You are on page 1of 149

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 H OH HO H COOH (+) COOH HO H H OH COOH (-) COOH H OH H OH COOH

Acid (+ mt s Acid () tartric gm -) tartricbng Acid meso-tartric quang (c nhau phn t i 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 CH3

OH

HO CH3

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.

Acid (+) lactic

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 b a
a

cis Xt v mt hnh hc th bn nhmtrans nm trn mt mt th 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 b

a b

a b trans

b a

cis

(a b)

Nm 1838, Liebig xc nh c s tn ti ca hai acid: maleic v fumaric l ng phn ca nhau. H COOH H H HOOC COOH HOOC H

acid maleic Mi n nm 1887, Wislicenus mi chng minh rng ng acid furamic 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 H H Cis (Meso) CH3 * H H CH3 H * ** 3 *3 CH H CH Trans 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.

H
H

CACH BIEU DIEN PHAN T METAN H H H H H H

H Cng thc H H chiu Fischer ca 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

- 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

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

H H mch chnh ca phn t Cng thc chiu Fischer:

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 H OH CH 2OH HO CHO H 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: COOH CHO PBr3
H * OH HgO H * OH CH2 OH Acid D-(+)-gliceric CH2 OH Acid D-(-)-gliceric

COOH H * OH CH2 Br Acid D-(-)-3-bromo-2-hidroxipropanoic Zn/HCl H

COOH * OH CH3 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 O H H O H O H C H 2O H D (+) glucoz H H O H H

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 H 2N H H OH CH 3 L (-) Treonin

HO H

CHO H OH CH 2OH

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.
H HO COOH OH H COOH

D (-) Treonin

Acid Ds (+) tartric Acid Lg (+) tartric

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 d c
d a

Cu hnh R

Cu hnh b S

1.5.3. Danh php E,Z i vi cc anken mang cc nhm th khc nhau


a b c 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 -CHO -C(N tng ng vi tng ng vi
O C H

C
O N

N 4. ng v c khi lng ln hn c sp xp trc: T > D > H 5. Cu hnh cis u tin hn trans; R u tin hn S Th d: COOH CH OH
2

H CH3
H H 3C

OH

H3C

OH CH2Br

(R)

CH 2-CH 3 CH 3

(S)

CH 2B r

(E)

H 3C

(Z)

CH 2O H

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 H
3NH 2

COOH H 2N H H HO HO H COOH COOH CH 3

(R) (R) (S)

CH COOH H H OH OH COOH

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) (4)

(5) (6)

(7)

(8)

(1)

(1) Ngun sng (2) Lng knh Nicol (3) nh sng phn cc (4) ng ng cht kho st

(5) Mt phng b quay (6) Thang chia (7) Lng knh Nicol phn tch (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

( t ( l c

: : : : :

gc quay o c trn my (tnh bng ) nhit khi o (0C) di sng ca nh sng s dng ca Hg ( = 546 nm ca Na ( = 589 nm chiu di ca ng ng cht kho st (dm) 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:

[] =

.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: [] = +11,98o 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 [M] = [] . M 100
t t D 20

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 3 quang hc lp thnh mt cp i quang :
COOH H OH HO COOH H

CH3 CH3 Acid (S) Lactic Acid (R) Lactic Th d 2: n = 2 c bn ng phn quang hc

Glucid tetroz
H HO CHO OH H CH2 OH HO H

CH 2 OH

* CHOH

* CHOH

CHO

CHO H OH CH2 OH

H H

CHO OH OH CH2 OH

HO HO

CHO H H CH2 OH

(A1) (2R,3R)

(A2) (2S,3S)

(A3) (2R,3S)

(A4) (2S,3R)

(A1) v (A2); (A3) v (A4) : (A1) v (A3); (A1) v (A4) (A2) v (A3); (A2) v (A4)

cp i quang cp bn i quang (ng phn lp th dia)

ng phn eritro treo


CHO HO H H OH CH2OH H HO CHO OH H CH2OH H H CHO OH OH CH2OH HO HO CHO H H CH2OH

(A1) (A1) (A3)

(A2) (A2) (A4) : :

(A3)

(A4)

; ;

ng phn Eritro 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 So nguyen t C*

Dng quang hot 2n-1 2n-1 2(n-1)/2

Dng meso 2(n-2)/2 2(n-1)/2

n = s chn n = s l
Th d: Acid tartric

* * HOOC CH CH OH OH

COOH

n = 2 c hai dng quang hot v mt dng Meso


H H COOH OH OH COOH H HO COOH COOH OH HO H H OH H 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 Mpx
C OOH OH H H OH H (I) 2 dang meso OH C OOH COOH H OH HO H H (II) OH COOH COOH H OH H OH HO (III) H COOH C OOH HO H HO H H OH C OOH (IV)

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 H OH CH 3 (1) H HO COOH OH H COOH (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 vtnh 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:
H CO OH H Ph Si * CH 3

OH

Acid CH 3 lactic (1)


H3 C O S

Metyl -naphtyl phenylsilan (2)


CH3 Ph 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 C C d c a C b C Q) C d c

b (a ( b) v (c ( d)

P) (P) ( (Q)

ALEN

b) Biphenyl: mang nhm th ng phn khng gian do s cn quay t do xung quanh lin kt n
COOH O2N HOOC NO2

HOOC NO2

COOH 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 H3 C H2N Br NH2 C H3

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 H3 C COOH HOOC H 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.

R N HOOC

Dn xut ca 4 - carboxiciclohexilidenimin
vi R: OH
NH C NH2
N

O 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 R H R H R

H
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 (CH2)8 O (A) (R) (B) H H H (S) H

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 Lasparagin v L-tritophan khng c mi v, cn L-leuxin v LTyroxin 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 Cl Cl
Cl

* CH

(C)

Cl

CCl3 (D)

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 2H C CH3 H COOH COOH

+ 2 Br2

Br

Br

2 HBr

CH3 (+)

CH3 (-)

Acid propionic
O H H H H OH H H H

Acid () -Brompropionic
CN H NC H OH H

HCN

+
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:
D1L1 + D2 D1D2 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 (+) + R-COOH (-) (hp chat Racemic) R1 N(-) R2 R3 - + R1 RCOO NH R2 R3 (-) (+) R-COOH (+) + - + R1 + RCOO NH R2 R3 (-) (-) R1 Cl R2 N H R3 (-)

ket tinh phan oan

muoi (+) (-) + HCl muoi (-) (-) + HCl

R1 R-COOH (-) + R2 NH C l 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 H (+)A NH2 + H2N CH3 Ph H CH3 (-)A
3 Acid (+) tartric * * (HOOC-CHOH-CHOH-COOH)

CH OH

Tartrat (+)(+A) Tartrat (+) (-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 Secbutylic ta tin hnh theo s sau:
OH C* C 2H5 + H O O O
_

H3 C

Piridin

COOH C O O

Ru (+)(-)
+ Bruxin (*) Tach 2 chat (+) va (-)

C 2 H5 C* H CH3

COO

C 2 H5 CH3
COOH

O *CH

H.Brunxin a tinh che


C 2H5 + Bruxin.HCl

(+)
+HCl

C O CH CH3 HO * H + C 2H5 O COONa +NaOH dd COONa hay +LiAlH4 CH3 CH2OH CH2 OH + HO CH3 * H C 2H 5

Cng thc ca Bruxin


N

CH3O CH3O O N 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

3.1. BN CHT CA NG PHN HNH HC


a C b P) Q) C b a

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

cis (X)

trans (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 H cis but-2-en. H 3C C 2H 5 CH 3 H H 3C H CH 3 H trans but-2-en. H 3C C 2H 5 H C 2H 5

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. (mc d c hai nhm etyl nm C H 2CH 3 C H 3CH 2

H C 2H 5 trans-3-metylhex-3-en.

H 3C

CH 2CH2CH 3

cng mt pha i vi mt phng)

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 C C Br H 3 C C C Cl

C H Z -1-Bromo-1-cloropropen l

Br H -1-Bromo-1-cloropropen E

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 Th d 1: hepta-2,4-dien

N = 2n-1 + 2(n-1)/2

CH3-CH=CH-CH=CH-C2H5 c bn ng phn hnh hc


H CH3 H cis - 2 - cis - 4 H H C 2H 5 CH3 H H trans - 2 - trans - 4 C2H5 H H

H H3 C H

H H

H3 C H C 2 H5 H

H C 2H 5 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 3C H C H3 H 3C H H H H CH 3

H H cis - 2 - cis- 4. H3 C H

trans - 2 trans - 4 . H CH
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 C b C C C b a

Th d: Nm 1959, Kuhn c lp c hai ng phn 1,4di-m-nitrophenyl-1,4-diphenylbuta.trien


NO 2 C NO 2 C NO C C O 2N

2 Trans Cis 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 H = 1,89 D cis

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 H3 C Cl H H3 C H Cl 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 C 2H5 OOC H H COOC 2H5

cis = 2,54 D

COOC 2H5 C 2H5 OOC

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.
Hp cht
CHCl = CHCl CH3 CH = CH - Cl CH3 CH = CH - CN C2H5OOC-CH=CH-COO C2H5

Tosi (oC) Cis


0,03 32,8 108 223

d20 (g/ml) Cis


1,2835 0,9350 0,8244 1,0520

n20 Cis
1,4486 1,4055 1,4182 1,4411

Trans
48,4 37,4 122 218

Trans
1,2565 0,9350 0,8239 1,0670

Trans
1,4454 1,4054 1,4216 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.
Hp cht HOOC CH = CH - COOH CH3 CH = CH - COOH Tonng chy (oC) Cis Trans
130 15,5 lng 287 72 125

pKa Cis
1,9 4,44 _

Thiu nhit Cis


327 486
1769

Trans
3 4,70 _

Trans
320 478 1739 1040

CH CH 68 133 3,96 4,44 1047 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 0,1nm

Vin UV 100nm

UV 200 nm

Kh kin 400nm 0,4

Cn IR 800nm 0,8

IR 8

Vi sng 25

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.
Hp cht
Stilben -metylstilben 1-phenylbutadien Acid cinamic

Cng thc
Ph-CH=CH-Ph Ph-C(CH3)=CH-Ph Ph-CH=CH-CH=CH2 Ph-CH=CH-COOH

TRANS max
295,5 270 280 295 29000 20000 28300 27000

CIS max
280 260 265 280

10500 11900 14000 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-1,2dicloroeten, 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 H H HJ = 12,3 Cps JH-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-but2-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 R H H H R R + Br + Br R H Br R H R Br H H 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 synhay antiH3C C H N OH H

..

H3C C N

OH

Syn Acetaldoxim

Anti Acetaldoxim
C N

..

(So snh v tr tng i gia nhm OH v H)

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

..

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.


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 H3C N CH3

Hp cht khc c ni i

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 HOOC N NH

..
O

..
C C N NH-C-NH2 O

Phenylhidrazon ca Acid O nitrophenylglioxilic

Monosemicarbazon ca benzyl

3.3.3. ng phn hnh hc ca hp cht c ni i N=N Diazoat


Ar

anti arildiazoat

..

..
N O

.
N Ar N

..
O

syn arildiazoat

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

N Ar

syn

CN

..

..

CN

anti

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

=0 trans azobenzen

..

.
N N

..

= 3D cis azobenzen

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 O N

cis azoxibenzen

trans azoxibenzen

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 H Cis H dimetylciclopropan 1,2

Trans 1,2 dimetylciclopropan H CH


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 H3C H H CH3 H H3C H C2H5 H H CH3 H CH3 C2H5 H H CH3

Cis cis

Cis trans ( Trans cis )

Trans trans

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) COOH HO OH HO H HOOC H HOOC tam oi xng H OH

H C OO H mat phang 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

_ Cng thc Newman:


H H H H H

cau trang lech

cau trang che khuat


H H

Nhn theo trc CarbonCarbon, thy H H cc ni CH ca mt H H 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 H H H H CH3 CH3 H H C H H CH3

H Cu trngH lch ca npentan i H

CH3 H H

H H C H

CHH 3 H H C H

H H

H3C

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 H Cu trng i lch trong nhexan H H H H H C H H H

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 H H H H Cl i lch H H Cl Cl H H Bn 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.
H Cl H H H H Cl

...H

O H

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

H i lch OH

Bn lch H

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 H H3C CH3 H Br meso (A)
Br H H Br Br Br H3C H CH3 H

Br Br H3C CH (A1)3 H H

H3C H3C

Br Br H H (A2)

H3C H3C

H H3C

Br 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
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

4.5.1. Phn t cha nhm

nguyn t Hidro che khut nhau c xc nhn bi ph nghim viba v nhiu x in t.


HO H CH
2

H3C

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 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 C O O H2C H C O
H C OCH3
O H C OCH3

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 H2C O

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 H CH2 H H2C H H

CH2

S_cis

S_trans

Cu trng ca buta1,3-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 transpent-3-en-2-on l mt hn hp cn bng cha cu trng Scis v Strans vi s lng bng nhau.
H O H3C C CH3 O H

H H3C C S_cis S_trans Cu trng ca Trans-pent-3-en-2-on . H

CH3

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.
Hp cht Cng thc Ro nng lng (Kcal/mol)

Etylen 2buten Acid butendioic Stilben

CH2=CH2 CH3CH=CHCH3 HOOC-CH=CH-COOH PhCH=CHPh

40 18 15,8 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 Cu trng ca hp cht vng nh 5.2. 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

_ Vi Brom, HBr, HI v H2SO4

80oC

CH3-CH2-CH3

+ +

Br2 HBr

CH2Br-CH2-CH2Br 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.

+
_ Vi HI:

Ni 180 oC

CH -CH -CH -CH


3 2 2 3

HI

t0

CH3-CH2-CH2-CH2I

_ 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 3 4 5 6 7 8 9 10

60 900 1080 1200 128,6 135 140 144

+24,7 +9,7 +0,7 5,3 9,6 12,8 15,3 17,3

n 11 12 13 14 15 16 17

147,3 150 152 154,3 156 157,5 159

18,8 20,3 21,5 22,4 23,3 24 24,7

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) n H/n 3 166,6 4 164,0 5 158,7 6 157,4 7 158,3 8 158,6 9 158,8 10 158,6 11 158,4 12 157,7 13 157,8 14 157,4 15 157,5 16 157,5 17 157,2 nankan 157,4

(3) H/n157,4 9,2 6,6 1,3 0,0* 0,9 1,2 1,4 1,2 1,0 0,3 0,4 0,0* 0,1 0,1 0,2 0

(4) 1/n(H/n157,4) 27,6 26,4 6,5 00 6,3 9,6 12,6 12,0 11,0 3,6 5,2 00 1,5 1,6 3,4 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 Cu trng ca ciclohexan

dng tu

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 Ciclopropan H

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 (e) (a) H H H H H H H H H H H

H Cu trng xp ca ciclobutan

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 H 3C H COOCH 3 H

COOCH 3 H

Cis ee
CH 3

H H

Cis aa
COOCH 3 H COOCH 3
3

HC

Trans ea 3metyl ciclobutan carboxilat metyl

Trans ae

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

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 4 e 5 e' a' a' e 3 a 2 e' 1 b b e e' a' 2 b' 4 a e a 3 b 1 a' 5 e'

b e a b Cu trng phong b ca ciclopentan 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 4 3 5 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 CH3 CH Cu trng 1,3dimetyl ciclopentan 3

Cis (ee)

Trans (ea)

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.
()

.
6

a
(e )

()

()

Trc i xng bc 3 Ni trc (a)


5 4 3 1

Ni xch o (e)
3 4 5 6 (a) (e) 2 1

(e) (a) ( hnh chiu Newman)

Cu trng gh ca ciclohexan

Khong cch gia hai nguyn t Hidro trong cu trng gh. Kiu Bn lch V tr 1He - 2He 1Ha - 2He Khong cch A0 2,49 2,49

Trans Nh trc

1 Ha - 2Ha 1Ha - 3Ha

3,00 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

bs

fp H 4 5 3
2.27A0

H fp 6 2 ab 1 bs
2.49A0

fp 6 5 4 1 3 bs 2

eb

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 Ct c Che khut Bn lch Trans Nh trc V tr 4fp 1fp 3eb 2eb 2ab 3ab 1bs 2eb 1bs 2ab 1fp 2eb 3eb 2ab 1fp 2ab Khong cch A0 1,84 2,27 2,27 2,49 2,49 2,49 3,00 3,00
fp 1 4 5 3 6 2 1 eb eb 5 bs bs 4 6 3 ab a
b

eb eb 2

abab

Cu trng tu 5.3.2.3. Cu trng tu xon

Hnh chiu Newman ca cu trng tu

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 4 3 1 5 2 H H H 4 6 5 2 1 H H

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 H H X H H

2,55A0

2,8A0

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.
H H H3C CH3 CH3 CH3 CH3 Nhm tertbutyl xch CH3

Nhm tertbutyl trc 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 CLVT Br I OH OCH3 OCOCH3 OTs SH SPh Nhm Go NH2 1,21,8 1,2 COOH 1,1 COOCH3 0,2 CN 1,7 CH3 1,8 C2H5 2,1 Pri 2,1 Bu 5,6 But 3,1 Ph Hiu s nng lng t do cu trng trong ciclohexan mang nhm th ((Go : Kcal/mol) Go 0,40 0,50 0,4 0,60,9 0,7 0,7 0,7 0,9 0,8

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

cis ea

CH3

3 cis ae CH3

HC

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
CH3 CH3

Cis CH3 aa
H3C

CH3

Trans ea

Trans ae

CH - Cu trng cis ee khng c tng tc butan bn3 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 H3C CH3 CH3

Trans ee
CH3 CH3 H3C

Trans aa

Cis ea

Cis ae

CH3

- 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 H3C H3C CH3 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 CH3 Cu trng tu xon

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 ee = 1,7 D + Trong CCl4 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

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.

( = 3,1 D) CisBr ea

Br

- 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 HO CH3

eee

Mentol (Trans trans)


CH3

eae

Neomentol (Cis trans)


CH3 OH

HO Isomentol eea (Trans cis)

Neoisomentol 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 OH CH3 OH Neocarvomentol (eae)

Carvomentol (eee)

CH3 OH

CH3

Isocarvomentol (aee)

OH Neoisocarvomentol (aae)

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 Hexaclorociclohexan (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 (b) aeaeae* eaeaea* 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:
1 7 6
5

8 5 10 H 4

. H 9 4

1 3

H 9 10

7 6

3 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
1 5 10 4 9 H 8 10 2 3
9 8 7 6 5 10 1 4 2 3

1 4 3

7 6

7 5

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(A) HO H H H H H OH

(B)

Transcis1decalol decalol

Transtrans1

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 H

(C)
H

(D)

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 HO H H 1 H HO H H H H 1 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).
H 1 OH OH 1 H 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 H HO H

(E)
Ciscis2decalol
H H OH H H H

(F)

OH H

(G)
Cistrans2decalol

(H)

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 5 8 3 1 2

Cng nh decalin, hidrindan c th tn ti di hai dng cis v trans.

4 9

TRANSHIDRINDAN: c hai vng sc hp bi hai ni xch o.


H

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


H H

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:
6 5 4 CH3 8 9 3 CH3 1 H 2 CH3

trans Dng Stroid

cis (metyltrc) cis (metylxch o) 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)
H 6 H 5 OH 4 9 3 H HO 5 H 1 4 H 2 cistrans H H 7 8 H 2 1

(B) ciscis
HO 6 7 H 5 4 8 1 H H 9 H 2

(C)

(D)
OH

3 Cu trng ca Cishidrindan5ol

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 Ha hc lp th ca polymer 6.2. 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 Sn cn bn 6.3.1. 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:
H3C H Ph CH3

* Si
Metyl - - naphtyl phenyl silan

* Si
H Ph

H3C

CH3

* Ge
H Ph

Ge* H 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 R R' R'' R''

N 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 R R' R'' R N R' R'' R R' N R'' R'' R' N 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.
R N R' Y Y X X N R' R

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 H3C N HO3S CH3 HOOC CH2 H3C N

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 H3C N N CH2 CH3 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 N H3C CH2 CH CH2 O N O CH3

[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-phenylbenzyl amoni iodur v cc mui amoni bc 4 thnh cc dng i quang.
CH3 CH3

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 X X

X X P ha tr 4

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

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-HOOCCH2-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
H3C

P
CH3

CH2 (CH2)2 CH3 CH2 (CH ) CH3 Hai i quang ca metylnbutylphenyl phosphin 2 2

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 R' (I)

R OR' (II)

R R' (III)

R''

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 ; CH3 H3C

Cc mui sulfonium, selenonium c c lp di dng trin quang t lu. 2+


HOOC-CH2 H3C H5C2 S

2-

PtCl6

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

Syndiotartic
R

Atartic

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

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 H CH2 H
n

CH CH2

CH2 H

H CH2

Cis polybuta 1,4-dien


CH2 H CH2 C CH CH2 H CH CH2
n

Trans poly buta-1,4-dien


CH2 C H CH CH CH2 CH2 CH2 C H
n

* C

Polybuta-1,4-dien Isotartic

Polybuta-1,2-dien 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-3,4c yu t polymer-1,2lp th ngu nhin.
CH2 H3C CH2 H
n

CH2 H3C

H CH2

Polymer cis 1,4 isopren


CH3 CH2 C

Polymer trans 1,4 isopren


CH2 CH C

*
CH

2 n Polymer 1,2 isopren

CH

Polymer 3,4 isopren n

H3C

CH2

S trng hp cc monomer kiu R-CH=CH-CH=CHR c th to thnh polymer :


CH R

CH

CH

* CH
R'
n

lm xut hin cc tm carbon bt i nn polymer c th tn ti 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 O H H H OH H OH OH OH H glucoz
CH2OH HO CH O OH H OH OH HO

CH2OH O OH OH

OH

OH glucoz
CH2OH CH O OH H H H OH H OH

Dng piranoz

glucoz

glucoz Dng furanoz Cng thc HAWORTH


HOH2C HO HO O OH OH

CH2OH HO HO

O OH

OH D glucopiranoz D glucopiranoz D-Fructoz: c th tn ti di dng furanoz tng ng vi hai ng phn (-D-Fructozfuranoz v (-DFructofuranoz bn cnh dng mch h.
CH2OH HO H H O H OH OH CH2OH 6 1 HOH2C O CH2OH 5 HO 2 OH H 4 OH 3 () 6 HOH2C O OH () 5 HO 2 CH2OH H 4 3 1 OH

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 HO HO O HO HO OH OH CH2OH OH CHO HO HO CH2OH O OH OH

HO

( D glucopiranoz

[ ]

20

mch h

( D glucopiranoz

= 1120 6.2.3.2. Disacarid

[ ]

20

= 19,20

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 HO HO 3 O 2

HOH2C OH O 4 HO 3

O 2 1

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

(hidroxiglucosid) OH OH

3 HO O 4 5 2

OH 1 O

OH

Nu hai nhm hidroxiglucosid ca hai loi ng (monosacarid) kt hp vi nhau th disacarid to thnh khng c tnh kh. Th d:

Lactoz

HOH2C 6

+ Sacaroz (sucroz) hay D glucopiranosil(Dfructofuranosid hoc (D fructofuranosilDglucopiranosid.


+ Trehaloz hay -D-glucopiranosil--D-glucopiranosid.
HOH2C HO HO O 1 CH2OH 3 OH

( )

O HO 4

5 CH OH 6 2

HO O 2 ()

Sacaroz
HOH2C HO HO O
() 1 OH

HO O

()

TREHALOZ

3 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 HO O 4 HOH2C O HO HOH2C 4' O

...

()
1' O HO

OH () O 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)

OH

...HO

HOH2C

O CH2OH HO O HO HO O HOH2C O HO O

( )
HO O

Amyloz

...

H O 2C H O H O 2C H O O

H O 2C H O H O 2C H

O 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 11 1 10 9 A 4 5 B 6 C 13 17

2 3

D 16 14 15 8

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.
28 21 12 1 2 3 4 11 19 9 5 18 17 16 14 15 20 22 24 23 27 29 25 26

13 8 7

10

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.
12 11 1 2 3 4 10 5 9 8 7 14 15 13

R
17 16 1 2 3 4

10

56

. .
5

17

13

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.
11 2 10 6 9 8 13 12

C
14

D
15

17 16

A
3 4

10 1

5
11

7
13 12 15 14 17 16

8 9 6 7

2 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).
3 11 19 3 2 12 10 9 4 7 6 1 8 5 13 16 14 15 17 18 H C O

H3C
CH3
13 11 17 12 8 9 6 7 14 15 16

CH3
2 1 10 4 3 5

HO

25 26 24 23 22 27

+H2
CH3

CH3 R

+H2

2 0 1

CH3
1

H
5

6 2 1 4 10

CH3
9

11

12

13 17

8 7

HO

HO
3

14

15

16

R C8HH 17

(t pha () ( )

COLESTEROL

(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)
CH Acid colic 3 CH
3

(a)
CH3
1 (e)

OH COOH
7

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 H H HO H HO H H3C OH H H

Estron

Estradiol

CH3 H3C OH H H H O H3C H3C C H O

Estriol

Progesteron
CH3 H H H O CH3 O CH3 CH3 O

HO

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

Cu to lp th ca
H3C O

H3C H HO

H H

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 Hiu ng cu trng 7.1.5. 7.1.6. Hiu ng orto Hiu ng qua nhn 7.1.7. 7.1.8. Tnh cht c nh ca cu trng _ Quy tc Ingold _ Quy tc Barton _ Quy tc cng endo Ha hc lp th ca cc phn ng 7.2. 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 ditertbutylceton 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 pKa Phenol 10,0 pnitrophenol 7,2 3,5dimetyl4nitrophenol 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 SH _ NH _ OH C _ _ Th d: 2
Br O

NaOH loang

H H3 C

O
O (S) lacton

H O H3 C Ion (R) bromopropionat

NaOH ac

HO

H O H3 C 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 H3C CH3

H H 2 bromobutan

- HBr E2

CH3

H3C

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 H H OTs H

- TsOH E2

CH3

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 H O
Anhidric maleic O

O Sn phm cng Endo

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 7.2. HA HC LP TH CA PHN NG
7.2.1. Phn ng th (substitution) 7.2.1.1. Phn ng SN2

OH

Phn ng SN2 xy ra vi s nghch chuyn cu hnh ca tm phn ng;

qua trng thi chuyn tip


C 2H5 H H3 C Br + ddNaOH SN2

HO H

C 2H5 Br CH3

-Br

C 2H5 HO H CH3

(S) 2 brombutan 7.2.1.2. Phn ng SN1

(R) butan-2-ol

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 R2 R3 + _

-X X g1
R2

R1 + R3

Y g2 R2

R1 Y R3

R1

+Y

R2 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 * Cl H (R) Ph

+ H2 O

H O H H

CH3 Cl Ph

CH3

- HCl

HO

(S)
H3C H Ph HO

+ H2 O
H O H H

- HCl
CH3 O Ph H H

10%
OH

Ph

CH3 H Ph

hn hp (()

90%

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 R2 R3

_ _ OH

Cl

- HCl
S O

R1 O R2 R3 Cl S O

t0

R1 Cl R2 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 R2 R3 _ _ O H

+ SOCl2
(piridin) - HCl

R1 O R2 R3 Cl S O

* + HCl

N H

+ *Cl

R1

*Cl

_
R2 R3

O S Cl O

t0 - SO2

*Cl

R1 R2 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
HH

R SN2'

+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 R2 R3

+
R1

-X

R1 R2

(M : kim loi)

R3

R1 COOH +
Hn hp (()

HOOC R3 R2

R2 1) + CO2 2) + H2 O R3 R1

H Hn hp (() H R2 R2 R3 Ngi ta gii thch s Racemic trn SE nh sau: phn ng SE R3 qua trung gian ion Carbanion tng t nh s nghch chuyn cu hnh ca NH3 v amin.
R1 M R2 R3 + M

R1

R1 R2 R3

R1 R2

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 C 2H 5 ClCH 2 Cl H

+ Cl (- HCl)

.
H 3C ClCH 2 Cl

CH 2Cl C 2H 5

+ Cl 2

H 3C CH 3 C 2H 5 hn hp (() 1,2 dicloroC 22 metylbutan H5

2Cl

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 H H Ph Ph NaOH / EtOH,t0 E2 H3C H Ph

+
Ph

HBr

Eritro 1 bromo 1,2 diphenylpropan


Br H H3C H Ph NaOH / EtOH,t0 E2 Ph

cis metyl stylben


H Ph CH3

+
Ph

HBr

Eritro

cis

Br Ph H H treo CH3 Ph NaOH / EtOH,t0 E2

Ph H

CH3 Ph

HBr

trans
Ph Ph

Br H

CH3 H

NaOH / E2

EtOH,t0

H Ph

+
CH3

HBr

Ph

treo

trans

Tch X2 (halogen) _ ng phn treo cho anken cis _ ng phn eritro cho anken trans
Br H H3C Br
Br H3C H CH3 Br

CH3 H

E2 (Aceton)

H H3C
H3C H

CH3 H

+
H

Br2

E2 (Aceton)

+
CH3

Br2

eritro 2,3 dibromobutan


Br H3C Br H H3C

trans but-2-en
CH3

H3C

E2 (Aceton)

+
H

Br2

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 H3C H3C H Cl H CH3 CH3

EtOH / EtONa t0 = 1250C

H3C

3 menten (78%)

H3C H3C

CH3

(nhanh) clorur neomentyl 2 menten (22%)


H3C H3C H3C Cl clorur mentyl CH3 H Cl CH3 H

H3C

Ngoi l:

2 H3C

menten (100%)

CH3

HCl

Theo quy tc Bredt, khng th to ni i ti u cu ca hp cht vng cu (kiu hon).

1 bromo-biciclo [2,2,1] heptan

Br

Khng tn ti

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:
-HCl (d dng)

Cl HH

H
kh (-HCl)

Cl

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.
R1 R2 A H B R3 R4 E2 R1 R3 R4 A

HB

A l : O, N, S R2 B l : O hay S Z l : R ; Ar ; SR ; OR ; NHPh ; Cl
CH3 H3C CH3

Th d1:
H3C H3C O H CH3S S H

t0 Ei

H3C H3C

+
H3C

CH3

Metylxantat neomentyl
SCH3 S O H3C H CH3 H

Ment-3-en (70%)
H3C H3C CH3

ment-2-en (30%)

t0 Ei

Ment-3-en(20%)

+
CH3

H3C

C O

SH

H3C H3C

Metylxantat mentyl

H3C

Ment-2-en(80%)

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


H3C H H O CH3 H 1300 C N CH3 CH3

Ei

H3C CH

But-2-en 21% cis 12% trans

CH

CH3

CH CH + H C but-1-en
3 2

CH2

7.2.3. Phn ng CNG AE 7.2.3.1. Phn ng cng i in t AE

a) Halogen: AE v
C C

theo kiu Trans.

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 Ankentrans
CH3 CH = CH C2H5 + Br2

hn hp treo (() hn hp eritro (()


CH3 CHBr CHBr C2H5

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

+
H

cis H

hn hp (() treo CH Br H
3

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

+
H

Br Br

eritro CH3 Br () H
C2H5 H H Br

+
CH3

Br2

C2H5 H Br

H CH3

Trans pent-2-en

eritro () 2,3 dibromopentan

b) Cng HX (HCl, HBr, HI, HO Cl) u theo c ch AE, kiu trans.

+
H3C CH3

HBr

AE

H3C

Br

H HC 3

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

H3C C C CH3

H2

Ni t0

H3C

CH3

C
H

C
H

+
cis 1,2 dimetylciclohexen
H3C CH3

H2

Ni t0

CH3 H3C H H

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.

+
H H

KMnO4

Na2 SO 3

O Mn O

O O

H2 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.
O

H
3 + CHCO3H

H H 3C H O

+
C2 H 5 _

3 CH COOH

H 3C

cis pent-2-en

C 2H5

__ treo __

HC

H HC O

H
5

OH (dd) N S2
H

7.2.4. Phn ng cng Nucleophile AN i vi hp cht carbonyl c khi C* () bt i xng

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 +Y Tb O N L _ R Tb _O Y N Y Tb _O N L R

(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:
H Br

Gi tn theo danh php (R,S) ca cc hp cht sau:


CHO H3C C2H5 CH(CH3)2 CH3 CH(CH3)2 Br H CH CH C2H5 H3C CH3 H CH2Cl COOH NH2 CH2-CH3 C(CH3)3

CH2OH CH3 H C2H5

(A)
CH2OH H H Cl Cl Cl H CH3

(B)
COOH H H H OH OH OH COOH H HO H

(C) 2
CHO OH H OH CH2OH H H3C H3C

(D)
COOC2H5 NH2 H C2H5 CH=CH2

(E)

(F)

(G)

(H)

Cu 2:
HO H

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


CHO CHO OH H H C2H5 CH3 Ph CH3 HO H CH3 OH C(CH3)3

(A1)

(A2)

NH2 COOH

(A3)

(B1)
H

CH3 OH

CH3 COOH

NH2 H3C OH H C(CH3)3 COOH H3C

CH3 CH2Br H

Cl

CH2OH

(B2)
CH3 Cl H CH3 CH2OH

(B3)

CH3 CH2Br

(T1)
Br C2H5 H Br CH2OH OHC H CH3

(T2)
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)
OH H3C H3C C2H5 NH2 H3C H H CH(CH3)2 COOH

C2H5 OH

(E1)
OH C2H5 H3C H H COOH H3C

(E2)
H

H3C

C(CH3)3 CHO

(E3)
C2H5 C2H5 CH3 NH2

Ph

(E4)
H COOH H2N H3C H C2H5

H3C H

COOH H C2H5 NH2

H COOH

(E5) (E6) (E7) Cu 4: Cho cc ng phn sau y ca: 1 Bromo 3 metylpentan-2-ol


CH2Br H OH H CH3 C2H5 OH H CH3 H C2H5 CH2Br CH2Br H H OH CH3 C2H5

(X1)
OH H BrH2C CH3 H C2H5

(X2)
CH2Br H OH C2H5

(X3)
CH2Br H H C2H5

H3C H

H3C HO

(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:
H CH3 Ph H2N COOC2H5 H H COOC2H5 NH2 H Ph CH3

(T1)
COOC2H5 H Ph NH2

(T2)

COOC2H5 H H2N CH3 Ph H

H3C H

(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: (chiu ng thi theo cc3C ch nh) H trc CH3 Cl Cl

Cu 7:

(A) (B) Gi tn y hai hp cht sau y:


H3C Cl NO2 Cl 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 (2R, 3S) dibromopentan (E) Cu 9: Hy chiu cc hp cht sau y sang cng thc Newman (X) Acid (2R) amino3Rclorobutanoic (Y) (3R, 4S) dimetylhexan-2-on. 2R, 3Sdibromo 4Zhexenoat etyl (Z) (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 (A4) C5H9Br (A3) C5H11Cl 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. (3metylciclobutyl)3metylciclobutan. c) 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)
CH3

(C)

(D)

CH3

(E)

(F)

CH3

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 O CH3

c)
C CH3

d)
H3C C

O C CH3

O O Cau 29: Biu din nhng phn t sau y sang cng thc phi cnh v Newman: Cau 30: a) O O

C O C

C O C O

b) 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

Cau 36: Gi s s thy gii Clorur ciscrotil bng nhng phn ng ring bit theo: - C ch SN1. - C ch SN2.

Clorur ankyl Acetat quang hoat Alcol quang hoat Tosilat Iodur (R) - 1 - phenyletyl

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 CH3 O X

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
(Aceton)

b)

Br Br

+ H 3C - COO
(Aceton)

OCOCH3 OCOCH3

OCOCH3

OCOCH3
O O CH3 CH3

c)

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

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

b)

COOH

O 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 H H NH2 CH3 C6H5 H H3C C6H5 NH2 H 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

+ 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 H Cl H Cl Cl

(A) H
CH3 C Br

(B)

Cl

(C)

Cau 46: Tin on sn phm chnh trong phn ng kh sau y a)


H3 C CH2 CH CH3 CH2 CH3

NaOH

ac

t0

b)
H3C

CH2OH CH3

H2SO4 t0

OH

c)

H3C

CH2

CH CH3

_ N (CH3)3OH

t0

d)
Br

(CH 3)3COK t0

Cau 47: Dng cng thc phi cnh biu th c cu lp th ca cc hp cht trong s sau:
OH Ph H H Ph CH3 H3C C 6H4 SO2Cl CH3 Ph CH OTs CH Ph

piridin

+ Br-

Ph

CH3 Br CH CH Ph
CH3 Br CHBr

(CH 3) 3COK

CH 3 Ph C CH Ph
CH3 Ph C C Br Ph

+ Br2

Ph

CBr

Ph

C2H5ONa

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-2ol. 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 Et C C 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

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:

d) Cho 2 hp cht: CH3 (A) (CH3)3C_CH2_C_Br CH3 CH3 (B)CH3_CH2_CH2_C_Br CH3

CH3__CH______CH___C_CH3 11 N(CH3)3 CH3 O

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.

You might also like