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Stereochemistry
HA HC LP THBin Son: Ths. Lm Tn Tng
NG PHNNG PHN PHNG NG PHN LP TH NG PHN CU HNH
NG PHN CU TRNG
NG PHN HNH HC
NG PHN QUANG HC
PHM VI NGHIN CU CA HA HC LP TH
L s kho st v cc kha cnh kin trc ca phn t trong khng gian tam th nguyn Xc nh cu hnh ca phn t: Cu to ca phn t l trt t sp xp cc ni ca 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 phi i xng.
Xc nh cu hnh ca phn t: 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 cu trng, ng phn hnh hc v ng phn quang hc.
LC S c tnh ca hp cht trin quangNm 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).
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.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).
Cng thc Fischer ca cc acid tartric
COOH H HO OH H COOH HO H
COOH H OH COOH H H
COOH OH OH COOH
Acid () tartric
Acid Meso-tartric
Thuyt carbon t din
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. H qu l hai s sp xp khc nhau c th tn ti nh vt v nh trong gng phng, khng chng ln nhau c
Acid lactic c hai ng phn quang hcCOOH COOH
H CH3
OH
OH CH3
H
Acid (+) lactic
Acid () lactic
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 saua a a b
b
b
b
a
Xt v mt hnh hc th bn nhm th nm trn mt mt phnga a a b
b
b
b
a
Cis
(a b)
Trans
Nm 1838, Liebig xc nh c s tn ti ca hai acid: maleic v fumaric l ng phn ca nhau.
H
H
H
COOH
HOOC
COOH
HOOC
H
acid maleic
acid furamic
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. 1,2 dimetylciclopropan c cc ng phnCH3 CH3 CH3 H H CH3
H
H
H
CH3
H 3C
H
Cis (Meso)
Trans (Cp i quang)
1.2.5. ng phn cu trng (cu dng, quay)
Nm 1885, Baeyer xut thuyt cng cho cc hp cht vng no Nm 1890, Sasche d on 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.
Ciclohexan
Dng gh
Dng tu
CCH BIU DIN NGUYN T CARBON T DIN Biu din phn t cha mt nguyn t C
CACH BIEU DIEN PHAN T METANH H
H
H
H
H
H H
H H
H
H
Cng thc phi cnh
Cng thc chiu Fischer ca Metan
1.3.2. Biu din phn t cha hai nguyn t C Cng thc tam th nguyn ca Etan (cng thc phi cnh)H H H H H H
Dng lch
Cng thc phi cnh: nhn theo trc C C
H
H
H
H H H
Cng thc chiu Newman
H H H H H H
Cng thc chiu FischerH H H H H H H H H H H H
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.
DANH PHP CU HNH Danh php D,L Xt gliceraldehidCHO H OH CH2 OH HO CHO H CH2 OH
D-(+)-gliceraldehid
L-(-)-gliceraldehid
K hiu: D, L l cu hnh tng i Du (+) hay (-) lin h n chiu quay
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).CHO CHO
H
OH CH2 OH
HO
H CH2 OH
Nhm D
Nhm L
CHO H HO H H OH H OH OH CH2 OH
CHO HO H H OHHO H HO
CHO OH H H CH2 OH
CH 2OH
D (+) glucoz
D (-) Eritroz
L(-)Arabinoz
i vi Aminoacid 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
COOH H2 N R H H
COOH NH 2 R
Nhm L
Nhm D
COOH H CHO CHO H 2N H 2N H H CH2 OH CH3 OH H CH2 NH 2
L-Serin
L-Treonin
D-Phenylalanin
Mirror CHOR
CHO HO H CS CH2OH CHO HO H CH2OH CHO HO H CH2OH L-()-Glyceraldehyde[]D = 13.5
C
HOH2C
OH H
CHO H OH CH2OH CHO H OH CH2OH D-(+)-Glyceraldehyde[]D = + 13.5
CHO (CHOH) n H C
CHO (CHOH) n
OH
HO
C
H
CH2OH D series
CH2OH L series CHO CH2OH O HO H H H OH
CHO H CHO H H H OH OH
H HO H H
OH H OH
OHCH2OH
OHCH2OH D-ribose
OHCH2OH
OHCH2OH D-fructose
D-glyceraldehyde
D-glocose
CHO HO CHO H H OH H CH2OH L-Xylose O HO
CH2OH
H H CH2OH
HO
H CH2OH
HO
HO
L-glyceraldehyde CO2H H2N D-Valine H
L-Ribulose CO2H H2N H
L-Valine
Danh php R,S
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:
Nu th t a, b, c theo chiu kim ng h th cu hnh ca C* l R. Nu th t a, b, c ngc chiu kim ng h th cu hnh ca C* l Sa d c b b d c a
Cu hnh R
Cu hnh S
Danh php E,Z i vi cc anken mang cc nhm th khc nhaua d
b
e
Xt theo qui tc th t u tin: a>b; d>e - Z khi a, d v tr cis i vi nhau - E khi a, d v tr trans i vi nhau
Cl H
Cl H
Cl H
H Cl
Z(Cis)
E(Trans)
Cl H
Cl Br
Cl F
Cl H
E(Cis)
Z(Cis)
Cl H 3C
CH 3 H
Cl H
CH 3 Cl
Z-
E-
NG PHN QUANG HC
S sp xp trong khng gian ca cc nhm xung quanh cacbon t din c th thy r qua vic m hnh ha phn t
hoc biu din bng vic chuyn i cu trc ngng t sang cu trc ba chiu dng cc ng gch ni v hnh ci nm
Br
M hnh ha cu trc lp th l mt yu t rt quan trng kim tra mt phng i xng ca cc phn t
Br
M hnh ha cu trc lp th l mt yu t rt quan trng kim tra mt phng i xng ca cc phn t
Mt phng i xng
Br
M hnh ha cu trc lp th l mt yu t rt quan trng kim tra mt phng i xng ca cc phn tMt phng i xng Khng c mt phng i xng
CH3
H qu ca hnh t din l mt mt phng khng i xng ni phn t, iu ny xy ra khi c bn nhm th khc nhau nh vi mt tm t din
H qu ca hnh t din l mt mt phng khng i xng ni iu ny xy ra khi c bn nhm th khc nhau nh vi mt tm t din
Khng c mt phng i xng
nh hng mng li ca s khng i xng ny lm pht sinh ra mt phn t mi m khng th chng kht ln trn phn t ban u gi l nh gng ca n
Mt phng gng
Mt nguyn t cabon c nh vi bn nhm th khc nhau c gi l cabon bt i xng(chiral carbon) v mt cp nh gng khng chng kht ln nhau gi l ng phn i nh(enatiomers)
Cp ng phn i nh
nh du trung tm bt i xng ca cc phn t di y bng vic nh du sao ln cacbon bt i xng
nh du trung tm bt i xng ca cc phn t di y bng vic nh du sao ln cacbon bt i xng
nh du trung tm bt i xng ca cc phn t di y bng vic nh du sao ln cacbon bt i xng
nh du trung tm bt i xng ca cc phn t di y bng vic nh du sao ln cacbon bt i xng
Khng c
nh du trung tm bt i xng ca cc phn t di y bng vic nh du sao ln cacbon bt i xng
nh du trung tm bt i xng ca cc phn t di y bng vic nh du sao ln cacbon bt i xng
nh du trung tm bt i xng ca cc phn t di y bng vic nh du sao ln cacbon bt i xng
nh du trung tm bt i xng ca cc phn t di y bng vic nh du sao ln cacbon bt i xng
Khng c tm bt i
nh du trung tm bt i xng ca cc phn t di y bng vic nh du sao ln cacbon bt i xng
Khng c tm bt i
nh du trung tm bt i xng ca cc phn t di y bng vic nh du sao ln cacbon bt i xng
nh du trung tm bt i xng ca cc phn t di y bng vic nh du sao ln cacbon bt i xng
28
Tm tm bt i s c
2
8
ng phn lp th
NG PHN TRONG TRNG HP PHN T C MT TM C*
Hai ng phn khc nhau ca 2-bromobutane l nh ca nhau qua gng v khng th xp trng kht ln nhau c gi l ng phn i quang (Enantiomers)
NG PHN I QUANG
Enantiomers
Hai ng phn i quang ch khc nhau v hot tnh quang hc
Cc ng phn khng i nh c tnh cht ha hc v tnh cht vt l ging nhau (ngoi tr khi chng tng tc vi phn t khng i xng khc) chng ch khc l lm quay mt phng nh sng phn cc theo hai hng khc nhau, do nhng hp cht c tm i xng thng c gi bng thut ng quang hot
Ngun Ngun sng B phn cc nh sng Bung cha mu B phn tch Gc quan st Cht hu c nh sng
Mt phng ca nh sng phn cc c th c m t bng vector in v vector t tng t, vector tng l mt phng thng ng
Phn in v phn t c hp th khc nhau; vector tng c thay th
Mt phng ca nh sng phn cc c th c m t bng vector in v vector t tng t; vector tng l mt phng thng ng
Phn in v phn t c hp th khc nhau; vector tng c thay th
Phn in v phn t c hp th khc nhau; vector tng c thay th
Mt phng ca nh sng phn cc c th c m t bng vector in v vector t tng t; vector tng l mt phng thng ng
V mt ng phaqn6 khng i nh khc phn Mt dung dch cha mt ng phn s lm quay nh sng phn cc khng i nh do lm quay nh sng theo hng ngc li phn cc theo mt hng
phn V mt ng phaqn6 khng i nh kh Mt dung dch cha mt ng phn s lm quay nh sng phn cc khng i nh do lm quay nh sng theo hng ng c li phn cc theo mt hng
Mt hn hp cha hai ng phn c cng nng , s khng lm quay mt Phng ca nh sng phn cc. Mt hn hp ca hai ng phn khng i nh c cng nng c gi l hn hp Racemic
TNH CHT CA PHN T BT I XNG: HOT TNH QUANG HC
Cht hot ng quang hc: lm quay mt phng ca nh sng phn cc Cht hu trin (+): lm quay mt phng nh sng phn cc v pha tay phi Cht t trin (-): lm quay mt phng nh sng phn cc v pha tay tri
TNH CHT CA PHN T BT I XNG: HOT TNH QUANG HC
quay cc ring, []: c: Nng dd (g/100mL) l: Chiu di ng nghim : Gi tr quay cc o c
Ngun sng
B phn cc
Gc quan st
Bung cha mu B phn tch
TNH CHT CA PHN T BT I XNG: HOT TNH QUANG HC
Hn hp tiu trin: cha 2 dng ng phn quang hc vi lng bng nhau Khi mt trong 2 dng ng phn hin din nhiu hn: % tinh khit quang hc (ee)
ee = % tinh khit quang hc = % ca mt dng ng phn - % ca dng cn liHoc:
V CU TRC NG PHN I QUANG: CNG THC PHI CNH
Hai ng phn i quang ca 2-bromobutane
NG PHN I QUANG
Cu hnh ringHng m trong mt phn t quang hot quay nh sng l ring bit cho tng phn t cho trc, nhng khng lin quan n s nh hng ca cc nhm phn t bao quanh tm bt i
C th l + hay -
Cu hnh ring biu th cu hnh tuyt i, mt h thng danh php c ra i trong cc nhm xung quanh tm bt i c sp xp theo tnh u tin. Nhm c tnh u tin thp nht c t ng sau mt phng m bn ang lm vic trn y, v hng(cng chiu hay ngc chiu kim ng h) ca cc ng ni cho cc nhm cn li c xc nh.
Cu hnh ring
biu th cu hnh tuyt i, mt h thng danh php c ra i trong cc nhm xung quanh tm bt i c sp xp theo tnh u tin. Nhm c tnh u tin thp nht c t ng sau mt phng m bn ang lm vic trn y, v hng (cng chiu hay ngc chiu kim ng h) ca cc ng ni cho cc nhm cn li c xc nh.
S Sinister ngha l triNgc chiu kim ng h l cu hnh S
Cu hnh ring
biu th cu hnh tuyt i, mt h thng danh php c ra i trong cc nhm xung quanh tm bt i c sp xp theo tnh u tin. Nhm c tnh u tin thp nht c t ng sau mt phng m bn ang lm vic trn y, v hng(cng chiu hay ngc chiu kim ng h) ca cc ng ni cho cc nhm cn li c xc nh.
R (rectus ngha l phi)
Cng chiu kim ng h l cu hnh R
Cu hnh ring
R (rectus--phi)
S (sinister--tri)
Nhc li qui tcCho cu hnh R v S Sp xp cc nguyn t nh trc tip vi tm cacbon bt i theo s hiu nguyn t. Nu c s rng buc bt k nguyn t no th nhn n nguyn t th 2 hoc th 3 cho n khi tm c s khc bit vi cc nguyn t khc. m cc lin kt bi xung quanh cng mt nguyn t Quay nhm c tnh u tin thp nht ra pha sau; nu mt ng ni ba nhm c tnh u tin cao nht theo th t gim dn theo chiu quay ca kim ng h th phn t l R, ngc li nu theo th t ngc chiu kim ng h th phn t l S
Xc nh cu hnh tuyt i ca phn t di y Trc ht xc nh tnh u tin
Xc nh cu hnh tuyt i ca phn t di y Trc ht xc nh tnh u tin
C hai nguyn t cacbon ca 2 nhm th nh vi nguyn t cacbon bt i do phi xem xt cc nguyn t nh vi cc nguyn t cacbon ny v sp xp li cc nhm
Sau , lt nghing phn t v pha bn, cho nhm c tnh u tin thp nht (nhm cc nguyn t hydro) ra pha ng sau.
Nhm c tnh u tin thp nht
Sau , lt nghing phn t v pha bn, cho nhm c tnh u tin thp nht (nhm cc nguyn t hydro) ra pha ng sau.
Nhm c tnh u tin thp nht
Nhm c tnh u tin thp nht
Sau sp xp cc nhm theo tnh u tin gim dn xc nh cu hnh
S
Xc nh cu hnh tuyt i ca phn t di y
Xc nh cu hnh tuyt i ca phn t di y
Xc nh cu hnh tuyt i ca phn t di y
Thp nht
Thp nht
Thp nht
R
Thp nht
Xc nh cu hnh tuyt i ca phn t di y
Xc nh cu hnh tuyt i ca phn t di y
R
Xc nh cu hnh tuyt i ca phn t di y
Xc nh cu hnh tuyt i ca phn t di y
Hydro ang hng v pha sau..
Hydro khng ch v pha sau nhng chng ta c th quay phn t xung quanh trc C--Br
Trong phn t ny chng ta cn lt Hydro ra pha sau..
Chng ta d dng quay phn t xung quanh trc CH sau lt ngc phn t ra pha sau
Nhm metyl c tnh u tin thp nht v phn t ng v tr ca n
Chuy n i c u trc 3 chi u c a phn t sang cng th c chi u Fischer
iu ny c th n gin ha bng cch dng cng thc chiu 2 D thay v biu din cc phn t dng 3D. Cng thc 2D m chng ta s thit lp thng c gi l cng thc Chiu Fischer.
Chuy n i c u trc 3 chi u c a phn t sang cng th c chi u Fischer
c c cng thc chiu Fischer, v phn t ca bn vi hai lin kt thng ng ang hng v pha bn, sau dt mng phn t thnh hnh phng.
Chuy n i c u trc 3 chi u c a phn t sang cng th c chi u Fischer
Kt qu l hnh v phng khng cn nguyn t cacbon trung tm m ch l hai ng thng ct nhau n gin. Cng c th hiu ngm rng v cng thc 2 chiu nh th ny l ni n ha lp th tuyt i v nn xem phng php ny l mt cch ngn gn v trung tm lp th.
Chuy n i c u trc 3 chi u c a phn t sang cng th c chi u FischerCc nhm nm ngang ang hng v bn Cc nhm thng ng ang hng ra pha sau
Kt qu l hnh v phng khng cn nguyn t cacbon trung tm m ch l hai ng thng ct nhau n gin. Cng c th hiu ngm rng v cng thc 2 chiu nh th ny l ni n ha lp th tuyt i v nn xem phng php ny l mt cch ngn gn v trung tm lp th.
Chuy n t cng th c chi u Fischer sang cng th c ph i c nh
Chuy n t cng th c chi u Fischer sang cng th c ph i c nh
Chuy n t cng th c chi u Fischer sang.
Chuy n t cng th c chi u Fischer sang cng th c ph i c nh
COOH H HO COOH OH H
COOH H HO COOH OH H H HO
COOH OH H COOH COOH H HO COOH H OH
COOH H HO HO COOH H
Xc nh cu hnh tuyt i ca phn t sau:
V li cu trc phn t dng 3D.
Xc nh cu hnh tuyt i ca phn t di y
Sp xp cc nhm theo tnh lp th..
Xc nh cu hnh tuyt i ca phn t di y
Xc nh cu hnh tuyt i ca phn t di y
Nhng iu g s xy ra nu bn ch n gin quay cng thc chiu Fischer?
Nhng iu g s xy ra nu bn ch n gin quay cng thc chiu Fischer?
Nhng iu g s xy ra nu bn ch n gin quay cng thc chiu Fischer?
Nhng chng ta bit l phn t cho c cu hnh
R
Vic quay cng thc chiu Fischer pht sinh ra mt ng phn i nh.
Qui tc vn dng cng thc chiu Fischer Khng bao gi quay phn t mt gc sinh mt ng phn i nh.
00 iu ny s lm pht 0
Qui tc vn dng cng thc chiu Fischer Khng bao gi quay phn t mt gc 00 iu ny s lm pht 0 sinh mt ng phn i nh.
Tht ra th vic sp xp li v tr ca cc nhm xung quanh nguyn t trung tm trong mt cng thc chiu Fischer c th pht sinh ra mt s ng phn i nh. y cng l mt cng c tt cho vic thnh lp mi quan h gia cc phn t bt i. N thng c xem l phng php chuyn i.
Nu ly cng thc chiu Fischer ca phn t ban u (cu hnh R) v hon v bt c 2 nhm bt k trong phn t s pht sinh ra mt cu trc i nh mi.
Nu ly cng thc chiu Fischer ca phn t ban u ( cu hnh R ) v hon v bt c 2 nhm bt k trong phn t s pht sinh ra mt cu trc i nh mi.
Nu ly cng thc chiu Fischer ca phn t ban u ( cu hnh R ) v hon v bt c 2 nhm bt k trong phn t s pht sinh ra mt cu trc i nh mi.
Hon v
Mt ln hon v pht sinh ra mt ng phn i nh
Thc hin hon v ln th hai
Hon v Ln 1n o H 2
ln v
.hon v ln th 2 a phn t v dng lp th ban u..
Qui tc vn dng cng thc chiu Fischer Khng bao gi quay phn t mt gc sinh mt ng phn i nh. Khi bn hon v cc nhm, ln th nht cho ra mt ng phn i nh, ln hon v th 2 a phn t quay v dng lp th ban u ln hon v th ba li to ra ng phn i nh.
900 iu ny s lm pht
Bn nn nh rng phng phphon v ch mang tnh hnh thc iu ny c ngha l n s khng lm thay i bt c mt tnh cht ha hc hay vt l no trong phn t.
Chuyn cc phn t di y sang cng thc chiu Fischer v xc nh cu hnh tuyt i ca chng.
Chuyn cc phn t di y sang cng thc chiu Fischer v xc nh cu hnh tuyt i ca chng.
Chuyn cc phn t di y sang cng thc chiu Fischer v xc nh cu hnh tuyt i ca chng.
Chuyn cc phn t di y sang cng thc chiu Fischer v xc nh cu hnh tuyt i ca chng.
Chuyn cc phn t di y sang cng thc chiu Fischer v xc nh cu hnh tuyt i ca chng.
H C CH3 NH3+ COO-
Chuyn cc phn t di y sang cng thc chiu Fischer v xc nh cu hnh tuyt i ca chng.
H C CH3 NH3+ COO-
H-
OOC
C H3C
NH3+
2-
H
1
OOC
3
SH3C
NH3+
Chuyn cc phn t di y sang cng thc chiu Fischer v xc nh cu hnh tuyt i ca chng.
Cl H3C C H2 C CH3 Br
Chuyn cc phn t di y sang cng thc chiu Fischer v xc nh cu hnh tuyt i ca chng.
Cl H3C C H2 C CH3
Cl C CH3
H3CH2CBr
Br
2 Cl 3H3CH2C
1
SCH3
Br
Xc nh cu hnh tuyt i ca mi trung tm bt i trong phn t di y
H H3C C2H5 OH OH CH3
Nguyn t carbon pha trn cha nhm th c tnh u tin thp nht nm pha trn cng ca phn t.
3H3C
H
1
R OH2CH3 OH
C2H5
Trong phn t ny, c hai nguyn t carbon, nm trn v nm di u c cu hnh tuyt i R
H H3C C2H5 OH
H
R
OH CH3
Hon v ln 1
H3C HO C2H5
OH CH3
H H3C HO
2
OH
1
RCH3
3
C2H5
Hon v ln th 2
Hy cho bit mi quan h lp th ca hai phn t di y?
i
Nguyn t carbon pha trn: yu cu hai hon v (H:CH3 v sau l CH3:OH) do chng ging nhau ( chng ta k hiu phn ging nhau bng ch i ngha l identical)
i i
Nguyn t carbon pha trn: yu cu hai hon v (H:CH3 v sau l CH3:OH) do chng ging nhau ( chng ta k hiu phn ging nhau bng ch i ngha l identical) Nguyn t carbon pha di: yu cu hai hon v (Etyl:CH3 sau l CH3:OH), do chng ging nhau.
Nh vy hai phn t ny ging ht nhau
Hy cho bit mi quan h lp th ca hai phn t di y?
Hy cho bit mi quan h lp th ca hai phn t di y?
e
Nguyn t carbon pha trn: yu cu hai hon v (H:CH3 v sau l CH3:OH) do chng c tnh i nh ( chng ta k hiu tnh i nh bng ch e c ngha l enantiomeric)
Hy cho bit mi quan h lp th ca hai phn t di y?
e e
Nguyn t carbon pha trn: yu cu mt hon v (H:CH3) do chng c tnh i nh ( chng ta k hiu tnh i nh bng ch e c ngha l enantiomeric) Nguyn t carbon pha di: chng mang tnh i nh
Do hai phn t ny l ng phn i nh ca nhau
Hy cho bit mi quan h lp th ca hai phn t di y?
Hy cho bit mi quan h lp th ca hai phn t di y?
i
Nguyn t carbon pha trn: yu cu mt hon v (H:CH3) do chng ging nhau.
Hy cho bit mi quan h lp th ca hai phn t di y?
e i
Nguyn t carbon pha trn: yu cu mt hon v (H:CH3) do chng ging nhau.
Nguyn t carbon pha di: yu cu mt hon v (OH:CH3) do chng mang tnh i nh.
Hy cho bit mi quan h lp th ca hai phn t di y?
i e
Nguyn t carbon pha trn: yu cu mt hon v (H:CH3) do chng ging nhau. Nguyn t carbon pha di: yu cu mt hon v (OH:CH3) do chng mang tnh i nh.
Do hai phn t khng l nhng ng phn i quang ca nhau
ng phn khng i quang l nhng ng phn lp th m chng khng l nh gng ca nhau. iu ny c ngha l nhng phn t c mt hoc hn mt trung tm lp th l ging nhau, v mt hoc hn mt trung tm lp th l i nh trong cu hnh ca chng.
Ging nhau
i nh
Hy cho bit mi quan h lp th ca hai phn t di y?
Hy cho bit mi quan h lp th ca hai phn t di y?
Nguyn t carbon pha trn: hai hon v (H:CH3 v CH3:OH) do chng i nh. Nguyn t carbon pha di: khng cn han v chng c sn tnh i nh.
Hy cho bit mi quan h lp th ca hai phn t di y?
Nguyn t carbon pha trn: hai hon v (H:CH3 v CH3:OH) do chng i nh. Nguyn t carbon pha di: khng cn han v chng c sn tnh i nh.
Do hai phn t l mt cp i quang
Hai ln hon v trn cu trc ca phn t bn phi r rng chuyn hai phn t sang dng vt nh v nh gng ca nhau
Hp cht MesoHp cht Meso l nhng hp cht c cc cha trung tm bt i, nhng li c tnh i xng ni phn t. Nhng loi phn t ny u c mt phng i xng ni phn t.
Mt phng i xng
Xc nh cc trung tm bt i trong phn t di y C mt phng i xng ni phn t no khng?
Mt ln hon v cho ra mt phng i xng ni ca ca phn t, do phn t ban u khng phi l hp cht meso
Xc nh cc trung tm bt i trong phn t di y C mt phng i xng ni phn t no khng?
Xc nh cc trung tm bt i trong phn t di y C mt phng i xng ni phn t no khng?
Meso
HP CHT MESO
CH3 Br H H Br CH3 CH3 H H Br Br CH3
CH3 H Br Br H CH3 CH3
H H
Br Br CH3
HP CHT MESO
HP CHT MESO
Hp cht meso c mt tm C* hoc nhiu hn v mt mt phng i xng Hp cht meso l mt achiral Hp cht meso khng hot ng quang hc
HP CHT MESO
HP CHT MESO
TNH CHT VT L
Hy cho bit mi quan h lp th ca cc phn t di y?
v
v
Hy cho bit mi quan h lp th ca cc phn t di y?
ng phn khng i nh
e i
Ging nhau
i vi mi phn t di y hy: i. Nu phn t l bt i xng hy xc nh xem c tt c bao nhiu tm i xng? ii. Nu phn t khng c tm bt i, xc nh tnh trng vt nh iii. Nu phn t l mt hp cht meso, khng cn xc nh tm bt i m hy xc nh meso
i vi mi phn t di y hy: i. Nu phn t l bt i xng hy xc nh xem c tt c bao nhiu tm i xng? ii. Nu phn t khng c tm bt i, xc nh tnh trng vt nh iii. Nu phn t l mt hp cht meso, khng cn xc nh tm bt i m hy xc nh meso
i vi mi phn t di y hy: i. Nu phn t l bt i xng hy xc nh xem c tt c bao nhiu tm i xng? ii. Nu phn t khng c tm bt i, xc nh tnh trng vt nh iii. Nu phn t l mt hp cht meso, khng cn xc nh tm bt i m hy xc nh meso
i vi mi phn t di y hy: i. Nu phn t l bt i xng hy xc nh xem c tt c bao nhiu tm bt i? ii. Nu phn t khng c tm bt i, xc nh tnh trng vt nh iii. Nu phn t l mt hp cht meso, khng cn xc nh tm bt i m hy xc nh meso
i vi mi phn t di y hy: i. Nu phn t l bt i xng hy xc nh xem c tt c bao nhiu tm i xng? ii. Nu phn t khng c tm bt i, xc nh tnh trng vt nh iii. Nu phn t l mt hp cht meso, khng cn xc nh tm bt i m hy xc nh meso
Khng c tm i xng hay cn gi l achiral c ngha l vt v nh gng c th chng kht ln nhau.
2
i vi mi phn t di y hy: i. Nu phn t l bt i xng hy xc nh xem c tt c bao nhiu tm i xng? ii. Nu phn t khng c tm bt i, xc nh tnh trng vt nh iii. Nu phn t l mt hp cht meso, khng cn xc nh tm bt i m hy xc nh meso
i vi mi phn t di y hy: i. Nu phn t l bt i xng hy xc nh xem c tt c bao nhiu tm i xng? ii. Nu phn t khng c tm bt i, xc nh tnh trng vt nh iii. Nu phn t l mt hp cht meso, khng cn xc nh tm bt i m hy xc nh meso
Khng c tm i xng hay cn gi l achiral c ngha l vt v nh gng c th chng kht ln nhau.
Meso
ng phn lp th ca 2-chloro-3-hexanol ?
CH3
CH Cl
2
CH OH
3
CH2 CH2
CH3
ng phn lp th ca Glixerol ? ng phn lp th ca 1,2,3-trimetylciclohexan ?
CH3
CH Cl
2
CH OHOH
3
CH2
CH2
CH3
HO3
C3H7 H
C3H73
C3 H 73
OH
HO3
C3H7 H
H3 C2
H Cl2
H H 3C2
Cl H H
CH3
Cl H H
Cl2
CH3
H H C3H7 Cl C3H7 ClR S S
H H OH Cl HO ClS S
HO H3 C
OH CH3
C3H7 H 3C
R R
C3H7 CH3
R
H (1)
H (2)
H (3)
H (4)
PHN NG CA HP CHT CHA TM C*
Nu phn ng khng lin quan n s t bt k lin kt xung quanh tm C*: S phn b tng i ca cc nhm th xung quanh tm C* l khng i.
Lu : Cu hnh tng i ca tc cht v sn phm khng i khng c ngha l cu hnh tuyt i ca chng s lun ging nhau!
PHN NG CA HP CHT CHA TM C*
S phn b tng i ca cc nhm th c duy tr: tc cht v sn phm c cng cu hnh tng i Th t u tin ca cc nhm th trong sn phm thay i: tc cht v sn phm c cu hnh tuyt i khc nhau
PHN NG CA HP CHT CHA TM C*
Nu phn ng c s t bt k mt trong s bn lin kt quanh tm C*: Ty theo c ch phn ng m sn phm s c cng cu hnh tng i hoc c cu hnh ngc li so vi tc cht ban u.
Cng cu hnh vi tc cht
Ngc cu hnh vi tc cht
Hp cht chiral khc
Nguyn t khc Carbon c mang 4 nhm th khc nhau cng l mt chiral Hp cht tng ng cng tn ti mt cp ng phn i quangH3C CH3CH2 CH3CH2CH2 N+ CH2CH2CH2CH3
H3C
Si OCH3
TM NITROGEN BT I XNG
S khc nhau v nng lng gia hai cu hnh rt nh, khong 5 kcal/mol nhit thng, s chuyn i cu hnh xy ra khong 1011 ln/giy Khng th c lp c hai dng ng phn i quang.H3 C CH3CH2 CH3CH2CH2 N N CH3 CH2CH3 CH2CH2CH3
HP CHT CU TRC THP KHC
S khc nhau v nng lng gia 2 cu hnh ca hp cht phospho l 30 kcal/mol S khc nhau v nng lng gia 2 cu hnh ca hp cht lu hunh l 35 kcal/mol C th c lp 2 dng ng phn quang hc. .. S CH CH O O .. P3 2
H3C
CH3CH2 H3C
ALLENE
ALLENE
BIPHENYL
BiN TH RAXEMIC Bn cht S to thnh bin th raxemic Tnh cht ca cc bin th raxemic S tch ring bin th raxemic thnh cc i quang Tng hp bt i xng
NG PHN HNH HC
L loi ng phn xut hin do s gii hn quay ca lin kt gy ra bi: Mt lin kt i Cu trc mch vng
HP CHT C NI I CARBON - CARBON
DANH PHP EZ
Quy tc CahnIngoldPrelog
Bc nguyn t cng ln th t u tin cng ln: I > Br > Cl > H Nguyn t u tin ging nhau: Xt tip nguyn t k tip cho n khi thy c s khc bit: CH2OH > CH(CH3)2 > CH3 Lin kt i: bng hai lin kt n, COOH > CHO > CH2OH
Gi tn theo danh php E, ZH H Me Me H H Me H Me H H H
(2Z,4Z)-hex-1,4-dienMe H
(2Z,4E)-hex-1,4-dien
H H H Me
(2E,4E)-hex-1,4-dien
Gi tn theo danh php E, Z
H
H Me
H
H H
Me H COOH
Cl H COOH
Gi tn theo danh php E, Z
H
H Me
Me
H H
Me H COOH
Cl H COOH
Acid (2E,4Z)-hex- 2,4-dienoic
Acid (2E,4Z)-5-clohex- 2,4-dienoic
Gi tn theo danh php E, Z
OH
CHO
Gi tn theo danh php E, Z
OH
(2E,4E,6E)-deca-2,4,6-trien-1-ol
CHO
(4E,6E,8E)-7,10-dimethylundeca-4,6,8-trienal
Tnh cht vt l ca ng phn hnh hc (Gio trnh) Momen lng cc Nhit nng chy, nhit si, t khi v chit sut phn ly ca acid Ph: T ngoi, hng ngoi, cng hng t ht nhn
Tnh Bn Tng iXt But-2-enMe Me Me H
H
H
H
Me
(Z)-but-2-en
(E)-but-2-en
Km bn
Bn
Do tng tc lp th ca hai nhm Me
V cu hnh bn ca a) 1,2-di-t-butyletilen b) 1,2-dibenzoyletilen
O H C(CH 3) 3 H
Ph H O
(H 3C)3 C
H
Ph
C
(E)-1,2-di-t-butyletilen
(E)-1,2-dibenzoyletilen
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): C5H10 C4H7Br 1,4-diphenylbuta-1,3-dien
Xc nh cu hnh Phng php vt l Phng php ha hc Lc acid Bit tnh lp th trong phn ng ca anken
HP CHT C NI I C=N V N=N
ng phn hnh hc ca oxim
N
OH
Sn c bn ca oxim
Danh Php
Ph N H OH
Me N Et OH
(E)-benzaldehyde oxime
(Z)-butan-2-one oxime
Ph HO N Ph N
OH
(1E,2Z)-benzil dioxime
Diazoat v diazocianurAr N N O Ar N N O
(Z)-AryldiazoatAr N N CN
(E)-AryldiazoatAr N N CN
(Z)-diazocianur
(Z)-diazocianur
AzoAzobenzen
N N N
N
(Z)
(E)
Azoxibenzen
N N N
N
O O (E) (Z)
HP CHT MCH VNG
HP CHT NH VNG
NG PHN CU TRNG ng phn cu trng l cc dng khc nhau trong khng gian ca cng mt cu hnh S di chuyn t mt cu trng ny sang mt cu trang khc c thc hin do s quay quanh mt hoc nhiu lin kt n Cu trng khc nhau ca cng mt phn t khng to nn cc ha tnh khc nhau. Kh c th c lp chng trong iu kin bnh thng (250C, 1atm) do ro nng lng gia chng chnh lch rt thp.
NG PHN CU TRNG
S quay xung quanh mt lin kt l c php
NG PHN CU TRNG C th c nhiu cch sp xp trong khng gian khc nhau ca cc nguyn t trong phn t H2O2
Cu trng (Conformation): L bt k cch sp xp trong khng gian 3 chiu ca cc nguyn t trong phn t c c do s quay xung quanh mt lin kt n
PHP CHIU NEWMAN
Cng thc phi cnh Cng thc phi cnh
Cng thc chiu Newman Cng thc chiu Newman
GC NH DIN (Dihedral angle Torsion angle)
L gc to bi mt phng H-C-C v mt phng C-C-H D dng quan st t cng thc Newman
ETHANE Tn ti v s cu trng khc nhau
Hai cu trng gii hn: Che khut v LchCu trng lch
Bn nht
Cu trng che khut
Km bn nht
ETHANE
ETHANE
SC CNG NH DIN (Torsional strain)
S khc nhau v nng lng gia cu trng lch v cu trng che khut: Khong 3 kcal/mol Sc cng nh din: sc cng do s tin n gn nhau ca cc nguyn t hoc cc nhm nguyn t t cu trng lch n cu trng che khut.
BUTHANES quay xung quanh lin kt C1-C2
Cu trng lch
Cu trng che khut
BUTHANE: Cu trng do s quay chung quanh C2-C3
Cu trng bn lch, = 60 (gauche conformation)
BUTHANE: Cu trng do s quay chung quanh C2-C3
Cu trng lch hon ton, = 180 (anti conformation)
BUTHANE: Lin kt C2-C3
BUTHANE: Lin kt C2-C3
SC CNG GC (Angle strain)
Xut hin khi gc lin kt trong phn t tr nn nh hn hoc ln hn so vi bnh thng Hoc xut hin khi mt lin kt tr nn ngn hn hay di hn so vi di bnh thng ca lin kt Xut hin do tng tc gia cc lin kt
Tng tc lp th (Steric strain)
L nng lng thm vo phn t khi cc nguyn t hoc cc nhm nguyn t qu gn nhau trong khng gian tng lc y Van der Waals gia cc m my in t Xut hin do tng tc gia cc nhm
CU TRNG CA PENTANE Mch carbon thng: Cu trng bn nht tng ng vi tt c cc lin kt C-C u cu trng anti Khung carbon sp xp theo kiu zigzag
Xc nh cu trng u i ca pentane
Me H H H H H H
Me H H H H
Me
Me
H H
H H
H H
i lch
Che khut mt phn
Bn lch
Che khut hon ton
CU TRNG CA HEXANE
Xc nh cu trng u i ca hexane
Biu din bng cng thc chiu newman (Chiu theo C3-C4)
HEXAN CHIU C3-C4
H H
H H
Dng i lch ( bn nht)
CU TRNG CA HIDROCACBON NO MANG NHM TH HALOGENUR ETYL Thay th mt nguyn t H trong etan bi mt nguyn t halogen khng lm thay i ng k ro nng lng 1,2-DICLOROETANCl H H Cl H H H H H Cl Cl H
i lch
Bn lch
ETANOL MANG NHM TH V TR S 2R CH2 CH 2 OH
R: OH, NH2, F, Cl, Br, OCH3, NO2, NHCH3H Cl Cl H H OH H H H O H
H H
Bn lch i lch Bn hn do to c lk hidro
ETILENGLICOLH OH R H OH H R H H R O O H R R H H O O H R H
i lch
Bn lch
Bn lch ng phn treo Bn
ng phn eritro (Meso)
CU TRNG CC HP CHT BT BO HA PHN T CHA NHM C=C, C=N, C=OOH H H H H HH O H
Acetaldehid
H CH
H C H H
H H
H
Propen
HH
OMe
OH
H H
H
H H
Me
Propanal
H
H CMe
H CH
H
H H
H
H H
Me
But-1-enH CH H
H H
t Bu
4,4-dimetylpent-1-en
PHN T C NI I LIN HPH2 C CH 2 H2 C H
H
H
H
CH 2
s-cis-buta-1,3-dien
s-trans-buta-1,3-dien
2-metylbuta-1,3-dien
H2 C
CH 2
H2 C
H
Me
H
Me
CH 2
S-cis
s-trans
metylacroleinH O CH 2 O H H CH 2
H
Me
H
s-cis
s-trans
CYCLOALKANETNH BN CA HP CHT VNG NO phn ng ca ciclopropan, ciclobutan Thuyt cng Baeyer
= (10928 ) : Gc trong ca vng
Thiu nhit v tnh bn tng i ca cicloankanL nhit lng ta ra khi t cht hon ton mt cycloankan vi oxi. Hp cht cng c nhiu sc cng th nng lng ta ra khi t chy cng ln H/n (Kcal/mol): thiu nhit tnh cho mi nhm CH2 ca hp cht cicloankan ( th kh) (H/n157) Kcal/mol: hiu s thiu nhit tnh cho mi nhm CH2 ca cicloankan v nankan tng ng n(H/n157) :Tng s sc cng ca ciclan
Hp cht vng 5 hoc 6 carbon hin din rt nhiu trong t nhin trong khi hp cht vng 4 hoc 3 carbon rt t: Do sc cng vng ?
Cyclopentane gn phng Cyclopropane phng Gc lin kt = 108 Gc lin kt = 60 (Gc lin kt trong t din = 1095)
Khi nim vng khng cng ca Sachse v MohrS 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.
CU TRNG CA CC VNG NH
CYCLOPROPANE: SC CNG VNG
S xen ph hiu qu
S xen ph km hiu qu
Xen ph sp3-sp3 km hiu qu
CYCLOPROPANE: SC CNG NH DINNgoi sc cng vng, vng cyclopropane cn chu sc cng nh din (torsional strain) do cc lin kt u b che khut
CYCLOALKANE MANG 2 NHM TH: NG PHN LP TH
ng phn trans bn hn
CYCLOPROPANE MANG 2 NHM TH
S quay t do quanh lin kt C-C l khng thc hin c. Khng th hiu chnh cu trng gim tng tc lp th. ng phn trans bn hn cis.
CYCLOBUTANE
Cu trng xp ca cyclobutan
CH3
H3 COOC
H 3C
COOCH3
Cis ee
Cis aa
CYCLOPENTANE
Cu trng phong b
R
1,3dimetylciclopentan c cu trng cis (ee) bn hn cu trng trans (ea) khong 0,59 Kcal/mol
CH 3
CH 3
CH 3 CH3
Cis ee
Trans ea
CYCLOHEXANE
CYCLOHEXANE: CU TRNG GH
CYCLOHEXANE: CU TRNG THUYN
CYCLOHEXANE
CYCLOHEXANE
CYCLOHEXANE MANG MT NHM TH
Ti sao nhm methyl v tr xch o bn hn?
CYCLOHEXANE MANG MT NHM TH
S khc nhau v nng lng: 7 kJ/mol
CYCLOHEXANE MANG MT NHM TH
CYCLOHEXANE MANG MT NHM TH
Nhm tert-butyl ln hn nhm methyl
1,4-DIMETYLCYCLOHEXANE
ng phn trans c nng lng thp hn (bn hn) ng phn cis 7 kJ/mol
1,4-DIMETYLCYCLOHEXANE
1,2-DIMETYLCYCLOHEXANE
Trans-1,2-Dimethylcyclohexane
1,2-DIMETYLCYCLOHEXANE
1,3-DIMETYCYCLOHEXANE
Cu trc bn ?1. 2. 3. 4.
trans-1-tert-Butyl-3-methylcyclohexane cis-1-tert-Butyl-3-methylcyclohexane trans-1-tert-Butyl-4-methylcyclohexane cis-1-tert-Butyl-4-methylcyclohexane
trans-1-tert-Butyl-3-methylcyclohexane
Nhm tert-butyl ln: v tr xch o Thm nhm methyl: v tr trans i vi nhm tert-butyl
cis-1-tert-Butyl-3-methylcyclohexane
trans-1-tert-Butyl-4-methylcyclohexane
cis-1-tert-Butyl-4-methylcyclohexane