TRNG I HC S PHM TP.

H CH MINH
( KHOA HA )

HA HC LP TH

V TH THU HNG

TP. H CH MINH-2002
 MC LC

Phn A: L thuyt
Chng 1: Khi nim c bn.......................................... 5
Chng 2: ng phn quang hc .................................. 17
Chng 3: ng phn hnh hc..................................... 38
Chng 4: ng phn cu trng ca hp cht khng vng
..................................................................... 50
Chng 5: Cu trng ca hp cht vng no .................. 62
Chng 6: Ha lp th ca d t v Polymer................. 92
Chng 7: Ha lp th ng......................................... 113
Phn B Bi tp
ng phn quang hc ................................. 128
ng phn hnh hc.................................... 132
ng phn cu trng................................... 135
Phn ng th SN ............................................................... 138
Phn ng tch ............................................. 141
Phn ng cng ............................................ 144
Ti liu tham kho.......................................................... 148
 LI NI U

Ho hc lp th (Stereochemistry) l mt khoa hc
nghin cu v cu trc khng gian ca vt cht v nh
hng ca cu trc ny n tnh cht ca chng.
Ho hc lp th c in ch ch trng n cc ng phn
lp th trng thi tnh nh ng phn hnh hc, ng phn
quang hc. Nhng gn y do s pht trin ca hc thuyt
v cu trng (conformation) v phn gii cu trng
(confornational analysis); v s tng hp nh hng lp th
trong cc phn ng ho hc; v quy tc bo ton tnh i
xng ca cc orbital... Cng vi s xut hin cc phng
php vt l nh quang ph t ngoi, quang ph cng hng
t ht nhn, nhiu x tia X, nhiu x electron.... Cc nghin
cu v ha hc lp th cho ta nhiu hiu bit mi v s
ph thuc ca cc tnh cht v nhng c tnh tinh vi v s
phn b khng gian ca cc nguyn t trong phn t, trong
vic gii thch c ch phn ng v c bit ha lp th cn
gii thch c hot tnh sinh l khc nhau ca cc ng
phn lp th.
Ha hc lp th ng nghin cu nhng chuyn ha cht
khc nhau ca cc ng phn lp th gy nn bi cc c
im cu trc khng gian ca chng nh hin tng racemic
ha trong phn ng th SN1, SR, SE, s nghch chuyn cu
hnh trong phn ng th SN2, s lu tr cu hnh trong phn
th SNi, epimer ha trong phn ng cng AN vo hp cht
carbonyl....
Nhiu cng trnh nghin cu v ha hc lp th c
nh gi cao, mt s c trao gii Nobel v ha hc, phn
nh vai tr tm c ca mn hc ny.
Vi tnh cht quan trng ca ha hc lp th, mt lnh
vc khng th thiu c i vi ha hc hin i, nn s ra
i quyn sch ny hy vng gip cc sinh vin chuyn ha
b sung kin thc v h tr cho qu trnh hc tp v nghin
cu ca mnh.
Do kh nng cn nhiu hn ch nn chc chn khng th
trnh nhng thiu st. Rt mong nhn c cc kin ng
gp chn thnh ca qu ng nghip v bn c sch
c hon chnh hn trong nhng ln ti bn sau.

Tc gi
 PHN A
L THUYT
Chng 1:KHI NIM C BN

V HA HC LP TH
1. 1
1.1. Phm vi nghin cu ca ha hc lp th
1.2. Lc s
1.2.1. c tnh ca hp cht trin quang
1.2.2. Thuyt carbon t din
1.2.3. ng phn hnh hc
1.2.4. ng phn quang hc
1.2.5. ng phn cu trng (ng phn quay)
1.3. Cch biu din nguyn t carbon t din.
1.3.1. Cng thc chiu hp cht c mt nguyn t C
1.3.2. Cng thc chiu hp cht c hai nguyn t C
1.3.2.1. Cng thc tam th nguyn
1.3.2.2. Cng thc phi cnh
1.3.2.3. Cng thc Newman
1.3.2.4. Cng thc Fischer
1.4. Cu hnh tng i v cu hnh tuyt i
1.5. Danh php cu hnh
1.5.1. Danh php D,L
1.5.2. Danh php R,S
1.5.3. Danh php E,Z
1.1. PHM VI NGHIN CU CA HA HC LP TH
Cng thc phng khng th m t y cc dng ca phn
t. S kho st v cc kha cnh kin trc ca phn t trong khng
gian tam th nguyn rt cn thit. l phm vi nghin cu ca
Ha lp th.
Mun hiu r hot tnh ca mt hp cht hu c, trc ht
ngi ta phi bit cch cu to ca n v k l xc nh cu
hnh ca phn t.
Cu to ca phn t l trt t sp xp cc ni cc
nguyn t trong phn t.
Cu hnh ca phn t l cch sp xp trong khng gian
ca nhng nguyn t (hay nhm nguyn t) quanh tm carbon i
xng.
Cu trng u i ca hp cht xc nh bi nh hng
cc nguyn t hoc cc nhm nguyn t gn nhau (tng tc
khng ni).
Kt qu ca ni cng ha tr nh hng l s to
thnh ng phn lp th gm c ng phn hnh hc v ng
phn quang hc.
Ha hc lp th c in ch ch trng n cc phn t
trng thi tnh lin h n cc ng phn lp th. Hin nay,
ha hc lp th tr thnh mt trong nhng ti quan
trng nht trong ha hc hu c l thuyt. Ha hc lp th
ng kho st s tng quan khng gian gia cc nguyn t
v cc nhm nguyn t chu phn ng, cng nh hng ca
s sp xp trn cn bng ha hc v vn tc phn ng.
1.2. LC S
1.2.1. c tnh ca hp cht trin quang
Nm 1811, Arago pht hin u tin kh nng quay mt
phng nh sng phn cc gi l tnh quang hot. Nm 1813, Biot
tm thy kh nng quay mt phng nh sng phn cc tinh th
thch anh. Nm 1815, Biot tm thy s quay tng t xy ra vi
mt s cht lng thin nhin: tinh du thng v dung dch ca mt
s cht rn (nh camphor). S khc bit quan trng gia hai d
kin thc nghim va k c Biot gii thch nh sau:
 - Kh nng quay mt phng ca nh sng phn cc ca
thch anh lin quan vi c cu c bit ca tinh th (v n mt hn
khi tinh th c nu chy).
- Cn tnh quang hot ca hp cht hu c phi c lin
kt vi tnh cht ca nhiu phn t ring bit (v hin tng ny
c quan st trng thi lng v trng thi kh cng nh
trng thi dung dch).
Nm 1821, Herschel chng minh rng mt dng ca tinh th
thch anh lm quay mt phng ca nh sng phn cc theo chiu
quay kim ng h, cn dng i quang (ng vi nh ca dng u
trong gng phng) quay mt phng phn cc theo chiu ngc
li. Nh vy nng sut quang hot lin quan mt thit vi tnh bt
i xng ca tinh th.
Sau nhiu nm (1848 1853) kho st tnh quang hot ca hai
acid trch t cn ru nho, Pasteur xc nhn s hin hu ca hai
acid tartric: mt acid hu trin: quay mt phng ca nh sng
phn cc v bn phi (acid (+) tartric) v mt acid khng quang
hot (tiu trin): khng quay mt phng ca nh sng phn cc
(acid () tartric). Ngoi ra, Pasteur thnh cng trong vic tch
hai acid tiu trin thnh acid (+): hu trin v acid (-): t trin
(quay mt phng ca nh sng phn cc v bn tri). Hai acid ny
gi l hai ng phn i quang (hai ng phn i hnh). Theo
Pasteur, tnh quang hot khng phi do tnh bt i xng ca tinh
th m tht ra lin quan vi tnh bt i xng ca chnh cc phn
t acid tartric quang hot. Sau , Pasteur cn tm thy mt acid
tiu trin khc gi l acid meso-tartric. y l mt acid i xng
nn khng quay mt phng ca nh sng phn cc.

Cng thc Fischer ca cc acid tartric:

COOH COOH COOH
H OH HO H H OH
HO H H OH H OH
COOH COOH COOH
(+) (-)
Acid
Acid () tartric (+ -)
gm mt s bng Acid
tartric nhau meso-tartric
phn t i quang (c
cu hnh ngc nhau) khng c tnh quang hot v l do b tr
ngoi phn t, nhng tch hai c thnh acid (+) tartric v acid
(-) tartric. Acid Meso-tartric khng quang hot v kh nng quay
phi ca mt nguyn t carbon bt i b hon ton cho nguyn
t carbon quay tri nn acid meso-tartric cn c coi nh mt
dng khng quang hot b tr ni phn t.
1.2.2. Thuyt carbon t din
Nm 1858, Kekule chng minh rng trong cc hp cht hu
c, nguyn t carbon c ha tr 4, ngha l c khuynh hng to
ni vi bn nguyn t hoc bn nhm. Khi nim ny rt quan
trng v gip cc nh ha hc lc by gi gii thch s tng
quan gia tnh quang hot v tnh bt i xng phn t.
Nm 1874, Le Bel v Vant Hoff nhn thy ng thi v c
lp vi nhau rng tnh bt i xng phn t c to ra khi bn
nhm khc nhau ni vi mt carbon khng phng. Chnh Vant
Hoff ngh s sp xp t din ca bn ha tr ca nguyn t
carbon, ngha l bn ha tr ny hng v bn nh ca mt t
din vi nguyn t carbon tm ca n.
Nguyn t C t din lin kt vi bn nguyn t (hay nhm
nguyn t) khc nhau gi l nguyn t bt i xng. Hu qu l
hai s sp xp khc nhau c th tn ti nh vt v nh trong
gng phng, khng chng ln nhau c.

Th d: Acid lactic c hai ng phn quang hc:

COOH COOH

H OH HO H

CH3 CH3
Acid (+) lactic Acid () lactic
Nu mt nguyn t carbon ni vi hai (hay nhiu hn) nguyn
t hoc nhm nguyn t th vt v nh s chng ln nhau c v
tnh quang hot mt hn.
 Nm 1913, Bragg chng minh c s phn b t din ca
nguyn t Carbon bi nhiu x tia X ca kim cng. Nhng
phng php vt l khc nh nhiu x in t v ph nghim
cng xc nhn ngh ca Vant Hoff.
1.2.3. ng phn hnh hc
T nm 1875, Vant Hoff ngh biu din ni i trong
etylen th abC=Cab bng m hnh hai t din chung nhau mt
cnh nh sau: a a b
a

b b b a
cis th bn nhmtrans
Xt v mt hnh hc th nm trn mt mt
phng. Do , s quay quanh ni i l khng cn na v s phn
b ca nhm th ging nhau c th cng pha hoc khc pha
ca mt phng cha ni i.

a a a b

b b b a
cis trans
(a b)
Nm 1838, Liebig xc nh c s tn ti ca hai acid:
maleic v fumaric l ng phn ca nhau.
H H H COOH

HOOC COOH HOOC H

acidn
Mi maleic acidmi
nm 1887, Wislicenus furamic
chng minh rng ng
phn thc s do s hin din ca mt ni i trong phn t. ng
phn hnh hc khng c nh hng trn nh sng phn cc phng,
v cc phn t c ni i khng bt i xng, ngoi tr trng
hp mt nhm gn trn ni i c mt nguyn t Carbon bt i
xng.
 ng phn hnh hc thng lin quan vi cc hp cht c ni
i Carbon - Carbon, hoc Carbon - Nit, hoc Nit-Nit.
Ngoi ra, cc hp cht cicloankan (vng no) cng c th c
ng phn hnh hc. ng phn hnh hc dng ny thng lin
quan vi ng phn quang hc.
Th d: 1,2 dimetylciclopropan c cc ng phn:
CH3 CH3 CH3 H H CH*
3
* *3 ** 3
H H H CH CH H
Cis Trans
(Meso) CAP OI QUANG

1.2.4. ng phn quang hc (xem chng 2)

1.2.5. ng phn cu trng (cu dng, quay)
Nm 1885, Baeyer xut thuyt cng cho cc hp
cht vng no. Theo Baeyer, cc cicloankan c cu to l
nhng a din u v phng, sc cng gc trong vng gim
dn t ciclopropan n ciclopentan, ri gia tng vi cc vng
ln hn. Thuyt Baeyer gii thch s tn ti cc vng nm,
su cnh vi s khim din ca cc vng nh v ln hn lc
by gi.
Nm 1890, Sasche cc vng c th ghnh p ng iu
kin gc t din v tn ti di cu trng khng phng v khng
cng. Sasche d on ciclohexan tn ti di hai dng gh v tu,
tuy nhin nhng c gng u tin c lp hai dng ny u tht
bi.

n nm 1911, Mohr gii thch hai dng gh v tu ca

ciclohexan bin i ln nhau d dng. Mohr cng tin on s tn
ti ca decalin di hai dng cis v trans khng cng, hai dng
ny c Huckel c lp vo nm 1925.
1.3. CCH BIU DIN NGUYN T CARBON T DIN
1.3.1. Biu din phn t cha mt nguyn t C
biu din cng thc tam th nguyn ca phn t
trn mt phng giy, ngi ta dng mt vng trn tng
trng cho nguyn t Carbon nm trong mt phng, cc ni
trn mt phng xut pht t mt im trong vng (m nt)
v cc ni di mt phng xut pht t mt im trn vng
trn (chm nt). n gin c th khng v vng trn.

CACH BIEU DIEN PHAN T METAN

H H
H
H H
H H
H
H
H Cng thc H
chiu FischerHca Metan
H H

H H H H

H H
1.3.2. Biu din phn t cha hai nguyn t C
- Cng thc tam th nguyn ca Etan
H
H
H

H
H
- Cng thc phi H
cnh: nhn theo trc C C
H H
H

H
H H
 - Cng thc chiu Newman: trc C C vung gc
vi mt phng chiu, nguyn t C gn nht c biu din bng
vng trn, cc lin kt vi C ny xut pht t tm vng trn.
H
H H

H H
- H
Cng thc chiu Fischer: mch chnh ca phn t
hng theo chiu thng ng, cc lin kt hai bn l nhng lin
kt hng v pha trn mt phng, cc lin kt u trn v u
di l nhng lin kt hng v pha di mt phng.
H H
H H H H
H H H H
H H
1.4. CU HNH TUYT I V CU HNH TNG I
- Cu hnh tuyt i: l cu hnh thc s ca phn t
trong khng gian. Danh t hu trin (quay phi) v t trin (quay
tri) cho bit chiu quay ca mt phng nh sng phn cc b tc
ng bi cht hu c. y l kt qu c t thc nghim, ngi ta
khng th tin on dng no trong hai dng i quang ng vi
dng t trin hay hu trin.
- Cu hnh tng i: Trc nm 1951, ngi ta
khng c phng php no xc nh cu hnh dng hu trin
hay t trin ca hai dng i quang. Tuy nhin, ngi ta c th
xc nh cu hnh ca cc cht quang hot i vi nhau v i vi
hp cht mu c cu hnh bit. Cu hnh ny gi l cu hnh
tng i.
1.5. DANH PHP CU HNH
1.1.1. Danh php D,L
Hp cht c chn lm mu l gliceraldehid:
- Cu hnh ca dng hu trin c Fischer qui nh l
D (+) gliceraldehid.
 - Cu hnh ca dng t trin c gi l L (-)
gliceraldehid.
CHO CHO

H OH HO H

CH 2OH CH 2OH

D-(+)-gliceraldehid L-(-)-gliceraldehid
K hiu: D, L l cu hnh tuyt i
Du (+) hay (-) lin h n chiu quay

Qui tc Fischer c chp nhn mt cch rng ri v cc hp

cht c cu hnh lin quan n D (+) gliceraldehid i vi chiu
hng ca H v OH gi l ng phn D, d chng l hu trin
hay t trin.
Th d:
CHO COOH PBr3
HgO
H * OH H * OH
CH2 OH CH2 OH
Acid D-(+)-gliceric Acid D-(-)-gliceric
COOH COOH
Zn/HCl
H * OH H * OH
CH2 Br CH3
Acid D-(-)-3-bromo-2-hidroxipropanoic Acid D-(-)-lactic
Trong s tng quan gia andehid D (+) gliceric vi acid D (-
) gliceric khng c phn ng no lm thay i cch sp xp bn
lin kt vi nguyn t Carbon bt i xng. V th cc hp cht
u c cu hnh D.
Nu phn t c nhiu nguyn t Carbon bt i xng, cu
hnh ca mt tm thng c lin kt trc tip hoc gin tip vi
gliceraldehid, cn cu hnh ca cc tm khc c xc nh i
vi tm th nht.
Th d: glucoz trong thin nhin c cng thc:
C H O
H O H
H O H
H O H
H O H
C H 2O H
D (+) glucoz
 Theo qui c dng cho hp cht ng, cu hnh chung ca
mt phn t c xc nh bi cu hnh ca nguyn t Carbon bt
i xng mang ch s cao nht vi gliceraldehid (Carbon s 5
trong glucoz).
i vi ( - Aminoacid hp cht mu l L (-) Serin
COOH
H2N H
CH OH
2
Cu hnh ca cc ( - Aminoacid c nhiu nguyn t Carbon
bt i xng c xc nh bi Carbon bt i xng c ch s
thp nht (nguyn t Carbon ( i vi nhm COOH).
COOH CHO
H 2N H HO H
H OH H OH
CH 3 CH 2OH
L (-) Treonin D (-) Treonin
So snh trt t: lin kt ca Treonin v Treoz c s ging
nhau, Treoz c cu hnh D theo qui c hp cht ng, cu hnh
L theo qui c hp cht aminoacid.
S kin ny a n mt s nhm ln quan trng trong vic
xc nh cu hnh cc hp cht khc ng v ( - aminoacid.
gii quyt vn ny, ngi ta dng ch g (gliceraldehid)
biu th qui c ng, v ch s (Serin) biu th qui c
aminoacid.
COOH Acid Ds (+) tartric
H OH Acid Lg (+) tartric
HO H
COOH
1.5.2. Danh php R,S

D (+) gliceraldehid v D (-) gliceraldehid c cu hnh ging

ht nhau nhng quay mt phng nh sng phn cc theo hai chiu
ngc nhau. Nh vy, khng c mt h thc no r rt gia cu
hnh ca mt hp cht v du chiu quay ca n. Mt khc, du
chiu quay ca mt vi hp cht thay i theo nhit , nng ,
dung mi, tnh acid ca dung dch hay mui trung ha.
 Mt danh php c h thng biu th cu hnh l cn thit.
H thng Cahn Ingold Prelog (1956) dng ch: R (rictus: phi)
v S (sinister: tri) xc nh cu hnh ca cc nguyn t bt i
xng C*abcd.
- Xt th t u tin ca cc nhm (theo qui tc th t u
tin) a > b > c > d.
- Nhn cch sp xp t din cc nhm a,b, c t pha xa nht
i vi nhm u tin thp nht d:
o Nu th t a, b, c theo chiu kim ng h th cu hnh
ca C* l R.
o Nu th t a, b, c ngc chiu kim ng h th cu
hnh ca C* l S

a a

d
c d c
b
Cu hnh R Cu hnh bS

1.5.3. Danh php E,Z

i vi cc anken mang cc nhm th khc nhau
a c

b d
Xt theo qui tc th t u tin: a>b; c>d
- E khi a, c v tr trans i vi nhau
- Z khi a, c v tr cis i vi nhau
Qui tc th t u tin
1. Cc nhm u tin c sp xp theo th t gim dn s
in tch ht nhn nguyn t ca nguyn t lin kt trc tip vi
C*
Th d -I > -Br > -Cl > -F
-SO3H > -OH > -NH2 > -CH3
2. Nu hai nguyn t gn trn C* ging nhau th xt
nguyn t lin kt trc tip vi nguyn t . Nu vn khng
chn c u tin th xt tip nguyn t th ba
Th d: -CR3 > -CHR2 > -CH2R > -CH3
 -NR2 > -NHR > -NH2
3. Mt nguyn t lin kt i hay ba tng ng vi hai
ni n hoc ba ni n vi nguyn t (ch c mt lin kt
tht, lin kt cn li gi nh c u tin thp hn).
Th d: -CH=CH- tng ng vi CH
C
-CHO tng ng vi O
C O
N
-C(N tng ng vi H
C N

4. ng v c khi lng ln hn c sp xp trc:

N

T > D > H
5. Cu hnh cis u tin hn trans; R u tin hn S
Th d: COOH CH OH 2

H OH H3C OH
CH3 CH2Br
(R) (S)
H CH 2-CH 3 F CH 2B r

H 3C CH 3 H 3C CH 2O H
(E) (Z)

Trong cng thc Fischer, xc nh cu hnh (R,S) ta c

th:
- i v tr ca hai nhm gn trn mt nguyn t C* dn
n dng i quang.
- V s trao i ln th hai hon li dng u. Sau khi i
lin tip hai ln cc nhm th ti mt nguyn t C* sao
cho nhm c u tin thp nht xung di, ri xt chiu
quay ca ba nhm cn li.

COOH COOH

H 3NH
2
H 2N CH 3 (R)
CH H
COOH H

H OH HO COOH (R)
(S)
H OH HO COOH

COOH H
 Chng 2: NG PHN QUANG HC
2. 1
2.1. nh sng phn cc v tnh cht ca n
2.2. Nhng cht quang hot
2.3. Phn cc k
2.4. Hp cht quang hot c hai hay nhiu Carbon bt i khc
nhau
2.5. Hp cht quang hot c hai hay nhiu Carbon bt i ging
nhau
2.6. Hp cht quang hot khng c Carbon bt i
2.6.1. Tnh bt i xng ca phn t
Trung tm khng trng vt nh
Tnh quang hot do c trc khng trng vt nh
Tnh quang hot do c mt phng khng trng vt nh
2.6.2. Tnh c th lp th ca cc qu trnh ha sinh
2.7. Bin th RACEMIC (dng tiu trin)
2.7.1. Bn cht ca bin th Racemic
2.7.2. S to thnh bin th Racemic
2.7.2.1. Phng php trn ln
2.7.2.2. Phng php tng hp
2.7.2.3. Phng php Racemic ha
2.7.3. Tnh cht ca bin th Racemic
2.7.3.1. Hn hp Racemic
2.7.3.2. Hp cht Racemic
2.7.3.3. Dung dch Racemic rn
2.7.4. S tch ring bin th Racemic thnh cc i quang
2.7.4.1. Phng php nht ring v kt tinh t pht
2.7.4.2. Phng php ha hc
2.7.4.3. Phng php to phc phn t
2.7.4.4. Phng php sc k
2.1. NH SNG PHN CC V TNH CHT
Theo thuyt in t ca nh sng th nh sng t nhin (nh
sng thng) gm nhiu sng in t, c vect in hng theo
tt c cc hng trong khng gian v vung gc vi phng
truyn sng.

(4

(2)

(3)

(1)

Hnh 1 S dao ng ca nh sng thng v nh

sng phn cc
(1) nh sng n sc (2) Lng knh Nicol
(3) nh sng phn cc (4) Mt phng phn cc
Nu cho tia nh sng t nhin qua knh lc mu to nh
sng n sc (c di sng ging nhau, cng dao ng trong
nhng mt phng thng gc vi phng truyn sng). Cho chm
tia n sc i qua lng knh Nicol v do s b tr nht nh ca
knh ny th ch c tia sng phn cc phng i qua, tia sng ny
ch dao ng trong mt mt phng thng gc vi phng truyn
gi l nh sng phn cc phng.
2.2. CHT QUANG HOT
Nm 1813, nh vt l hc ngi Php Biot khi nghin cu s
tng tc ca nh sng phn cc vi cht pht hin trong thin
nhin tn ti hai dng tinh th thch anh: mt dng lm quay mt
phng ca nh sng phn cc phng sang phi v dng kia lm
quay sang tri. Tng t, mt s hp cht khc: HgS, NaCl,
ZnSO4 cng c c tnh trn.
n nm 1815, Biot li pht hin c rng mt s cht hu
c: ng, du thng, campho, acid tartric cng lm quay mt
phng dao ng ca nh sng phn cc phng v khi trong dung
dch hay trng thi lng chng vn gi c tnh ny.
Do , tnh quang hot khng phi do cu trc tinh th m do
cu trc ca nhng phn t ring bit. Nh vy, tnh cht lm
quay mt phng ca nh sng phn cc c gi l tnh quang
hot v cht tng ng c gi l cht quang hot.
2.3. PHN CC K
Phn cc k l dng c dng o quay cc ca cc cht
quang hot.
Phn cc k gm cc b phn chnh sau:
- Lng knh Nicol c nh dng lm knh phn
cc chuyn nh sng n sc chiu vo n thnh nh sng
phn cc.
- Lng knh Nicol th hai dng lm knh phn
tch, lng knh ny quay c, gc quay c th tnh theo
thang chia .

(2) (3) (8)

(5) (7)
(4)
(6)
(1)

(1) Ngun sng (5) Mt phng b quay

(2) Lng knh Nicol (6) Thang chia
(3) nh sng phn cc (7) Lng knh Nicol phn tch
(4) ng ng cht kho st (8) Th knh
Lng knh Nicol phn tch phi c b tr sao cho khi n v
tr s khng th cc trc ca nhng tinh th ca hai lng knh song
song nhau. Khi , nh sng phn cc c sinh ra bi lng knh
th nht d dng i qua lng knh th hai. Nh vy knh phn tch
dng xc nh xem mt phng phn cc b quay i mt gc bao
nhiu di nh hng ca cht kho st. t ng ng cht
lng tinh khit hoc dung dch cht kho st gia knh phn tch
v knh phn cc.
quay cc ring ca cht quang hot:
t
[] = 100
l.c
 ( : gc quay o c trn my (tnh bng )
t : nhit khi o (0C)
( : di sng ca nh sng s dng
ca Hg ( = 546 nm
ca Na ( = 589 nm
l : chiu di ca ng ng cht kho st (dm)
c : s gam cht c trong 100 ml dung dch
i vi cht lng tinh khit:
t
[] =
l.d

Thc t, ngi ta ha tan a gam cht vo 1 bnh nh dung tch

V ml:
t
[] = .V
l.a
Gc quay ca cht quang hot ph thuc vo:
- di sng ca nh sng phn cc (()
- Nhit khi o (t0C)
- Chiu di ca dng c ng cht (l)
- Dung mi v nng ca dung dch (i vi dung
dch)
Th d: i vi dung dch 20% trong nc ca acid (+)
tartric, o 200C, di sng D th quay cc ring:
20
[] = +11,98o
D
quay cc ring ca mt cht l mt hng s, c trng cho
hp cht quang hot, tng t nh nhit si, nhit nng
chy c dng c trng cho hp cht hu c.
quay cc phn t gam

t
[M] = [] . M
t

100
M : phn t gam ca cht quang hot
2.4. HP CHT QUANG HOT C HAI HAY NHIU
CARBON BT I KHC NHAU
Rt nhiu hp cht t nhin nh: glucid, protid, steroid,
ancaloid trong phn t c nhiu nguyn t C*, cho nn vic
nghin cu v mt ha hc lp th nhng hp cht loi ny l rt
quan trng.
Hp cht c n nguyn t C* bt i khc nhau th c:
N = 2n ng phn quang hc
Th d 1: n = 1 OH
Acid lactic H C CH COOH c hai ng phn
quang hc lp thnh mt cp i quang :
3

COOH COOH

H OH HO H

CH3 CH3
Th d 2: n = 2 cAcid
bn(R)
ng phn quang hc Lactic
Lactic Acid (S)
Glucid tetroz CH 2 OH
*
CHOH
*
CHOH CHO

CHO CHO CHO CHO

H OH HO H H OH HO H
HO H H OH H OH HO H
CH2 OH CH2 OH CH2 OH CH2 OH

(A1) (A2) (A3) (A4)

(2R,3R) (2S,3S) (2R,3S) (2S,3R)
(A1) v (A2); (A3) v (A4) : cp i quang
(A1) v (A3); (A1) v (A4) cp bn i quang
(A2) v (A3); (A2) v (A4) (ng phn lp th dia)
 ng phn eritro treo
CHO CHO
CHO CHO
H OH HO H
HO H H OH
H OH HO H
H OH HO H
CH2OH CH2OH
CH2OH CH2OH
(A1) (A2) (A3) (A4)

(A1) ; (A2) : ng phn Eritro

(A3) ; (A4) : ng phn Treo

ng phn eritro: khi quay quanh trc lin kt C2*-C3*

sao cho cc cp nhm (hay nguyn t) ging nhau n v tr che
khut tng i mt.
ng phn treo: cng quay tng t trn nhng khng
th em cc cp nhm ging nhau n v tr che khut vi nhau
cng mt lc c.
ng phn lp th bn i quang cn gi l ng phn
lp th khng i quang hay ng phn lp th dia.
Hin nay, khi nim ng phn lp th dia c m rng hn
v bao gm hai hin tng ha hc lp th ring r nhau:
- ng phn lp th (-dia: l ng phn lp th khng i
quang do c mt t hai nguyn t C* bt i tr ln; cng nh
cc ng phn cis trans cc dn xut hai ln th ca vng
no.
- ng phn lp th (-dia: thuc loi ng phn cistrans
ca hp cht c lin kt i trong phn t.
Trong mi trng i xng, tnh cht ca cc ng phn i
quang l ging nhau, cn ca cc ng phn lp th khng i
quang (bn i quang) th li khc nhau rt nhiu v tnh cht vt
l v ha hc. Trong phn t cc cht i quang, khong cch
gia cc nguyn t (hay nhm nguyn t) l ging nhau, do
kh nng phn ng ca chng i vi mt tc nhn i xng l
hon ton ging nhau. Nhng khi tc dng vi tc nhn bt i
xng, cc i quang li c kh nng phn ng khc nhau (th d
trong phn ng ha sinh thng ch c mt trong hai i quang
tham gia phn ng vi enzim). iu ny gii thch s khc
nhau v mi, v v hot tnh dc l ca cc i quang. Cn cc
ng phn bt i quang, khong cch gia cc nguyn t (hay
nhm nguyn t) khc nhau nn c s khc nhau v nhit si,
nhit nng chy, tnh tan v cc c trng v ph Nng
lng t do ca cc ng phn bn i quang khng ging nhau
nn chng c kh nng phn ng khc nhau.
2.5. HP CHT QUANG HOT C HAI HAY NHIU
CARBON BT I GING NHAU
* Hp cht c n C* ging nhau

So ong phan
Dng quang hot Dng meso
So nguyen t C*

n = s chn 2n-1 2(n-2)/2

n = s l 2n-1 2(n-1)/2 2(n-1)/2

Th d: Acid tartric

*
* CH COOH
HOOC CH
OH OH
n = 2 c hai dng quang hot v mt dng Meso
COOH COOH COOH
H OH H OH HO H
H OH HO H H OH
COOH COOH COOH
Acid Meso-tartric Acid () tatric
* Hn hp ng phn t acid (+) tartric v acid (-) tartric l mt
dng khng quang hot (bin th racemic; hn hp tiu trin) l
do b tr ca hai phn t i quang.
* ng phn acid meso-tartric khng quang hot do s b tr
ni phn t, khng th dng phng php tch ring tch n
thnh hai i quang c.
 Th d 2: Acid 2,3,4 - Trihidroxiglutaric (n = 3C*) c hai dng
quang hot v hai dng meso
C OOH COOH COOH C OOH
H OH H OH H OH HO H
Mpx H OH HO H H OH HO H
H OH H OH HO H H OH
C OOH COOH COOH C OOH
(I) (II) (III) (IV)
2 dang meso 2 dang quang hoat

S khc nhau v tnh cht vt l gia hai dng meso, dng

meso ( I ) d dng to thnh dng lacton (c nhit nng chy
khng r) cn dng meso (II) li b nng chy (Tnc = 1520C) m
khng c s thay i v mt ha hc.
Hai dng i quang (III), (IV) u c nhit nng chy bng
1280C.
Ch : C3* ch l bt i trong hp cht meso (I), (II) nn
gi l C3* bt i xng gi nh.
C3 khng bt i trong hp cht (III), (IV) v cu hnh
ca C2, C4 hon ton ging nhau.
2.6. HP CHT QUANG HOT KHNG C CARBON
BT I
2.6.1. Tnh bt i xng ca phn t
Khi nim tnh quang hot t lu gn lin vi s bt i
xng ca phn t. Vy thut ng s khng trng vt-nh
(chirality) c ngha l g?
Th d: xt hai cht quang hot l acid lactic (1) v acid
tartric (2)
COOH
COOH
H OH
H OH
HO H
CH 3 COOH
(1) (2)

(1) l mt phn t bt i xng

(2) c trc i xng bc hai i qua tm ca phn t
(trc ny vung gc vi mt phng v) v do phn t acid
tartric khng th xem l bt i xng, m l khng trng vt-
nh
Do , iu kin xut hin ng phn quang hc l s
bt i xng; song khng phi l iu kin cn, iu kin cn v
l s khng trng vt-nh.
2.6.1.1. Trung tm khng trng vt nh
Trung tm khng trng vt nh c th l C*, Si*, P*, S*
(xem cp electron t do l nhm th th t).
Th d: Ph
CO OH
H Si * CH 3
H * OH

Acid CH
lactic
3
Metyl -naphtyl phenylsilan
(1) (2)

H3 C
S
O
Ph
CH3
P .
OC H 3

CH3

Metyl paratolylsulfoxit Orto-Anisylmetylphenylphosphin

(3) (4)

Trong hp cht (3), (4) cc nhm th xung quanh trung tm

vt khng trng vt-nh c phn b theo hnh thp, tuy nhin
nhng cu trc ny c th dn n t din, nu xem cp electron
t do l nhm th th t.
2.6.1.2. Tnh quang hot do c trc khng trng vt nh
a ( b v c ( d
(a c th ging c v
b c th ging d)

Nu trong phn t bn nhm th a, b, c v d tng i mt

phn b trn mt trc v khng nm trong cng mt mt phng,
nh c biu din di dng mt t din b ko cng th xut
hin tnh quang hot. Trc ca phn t nh vy gi l trc
khng trng vt-nh.
* Trc khng trng vt-nh tn ti cc h:
 a) Cumulen: (s chn ni i nh alen)

a c
a c
C C C
C C C
b Q) d
b d P)
(a ( b) v (c ( d) (P) ( (Q)
ALEN

b) Biphenyl: mang nhm th

ng phn khng gian do s cn quay t do xung quanh
lin kt n

COOH HOOC
O2N NO2

HOOC COOH
NO2 O2N
Acid 6,6- dinitro-biphenyl- 2,2-dicarboxilic
Trong phn t biphenyl, hai nhn benzen c th quay t do
quanh trc Carbon - Carbon trung tm; nhng khi phn t c
mang nhm th c kch thc ln ti cc v tr (2, 6, 2, 6) th s
quay b cn tr, hai nhn benzen khng cn v tr cng phng do
tr ngi lp th pht sinh t nhng nhm th c kch thc ln
cc v tr orto, v th h phn t tr nn cng chc.
Thc t, ngi ta tch hai c hai dng i quang ca
acid trn.
* iu kin ch yu biphenyl th c tnh quang hot l cc
nhm th phi c kch thc kh ln cn tr s quay t do v
mi nhn benzen phi c th khng i xng. Ngoi ra, hai
nhm th orto khng cn phi gn trn hai nhn khc nhau.
Th d: 3,3- diamino - 2, 6 dibromo - 4, 4 - dimetyl
biphenyl cng c tch hai.
Br
NH2
H3 C C H3

H2N Br
 c) Ankiliden ciclan:
Nu thay th mt ni i trong alen bng mt vng, v mt
hnh hc ca phn t khng thay i. Cc ankiliden mang nhng
nhm th thch hp c th c ng phn quang hc.
Th d: vi Acid 4 - metylciclohixiliden acetic c tch
hai thnh hai dng i quang :

H COOH HOOC H

H3 C H H CH3

Mt s hp cht c lin kt i C=N nh oxim, semi carbazon,

phenyl hidrazon cng c tch hai, nhng cc ng phn
quang hc ny khng bn v b racemic ha nhanh chng.

HOOC
N .
Dn xut ca 4 - carboxiciclohexilidenimin
vi R: OH
NH C NH2
O
N C Ph
Ph O
d) Spiran: s thay th hai lin kt i trong Alen bng hai
vng dn n mt h vng c chung mt cnh (hai vng i
nh): Spiran. Nu hai vng mang nhng nhm th trn hai
nguyn t carbon ti hai u ca h nm trong hai mt phng
thng gc vi nhau th chng c ng phn quang hc.
Th d: Acid spiro [3,3] heptan - 2, 6 - dicarboxilic v 2, 6 -
diamino spiro [3,3] heptan

H H H H
R R R R
 R = _ COOH hay _ NH2
2.6.1.3. Tnh quang hot do c mt phng khng trng
vt nh
Mt phng khng trng vt-nh c cc hp cht
ansa.
Th d: (A) * (R) - 14 Bromo - 1,12 - dioxa [12]
paraciclofan
(B) * (E) ciclo octen
u c mt phng khng trng vt-nh nm trong mt phng giy
O
Br
H H
(CH2)8
H H

O (R) (S)
(A) (B)
2.6.2. Tnh c th lp th ca cc qu trnh ha sinh
Cc i quang khng khc nhau v l tnh v ha tnh
thng thng nhng nhiu khi li khc nhau r rt v tc
dng sinh l.
Th d: (-) Nicotin c trong thuc l c hi hn (+) Nicotin
vi ln hoc cc i quang ca aminoacid c v khc nhau nh L-
asparagin v L-tritophan khng c mi v, cn L-leuxin v L-
Tyroxin c v ng trong khi cc ng phn D - tng hp c v
ngt.
Acid L-glutamic thin nhin c v ngt, mui Natri ca acid
L-glutamic l bt ngt (m chnh) dng lm gia v thc phm; cn
acid D-glutamic khng c c tnh y.
Do c tc dng sinh l khc nhau, cc i quang ca nhiu
hp cht c dng lm thuc cha bnh.
Th d: R (-) epinephrin thin nhin, mt hormon chnh ca
tuyn thng thn. Do khi cho ngi bnh ung epinephrin
tng hp, th ch R (-) epinephrin c hiu ng kch thch ging
nh hormon thin nhin, cn S (+) epinephrin khng c hiu ng
kch thch m li gy c nh.
Tnh c th lp th cng biu hin r cc hp cht bo v
thc vt. Th d trong tm ng phn ca C6H6Cl6 (6,6,6) ch c
ng phn ( c hot tnh tr su mnh.
Cl
*
Cl CH
Cl Cl CCl3
Cl X X
(C) (D)
Cl
ng phn ( _ ca 6,6,6 (D.D.T)
 Hoc khi nghin cu mt lot cc ha cht tr su v kh
nng quay t do trong phn t kiu D.D.T, ngi ta nhn thy nu
cc hp cht kiu (D), cc nhm th X v tr orto lm gim tnh
tr su.
* Acid cis-cinamic kch thch mnh s tng trng ca cy,
trong khi acid trans-cinamic li khng c hot tnh y.
Nguyn nhn ca nhng khc nhau v hot tnh sinh l l s
khc nhau v cu trc khng gian (khc nhau v cu hnh) v c
th gii thch nh sau:
i) Cc i quang c th c phn b khc nhau
trong m t bo ca c th sng.
2i) Cc i quang c th c i lc khc nhau i vi c
quan th cm (Receptor). S khc nhau ny l do vi nhng i
quang no chng c kh nng tng tc c ch khng do tnh
cht bt i xng.
3i) Cc enzim trong c th sng u bt i xng nn
chng c kh nng phn bit cc i quang, thng thng ch mt
trong hai i quang l ph hp vi tm enzim.
2.7. BIN TH RACEMIC (dng tiu trin)
2.7.1. Bn cht ca bin th racemic
Bin th racemic (dng tiu trin) l mt hn hp
ng phn t (equimolar) ca hai ng phn i quang ca
mt cht c phn t bt i xng. Do tr s quay cc ca
tp hp ny bng khng. Thng c k hiu l () hay
D,L.
2.7.2. S to thnh bin th Racemic
2.7.2.1. Phng php trn ln
Phng php n gin nht iu ch cc bin th racemic
l trn k s lng ng phn t ca hai dng ng phn hu trin
(quay phi) v t trin (quay tri): qu trnh ny gn lin vi s
thay i Entropi bi v bin th racemic trng thi hn lon hn
cc i quang ring bit.
Entropi ca s trn ln: (S = - Rx1Lnx1 = Rx2Lnx2 (bin th
racemic: x1 = x2 = 1/2) ( (S = 5,8 ( J/mol. S thay i nng
lng t do khi to thnh bin th racemic t cc i quang s l
(F = - T(S = -1,755 KJ/mol nhit phng.
2.7.2.2. Phng php tng hp
Bng phng php tng hp cc phn t bt i xng, ngi
ta nhn c bin th racemic nu i t cc phn t i xng ny
t bin th racemic m khng dng tc nhn quang hot, xc tc
hay mt tng tc vt l bt i xng no.
COOH COOH COOH
P
2H C H + 2 Br2 Br C H + H C Br + 2 HBr
CH3 CH3 (+) CH3 (-)

Acid propionic Acid () -Brompropionic

O OH NC H OH
H H H CN H
+ HCN H +
H H H
H H H
* Phn ng cng HCN v acetaldehid (CH3-CHO) cho hn
hp hai i quang vi s lng bng nhau.
2.7.2.3. Phng php racemic ha
Php bin i mt dng i quang tinh khit ca mt cht
quang hot to thnh hn hp racemic tng ng gi l s
racemic ha. S racemic ha c th xy ra di nh hng ca
nhit, nh sng hay ha cht.

2.7.3. Tnh cht ca cc bin th racemic

Thng thng trng thi kh, lng hay dung dch,
bin th racemic l hn hp (gn nh l tng) ca nhng
lng bng nhau ca cc phn t i quang c tnh cht vt
l (nhit si, khi lng ring, chit sut, ph hng ngoi)
ging tnh cht vt l ca cc dng i quang tinh khit.
i vi trng thi rn, tnh cht ca cc (dng tiu trin) bin
th racemic v cc i quang khc xa nhau do lc gia cc tinh
th rt c th v rt nhy k c khi thay i mt cht v mt hnh
hc. Kt qu l trng thi rn ngi ta thng gp s khc bit
v tnh cht l tng v c kh nng trong ba trng hp sau:
2.7.3.1. Hn hp racemic (racemic mixture)
C trng hp l trong tinh th, mt i quang c i lc i
vi nhng phn t cng loi i quang ln hn l i vi
nhng phn t ca i quang kia. Trong trng hp ny, nu s
to thnh tinh th bt u t phn t ca dng (+) th ch c nhng
phn t (+) s tham gia vo s ln ln v sau ca tinh th. Do
tinh th v m s tng ng vi dng (+) [cng tng t nh th
i vi dng (-)]. Nh vy bin th racemic l hn hp cc tinh
th ca c hai dng ny.
Tonng chy tan

0% 50%(+) 100%(+) 0% 50%(+) 100%(+)

100%(-) 50%(-) 0% 100%(-) 50%(-) 0%(-)
( Gin nhit nng chy v tnh tan ca hn hp racemic.)

Hn hp racemic l mt hn hp cc tinh th dng (+) v

dng (-), tnh cht ca n ging tnh cht ca cc i quang tinh
khit. iu th hin r nh chp tia X ca dng bt v ph
hng ngoi trng thi rn.
Tuy nhin, nhit nng chy ca hn hp racemic thp hn
nhit nng chy ca cc i quang tinh khit. Cn tan ca
hn hp racemic th li cao hn tan ca cc i quang.
2.7.3.2. Hp cht racemic (racemic compound)
Nhng phn t ca mt i quang ny thng c i lc i vi phn t
ca i quang kia ln hn l i vi nhng phn t cng loi.
Trong trng hp ny cc phn t i quang ngc du c kt
hp i thnh t bo c bn ca tinh th. Nh vy t bo s cha
mt lng bng nhau ca cc phn t (+) v (-). Hp cht loi ny
gi l hp cht racemic (thng tn ti trng thi rn). Cc
hp cht racemic l nhng hp cht thc chng khc bit vi cc
i quang v tnh cht vt l nh khc nhau v ph hng ngoi
trng thi rn, khc nhau v nh chp tia X dng bt, khc v
nhit nng chy v tan.
Tonng chy tan

0% 50%(+) 100%(+) 0% 50%(+) 100%(+)

100%(-) 50%(-) 0% 100%(-) 50%(-) 0%(-)
(Gin Tonng chy v tan ca hp cht racemic)

2.7.3.3. Dung dch racemic rn (racemic solid solution)

Cc bin th racemic (i khi trng thi rn) c
c tnh cht gn nh l tng, l trng hp ch c s
khc nhau rt nh v i lc gia cc phn t c cng v khc
nhau v cu hnh. Trong trng hp ny, s phn b ca cc
phn t trng thi rn sp xp mt cch ngu nhin to
thnh dung dch racemic rn.
Cc tnh cht vt l ca dung dch racemic rn (nhit nng
chy, ha tan) ging tnh cht ca cc dng i quang.

Tonng chy

0% 50%(+) 100%(+)
100%(-) 50%(-) 0%
( Gin Tonng chy ca dung dch racemic rn)

C th phn bit: hp cht racemic, hn hp racemic hay dung

dch racemic rn bng cch so snh ph hng ngoi ca n trng
thi rn vi ph hng ngoi ca cc i quang. Ch c quang ph
ca hp cht racemic l khc vi quang ph ca i quang.
Cng c th phn bit ba dng racemic bng cch dng gin
nhit nng chy, tan hay dng phng php xc nh t
bo c bn nh nhiu x tia X (t bo tinh th c bn ca hp cht
racemic c cha nhng lng bng nhau ca cc phn t ca hai
dng i quang; cn ca hn hp racemic hay dung dch racemic
rn ch gm cc phn t ca mt i quang m thi)
2.7.4. S tch ring bin th racemic thnh cc i quang
2.7.4.1. Phng php nht ring cc tinh th bt i xng
v kt tinh t pht
i vi hn hp racemic thng tn ti cc kiu tinh th ring
bit ca dng (+) v dng (-) i xng nhau, nu kch thc ca
nhng tinh th ny ln v nhn bit c bng mt thng th
ta c th dng kp nht ring cc phn t c cu hnh khc nhau.
Nm 1948, Pasteur l ngi u tin tch ring c tinh th D
- v L - Natri amoni tartrat; chng kt tinh ring bit nhau t mt
dung dch ca hn hp racemic ca hai cht i quang (t ( 270C).
a s cc bin th racemic u kt tinh thnh hp cht
racemic nn ch c mt s t hp cht quang hot c tch ring
bng phng php kt tinh t pht.
Gn y , ngi ta cho tp cht c ch vo dung
dch kt tinh ngn cn s ln ln ca mt trong cc thnh
phn hn hp racemic. Bng phng php ny, ngi ta
nhn c cc aminoacid c tinh khit quang hot n
90%, v n tinh th hidrobenzoin nng 3 gam c tinh
khit quang hot gn 100%.
2.7.4.2. Phng php ha hc da trn s to thnh cc
ng phn lp th khng i quang (bn i quang). Da trn s
sau:
D1D2
D1L1 + D2
L1D2
Khi tc dng ln bin th racemic D1L1 bng mt tc nhn
bt i xng D2 thu c hai cht mi D1D2 v L1D2 l hai
ng phn bn i quang. Cc ng phn bn i quang khc
nhau v: tan, p sut hi, h s hp th nn c tch ring
nhau ra.
S tch ring bin th racemic qua s to thnh cc ng phn
lp th bn i quang gm ba giai on:
To thnh hai ng phn bn i quang
 Tch ring hai ng phn da vo tnh cht khc nhau.
Ph v phn t ng phn lp th bn i quang tinh
khit ti to li dng i quang ban u v tc nhn
bt i xng.
a) Tch ring acid
Theo s
R-COOH (+) R1 - + R1 - + R1
+ N(-)
R2 RCOO NH R2 + RCOO NH R2
R-COOH (-) R3 R3
R3
(hp chat Racemic) (+) (-) (-) (-)

R1
muoi (+) (-) + HCl R-COOH (+) + R2 N HCl
ket tinh R3 (-)
phan oan R1
muoi (-) (-) + HCl R-COOH (-) + R2 NH Cl
R3 (-)

tch ring cc acid racemic thnh i quang, ta

dng cc ancaloit sn c trong thin nhin nh: Bruxin,
strichnin, ephedrin, quinin, cinchonin, morphin hoc cc baz
tng hp nh ( - phenyl etylamin; metylamin.
b) Tch ring amin
tch ring cc amin racemic ta dng tc nhn bt i xng
c tnh acid: acid tartric, acid malic, acid glutamic (acid malic:
HOOC - CH2 - C*HOH - COOH)
Th d: tch ri hp cht racemic ( - phenyletylamin ta
dng acid (+) tartric lm tc nhn bt i theo s :
Ph Ph Tartrat (+)(+A)
CH OH
H NH2 + H2N H +Acid (+) tartric 3

* *
(HOOC-CHOH-CHOH-COOH) Tartrat (+) (-A)
CH3 CH3
(+)A (-)A
Mui tartrat (+)(-A) tan trong CH3OH km hn mui tartrat
(+)(+A) do ng phn (+)(-A) kt tinh ngay di dng tinh
khit, nht l khi a vo dung dch vi tinh th mui (+)(-A) c
sn lm mm kt tinh. c mui hon ton tinh khit
thng phi kt tinh li mt ln trong H2O ri ph v mui ny
bng dung dch kim v tch ring (-) (-phenyletylamin ra khi
dung dch Natri tartrat. Bi v acid (+) tartric l mt tc nhn r
tin nn vic ti sinh tc nhn bt i xng trong trng hp ny
l khng cn thit.
c) Tch ring ancol:
Cc ancol racemic thng c tch ring thnh i quang
bng hai phng php sau:
- Este ha ancol racemic bng acid quang hot ri tch
ring cc este bng phng php kt tinh phn on.
- Este ha ancol bng diacid chuyn thnh bn este c
kh nng to mui vi cc baz quang hot.
Th d: tch ring hai ng phn (+), (-) ca ru Sec-
butylic ta tin hnh theo s sau:
O
OH
COOH
Piridin C 2 H5
H3 C C* C 2H5 + O
H C O C* H
Ru (+)(-) O
O CH3
_
+ Bruxin (*) COO
C 2 H5
Tach 2 chat H.Brunxin
C O *CH
(+) va (-)
CH3
(+) O a tinh che
COOH
+HCl C 2H5 + Bruxin.HCl
C O CH
CH3
O CH3
CH3 CH2OH
COONa hay
* H + + HO * H
HO +NaOH +LiAlH4
COONa dd CH2 OH
C 2H5 C 2H 5
Cng thc ca Bruxin
N
CH3O

CH3O N

O O
2.7.4.3. Phng php to phc phn t
Khi ch ha bin th racemic bng tc nhn bt i
m to thnh c phc tinh th th c th thu c hai phc
ng phn bn i quang khc nhau v ha tan v s c
mt ng phn kt ta trc. Sau ph v phc ny bng
cch un nng, ha tan, bng sc k hay ch ha ha hc ta
thu c mt trong hai i quang ban u.
2.7.4.4. Phng php sc k
tch ring bin th racemic () X thnh hai cht i quang,
ta cho () X qua ct nhi cht hp th bt i xng (vit tt l (-)
Chp), cc i quang to phc yu vi cht nhi bt i xng (nh
lin kt hidro) v ta c cc phc bn i quang (-) Chp (-) X v ()
Chp (+) X. Nhng phc ny c tnh cht vt l khc nhau, khc
nhau v nng lng lin kt, v hng s cn bng to phc, do
chng c bn khc nhau, ngha l mt cht i quang (t bn
vng) i qua ct nhi cht hp th bt i xng nhanh hn i
quang kia v nh vy hai i quang c tch ring.
Hin nay, phng php sc k c vai tr quan trng trong vic
iu ch hp cht quang hot v bao gm c ba loi: sc k lng,
sc k lp mng v sc k lng cao p.
Chng 3: NG PHN HNH HC
3.1. Bn cht ca ng phn hnh hc
3.2. Hp cht c ni i Carbon - Carbon
3.2.1. Danh php
3.2.2. Hp cht c mt ni i v nhiu ni i
3.2.3. Tnh cht vt l ca ng phn hnh hc
3.2.3.1. Momen lng cc
3.2.3.2. Nhit : nng chy, si, t khi v chit sut
3.2.3.3. phn ly ca acid
3.2.3.4. Ph: t ngoi, hng ngoi, cng hng t ht
nhn
3.2.4. bn tng i v s chuyn ha tng h gia cc
ng phn hnh hc
3.3. Hp cht c ni i C=N v N=N
3.4. Hp cht vng no

C
3.1. BN CHT CA NG PHN HNH HC

iu kin a ( b
a a
iu kin a ( b
C C (Q) cha lin kt (
b b (P) (Q)
P)
Q)

Theo cch gii thch hin nay th nguyn t Carbon mang

ni i trng thi lai ha sp2 ngha l ch c hai trong s ba
electron p c lai ha vi electron s to thnh ba orbital lai
ha sp2. Ba orbital ny nm trn cng mt mt phng, c trc
i xng hp nhau nhng gc 1200. Hai nguyn t Carbon
dng hai orbital sp2 xen ph ln nhau to lin kt ( (C-C) v
dng cc orbital sp2 cn li xen ph vi cc orbital khc to
cc lin kt ( (C-a; C-b) nm lin kt ( nm trong cng mt
phng. Mi nguyn t Carbon cn li mt electron orbital 2p,
chng xen ph bn vi nhau to lin kt ( vung gc vi mt
phng cha cc lin kt (. Do s hnh thnh lin kt ( trit
tiu s quay t do v dn n xut hin ng phn cis - trans.
Cu hnh cis - trans (a ( b)
a a a b

b cis b b trans a
(X) (Y)
Khong cch gia cc nguyn t trong phn t (X), (Y) khc
nhau rt ln, do v phng din hnh hc th (X), (Y) c hnh dng,
kch thc phn t khc nhau nn i lng Entalpi t do to thnh
cng khc nhau, cc hng s vt l, cc c trng v ph v cui cng
l tnh cht ha hc cng khc nhau r rt.
3.2. HP CHT C NI I
3.2.1. Danh php
- Nu hp cht mang mt ni i C=C, mang hai nhm hay ba
nhm th khc nhau, ta dng cu hnh:
CIS: ch hai nhm ging nhau ( hai nguyn t C) nm
cng mt pha i vi mt phng cha lin kt (
TRANS: ch hai nhm ging nhau nm hai pha i vi
mt phng cha lin kt (.
H 3C CH 3 H 3C H

H H H CH 3
cis but-2-en. trans but-2-en.

H 3C C 2H 5 H 3C H

H C 2H 5 C 2H 5
C 2H 5
trans-3-metylhex-3-en. cis-3-metylhex-3-en.
- Vi anken phc tp, cu hnh c chn l cu hnh ca
mch Carbon lin tc di nht xuyn qua lin kt i.
C H 3CH 2 C H 2CH 3 (mc d c hai nhm etyl nm
cng mt pha i vi mt
phng)
H 3C CH 2CH2CH 3
Trans-4-etyl-3-metylhept-3-en
- Nu anken mang bn nhm th khc nhau m khng chn
c mch chnh th dng danh php E-Z.
Th d:
H 3C Br 3H C Cl
C C C C
H C H Br
Z -1-Bromo-1-cloropropen
l E-1-Bromo-1-cloropropen

3.2.2. Hp cht c mt v nhiu ni i

Tng s ng phn hnh hc ca mt hp cht c n ni i
trong phn t l:
* Hp cht bt i xng N=2n
* Hp cht i xng
n = s chn N = 2n-1 + 2(n-2)/2
 n = s l N = 2n-1 + 2(n-1)/2

Th d 1: hepta-2,4-dien
CH3-CH=CH-CH=CH-C2H5 c bn ng phn hnh hc
H H CH3 H
C 2H 5 H
CH3 H
H H H C2H5
cis - 2 - cis - 4 trans - 2 - trans - 4

H H H3 C H
H C 2H 5
H3 C H
H C 2 H5 H H
cis - 2 - trans - 4 trans - 2 - cis - 4
Th d 2:
CH3-CH=CH-CH=CH-CH3 ch c ba ng phn hnh hc
H H C H3 H 3C H
H
H 3C H
H H H CH 3
cis - 2 - cis- 4. trans - 2 trans - 4 .
H3 C H
CH
H 3
H H
trans - 2 cis-4 ( hoac cis - 2 trans-4 )
Hp cht c ni i ly tch
Cumulen vi s chn ni i c ng phn quang hc.
Cumulen vi s l ni i c ng phn hnh hc.
a a
C C C C
b b
 Th d: Nm 1959, Kuhn c lp c hai ng phn 1,4-
di-m-nitrophenyl-1,4-diphenylbuta.trien
NO 2

C C C C

NO 2 2 NO O 2N
Cis Trans
3.2.3. Tnh cht vt l ca ng phn hnh hc
3.2.3.1. Momen lng cc
Hp cht kiu abC = Cab nu lin kt C-a c momen
lng cc ln, lin kt C-b khng c momen lng cc th ng
phn cis phi c momen lng cc rt ln, mt khc ng phn
trans c trung tm i xng nn momen lng cc tng bng
khng.
Th d: 1,2 dicloroeten
Cl Cl H Cl

Cl H
Hcis = 1,89 DH trans = 0
Nu nhm a- y electron, cn nhm b- rt
electron th momen lng cc ca phn t bng tng s momen
lng cc ca chng. Do ng phn trans c gi tr momen
lng cc ln hn ca ng phn cis.
H Cl H3 C Cl

H3 C H H H
trans = 1,97 D cis = 1,71 D
Khi tnh Momen lng cc ca nhng anken mang nhm
th phc tp s gp nhiu kh khn.
H H H COOC 2H5

C 2H5 OOC COOC 2H5 C 2H5 OOC H

cis = 2,54 D trans = 2,38 D
3.2.3.2. Tnh cht vt l
 Nhit nng chy: Nhit nng chy ca ng phn
trans thng ln hn ca ng phn cis (tr mt s
trng hp ngoi l), do ng phn trans c tnh i xng cao
hn ng phn cis nn mng tinh th sp xp cht hn.
Nhit si, t khi, chit sut l nhng hm nghch ca
th tch phn t cho nn ng phn no m mt trong ba
c tnh va ri c tr s ln th thng thng hai c tnh kia
cng c tr s ln.
Tosi (oC) d20 (g/ml) n20
Hp cht
Cis Trans Cis Trans Cis Trans
CHCl = CHCl 0,03 48,4 1,2835 1,2565 1,4486 1,4454
CH3 CH = CH - Cl 32,8 37,4 0,9350 0,9350 1,4055 1,4054
CH3 CH = CH - CN 108 122 0,8244 0,8239 1,4182 1,4216

C2H5OOC-CH=CH-COO C2H5 223 218 1,0520 1,0670 1,4411 4,4415

Tnh cht vt l ca mt s ng phn hnh hc

ha tan, thiu nhit, nhit hidrogen ha v hng s ion ha
ca cc ng phn trans thng thp hn ca ng phn cis.
Tonng chy
pKa Thiu nhit
Hp cht (oC)
Cis Trans Cis Trans Cis Trans
HOOC CH = CH - COOH 130 287 1,9 3 327 320
CH3 CH = CH - COOH 15,5 72 4,44 4,70 486 478
lng 125 _ _ 1769 1739
CH CH 68 133 3,96 4,44 1047 1040
CH CH COOH
Cc hng s vt l ca mt s ng phn hnh hc

3.2..3.3. phn ly ca acid

phn ly ca acid etylendicarboxilic ph thuc nhiu vo
cu hnh.
Acid maleic (cis) K1 = 1,3.10-2 K2 = 3,2.10-7
-3
Acid fumaric (trans) K1= 10 K2 = 3,2.10-5
Acid cis - crotonic pKa = 4,44
Acid trans - crotonic pKa = 4,70
3.2.3.4. Cc loi ph
Ph t ngoi (UV) (Ultraviolet Spectrum)
 Tia X Vin UV UV Kh kin Cn IR IR Vi sng
0,1nm 100nm 200 400nm 800nm 8 25
nm 0,4 0,8

Cc ng phn cis - trans ca nhng anken n gin (but-2-en)

hp th nhng di sng khc nhau di 200 nm trong vng t
ngoi, nhng khc nhau ny kh phc tp v nm trong vng m thc
nghim khng d g o c.
Nhng nhng khc nhau gia cc ng phn cis, trans trong
cc olefin kiu abC = Cbd th d dng quan st v y cc nhm
th a, d c th tham gia lin hp vi h olefin (a, d c th ging
nhau).
Trong nhiu trng hp, cc ng phn cis c cc i hp th
di sng ngn hn (() ng thi h s hp th (() ng
phn cis trong mi trng hp u nh hn nhiu so vi ng
phn trans. iu c th gii thch rng trong ng phn cis do
nh hng khng gian nn s lin hp trong phn t b vi phm,
cn cc ng phn trans s lin hp vn bnh thng.
TRANS CIS
Hp cht Cng thc
max max
Stilben Ph-CH=CH-Ph 295,5 29000 280 10500
-metylstilben Ph-C(CH3)=CH-Ph 270 20000 260 11900
1-phenylbutadien Ph-CH=CH-CH=CH2 280 28300 265 14000
Acid cinamic Ph-CH=CH-COOH 295 27000 280 13500
Ph t ngoi ca mt s ng phn t ngoi
Ph hng ngoi (IR) Infrared Spectrum
Cc ng phn hnh hc c ph hng ngoi khc nhau vng
1650 cm-1 (dao ng ha tr C=C) v cc vng 970,69cm-1 (dao
ng bin dng phng =C-H).
Mun cho dao ng phn t c th gy nn s hp th trong
vng hng ngoi th momen lng cc ca phn t phi thay i.
Hin nhin l s thay i nh vy khng xy ra khi c dao ng
ha tr C=C. Trong trans-1,2-dicloroetylen, v momen lng cc
ca phn t bng khng v vn gi nguyn gi tr trong sut
thi gian dao ng. Kt qu l trong ph hng ngoi ta khng
thy nhng tn s dao ng ha tr thuc v ni i ca trans-1,2-
dicloroeten, mt khc cis-1,2-dicloroeten li hp th mnh 1590
cm-1 trong ph hng ngoi.
 Nh ph hng ngoi c th phn bit c S-cis v S-trans
ca cc (, ( khng no. So vi hp cht S-trans th hp cht S-cis
c di mnh hn, ng vi dao ng ha tr ca lin kt C=C
(khong 1.625 cm-1), ca lin kt C=O (khong 1700 cm-1). Nh
vy t s cng ca cc di C=O v C=C i vi cc ng
phn S-cis vo khong 0,7 _ 2,5, cn i vi ng phn S-trans
vo khong 6 _ 9.
Ph cng hng t ht nhn (NMR)
(Nuclear Magnetic Resonance Spectrum)
Ph NMR cng c th c dng xc nh cu hnh ca
cc ng phn hnh hc anken dng aCH=CHb.
Proton trans-vinyl ghp vi nhau mnh hn proton cis-vinyl.
Do , hng s ghp JHH ca ng phn trans (11-18 Cps) cao
hn hng s ghp ca dng cis (6-14 Cps) tng ng.
Ph H Ph COOH

COOH HJ = 12,3HCps
JHH-H= 15,8 Cps H-H
Acid cinamic
3.2.4. bn tng i v s chuyn ha tng h gia
cc ng phn hnh hc
bn c th l v mt nhit ha hc v c o bi nhit
hnh thnh, hoc l v mt nhit ng hc c o bi nng lng
hnh thnh. Do s khc nhau v bn gia cc ng phn cis
v trans c th c biu din s khc nhau v Entalpi hay nng
lng t do.
C th o mc khc nhau v bn nhit ha hc ca cc
ng phn hnh hc bng cc i lng ca thiu nhit. Nhng
chnh xc ca phng php ny cng b hn ch, bi v cc thiu
nhit rt ln nhng s khc nhau ca chng th li nh.
V tnh bn nhit ng tng i ca cc ng phn hnh hc
c th d on theo nng lng t do hnh thnh nu bit c
nng lng ny.
Th d: nng lng t do hnh thnh ca trans-but-2-en 25oC
ln hn nng lng t do hnh thnh ca ng phn cis l 2,884
KJ/mol. Cn ch rng i lng ny nh hn hiu s tng ng ca
entalpi (3,971 KJ/mol) bi v cis-but-2-en c entalpi ln hn trans-but-
2-en l 4,347 kJ/mol.
 Nng lng t do hnh thnh i vi nhiu i ng phn
hnh hc vn cn cha bit ht. Tuy vy, c hai ng phn trong
cn bng ha hc v t trng thi cn bng c tnh trc tip hiu
s nng lng t do.
Th d: trong hn hp cn bng ca cis-, trans-but-2-en
3900C cha 52,8% ng phn trans.
Phng php n gin nht c s chuyn ha tng h
ca cc ng phn hnh hc l un nng chng.
Th d: i vi Stilben hng ro nng lng ca s chuyn
ha tng h bng 167,2(188,1KJ
thc hin qu trnh ng phn ha cis-trans c th dng
cc xc tc khc nhau nh: gc t do, ngun sinh ra gc t do nh
NxOy, cc halogen (c mt nh sng), cc axit: HX (X: halogen),
H2SO4, BF3, kim loi kim (natri), tc nhn hidro ha,dehidro
ha nh Pt, Se.
Th d: s ng ha cis-trans vi xc tc gc t do:
R H
R Br Br
R + Br H R
H
R H R H
H

H
R + Br
R
Mun c Br(Hta dng Br2 vi nh sng c di sng tng
i ln (cc i hp th i vi Brom l 415A0)
3.3. HP CHT C NI I C=N HAY N=N
3.3.1. ng phn hnh hc ca Oxim
Aldoxim, cetoxim c ng phn hnh hc c gi l syn-
hay anti-

H3C
.. H3C OH

..
C N C N
OH
H
H
Syn Acetaldoxim Anti Acetaldoxim
(So snh v tr tng i gia nhm OH v H)

C N
 Cetoxim: c ng phn hnh hc khi nguyn t carbon (sn
phm) lin kt vi hai nhm khc nhau.
H3C OH

..
C N

Syn metylphenylcetoxim hay Anti metylphenylcetoxim

xc nh cu hnh syn- hay anti- ta so snh v tr tng
i ca nhm OH vi nhm th c c trc.
Hp cht khc c ni i C N
Nitron: s ankyl ha oxim thng cho mt hn hp
dn xut O-ankyl v N-ankyl. ng phn hnh hc ca N-ankyl
gi l NITRON c chng minh bi hp cht sau

O
C N

CH3
H3C
phenyl p totyl N metylnitron
bng s kho st momen lng cc.
Phenyl hidrazon v semicarbazon
Phenyl hidrazon ca acid O-nitrophenyl glioxilic v
monosemicarbazon ca benzyl cng c ng phn hnh hc.

NO2
.. ..
C N C N
O
HOOC NH C NH-C-NH2
O
Phenylhidrazon Monosemicarbazon ca benzyl
ca Acid O nitrophenylglioxilic
 3.3.3. ng phn hnh hc ca hp cht c ni i N=N
Diazoat

Ar
.. . ..
.. N

anti arildiazoat
N
O Ar
N

syn arildiazoat
N
O

syn-diazoat khng bn, anti-diazoat bn. ng phn syn- hp th

di sng ngn hn v cng hp th thp hn ng phn
anti.
Diazocianur

.. .. Ar
..
Ar
N

syn
N
CN
.. N

anti
N
CN

ng phn syn khng bn v chuyn ha thnh ng phn

anti d dng khi yn hay un nh, ngc li ng phn anti
chuyn thnh syn di nh hng ca s chiu x.

Azobenzen
.. . ..
. N
=0
N

trans azobenzen
N
= 3D
cis azobenzen
N

Thng thng ng phn trans bn hn ng phn cis, di s

chiu x bng nh sng t ngoi, ng phn trans bin i mt
phn thnh ng phn cis, c th c lp c bng phng php
kt tinh hay ngoi hp trn Al2O3.
C cu ca hai dng ny c xc nh bng nhiu x tia
X. Trans azobenzen l mt phn t c c cu gn phng, cn
ng phn cis azobenzen c c cu ghnh, trong hai nhn
benzen nm ngoi mt phng cha hai nguyn t Nit, to thnh
gia hai nguyn t Carbon i din mt khong trng chng
3,34A0.
 Azoxibenzen: cng c hai ng phn hnh hc:

O
N N

cis azoxibenzen
. trans azoxibenzen
N N
.
Khi un trn nhit nng chy, ng phn cis chuyn thnh
ng phn trans.
3.4. HP CHT VNG NO
Cc cicloankan mang nhng nhm th thch hp cng c ng
phn hnh hc.
CH3 CH3 H CH3

Cis H
1,2 dimetylciclopropan
H Trans 1,2
CH dimetylciclopropan
H
3

Cc vng c nhiu s nguyn t Carbon v mang nhiu nhm

th cng c tng s ng phn hnh hc nhiu hn (c c ng phn
quang hc)
C2H5 CH3 C2H5 H C2H5 H

H3C H3C H H CH3

H H H CH3

H H CH3
Cis cis Cis trans Trans trans
( Trans cis )
Chng 4: NG PHN CU TRNG
CA HP CHT KHNG VNG
1.
1.1. Khi nim v cu trng (conformation)
1.2. Php phn gii cu trng
1.3. Cu trng ca hidrocarbon no
1.3.1. Etan
1.3.2. nbutan
1.3.3. npentan
1.3.4. nhexan
1.4. Cu trng ca hidrocarbon no mang nhm th
1.4.1. Halogenur etyl
1.4.2. 1,2dicloroetan
1.4.3. Etanol mang nhm th v tr s 2
1.4.4. 2,3dibromobutan
1.5. Cu trng ca hp cht khng no
1.5.1. Hp cht c ni i C=O, C=C, N=C
1.5.2. Hp cht c ni i lin hp
1.5.3. S quay quanh ni i
4.1. KHI NIM V CU TRNG
Khi nim v cu trng dng ch cc dng hnh hc ca
phn t c to thnh do s quay quanh lin kt n m khng
b gy lin kt (nn cn gi l ng phn quay Rotamer)
V mt l thuyt, mt phn t c v s cu trng vi mc
nng lng khc nhau, ty theo bn cht ca cc nguyn t lin
kt cng ha tr v nh hng gia cc nguyn t khng lin kt
trong phn t, cu trng c coi l n nh nht ng vi mc
nng lng thp nht, khi tng tc gia cc nhm nguyn t
trong phn t t nht. Tuy nhin, v hiu s nng lng v thi
gian cc nguyn t ti nhng v tr khc nhau rt nh nn cc
cu trng khng th c lp c (tr vi trng hp c bit).
Th d: Acid mesotartric c hai cu trng (cng mt cu
hnh = Configuration)
OH HO COOH
HO

H
H H
HOOC H HOOC
C OO H OH
mat phang oi xng
tam oi xng
Hai cu trng ca acid Mesotartric

4.2. PHP PHN GII CU TRNG

Trong a s trng hp, s quay quanh cc ni n khng
hon ton t do v vi cu trng bn hn cu trng khc. Php phn
gii cu trng gii thch phn ng v tnh cht ca hp cht da trn
cu trng ca n: trng thi cn bn, trng thi kch thch v trng thi
chuyn tip.
Cu trng ca mt phn t c th xc nh bi:
_ Phng php vt l: nhiu x in t, nhiu x tia X,
ph t ngoi, hng ngoi, cng hng t ht nhn, momen lng
cc, tn sc quang hot
_ Phng php ha hc:
ng hc c th dng c nh kho st v vn
tc phn ng este ha, dung mi gii carboxilat, cc tosilat
 Nhit ng lc hc cng c th cho bit cu trng
u i, suy ra t trng thi cn bng gia cc hp cht ng phn
lp th.
S phn gii cu trng c p dng trc ht cho cc h
vng ciclohexan sc hp: Stroid, triterpenoid v c cu cng
rn ca cc hp cht ny thng ch a n mt cu trng duy
nht nn kt qu rt kh quan.
4.3. CU TRNG CA HIDROCARBON NO
4.3.1. Etan
Theo ha hc c in, hai nhm metyl ca etan c th quay
quanh ni n CarbonCarbon mt cch t do, nhng vi phng
php phn gii cn i ngi ta chng minh rng ch c s dao
ng quanh mt vi v tr c u, hai cu trng cc oan ca etan
l cu trng lch v cu trng che khut c biu din bi cng
thc chiu sau y:
_ Cng thc phi cnh

cau trang lech cau trang che khuat

_ Cng thc Newman:
H H
H
H H

H H H
Nhn theo trcH CarbonCarbon, thyH Hcc ni CH
H ca mt
nguyn t carbon trong cu trng lch l nhng ng phn gic
ca cc gc HCH ca nguyn t carbon kia. Etan c ba cu trng
lch ging nhau, to thnh khi nhm metyl ca cu trng lch
quay 1200 quanh ni n CarbonCarbon.
Gc quay c xc nh chnh xc hn bi gc xon (gc nh
din), l gc gia hai mt phng:

1C C2

__ Gc xon __
mt mt phng xc nh bi mt ni CH ch nh ti nguyn t
Carbon s 1 vi ni C1C2 v mt phng th hai xc nh bi
mt ni CH ch nh ti nguyn t Carbon s 2 vi ni C2C1
Trong cu trng lch, gc xon ( = 600 cn trong cu trng
che khut gc xon ( = 00
Gc xon bin thin t 00 n 3600 khi nhm metyl quay
quanh lin kt CC.
S bin thin nng lng theo gc xon l mt ng cong
gn hnh sin vi ba cc i v ba cc tiu, cao ca ro nng
lng trong etan l 2,8 Kcal/mol.
Cu trng lch bn nht, v c mc nng lng ti thiu, cu
trng che khut ng vi mc nng lng cao nht nn khng bn.
Nh vy, bnh thng Etan c cu trng lch cn cu trng che
khut l mt trng thi chuyn tip to ra khi phn t Etan quay t
cu trng lch ny n cu trng lch khc.
V ro nng lng ca s quay kh thp, cc phn t c dy
h c coi nh quay t do quanh ni n, nhit thng.

Biu nng lng quay ca Etan

4.3.2. nbutan CH3CH2CH2CH3

S bin thin nng lng trong nbutan vi gc xon l
ng cong hnh sin (tng t vi etan) ng vi cc cu trng:
 Che khut ton phn (( = 0): do sc y gia hai
nhm metyl che khut lm cho mc nng lng tng thm 3
Kcal/mol.
Che khut mt phn (( = 1200, ( = 2400): sc y
Van Der Waals gia hai nhm metyl gim xung khong 0,8
Kcal/mol. ng vi trng thi ny c tng tc gia nhm Metyl
v Hidro che khut vi mc nng lng khong 1 Kcal/mol. Tuy
nhin, cu trng che khut mt phn v cu trng che khut ton
phn khng phi l ng phn cu trng v ch c xem l
nhng trng thi chuyn tip gia ng phn bn lch v i lch.
_ Cu trng bn lch: ng vi mc nng lng khong 0,8
Kcal/mol vi gc xon ( = 600 hay ( = 3000, cn gi l cu trng
ghnh hay syn.
_ Cu trng i lch: n nh nht vi mc nng lng
thp nht, vi gc xon ( = 1800. Cu trng i lch cn gi l
cu trng trans hay anti.
nhit thng, nbutan l mt hn hp ng phn cu
trng i lch v bn lch, trong cu trng i lch chim
thnh phn nhiu hn.

Nng lng quay trong nbutan

tng tc Metyl H
tng tc Metyl Metyl
ro nng lng trong Etan (tng tc H H)
 Nng lng ton phn

4.3.3. npentan
Vi hai trc quay trong C2C3 v C3C4 th phn t n
pentan c th c tt c by cu trng (i lch v bn lch). Ph
Raman cho bit c hai cu trng tn ti trong npentan th lng,
cu trng u i c nhm CH3 v C2H5 i lch, k l cu
trng bn lch. Hiu s nng lng gia hai cu trng c chng
0,5 0,7 Kcal/mol. Cc cu trng khc cha nhiu dng bn lch
hn do t bn hn.
CH3
CH3 H H
H H
CH3
C H H
H H
C CH3
H trngHi lch ca npentan
Cu
H CHH
3
CH3 H H
H H
H
C H H
H H
C H
H3C H
H3C
Cu trng bn lch ca npentan H
4.3.4. nhexan
Phn t nhexan c ba trc quay trong v c th c 12 cu
trng, cu trng i lch chim ( nhiu nht trong cn bng, tng
t npentan, phn t nhexan cng c hiu s nng lng gia
cu trng i lch v bn lch c chng 0,5 Kcal/mol.
H
H H H H
C
H H
H
H trngHi lch
H trong nhexan H H
H Cu
Theo ph Raman, nankan c 12 nguyn t Carbon c cu
trng hon ton i lch trng thi kt tinh. Tuy nhin, trng
thi lng c mt s cu trng bn lch ng k ti bt c ni no
v bt c lc no. Hiu s nng lng gia cu trng i lch v
bn lch c chng 0,8 Kcal/mol.
4.4. CU TRNG CA HIDROCARBON NO MANG
NHM TH
4.4.1. Halogenur etyl
S thay th mt nguyn t Hidro trong etan bng mt nguyn
t Halogen khng lm thay i ro nng lng mt cch ng k.
Dng phng php ph nghim, ngi ta tm thy tr s ro nng
lng nh sau:
CH3CH2F CH3CH2Cl CH3CH2Br
3,33 3,50 3,50 (Kcal/mol)
4.4.2. 1,2dicloroetan
Vi cc phn t phc tp, ngi ta cn xt n nhng tng
tc khc hn tng tc lp th nh: tng tc lng cc, lc ni
hidrogen ni phn t
Phn t 1,2dicloroetan c cu trng bn lch km bn hn
cu trng i lch, do lc x y lng cc mnh hn, mc d
tng tc lp th km bn hn trong nbutan.
Cl Cl
H H H Cl

H H H H

i
Cl lch Bn
H lch

Cu trng ca 1,2
dicloroetan
Nhiu x tia X chng minh 1,2dicloroetan kt
tinh hon ton di cu trng i lch.
Ph hng ngoi v Raman cho thy 1,2
dicloroetan trng thi rn c mt tm i xng, nh vy tn ti
di cu trng i lch, khi ha lng mt s phn t bin i
thnh cu trng bn lch (c chng minh bng s gia tng s
vch trong ph hng ngoi v Raman)
Nhiu x in t cho thy 1,2dicloroetan trng
thi kh cha 73( cu trng i lch v 27( cu trng bn lch (
220C), hiu s nng lng gia hai cu trng ny khong 1,03
1,32 Kcal/mol.
Momen lng cc ca cu trng u i c tr s
bng 0 (cu trng i lch). Thc nghim cho bit momen lng
cc tht s ca 1,2dicloroetan thay i theo nhit t 1,12 D
320C n 1,54 D 2700C, s kin ny ph hp vi mt cn bng
gia cc cu trng i lch v bn lch.
4.4.3. Etanol mang nhm th v tr s 2
RCH2CH2OH
R: OH, NH2, F, Cl, Br, OCH3, NO2, NHCH3
Thng thng cu trng i lch bn hn cu trng bn lch.
Tuy nhin, t l n nh c th o ngc vi mt s hp cht c
c cu c bit.
Th d: cu trng bn lch ca etylen clorhidrin bn hn cu
trng i lch bt c iu kin no, th rn ch c cu trng
bn lch tn ti; th lng hoc kh, mt cn bng c thit lp
gia cu trng bn lch v i lch, nng lng ca cu trng bn
lch thp hn nng lng ca cu trng i lch 0,95 Kcal/mol do
cu trng bn lch c lin kt Hidro ni phn t.

Cl
H
...H
Cl
H H O

H H H
iH lch
OH
Bn
H
lch

Cu trng ca
Etylenclohidrin
Tng qut, tt c cc RCH2CH2OH vi R l OH,
NH2, F, Cl, Br, OCH3, NO2, NHCH3 u c cu trng
bn lch n nh hn cu trng i lch nh lin kt hidro ni
phn t gia nhm R vi OH, mc d c s x y lp th v
lng cc gia hai nhm ny.
4.4.4. 2,3dibromobutan
2,3dibromobutan c hai ng phn: Eritro (cng l Meso) v
Treo.
Nhiu x in t cho bit ng phn Meso tn ti di cu
trng i lch A; cn ng phn Treo tn ti di cu trng B c
hai nguyn t Brom i lch nhau, hai nhm CH3 bn lch
Br Br Br
H CH3 Br H H3C Br

H3C H H3C H H3C H

Br (A)
meso CH)3
(A H)
(A
1 2

Br Br Br
H3C Br H Br
H CH3

H3C H H H3C H
H3C
Br H CH3
treo (B) (B1) (B2)

_ ng phn meso cho kt qu bt ng l cc cu trng bn

lch ng gp n 30% trng thi lng tinh khit, nhng trong
CS2 t l trn bnh thng gim xung 20%.
_ ng phn treo cha khong 20% cu trng B2, v phn
cn li l cu trng B v B1.
Trong dung mi khng cc; hai nguyn t Brom bn lch t
thun li hn hai nguyn t Brom i lch. Cu trng B c hai
nguyn t Brom i lch v hai nhm metyl bn lch, cn cu
trng B1 c hai nguyn t Brom bn lch v hai nhm metyl i
lch.
4.5. CU TRNG CA HP CHT KHNG NO
4.5.1. Phn t cha nhm C CH2 , N CH2 , C O
Trong phn t aldehid acetic CH3CH=O v propen CH3
CH=CH2 u tn ti di cu trng vi ni i C=O hay C=C v
nguyn t Hidro che khut nhau c xc nhn bi ph nghim
viba v nhiu x in t.
HO H CH H3C
2 O

H H H H H H
H H H
CH3CHO CH3CH=CH2 CH3CH2CHO
Trong phn t propanal, xc nh bi hng s ghp cng
hng t ht nhn nhm CH3 che khut ni i C=O. Kt qu
ny c th gii thch bi sc ht lng cc gia CCH3 vi
C=O. O O
H C OCH3 H C OCH3
Vi cc phn t ; CH3OCH=CH2 ;
th cu trng u i ng vi ni i C=O, C=C, C=N u che
khut nhm CH3. iu ny c chng minh bi ph hng
ngoi, ph viba v nhiu x in t.
H H
C O C O
O H2C
Metyl formiat CH3 Metyl vinyl eter CH3
Cu trng u i ca formaldoxim c ni i C=N v ni OH
i nhau. H
N O
H2C
iu ny c th c gii thch bi s x y gia electron p
v ( trong metyl formiat, metyl vinyl eter ; v gia in t p trong
formaldoxim.
4.5.2. Phn t c ni i lin hp
Phn t c ni i lin hp c th c ng phn cu trng,
l ng phn Scis v Strans (Single: n). Tip u ng S t
trc ch cis v trans ch cu trng lin h n ni n trong
h lin hp.

H2C CH2 H2C H

H H H CH2
 S_cis S_trans

Cu trng ca buta-
1,3-dien
Kt qu thc nghim da trn tnh cht nhit ng hc, nhiu
x in t, ph nghim hng ngoi v viba cho bit cu trng S
trans ca buta-1,3-dien bn hn cu trng Scis t nht 2
Kcal/mol.
Ngoi ra, ph hng ngoi v Raman chng minh trans-
pent-3-en-2-on l mt hn hp cn bng cha cu trng Scis v
Strans vi s lng bng nhau.
H
C CH3
O O H

H3C H H3C C CH3

S_cis S_trans
Cu trng ca Trans-pent-3-en-2-onH .
Phn t buta-1,3-dien cho phn ng dielalder d dng, chng
t phn t t n cu trng Scis khi cn thit. Tht ra, ro nng
lng trong s quay quanh ni n c tr s khong 4,9 Kcal/mol.
4.5.3. S quay quanh ni i
Ro nng lng ca s quay quanh ni i CarbonCarbon c
tr s kh cao (40 Kcal/mol vi etylen) so vi s quay quanh ni
n (2,8 Kcal/mol).
Tnh bn vng ca ni i CarbonCarbon c gii thch bi
s hnh thnh orbitan (. Nu mt phng ca mt nguyn t Carbon
ni i quay 900 quanh ni sigma (cc; orbitan phn t b ph
hy v trc i xng ca hai orbitan vung gc nhau nn khng
xen ph ln nhau.
Ro nng lng
Hp cht Cng thc
(Kcal/mol)
 Etylen CH2=CH2 40
2buten CH3CH=CHCH3 18
Acid butendioic HOOC-CH=CH-COOH 15,8
Stilben PhCH=CHPh 42,8
ng phn trans-but-2-en bn hn cis-but-2-en khong 1
Kcal/mol.
Cn trans1,2dicloroeten li t bn hn cis tng ng 0,5
Kcal/mol.
V 2,2,5,5tetrametylhex-3-en c cu hnh trans bn hn cu
hnh cis khong 9Kcal/mol.
Chng 5: CU TRNG
CA HP CHT VNG NO
5.
5.1. Tnh bn ca hp cht vng no
5.1.1. phn ng ca ciclopropan, ciclobutan
5.1.2. Thuyt cng Baeyer
5.1.3. Thiu nhit v tnh bn tng i ca cc
cicloankan
5.1.4. Khi nim vng khng cng ca Sachse v Mohr
5.1.5. Sc cng Pitzer
5.2. Cu trng ca hp cht vng nh
5.2.1. Ciclopropan
5.2.2. Ciclobutan
5.3. Cu trng ca hp cht vng trung bnh
5.3.1. Ciclopentan
5.3.2. Ciclohexan
5.3.2.1. Cu trng gh
5.3.2.2. Cu trng tu
5.3.2.3. Cu trng tu xon
5.3.3. Ciclohexan mang nhm th
5.3.3.1. Ciclohexan mang mt nhm th
5.3.3.2. Ciclohexan mang hai nhm th
5.3.3.3. Ciclohexan mang nhiu nhm th
5.4. Cu trng ca vi hp cht hai vng sc hp
5.4.1. Decalin
5.4.2. Hidrindan
5.4.3. Decalol
5.4.4. Hidrindanol

5.1. TNH BN CA HP CHT VNG NO

Cc hp cht vng no bit trc nm 1880 u l chuyn ha
cht ca ciclohexan. Vi nh ha hc nh Meyer (1876) cho rng
cc vng khc hn vng c su nguyn t khng th to thnh.
Tuy nhin, nm 1881, Markovnikov tng hp mt chuyn ha
cht ca ciclobutan v Freund iu ch ciclopropan. Nm 1883,
Perkin kho st cc hp cht c vng nh v iu ch mt s
chuyn ha cht ca ciclopropan, ciclobutan v ciclopentan
trng thi tinh khit.
5.1.1. phn ng ca ciclopropan, ciclobutan
Thng thng tnh cht ca cc cicloankan ging tnh cht ca
ankan tng ng. Nhng cc vng nh ciclopropan v ciclobutan
c ha tnh tng t cc anken. Do , etylen c xem nh hp
cht vng nh nht ch gm hai nguyn t Carbon.
Ciclopropan tham gia phn ng vi:
_ Hidro Ni
+ H2
80oC
CH3-CH2-CH3
_ Vi Brom, HBr, HI v H2SO4
+ Br2 CH2Br-CH2-CH2Br

+ HBr CH3-CH2-CH2Br
_ Khc hn vi propen, ciclopropan khng b oxi ha bi dung
dch KMnO4.
Ciclobutan t c khuynh hng cho phn ng cng
hn ciclopropan, nhng c th hidrogen ha vi xc tc Ni,
1800C cho nbutan.

Ni CH -CH -CH -CH

+ H
2 180o 3 2 2 3
C
_ Vi HI:

t0 CH3-CH2-CH2-CH2I
+ HI
_ Vi Br2, HBr, KMnO4 cng khng tc dng vi ciclobutan.
5.1.2. Thuyt cng Baeyer
Baeyer gi s cicloankan l nhng a gic u v phng v
tnh lch ca gc ni trong cc cicloankan i vi t din bnh
thng.
lch ca ( mi gc ni trong vng gi l sc cng gc hay
sc cng Baeyer.
 1
= (109,5o )
2
* ( l gc trong ca vng
* H s gii thch s
phn phi sc cng ng u
gia hai ni lin h
n = s cnh ca vng
lch gc ca cicloankan

N n
0
3 60 +24,7 11 147,3 18,8
4 900 +9,7 12 150 20,3
5 1080 +0,7 13 152 21,5
6 1200 5,3 14 154,3 22,4
7 128,6 9,6 15 156 23,3
8 135 12,8 16 157,5 24
9 140 15,3 17 159 24,7
10 144 17,3

T cc tr s trn cho thy:

lch ca gc ni trong ciclopropan (+24,70) ln
hn ca gc ni trong ciclobutan (+9,70) nn ciclopropan cng
hn ciclobutan, do ciclopropan t bn hn v cho phn ng m
vng d dng hn ciclobutan.
Ciclopetan c lch b nht (+0,70); c th xem nh
khng cng ngha l theo Baeyer ciclopentan l hp cht vng bn
nht.
Ciclohexan c lch ng k (5,30), gy ra mt sc
cng nh trong phn t (im ny khng ng).
T ciclohexan tr i, lch tng dn v u,
ciclopropan c lch ging nh cicloankan c 17 nguyn t
Carbon.
Tm li, Baeyer cho rng cc vng nh hn hoc ln hn
ciclopentan v ciclohexan u khng bn nn cho phn ng m
vng d dng vi ciclopropan v ciclobutan; mt khc cc vng
ln hn gp nhiu kh khn trong iu ch (iu ny cng
khng ng).
5.1.3. Thiu nhit v tnh bn tng i ca cicloankan
Tnh bn tng i ca cc hp cht mt vng c th xc nh
bi thiu nhit.
Thiu nhit c tr s thc nghim cao nht vi ciclopropan,
gim dn n cc tiu vi ciclohexan ri gia tng n cc i vi
ciclononan, sau cng gim xung cc tiu vi ciclotetradecan.

(2) H/n (Kcal/mol): thiu nhit tnh cho mi nhm CH2 ca hp cht
cicloankan ( th kh)
(3) (H/n157) Kcal/mol: hiu s thiu nhit tnh cho mi nhm CH2
ca cicloankan v nankan tng ng
(4) Tng s sc cng ca ciclan

(1) (2) (3) (4)

n H/n H/n157,4 1/n(H/n157,4)
3 166,6 9,2 27,6
4 164,0 6,6 26,4
5 158,7 1,3 6,5
6 157,4 0,0* 00
7 158,3 0,9 6,3
8 158,6 1,2 9,6
9 158,8 1,4 12,6
10 158,6 1,2 12,0
11 158,4 1,0 11,0
12 157,7 0,3 3,6
13 157,8 0,4 5,2
14 157,4 0,0* 00
15 157,5 0,1 1,5
16 157,5 0,1 1,6
17 157,2 0,2 3,4
nankan 157,4 0 00
Thiu nhit ca cicloankan tnh cho mi nhm metylen (Kcal/mol)
 Thiu nhit tnh cho mi nhm metylen trong ciclopropan v
ciclobutan cao hn thiu nhit tng ng ca nankan bi 9,2 v
7,6 Kcal/mol theo th t, ngha l ciclopropan v ciclobutan cha
nhiu nng lng tnh cho mi nhm metylen hn do chng
km bn hn propan v butan. iu ny ph hp vi thuyt
Baeyer.
Thiu nhit ca ciclohexan b nht, bng ca nhexan nn
ciclohexan l hp cht bn nht ch khng phi l ciclopentan
nh Baeyer nu.
Thiu nhit ca cc vng c t 7 n 11 nguyn t Carbon
u ging thiu nhit ca npentan v thiu nhit ca cc vng
c t 12 nguyn t Carbon tr ln khng th phn bit vi thiu
nhit ca nankan. Nh vy, tri vi thuyt Baeyer, tnh bn ca
cc vng ny khng km hn cc hp cht mch h mt cch
ng k. Hn na, cc vng ln t ciclotetradecan tr ln u
hon ton khng cng v khng c khuynh hng cho phn ng
m vng nh ciclopropan v ciclobutan.
Da vo thiu nhit, Eliel (1962) chia hp cht vng
thnh bn nhm:
_ Vng nh vi n = 3 v 4.
_ Vng bnh thng vi n = 5; 6; 7.
_ Vng trung bnh vi n = 8 ( 9; 10; 11
_ Vng ln vi n ( 12.
5.1.4. Khi nim vng khng cng ca Sachse v Mohr
Nm 1890, Sachse cho rng ciclohexan v cc vng ln hn
c th ghnh p ng iu kin gc t din v tn ti di
nhng cu trng khng phng v khng cng, quan im ny
khng c chp nhn lc u v n d on ciclohexan phi tn
ti di hai dng: gh v tu trong khi ch c mt dng c bit
lc by gi.

dng gh dng tu
Cu trng ca ciclohexan
 Nm 1918, Mohr gii thch rng hai dng gh v tu bin i
ln nhau rt nhanh nn khng th c lp c.
5.1.5. Sc cng Pitzer
Nng lng ca cc hp cht vng gia tng vi sc cng
Baeyer do s bin dng ca gc ha tr.
Nng lng cng c th gia tng bi s to thnh mt cu
trng c dung tch nng lng bt li. S gia tng nng lng khi
mt cu trng lch thun li bin i thnh mt cu trng che
khut bt thun li, gi l sc cng Pitzer trong phn t.
Sc cng Pitzer do s x y gia cc nguyn t k cn khng
ni cn gi l sc cng i ni hay sc cng xon.
Sc cng Pitzer tr nn ng k i vi cc vng nh trong
cc nhm tr hon bt buc phi che khut nhau. Th d sc cng
Pitzer lm cho ciclopentan khng th c c cu phng ng thi
bin dng gc t din, ngha l a n sc cng Baeyer. Mc d
s kin ny gia tng nng lng, dng khng phng ca
ciclopentan c th nng thp hn th nng ca dng phng, v cu
trng tng ng thun li hn v mt nng lng.
5.2. CU TRNG CA CC VNG NH
5.2.1. Ciclopropan H H
H
H H

H
Ciclopropan
Vi ba nguyn t Carbon trong vng, ciclopropan c c cu
phng, gc trong ca ciclopropan bng 600 nn phn t ht sc
cng, do ciclopropan rt d m vng. Ngoi ra cc ni CH
cng mt bn mt phng che khut nhau, lm cho phn t cng
khng bn.

S xen ph ca cc orbitan trong ciclopropan

 C th trong ciclopropan c s khc nhau no so vi s
phn b bnh thng ca cc gc ha tr, y bn lin kt ca
nguyn t Carbon khng c c tnh ging nhau l sp3 na; m
lin kt CC gn ging vi p(() hn; cn lin kt CH gn ging
c tnh s((). Nh vy, lin kt CH c cng c thm, cn gc
ha tr HCH v CCH ln hn, cc lin kt CC b lng ra (do
gc t din b nh li). Do c s thay i cc gc ha tr nn cc
gc ny phn no b lch khi v tr thng thng v mt phng
ca vng khng cn l mt phng i xng na.
Theo thuyt c hc lng t; trong iu kin cc gc lin kt
600 th khng th no c s lai ha c, bi v trc ca hai
orbitan lai ha sp3 xut pht t mt nguyn t Carbon bao gi
cng lp vi nhau mt gc t nht l bng 900. Tuy nhin, nu
trc ca cc orbitan lai ha sp3 c hng nh trong hnh v th
cc orbitan lai ha khng th tc dng thng trc tip vi nhau
c, do chng hi b un cong lm cho s xen ph km i
dn n l lin kt CC trong phn t c mt sc cng.
5.2.2. Ciclobutan
Bng nhiu x in t hay cc php o ph nghim v nhit
ng lc hc chng minh rng: ciclobutan c c cu ghnh. V
nu c c cu phng, cc ni CH cng mt bn mt phng (k
cn) s che khut nhau v tng tc khng ni gia cc Hidrogen
lm cho ciclobutan phi ghnh i, l cu trng xp.
H H H
H
H
H (e) H H H
H
(a) H
H H Cu trng xp ca ciclobutan H
Nhiu x in t cho bit nguyn t Carbon ngoi mt
phng ca ba nguyn t Carbon cn li to vi mt phng ny mt
gc khong 200.
Cc ni trong cu trng xp ca ciclobutan chim v tr trc a
(axial) v xch o e (equatorial) (tng t nh trong ciclohexan).
Vng bn cnh t cng hn vng ba cnh nn c th chp nhn
bn nguyn t carbon ca ciclobutan trng thi lai ha (sp3).
Vi hai nhm th gn ti v tr 1,3 nh:
 CH 3 COOCH 3
H 3C COOCH 3 H H
H H
Cis ee Cis aa
H COOCH 3
3
H COOCH 3 H
CH 3 H HC
Trans ea Trans ae
3metyl ciclobutan carboxilat metyl
ng phn cis ee bn hn trans ea, iu ny c xc nhn
bi thc nghim.
Nhng ng phn transciclobutan-1,3-dicarboxilat dimetyl
bn hn ng phn cis tng ng do sc y tnh in gia cc
trng cc mnh hn hiu ng lp th.
5.3. CU TRNG CA HP CHT VNG TRUNG BNH
5.3.1. Ciclopentan
Ciclopentan phng s c nm nhm metylen hon ton che
khut a n sc cng Pitzer khong 14 Kcal/mol.
gim sc cng Pitzer vng ciclopentan phi c cu trng
(hi ghnh) phong b: mt nguyn t Carbon nm ngoi mt
phng ca bn nguyn t Carbon cn li.
a
e e
b a e
b
Cu trng phong b caaciclopentan
Cu trng na gh: ba nguyn t Carbon ca
vng nm trong mt mt phng, cn hai nguyn t kia trn
v di mt phng .
a a
4 3 b a'
e 5 e' e 1 5
b
1 e' e'
a' a'
2 b' e
2 b a'
e e' 4
3 a
a
 Cu trng na gh ca ciclopentan

Trong cu trng phong b hay na gh u c ba kiu ni:

Ni trc (a) v ni xch o (e) ging nh trong
ciclohexan.
Ni ta trc (a) v ta xch o (e).
Ni song thit din (b) (biseetional) chim mt v tr gia
ni trc v ni xch o to thnh gc 54,70 vi mt phng
ca phn t.
Cu trng na gh cng linh ng nh cu trng phong b,
nng lng ca hai cu trng ny khng khc nhau nhiu lm.
Ciclopentan mang mt nhm th
Nguyn t Carbon mang nhm th lch ra khi mt phng ca
bn nguyn t Carbon cn li. trnh s tng tc gia nhm
th R vi hai nhm metylen v tr 2 v 5 th nhm R v tr
xch o (e) thun li hn v tr a (trc).
Th d: metyl ciclohexan c cu trng phong b c an nh
hn cu trng xp khong 0,9 Kcal/mol

1
R
5
4

3 2

Ciclopentan mang hai nhm th:

Th d: 1,3dimetylciclopentan c cu trng cis (ee) bn hn
cu trng trans (ea) khong 0,59 Kcal/mol.

H3C H3C

Cis (ee) CH3 Trans (ea)

Cu trng 1,3dimetyl ciclopentanCH3

Ph hng ngoi ca ciclopentanol c hai chn ng
ha tr: C(OH) trong vng 1065 v 996 cm1 ch nh cho nhm
OH ta xch o v song thit din theo th t. Nh vy
ciclopentanol tn ti di hai cu trng phong b v na gh.
 5.3.2. Ciclohexan
5.3.2.1. Cu trng gh: ca ciclohexan khng c sc cng
Baeyer v Pitzer, v cc cp nguyn t Hidro gn trn hai nguyn
t Carbon k cn u hon ton lch, nh vy th nng ca hp
cht mc ti thiu.
Nm 1943, Hassel nhn thy ln u tin rng cc ni CH
trong cu trng gh c hai nhm:
6 ni CH song song vi trc i xng bc 3 ca
phn t, gi l ni trc (a).
6 ni sp xp quanh vng gn st mt phng trung
bnh ca vng, gi l ni xch o (e).
Trong cu trng gh, mi nguyn t Carbon c mt ni trc v
mt ni xch o. Cc ni trc v ni xch o lun phin trn
v di mt phng trung bnh.
Cc nguyn t hay nhm nguyn t gn trn nguyn t
Carbon c cu hnh ( khi chng hng xung; cu hnh ( khi
chng hng ln so vi mt phng trung bnh.
() a

. () ()
(e)

Trc i xng bc 3
Ni trc (a) Ni xch o (e)
(a)
5 3
1 (e)
6
5 1
4 2
4 3 (e)
2 6
(a)
( hnh chiu Newman)
Cu trng gh ca ciclohexan

Khong cch gia hai nguyn t Hidro trong cu trng gh.

Kiu V tr Khong cch A0

Bn lch 1He - 2He 2,49
1Ha - 2He 2,49
 Trans 1 Ha - 2Ha 3,00
Nh trc 1Ha - 3Ha 2,50

5.3.2.2. Cu trng tu: ca ciclohexan khng c sc cng

Baeyer nhng c sc cng Pitzer v bn cp nguyn t Hidro gn
hai bn hng tu (2,3 v 5,6) che khut nhau. Mt khc, s
tng tc gia nhng nguyn t hidrogen ( gn ti hai Carbon
mi tu v li tu (1 v 4) ch gn nhau khong 1,84A0, trong
khi bn knh Van Der Waals l 2,4A0. Cu trng tu km bn hn
cu trng gh v hiu s nng lng tnh cho hai cu trng l 6,9
Kcal/mol.

1.84A0
fp
fp H H fp
bs bs
1 bs 1
4 5 6 6 2
2.49A0

eb 4
5 3
3 2
ab
2.27A0
nhn bn nhn dc
Khong cch gia cc nguyn t Hidro gn trn hai nguyn t
C gn nhau trong cu trng tu ca ciclohexan
Kiu V tr Khong cch A0
Ct c 1fp 4fp 1,84
Che khut 2eb 3eb 2,27
2ab 3ab 2,27
Bn lch 1bs 2eb 2,49
1bs 2ab 2,49
1fp 2eb 2,49
Trans 2ab 3eb 3,00
Nh trc 1fp 2ab 3,00

fp
1 bs

eb 4
4 1 eb
5 6 eb bs eb
6 3
5 2
3 2
abab ab a
b
 Cu trng tu Hnh chiu Newman ca
cu trng tu

5.3.2.3. Cu trng tu xon

Cu trng gh l mt cu trng cng rn, khng th vn mo
c. Cu trng tu, cn gi l cu trng mm do, l mt cu
trng linh ng, c th un c d dng thnh nhiu cu trng
khc nhau.
Cu trng tu quen thuc khng phi l ng phn cu trng,
n ch l trng thi chuyn tip gia hai cu trng. Cu trng tu
xon l mt ng phn cu trng, km bn hn cu trng gh.

H
H
1 5 2
H 4 H H H
5
2 4 1
H 3 6 H
3 6
Cu trng tu xon ca ciclohexan

Trong cu trng tu xon hai nguyn t Hidro ct c (ti C1

v C4) x dch ra xa hn; cn hai nguyn t Hidro trc tu ti
C3 v C6 s di chuyn li gn nhau hn. Do , s tng tc ct
c gim n mc ti thiu ng thi sc cng Pitzer ti cc ni
C2C3 v C5C6 cng gim i mt phn.
Mt khc bn nguyn t H trc tu tr nn lch mt cch quan
trng, mc d cha hon ton lch hn.
S bin thin nng lng ca ciclohexan vi cu trng
 V cu trng gh bn nht, nng lng ca n mc ti thiu
(im a). Khi vn chn gh ln hay b lng gh xung, cu trng
gh bin thnh cu trng tu xon I (im c) t bn hn cu trng
gh khong 5,6 Kcal/mol, nhng phi vt qua mt ro nng
lng khong 11 Kcal/mol, ng vi cu trng na gh I (im b).
Cu trng tu xon I c th bin i thnh cu trng tu xon
II (im e) ngang qua trung gian tu (im d) t bn hn cu trng
tu xon khong 1,6 Kcal/mol. Cui cng cu trng tu xon II
(im e) bin thnh cu trng gh II (im g) i hnh vi cu
trng gh I v trung gian trong giai on ny l cu trng na gh
II (im f).
Kt lun:
_ Phn t ciclohexan c hai cu trng gh i hnh bin i
ln nhau rt nhanh nhit thng.
_ Cc nguyn t Hidro (trc) trong cu trng th I tr thnh
xch o trong cu trng th II v ngc li.
_ Hiu s nng lng gia cu trng gh v cu trng tu
xon ca phn t ciclohexan a n mt hn hp cha khong
10.000 cu trng gh v mt cu trng tu xon ( 250C).
5.3.3. Ciclohexan mang nhm th
5.3.3.1. Ciclohexan mang mt nhm th
2,55A0 X
H

X
H 2,55A0
H
H 2,8A0
H

a) Ankylciclohexan
_ Metylciclohexan
Khi nhm CH3 v tr xch o, khong cch
gia cc nguyn t Hidro ca CH3 v cc nguyn t Hidro gn
nht ca vng l 2,5A0, ngha l ln hn tng s bn knh Van
Der Waals ca hai nguyn t H (2,4A0).
Khi nhm CH3 v tr trc, mt nguyn t H ca
nhm ny (hng v vng) gn cc nguyn t H trc ca vng
c chng 1,8A0 nn nhm CH3 (a) phi chu sc y Van Der
Waals; sc y ny tng ng vi s tng tc nbutan bn lch.
Do , mun bit metylciclohexan c cu trng no bn nht,
ngi ta so snh tng s n v butan i lch v butan bn lch
trong hai cu trng.
Metylciclohexan trc c hai tng tc butan bn
lch, cn metylciclohexan xch o c hai tng tc butan i
lch nn ng phn xch o bn hn ng phn trc khong 1,6 (
1,8 Kcal/mol. Kt qu ny c xc nh bi ph cng hng t
ht nhn, nhit thng hn hp cn bng cha 95% CH3 (e)
v 5% CH3 (a).
- Khi nhm th l C2H5, isoC3H7 th cu trng
xch o vn bn hn cu trng trc.
- Nhm th tertbutyl khc hn nhm ankyl khc,
nu But(a) th mt trong ba nhm CH3 bt buc phi hng v
vng v gy ra s tng tc vi hai nhm CH2 v tr 3 v 5 c
tr s ln hn 5 Kcal/mol. Nng lng ny qu cao nn tertbutyl
khng th v tr trc trong cu trng gh nn n ch tn ti v
tr xch o.
H3C CH3
H
CH3
H
CH3

CH3
Nhm tertbutyl trc Nhm tertbutyl
CH3 xch
o
Cu trng ca tertbutyl ciclohexan

b) Ciclohexanol
Ciclohexanol tn ti di cu trng vi nhm OH xch o
(6290%)

OH

Cu trng ca ciclohexanol OH
c) Halogenociclohexan
 Theo nhiu x in t v nhiu x tia X hay php o momen
lng cc, cu trng u i ca clorociclohexan trng thi kh
c nguyn t Clor v tr xch o (55%60%). Hiu s nng
lng gia hai cu trng l 0,3 0,4 Kcal/mol, chng minh c
khong 40% cu trng trc trong hn hp cn bng.
trng thi lng, c hai cu trng trc v xch o u c mt
i vi clorociclohexan v bromociclohexan, ph hng ngoi cho
bit thm c 40% cu trng trc tn ti trong hn hp cn bng,
hiu s nng lng gia cu trng xch o v cu trng trc c
c lng l 0,3 0,5 Kcal/mol bi ph cng hng t ht nhn.
Nhm Go Nhm Go
CLVT 0,40 NH2 1,21,8
Br 0,50 COOH 1,2
I 0,4 COOCH3 1,1
OH 0,60,9 CN 0,2
OCH3 0,7 CH3 1,7
OCOCH3 0,7 C2H5 1,8
OTs 0,7 Pri 2,1
SH 0,9 Bu 2,1
SPh 0,8 But 5,6
Ph 3,1
Hiu s nng lng t do cu trng trong ciclohexan
mang nhm th ((Go : Kcal/mol)
i vi nhm OH, NH2: tr s nh ng vi dung mi
khng cha H+; tr s ln ng vi dung mi c proton.
5.3.3.2. Ciclohexan mang hai nhm th
5.3.3.2.1. Diankylciclohexan
a) Dimetylciclohexan
1,1dimetylciclohexan (ch c mt cu trng)

CH3

CH3

1,2dimetylciclohexan c ba ng phn cu trng

 CH3 CH3
CH3

Trans ee Trans aa CH
3

_ Trans ee c mt tng tc butan bn lch ng vi 0,85

Kcal/mol.
_ Trans aa c bn tng tc butan bn lch ng vi 3,4
Kcal/mol

CH3

HC3
CH3
cis ea cis ae CH3
Cu trng cis ea c ba tng tc butan bn lch ng vi 2,55
Kcal/mol.
nhit thng, 1,2dimetylciclohexan tn ti gn nh
hon ton (99%) di cu trng ee.
1,3dimetylciclohexan c ba ng phn cu trng.

H3C CH3

Cis ee Cis CH
aa 3
CH3
CH3
H3C
CH3
Trans ea Trans ae
CH3
- Cu trng cis ee khng c tng tc butan bn lch.
- Cu trng cis aa c mt tng tc nh trc (3,7
Kcal/mol) v hai tng tc butan bn lch (1,7 Kcal/mol)
Gaa = 3,7 + 1,7 = 5,4 Kcal/mol
- Cu trng trans ea c hai tng tc butan bn lch ng
vi 1,7 Kcal/mol.
1,4dimetylciclohexan c ba ng phn cu trng
CH3
CH3
H3C

CH3
 Trans ee Trans aa

CH3
H3C
CH3 CH3
Cis ea Cis ae
- Cu trng trans ee bn nht v khng c tng tc butan
bn lch.
- Cu trng cis ea c hai tng tc butan bn lch.
- Cu trng trans aa c bn tng tc butan bn lch.
Nn nhit thng, 1,4dimetylciclohexan tn ti hon
ton di cu trng ee.
Khi hai nhm th khc nhau: A ( B th cu trng n nh nht
ng vi nhm th to v tr e.
b) Ciclohexan mang nhm ankyl ln
Nu hai nhm th u c kch thc ln nh tbutyl phn
ng gp ca cu trng mm do tr nn ng k.
Th d: 1,3ditert butylciclohexan
* Cis ee
H3C
CH3
H3C
H3C CH3
CH3
* Trans ae khng th tn ti cu trng gh v c nhm tert
butyl v tr trc gy tng tc nh trc rt ln, nn cu trng gh
chuyn sang tu xon c hai nhm tbutyl u v tr e.
H3C

H3C
H3C CH3

CH3
Cu trng tu xon CH3

5.3.3.2.2. Dihalociclohexan

1,2dibromociclohexan
Br
Br
Br

Br
 =0

= 3,1 D
(60%) Trans ee Trans aa (40%)
Bnh thng ng phn trans ee bn hn trans aa nhng
momen lng cc cho thy c hai cu trng ee v aa u hin din
trong dung dch.
_ Momen lng cc ca trans aa = 0 (tnh
_ Momen lng cc ca trans ee = 3,1 D ton)
Momen thc nghim ty thuc vo dung mi s dng
+ Trong benzen ee = 2,1 D
+ Trong CCl4 ee = 1,7 D
Cu trng cis ee thun li v mt lp th nhng c s x y
lng cc gia 2 nguyn t Brom; nhiu x in t cho bit hn
hp cn bng ca hp cht trans1,2dibromociclohexan th kh
cha khong 60% cu trng ee v 40% cu trng aa.

Br
Br
( = 3,1 D) CisBr
ea Cis ae ( = 3,1 D) Br
Momen lng cc tnh cho cis1,2dibromociclohexan c gi
tr bng 3,1 D ((trans) v khng ty thuc vo dung mi.
(Tr s thc nghim = tr s l thuyt)
1,2diclorociclohexan
Momen lng cc tm thy dng trans ee l 2,6 D trong
benzen; 2,2 D trong CCl4 (momen tnh vn l 3,1 D).
ng phn cis ae c gi tr thc nghim v l thuyt u bng
3,1 D.
Nh vy momen lng cc ca hp cht trans1,2
diclorociclohexan ln hn ca trans1,2dibromociclohexan,
ngha l cn bng cu trng vi hp cht dicloro ciclohexan cha
t cu trng aa hn hp cht dibromo ciclohexan.
Cc kt qu v momen lng cc ca 1,2dihalociclohexan
c xc nhn bi ph Raman v ph hng ngoi.
 - trng thi lng, trans1,2diclorociclohexan c khong
50% cu trng ee; cn 1,2dibromociclohexan c khong 40%
cu trng trans ee.
- Ph cng hng t ht nhn cho bit trans1,2
dibromociclohexan c khong 30% cu trng ee trong dung mi
khng cc.
- Ph Raman v hng ngoi chng minh rng trng thi
rn, trans1,2diclorociclohexan c cu trng ee; cn trans1,2
dibromociclohexan c cu trng aa.
1,3dihalociclohexan: c cu trng ee u i hn aa
1,4dihalociclohexen
trng thi kh, 1,4diclorociclohexan v 1,4
dibromociclohexan u cha cu trng ee v cu trng aa vi s
lng gn bng nhau.
trng thi rn, ch c cu trng ee tn ti.
trng thi lng c hai cu trng u hin din
5.3.3.3. Ciclohexan mang nhiu nhm th
Ciclohexan th v tr: 1,2,3 ; 1,2,4 hay 1,3,5 c th c
bn ng phn cu hnh: ciscis; cistrans; transtrans;
transcis. Ngoi ra mi ng phn cu hnh c th c hai cu
trng nn mi ng phn ciclohexan mang ba nhm th khc
nhau c th c tm ng phn cu trng.
Cu hnh Cu trng
Transcis eA; eB; eC aA; aB; aC
Ciscis eA; aB; eC aA; eB; aC
Transtrans eA; eB; aC aA; aB; eC
Cistrans eA; aB; aC aA; eB; eC
1A; 2B; 3C ciclohexan

a. Mentol: c bn cu trng u i vi nhm

isopropyl v tr xch o.
OH
CH3 CH3

HO
 Mentol Neomentol
eee (Trans trans) eae (Cis trans)

CH3 CH3
OH

HO
Isomentol Neoisomentol
eea (Trans cis) eaa (Cis cis)

_ Mentol c cu trng bn eee.

_ Neoisomentol (eaa) c th c mt cu trng th nh aee v
hai cu trng cng tn ti trong cn bng v hiu s nng lng
gia v tr a v e ca nhm (CH3)2CH (2,3 Kcal/mol) tng
ng vi s tng tc Me/OH nh trc (2,4 Kcal/mol).
Cu trng cc mentol ng phn c xc nh bi phng
php ha hc da trn vn tc tng i ca phn ng este ha
nhm OH bi nnitro benzoyl clorur trong piridin.
b. Carvomentol.

CH3
CH3
OH

Carvomentol (eee) Neocarvomentol (eae)

OH

CH3 CH3

OH

Isocarvomentol (aee) OH (aae)

Neoisocarvomentol
Carvomentol c cc ng phn cu trng u i vi nhm
isopropyl xch o.
_ Tng t cc mentylamin cng c cc ng phn cu trng
tng t mentol (OH c thay bng NH2).
 _ Cc carvomentylamin cng c cc ng phn cu trng nh
carvomentol. Tuy nhin v tr cn bng cu trng cha c kho
st y .
Ciclohexan mang su nhm th Hexacloro-
ciclohexan (C6H6Cl6) tn ti di cc ng phn cu trng sau:
S th t Cu trng Th t tm thy
1 eeeeee aaaaaa
2 aeeeee eaaaaa
3 aaeeee eeaaaa
4 aeeaee eaaeaa
5 aeaeee eaeaaa
6 aaeaee eeaeaa
7
aeaeae* eaeaea* (b)
8
aaaeee**eeeaaa**
V mt l thuyt hexaclorociclohexan c 16 ng phn cu
trng, s ny gim xung cn 13 v hai cu trng ca (7)* v ca
(8)** ging ht nhau, cu trng (6) c hai dng (+) () bin i
ln nhau c v v cc vng c th bin i ln nhau nn ch c
tm ng phn tch ri c.
S nguyn t Clor trc cng nhiu cu trng tng ng cng
km bn, hai nguyn t Clor 1,3 nh trc c th hin din m
phn t khng bt buc phi xon, nu c ba nguyn t Clor trc
nh trong (hexaclorociclohexan s xon gc t din s xy ra
trong phn t.
Da trn nhiu x in t trng thi hi, cu trng cc ng
phn (, (, (, ( v ( c xc nh d dng, v cn bng cu trng
hng hon ton v pha cu trng bn nht (cc cu trng ny
cng c xc nh bi php o momen lng cc).
5.4. CU TRNG CA VI HP CHT HAI VNG SC
HP
5.4.1. Decalin (Biciclo [4.4.0] decan)
Decalin tn ti trong rt nhiu hp cht thin nhin thuc
nhm sesquiterpen, diterpen. Decalin l mt h khng cng, tn
ti di hai dng trans v cis, ty theo hai nguyn t Hidro gn ti
C9 v C10 hai bn hoc cng mt bn mt phng trung bnh
ca phn t.
Theo Mohr (1918) cisdecalin c cu to bi s dung hp
hai dng tu ca ciclohexan, cn transdecalin do s dung hp hai
dng gh.
Theo Hassel (1946) xc nh bi nhiu x in t cu trng
u i ca cisdecalin phi do hai dng gh sc hp.
TRANSDECALIN:
. H
1 7
8 9 2
1

6 5 4
10 3
H
5 H 4
7 9
10 2
6 3
8 H 1
Transdecalin c hai vng ciclohexan dung hp vi nhau hai
ni xch o, l mt phn t cng rn, vi mt tm i xng (
ngay gia hai nguyn t C9C10) v mt trc i xng bc II
(xuyn qua gia C2C3, C9C10, C6C7)
Transdecalin khng th nghch chuyn thnh dng i hnh
v s dung hp hai vng ciclohexan gh ch xy ra vi hai ni ee
v khng th thc hin vi hai ni aa. Nn transdecalin l mt
phn t khng c tnh trin quang.
CISDECALIN:
H
H 9
H 1 2
9
7 8 H 8
1 4
5 10 10 3
6 2 7
6
5
4 3

4
9 2
10 3
8
1
7 5
6
 Cisdecalin dung hp vi nhau bi mt ni xch o v mt
ni trc, cisdecalin c trc i xng bc II (xuyn qua gia C9
C10 v thng gc vi ni ny, trong mt phng phn gic gc nh
din gia hai nguyn t Hidro 9 v 10).
Cisdecalin l mt phn t mm do, bt i xng, c th bin
i d dng thnh dng i hnh (nh cisdimetylciclohexan).
Cisdecalin l mt cp (() khng th tch hai c.
Cu trng cisdecalin c ba tng tc butan bn lch, cn
transdecalin khng c tng tc butan bn lch. Nh vy, cis
decalin km bn hn transdecalin, hiu s nng lng gia hai
ng phn l 3 ( 0,85 = 2,55 Kcal/mol.
Cn bng gia cis v trans l thuc nhit , s kho st cn
bng ny nhit cao, xc tc Pt a n hiu s nng lng
trng thi lng l 2,72 Kcal/mol, ph hp vi tr s tnh.
DECALOL
Decalin mang nhm th v tr 1; 2 tn ti di bn dng
ng phn lp th: ciscis; cistrans; transcis; transtrans.
Cu hnh ca bn dng Racemic ca 1decalol v ca bn
dng Racemic ca 2decalol c xc nh dt khot bi
phng php: iu ch, ha tnh v l tnh. Nhng s phn gii
cu trng da trn cc d kin ng hc (x phng ha ester
carboxilat); dung mi gii ester sufonic v ph hng ngoi c
phn phc tp.
* TRANSDECALOL: cu trng cng rn ca
trans 1 v 2decalol.

H H H OH
H

H HO H

H(A) H (B)
Transcis1decalol Transtrans1
decalol
 ng phn transcis1decalol c ba tng tc nh trc
1,3 gia nhm OH vi cc H(a) ti C3, C8, C10.
ng phn transtrans1decalol c mt tng tc peri
vi nguyn t H(e) ti C8, tng ng vi mt tng tc
nh trc 1,3.

H H OH
H
H
OH
(C) (D)
H H
Transcis2decalol Transtrans2decalol
Cu trng cng rn ca trans2decalol

Cu trng ca decalol c xc nh bi ng hc cc phn

ng ha hc, nh s saron ha hidrogensucinat decalil v s
dung mi gii tosilat decalil. Vn tc tng i ca s x phng
ha hidrogen sucinat trans1 v 2decalil bi NaOH trong dung
dch H2O, 400C, gim dn theo th t:
Transcis2 transtrans1 transtrans2 transcis1
S x phng ha hidrogensucinat transcis2decalil xy ra
khong 8 ln nhanh hn s x phng ha hidrogensucinat trans
trans2decalil. iu ny ph hp vi cu trng xch o ca
OH trong transcis2decalol v trc trong transtrans2decalol.
Tng t vi trans1decalol: s x phng ha transtrans1
decalol nhanh gp 18 ln ng phn transcis1decalol.
Vn tc x phng ha hidrogensucinat transtrans1decalil
xch o thp hn (khong 5,5 ln) vn tc x phng ha
hidrogensucinat transcis2decalil xch o; nhng vn cao hn
(gp 1,5 ln) vn tc x phng ha hidrogensucinat transtrans2
decalil trc, do C8 c hiu ng peri ng k. Sau cng, vn tc x
phng ha hidrogensucinat transcis1decalil trc thp nht (13
ln chm hn vn tc x phng ha hidrogen-sucinat transtrans
2decalil trc) do cu trng A c hiu ng gim thiu bt thng
(tng tc nh trc 1,3).
* CISDECALOL: tri vi transdecalol, nhm
OH trong cisdecalol khng c cu hnh c nh.
 Ciscis1decalol: c hai cu trng khng tng ng
X, Y. H
H 1
H
1 HO H
H H
HO
H H H
(X) (Y)
Cu trng (Y) c OH (e) nhng tng tc khng ni xy ra
gia OH v nguyn t H (e) C8, tng tc ny tng ng
vi tng tc 1,3 nh trc.
Cu trng (X) c tng tc nh trc gia nhm OH v
nguyn t H (a) ti C5 v C7.
Do , cu trng (Y) OH v tr xch o bn hn cu trng
(X) OH v tr trc.
Cistrans1decalol cng c hai cu trng khng
tng ng (T) v (Z).
OH H
H OH 1
1 H

(T) (Z)

Cu trng (T) c tng tc peri gia nhm OH (xch o) vi

nguyn t H (e) ti C8; tng tc ny khng hin din trong cu
trng (Z), nhng tng tc nh trc 1,3 gia nhm OH vi
nguyn t Hidro (trc) ti C3 v C10. Tuy nhin, hiu s nng
lng gia (T) v (Z) khng quan trng nh hiu s nng lng
gia hai cu trng xch o v trc ca ciclohexanol.
Tng t, s tng tc khng ni trong hai cu trng (E), (F)
ca ciscis2decalol v hai cu trng (G), (H) ca cistrans2
decalol cho thy cu trng u i l cu trng vi nhm OH(e)
(E); (H).
H H H

OH HO
H H
 (E) (F)
Ciscis2decalol

H OH OH
H
H H
H H

(G) (H)

Cistrans2decalol
Vn tc x phng ha cc hidrogen sucinat cis1 v 2decalil
bi NaOH trong H2O, 400C gim dn theo th t:
Ciscis2 cistrans2 ciscis1 cistrans1
1,16 0,70 0,45 0,13
Kt qu thc nghim hp l, v tnh linh ng ca chng, cc
ester cisdecalil l nhng hn hp cn bng gia cu trng vi
nhm OH (e) (nhiu) v cu trng vi nhm OH (a) (t) nn s
x phng ha xy ra chm hn mt ester xch o thun ty.
Ngoi ra, ng phn ciscis1 b chng ngi lp th gy ra bi
nguyn t Hidro ti C9.

5.4.2. Hidrindan (Biciclo [4.3.0] nonan)

7
6
8 1 Cng nh decalin, hidrindan c th tn
2
ti di hai dng cis v trans.
5
4 9 3
TRANSHIDRINDAN: c hai vng sc hp bi hai
ni xch o.
H

H
 CISHIDRINDAN: c hai vng sc hp bi mt
ni xch o v mt ni trc.

Trong cis v transdecalin, s sp xp hai vng su nguyn

t ca mi ng phn khng c sc cng. Tuy nhin, trong
hidrindan, vng su nguyn t phi sc hp vi vng nm nguyn
t nn hai ni CH ca ciclohexan phi xon khi v tr bnh
thng, khin cho phn t hidrindan cng hn decalin.
Tnh bn tng i ca hidrindan ng phn cng c xc
nh bi s cn bng ha vi xc tc Pd, 193oC transhidrindan
bn hn ng phn cis, ngc li t 193(365oC, cishidrindan
bn hn transhidrindan. L do, trong khong nhit trn,
entropi ca cishidrindan cao hn entropi ca ng phn trans
hidrindan.

5.4.2.1. 8metylhidrindan:

CH3 CH3
6 8
7 1
H
5 4 CH3
9 3 2
trans cis (metyltrc) cis (metylxch o)
Dng Stroid Dng khng Stroid

Trans8metylhidrindan vi nhm metyl v tr trc lm gia

tng nng lng ca phn t do CH3 gy tng tc butan bn
lch vi vng su cnh ti C4 v C6.
Cis8metylhidrindan c th c hai cu trng:
- Metyl chim v tr xch o i vi vng su cnh cu
trng tng ng (dng khng Stroid) bn hn cu trng ca ng
phn trans khong 1,37 Kcal/mol.
- Metyl chim v tr trc (dng Stroid) nng lng ca
cu trng tng ng cao hn dng khng Stroid khong 0,25
Kcal/mol.
 ng phn cishidrindan trong dng Stroid nhm CH3 b
a ra xa khi vng 6C, cn trong ng phn trans th CH3 b
y li gn vng 6C nn ng phn cis bn hn ng phn trans
hidrindan.
5.4.2.2. Hidrindanol
Cu hnh ca cc hidridan mang nhm th: ciscis, cistrans,
transcis, transtrans. Trong cis (th nht) lin h n s sc
hp gia hai vng; cis (hoc trans th hai) lin quan n v tr
ca nguyn t Hidro ti Carbon mang nhm th vi nguyn t
Hidro u cu gn nht.
Trong s cc hidrindanol c nhm OH gn trn vng 5C, cu
hnh ciscishidrindan1ol v cistranshidrindan1ol xut
pht t phng php iu ch cng vn tc dung mi gii cao ca
tosilat ciscis hidrindan1il.
Tuy nhin, cu hnh ca hai cishidrindan2ol khng th
nh r bi vn tc saron ha sucinat hay dung mi gii tosilat, v
vn tc khng khc nhau lm.
Tnh bn ca cc cishidrindan5ol c kho st y
hn. Mi ng phn ciscis v cistrans c th c hai cu trng.

(A) (B)
H ciscis H
6 8 H
7 1 5 9
H HO 4 3
H
5 4 H
9 2 6 7
OH 8 2
(C) 3 (D) 1
H OH H
1
HO H H
5 4 H
H 2 cistrans
3 ca Cishidrindan5ol
Cu trng

Trong s cn bng ha vi Natri trong xilen, hay s kh cis

hidrindan5on bi Natri v alcol, ng phn cistrans (C) v (D)
c u i. Nu nhm OH trong ng phn ciscis v tr trc
(A) c s tng tc gia nhm OH vi cc nguyn t Hidro ti
C3. Tng tc ny khng c trong cu trng (C); (D) ca ng
phn cistrans bn nht v mt nhit ng lc hc.
Chng 6: HA LP TH CA D T
POLYMER
2.
6.1. Ha hc lp th ca hp cht cha d t
6.1.1. Hp cht cha Si, Ge
6.1.2. Hp cht cha Nit, Phosphor
6.1.3. Hp cht cha lu hunh
6.2. Ha hc lp th ca polymer
6.2.1. Polyetylen; PVC
6.2.2. Cao su
6.2.3. Glucid
_ Monosacarid
_ Disacarid
_ Polysacarid
6.3. Ha hc lp th ca Stroid
6.3.1. Sn cn bn
6.3.2. Cu trng
6.3.3. Strol
6.3.4. Acid mt
6.3.5. Kch thch t phi tnh
6.1. HA HC LP TH CA HP CHT CHA D T
6.1.1. Hp cht cha Silic, Germani
Nhng hp cht hu c c tnh quang hot nh s c mt ca
nhng nguyn t bt i xng khc Carbon nh: Silic, Germani,
Nit, Phosphor, Arsen, lu hunh
Cc nguyn t nhm IVA trong bng h thng tun hon: Si,
Ge, Sn, Pb u c bn lin kt phn phi t din nh Carbon no,
nu chng lin kt vi bn nguyn t (hay nhm nguyn t) khc
nhau th c th tn ti di hai dng i quang:
CH3
H3C
Si* *Si
H H
Ph Ph
Metyl - - naphtyl phenyl silan

H3C CH3

Ge* Ge*
H H
Ph Ph
Metyl - - naphtyl phenyl germani

6.1.2. Hp cht c cha Nit, Phosphor

Nit l nguyn t ha hc nhm VA, chu k 2 trong bng h
thng tun hon, Nit c ha tr 3 khi lin kt cng ha tr c
to thnh vi s tham gia ca cc orbital lai ha sp3. Nit ha tr
3 c c cu hnh thp, Nit c th coi nh nh ca hnh thp
vi y l mt tam gic cn ba ha tr c hng v ba gc, iu
ny c xc nhn cc d kin ca phng php nhiu x tia
X v nhiu x electron. Theo cc d kin ny th trong phn t
NH3, gc HNH bng 106,50, di lin kt N-H bng 1,014,
chiu cao hnh thp bng 0,381.
Cp electron t do ca nguyn t Nit trong NH3 c xem
nh l nhm th th t v NH3 c biu din di dng mt
m hnh t din.
6.12.1. ng phn quang hc ca cc amin
 N N

R R'' R'' R
R' R'
Cc amin bc II hay bc III ng l phi c tnh quang
hot do s bt i xng ca phn t, nhng vic tch hai
ng phn i quang u khng c kt qu do s chuyn rt
nhanh t dng ny sang dng khc (s racemic ha), trong
nhng phn t ny, nguyn t Nit dao ng gia nhng mt
phng ca ba nhm th, v nh vy vic chuyn t mt i
quang ny sang mt i quang khc phi qua mt trng thi
trung gian c dng phng:
N
N R R''
R R''
N R'
R'' R
R R''
R' N R'
R'
Nng lng hot ha cn thit quay cu hnh ca mt ng
phn quang hc bn nhit phng l 104,5 KJ/mol. Trong ph
hng ngoi ca NH3, c nhng vch trng ln nhau trong s dao
ng ca nguyn t Nit (400 ln/giy) qua mt phng cha cc
nguyn t Hidro vi nng lng chuyn ha l 22,75 KJ/mol (i
vi amin bc III cng c nng lng tng ng) nn vic tch cc
amin trn thnh hai i quang l khng thc hin c.

Tuy nhin, trong mt s trng hp ring bit, ngi ta vn c

th tch ring amin vi nguyn t Nit bt i (ha tr 3) thnh
hai dng i quang.
X X
R R
N N
R' R'
Y Y
Cc arylamin mang nhm th orto cn tr s quay t do gia
nguyn t Nit v nhn thm c phn b trong nhng mt
phng vung gc vi nhau v nh vy ton b phn t tr thnh

H3C
O
H3C N
N CH3 HOOC CH2
H3C
HO3S
H3C
bt i xng, nhng hp cht kiu ny c iu ch v tch
ring thnh hai dng i quang bi Minc (1937) v Adam (1949)

Nm 1944, Prelog thnh cng trong vic tch mt

diamin bc 3 thnh hai dng i quang ca baz Troger bng
php sc k ct, vi ct cha D-lactoz.

CH2 N CH3 H3C N CH2

H3C N CH2 CH2 N CH3

Hai i quang ca baz TROGER

Bt i xng nguyn t y l do cu hnh ca cc

nguyn t Nit, m nguyn t ny b gi cht trong h thng
vng phc tp, nn khng xy ra s racemic ha c.

6.1.2.2. ng phn quang hc ca aminoxid v mui

amoni bc bn.
Mt s amin bc II v bc III vi nhng gc khc
nhau c oxi ha thnh cc aminoxid tng ng v
nhng hp cht ny c th tch ring thnh hai dng i
quang, cc hp cht ny c gi tr quay phn t tng theo s
tng ca cc nhm th. Khi b oxi ha cc aminoxid c cha
nguyn t Nit ha tr 4 nn c c cu t din v hai electron
t do khng cn na nn khng c kh nng racemic ha.
Cc aminoxid ny c tch thnh hai dng i quang:
C6H5 O CH3
N
N
CH2 CH O
H3C CH2
[M]D = ( 3o (trong nc) [M]D = ( 49o (trong nc)
 Nguyn t Nit ha tr 4 cng cn c gp trong cc mui
amoni bc 4 kiu [R1R2R3R4N](+)X(-) tng t nh hp cht
cha Carbon, mui amoni bc 4 cng tn ti hai dng i quang.
Ngi ta thnh cng trong vic tch ring metyl-alyl-phenyl-
benzyl amoni iodur v cc mui amoni bc 4 thnh cc dng i
quang.
CH3 CH3

N N
H2C CH CH2 CH2 CH2 H2C HC CH2

Cu to t din ca hai i quang ca cation

metyl alyl phenyl benzyl amoni bromur
6.1.2.3. Hp cht hu c c Phosphor
Nguyn t phosphor c cu trc phc tp hn Carbon, Nit. Cu
hnh electron ca phosphor: 1s2 2s2 2p6 3s2 3p3
V lp M (n=3) trong nguyn t trung tnh ca phosphor
khng c khuynh hng chuyn thnh cu hnh electron ca
argon: 1s2 2s2 2p6 3s2 3p6 nn n c ha tr 3.
Khi to thnh nhng lin kt cng ha tr th ty thuc vo
bn cht ca cc orbital thun khit v lai ha ca nguyn t
phosphor, ta c cc loi cu trc chnh: sp3 (ha tr 4); 3p3 (ha tr
3); sp3d (ha tr 5); sp3d2 (ha tr 6).
P X

X P X
X
X
X X
P ha tr 3 P ha tr 4
X
X

X X X
X P P
X X
X

X
X
 P ha tr 5 P ha tr 6
Cu hnh khng gian ca Phosphor
Phosphin bc 3 vi nhng gc th khc nhau c th c tnh
quang hot do s c mt trong phn t mt nguyn t phosphor
bt i (k c orbital cha hai electron t do).
Ngi ta iu ch c phosphin quang hot, th d tch
ring metylnpropylphenyl phosphin thnh nhng i quang
bn vng. Khi lm vic vi ng phn quay phi th ngi ta thy
c s racemic ha rt chm trong toluen.
Tng t nh aminoxid, ngi ta c th iu ch
phosphinoxid mt cch d dng bng tc dng ca oxi ln
phosphin bc 3, n c tnh quang hot do cu trc t din ca
phosphor ha tr 4.
Ngi ta dng acid (+) bromocamphorsulfonic tch
metyletylphenyl phosphin oxit thnh cc i quang.
Cc phosphin bc 3 phn ng d dng vi lu hunh dn n
nhng phosphin sulfua c cu trc ging nh ca phosphin oxit.
Nm1944, W.C.Davies thnh cng trong vic tch thnh
cc i quang phosphin sulfua bc 3 (n-C4H9)(C6H5-) (p-HOOC-
CH2-O-C6H4-) PS vi [(]p=+9,6 v -9,7; tng t cc mui bc 4
ca phosphoni vi nhng gc khc nhau ging nh mui amoni
bc 4 tn ti di dng nhng ng phn quang hc do cu trc t
din ca phosphor ha tr 4.
P P
H3C CH3

CH2 (CH2)2 CH3 CH2 (CH2)2 CH3

Hai i quang ca metylnbutylphenyl phosphin
Vic tch ri hai i quang trn khng t kt qu. Tuy vy,
metyl-etyl-benzyl phosphoni iodur c tch ra di dng D(-)
v L(+) dibenzoyltartrat bng kt tinh phn on (k c cc mui
phosphoni khc cng c tch ra thnh hai i quang).
Mt s nhng hp cht phosphonic hay phosphoric, dn xut
ca acid hypophosphor (H3PO2) v acid phosphor (H3PO3)
trong Hidro c th c thay th bng nhng gc hu c hay
nhng nhm OH c thay th bng halogen, c th c tch
ring thnh hai dng i quang.
6.1.3. Hp cht c cha lu hunh.
Vi cu hnh electron ca lu hunh: 1s2 2s2 2p6 3s2 3p4 nn
lu hunh d dng to thnh hai lin kt cng ha tr nh hai
orbital 3p c cha hai electron c thn, v cn hai cp electron t
do nn c kh nng to lin kt phi tr c ha tr ba v bn.
Mt khc, lu hunh cn c orbital 3d trng nn c th lai ha
to ha tr 6. Selen v Telur cng tng t nh vy.
Sulfoxid, ester ca acid sulfinic v mui sulfoni quang hot.
Lu hunh ha tr 3 c c cu hnh thp ging nh
Nit (ha tr 3), do cc sulfoxid ester ca acid sulfinic v
mui sulfoni vi nhng gc khc nhau th c ng phn
quang hc:
(+) (-)
S S S X

R O R O R R''

(I)
R' OR'
(II) R'
(III)
S nh hng khng gian ca lu hunh trong cc hp cht
(I) Sulfoxid, (II) Ester ca acid sulfinic, (III) mui sulfoni

Ngi ta tch ring ra thnh cc i quang ca cc sulfoxid

vi R- l ; ;
H2N HOOC
R- l H3C ; CH3
Cc mui sulfonium, selenonium c c lp di
dng trin quang t lu. 2+
HOOC-CH2

S
. PtCl6
2-
H3C
H5C2
Cloroplatinat carboximetyletylmetyl sulfonium
 Selen v telur cng c nhng hp cht ging lu
hunh do n cng c nhng loi ng phn khng gian
tng t lu hunh.

6.2. HA HC LP TH CA POLYMER
6.2.1. Polyetylen (P.E); polyvinylclorua (PVC).
Trong polymer xut hin nhiu tm Carbon bt i
(nh PVC, polystyren, polyvinylacetat) khng c cu to
tinh th, do cu hnh bt thng ca nhng tm bt i. V
s xut hin nhng tm bt i trong phn t nn c hin
tng ng phn quang hc. C ba dng:
Polymer isotartic: tt c tm Carbon bt i c cng
cu hnh.
Polymer syndiotartic: cu hnh ca cc Carbon bt i
lun phin xen k.
Polymer atartic: cu hnh ca cc tm Carbon bt i
ngu nhin.
Polymer iu ha lp th (isotartic, syndiotartic) c t khi ln
hn, tan chy cao hn, ha tan thp hn polymer khng
iu ha lp th (atartic) v thng c th ko si c.
Cc polymer iu ha lp th c cu to tinh th th polymer
atartic c cu to v nh hnh.
R R R R R
Isotartic

R R R
Syndiotartic

R R R
R R
Atartic

R R R
 Polymer c th c nhng on mch (vi chiu di ng k) l
isotartic lun phin vi nhng on mch atartic hoc
syndiotartic, nhng polymer kiu ny gi l polymer
stereoblock (polymer khi lp th).
6.2.2. Cao su
Trong s trng hp butadien-1,3 c th thu c
polymer-1,2-olefin isotartic v syndiotartic,
CH CH 2
n
CH CH2
hay polymer 1,4-(-CH2-CH=CH-CH2-)n. V phn t c lin kt
i, nn c ng phn hnh hc, polymer c th c cu hnh ton
cis- hoc ton trans- hay hn hp ca c hai loi.

CH2 CH2 H
CH2

H H H CH2
n n
Cis polybuta 1,4-dien Trans poly buta-1,4-dien

CH2 CH2 CH2 CH2

*
C C C C
H H H H
CH CH CH CH
CH2 CH2 CH2 CH2
n n

Polybuta-1,4-dien Polybuta-1,2-dien
Isotartic Syndiotartic

Vi xc tc chn lc, polymer 1,4- iu ha lp th

ton cis hay ton trans c th t c.
Th d: s trng hp Isopren cho ta:
+ Polymer 1,4 ton cis: cao su thin nhin
+ Polymer 1,4 ton trans: G perchsa cng vi
polymer-3,4- c yu t
polymer-1,2- lp th ngu nhin.

CH2 CH2 H
CH2

H3C H H3C CH2

n n
 Polymer cis 1,4 isopren Polymer trans 1,4 isopren
CH3
CH2 CH
CH2 C * C
CH CH H3C CH2
2
Polymer 1,2 isopren
n Polymer 3,4 isopren n

S trng hp cc monomer kiu R-CH=CH-CH=CH-

R c th to thnh polymer :
lm xut hin cc tm carbon bt
*
CH CH CH *CH i nn polymer c th tn ti
R R' n dng Eritro- hoc Treo-
6.2.3. Glucid
6.2.3.1. Monosacarid
Cng thc ca monosacarid c biu din di dng piranoz
hay furanoz l s ci tin ca cng thc Fischer.
Vng Furanoz gn nh phng, nhng vng khng
cng su nguyn t (piranoz) khng th phng.
Thc t, D-glucopiranoz tn ti di dng gh ng vi hai
ng phn (- v (.
CH2OH CH2OH
O H O
H OH
H
OH H OH OH
OH OH
H glucoz
OH glucoz
OH
Dng piranoz
CH2OH CH2OH
HO CH O HO CH O OH
OH OH H
H OH H H
OH H OH
 glucoz glucoz
Dng furanoz
Cng thc HAWORTH
CH2OH HOH2C
O O
HO
HO HO OH
HO
OH
OH
D glucopiranoz
OH D glucopiranoz
D-Fructoz: c th tn ti di dng furanoz
tng ng vi hai ng phn (-D-Fructozfuranoz v (-D-
Fructofuranoz bn cnh dng mch h.
CH2OH
O 6 6
1 HOH2C
HO H HOH2C O CH2OH O OH ()
5
H OH 5 HO 2 HO 2
H 4 CH2OH
H OH H 4 OH
3 1
OH 3 () OH
CH2OH D fructofuranoz
Tnh a trin (mutarotation): quay ca
dung dch va mi iu ch ca vi hp cht quang hot bin i
t nhin theo thi gian, c th do s ngoi ng phn ha t nhin
hoc do s bin i t nhin c cu ca phn t.
Th d:
(-glucoz c nng sut quang hot:
[]20 = + 1120 (trong H2O)
(-glucoz c nng sut quang hot:
[]20 = + 19,20 (trong H2O)
Nng sut quang hot ca hn hp cn bng l:
[]20 = + 52,50 (trong H2O)
ng vi hn hp gm 30% (-glucoz v 62% (-glucoz.
Tnh a trin ca (+) glucoz lin h n s bin i cu hnh
ca nguyn t Carbon s 1 do s m v ng li vng hemiacetal,
trung gian l dng andehid mch h, hin din trong dung dch
vi nng d khng ng k.
HOH2C CH2OH CH2OH
O OH O
HO HO HO OH
HO HO
HO CHO OH
HO OH
OH
( D glucopiranoz mch h ( D glucopiranoz
20 20
[ ] = 1120 [ ] = 19,20
D D

6.2.3.2. Disacarid
Disacarid l nhng glucid cu to bi hai n v
monosacarid, do disacarid lm mt glucosid trong
phn t th hai lin kt vi nhm hidroxiglucosid ca phn
t th nht.
Nu nhm ny l mt nhm OH khc hn nhm
OH glucosid th disacarid c tnh kh v tnh a trin.
Th d: maltoz hay 4-0-((-D-glucopiranosil)-(-D-glucopiranoz;
Lactoz hay 4 0 ( D galactopiranosil)
Dglucopiranoz.
HOH2C
O
2
HO 1
HO HOH2C
OH O
3
O 4 2
HO 1
3 OH (hidroxiglucosid)
Maltoz OH *
( )
6
HOH2C O 3 OH 1
2 HO
HO 4 5 O 4 5 *
HO 2 OH
OH 1 O
3 HOH2C
6
Lactoz
Nu hai nhm hidroxiglucosid ca hai loi ng
(monosacarid) kt hp vi nhau th disacarid to thnh khng c
tnh kh.
Th d:
 + Sacaroz (sucroz) hay D
glucopiranosil(Dfructofuranosid hoc (D
fructofuranosilDglucopiranosid.
+ Trehaloz hay -D-glucopiranosil--D-glucopiranosid.

HOH2C O ( )
1
CH2OH O
HO 5
HO HO
HO O 2
() 3 CH OH
4 6 2
OH

Sacaroz
HOH2C O

HO
HO ()
HO 1 OH
O ()

O 2

3
TREHALOZ 5
OH
4
HOH2C6
HO
 6.2.3.3. Polysacarid
6.2.3.3.1. Celuloz
Celuloz c to thnh do nhiu n v ( D glucoz
ti v tr 1 ca vng th I v v tr 4 ca vng th II
OH 1 HOH2C
4'
HO O () OH ()

... O 4
O
O
HO
1' O
HO
O
...
HOH2C
OH O
HOH2C
6.2.3.3.2. Tinh bt
Tinh bt c to thnh do nhiu n v (D
glucoz gm hai loi:
Amyloz (20%) tan trong nc, s kt hp ti
v tr 1,4 ca (Dglucopiranoz c c cu thng.
Amylozpectin (80%) khng tan trong nc,
nguyn t C1 ca mi dy amyloz (gm khong 20-25 n v (
Dglucoz) lin kt vi dy k tip nguyn t Carbon s 6 nn
amylozpectin c c cu nhnh.
Cc sinh vt cng tn tr glucoz trong nhng cht
gi l glicogen. C cu ca glicogen ging amylozpectin hn
amyloz nhng cc dy ngn hn (12-18 n v glucoz) v c
nhiu nhnh hn (lin kt 1,4 v 1,6glucosid)

HOH2C O

...HO
O
CH2OH O
HOH2C
HO ( )
O
HO
Amyloz
HO
O HO HO
O
...

H O 2HC
O

H O 2HC
O
O

H O 2HC
O
O
H O 2HC
O

O
 Amyloz pectin

6.3. HA HC LP TH CA STROID
Steroid to thnh mt nhm hp cht thin nhin rt phong
ph, trch ly t ng vt v thc vt, nh sterol (colesterol), acid
mt (acid colic,acid litocolic), kch thch t thuc phi tnh
(estron, progesteron), kch thch t v thng thn (cortison,
aldosteron), glucosid tr tim, sapogenin, alcaloid steroid
6.3.1. Sn cn bn
Sn cn bn chung l perhidrociclopentanophenatren, c su
nguyn t Carbon bt i xng: C5, C8, C9, C10, C13 v C14.
12
13 17
11
1 C D 16
10 9
2 8 14 15
A B
3 5 7
4 6
Cc nhm th thng c mt trong sn cn bn ca
steroid thin nhin l:
- Mt nhm -CH3 ti C10 ; C13
- Mt dy nhnh ankyl ti C17.
 Trong vi trng hp nhm CH3 ti C10 v C13 c th thay
bng nhm formyl hay hidroximetyl. Mch nhnh ti C17 c 2, 3,
5, 8, 9 hay 10 nguyn t Carbon, nu mch nhnh b loi, v tr 17
thng mang mt nhm chc oxi ha.
- Nhm OH c th gn ti Carbon s 3, 7, 11 hay 12.
- Nhm CO (carbonyl) thng thng gn ti Carbon 3
hay 11.
- Mt lin kt i c th hin din gia hai nguyn t
Carbon 4-5, 5-6 hoc 7-8. Sau cng, nhn A v i khi c
nhn A v B l nhn benzen, trng hp ny, nhm C10
metyl b loi.
29
28
21 22 24
20 25 26
18 23
12
11 17
19 27
13
1 16
2 9 14 15
10 8
3 5 7
4 6
Cu hnh ti C5 c biu th
- Nhm 5( (A/B trans) khi 2 vng A, B sc hp kiu trans.
- Nhm 5( (A/B cis) khi 2 vng A, B sc hp kiu cis.

R R
12
11 17 17

.
13 13
1 16
1

.
2 9 14
10 8 15 2
10
3 7 3
5
5
4 56 4 5
Cu hnh ca Steroid

Cng nh trong trng hp cc hp cht hu c khc,

tn ca steroid dn xut t tn ca hidrocarbon tng ng.
6.3.2. Cu trng
 Hu ht cc stroid u c cu to vi dng gh ca
ciclohexan; cu to duy nht nhn c l mt h thng cng rn
v mi s bin i ln nhau cc dng gh khng xy ra c vi
s dung hp A/B trans (5(steroid) phn t c mt cu trng dp
gn nh phng, dn xut t cu hnh transantitransantitrans,
cn cu hnh ca 5(steroid l cisantitransantitrans.
Cu trng ton gh ca stroid c xc nhn bng nhiu
x tia X vi Clorur colesteril.
V stroid c cu trng c nh nh Transdecalin, v tr trc
hoc xch o ca nhm th c xc nh r rng cho mi
nguyn t Carbon, tri hn vi trng hp cc dn xut n gin
ca ciclohexan v Cisdecalin. Tuy nhin, trong vi trng hp,
vng A c th tn ti di dng tu hay tu xon.
13
11
12 17
D
2 10 9 C 15
1 8
16
B 14
A 6
3 4 7
5
5
13
11 17
12
10
16
8 15
1
9 14
6
5 7

5
2

3 4
Cu trng ca Stroid

6.3.3. Sterol
Cholesterol l thnh phn chnh trong sn mt ca
ngi, l nhn t gy ra bnh v tun hon, x cng ng
mch. Cholesterol tn ti di dng t do hay di dng
ester v c phn b rng trong c th, c bit trong m
thn kinh v no.
 V mt lp th, Cholesterol c tm nguyn t Carbon bt i,
phn t gm nhn perhidrociclopentanophenantren vi C10CH3;
C13CH3; C17nhm ankyl c tm nguyn t Carbon, OH ti C3
c cu hnh (, mt ni i ti C5 v C6. S hidro ha ni i to
ra hai nguyn t C bt i mi v hai ng phn. S hidro ha t
pha trn dn n 5(H vi s dung hp A/B cis to nn sn phm
Coprostanol, ngc li s hidro ha t pha di s cho
Colestanol (5(H vi s dung hp A/B trans).

H3C
3
11
3
2
12
10
9
4
7
6
1
8
5
13
16
14
15
17
18
19
H
C
O
CH3 R
13
11 17
CH3 12
15
14 16
2 8
1 10
9 7
HO 4
25
26
24
23
22
27
5 6
3 2
+H2 +H2 1
0
CH3
R
CH3

CH3
1 R
H 11 13
12
6 CH3 17
5
2 2 10 9
1 8 15 16
14
3 4 HO
HO 4 6
3 5 7
R C8H17
H

COLESTEROL

(t pha () (t pha ()

( )
 COPROSTANOL COLESTANOL
( )
Mc d, Colesterol khng tn ti trong thc vt, nhng ngi
ta thy trong cy nhng sterol tng t gi l Phytosterol, cht
quan trng nht trong loi ny gi l Ergosterol, di tc
dng ca tia t ngoi, ergosterol cho vitamin D2 (chng bnh
ci xng, ging vitamin D) l yu t chnh trong s tng trng
bnh thng ca xng v rng ca ng vt.
6.3.4. Acid mt
Acid mt cng c sn cn bn nh sterol, phn t c cha
OH ti C3, C7 v C12, nhm OH ny nh hng ( vi A/B cis.
Acid mt phong ph nht l acid colic v acid desoxicolic (khng
c OH C7).
S phn gii cu trng gii thch ti sao s acetyl ha OH ti
C3 d hn ti C7 v C12. Nhm OH xch o d gim cp hn
nhm OH trc nn d b tn cng bi RCO. Ch c OH C3
trong acid colic l chim v tr xch o.

(a)

Acid
CH colicCH3
3
(a)
CH3
OH
1 (e)
COOH
H
7
2
OH

OH
 6.3.5. Kch thch t phi tnh.
( Kch thch t n gi l Estrogen.
( Kch thch t nam gi l Androgen.
Estradiol l mt estrogen chnh v hai dn xut estron v
estriol u c hot tnh sinh l.
Progesteron cng l mt kch thch t n khc, c tit ra t
th vng ca non so, c chc nng hnh thnh v duy tr thai
nhi.
Testosteron v androsteron l nhng androgen chnh.
Testosteron c tit ra bi dch hon l mt kch thch t
nam. Androsteron c sn sinh t s chuyn ha ca
testosteron.
H3C O H3C OH

H H

H H H H
HO Estron HO Estradiol

CH3
H3C OH
H3C C O

H H3C
H
H H

Estriol Progesteron
CH3 CH3
CH3
O O
H CH3

H
HO H
O
Cu to lp th ca Estron Cu to lp th ca
Progesteron
H3C OH H3C O
H3C H
H H3C
H

H H H H
O HO
Testosteron Androsteron
H
Chng 7: HA LP TH NG
7.
7.1. Hiu ng lp th
7.1.1. Khi nim
7.1.2. Hiu ng khng gian loi 1
7.1.3. Hiu ng khng gian loi 2
7.1.4. Hiu ng k
7.1.5. Hiu ng cu trng
7.1.6. Hiu ng orto
7.1.7. Hiu ng qua nhn
7.1.8. Tnh cht c nh ca cu trng
_ Quy tc Ingold
_ Quy tc Barton
_ Quy tc cng endo
7.2. Ha hc lp th ca cc phn ng
7.2.1. Phn ng th vo Carbon no
7.2.2. Phn ng tch
7.2.3. Phn ng cng Electrophile
7.2.4. Phn ng cng Nucleophile
7.1. HIU NG LP TH
7.1.1. Khi nim
Hiu ng lp th l hiu ng do kch thc ln ca
cc nguyn t hay nhm nguyn t v do bin dng ca gc
ha tr hay ca cc lin kt to nn. Hiu ng lp th c
biu hin qua s cn tr khng gian, qua sc cng gc ha tr
hay lin kt lm nh hng n hng v tin trnh lp th
ca phn ng, n tnh cht v bn ca cc ng phn.
7.1.2. Hiu ng khng gian loi 1
L hiu ng gy ra bi cc nhm th c kch thc tng
i ln lm cn tr s tng tc ca tc nhn i vi tm phn
ng hoc lm thay i hiu s nng lng t do gia phn t v
trng thi chuyn tip.
_ nh hng n phn ng lng phn t c th do
tc nhn hoc cht nn.
_ nh hng n s hon thnh trng thi chuyn
tip, lm tng nng lng hot ha v do lm gim tc phn
ng.
Th d: so snh kh nng phn ng ca aceton v ca ditert-
butylceton vi dung dch bo ha NaHSO3
7.1.3. Hiu ng khng gian loi 2
L hiu ng gy ra bi cc nhm c kch thc ln vi
phm n tnh song song ca trc cc orbital p trong h lin
hp lm cho hiu ng lin hp mt tc dng, thay i tnh
cht ca phn t.
Th d: so snh kh nng phn ng ca N,N-dimetyl anilin v
ca 2,6-dimetyl-N,N-dimetyl anilin vi mui benzen diazonium
Th d: gii thch cc gi tr pKa ca:
Cht Phenol pnitrophenol 3,5dimetyl4nitrophenol
pKa 10,0 7,2 8,2
7.1.4. Hiu ng k
 Hiu ng k xut hin khi phn t cht phn ng c mang
nhng nhm chc khc -Z vi nhng i electron t do v mt
v tr thch hp (thng cch tm phn ng 2, 3, 4 nguyn t)
Nhm -Z ny c kh nng tn cng vo tm phn ng trc
khi tc nhn Y tc dng, nh hng n cu hnh ca sn phm.
Z: ; ; ; ; ;
_ _ _ _ (-) _
;
__ _ _O __ _
O _ C CH3
NH2 _ OH
Th d: _ SH _ C _
Br O O H O O
NaOH loang
H H3 C
H3 C O O
Ion (R) bromopropionat (S) lacton
HO O
NaOH ac
H
H3 C O
Ion (R) lactat

7.1.5. Tnh cht c nh ca cu trng

7.1.5.1. Qui tc Ingold.
C ch tch E2 ch xy ra thun li khi bn tm tham gia phn
ng phi nm trong cng mt phng, ngha l cc nguyn t
(nhm nguyn t) tham gia phn ng phi v tr trans (anti) i
vi nhau.
Th d: Br
H CH3
H CH3
- HBr
E2 H3C H
H3C H
H
2 bromobutan trans but-2-en
7.1.5.2. Qui tc Barton
S tch E2 trong h vng ch xy ra thun li khi cc nhm b
tch cu trng trans diaxial (hai nhm b tch v tr trans v
trc)

CH3
CH3
H H - TsOH
H E2
H H
OTs
 O
H3C S OH
O

TsOH l

7.1.5.3. Qui tc Endo

Trong phn ng cng Dieles-Alder ca mt dien vi
mt cht thn dien (Dienophile) nh anhidric maleic qua mt
trng thi chuyn tip trong dien v cht thn dien nm
trong hai mt phng song song, vi s tp trung ti a s lin
kt ( ca hai cht.
Dien

H
O O
H
O
Anhidric maleic O Endo
Sn phm cng
O
7.1.6. Hiu ng orto
L hn hp ca cc hiu ng lp th loi 1, loi 2,
hiu ng cm, hiu ng trng, lin kt hidro (nu c).
Th d: Orto R C6H4 NH2 c tnh baz nh hn cc ng
phn meta, para R C6H4 NH2.
7.1.7. Hiu ng cu trng
Sc cng Baeyer gii thch km bn ca vng 3C,
4C v cc vng khc c cu trng thch hp trnh sc
cng Baeyer.
_ Sc cng Pitzer
_ Sc cng Prelog
_ Sc cng ca cc lin kt
 Cc sc cng lp th ny to ra cc hiu ng cu trng
nh hng n bn v tnh cht ca phn t.
7.1.8. Hiu ng qua nhn
L hiu ng ca cc nhm c th gy nh hng hoc tc
dng trc tip xuyn qua nhn (vng ) do chng gn nhau.
OH
O
+ H2 Ni

O OH
7.2. HA HC LP TH CA PHN NG
7.2.1. Phn ng th (substitution)
7.2.1.1. Phn ng SN2
Phn ng SN2 xy ra vi s nghch chuyn cu hnh ca tm phn ng;
qua trng thi chuyn tip
C 2H5 - C 2H5
C 2H5 -
+ ddNaOH -Br HO
Br HO Br H
H SN2 CH3
H CH3
H3 C
(S) 2 brombutan (R) butan-2-ol

7.2.1.2. Phn ng SN1

Phn ng SN1 xy ra vi s Racemic ha ngha l thu c
hn hp hai cht i quang vi s mol bng nhau.
C ch phn ng xy ra qua hai giai on:
_ Giai on 1: to thnh ion Carbonium (chm)
_ Giai on 2: Y(-) tn cng vo C+ to sn phm
(nhanh).
R1 _ R1 _ R1 R1
-X Y
R2
X
g1 +
g2 R2
Y +Y R2
+ R2 R3
R3 R3
R3
 50% (+) 50% (-)
Nhng do nh hng ca dung mi m phn ng SN1 xy ra
vi hn hp sn phm c cu hnh nghch chuyn cao hn.
Th d: S thy phn Clorur (R)1 phenyl etyl
H3C CH3 CH3
+ H2 O H
* Cl - HCl
O Cl HO
H (R) H (S) H
H Ph Ph
Ph
H3C
10%
+ H2 O - HCl
OH
CH3 H
H H
Ph
O O CH3
H H
H Ph HO
hn hp (() 90% H
Ph
7.2.1.3. Phn ng SNi
Cho sn phm c cu hnh ging ban u. Khi cho mt alcol
tc dng vi Clorur tionyl (SOCl2), phn ng qua trung gian
clorosulfit ankyl, c th c lp c, sau nhit phn clorosulfit
ankyl ta c clorur ankyl.

R1 Cl - HCl R1 t0 R1
_
O
_
OH + S O
R2
Cl
R2 S O R2
Cl
R3 R3 R3
Cl
Clorosulfit ankyl
Nu phn ng xy ra trong mi trng baz hu c (nh
piridin) th phn ng din ra theo c ch SN2.

R1 R1
_ + SOCl2 O
_ H
O
R2 (piridin) R2
- HCl S O
R3 R3 Cl
_
+ HCl* N
+ *Cl
N +
H
 R1
R1
t0 _
_

_ O - SO2 *Cl + Cl
*Cl R2 S O
R2
R3 R3
Cl
7.2.1.4. Phn ng SN2 (c s di chuyn ni i)
Trong phn ng SN2 tc nhn Y(-) tn cng vo phn t
cng mt pha vi nhm b th X(-).
R R
SN2'
HH
+ X
+Y Y
Y X
(X, R : Trans) (Y, R : Trans)
7.2.1.5. Phn ng SE
S chuyn ha mt halogenur quang hot (C*X)
thnh mt hp cht c kim, thng dn n sn phm
racemic.
R1 R1
-X
* X + M * M
R2 R2
R3 (M : kim loi) R3

R1 R1
COOH + HOOC
R2 Hn hp (() R2
1) + CO2 R3 R3
2) + H2 O
R1 R1
H Hn hp (() H +
R2 R2
Ngi ta gii thch s Racemic
R3 trn SE nh sau: phn ngRSE
3
qua trung gian ion Carbanion tng t nh s nghch chuyn cu
hnh ca NH3 v amin.
R1

R2
M M
+
+
R1
. . R1

R2
R2
R3 R3 R3
 7.2.1.6. Phn ng SR Ion Carbanion
V phn ng th SR qua trung gian gc t do m gc t do c
c cu phng, orbital cha mt electron c thn c trc i xng
vung gc vi mt phng trn. Nn tc nhn c th tn cng vo
tm phn ng t hai pha vi xc sut bng nhau cho ta hn hp
racemic.

ClCH 2

H 3C
H
+ Cl
(- HCl)
. CH 2Cl
+ Cl 2

C 2H 5 H 3C C 2H 5

ClCH 2 ClCH 2
Cl + Cl + 2Cl
H 3C CH 3
C 2H 5 hn hp (() 1,2 dicloroC22H5 metylbutan

7.2.2. Phn ng tch (Elimination)

7.2.2.1. Phn ng tch E2
C bit tnh lp th cao. Phn ng tch E2 xy ra d dng, nu
phn t cht phn ng c th quay t do cc nhm b tch C(
v C( cng phng v v tr trans i vi nhau to iu kin thun
li cho s xen ph cc i cc orbital trong qu trnh hnh thnh
lin kt (.
Tch HX trn dn xut halogen:
_ ng phn eritro cho anken cis
_ ng phn treo cho anken trans
Br
H3C Ph H3C Ph
NaOH / EtOH,t0
+ HBr
H Ph E2
H Ph
H
 Eritro cis metyl stylben
1 bromo 1,2 diphenylpropan
H3C Ph CH3
Br H
NaOH / EtOH,t0
E2
+ HBr
H Ph
H Ph Ph
Eritro cis
 Br
Ph CH3 Ph CH3
NaOH / EtOH,t0
+ HBr
H Ph E2
H Ph
treo
H trans

Ph CH3 Ph
Br H
NaOH / EtOH,t0
E2
+ HBr
H CH3
H Ph Ph
treo trans
Tch X2 (halogen)
_ ng phn treo cho anken cis
_ ng phn eritro cho anken trans
Br
H CH3 H CH3
E2 + Br2
H3C H (Aceton) H
H3C
Br
H CH3 H
Br H3C
E2 + Br2
Br (Aceton) CH3
H3C H H
eritro trans
2,3 dibromobutan but-2-en

H3C H CH3
Br H3C
E2 + Br2
Br (Aceton) H
H3C H H
treo cis

Phn ng tch E2 trn hp cht vng no

Theo quy tc Barton, cc nhm b tch v tr trans v trc.
H3C
CH3
H3C
H3C Cl CH3 3 menten (78%)
EtOH / EtONa
H3C H
t0 = 1250C
H H3C
CH3
H3C
 (nhanh)
clorur neomentyl
2 menten (22%)

H3C CH3

H3C CH3 H
H
H3C Cl mentyl
clorur Cl

H3C
CH3 + HCl
H3C2 menten (100%)
Ngoi l:
Theo quy tc Bredt, khng th to ni i ti u cu
ca hp cht vng cu (kiu hon).

Br
X Khng tn ti
1 bromo-biciclo [2,2,1] heptan
Vi cu trc rn chc ca hp cht vng cu, th s quay
quanh lin kt C( C( khng tin hnh c, nn phn ng
tch E xy ra th phi c s chn lc gia tnh phng v tnh trans
ca hai nhm b tch. Thc nghim cho thy tnh phng u tin
hn, lc hai nhm b tch v tr cis.
Th d:

Cl -HCl H
HH (d dng)
Cl
kh (-HCl)
Cl
trans 2,3 dicloronorbornan

Cl
H Cl

H
 cis 2,3 dicloronorbornan
7.2.2.2. Phn ng tch Ei
Phn ng tch Ei qua mt trng thi chuyn tip vng gm 5
hay 6 nguyn t, trong hai nhm b tch v tr cis i vi
nhau. Trng thi chuyn tip c cu trng che khut v cc nhm
trong cu trng s v tr cis trong anken hnh thnh.
R3
R3 A
R1
E2 R1
R4 + HB C
A R4
R2 z
H B A l : O, N, S R2
z B l : O hay S
Z l : R ; Ar ; SR ; OR ; NHPh ; Cl
Th d1:
H3C CH3
H3C H3C
CH3
H3C t0 CH3 +
O H3C
H
Ei
S H H3C
CH3S Ment-3-en ment-2-en
Metylxantat neomentyl (70%) (30%)
H3C
SCH3 CH3
S H3C
O
t0 Ment-3-en(20%)
H3C CH3
Ei
+ H3C S C SH
H H3C O
CH3
H3C H
Metylxantat mentyl H3C
Ment-2-en(80%)

Th d 2: Phn ng Cope (nhit phn oxit amin bc 3)

H3C CH3
Ei
H H 1300 C
H3C CH CH
But-2-en
CH3 + H C but-1-en
3
CH CH 2
CH2

H N CH3 21% cis

O
CH3 12% trans

7.2.3. Phn ng CNG AE

7.2.3.1. Phn ng cng i in t AE
 a) Halogen:
AE v theo kiu Trans.
C C
Phn ng cng AE qua phc trung gian vng, ion Carbonium
khng th quay t do quanh ni C C, nn ion X tn cng vo
ion Carbonium v pha i din .
Ankencis hn hp treo (()
Ankentrans hn hp eritro (()

CH3 CH = CH C2H5 + Br2 CH3 CHBr CHBr C2H5

Br
H CH3
C2H5
C2H5 H3C C2H5 H
H3C _ _ Br
+ Br2 - Br +
+ Br
H H
H Br Br H C2H5
cis
H

hn
H hpCH
(() treo
Br
3

Br
H CH3
H
C2H5 H C2H5 C2H5
H _ _ Br
+ Br2 - Br +
+ Br
H3C H C2H5
H Br Br H
H3C trans

eritro
H ()3 Br
CH

Br
C2H5 H C2H5 H
+ Br2
H CH3 H CH3
Trans pent-2-en
Br
 eritro ()
2,3 dibromopentan
b) Cng HX (HCl, HBr, HI, HO Cl)
u theo c ch AE, kiu trans.

AE Br
H3C
+ HBr
H
H3C CH3 HC 3

7.2.3.2. Phn ng cng ng thi

a) Hidro ha xc tc d th (Ni, Pd, Pr)
Phn ng cng theo kiu cis.

H3C CH3
Ni
H3C C C CH3 + H2
t0 H
C C
H

CH3
Ni
+ H2
t0
H3C
H
H3C CH3
H
cis 1,2 dimetylciclohexen cis (ea)
1,2 dimetylciclohexan
b) Hidroxil ha
S hidroxil ha ni i C=C bng dd KMnO4 hay OsO4
din ra theo hng cng cis phn ng qua trung gian Ester vng.

Na2 SO 3
+ KMnO4
O O H2 O
H H Mn
O O
cis ciclopentan-1,2-diol
HO OH
 S hidroxil ha bng peracid: phn ng tin hnh qua Eter
vng, sn phm hnh thnh theo kiu trans.

H O
H H H
+ CHCO
3 3H
+ CH3 COOH
C 2H5 H 3C C2 H 5
H 3C
cis pent-2-en _
H
O OH (dd)
3 N
HC H S2
__ treo __ 2
H
H
HC 5
O
7.2.4. Phn ng cng Nucleophile AN
i vi hp cht carbonyl c C* bt i xng
khi ()
phn ng AN cho hn hp hai ng phn bn i quang vi t l
khc nhau, sn phm chng theo ng hng quy tc Cram: phn
t cht carbonyl c sp xp sao cho nhm >C=O
nm trong nh din (Tb, L* C ( , N) v tc nhn thn hch Y tn
cng vo tm phn ng t pha nhm c kch thc nh hn (N).
R
L L
L _ R
R Y Y
+Y

Tb Tb N Tb N
N
O _O _O
(sn phm chnh) (sn phm ph)
L, Tb, N: k hiu cc nhm c kch thc ln lt l ln,
trung bnh, nh.
 PHN B

BI TP
NG PHN QUANG HC
Cu 1: Gi tn theo danh php (R,S) ca cc hp cht sau:
CH2OH CHO C2H5 COOH
H CH3 H3C CH(CH3)2 Br CH3 H3C NH2
Br H C2H5 CH3 H CH2Cl H CH2-CH3
C2H5 CH(CH3)2 CH C(CH3)3
CH
(A) (B) (C) 2 (D)
CH2OH COOH CHO COOC2H5
H Cl H OH H OH H NH2
H Cl H OH HO H H3C H
Cl H H OH H OH H3C C2H5
CH3 COOH CH2OH CH=CH2
(E) (F) (G) (H)

Cu 2: Gi tn (R,S) ca cc hp cht sau:

CHO CH3 Ph
HO CHO H CH3 HO CH3

H OH C2H5 NH2 H OH
H COOH C(CH3)3
(A1) (A2) (A3)

NH2 CH3
H CH3 Cl
CH3 H3C OH CH2Br
(B1)
COOH H COOH
H OH H3C H CH2OH
C(CH3)3
 (B2) (B3)

CH3
Cl CH3
H
CH2Br
CH3 CH2OH

(T1) (T2)
Br CH3
CH2OH OHC
C2H5 H

H Br CH3
(T3) (T4)

Cu 3: Hy chiu cc cng thc sau y sang cng thc

Fischer v gi tn chng theo danh php (R,S)
H3C C2H5 NH2
OH
H3C H
H COOH
H3C C2H5 OH
CH(CH3)2
(E1) (E2)
OH H3C C(CH3)3
C2H5 H3C H

H COOH CHO
H3C H Ph
(E3) (E4)
COOH H COOH
CH3
H3C H C2H5 NH2
C2H5
H NH2 C2H5 H H2N H
C2H5 COOH H3C
 (E5) (E6) (E7)
Cu 4: Cho cc ng phn sau y ca:
1 Bromo 3 metylpentan-2-ol
H OH H CH3
CH2Br CH3
H CH3 H OH

C2H5 H CH2Br C2H5

H OH C2H5 CH2Br
(X1) (X2) (X3)
OH CH2Br CH2Br
H CH3 H3C H H3C H

BrH2C H H OH HO H
C2H5 C2H5 C2H5
(X4) (X5) (X6)
Hy chiu cc cng thc trn sang cng thc chiu Fischer v cho
bit tng quan lp th gia:
(X1) v (X2) ; (X1) v (X3) ; (X1) v (X6).
(X4) v (X5) ; (X1) v (X4) ; (X2) v (X6).
Cu 5: Tng t cu (4) vi cc ng phn sau y:
COOC2H5 H Ph
H CH3 NH2

H2N H CH3
Ph H COOC2H5
(T1) (T2)
COOC2H5 COOC2H5
H3C H H Ph

H NH2 H2N H
Ph CH3
(T3) (T4)
Cho bit tng quan lp th gia:
(T1) v (T2) ; (X1) v (T3) ; (T2) v (T4).
Cu 6: Dng cng thc chiu Newman hy biu din cc hp
cht sau:
Cl (chiu
Cl ng thi theo cc trc chCH
H3C nh)
3
 (A) (B)
Cu 7: Gi tn y hai hp cht sau y:
Cl Cl
H3C NO2 Br
CH3

(X) Cl (Y)

Hy chiu ng thi theo cc trc ch nh hp cht (X) v

(Y) sang cng thc Newman.
Cu 8: Hy chiu cc hp cht sau y sang cng thc phi
cnh:
(A) Acid 2Samin3Sbromopentanoic
(B) 2RCloro3Shidroxibutandial
(C) Acid mesotartric
(D) Acid (2R, 3S) tartric
(E) (2R, 3S) dibromopentan
Cu 9: Hy chiu cc hp cht sau y sang cng thc
Newman
(X) Acid (2R) amino3Rclorobutanoic
(Y) (3R, 4S) dimetylhexan-2-on.
(Z) 2R, 3Sdibromo 4Zhexenoat etyl
(T) 2R, 3Sdibromo 4Ehexenoat etyl
Cu 10: Vit cng thc cu to ca cc hp cht sau y
chng c ng phn quang hc:
(A1) C4H8Cl2 (A2) C4H8ClBr
(A3) C5H11Cl (A4) C5H9Br
Cu 11: Vit c cu nhng ng phn lp th c th c ca
metylciclohexanon, c cu no c tnh quang hot?
Di tc dng ca baz, ceton quang hot hon ton b racemic
ha. Vy c cu no thch hp? Gii thch.
Cu 12: Xt phn ng:
RCOOH + [H] RCH2OH
 p dng cho mt hidroxiacid (A) C4H8O3 cho mt dialcol
(B) C4H10O2. Cho bit c cu c th c ca (A) trong nhng
trng hp sau:
a) (A) khng tch hai c v (B) khng tch hai c.
b) (A) quang hot v (B) khng tch hai c.
c) (A) quang hot v (B) quang hot.
Cu 13: Acid carboxilic (A) cha mt hay nhiu lin kt a
(c th c hoc khng c vng) c th hidro ha thnh
mt acid (B) bo ha.
Cho bit c cu ca (A) trong nhng trng hp sau:
a) A (C5H8O2) c th tn ti di hai dng u khng
tch hai c v B (C5H10O2) c th tch hai c.
b) A (C5H6O2) c tnh quang hot v B (C5H8O2)
khng tch hai c.
Cu 14: Mt hidroxiceton A (C5H10O2) c th kh thnh
mt diol B (C5H12O2).
Cho bit c cu ca A v B trong nhng trng hp sau:
a) A v B quang hot.
b) A khng tch hai c v B quang hot.
 NG PHN HNH HC
Cu 15: Vit cc cng thc cc ng phn hnh hc c th c
ca:
a) 1,2,3trimetylciclopropan.
b) 1,3dicloro ciclopentan.
c) (3metylciclobutyl)3metylciclobutan.
d) 1,4diphenylbutadi-1,3-en.
e) Acid butendioic.
f) antiOxim ca (naphtaldehid.
g) Etyl phenyl cetoxim.
h) 1,3dibromociclobutan.
Cau 16: Vit cng thc cu to cc ng phn hnh hc ca
nhng hp cht sau, gi tn chng theo danh php cu
hnh (E,Z)
a) C5H10
b) C4H7Br
c) C6H9Cl (Ankadien)
d) Aldehid C5H8O.
Cau 17: Acid 2,5dimetylhex-3-endioic c bao nhiu ng phn
lp th?
Hy biu din chng di dng cng thc Fischer v gi tn
theo danh php cu hnh.
Cau 18: Xc nh tng s ng phn lp th ca cc cht sau v
cho bit bn cht ca chng:
1. (A) 2hidroxipent3enal.
2. (B) 2,3dibromo hex4enoat etyl.
3. (C) 5metyl hept3en2ol.
Biu din hai ng phn trong s ny bng hnh chiu
Newman v xc nh bn cht ca chng.
Cu trng no ca mt ng phn trong s ny c th coi l
n nh nht? Gii thch.
Cau 19: Vit cng thc cu to ca C4H6ClBr hp cht c
ng phn:
a) Hnh hc.
b) Quang hc.
 c) Hnh v quang hc.
Cau 20: Vit cng thc cu to ca aminoacid c CTPT
(C4H7NO2) hp cht c ng phn:
a) Hnh hc.
b) Quang hc.
c) Hnh v quang hc.
 NG PHN CU TRNG

Cau 21: Dng cu hnh gh biu din su ng phn

dimetylciclohexan. Trong mi cp, cho bit ng phn
no bn hn v cui cng sp xp tt c su ng phn
theo th t bn gim dn.
a) Cis v trans 1,2dimetylciclohexan.
b) Cis v trans 1,3dimetylciclohexan.
c) Cis v trans 1,4dimetylciclohexan.
Cau 22: Dng cu hnh gh biu din cc ng phn cu trng
c th c ca:
a) 1etyl2metylciclohexan.
b) 1etyl3metylciclohexan.
c) 4etyl ciclohexanol.
d) 3etyl ciclohexanol.
e) 1,3dietyl5metylciclohexan.
f) 1etyl3,5dimetylciclohexan.
g) 3etyl5metylciclohexanol.
h) 5metylciclohexan-1,3-diol.
Tnh nng lng cc cu trng tng ng. (Da vo s liu
trang 84 - ha hc lp th )
Cau 23: Cho bit cu trng u i ca cc phn t sau y v
c nh nng lng cng ca chng:
a) 1,2,4trimetylciclohexan.
b) 1,2,4ciclohexantriol (tt c u cis).
c) Ciclohexan-1,3,5-triol (tt c u cis).
d) Cis1etyl3isopropylciclohexan.
e) Trans1metyl-3-phenyl ciclohexan.
f) 3tertbutyl4phenylciclohexanol (tt c u cis).
g) Acid cis 4-cloro-trans3metyl ciclohexan carboxilic.
h) Acid cis 3metyltrans4nitrociclohexan carboxilic.
Cau 24: V cu trng u i (trong dung mi khng phn cc)
ca cc cht:
a) 2bromociclohexanon.
b) 4tert butylciclohexanon.
c) 2bromo4,4dimetylciclohexanon.
d) Cis2,6dibromociclohexanon.
 e) 2bromo4tertbutylciclohexanon.
f) Trans 1,2dibromociclohexan.
g) Cis 1,3dihidroxiciclohexan.
h) Trans 1,3ditertbutylciclohexan.
i) 2,4ditertbutylciclohexanon.
Gii thch cu trng no c chn trong mi trng hp.
Cau 25: V cu trng ca nhng hp cht sau v sp xp chng
theo th t gim dn bn:
CH3 CH3 CH3

(A) (B) (C)

CH3

CH3 CH3
(D) (E) (F)
Cau 26: Xt cu hnh v tnh bn tng i ca:
a) Cis v transdecalin.
b) Cis v trans 9metyldecalin.
c) Cis v trans 9,10dimetyldecalin.
d) Cis v trans 1,3dimetyldecalin.

Cau 27:
a) Dng cng thc chiu Newman biu din cc ng
phn ca 9,10dihidroxidecalin. Cho bit cu trng no u i
nht? Gii thch.
b) Tng t cu hi trn, vi hp cht:
Ciclohexan-1,2-diol.
Ciclohexan-1,3-diol.
Cau 28: Dng cng thc chiu Newman biu din cc ng
phn ca nhng phn t sau y theo nhng trc ch
nh:
a)
CH2
 b)
CH3

C CH3

O
c)

C CH3

O
d)
H3C C C CH3

Cau 29: Biu din nhng

O O
phn t sau y sang cng thc phi
cnh v Newman:
Cau 30:
a) O O

C C
O O
C C

b) O O

c)
(ch chiu theo phi cnh)
 PHN NG TH SN

Cau 31: Gii thch kt qu thc nghim sau:

a) quang hat ca dung dch (+) 2phenyl
pentan-2-ol trit tiu khi un si trong HCOOH.
b) quang hat ca dung dch NaBr v (+)2
bromopentan trong aceton cng trit tiu dn dn.
Cau 32: Cho bit cc sn phm c th thu c ca (S) 1
phenyl1bromobutan trong acid acetic un si v trong
dung dch natri acetat vi aceton.
Cau 33: Di tc dng ca HBr :
Treo3bromobutan 2 - ol bin i thnh (() 2,3
dibromobutan.
Eritro3bromobutan 2 - ol bin thnh meso2,3
dibromobutan.
Kt qu trn c ph hp vi c ch [SN1] hay[SN2] khng?
Nu khng, hy gii thch.
Cau 34: Kho st s dung mi gii ca hai hp cht quang hot
sau y trong mi trng CH3COOH:
a) 3phenyl2tosiloxibutan.
b) 3phenyl2tosiloxipentan.
Cau 35: Dng cng thc tam th nguyn, hy gii thch ha hc
lp th ca cc s phn ng sau y:
a) (S) butan-2-ol Br
Tosilat Aceton Bromur

OH Alcol + Olefin
b) (R) - 1 - phenyletanol Clorur ankyl
Acetat quang hoat Alcol quang hoat
Tosilat Iodur (R) - 1 - phenyletyl
Cau 36: Gi s s thy gii Clorur ciscrotil bng nhng phn
ng ring bit theo:
- C ch SN1.
- C ch SN2.
 Trong mi trng hp, hy cho bit alcol crotil to thnh l
ng phn cis hay trans, hoc mt hn hp hai dng trn. Gii
thch.
Cau 37: D on sn phm to thnh trong phn ng ca SOCl2
vi:
a) R1phenyletanol.
b) OH
CH3

Cau 38: Sp xp cc nhm sau y theo th t gim dn phn

ng trong cc trng hp sau:
a) Phn ng aceto gii:
CH2Cl (CH3)2CHCl ; CH3CH2CH2Cl

CH2Cl

b) Phn ng vi KI trong aceton:

CH3OTS ; CH2=CHCH2OTS ;
(CH3)2CHOTS ;
H3C CH3
OTS

c) S metanol gii trong nhm xut l anion ca acid:

CH3
Ph C O C X
CH3 O

X: H; I; F; NO2; OCH3; CH3

Cau 39: Gii thch cc kt qu thc nghim sau:
a) S thy gii CH3OCH2Cl xy ra 1600 ln nhanh
hn s thy gii CH3SCH2Cl.
 b) Trong iu kin phn ng SN2, s thy gii halogenur
(metyl alyl xy ra 100 ln nhanh hn s thy gii halogenur
tert butyl alyl.
c) Clorur neopentyl khng tc dng vi NaOH d un
nng, nhng li cho phn ng vi hn hp Ag2O v H2O.
d) Tosilat neopentyl phn ng chm vi LiI v khng
phn ng vi LiCl. Tri li, tosilat nbutyl cho phn ng vi LiI
v c vi LiCl.
e) Cloro sunfit Sbutyl quang hot un trong dioxan s
cho clorur Sbutyl vi 97% lu gi cu hnh. Tri li, nu thc
hin phn ng trong Isooctan th s c 43% nghch chuyn.
Cau 40: Gii thch c ch cc phn ng sau:
a)
Br
Br + H 3C - COO
OCOCH3
(Aceton)
OCOCH3
Br OCOCH3
b) + H 3C - COO
Br
(Aceton)
OCOCH3

O C CH3 O CH3
c) + H3 C - COONa
O C
OTs (EtOH) O CH3

Cau 41: Dng cng thc phi cnh biu din ha hc lp th

ca cc phn ng theo s sau:
a) OH OH
O
Br CN
O
b) I COOH
C
O

Cl Cl

Cho bit tc cht cn thit trong mi giai on.

 PHN NG TCH

Cau 42: Khi metyl ha ti a v tch Hofmann, amin (A) cho

cis1,2diphenylpropen; trong khi amin (B) cho
transanken.
C6H5 C6H5
H NH2 H NH2
H CH3 H3C H
C6H5 C6H5
(A) (B)
a) Cho bit ha hc lp th ca phn ng tch Hofmann.
b) D on sn phm to thnh trong s tch Hofmann
ca mentylamin.
Cau 43: Tc dng ca ion iodur I( trn 1,2dibromo ankan to
thnh anken theo s :

C C + 2I C C + I2 + 2 Br
Br Br

Trong bn ng phn lp th ca 3tbutyl2,3

dibromociclohexan, ch c mt ng phn tham gia phn ng trn. Vit
cu hnh ca nhng ng phn ny v cho bit ng phn no c th
cho phn ng trn. Gii thch.
Cau 44:
a) un alcol neopentyl vi acid bin i t t thnh mt
hn hp hai alken c CTPT (C5H10) theo t l 85/15. Cho bit c
cu cc alken ny v gii thch s to thnh chng.
b) Bromur neopentyl c th cho phn ng tch theo c
ch E2 khng? un bromur neopentyl trong alcol long, dn dn
ta nhn c mt hn hp cc alken tng t trn. Gii thch.
Cho bit ti sao phn ng tng t nh trn m khng
cn n xc tc acid?
Cau 45: Sp xp cc hp cht sau y theo th t tng dn phn
ng E2. Gii thch.
Cl Cl Cl
Cl
H Cl
H

Cl
(A) H (B) (C)
Cau 46: Tin on sn phm chnh trong phn ng kh sau y
a)
CH3
H3 C CH2 CH C CH2 CH3 + NaOH t0
ac
CH3 Br
CH2OH
b) H2SO4

CH3
t0
H3C OH

+ _
c) H3C CH2 CH N (CH3)3OH t0

CH3

d) (CH 3)3COK
Br t0

Cau 47: Dng cng thc phi cnh biu th c cu lp th ca

cc hp cht trong s sau:
OH
CH3 OTs
Ph H H3C C 6H4 SO2Cl
Ph CH CH Ph
H Ph piridin
+ Br-
CH3 CH3 Br (CH 3) 3COK CH 3
Ph CH CH Ph Ph C CH Ph

CH3 Br CH3
+ Br2 C2H5ONa
Ph CBr CHBr Ph Ph C C Ph

Br
Cau 48: Xt cc ng phn cu trng ca diclorostilben
a) Biu din ba cu trng ng ch ca dng meso v
ca dng treo bng cng thc chiu Newman.
b) Momen lng cc ca dng meso ((=1,27D) nh hn
momen lng cc ca dng treo ((=2,75D). Gii thch.
c) Cho bit sn phm kh HCl ca hai dng trn.
Cau 49:
a) Tc dng ca C2H5ONa trn Eritro3,4dimetyl3
bromohexan quang hat trong mi trng C2H5OH a n mt
hn hp sn phm lm quay mt phng nh sng phn cc, trong
c bn cht (cha lin kt i C=C v cha eter).
Vit c cu cc sn phm phn ng v gii thch c ch.
b) Tc dng ca C2H5ONa trn Treo2bromo3
metylpentan quang hat trong C2H5OH cng cho mt hn hp
lm quay mt phng nh sng phn cc, hn hp ny ch cha hai
cht (c ni i C=C v cha eter).
Cho bit ha hc lp th ca cc sn phm phn ng.

Cau 50:
a) Kho st s cng brom vo trans v cisstilben. Vit
cng thc chiu Newman ca cc sn phm to thnh.
b) S tch HBr trong dibromur stilben bng dung dch
baz l phn ng bc hai.
Cho bit sn phm to thnh vi mi ng phn lp th
nguyn thy (dng cng thc chiu Newman gii thch).
c) Nu mt nhm CH3 thay th mt nhm phenyl trong
dibromur stilben, phn ng tch HBr xy ra nh th no?
d) Trong mi trng hp trn, sn phm no to thnh
nhanh nht?
 PHN NG CNG

Cau 51: Cc phn ng sau y c thc hin vi cis v trans

stilben:
a) Cng brom.
b) Cng acid performic, k thy gii hp cht nhn
c trong mi trng acid.
c) Hidrogen ha c xc tc.
d) Hidroxil ha bi H2O2 vi s c mt ca OsO4.
Trong nhng phn ng trn, phn ng no cho sn phm
ging nhau vi c hai ng phn, phn ng no khng cho sn
phm ging nhau?
Da vo c ch, gii thch cc kt qu nhn c.
Cau 52:
a) S brom ha trans1phenyloct-1-en. to thnh mt
hp cht c hai tm phi i xng, nh vy c th c hai dng bn
i quang. C hai dng ny c th to thnh cng mt lc c
khng? Cho bit tnh quang hot ca chng. Gii thch.
b) Bin lun v ha hc lp th cc sn phm to thnh
do s brom ha cc dng quang hot ca cis v trans. pent-3-en-2-
ol.
c) Tng t vi hp cht quang hot cis v
trans4bromopent-2-en.
Cau 53:
a) Tc dng ca acid peracetic trn cis1ciclohexil
propen cho mt hp cht A. Cho bit c ch phn ng ca A vi
dung dch NaOH v ha hc lp th ca sn phm B thu c.
b) Tc cht no c th dng c bin i trans1
ciclohexilpropen thnh sn phm B?
c) Cho bit c ch phn ng ca A vi dung dch HCl v
ha hc lp th ca sn phm nhn c.
Cau 54:
S brom ha acid succinic to thnh acid 2bromo
succinic (A) racemic nhng tch hai c. S thy gii (A) v
kh nc k tip a n B (C4H4O4).
Di tc dng ca brom, (B) bin thnh (C)
C4H4Br2O4 tiu trin v khng tch hai c.
 un trn dung im ca n (B) cho (D) C4H2O3, c th
thy gii rt d dng cho (E) ng phn ca (B).
Khi un nh, (E) ti sinh (D) nhanh chng, nhng khi
un trong dung dch nc, (E) bin i chm thnh (B).
Tc dng ca brom trn (E) cho (F) l ng phn ca
(C) nhng c th tch hai c.
Dng cng thc phi cnh (hoc Newman) xc nh
cu trng ca cc hp cht t (A) n (F).
Cau 55: Cho hp cht (A)
Ph Et
C C
Et

OMe
a) Tc dng vi HOCl, sau x phng ha phm vt
to thnh. Cho bit c cu ca hp cht (B) nhn c.
b) un (B) trong mi trng acid. Hp cht (C) to thnh
c tnh quang hot khng? Vit c ch phn ng.
c) Cho (C) tc dng vi LiAlH4, sau un trong mi
trng acid. Cho bit c cu hp cht (D) to thnh. (D) c hon
ton ging (A) khng?
Cau 56: nhit thng, 1,2dimetilenciclobutan cng mt
phn t anhidric maleic cho hp cht A (3 vng)
C10H10O3. 1500C, A ng phn ha thnh B (2
vng) v phn ng cng mt phn t anhidric maleic th
hai vo B thnh cht C (4 vng) C14H12O6. Xc nh
c cu ca A, B, C.
Cau 57: Xt phn ng ca CH3OH vo 1,2epoxypropan vi s
c mt ca:
a) CH3ONa.
b) H2SO4.
Cho bit c ch phn ng v c cu nhng sn phm to
thnh trong mi trng hp.
Cau 58: S kh (R) 3phenylbutan-2-on quang hot (A) bng
LiAlH4 cho hn hp hai ng phn (B) v (C) vi t l
5:2.
a) Xc nh c cu ca (B), (C) v gii thch ha hc lp
th ca phn ng.
 b) Kho st s dung mi gii dn xut Tosilat ca hai
alcol (B) v (C) trong CH3COOH. Cho bit c cu cc sn phm
v ha hc lp th ca phn ng.
Cau 59: Mt aldehid quang hot A (C9H10O) tc dng vi
CH3MgBr cho hai cht bn i quang B v C
(C10H14O) (B nhiu hn C). Cc bromur dn xut t B
v C (C10H13Br) ln lt tc dng vi KOH trong alcol
nhit cao cho hai alken ng phn D v E
(C10H12). S ozon gii D cho acetophenon v aldehid
acetic.
Dng cng thc chiu Newman biu din cng thc cc hp
cht A, B, C v gii thch cc phn ng xy ra.

Cu 59 Gii thch cc kt qu thc nghim sau y:

a) Khi lc hp cht 3,6-dimetyloctan-4-ol vi dung dch kim
, ch mt tm bt i xng b Racemic ha, cn tm kia
khng b Racemic ha.
b) Alcol neopentyl vi HCl cho 1 t sn phm l clorur
neopentyl, ngc li nu dng SOCl2 s c mt lng
ng k clorur neopentyl.
O
c) (S) Ph_CH_O_C_Cl t (S) Ph_CH_Cl + CO 2
1
CH3 O CH3
Di nhng iu kin c th thy gii c clorur tert-butyl
th hp cht (CH3)2C_COOC2H5 khng cho phn ng.
Cu 60 Gii thch kt qu thc nghim sau y:
a) Dng treo ca Ph_CH__CH_Ph
CH3 N(CH3)3I
phn ng vi C2H5ONa xy ra khang 50 ln nhanh hn dng
eritro
b) 2-Bromo-3-hidroxi ciclohexan carboxilat metyl b kh
HBr d dng trong mi trng baz yu, tri li lacton ca hp
cht ny li khng cho phn ng
c) Di tc dng ca baz, hp cht sau y cho 1 anken c
nhiu nhm th:
 CH3__CH______CH___C_CH3
11
N(CH3)3 CH3 O
d) Cho 2 hp cht: CH3
(A) (CH3)3C_CH2_C_Br
CH3
CH3
(B)CH3_CH2_CH2_C_Br
CH3
S kh HBr t (A) cho 1 anken t nhm th; cn t (B) cho
anken c nhiu nhm th.
e) Di tc dng ca baz mnh, 4-tert-butyl-ciclohexen c
to thnh t ng phn cis-1-Bromo-4-tert-butyl
ciclohexan nhanh hn t ng phn trans tng ng.
Cu 61 Di tc dng ca KI trong Aceton:
meso_ 2,3-dibromobutan cho trans- 2- buten.
treo(+;-) 2,3- dibromobutan cho cis- 2- buten.
Nhng meso- 1,2- dibromo- 1,2- dideuteroetan ch bin i thnh
cis-1,2- dideuteroetan.
Gii thch kt qu thc nghim trn.
 TI LIU THAM KHO

1. L Vn Thi, Ha hc lp th (tp 1), Si Gn, 1974.

2. ng Nh Ti, C s ha hc lp th, H Ni, 1988.
3. Trn Quc Sn, C s l thuyt ha hu c, H Ni, 1977.
4. Trn Quc Sn, Phan Tng Sn, ng Nh Ti, C s ha hc hu
c, H Ni, 1980.
5. Trn Quc Sn, Danh php ha hc hu c, H Ni; 2000.
6. Trn Quc Sn, Mt s phn ng ca hp cht hu c, H Ni, 1998.
7. Eliel, E.L., Stereochemistry of carbon compounds, Mc.Graw-Hill;
New York, 1962.
8. Hanack, M., Conformation theory, Acedemic Press, New York, 1964.
9. Eliel, E.L., Elements of Stereochemistry, Wiley, New York, 1969.
10. Clayden, Greeves, Warren and Wothers, Organic chemistry; Oxford
New York, 2001.
 HA HC LP TH

Ngi bin son: V Th Thu Hng

Chu trch nhim bin tp & phn bin: TS. Trn Th Tu

GIO TRNH HA HC LP TH ca Khoa Ha trng HSP TP.HCM

ng k trong k hoch nm 2003. Ban n Bn Pht hnh Ni b HSP sao
chp 500 cun, kh 14,5 x 20,5 theo Bin bn s 155/CTGT ngy 06 thng 10
nm 2003, xong ngy 25 thng 12 nm 2003.