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biz/phim/ Chng 1 : NG PHN HC

Phn loi ng phn - ng phn cu tao (cng cng thc phn t, khc nhau v cu to ha hc) : ng phn mch C, ng phn v tr nhm chc, ng phn nhm chc. V d - ng phn lp th (cng cu tao ha hc, khc nhau v cu trc khng gian) : ng phn hnh hc, ng phn quang hc. V d 1. NG PHN PHNG

1.1.ng phn v tr nh ngha: L nhng ng phn c cng nhm chc nhng khc nhau do dng ca mch carbon hoc do v tr khc nhau ca nhm chc trn mch carbon. Th d: * C4H10 c 2 ng phn khc nhau bi dng ca b khung carbon : CH3 CH2 CH2 CH3 n-butan s = 0 (T 0C)
CH3 CH3

CH3 CH CH3 CH3 isobutan s(T 10 = 0C)

CH3

* o-cresol, m-cresol v p-cresol l nhng ng phn v tr:

OH OH

Cc ng phn v tr c tnh cht ho hc ging nhau, ch mt vi tnh cht khc nhau cho php phn bit chng. Cc tnh cht vt l l khc nhau, nhng khng nhiu. 1.2. ng phn cu to nh ngha: L nhng hp cht c cng mt cng thc phn t nhng c ho chc khc nhau dn n c nhng tnh cht vt l v ho hc khc nhau. V d : C3H6O c cc ng phn sau: Tn CH2=CH CH2OH Alcol ethylenic CH3 CH CH2 O CH3 O CH CH2 CH3 CH2 C CH3 C CH3 O O H aceton Loi nhm chc epoxyd

OH

ether oxyd ethylenic ete aldehyt ceton

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2. NG PHN LP TH S phn b khc nhau trong khng gian ca cc nguyn t hoc nhm nguyn t trong phn t cc hp cht hu c c cng s lng, bn cht v th t lin kt ca cc nguyn t trong phn t, c gi l ng phn lp th. C ba loi ng phn lp th: - ng phn hnh hc. - ng phn cu dng. - ng phn quang hc. 2.1. ng phn hnh hc ng phn hnh hc c th xut hin nhng hp cht c lin kt i hoc nhng hp cht vng no 2.1.1.ng phn cis-trans hoc E/Z hp cht ethylenic ng phn cis-trans l do s phn b khc nhau trong khng gian ca cc nhm th so vi lin kt i. Mt alken m mi C lai sp2 mang 2 nhm th khc nhau, c th tn ti di 2 dng ring bit v c th phn lp:
R C H C H H R R C C R H

cu h cis (hay Z) nh

cu hnh trans (hay E)

iu kin duy nht xut hin ng phn cis-trans hp cht kiu RR1C=CR2R3 l mi carbon cha lin kt i phi lin kt vi hai nguyn t hoc hai nhm nguyn t khc nhau: R R1 v R2 R3. Trong trng hp cc nhm th khc H, s dng qui c xc nh th t u tin ca cc nhm th khc nhau da trn s th t nguyn t, gi l qui tc u tin ca Cahn, Ingold v Prelog. Qui tc ny nh sau: - Nu 4 nguyn t lin kt vi trung tm bt i l khc nhau nguyn t no c s th t ln hn th c mc u tin cao hn. I > Br > Cl > S > F > O > N > C > H - Trng hp hai nguyn t ging nhau th phi xt tip cc nguyn t tip theo th hai, ri th ba ( v d : 2OH u tin hn 3 do oxy u tin hn hydro) CH CH - Lin kt i hoc lin kt ba c tnh bng hai hay ba lin kt n Nu 2 nhm th u tin cng 1 pha ca lin kt i, l cu hnh Z ("Zusammen" l cng). S phn b ngc li, l cu hnh E ("Entgegen" l ngc li):
nhm th u tin C nhm th C nhm th
nhm th

nhm th u tin nhm th u tin

C C

nhm th

nhm th u tin

ng ph n Z

n g ph n E

V d:

CH3 C H C

Br Cl

CH3 C H C

Cl Br

(Z)-1-bromo-1-cloropropen

(E)-1-bromo-1-cloropropen -2-

Ch : K hiu cis-trans l k hiu c s dng khi lin kt i mang 2 nguyn t hydro. K hiu E/Z c th p dng mi trng hp. i vi dien lin hp kiu RCH=CH CH=CHR' c th c 4 ng phn hnh hc:
R C H C C C H H H R C C H C C H R'

H R' trans - trans (E - E) R C H C C C H R'

H cis - trans (Z - E) H H C C C C R'

H H H H trans - cis (E - Z) cis - cis (Z - Z) Nu R = R' th s ng phn gim cn 3, bi v cc ng phn cis-trans v transcis tr thnh tng ng.

ng phn cis v trans khc nhau v tnh cht vt l. Nhit nng chy ca cis thp hn trans, nhng nhit si ca cis li cao hn nhit ca trans. 2.1.2. ng phn hnh hc cc cycloalkan Cc cycloalkan cha 2 nhm th c th tn ti di 2 dng ng phn cis-trans tu thuc vo s sp xp ca cc nhm th cng hay khc pha so vi mt phng ca vng. V d: cyclobutan to ra hai hp cht 1,2-diclocyclobutan:
H C H C H C H C H Cl C Cl C H H H H C H cyclobutan H C H C H H C Cl C H H C H

H Cl H H cis-1,2-diclorocyclobutan trans-1,2-diclorocyclobutan

2.2. ng phn cu dng 2.2.1. Khi nim cu dng Th d : Xt s quay xung quanh lin kt n C- C trong phn t etan. Hai nhm -CH3 trong phn t etan c th quay xung quanh trc lin kt n C Etan c v s cu dng. C. Ch nht l cu dng che khut v cu dng xen k, c biu din theo cng thc Newman nh sau:

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H H

H H H H H c h e k h u tc u d n g x e n k

H H

H H H H cu dng che khut

H H cu dng xen k

H H c u

d n g

Cu dng che khut km bn vng hn, c mc nng lng cao hn cu dng xen k do c tng tc gia cc nguyn t hydro trong phn t. Cu dng xen k nm mc nng lng cc tiu nn bn vng hn v l cu dng chim u th. 2.2.2. ng phn v cu dng ca cycloalkan Cyclohexan l cycloalkan quan trng nht v n c trong phn t ca nhiu hp cht thin nhin v nhiu hp cht thuc. Vng cyclohexan khng phng, c th c nhiu cu dng khng c sc cng gc, trong ng lu nht l cu dng gh v cu dng thuyn :
H H H
1 6 5

H H
4

H H H H H
2 3

H
6 5

H H
2

CH2

H H

H
3

H H

CH2 H

Cu dng gh ca cyclohexan
1

H H
6 5

H H H
3

H H H

H H H

H H

3 2

CH2 CH2
1 6

H H

H
2

HH

HH

Cu dng thuyn ca cyclohexan Do c bn ln hn, cu dng gh chim u th (hn 99% trong hn hp cn bng). C th nhn thy l hu ht cc dn xut ca cyclohexan u c cu dng gh. Hng ca cc lin kt ngoi vng: Mi nguyn t carbon ca cyclohexan cn c 2 lin kt ni vi 2 nguyn t H (c th thay th bng cc nhm th khc), mi lin kt c mt hng c trng. C 2 loi lin kt ngoi vng l: - Lin kt trc (lin kt axial, k hiu l a) l lin kt c hng vung gc vi mt phng trung bnh ca phn t (mt phng song song v cch u 2 mt phng C1C3C5 v C2C4C6), cc lin kt trc t lun phin trn v di mt phng . - Lin kt vnh (lin kt equatorial, k hiu l e) l lin kt c hng gn song song vi mt phng trung bnh, nm gia 2 mt phng C1C3C5 v C2C4C6 , hng ra vng bin ca phn t. Nh vy, mi carbon ca cyclohexan c 1 lin kt trc v 1 lin kt vnh vi nguyn t H (hoc nhm th).
a e e a e e a a a a e e e a e e a e
o 0,5 A

e a a

a e

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 ng phn hnh hc ca dn cht cyclohexan : - Dn cht th 1 ln khng c ng phn hnh hc. - i vi cyclohexan th 2 ln (xt cu dng gh) th phi xt n hng trc hay vnh ca mi nhm th xc nh phn t dng cis hay trans. Th d : H H + Trng hp th 1,4 (hay para):
R2 R1 H R1 cis (a)(e)
R2 H R1 trans (a)(a) H trans (e)(e) H H R1 R2

H R2 cis (e)(a)

+ Trng hp th 1,2 (ortho) v 1,3 (meta): cng c cu dng cis hay trans tng t 2.3. ng phn quang hc 2.2.1. Khi nim : ng phn quang hc l nhng ng phn khng gian c cu trc v tnh cht vt l v ho hc ging nhau nhng khc nhau v kh nng quay mt phng nh sng phn cc. Nguyn nhn gy ra ng phn quang hc l do phn t khng c yu t i xng no trong phn t (trc, tm i xng...). Hay ni cch khc l do trong phn t c cha nguyn t C bt i (C* lin kt vi 4 nhm th khc nhau) gi l trung tm khng trng vt nh hay trung tm Chiral.Trung tm khng trng vt nh c hai cu trc ng phn i xng vi nhau qua mt mt phng gng gi l ng phn gng (vt v nh trong gng khng c kh nng chng kht tng nhm th vi nhau nh bn tay tri v phi). 2.3.2. Cht hot quang nh sng phn cc l nh sng dao ng theo mt phng nht nh, trong mt mt phng. Mt phng vung gc vi mt phng dao ng nh sng phn cc l mt phng phn cc. Nu cht c kh nng lm quay mt phng ca nh sng phn cc mt gc no , ngi ta gi cht l cht hot quang (hot ng quang hc). o gc quay ca nh sng phn cc i vi mt cht, ngi ta dng phn cc k.

n h s L n gn g t h np gh n

n g c h a k n nh h N s i dc n u g n g d c h o l L n g c cp h n cc h c t h o t q up ah n gn

k n h tc h

i c o l

Hnh 1. S phn cc k

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Nu cht lm quay mt phng phn cc theo chiu kim ng h khi ngi quan st nhn v pha tia sng th l cht quay phi (hu tuyn) v gc mang du (+) v theo chiu ngc kim ng h, l cht quay tri (t tuyn) v gc mang du (-). Nu cht khng lm quay mt phng phn cc, l cht khng hot quang. 2.3.3. Cu hnh tng i :Cu hnh D v L Cc cu hnh c em so snh vi cht chun glyceraldehyd.
CHO H C OH HO CHO C H

CH2OH D-(+)-glyceraldehyd

CH2OH L-(-)-glyceraldehyd

Cu hnh D l cu hnh c nhm th c trng lin kt hng ra pha phi ca carbon bt i, cn cu hnh L c nhm th pha tri:
R1 R2 C R3 cu hnh D X X R1 C R3 cu hnh L R2

Nhng hp cht c cu hnh tng t D-(+)-glyceraldehyd u thuc dy D; cn * Cch xc nh ng phn D, L da vo cng thc chiu Fischer - ng phn c nhm OH ( hoc nhm th khc H ) bn phi l D - ng phn c nhm OH ( hoc nhm th khc H ) bn tri l L - Cc hp cht kiu R-CH(Y)R tng t cu hnh ca glyceraldehyd 2.3.4. Cu hnh tuyt i : Cu hnh R v S Nguyn t carbon lin kt vi 4 nguyn t hoc nhm nguyn t khc nhau C abcd. Trnh t u tin ca nhm th carbon bt i: a > b > c > d. Quan st phn t theo trc t C d. Nu t a b c i theo chiu kim ng h th cu hnh l R (Rectus = phi); ngc chiu kim ng h th cu hnh l S (Sinister = tri): a a a C c b d c b C d c a d b C c C b

a C b c

cu hnh R a d b c cu hnh S C

Dng qui tc Cahn-Ingold-Prelog sp xp cc nhm th theo mc u tin.

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 ch r mt phn t bt i, cn phi trnh by cu hnh tuyt i (R hoc S) v b sung thm du ca gc quay cc (+ hoc -). V d v cu hnh tuyt i ca R-glyceraldehyd v S-glyceraldehyd:
C CHO (b) H (d) (c) HOH2C (a) HO S-(-)-glyceraldehyd (d) H CH2OH (c) OH (a) R-(+)-glyceraldehyd CHO (b)

2.3.5. Cc cht hot quang c nguyn t carbon bt i 2.3.5.1. Hp cht c mt nguyn t carbon bt i: V d : alcol sec-butylic CH3CH2C(CH3) OH (I). L mt hn hp ca hai dng ng phn (II) v (III); hai ng phn ny i vi nhau nh vt v nh ca n trong gng, c gi l cc i quang
H3C C H OH C2H5 (II) HO H5C2 C H CH3

(III) mt phng gng

Mt hp cht hu c c mt carbon bt i xng c th tn ti di cc dng: - ng phn hu tuyn, k hiu (+). - ng phn t tuyn, k hiu (-). - Hn hp racemic, k hiu ( ). 2.3.5.2. Hp cht c nhiu nguyn t carbon bt i: Ni chung, mt hp cht c n nguyn t carbon bt i c th tn ti 2n ng phn quang hc (vi iu kin l khng c ng phn no c mt phng i xng gy ra bi nhng nhm th ging nhau cc nguyn t C*, ging nh cc dng meso). Hp cht c hai nguyn t carbon bt i ging nhau: Acid tartric l diacid c 4 C, c 2 nhm hydroxyl, c 2 carbon bt i ging nhau: HOOC CH(OH)

CH(OH)

COOH

Rt d hnh dung tt c v tr c th c ca H v OH da vo cng thc chiu Fischer (ng thng ng ch mch chnh vi C1 t trn, nhm nguyn t trn ng nm ngang gn ngi quan st, nhm nguyn t trn ng nm thng ng xa ngi quan st).
COOH H HO OH H COOH (+) (I) HO H COOH H COOH - 7 (-) (II) OH H H COOH OH OH COOH meso (III) (IV) HO HO COOH H H COOH

(I) v (II) l cp i quang, v chng i xng vi nhau, nh nh ca nhau qua gng v khng chng kht ln nhau c. (I) + (II) l hn hp racemic. (III) v (IV) l i xng vi nhau, nhng chng chng kht ln nhau c sau khi quay mt trong hai dng 1800 trong mt phng (dng meso) v khng hot quang Cu hnh tuyt i ca cc ng phn ny:
COOH COOH
2 3

COOH COOH
2 3

COOH COOH
2 3

HO OH

H HO

H H

OH H

H OH

OH

(I) 2(R),3(R) (+)

(II) 2(S),3(S) (-)

(III) = (IV) 2(R),3(S)

Hp cht c hai nguyn t carbon bt i khc nhau: Kho st cc cp i quang ca 2,3,4-trihydroxybutanal, ngi ta thng gi l O erythrose v threose: C CH(OH) CH(OH) CH2OH H
CHO H H OH OH CH2OH (-) (I) HO HO CHO H H CH2OH (+) (II) H HO CHO OH H CH2OH (+) (III) HO H CHO H OH CH2OH (-) (IV)

hai i quang erythrose

hai i quang threose

Erythro ch nhng cu trc c 2 C* m nhng nhm th ging nhau mt bn lin kt gia hai trung tm bt i. Threo ch nhng cu trc c cc nhm th ging nhau bn ny v bn kia lin kt gia hai trung tm bt i.
CH2OH
3

CH2OH
3

CH2OH
3

CH2OH
3

CHO
2

H OH

OH HO

CHO
2

HO H

CHO
2

HO OH

H HO

CHO
2

H H

OH

I 2(R),3(R) (-)

II 2(S),3(S) (+)

III 2(R),3(S) (+)

IV 2(S),3(R) (-) hai i quang threose

hai i quang erythrose

* Cch xc nh ng phn R, S da vo cng thc chiu Fischer - Nu nhm th nh nht nm trn ng nm ngang th th t gim dn hn cp ca cc nhm th cn li theo chiu kim ng h l cu hnh S, ngc chiu l R. - Nu nhm th nh nht nm trn ng thng ng th th t gim dn hn cp ca cc nhm th cn li theo chiu kim ng h l cu hnh R, ngc chiu l S.

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2.3.6. ngha thc t ca ng phn quang hc Cc phn ng sinh hc thng c kh nng phn hu hoc to nn mt i quang ny nhiu hn i quang kia. Mt s ln cc hp cht hot quang c ngun gc sinh vt: cc vitamin (acid ascorbic), cc hormon (adrenalin) hoc cc cht trung gian trong qu trnh chuyn ho (cc acid amin, cc ose). Nhiu hp cht trong s cc hp cht ny c th thu c bng con ng tng hp nhng di dng racemic, sau phi phn i. Tnh cht cm quan ca cc i quang c th rt khc nhau. Th d: asparagin hu tuyn c v ngt, asparagin t tuyn c v ng, trong khi asparagin racemic khng v: HOOC CH CH2 CONH2 NH2 C th l mi dng ng phn c kh nng kch thch ln b phn tip nhn cm quan khc nhau. - V mt dc l, s khc nhau v hot tnh gia cc ng phn rt r. Th d : + Adrenalin thin nhin (t tuyn) tc dng ln thnh mch mu mnh gp 15 ln so vi adrenalin hu tuyn. + Hyoscyamin thin nhin (t tuyn) c hot tnh mnh hn atropin (racemic). + Long no racemic (tng hp) v long no hu tuyn (thin nhin) c tc dng gn ging nhau ln tim. + Glucose c dng trong ngnh Dc lm thuc b dng di cc dng khc nhau: dung dch 30% trong nc gi l huyt thanh ngt u trng, cn dung dch 5% trong nc gi l huyt thanh ngt ng trng CHO CH2OH CH2OH O O

-D-glucopyranose ( 66% )

CH2OH D-glucose

-D-glucopyranose ( 34% )

Glucose cn c dng lm t dc, lm ngt thuc v dng nh mt thc phm. D-glucose c di dng t do trong cc qu chn cng vi D-fructose v sacarose. Trong mu ngi v cc ng vt lun lun c mt t l nht nh D-glucose. D-fructose l 1 ceto hexose c v ngt gp 3 ln v ngt ca D-glucose. CH2OH O CH2OH CH2OH O CH2OH O CH2OH -D-fructofuranose CH2OH -D-fructofuranose D-fructose D-fructose dng t do trong qu chn, c bit c nhiu trong mt ong.

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BI TP NG PHN 1. Axit sucxinic c cng thc : HOOC - (CH2)2 - COOH Hy vit cng thc chiu ca tt c cc dng ng phn lp th ca axit 2 - brom - 3 metyl sucxinic .Ch ra cc ng phn i quang v khng i quang 2. C bao nhiu ng phn lp th i vi hp cht c cng thc sau : CH3CH(Cl)CH=CHCH3 3. Vit cng thc cu to ca alken c s nguyn t C t nht nhng tn ti ng thi ng phn hnh hc v ng phn quang hc. Biu din cc ng phn . 4. Biu din cc ng phn cu dng (dng gh) ca 2clo1,3dimetylxiclohexan 5. Ch ra cu hnh R, S ca cc ng phn sau : CH3 COOH CHO HO H HO CH3
Axit ( ... ) - lactic

HO

H CH2OH

H CH3

OH

( ... ) - glyceraldehyd

Butadiol - 2(...), 3(...) CHO

COOH H HO C2H5
Axit 2(...)-hydroxy-3(...)-metyl - 3(...)- hydroxy valeric

OH CH3

H HO H H CH2OH (...) - glucose

OH H OH OH

6. Geraniol c th c bao nhiu ng phn cis-trans : (Chn 1 p n ng trong cc p n sau) : a) 2 b) 3 c) 4 d) 6

c h 2o h

Geraniol 7. Vit cng thc chiu Fischer ca R -3 clo buten -1 8. Vit cc ng phn quang hc, ch r cc i quang, ng phn meso, erythrose, threose ca : 2,3- dibrombutan ; Axit 2,3,4 trihydroxypentanoic ; Ancol C5H11OH 9. Thuc khng sinh amoxicillin c bao nhiu ng phn quang hc ? Gii thch. Cho bit cng thc ca amoxicillin c cng thc di y ?
OH CONH N NH2 O S CH3

CH3 COOH

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10. Hy biu din cc ng phn quang hc ca Cloramphenicol l 1 khng sinh c dng trong y hc c cng thc nh sau : ch ch ch 2oh
o 2n oh nh c o ch 2c l2

11. nh du * cc nguyn t cc bon bt i xng trn cng thc ca morphin :

HO

O N CH3

HO

12. A v B cng cng thc dng :

Br

COOH COOH

Br Bit trong phn ng decacboxyl A to thnh 1 sn phm v B to thnh 2 sn phm :

Br

COOH COOH
Br

t0

Br

H COOH
Br

+ CO2

Hy xc nh cu trc ca A v B . Mt s bi tp Bi 1: Hy ch r cu hnh cc hp cht sau bng cc k hiu cis, trans, Z, E:

H3C C H C CH(CH3)2
CH3 C H3C C CH2CH3

CH2CH3

BrH2C C H3C
H C H3CH2C C

CH3 C CH2CH3
CH2Cl

Br

COOH

Bi 2: Vit cng thc cc ng phn lp th ca (ClCH=CH)2C=CHCH2OH Bi 3: Hy so snh cp ca cc nhm trong cc dy sau: a) CH3-; CH3CH2-; CH2=CH-; CHC-; (CH3)3C-; (CH3)2CH-

b) COOH; -CHO; -CN; -CH2OH; -CC-R. Bi 4: Hy ghi cc k hiu R, S, D, L cho cc hp cht sau:

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NH2
H

H3C HO

CH2CH3

BrH2C H3C

H3C HOOC

Cl

CH2OH D H3CH2C H

CH3 H OH CH=CH2 COOH H C6H5 H

N OH

CH2OH CH2CH3 H C6H5 CH3

Bi 5: Hy vit cng thc phi cnh cho cc hp cht sau: CH2OH CH3 Cl CH3 H Br Cl CH2CH3 H2N

Bi 6: Vit cng thc chiu fise cho tt c cc ng phn quang hc ca cc cht sau: a) Propan 1,2 diol b) axit tactric v monokali tactrat c) 2,3 diclobutan v 2 clo 3 brombutan K hiu mi ng phn theo h danh php R S. Bi 7: Vit cu dng bn cho mi cht sau: propan, 2 metylbutan, propylene, etanol amin, etylen glycol Bi 7: nhng cht no sau y c th c ng phn hnh hc. Vit cc ng phn hnh hc v gi tn theo h thng cis trans v h thng Z E. a) CH3CH=CHCH3 b) (CH3)2C=CHCH3 c) CH3CH=CHF; d) CF2=CF2 e) HOOCCH=CHCOOH f) ClCH=C=CHCl g) CH3C=C=C=CHCH3 h) CH2=C=C=CH2 i) 1,1 - dicloxiclohexan Bi 8: Da vo cc gi tr momen lng cc ca cc ng phn hnh hc hy cho bit ng phn no (A hay B) l cis, ng phn no l trans? a) CHF=CHF A = 0 B = 2,24D b) CH3CH=CHBr A = 1,57D B = 1,69D c) p-NO2-C6H4CH=CHC6H4-Br-p A = 3,11D B = 4,52D Bi 9: Ch ra nguyn t cacbon bt i trong hidrocacbon X, s ng phn quang hc ca X l bao nhiu? Bit CTCT ca X:

Bi 10: Cht no sau y c th c ng phn quang hc? s lng ng phn l bao nhiu? (A) CH3CHBrCH3 (B) CH3CH(OH)COOH (C) CH3CHBrCH2CH3 (D) HOOCCH2CH(NH2)COOH

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(E) CH3CHBrCHBrCH3 (G) CH3CHBrCHBrCH2CH3

(F) HOOCCH(OH)CH(OH)COOH (H) HOCH2CH(OH)CHO

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