu lm can tro su quay tu do cua cc nhm th xung quanh truc lin kt.
3. Diu kin xut hin dng phn hnh hc
- Phn tu phai c b phn cung nhc can tro su quay tu do cua hai nguyn tu o b phn d.
- O mi nguyn tu cacbon cua lin kt di v o t nht hai nguyn tu cacbon cua vng no phai c hai nguyn tu
hoc nhm nguyn tu khc nhau.
V du: abC=Cab
* Cc trung hp c dng phn hnh hc
a/ Trung hp c mt lin kt di
- H abC = Ccd:
, a b c d c hai dng phn hnh hoc d cp a-b v c-d c trng nhau hay khng.
- Di voi cc loai hop cht andoxim, xetoxim khng di xung, hidazon, hop cht azo c lin kt:
+ abC = Nc: a b c hai dng phn hnh hoc d c trng voi a hoc b
C = N
H
H
3
C
OH
C = N
H
H
3
C
OH
syn - axetandoxim
anti - axetandoxim
+ aN=Nb: c hai dng phn hnh hoc d a trng voi b hay a khc b
N = N
H
H
5
C
6
C
6
H
5
N = N
H
H
5
C
6
C
6
H
5
cis hay syn- azobenzen
trans hay anti - azobenzen
b/ Trung hp c nhiu lin kt di
- H gm mt s le lin kt C=C lin nhau (h cumulen): abC=C=C=Ccd
H ny giu vai tr nhu mt lin kt C=C, nn nu , a b c d s c hai dng phn hnh hoc.
V d:
C =C =C= C
m -NO
2
H
4
C
6
C
6
H
5
C
6
H
4
NO
2
- m
C
6
H
5
C = C = C
C
6
H
5
m-NO
2
H
4
C
6
C
6
H
4
NO
2
-m
C
6
H
5
Z (cis)
E (trans)
- H gm hai hoc hon hai lin kt C=C lin hop:
abC=CH-[-CH=CH-]
n
-CH=Ccd
+ Nu cp a-b khng dng nht voi cp c-d th s c 2
n
dng phn.
V d: CH
3
-CH=CH-CH=CH-COOH c 4 dng phn:
C = C
CH
3
H
H
C = C
H
COOH H
C = C
CH
3
H
H
C = C
COOH
H H
E-E (trans-trans)
Z-E (cis-trans)
C
CH
2
Ca'b' ab
a b a' b'
C = C
H
H
3
C
H
C = C
H
COOH
H
H
C = C
H
H
3
C
H
C = C
COOH
H
H
H
E-Z (trans-cis)
Z-Z (cis-cis)
+ Nu cp a-b dng nht voi cp c-d s dng phn s t hon 2
n
N= 2
n-1
+ 2
p-1
N: S dng phn hnh hoc
p= n/2 nu n chn
p= (n+1)/2 nu n le
V d: C
6
H
5
-CH=CH-CH=CH-C
6
H
5
c N= 2
2-1
+ 2
1-1
= 3 dng phn.
C = C
C
6
H
5
H
H
C = C
H
C
6
H
5
H
C = C
H
c
6
H
5
H
C = C
C
6
H
5
H H
E-E (trans-trans) Z-Z (cis-cis)
C = C
C
6
H
5
H
H
C = C
c
6
H
5
H H
E-Z (trans-cis)
c/ Trung hp cc hp cht vng no
- Dn xut hai ln th cua xiclopropan v xiclobutan c dng phn cis- trans di voi mt phng vng.
- Dn xut 1,2-; 1,3-; 1,4- hai ln th cua xiclohexan du tn tai o dang cis hoc trans v c d bn tuong di
khc nhau.
V d: trans-1,2-dimetylxiclohexan
4. Danh php dng phn hnh hc
a/ H danh php cis- trans
Theo h danh php ny, dng phn no c hai nhm th tuong duong duoc phn b o cng mt pha di voi
mt phng cua ni di hay vng no th duoc goi l cis-, tri lai nu khc pha duoc goi l trans-.
Vic p dung h danh php ny gp nhung kh khn trong mt s truong hop:
V d:
CH
3
H
CH
3
H
(a,a) 1%
H
CH
3
H
CH
3
(e,e) 99%
Cl
Cl Cl
Cl
Cl
Cl
Cl
Cl
(cis) (trans) (cis)
(trans)
H
H
H
H
3
C
H
CH
3
H
H
H
H
3
C
CH
3
H
(cis-)
(trans-)
C = C
Cl
Br
CH
3
I
C = C
CH
3
CH
2
H
3
C
CH
2
CH
3
CH
2
CH
2
CH
3
b/ H danh php syn- anti
H danh php ny thuong dng cho cc hop cht c lin kt di -C=N- v -N=N-. Thuong th dang syn- l
dang m hai nhm th o cng pha (tuong tu cis-), nguoc lai l anti- (tuong tu trans-). Trong truong hop cc andoxim
RCH=NOH, nguoi ta lai cn cu vo vi tr khng gian cua H (khng phai R) v OH d goi cu hnh l syn hay anti.
V d:
C = N
C
6
H
5
H
OH
C = N
H
5
C
6
H
OH
syn-
anti-
N =NC
H
5
C
6
C
6
H
5
C = C
H
5
C
6
C
6
H
5
syn-
anti-
Ngy nay nguoi ta rt t dng h danh php ny.
c/ H danh php Z-E
H danh php Z-E bao trm duoc ca hai h danh php cis- trans, syn-anti v c th p dung duoc vo nhung
truong hop m hai h trn gp kh khn.
Theo h danh php ny, mun goi tn cu hnh cua hop cht c ni di, cn thuc hin hai buoc: so snh d hon
cp v xc dinh tn cu hnh Z- E.
* So snh d hon cp cua cc nguyn tu ho}c nhm nguyn tu o ni di.
abC=Ccd abC=Nc
D hon cp cua nhm th dnh voi C
sp
2
duoc xc dinh theo s hiu nguyn tu hay s din tch hat nhn Z cua
nguyn tu dnh voi C
sp
2
Br > Cl > S > P > F > O > N > C > H
(35) (17) (16) (15) (9) (8) (7) (6) (1)
- Nu hai nguyn tu truc tip gn voi C
sp
2
l ging nhau th cn xt dn lop tip theo.
V du: -CH
2
-Cl > -CH
2
-OH > -CH
2
-CH
3
> -CH
2
-H
(RO)
3
C- > (RO)
2
CH- > ROCH
2
-
C (O,O,O) C (O,O,H) C (O,H,H)
- Cc nguyn tu chua lin kt bi duoc tnh bi ln (ni di tnh gp di, ni ba tnh gp ba)
O O O
-C > -C > -C > -C = N > -C = CH
OH R H
C (O,O,O) C (O,O,C) C (O,O,H) C (N,N,N) C (C,C,C)
- Trong s dng vi, nguyn tu c s khi lon hon th c d hon cp lon hon.
D > H
* Xc d|nh tn cu hnh Z E
Gia su sau khi xc dinh d hon cp tuong di thy a>b v c>d, ta xt vi tr khng gian cua a v c.
+ Nu a,c cng pha di voi b phn cung nhc ta c dang Z
C = C
a
b
c
d
+ Nu a,c khc pha voi b phn cung nhc ta c dang E
C = C
a
b
d
c
C = N
a
b
c
V d:
C = C
Cl
Br
Br
I
C = C
H
H
CH
3
CH
3
C = N
H
Br
OH
CH
3
(Z)-1,2-dibrom-1-clo-2-iotetilen (E)-But-2-en (E)-Axetandoxim
- Danh php Z ,E trong nhiu truong hop ph hop voi danh php cis- trans, nhung cung c truong hop khng
dng, v du :
C = C
H
3
C
H
CH
3
H
C = C
Cl
H
Cl
Br
cis- (Z) cis-(E)
5. Nhit d nng chay, nhit d si, ti khi, chit sut
Dua vo nhit d nng chay (tru mt s t ngoai l) ta xc dinh duoc cu hnh dng phn hnh hoc.
Nhit d nng chay cua dng phn E thuong cao hon dng phn Z, do dng phn E c tnh di xung cao hon
dng phn Z, cho nn mang luoi tinh th cua n sp xp cht hon.
Nhit d nng chay cua mt s hp cht chua no
Hp cht Dnc,
0
C cua cis(Z) Dnc,
0
C cua trans(E)
1,2-diclotilen -80,5 -50,0
1,2-diittilen -14,0 72
Stinben 1 125
Axit butten-2-ic 15 72
Axit tilen-1,2-dicacboxylic 130 300
- Di voi mi lin h giua nhit d si, ti khi v chit sut voi cu hnh hnh hoc cua phn tu khng duoc cht
ch nhu di voi nhit nng chay. Xong, trong nhiu truong hop di voi mt dng phn no d, nu mt trong ba hng
s d lon hon o dng phn kia th hai hng s cn lai cung lon hon. Mt khc, dua vo quy tc momen lung cuc, dng
phn no c momen lung cuc lon hon phai c cc phai c cc hng s vt l lon hon, do d ta cung xc dinh duoc cu
hnh dng phn hnh hoc.
MT S BI TAP THAM KHAO
Bi 1 :
Nhung hop cht no duoi dy c th c dng phn hnh hoc. Goi tn cc dng phn d theo h thng cis- trans v
h thng Z- E
a/ CH
3
CH=CHCH
3
e/ HOOC-CH=CH-COOH
b/ (CH
3
)
2
C=CHCH
3
g/ CHCl=C=CHCl
c/ CH
3
CH=CHF h/ CH
3
CH=C=C=CHCH
3
d/ CF
2
=CF
2
i/ CH
2
=C=C=CH
2
Bi 4 :
Vit cng thuc cu trc cua cc hop cht :
Propen, (E)-but-2-en; (Z)-but-2-en ; (E)-hex-2-en v (Z)-hex-2-en.
Sp xp cc cht trn theo trnh tu tng dn v mi tnh cht vt l sau: nhit d nng chay, nhit d si, khi
luong ring.