hoa huu co 2
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B Y t
V khoa hc v o to
Hp cht hu c n chc v a chc(Sch dng o to dc s i hc)
M s: 20 Y13
Tp II
Nh xut bn Y hc
H ni - 2006
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Ch bin:
PGS. TS. Trng Th K
Tham gia bin son:
ThS. Nguyn Anh Tun
TS. Phm Khnh Phong Lan
ThS. Th Thu
PGS. TS. ng Vn Tnh
ThS. Trng Ngc Tuyn
Tham gia t chc bn tho:
TS. Nguyn Mnh Pha
ThS. Ph Vn Thm
Bn quyn Thuc B Y t (V Khoa hc v o to)
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Li gii thiu
Thc hin Ngh nh 43/2000/N-CP ngy 30/08/2000 ca Chnh ph quynh chi tit v hng dn trin khai Lut Gio dc, B Gio dc v o to vB Y t ph duyt, ban hnh cc chng trnh khung cho o to Dc s ihc. B Y t t chc thm nh sch v ti liu dy hc cc mn hc c s vchuyn mn theo chng trnh mi nhm tng bc xy dng b sch chun trongcng tc o to Dc s i hc ngnh Y t.
B schHo hu cc bin son theo chng trnh o to mn Ho hchu c thuc chng trnh gio dc ca i hc Y Dc thnh ph H Ch Minhtrn c s chng trnh khung c B Gio dc & o to, B Y t ph duyt.
Ni dung b sch ch cp nhng kin thc l thuyt v ho hu c, gm40 chng v chia lm 2 tp trnh by nhng kin thc c bn v danh php, cutrc, c ch phn ng, tnh cht l hc v tnh cht ho hc ca cc hp chthydrocarbon, cc hp cht n chc, cc hp cht a chc, hp cht tp chc, hpcht thin nhin v hp cht cao phn t.
i tng s dng b sch ny l cc sinh vin ang theo hc ti Trng ihc Dc, khoa Dc thuc cc trng i hc ngnh Y t. ng thi cng l tiliu tham kho tt cho nhng hc vin sau i hc.
SchHo hu cc cc ging vin giu kinh nghim ca Khoa Dc - i
hc Y Dc Thnh ph H Ch Minh bin son. Sch c Hi ng chuynmn thm nh sch gio khoa v ti liu dy hc chuyn ngnh Dc ca B Yt thm nh v c B Y t ban hnh lm ti liu dy hc chnh thc dngo to dc s i hc ca Ngnh Y t trong giai on hin nay. Trong thi giant 3 n 5 nm, sch cn c chnh l, b sung v cp nht.
V Khoa hc v o to, B Y t xin chn thnh cm n Khoa Dc - ihc Y Dc Thnh ph H Ch Minh cng cc tc gi b nhiu cng sc bin son cun sch ny. V l ln u xut bn nn chc chn cn nhiu thiust, chng ti mong nhn c kin ng gp ca ng nghip v bn c cun sch ngy cng hon thin.
V khoa hc v o to
B Y t
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MC LC
M u 9
HP CHT TP CHC 11Chng 25: Halogenoacid (ThS. Th Thy) 13
1. Phng php iu ch 13
2. Cc phn ng ha hc ca halogenoacid 14
3. Mt s halogenoacid c nhiu ng dng 16
Chng 26: Hydroxyacid (ThS. Th Thy) 18
1. Danh php 182. ng phn 18
3. iu ch 19
4. Tnh cht l hc 21
5. Tnh cht ha hc 21
6. ng dng 24
Chng 27: Hp cht hai chc c nhm carbonyl (ThS. Th Thy) 28
1. Hydroxy - aldehyd v hydroxy - ceton 28
2. Ceto-aldehyd, ceto-acid, ceto-ester 30
Chng 28: Carbohydrat (ThS. Th Thy) 33
1. Monosaccharid 33
2. Oligosaccharid 51
3. Polysaccharid 56
Chng 29: Acid amin, peptid v protid (TS. Phm Khnh Phong Lan) 62
1. Acid amin 62
2. Peptid 73
3. Protid 75
HP CHT D VNG 79Chng 30: Hp cht d vng (TS. Phm Khnh Phong Lan) 79
1. nh ngha 79
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2. Phn loi hp cht d vng 79
3. Danh php hp cht d vng 81
4. Cu to cc d vng thm 88
5. Tnh cht ha hc ca d vng c tnh thm 91
Chng 31: Hp cht d vng 5 cnh 1 d t(TS. Phm Khnh Phong Lan) 931. Nhm furan 94
2. Nhm pyrrol 97
3. Nhm thiophen 101
Chng 32: Hp cht d vng 6 cnh 1 d t - D t l nit hoc oxy
(TS. Phm Khnh Phong Lan) 105
1. Pyridin 105
2. Pyran 117
Chng 33: Hp cht d vng 5 cnh nhiu d t(TS. Phm Khnh Phong Lan) 120
1. Nhm oxazol 120
2. Nhm thiazol 122
3. Nhm imidazol 124
4. Nhm pyrazol 126
Chng 34: Hp cht d vng 6 cnh 2 d t(TS. Phm Khnh Phong Lan) 128
1. Hp cht d vng 2 d t l nit 129
2. Hp cht d vng 2 d t l nit v lu hunh 1343. Hp cht d vng 2 d t l nit v oxy 136
4. Hp cht d vng 2 d t l oxy 136
Chng 35: Hp cht d vng 7 cnh (TS. Phm Khnh Phong Lan) 137
1. Azepin 138
2. Oxepin v thiepin 139
3. Diazepin v benzodiazepin 140
Chng 36: Hp cht d vng ngng t(TS. Phm Khnh Phong Lan) 142
1. Dng h bin ca vng lactam 142
2. Tnh cht ca purin 143
3. Mt s alcaloid c khung purin 143
HP CHT THIN NHIN 145Chng 37: Acid nucleic (TS. Phm Khnh Phong Lan) 145
1. nh ngha 145
2. Phn ng ca acid nucleic 146
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3. Phn base ca acid nucleic 146
4. Cu to ca cc nucleosid 147
5. Cu to ca nucleotid 148
6. Cu to ca acid nucleic 148
Chng 38: Terpen (TS. Phm Khnh Phong Lan) 1501. nh ngha v phn loi 150
2. Monoterpen 151
3. Sesquiterpen 161
4. Diterpen 165
5. Triterpen 166
6. Tetraterpen 167
7. Polyterpen 170
Chng 39: Steroid (TS. Phm Khnh Phong Lan) 173
1. nh s trn khung steroid 174
2. Cu hnh v danh php ca khung steroid 174
3. Cu hnh v danh php cc nhm th trn khung steroid 175
4. Cu dng ca steroid 175
5. Sterol 176
6. Cc acid mt 179
7. Cc hormon 181Ti liu tham kho 183
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M U
i tng ca ha hc hu c:
Ha hc hu c l mn khoa hc nghin cu thnh phn v tnh cht cchp cht ca carbon.
Trong thnh phn hp cht hu c, ngoi carbon cn c nhiu nguyn tkhc nh H, O, N, S, P, halogen... nhng carbon c xem l nguyn t c bn cuto nn hp cht hu c.
S lc lch s pht trin ca Ha hc hu c
T xa xa ngi ta bit iu ch v s dng mt s cht hu c trongi sng nh gim (acid acetic long), ru (ethanol), mt s cht mu hu c.Thi k gi kim thut cc nh ha hc iu ch c mt s cht hu c nhur, ether etylic...
Cui th k 18 u th k 19, cc nh ha hc chit tch t ng, thcvt nhiu acid hu c nh acid oxalic, acid citric, acid lactic ... v mt s base huc (alcaloid). Nm 1806 ln u tin nh ha hc ngi Thy in Berzelius dng danh t Ha hc hu c ch ngnh ha hc nghin cu cc hp cht cngun gc ng vt v thc vt. Thi im ny c th xem nh ct mc nh dus ra i ca mn ha hc hu c.
Nm 1815 Berzelius a ra thuyt Lc sng cho rng cc hp cht hu cch c th c to ra trong c th ng vt v thc vt nh mt lc sng chcon ngi khng th iu ch c. Thuyt duy tm ny tn ti trong nhiu nmnhng dn dn b nh bi cc cng trnh tng hp cc cht hu c t cc chtv c.
Nm 1824, nh ha hc ngi c Wohler tng hp c acid oxalic bngcch thy phn dixian l mt cht v c. Nm 1828 cng chnh ng, t cht v camoni cyanat tng hp c ur. Tip theo Bertholet (Php) tng hp ccht bo nm 1854 v Bulerov (Nga) tng hp ng glucose t formalin nm
1861.Cho n nay hng triu cht hu c c tng hp trong phng th
nghim v trn quy m cng nghip. Con ngi khng ch bt chc tng hp cccht ging thin nhin m cn sng to ra nhiu cht hu c, nhiu vt liu huc cc k quan trng v qu gi m t nhin khng c.
Tuy nhin tn gi hp cht hu c vn c duy tr, nhng khng phi chvi ngha l cc cht c ngun gc ng vt v thc vt m mang ni dung mi: l cc hp cht ca carbon.
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c im ca cc hp cht hu c v phn ng hu c
Mc d ra i mun hn ha hc v c nhng cc hp cht hu c rt phongph v s lng, chng loi. S lng cht hu c cho n nay nhiu gp vi chcln cc cht v c bit. Nguyn nhn c bn l do carbon c kh nng tothnh mch di v tn theo nhiu kiu khc nhau. Ni cch khc hin tng ng
phn (tc l cc cht c cng thnh phn phn t nhng khc nhau v cu to) lcc k ph bin v c trng trong ha hc hu c.
Cu trc phn t ca hp cht hu c c th n gin nhng cng c th rtphc tp, vic xc nh cu trc ca chng nhiu khi rt kh khn, phi s dngnhiu phng php ha hc v vt l hc hin i.
Nu nh lin kt ion kh ph bin trong hp cht v c th lin kt chyu gia cc nguyn t trong phn t hu c li l lin kt cng ha tr. cim ny nh hng nhiu n tnh cht l ha v c bit l kh nng phnng ca chng.
Cc phn ng hu c thng xy ra vi tc chm, khng hon ton vthng theo nhiu hng khc nhau, v vy vai tr ca nhit ng hc, ng hcv xc tc trong ha hu c rt quan trng.
Vai tr ca ha hc hu c
Cc cht hu c c vai tr rt quan trng trong i sng ca con ngi.Khng nhng hu ht thc phm chng ta n (glucid, protid, lipid), vt dnghng ngy (cellulose, si tng hp, cao su, cht do...) l cc cht hu c m nhiucht hu c cn l c s ca s sng (protid, acid nucleic..). Nhin liu cho ng ct trong, cho nh my nh xng, du l hn hp hydrocarbon mch di ngnkhc nhau. Cc vt liu hu c nh, khng han g, tin s dng, nhiu mu sc adng ang ngy mt thay th cho cc kim loi, hp kim trong nhiu lnh vc, kc nhng lnh vc tng nh khng th thay th c nh bn dn, siu dn...
Do tt c nhng c im trn, ha hc hu c c tch ra nh mt ngnhkhoa hc ring i hi nhng phng php nghin cu v thit b ngy cng hini hn, i hi n lc khng ngng ca cc nh ha hc khng nhng btchc thin nhin tng hp nn cc cht phc tp phc v cho nhiu lnh vc cacuc sng m cn vt xa hn c thin nhin. T c s ha hc hu c, c rtnhiu ngnh nghin cu ng dng ra i: ha cng nghip, ha du, cng nghip
dt, ha thc phm, dc phm v ha m phm.
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HP CHT TP CHC
nh ngha
Hp cht tp chc l hp cht hu c, trong phn t c t nht hai nhmchc khc nhau. Cng c th xem hp cht tp chc l dn xut ca hydrocarbonm t nht c hai hydro c thay th bi cc nhm chc hon ton khc nhau.
CH3 - CHOH - CH = O phn t c chc alcol v chc aldehyd
CH3 - CH(NH2) - COOH phn t c chc amin v chc acid
CH2Cl - CHCl - CH2OH phn t c Cl v chc alcol
HOC6H4COOH phn t c chc phenol v chc acidH
2NC6H4COOH phn t c chc amin v chc acid
HOC6H4CHO phn t c chc phenol v chc aldehyd
Phn bit
Hp cht a chc:nhiu nhm chc cng mt loi.
Hp cht tp chc: nhiu chc khc nhau (xut hin tnh cht mi).
Trong cc hp cht tp chc cc nhm chc nh hng ln nhau lm tnghoc gim kh nng phn ng ca nhm chc c bn hoc to ra nhng tnh chtphn ng c th ca hp cht tp chc.
V d: Phenol c tnh acid yu hn acid carbonic. Phenol khng tc dng viNa2CO3nhng clorophenol li tc dng vi Na2CO3
OH
Cl
ONa
Cl
+ NaHCO3+ Na2CO3
iu chng t rng nguyn t clor nh hng n tnh acid ca chcphenol.
Hp cht tp chc c nhiu nhm chc khc nhau rt ph bin trong isng hng ngy. Cc dc phm thng c nhiu nhm chc khc nhau trongphn t.
Danh php
Cc hp cht tp chc c loi gi theo danh php thng thng nh cc acidamin, nhng gi tn theo danh php quc t l chun mc bit r cu trc
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ca mt hp cht tp chc phc tp. C nhng quy c khi gi tn theo danhphp h thng:
a- Chn mch di nht cha nhm chc c u tin cao nht.
b- Cc nhm chc cn li c gi tn theo tip u ng.
c- nh s trn mch chnh t nhm chc.Gi tn hp cht c mch chnh tng ng vi nhm chc u tin c tip v
ng ca nhm chc v v tr, tip u ng ca cc nhm chc khc theo th tu tin.
Bng lit k sau trnh by th t u tin ca cc nhm chc:
Tn gi tip v ng, tip u ng v th tu tin ca cc nhm chc
Nhm chc Tip v ng Tip u ng
Cation oni onioAnion at, id, ur ato, ido
-COOH oic, carboxylic carboxy
-SO3H sulfonic sulfo
-COX oylhalogenid,carbonylhalogenid
haloformyl
-CONH2 amid, carboxamid carbamoyl
-CONHCO- imid, dicarboximid. iminodicarbonyl
-CN nitril, carbonitril. cyano
-CHO al, carbaldehyd. oxo, formyl
C=O on oxo
S=O thion thioxo
-OH ol hydroxyl, hydroxy
-SH thiol mercapto
-NH2 amin amino
=NH imin imino
V d V:
CH3 CH C
C N
O
Cl
H2N CH2 CH CH2 CH COOH
NH2OH4-Hydroxy-2,5-diaminopentanoic 2-Cyanopropanoyl clorid
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Chng 25
HALOGENOACID
Mc tiu
1.c c tn cc halogenoacid.
2.Nu c ha tnh ca halogenoacid v ng dng ca mt s cht in hnh.
Halogenoacid l nhng hp cht c to thnh do s thay th mt haynhiu nguyn t hydro trn gc hydrocarbon ca acid carboxylic bng cc nguyn
t halogen. Cc halogenoacid ca acid monocarboxylic no c nhiu ng dng, cbit l cc -halogenoacid.
R CH COOH
X
R CH CH2X
COOH R CH CH2X
CH2 COOH
-Halogenomonocarboxylic2-Halogenocarboxylic
-Halogenomonocarboxylic3-Halogenocarboxylic
-Halogenomonocarboxylic4-Halogenocarboxylic
1. Phng php iu ch
1.1. Halogen ha acid carboxylic
Acid -monocarboxylic no c th c iu ch bng cch halogen ha trctip bng fluor (F2), clor (Cl2), brom (Br2) khi c mt ca acid cha proton, acid
Lewis. Nu c xc tc nh sng (h), phn ng th xy ra theo c ch th gc vkhng th vo v tr .
CH3 CH2 COOH
CH3 CH COOH
Cl
CH2 CH2 COOHCl
+ HCl
+ HCl
+ Cl2(H+)
+ Cl2(h)
Trong phn ng halogen ha acid, thu c sn phm th vo v tr thng s dng thm phosphor (P) vi vai tr to acylhalogenid v s halogenha vo acylhalogenid xy ra nhanh hn vo acid carboxylic.
2P + X22PX3
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R CH2 CO
OHR CH2 C
O
XR CH C
OH
X
R CH CO
X
X
R CH CO
OH
X
+ RCH2COOH
PX3
+ X2 - HX
R CH2 CO
X+
Nhm COX c hiu ng - I mnh cho nn hydro ca C _H v tr c tnhacid hn so vi cc hydro khc trong phn t acid RCH2CH2COOH.
Halogen ha acid benzoic bng halogen c xc tc Lewis to acid meta -halogenobenzoic.
COOH
X
COOH
+ X2AlCl3 + H
Acid carboxylic - RCOOH hoc CH2(COOH)2 b halogen ha d dng khi
tng tc vi thionylclorid (SOCl2).
1.2. Cng hp HX vo acid cha no
Cng hp HX vo acid ,-cha no thu c -halogenoacid. Phn ng triquy tc Markonikov.
CH2=CH-COOH + HX X - CH2-CH2-COOH
2. Cc phn ng ha hc ca halogenoacid
2.1. Phn ng th i nhn - Phn ng thy phn
Halogenoacid l acid mnh hn acid carboxylic. Nguyn t halogen cahalogenoacid thuc dy aliphatic tham gia phn ng th i nhn. Halogenoacidrt d thy phn.
+ OH - R-CHOH-COOR-CHX-COOH
Nhm carboxyl nh h
ng n s phn cc ca lin kt C -X. Phn ng thxy ra theo c ch SN2 v khng thay i cu hnh. Gii thch nh sau:
-
:
: ....
......
.. ..
..
....
-Lacton
- Br --H+
..
C
C
O
O
HR
C
C
OO
BrH
R
C
C
OHO
BrHR
S
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- OH
C
C
OO
OH
H
R
COOH
COHH
R
..
C
C
O
O
H
R
..
....
:....:
+ H+
..
..: ..-
Acid -hydroxycarboxylicS
Cc gem -dihalogen acid thy phn bng H2O to thnh oxo acid:
Acid glyoxalicAcid dicloroacetic
+ 2HClCH O
COOH+ H2O
CHCl2
COOH
Cc hp cht , v -halogenoacid c kh nng to cc vng lacton tng ng:
utyrolacton ,Butanolid
O
CO
CH3
H2O , CHCl3
-Br-CH3 CH CH2 COOH
Br
Acid 6-hydroxycaproic; 6-Hydroxyhexanoic
HO (CH2)5 CO
OH
O
C
O
H2O , Ag2OBr (CH2)5 C OOHCaprolacton , (1,6-hexanolid)
2.2. Phn ng tch loi to acid cha no
Trong mi trng kim c - alcol, c phn ng loi HX.
-hydroxybutyrat natri
Acid -clorobutyric Nnatric crotonatCH3 CH = CH COONa
2NaOH
CH3 CHOH CH 2 COONa
CH3 CH CH2 COOHCl
+ NaCl + H2O
+ NaCl + 2H2O
2NaOH
Phn ng ph xy ra khi tch loi c th l s decarboxyl ha v to hydrocarboncha no. Phn ng ph ny thng xy ra i vi hp cht -halogenoacid.
+ CO2 + XR CH CH2-: ..
..
:
Halogenocarboxylat
X CH CH2 C
R
O
O-
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3. Mt s halogenoacid c nhiu ng dng
3.1. Monocloroacetic ClCH2COOH
Monocloroacetic c iu ch bng cch clor ha acid acetic trong hn hpanhydrid acetic v acid sulfuric m c hoc thy phn tricloroetylen bng acid
sulfuric 75% 140C.
+ 2HClCl-CH2-COOH2 H2O , H2SO4
C CCl
Cl
Cl
H
Monocloroacetic l tinh th, tnc = 63C, d tan trong nc v etanol, c sdng tng hp acid malonic, ester malonat v cc cht mu.
3.2. Dicloroacetic - Cl2CHCOOH
iu ch dicloroacetic bng cch un cloralhydrat vi calci carbonat c xctc l natri cyanid NaCN.
2CaCO3 , NaCNCl3-CH(OH) 2 (Cl2 CH-COO ) 2Ca
-2CO2 , -CaCl 2 , -2H2O
2Cl2CH-COOH+ 2 H+
-Ca2+
Hoc thy phn tetracloroetylen bng hi nc:
C C
Cl
Cl
Cl
Cl
2H2OCl2 CH-COOH + 2HCl
iu ch dicloroacetylclorid: Oxy ha tricloroetylen bng khng kh 70-100C. Cht trung gian l tricloroxiran khng bn b chuyn v.
O2 ,Cl2CH C
O
ClC C
H
Cl
Cl
Cl
O
C CH
Cl
Cl
Cl
Gc dicloroacetyl c trong thnh phn ca chloramphenicol.
3.3. Tricloroacetic - Cl3C-COOH
Oxy ha cloralhydrat bng acid nitric HNO3 m c thu c tricloroacetic.
Cl3-CH(OH) 2 Cl3 C-COOH + H2O[O] ,HNO 3
Oxy ha tetracloroetylen bng oxy khng kh thu c tricloroacetylcloridCl3C-COCl. Tricloroacetic l mt acid mnh. Khi un nng tricloroacetic vi dungdch kim long hoc hi nc s thu c cloroform.
+ CO2
[H2O ]Cl3 C-COOH Cl3 CH
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C ch:
:CClCl
ClC CClCl
ClO
O
+.. :--
Cl3C_ H
H+
C O
O
:
Bi tp
1.Vit cng thc cu to ca cc cht sau:
a- Acid -bromopropionic.
b- Acid-cloro--metylbutyric
c- Acid o-clorobenzoic.
d- ,-Dibromopropionat kali.
e- 2,3-Dicloropropionylclorur.
g- Acid p-bromophenylacetic.
2- Vit phn ng ca acid-bromobutyric trong cc iu kin sau:
a- Thy phn trong mi trng base.
b- Thu phn khi c Ag2O.
c- Tch loi trong mi tr
ng alcol /KOH.
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Chng 26
HYDROXYACID
Mc tiu
1.c c danh php cc hydroxyacid theo IUPAC v thng thng.
2.Trnh by c ha tnh ca hydroxyacid v tnh cht tng h gia hai nhmchc.
Hydroxyacid cn c gi l hp cht oxyacid.
C hai loi hp cht hydroxyacid quan trong:
Acid carboxylic cha chc alcol: HO -R-COOH (Alcol-acid)
Acid carboxylic cha chc phenol: HO -Ar-COOH ( Phenol-acid)
1. Danh php
Tn v v tr nhm OH + Tn acid tng ng
nh s hoc dng ch ci , ,,.. ortho, meta, para ch v tr ca nhm OH.
HydroxycaproicAcid
CH3-CH2-CH2-CHOH-CH2-COOH
COOH
OH
COOH
OH
Acid 3-HydroxybenzoicAcid m-Hydroxybenzoic
Acid 4-Hydroxybenzoic
Acid p-Hydroxybenzoic
2. ng phn
S ng phn ph thuc v tr nhm OH.
Thng c ng phn quang hc.
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Cng thc Danh php ng phn quang hc
HO-CH2-COOH Acid glycolic -
CH2-CHOH-COOHAcid lactic
R- Lactic
S-Lactic
R,S-Lactic
HOOC-CHOH-CH2-COOH Acid malic
R-Malic
S-Malic
R,S-Malic
HOOC-CHOH-CHOH-COOH Acid tartaric
2R,3R-Tartaric
2S,3S-Tartaric.
2R,3S-Mesotartaric
CH2 COOH
C
CH2 COOH
COOHHO
Acid citric -
C6H5 CH COOH
CH2OH
Acid tropic R(+)-Tropic
S(-)-Tropic
R,S-Tropic
C6H5-CHOH-COOH Acid mandelic R(-)-Mandelic
3. iu ch
3.1. Thy phn halogenoacid
R CHCl-COOH + H2O R -CHOH-COOH + HCl
3.2. Kh ha ester ca oxoacid (aldehyd-ceton acid)
Kh ha bng hydro mi sinh (hn hng natri) hay H2/ Ni
Aacid -hydroxy butyric
CH3 CHOH CH 2COOHH2 / NiCH3 CO CH 2CO2Et CH 3 CHOH CH 2CO2Et
-Hydroxy butyrat ethylAceto acetat ethyl 120oC ,100 atm -EtOH
H2O
CH (CH2) nR
OH
COOHCH (CH2) nR
OH
COOR-ROH
H2O
to
2 H (Ni)C (CH2) nR
O
COOR
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3.3. T aldehyd -ceton
Cng hp HCN vo aldehyd - ceton, thy phn tip theo thu c -hydroxyacid.+H3OR CH2 CH = O
H CNR CH2 CHOH CN R CH2 CHOH COOH
3.4. T cc hp cht etylen oxydEtylen oxyd tc dng vi HCN v thy phn tip theo thu c - hydroxyacid.
HO CH2 CH2 CO2HHO CH2 CH2 CN
O
CH2 CH2H3OHCN
+
3.5. Phn ng Reformatski (1889)
Ester ca acid -halogencarboxylic tc dng vi aldehyd hoc ceton c Znlm cht trung gian s to thnh acid -oxycarboxylic. Phn ng xy ra nh sau:
H2O
Zn
Br CH2 CO2EtR'
RC = O
R'
RC
O Zn Br
CH2CO2Et
R'
RC
O H
CH2CO2Et
3.6. T acid amin
Acid amin tc dng vi HNO2
+ + H2OHO N = OCH3 CH (NH 2) CO2H CH3 CH OH CO 2H
AalaninAacid lactic
-
+ N2
3.7. iu ch cc phenolacid
Phng php Kolbe -Schmitt
Phenolat kh tc dng vi CO2 c nhit v p sut.
ng dng sn xut acid salicylic trong cng nghip.
OHCOONa
ONaOH
COONaNatri salisilatOxybenzoat natri
200oC
CO2 CO2
125oC , 7 atm
p -
Cc phenol khc c phn ng tng t:
-Naphtolat natri
ONa OHCOO Na
130oC , 5 atm
CO2
250oC , 5 atm
CO2
COO Na
OH
-2-carboxylat natri-1-carboxylat natri
3-Hydroxy-naphtalen-2- Hydroxy-naphtalen-
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4. Tnh cht l hc
Hydroxyacid thng l cht kt tinh, c lin kt hydro tan tt trong nc, dphn hy khi c nhit .
5. Tnh cht ha hc
Cc hydroxyacid th hin tnh cht c trng ca chc acid COOH, chc OHca alcol hay chc OH ca phenol.
5.1. Cc phn ng ca alcolacid (HO -R-COOH)
Phn ng ca chc-COOH (tnh acid, to ester...)
Phn ng ca chc -OH (to ester vi dn xut acid, phn ng SN...)
5.2. Phn ng tch nc
Ty thuc v tr nhm OH, khi c nhit , phn ng tch nc ca hydroxyacidxy ra trong cc trng hp sau y:
5.2.1. Vi-hydroxy acid
2 phn t -hydroxy acid tch 2H2O to vng lactid (diester vng).
HC
C
O
CH
CO O
O
R
R
- Hydroxy acid
+
LactidHO
HO
C
O
RC
OH
C
OHO
R
C+ 2 H2O
Cc lactid khng bn d b thy phn. Khi chng ct, cc lactid d bdecarbonyl ha (gii phng CO) v to thnh aldehyd.
5.2.2. Vi- hydroxy acid.
-Hydroxacid khi tch H2O ni phn t to acid cha no ,-etylenic
R _ CH OH _ CH2_ CO2H
-Hydroxy acid
R _ CH = CH _ CO2H H 2O
Aacid - ethylenic
+
5.2.3. Vi, -hydroxy acid
Khi c nhit hoc xc tc acid, cc phn t hoc -hydroxy acid tchH2O to vng v -lacton. Nhm OH alcol v nhm OH ca acid b loi nc toester ni phn t (vng lacton).
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-Butyrolacton
Acid -hydroxybutyric
Hoc
OH HO
C
CH2CH2
H2C O
H2C
H2C H2C
C
O
O
+ 2 H2O
H+
CH2CH2
H2C
OH HO
C
CH2
O
CH2
H2CO
C
CH2
CH2
O+ H2O
Acid -Hydroxyvaleric Valerolacton
Hoac H+
Khng th iu ch vng -lacton trc tip t -hydroxyacid. C th iuch vng -lacton bng cch cho hp cht ceten tc dng vi aldehyd formic:
Propiolacton
+
H2C O
H2C C O CH2
CH2 O
C O
Cc hydroxy acid c nhm OH cc v tr v xa hn na thng khng to vnglacton. Trong nhng iu kin nh trn cc acid ny thng to thnh cc polyester.
Bng cc phng php ha hc c bit, c th tng hp cc lacton c vng ln:
CH2
(CH2)6O
C
(CH2)6
CH2
O
CH2
(CH2)8O
C
(CH2)5
CH2
O O C
OHH
O
Eczaltolid Ambrettolid Mevalolacton Vng lacton nh l mt ester ni phn t, do nhng hp cht c vng
lacton rt d b thy phn. Mt s phn ng c trng ca vng lacton:
CH2
CH2 CH2
CO
O
HO (CH2)2COOH
CH3(CH2)2COOH
HO(CH2)4OH
X(CH2)3COOH
NC(CH2)3COOK
NaOH ,
2H [Na/Hg]
4H[LiAlH4]
HX
KCN
NH3
-H2O
CH3NH2
CH2
CH2 CH2
CN
O
H
CH2
CH2 CH2
CN
O
CH3
ButyrolactonPyrrolidon
N-Metylpyrrolidon-H2O
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Cc vng lacton c vai tr quan trng trong mt s dc phm:
Artemisinin l mt cht hu c chit c t cy Thanh hao hoa vng(Chenpodium ambrosioides) c cha vng lacton. Artemisinin v cc dn xut can c tc dng cha bnh st rt.
Natri artesunat
OO
O
OCH CH3
CH3
H HH
O C CH2CH2COONaO
Hydroartemisinin
OO
O
OCH CH3
CH3
H HH
OH
Artemisinin
OOO
OC CH3
CH3
H H
H
O
5.3. Cc phn ng ca phenolacid (HO -Ar-COOH)
5.3.1. Tc dng vi FeCl3
Acid salicylic cho mu tm.
Acid p-hydroxybenzoic cho mu .
Acid m-hydroxybenzoic khng cho mu
5.3.2. Phn ng vi Na2CO3 v NaOH
Ch c chc acid mi tc dng vi Na2CO3
Acid salicylic
+ NaHCO 3+ Na 2CO3
OHCOO H
OHCOO Na
Vi NaOH c 2 chc cng phn ng.
+ 2H2O+ 2NaOHAcid salicylic
OHCOO H
COO NaONa
5.3.3. Phn ng acetyl ho vo chc phenol to ester
Acid salicylic
+ Pyridin.CH3COOHPyridin
Aspirin
OHCOO H
(CH3CO)2O
O - COCH 3COO H
+
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5.3.4. Kh ha acid salicylic to acid pimelic
H bin
COOHO
HCOOHOH
COOHOH
COO H
Na / C5H11 OH
4 [ H ]
Acid pimelic
CH2COOH
Acid salicylic
H2O
Acid pimelic hay heptandioic hay 1,5-pentandicarboxylic
Acid salicylic c tnh acid mnh hn acid benzoic v cc ng phn meta vpara. Acid salicylic c lin kt hydro ni phn t to iu kin thun li cho sphn ly proton.
CO
O H
OH
...C
O
O H
O
... + H+
pKa =2,79
-
6. ng dng
6.1. Mt s alcol acid ph bin
Acid glycolic:HOCH2-COOH (Acid hydroxyacetic, hydroxyetanoic).
iu ch acid glycolic bng phng php in phn acid oxalic hoc tnghp t formaldehyd v oxyd carbon:
HCHO + CO HO-CH2-COOHH+ , + H2O+ H2O
Acid lactic: CH3CHOH-COOH (Acid -hydroxypropionic, 2-oxypropanoic).
Phn t c 1 carbon khng i xng. Nm 1780 Scheeler pht hin acid R,S-lactic c trong sa chua khi ln men sa. Acid S (+)-lactic c trong cc c bp cangi v ng vt, l sn phm trung gian ca qu trnh glycolyse.
Acid R(-)-lactic thu c t dung dch acid R,S-lactic.
Acid L(+) lactic, acid R(-)-lactic u th rn. Acid R,S-lactic dng lng.
iu ch acid lactic bng phng php ln men lactose, maltose hoc glucose.
C12H22O11 + H2 O 4 CH3-CHOH-COOH (raxemic)Men Bacillus acidi lacti
Oxy ha acid lactic bng thuc th H2O2/Fe2+ to ra acid pyruvic (2-oxopropanoic)
Acid pyruvic
CH3 C COOH
O
CH3 CH COOH
OH
+2H2OH2O2, Fe2+
Cc lactat c nhiu ng dng trong dc phm, thc phm v cng nghip.
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Acid malic:HOOC-CHOH-CH2-COOH (Acid hydroxysuccinic; 2-hydroxybutandioic).
Dng racemic to thnh do phn ng tng hp t acid R,S-bromomalic v AgOH
hoc phn ng hp nc ca acid maleic.
CH2 CH COOH
OH
HOOCCH2 CH COOH
Br
HOOC C CCOOHHOOC
HH+ AgOH + H2O (H+)-AgBr
Acid R,S-MalicAcid R,S-Bromomalic Acid R,S-Maleic
Dng R (+)v Sv (-)-malic u dng tinh th.
Acid tartaric: HOOC-CHOH -CHOH-COOH (Acid ,,-dihydroxysuccinic; 2,3-dihydroxybutandioic)
Acid 2R,3R-(+)-tartaric tn ti dng t do hoc dng mui tartarat kali ctrong dch qu nho. Acid 2S,3S-(-)-tartaric khng c trong thin nhin.
Khi un nng vi s c mt ca KHSO4, acid tartaric b loi nc, loicarbon dioxyd v to thnh acid pyruvic. Phn ng nh sau:
CH
CH
COOHHO
COOHHO
C
C
COOHHO
COOHH
C
CH2
COOHO
COOH
C
CH3
COOHO
Acid oxymaleic Acid pyruvicAcid tartaric
KHSO4
-H2O - CO 2
Mui kali, natri tartarat (mui Seignette)
c s dng pha thuc thFehling.
Acid citric: HOOC-CH2 -C(OH)(COOH)-CH2 COOH (Acid 2-hydroxypropan-1,2,3-tricarboxylic, acid -hydroxytricarballylic).
Acid citric c trong nhiu hoa qu, trong sa v trong mu. Trong dch ncchanh c t 6 - 10% acid citric. Acid citric c vai tr quan trng trong cc chutrnh chuyn ha.
Sn xut acid citric trn quy m cng nghip bng phng php ln men ccmono hoc disaccharid. un nng 175C acid citric b loi 1 phn t nc toacid cha no aconitic. Acid citric tc dng vi acid sulfuric m c hoc oleumto thnh acid acetondicarboxylic.
CH2
C
COOH
COOHHO
CH2 COOH
CH2
C
COOH
O
CH2 COOH
CH
C
COOH
COOH
CH2 COOH
-H2O
Oleum
-HCOOH
Acid acotinic Acid acetondicarboxylic(3-oxopetandioc)
Acid citric
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6.2. Mt s phenol acid
Cc ester ca phenolacid c nhiu ng dng:
Acid o-hydroxybenzoic
Acid o-hydroxybenzoic hay acid salicylic c dng iu chmetylsalicylat c tc dng gim au, c dng lm hng liu trong mt s dcphm v iu ch aspirin (acid acetyl salicylic), phenylsalicylat (salol) c tc dngkhng nm.
Metylsalicylat Phenylsalicylat (Salol) Acid acetylsalicylic (Aspirin)
OCOCH3
COOH
OH
COOC6H5
OH
COOCH3
Acid p-hydroxybenzoic Acid p-hydroxybenzoic c s dng iu ch cc ester nh metyl -p-
hydroxybenzoat (Nipagin), isopropyl-p-hydroxybenzoat (Nipazol) dng lm chtchng oxy ha trong dc phm v thc phm.
COOH
OH
H2SO4
OH
COOR
+ H2Oto+ ROH
R = -CH3 NipaginR= -C3H7(n) Nipazol
Acid o-hydroxy cinnamic
Acid o-hydroxycinnamic cn gi l acid o -coumaric tn ti 2 dng ng phnhnh hc cis v trans. Loi nc t acid coumaric to thnh coumarin.
Coumarin c th c tng hp t aldehyd salicylic (phng php Perkin),coumarin c dng trong k ngh hng liu, dc phm.
Aacid o-coumaric (dng cis) Acid o-coumaric (dng trans)Coumarin
H2O_
H
C
H
OH
COOHC
H
CH
OHCOOH
C
OC
H
CHC
O
+
Coumarin
_H2O
. . ....H
CH3CO
+ K2CO3
O
CH = O CH2CO
_ CH3COO HOHO O.
...........
H
OCO
CH
OH
CH
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Acid Galic:Acid 3,4,5-trihydroxybenzoic
COOH
OHHO OH
Trong thin nhin acid galic ch tn ti di dng ester. Tannin l ngunnguyn liu chnh iu ch acid galic. Acid galic d b decarboxyl ha di tcdng ca nhit.
to + CO2
OHHO OH
COOH
OHHO OH
Acid tc dng vi alcol n -propylic to ester n -propylgalat ng dng lmcht bo qun trong thc phm v dc phm.
H2SO4
COOH
OHHO OH
OHHO OH
COOC3H7(n)
+ H2O
to+ n-C3H7OH
Ester n-propylgalat
Acid galic rt d b oxy ha. Vi dung dch FeCl3, acid galic cho mu xanh en.
Bi tp1. Vit cng thc cu to v gi tn theo danh php quc t ca cc acid sau:
a- Acid lactic
b- Acid malic
c- Acid tartaric
d- Acid mandelic
e- Acid citric
2. Hy vit phn ng cc qu trnh tng hp cc acid sau:a- Acid glycolic t acid acetic
b- Acid lactic t acetylen
c- Acid mandelic t toluen
3. Hy lp s tng hp cc acid sau y theo phn ng Reformatski:
a- Acid n-valeric
b- Acid ,-dimetylvaleric t ester malonic
4. Khi un nng 10-hydroxydecanoic to thnh hp cht c phn t lng ln
(1000-9000). Vit phn ng.
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Chng 27
HP CHT HAI CHC C NHM CARBONYL
Mc tiu
1. c c tn cc hp cht c hai nhm chc carbonyl
2. Trnh by c ha tnh ca cc hp cht trn
1. Hydroxy aldehyd v hydroxy - ceton
1.1. iu ch
-Hydroxy-ceton c iu ch bng cch kh ha ester bng natri kim loitrong dung mi tr v ha hc.
2
OH
CH3CH2CH2C_CHCH2CH2CH+ 4Na- 2C2H5ONa
NaO ONa
CH3CH2CH2C= CH 2CH2CH3CH3CH2CH2COC2H5
OO
H2O3
Sn phm -hydroxyceton c lin kt -CO-CHOH- l acyloin, v vy phnng trn gi l phn ng ngng t acyloin. C ch phn ng tng t vi phnng pinacolin v cng ging phn ng ngng t Claisen.
1.2. Cc phn ng ha hc
1.2.1. Loi nc
Trong mi trng acid hoc base, cc -hydroxy-aldehyd hoc -hydroxy-ceton u c kh nng b loi nc v to aldehyd hoc ceton cha no.
Trong mi trng acid:
OH O
CCHC
O
CCC + H2OH+
C ch:
H+
- H2O
OH O
CCHC
OHCCCOH OH2
CCCOH
CCCOH+
+
CCC
OH+
CCC
O
+ H+
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Trong mi trng base:
OH O
CCHC OH
O
CCHC + H2O
HO-
C ch C:
- H2O
O
CCCOH O
CCHC
OHCCCO
+ HO-
-+ HO
-
1.2.2. Phn ng oxy ha
-Hydroxy-ceton b oxy ha bi acid periodic HIO4, mch carbon b ct tto acid v aldehyd.
+CH3CHCCH3
OHO
+ HIO4 CCH3
O
OH CCH3
O
H + HIO3
1.2.3 Phn ng to bn acetal v bn cetal vng
O OH
HHOCH2CH2CH2CHO
Ban acetal vong
HOCH2CH2CH2CH2CCH3Ban cetal vong
O
O
CH3
OH
Cc bn acetal vng l nhng cht trung gian tng hp nhiu hp chthu c.
Ester
Lacton
2-1-
H2Cr2O7
CH3COCl
H3O+
CH3MgBr
H2NOH
NaBH4
O
C
O
O
H
OCOCH3
OH
HOCH2CH2CH2CH2CHCH3
HOCH2CH2CH2CH2CH=NOH Aldoxim
HOCH2CH2CH2CH2CH2OH
O
H
OH
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2. Ceto-aldehyd, ceto-acid, ceto-ester
2.1. Cng thc cu to
R1 C
O
(CH2)n COOR2
Ceto-ester
R C
O
(CH2)n COOH
Ceto-aldehydCeto-aldehyd
R C
O
(CH2)n CHO
2.2. Phng php tng hp
2.2.1. Oxy ha trc tip cc ceton n gin bng selen dioxyd (SeO2)
C6H5 C CH3O
C6H5 C CHO
O
H2O+ SeO2Dioxan , 50oc 70%
2.2.2. ng dng phn ng ngng t Claisen
Ceton ngng t vi ester thu c -diceton v -ceto-aldehyd:
CH3 C CH3O 85%
CH3 C OC2H5O
+Base
EtherH3O
+CH3 C CH2
O
C CH3O
+ HCOOC2
H5
H3O+
O
NaOC2H5
C2H5OH
OCHOH
OCHO
75%
Hai phn t ester ngng t vi nhau:
Phn ng xy ra trong mi trng base v to thnh ceto -ester.
CH3 C OC2H5O
H3O+NaOC2H52 CH3 C CH2COOC2H5
O
2.3. Tnh cht2.3.1. Cn bng ceton -enol
Nguyn t hydro ca nhm methylen gia 2 nhm carbonyl thng rt linhng, s chuyn v ca nguyn t hydro ny to nn s cn bng ceton -enol.
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92%8%Dung dch hexan16%84%Dung dch nc
EnolCeton
C CH3
OO
CH3 CCH
H
C CH3CH2
CCH3
OO
S cn bng ny thng xy ra trong cc hp cht c nhm carbonyl.
2.3.2.Tnh acid ca hp cht c 2 nhm carbonyl
Hydro trong nhm methylen ca ceto-aldehyd, ceto-acid, ceto-ester c tnhacid. Di tc dng ca base, carbanion c to ra. Carbanion ny bn vng dos khng nh v ca in tch m.
CCH2
C
OO
C
O
C
O
C
OO
CCHCH
C
O
-- H+
CHC
O- -
acid ca mt s hp cht c 2 nhm carbonyl c trnh by di y:
1311111199pKa:
Hp cht:
O OOOOOOO
CH3
CH3OCCH2COCHNCCH2CNCH3CCHCCH 3CH3CCH2COCH3CH3CCH2CCH3NCCH2COCH3
2.3.3. Cc phn ng ha hc
a. Hp cht -diceton tham gia chuyn v benzylic.
Trong mi trng base mnh, -diceton b chuyn v v to -hydroxyacid.
C C C6H5C6H5
OO
C C OHC6H5
O
C6H5
OHKOH
H2O , C2H5OH
H3O+
Acid benzylic
95%Benzil
C ch:
C C RR
OO- OH + H2OC C RHO
OO
R
-- OH
C C RO
OO
R
--+ +
+ - OH-
C C RO
O OH
R
+ H2O-
-C C RO
OO-
-C C RO
OO
R
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Nu hp cht -diceton vng, sau khi chuyn v kiu benzylic s thu csn phm c vng b hn.
80%
OH
COOH250oC
H3O+
H2O
NaOHO
O
b. Phn ng decarboxyl.
Khi c tc dng ca nhit, hp cht -ceto-acid d b decarboxyl ha v to ceton.
H2O, 2gi
50oC CH3CH2CH2CCH2CH2CH3
C2H5
O O
CH3CH2CH2CCHCOOH + CO2
c. Cc ceto-ester c kh nng ngng t ni phn t v to hp cht vng.
NaOH
EtOH
H3O+
90%C
COOEt
O OO
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Chng 28
CARBOHYDRAT
Mc tiu
1.Nm c cch phn loi cht ng, cu to, danh php ca chng.
2.Nu c ha tnh ca glucose.
3.Gii thch c tnh kh ca cht ng.
Carbohydrat l hp cht thin nhin c thnh phn chnh l C, H v O.
C th xem carbohydrat nh l hp cht m nguyn t carbon b hydrat ha.
Cn(H2O)n
Phn loi:
Tu theo cu trc, tnh cht l hc v ha hc, c 3 loi carbohydrat:
Monosaccharid
Oligosaccharid
Polysaccharid
1. Monosaccharid
Monosaccharid cn gi l ng n, v chng l thnh phn n gin nhtca carbohydrat v khng b thy phn. Monosaccharid c xem nh l snphm oxy ha khng hon ton ca cc polyalcol c chc aldehyd hoc ceton.
Cc monosaccharid c s carbon bng s oxy trong cng thc phn t.
1.1. Danh php
Cc carbohydrat u c tip v ng l ose Monosaccharid c chc aldehyd gi l aldose
Monosaccharid c chc ceton gi l cetose
1.1.1. Tn gi monosaccharid ph thuc s oxy, chc aldehyd hoc ceton.
Biose, triose, tetrose, pentose, hexose l tn gi chung cc monosaccharid c2,3,4,5,6 nguyn t oxy (cng l s nguyn t carbon).
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Tn gi chung cc monosaccharid c chc aldehyd v ceton:
C2H4O2C3H6O3
C4H8 O4C5H10O5
Aldo-diose
C6H12O6
Ceto-trioseAldo-triose
Aldo-tetroseAldo-pentose
Aldo-hexose
Ceto-tetroseCeto-pentoseCeto-hexose
Aldose CetoseS C v s O Cng thc
2
3
4
6
5
Ceto-diose
1.1.2. Monosaccharid c tn ring cho mi cht ty thuc vo v tr cc nhm OH.
V d: Glucose, Fructose, Mannose, Galactose, Ribose, Arabinose...
1.1.3. Tn gi monosaccharid ty thuc vo ng phn quang hc
Danh php D v LMonosaccharid dng mch thng c nhm OH nguyn t carbon khng i
xng xa nht so vi nhm carbonyl c cu hnh ging D -Aldehyd glyceric hocging L -Aldehyd glyceric th monosaccharid thuc dy D hoc dy L.
CHO
C
CH2OH
HHO
(S-Aldehyd glyceric)
L- Aldehyd glyceric
CHO
C
CH2OH
OHH
(R-Aldehyd glyceric)D- Aldehyd glyceric
Cc ng phn dy D ca monosaccharid:
D- Aldehyd glyceric C
CH2OH
OHH
CHO
C
C
HHOCHO
OHH
CH2OH
D- Threose (Thr)
C
C
OHHCHO
OHH
CH2OH
D-Erythrose (Ery)
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C
C
HHO
CHO
OHH
C
CH2OH
OHH
D-Arabinose (Ara)
C
C
OHH
CHO
OHHC
CH2OH
OHH
D-Ribose (Rib)
C
C
OHH
CHO
HHO
C
CH2OH
OHH
D-Xylose (Xyl)
C
C
HHO
CHO
HHO
C
CH2OH
OHH
D-Lixose (Lix)
C
C
OHH
CHO
OHH
CC
OHHOHH
CH2OH
D-Allose(All)
C
C
HHO
CHO
OHH
CC
OHHOHH
CH2OH
D-Altrose(Alt) (Man)
D-Mannose
C
C
HHO
CHO
HHO
CC
OHHOHH
CH2OH
(Glu)D-Glucose
C
C
OHH
CHO
HHO
CC
OHHOHH
CH2OH
(Gal)D-Galactose
C
C
OHH
CHO
HHO
CC
HHOOHH
CH2OH
(Tal)D-Talose
C
C
HHO
CHO
HHO
CC
HHOOHH
CH2OH
(Gul)D-Gulose
C
C
OHH
CHO
OHH
CC
HHOOHH
CH2OH
(Ido)D-Idose
C
C
HHO
CHO
OHH
CC
HHOOHH
CH2OH
1.1.4. Monosaccharid cu to vng c tn gi theo vng
Cc monosaccharid c cc vng tng t vng pyran v vng furan.
O
Opyran Furan
Cho nn cc monosaccharid dng vng c tn gi pyranose v furanose.
V d:
Glucopyranose (vng 6 cnh) Glucofuranose (vng 5 cnh)
Fructopyranose (vng 6 cnh) Fructofuranose (vng 5 cnh)
Mannopyranose (vng 6 cnh) Mannofuranose(vng 5 cnh)
Galactopyranose (vng 6 cnh) Galatofuranose (vng 5 cnh)
-D-Galactopyranose-D-Galactopyranose -D-Galactopyranose
5
5
1 1
1
C
C
OHH
C
HHO
C
C
HHO
H
CH2OH
OOHH
O
OH
HOH
H
OH
H
H
CH2OH
OH
HC
C
OHH
CHO
HHO
C
C
HHO
OHH
CH2OH
D-Galactose
5
1
O
OH
HOH
H
OH
H
H
CH2OH
H
OH
11
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Danh php Cahn -Ingol-Prelog (danh php R,S).
D(+)-Glucose v L (-)-Glucose c gi theo danh php R, S nh sau:
(2R,3S,4R,5R)-Pentahydroxy-2,3,4,5.6-hexana
CHO
CC
C
C
CH2OH
OHH
OH
OH
HHO
H
H
D (+)Glucose
1
2
3
4
5
6
6
5
4
3
2
1
L (-)-Glucose
CHO
C
C
C
C
CH2OH
OH
H
OH
H
H
HO
H
HO
(2R,3S,4R,5S)-Pentahydroxy-2,3,4,5.6-hexana
t s dng danh php R, S gi tn monosaccharid.
Ch :Mt s monosaccharid b loi nguyn t oxy (deoxy) th gi tn chnhmonosaccharid v thm tip u ng deoxy.
2-Deoxy-D- Glucopyranose
O
OHH
HOH
CH2OHOH
H
H HH
O
H
HOH
H
OH
H
H
CH2OH
OH
H
1
1
5
5
C
C
C
C
C
CH2OH
H
H
OH
H
HO
H
H
OHH
O
1
2
3
4
5
6
CHO
C
C
C
C
CH2OH
H
H
OH
OH
H
HO
H
H
2-Deoxy-D Glucose
1
2
3
4
5
6
CHO
C
C
C
C
CH2OH
OH
H
OH
OH
H
HO
H
H
D (+)Glucose
1
2
3
4
5
6
1.2. Cu to
1.2.1. Cu to mch thng ca monosaccharid
Cng thc phn t C6H12O6 c cc cng thc cu to nh sau:
FructoseMannoseGlucose
HOCH2 CH CH C CH C
OH OH H OH
O
H
OH1235 4
HOCH2 CH CH C C
OH OH H
CH2OH
O
OH6 45 123
HOCH2CH CH CH CH C
OH OH
O
H
OHOH4
12
356
1.2.2. Cu to mch vng ca monosaccharid
Monosaccharid tn ti dng vng 6 cnh, 5 cnh. Trong vng c nguyn t oxy.
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Cng thc chiu Fischer:
6
54
3
2
1C
C
C
CC
CH2OH
OH
H
OH
H
HO
HH
O
OHH
-D-GlucopyranoseI II
-D-Glucopyranose
C
C
C
CC
CH2OH
OH
H
OH
H
HO
HH
O
HHO2
3
45
6
1
-D-Fructofuranose
1
2
3
45
6
C
C
CC
CH2OH
H
OH
HO
HO
HH
CH2OH
O
III
Cng thc chiu Haworth:Vng phng
5
1
-D-Glucopyranose
H
H
HH
CH2OH
OHOH
OH
OH
O
H
6
5
1
-D-Mannopyranose
H
H
HH
CH2OH
OHOH
H
OH
O
OH
2
6
5
1
-D-Fructopyranose
CH2OH
OH
HH
H
OHH
H
OH
O
OH
5
1
6
2
-D-Fructofuranose
O
OH
OH
CH2OH
CH2OHH H
H
OH
Cng thc vng ca monosaccharid l dng bn acetal hoc bn cetal vng.Bn acetal vng c to thnh do s tng tc gia chc alcol ti carbon s 5 vchc aldehyd hoc ceton.
Cng thc cu dng (Reeves):
Glucose c cng thc cu dng gh bn vng
D-Glucopyranose1
O
OHHO
HOHO
CH2OHH
H
H HH
Cc cu dng lp th ca vng pyranose: c 8 cu dng khc nhau
2 BB21CC1
O O O O
OOO
O
B1 1B B3 3B
Theo Reeves cu dng C1 l bn nht v c nhiu OH c lin kt e (equaterial).
Cc monosaccharid vng 6 cnh thng c cu dng gh.
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Vng 6 cnh (pyranose) ca monosaccharid tn ti 2 cu dng gh C1 v 1C nh sau:
O
3
4
5
12
Dang C1
2
O1
34
5
Dang 1C
Mi monosaccharid vng 6 cnh u c kh nng tn ti theo 2 loi cu dngtrn.
V d:-D-glucopyranose c th c 2 cu dng nh sau:
Dang C1 D-Glucopyranose1
O
OHHO
HO
HO
CH2OHH
H
H H
H
O
OH
OH
OH
CH2OH
OH
H
HH
H
Dang 1C D-Glucopyranose
1
Dng C1, -D-glucopyranose cc nhm OH v CH2OH c v tr equatorial (e)(tr nhm OH carbon s 1 c v tr axial a).
Dng 1C, -D-glucopyranosecc nhm OH v CH2OH c v tr axial (a) trnhm OH carbon s 1 c v tr equatorial e.
Dng C1 -D-glucopyranose bn hn v cc nhm OH v CH2OH c nnglng thp hn dng 1C -D-glucopyranose.
Ch : Trong cc monosaccharid dng vng, glucose c cc nhm OH vCH2OH lun v tr equatorial (tr nhm OH v tri s 1).
Cc monosaccharid khc th cc nhm c v tr ty thuc vo cc cht cth.
3 2
6
54
1
-D-Galactopyranose
HOCH2 O
HH
OH
H
H
OHHO
HO
H
6
54
13 2
-D-Mannopyranose
HOCH2
OOH
H
H
H
H
OHH
HO
HO
1.3. ng phn ca monosaccharid
Cc monosaccharid cng cng thc phn t c cc loi ng phn sau:
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1.3.1. ng phn chc
Glucose v fructose l nhng ng phn chc vi nhau.
1.3.2. ng phn do v tr ca cc nhm OH alcol
Cc aldohexose c cc ng phn dy D mch thng do v tr nhm-OH
I (All)D-Allose
CHO
C
C
C
C
CH2OH
OH
OH
OH
OH
H
H
H
H
CHO
C
C
C
C
CH2OH
H
OH
OH
OH
HO
H
H
H
D-AltroseII (Alt)
D-Glucose
CHO
C
C
C
C
CH2OH
OH
H
OH
OH
H
HO
H
H
III (-Glc)
CHO
C
C
C
C
CH2OH
H
OH
OH
OH
HO
HO
H
H
D-MannoseIV (Man)
CHO
C
C
C
C
CH2OH
OH
OH
H
OH
H
H
HO
H
D-GuloseV (Gul)
CHO
C
C
C
C
CH2OH
H
OH
H
OH
HO
H
HO
H
D-IdoseVI (Ido)
CHO
C
C
C
C
CH2OH
OH
H
H
OH
H
HO
HO
H
D-Galactose
VII (Gal)
CHO
C
C
C
C
CH2OH
H
H
H
OH
HO
HO
HO
H
D-Talose
VIII (Tal)
1.3.3. ng phn quang hcMonosaccharid c nguyn t carbon khng i xng nn c ng phn quang
hc.
S ng phn quang hc ty thuc vo s carbon khng i xng v cu tophn t.
Cc aldohexose dng thng c 16 ng phn quang hc.
Cetohexose c 8 ng phn quang hc.
Monosaccharid dng mch vng c s carbon khng i xng nhiu hn
dng thng tng ng nn s ng phn quang hc dng vng tng ln.ng phn quang hc quyt nh kh nng tc dng sinh hc ca
monosaccharid.
1.3.4. ng phn epimer
Cc monosaccharid cng cng thc phn t c cu hnh ca cng mt carbonbt i xng (k t chc aldehyd) hon ton khc nhau th gi l ng phnepimer. Glucose, mannose, fructose l cc ng phn epimer vi nhau.
V d: 4 cp ng phn ca aldohexose dy D l 4 cp epimer. Tng t c 4cp ca dy L hoc cp ng phn epimer D (+)-erythro v D (+)-threo.
Khac nhau
Giong nhau
111
222
CHO
C
C
C
C
CH2OH
OH
H
OH
OH
H
HO
H
H
CHO
C
C
C
C
CH2OH
H
H
OH
OH
HO
HO
H
H
CH2OH
C
C
C
C
CH2OH
H
OH
OH
H
H
O
HO
D-Glucose D-Mannose D- Fructose
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1.3.5. ng phn anomer
Trong cng thc chiu mch thng Fischer ca phn t D -glucose, nguynt carbon s 1 thuc chc aldehyd l carbon i xng. Khi D -glucose dng vng,carbon s 1 mang chc OH v tr thnh carbon khng i xng. Nguyn tcarbon s 1 gi l carbon anomer. NhmOHti carbon anomer c to thnh do
tng tc gia nhm OH alcol ti carbon s 5 v chc aldehyd (ging phn ngto bn acetal gia aldehyd v alcol). Nhm OH ny gi l nhm OH bn acetal ctnh cht khc vi nhng chc alcol khc.
Trong cng thc chiu vng (Fischer) nhm OHbn acetal bn phi vng(cng pha vi vng) gi l -D-glucose (cng thc I), nhm OH bn tri vng(khc pha vi vng) gi l -D-glucose (cng thc II). -D-glucose v -D-glucosel 2 ng phn anomer vi nhau.
I-D-Glucopyranose
C
C
C
C
C
CH2OH
OH
H
OH
H
HO
H
H
O
OHH1
23
4
5
6
II-D-Glucopyranose
C
C
C
C
C
CH2OH
OH
H
OH
H
HO
H
H
O
HHO23
4
5
6
1
CHO
C
C
C
C
CH2OH
OH
H
OH
OH
H
HO
H
H
D-Glucose
1
2
3
4
5
6
Biu din cc ng phn anomer theo cng thc chiu Haworth:
Nhm OH bn acetal v pha di vng l ng phn -D-glucose.
Nhm OH bn acetal pha trn vng l ng phn-D-glucose.
Cch biu din cc nhm OH t cng thc chiu Fischer sang cng thcchiu Haworth:
Trn cng thc chiu Fischer nhm OH bn acetal bn phi so vi mchthng ng ca carbon.
Trn cng thc chiu Haworth nhm OH bn acetal pha di ca vng.Nhm OH bn acetal bn tri so vi mch thng ng ca carbon thtrn cng thc chiu Haworth pha trn ca vng.
6
5
1
-D-Glucopyranose
H
H
HH
CH2OH
OH
OH
OH
OH
O
H
6
5
1
-D-Glucopyranose
OH
H
HH
CH2OH
OH
OH
OH
H
O
H
Trn cng thc -D-glucopyranose 2 nhm OH ti carbon 1 v 2 c v trcisv trn cng thc -D-glucopyranose 2 nhm OH ti carbon 1 v 2 c v tr trans.
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Cc ng phn anomer c th chuyn ha ln cho nhau.
Trong dung dch glucose, khi cc ng phn v c thit lp s cnbng th c hn hp gm 36% ng phn v 64% ng phn .
Biu din cc ng phn anomer ca monosaccharid theo cng thc cu
dng:
D-Glucopyranose
1
O
OHHO
HOHO
CH2OHH
H
H HH
a
O
OHHO
HOHO
CH2OHH
H
H
H
H
D-Glucopyranose
1e
ng phn c nhm OH bn acetal v tr axial (a). ng phn c nhm
OH bn acetal v trequatorial (e). Hin tng bi quay (Mutarotation).
Tinh th -D-(+)-glucose c nhit nng chy 146C.
Khi ha tan vo nc c dung dch c quay cc +112. Mt thi giansau quay cc gim dn v t n gi tr khng i +52,7. Mt khc tinh th -D(+)-glucose kt tinh nhit 98C c nhit nng chy 150C, khi ha tanvo nc c dung dch c quay cc +19 v dn dn tng ln n gi trkhng i + 52,7.
Gii thch hin tng bi quay:
Quay
O
HHO
HOHO
CH2OHH
H
H O HH O H
C
OH
HO
HO
HO
CH2OHH
H
HH
H
O H
C
OHHO
HO
HO
CH2OHH
H
HH
HO
OHHO
HO
HO
CH2OHH
H
H HH
D-Glucopyranose
+ H+H+O
OHHO
HO
HO
CH2OHH
H
H HH
+
+
O
OH
HO
HOHO
CH2OHH
H
H
H
H
H+
-H+
M vong
ong vong
D-Glucopyranose
S thay i gc quay cc t n gi tr cn bng ca mi loi ngphn ny gi l s bi quay (mutarotation). Tt c cc monosaccharid u c hintng bi quay (tr mt vi cetose). Hin tng bi quay l nguyn nhn to racc ng phn anomer (s anomer ha) trong cc monosaccharid.
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5
4
3
2
1CHO
C
C
CCH2OH
OH
OH
OH
H
H
H 5
4
3
2
1CHO
C
C
CCH2OH
H
H
OH
H
HO
H4
3
2
1C
C
C
C
H
H
H
HO
H
HHO
CH2OH
O
D-Ribose (Rib)
OCH2OH
OH
H
H
OH
HH
H
2-Deoxy- D-Ribose 2-Deoxy-D-ribofuranose 1.4. Tnh cht l hc ca monosaccharid
Monosaccarid dng rn, kt tinh c, khi chng ct b phn hy, khngmu, d tan trong nc, rt kh tan trong ether hay cloroform, trung tnh, c vngt khc nhau, c tnh quang hot []D.
C hin tng bi quay v c cn bng ng
1.5. Tnh cht ha hc ca monosaccharid
1.5.1. Phn ng oxy ha
Ging nh cc hp cht -hydroxycarbonyl (-oxycarbonyl), monosaccharidrt d b oxy ha v to cc acid tng ng bi cc tc nhn oxy ha nh thucth Fehling Cu (OH)2, thuc th Tollens Ag (NH3)2NO3.
O OH
HO
HOHO
CH2OHH
H
H
H
H
COO-
C
C
C
C
CH2OH
OH
H
OH
OH
H
HO
H
H+ 2 Cu(OH)2+ Cu2O + 2H2O
Mau o gach
OOH
HO
HO
HO
CH2OHH
H
H
H
H
COOH
C
C
C
C
CH2OH
OH
H
OH
OH
H
HO
H
H+ 2Ag+ + 2Ag+ H2O
D-Glucose Acid Gluconic
Cc phn ng ny dng nh lng hm lng ng trong nc tiu v mu.
Cc monosaccharid b oxy ha bi thuc th Fehling v Tollens gi l ng kh
Fructose khng b oxy ha bi cc thuc th trn.
Mt s cht oxy ha khc c th oxy ha chc alcol bc 1 v to thnh diacid.
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OOH
HO
HOH
CH2OHOH
H
H
H
H
COOH
C
C
C
C
COOH
OH
H
H
OH
H
HO
HO
H
+ 3[O]
- H2O
Acid GalactaricD-GlactoseAcid Galactosaccharic
OOH
HO
HOHO
CH2OHH
H
H
H
H
COOH
C
C
C
CCOOH
OH
H
OH
OH
H
HO
H
H
+ 3[O]
- H2O
D-Glucose Acid SaccharicAcid periodic tc dng vi monosaccharid, mch carbon b ct t v to dialdehyd.
D-Glucose
2
4
+ HIO 3+ HCOOH
CHOC
CH2OH
H
C
CHO
OHH
O+ HIO 4
C
C
C
C
C
CH2OH
H
OH
OH
HO
H
H
H
OHH
O
1
2
3
4
5
6
Cat mach carbon
- HIO3
Metyl -D-2-Deoxyribopyranosid
O
C
CO CH 3
OO
H
H HH
H
CHO
C
O
C
C
CHO
H
H
H
H
CH3O
H
OO CH 3
H
HO
H
OH HH
H+ HIO4
1.5.2. Phn ng kh
Kh ha nhm carbonyl ca monosaccharid bng hn hng natri trongH2SO4 long, natrihydrid bo (NaBH4) hoc bng H2 c xc tc th to thnh ccpolyalcol no. Polyalcol to thnh c tn gi nh monosaccharid tng ng nhngthay tip v ng ose bng it hoc itol.
D-Sorbit , D-Glucitol L-GlucoseD-Glucose
[ H ]H2-Ni
CH2OH
C
C
C
C
CHO
OH
OH
OH
H
H
H
HO H
CH2OH
C
C
C
C
CH2OH
OH
OH
OH
H
H
H
HO H
CHO
C
C
C
C
CH2OH
OH
OH
OH
H
H
H
HO HO OHHO
H
H HOH
H
CH2OH
HHO
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D - FructoseD - Mannit , MannitolD - Mannose
NaBH4NaBH4
CH2OH
C
C
C
C
HHO
OHH
OHH
CH2OH
O
CH2OH
C
C
C
C
HO H
HHO
OHH
OHH
CH2OH
CHO
C
C
C
C
HO H
HHO
OHH
OHH
CH2OH
NaBH4
D-glucose
NaBH4
D-sorbitol
NaBH4 NaBH4
D-manose D-manitol D-fructose
CH2OH
CH2OH
HO
OH
HOOH
CH = O
CH2OH
HO
OH
HOOH
CH = O
CH2OH
OH
OH
HOOH
CH2OHC
CH2OH
O
OH
HOOH
CH2OH
CH2OHOH
HOOH
OH
1.5.3. Phn ng epimer ha
Trong mi trng kim long hoc pyridin, mi monosaccharid nh D-glucose, D-Mannose, D-Fructose b epimer ha v to thnh hn hp 3 epimer. Sepimer ha xy ra nh sau:
Trong mi trng kim long
CHO
C
C
C
C
CH2OH
OH
OH
OH
H
H
H
HO H
D-Glucose D- Mannose
CHO
C
C
C
C
CH2OH
H
OH
OH
HO
H
H
HO H
Giong nhau
D-Fructose
CH2OH
C
C
C
C
CH2OH
O
OH
OH
H
H
HO H
CHOH
C
CC
C
CH2OH
OHHO H
OH
OH
H
H
S epimer ha cng c kh nng xy ra trong iu kin khi monosaccharidtip xc vi dung dch brom, pyridin v tip theo l qu trnh kh ha.
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Br2+H2O +Na(Hg), CO2-H2O
D- Mannose
CHOC
C
C
C
CH2OH
H
OH
OH
HO
H
H
HO H
CHOC
C
C
C
CH2OH
OH
OH
OH
H
H
H
HO H
D-Glucose
Pyridin
COOHC
C
C
C
CH2OH
H
OH
OH
H
H
HO H
HO
Hn hp epimer acid gluconic
COOHC
C
C
C
CH2OH
OH
OH
OH
H
H
HO H
H
Gluconolacton
CC
C
C
C
CH2OH
H
OH
H
H
HO H
HOO
O
Ch :Trong mi trng kim c mch carbon b ct t v to thnh cccht c mch carbon ngn hn. V d D -Fructose trong mi trng kim c tothnh hn hp gm 1,3-dioxyceton, glycerin, aldehyd glycolic v aldehyd formic.
1.5.4. Phn ng loi nc - dehydrat ha
Khi un vi acid, cc pentose b loi 3 phn t H2O to furfural.
Furfurol , FurfuralPentose
+ 3 H2 OAcid
un nongC5H10O5
O
Phn ng Selivanop
Di tc dng ca HCl, cc pentose, hexose to ra furfural v chuyn hanhanh thnh hydroxymethylfurfural, n ngng t tip vi resorcinol to phm
vt mu anh o (phn ng ny dng phn bit aldose v cetose).
CHO
Resorcinol
O
OH
HOH
HOHO
H
HH
H
CH2OH
CHO
C
C
C
C
CH2OH
OH
H
H
OH
OH
H
HO
H
OCH=OCH2OH
O
OHHO
CH2OHCH2OH
CH2OH
C
C
C
C
CH2OH
O
OH
HO
OH
H
H
H
HCl
NhanhD-fructose
-D-glucose
-3H2O
ngng tu4-Hydroxymethylenfurfural
Cham
OH
OH
D-glucose
San pham co
mau o anh ao
HCl-3 H2O
D-fructofuranose
1.5.5. Phn ng to osazon
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Monosaccharid tc dng vi 3 mol phenylhydrazin to phn t osazon.
;;
-NH3
D-Glucozazon
-2 H2O- C6H5-NH2
+ 3C6H5-NH-NH2
CH
C
C
CC
CH2OH
OHOH
H
HH
HO H
N NH C6H5N NH C6H5
OH
CHCHO
HO
H
H N
CH2OH
HN NH C6H5
NH C6H5
CHO
C
C
CC
CH2OH
OH
OHOH
H
HH
HO H
D-Glucose
Cc ng phn epimer u cho cng mt loi osazon.
Osazon l cht kt tinh c hnh th xc nh, c th dng nhn bit ccmonose
Cc ng phn epimer ca aldose v cetose c cu hnh *C3,*C4,*C5 ging nhau,
chng c cng 1 osazon v khi to osazon khng cn carbon bt i xng ti C2.V d: D-glucose, D-mannose v D-fructose c chung mt osazon.
Theo Fischer, osazon bn l do to "phc cng cua".
Bng ph hng ngoi (IR), cho thy phn t osazon bn v tn ti h lin hpv c lin kt hydro ni phn t (C - O... H - N).
.
..
..
.....
.......N
CHC
N
HN
NH
OC
CH2OH(HOCH)2
HN
CH2OH
NH
NC
CH
N
Theo Fischer :
...
Theo IR :
Osazon cua D-glucose
1.5.6. Phn ng to acetal vng v cetal vngMonosaccharid c 2 nhm OH cnh nhau v tr cisngng t vi ceton to cetal
+ 2H2O+ 2 C CH3H3C
O
cis
cis
OH
H
HCH2OH
H
O
O
C
CH3
CH3
OOCH3
CH3
OH
HOH
OH
H HOOH
H
CH2OH
H
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1.5.7. Phn ng to glycosid
Alcol hoc phenol tc dng vi nhm OH bn acetal ca monosaccharid tothnh hp cht alkyl (hoc aryl) glycosid.
O
HHOHO
H
H HOOH
H
CH2OH
HLien ket glycosid+ ROH
+ H2 O
Alkyl -glucosid-glucose
HCl khoR O
H
CH2OH
H
OHH
HOHO HO
H
+ ROH
O
H
HOHO
H
H
OH
OH
HCH2OH
H
O
H
HOHO
H
O
OH
HCH2OH
H R
Lien ket glycosid
+ H2O
Alkyl -glucosid-glucose
HCl kho
H
Glycosid to thnh t glucose th gi l glucosid; t mannose th gi lmannosid; t galactose gi l galactosid; t fructose gi l fructosid.
O
H
HOH
OH
H
OCH3
OH
H
CH2OH
H
O
H
HOHO
H
O
OH
H
CH2OH
H CH3
H
O
H
HOHO
H
H
OCH3
H
OH
CH2OH
H
Methyl -glucosid Methyl -galactosid Methyl -MannosidCc glycosid bn vng trong mi trng kim nhng rt d phn ly thnh
monosaccharid v alcol trong mi trng acid v di tc dng ca enzym.
+ ROH
O
H
HOHO
H
H
OH
OH
H
CH2OH
H
O
H
HOHO
H
O
OH
HCH2OH
H R
H
+ H2 O
Alkyl -glucosid -glucose
Acid hoc men
Cc enzym c tc dng thy phn rt chn lc.
V d:Enzym maltase ch thy phn -glycosid.
Enzym tc dng nh ha ch tc dng vi -glycosid.
Lin kt glycosid cn c to thnh gia cc phn t monosaccharid vinhau cho ra oligosaccharid (di, tri, tetraose) v polysaccharid.
Cc glycosid khng c hin tng bi quay (Mutarotation) v khng tc dngvi thuc th Fehling v thuc th Tollens.
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1.5.8. Phn ng to ether
Glucosid tc dng vi dimethylsulfat hoc methyliodid trong mi trngkim to thnh methyl tetra o -methyl glucosid.
V d: Khi cho Methyl -D-glucosid tc dng vi methyliodid hoc
dimethylsulfat v NaOH to hp cht c chc ether l methyl -2,3,4,6-tetra-O-methyl-D- glucosid.
Methyl - D-glucosid Methyl -2,3,4,6-tetra-o-methyl D-glucosid
- 4 CH3OSO3H
, NaOH+ 4 (CH 3O)2SO2
O
OCH3
HO
HO
HO
H
H
H
H
H
CH2OH CH2OCH3O
OCH3
CH3O
CH3O
CH3O
H
H
H
H
H
Hp cht methyl -2,3,4,6-tetra-O-methyl-D-glucosid tc dng vi H2O trongmi trng acid th ch c lin kt osid O-CH3 ti nguyn t carbon s 1 b thyphn. Cc nhm O -CH3 khc hon ton khng b thy phn(v chng l lin ktether).
O
OCH3
CH3O
CH3O
CH3O
H
H
H
H
H
CH2OCH3
- CH3OH
+ H2O , H+
-2,3,4,6-tetra-o-methyl D-glucoseMethyl -2,3,4,6-tetra-o-methyl D-glucosid
O
OH
CH3O
CH3O
CH3O
H
H
H
H
H
CH2OCH3
2,3,4,6-Tetra-O-methyl-D-Glucose
CHOC
C
C
CCH2OCH3
OCH3
OCH3
CH3O H
H
H
H
OH
2,3,4,6-Tetra-O-methyl- -D-Glucopyranose
C
C
C
C
CCH2OCH3
OCH3
OCH3
CH3O H
H
H
H
H
O
HO
1.5.9. Phn ng to ester
Aldohexose b acetyl ha (to ester) bi anhydrid acetic to hp chtacetylpyranose.
V d: -D-Glucose tc dng vi anhydrid acetic to hp cht -D
pentaacetylglucose.
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1
+5 (Ac) 2O
-D-glucose
- 5CH3COOH
CH2OHO
OH
HO
HO
HO
H
H
H
H
H
1
CH2OAcO
OAc
AcO
AcO
AcO
H
H
H
H
H
- D-Pentaacetylglucose
Khi cho -D-pentaacetylglucose tc dng HBr trong mi trng acid aceticth ch c chc ester ti carbon s 1 tham gia phn ng.
1
-Brom-2,3,4,6-tetra-acetyl- - D-Glucopyranose
+ HBr
1
CH2OAcO
Br
AcO
AcO
AcO
H
H
H HH
1
CH2OAcO
OAc
AcO
AcO
AcO
H
H
H
H
H
- CH3COOH
1,2,3,4,6-Penta-acetyl- -D-GlucopyranosePhn ng gia 1-brom-2,3,4,6-tetraacetyl--D-glucose vi phenolat hoc
alcolat v sau phn ng vi alcol methylic trong amoniac (thc hin phn ngtrao i ester) s thu c phenyl --D-glucosid hoc alkyl --D-glucosid.
Alkyl-- D-Glucopyranosid
Phan ng trao oi ester
CH2OH
+ 4CH3OH (NH3)
-RO-
O
OR
AcO
AcO
AcO
H
H
H
H
H
CH2OAc
1
O
Br
AcO
AcOAcO
H
H
H HH
1-Brom-2,3,4,6-tetra-acetyl- - D-Glucopyranose
-Br1
CH2OAc
O
OR
HO
HO
HO
H
H
H
H
H
1 - 4CH3COOCH3
Trong thin nhin thng gp mt s glucosid nh sau:
CH2OH
Vanilin-- D-Glucopyranosid
1
O
O
HO
HOHO
H
H
H
H
H
CH3O
CHO
CH2OH
1
O
O
HO
HOHO
H
H
H
H
H
CH3O
CH=CH CH2OH
CH2OH
Coniferin-- D-Glucopyranosid
1
O
O
HO
HO
H
H
H
H
H
CH3O
CH=CH CH2OHHO
Amygdalin
1
CH2OH
HOHO
HO
O
O
CH2
CN
H
C6H5C
HOHO
HO
O
O
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1.5.10. Phn ng to phc mu xanh vi Cu (OH)2
Cc 3,4-diol ca 2 monosaccharid c th quay ngc nhau to phc ng
phc ong
Cu (OH)2
O
OHOH
HOHO
CH2OHH
HH
O
OHOH
OO
CH2OHH
HH
HCu
OO
OHOH
O
H
H
HOH2C H
H
4 4
4
1 11
1.5.11. Phn ng tng mch carbon
Khi cho cc aldose tc dng vi HCN, thy phn, to lacton v sau khha th mch carbon ca aldose c tng ln.
V d: T aldopentose s to thnh aldohexose.
Cyanhydrin Acid Gluconic
- H2O
+ H2O
H+
H+
CC
C
C
CH2OH
H
OH
H OH
HO
H
HHOCOOH
CC
C
C
CH2OH
H
H OH
HO
H
OHH
C O
O
CC
C
C
CH2OH
H
OH
H OH
HO
H
HHOCN
Gluconolacton
CC
C
C
CH2OH
H
H OH
HO
H
HHOC O
O
CO2
Na (Hg)
Aldohexose
CC
C
C
CH2OH
H
OH
H OH
HO
H
HHOCHO
+ H2O
CC
C
C
CH2OH
H
OH
H OH
HO
H
OHH
CN
- H2O
CC
C
C
CH2OH
H
1.5.12. Phn ng gim mch carbon
C th gim mch carbon ca aldose theo cc bc sau:
Oxy ha aldose bng dung dch brom.
Chuyn ha thnh mui calci. Oxy ha mui calci bng H2O2 vi s cmt ca mui st Fe3+, aldose to thnh c s carbon gim mt nguyn t.
OH
H OH
HO
H
H
COOH
OH
CO2
Na (Hg)
CC
C
C
CH2OH
H
OH
H OH
HO
H
OHH
CHO
Aldopentose
+ HCN
CHOC
C
C
CH2OH
H
OH
H OH
HO
H
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AldopentoseCalci gluconatAcid GluconicAldohexose
Fe3+
+ H2O2 2 -+ CO3
C
C
CCH2OH
H
OH
H OH
HO
H
CHO2
CC
C
C
CH2OH
H
OH
H OH
HO
H
OHHCOO- Ca
+ CaCO3Br2 + H2O
CC
C
C
CH2OH
H
OH
H OH
HO
H
OHH
COOHCC
C
CCH2OH
H
OH
H OH
HO
H
OHH
CHO
Cc phn ng to glycosid, to ether, ester, tng, gim mch carbon lnhng phn ng quan trng xc nh cu to cu monosaccharid.
1.5.13. Phn ng ln men
Ln men l qu trnh sinh ha rt phc tp xy ra do enzym tc dng ln c
cht, ngoi sn phm chnh cn c sn phm ph:
HOOCCH2CCH2COOH
COOH
OH
H23 CO2 ++C2H5OH
2 CO2+ 2 H2
++
+
+
+
Len menAceton-Butylic
Len men Citric
Len men Lactic
Len men Butyric
C6H12O6
Len men Ru
H2O
D-glucoseCH3CH2CH2CO2H
2CH3CHOHCO 2H
CH3COCH3
2 CO2
C4H9OH
2 C2H5OH
2. Oligosaccharid
Oligosaccharid l nhng hp cht c to thnh do cc monosaccharid kthp vi nhau bng lin kt glycosid.
Oligosaccharid (oligo: mt vi) b thy phn cho mt vi monosaccharid.
Trong t nhin c: maltose, cellobiose, saccharose (ng ma), lactose
(
ng sa), melibiose, gentiobiose, manniotriose, raffinose, gentianose.n gin v quan trng nht l cc disaccharid.
2.1. Disaccharid
Disaccharid c cng thc phn t: C12H22O11.
Thy phn disaccharid to ra 2 phn t monosaccharid.
C12H22O11 + H2O C6H12O6 + C6H12O6
C th chia disaccharid thnh 2 loi: ng kh v ng khng kh.
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2.1.1. Disaccharid c tnh kh: Maltose, cellobiose, lactose
ng kh l ng cn nhm OH bn acetal c th chuyn v dng aldehyd.
(+) Maltose hay[4-O-(-D-glucopyranosyl)]-D-Glucopyranose.
Thy phn maltose to ra 2 phn t -glucose. Biu din cng thc cu to
ca maltose di dng cng thc chiu Fischer, cng thc chiu Haworth, cngthc cu dng nh sau:
Cong thc cau dang cua (+) Maltose
O
OHHO
HO
CH2OH
O
HH
H
H
H
H
H
H
HH
OH
CH2OH
HOOH
O
LK glycosid
HO ban acetal
D- GlucopyranoseD- Glucopyranose
12
4
1
4
2
Maltose do 2 phn t -D-glucose to thnh. Lin kt glycosid trong phn tmaltose do nhm OH bn acetal ca phn t -glucose th nht tc dng vinhm OH alcol v tr s 4 ca phn t -D- glucose th 2. Trong phn t(+)maltose cn c nhm OH bn acetal. Nhm OH bn acetal ny c th chuyn vchc aldehyd. Vy (+)maltose tc dng vi thuc th Fehling v thuc thTollens. (+)Maltose l mt ng kh.
Maltose tc dng vi phenylhydrazin to osazon C12H20O9 (=N-NH-C6H5).
2
4
1
4
21
O
OHHO
HO
CH2OH
O
HH
H
H
HH
H
H
CH2OH
HO
N
CCH
OH
N NH C6H5NH C6H5
Osazon cua (+) maltose
Maltose tc dng vi dung dch nc brom to acid maltobionic (C11H21O10)COOH
Acid maltobionic
O
OHHO
HO
CH2OH
O
HH
H
H
HH
H
H
CH2OH
HO C COOH
OHH
OH
1
2
4
1
4
2
(+)-Maltose cng tn ti anomer v . Di tc dng ca enzym maltase hocthy phn acid, maltose chuyn ha hon ton thnh 2 phn t -(+)-D- glucose.
Phn ng chng minh (+)matose l [4-O-(-D-glucopyranosyl)-D-glucopyranose:
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O
Acid D-maltobionic
OHHO
HO
CH2OH
O
HH
H
H
HH
H
H
H
CH2OH
HOOH
C
OH
COOH
O
OCH3CH3O
CH3O
CH2OCH3
O
HH
H
H
HH
H
HH
CH2OCH3
3OOCH3
C
OCH3
COOHCH
(CH3)2SO4 , NaOHMethyl hoa
Acid octa-O-methyl-D-maltobionic
O
OHHO
HO
CH2OH
O
HH
H
H
H
H
H
H
HH
OH
CH2OH
HO
OH
O
(+) Maltose , Anomer+ Br2 , H2OOxy hoa
H2O , H+Thuy phan
2,3,4,6-Tetra-O-methyl-D-glucopyranose
O
OCH3CH3O
CH3O
CH2OCH3
HH
H
H
H
OH
( Anomer )
CC
C
OHHHCH3O
C
COOH
H OCH3
OCH3HCH2OCH3
+
Acid-2,3,5,6-Tetra-O-methyl-D-gluconic
Enzym maltase l enzym chn lc c trng ch thy phn vi lin kt -glycosid.
Cellobiose hay[4-O-(-D-glucopyranosyl)]-D-glucopyranose.
Cellobiose l sn phm phn hy ca cellulose. Cellobiose thuc loi ngkh. Hai phn t -D-glucose lin kt vi nhau ti v tr 1 v to phn t cellobiosec lin kt 1,4--glycosid.
2
4
1 4
21
D- Glucopyranose
LK glycosid
O
OHHO
HO
CH2OH
HH
H
H
O
H
H
H
H
H HOH
CH2OH
HOOH
O
Cong thc cau dang cua (+) Cellobiose
5
6
53
3
D- Glucopyranose
( anomer)
6
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Lactose hay [4-(-D-galactopyranosido)-D-glucopyranose: ng sa.
Thy phn lactose to ra phn t-D-galactose v D -glucose. Lactose cngging phn t maltose c 2 dng ng phn v .
2
4
1 4
2 1
D- Galactopyranose
LK glycosid
O
OHHO
H
CH2OH
HH
H
OH
O
H
H
H
H
H HOH
CH2OH
HOOH
O
Cong thc cau dang cua Lactose
56
53
3
D- Glucopyranose
( anomer)
6
Tnh cht: Cc loi ng kh u tham gia cc phn ng nh cc aldose:
O
H
OHH
H
HH
CH2OH
OHHO
OH
D (+)-Galactose
O
H
OHH
H
HH
CH2OH
OHHO
OH
C=N
C=N
NHC6H5
NHC6H5C
C
C
OH
OH
HO
H
H
H
CH2OH
H
COOOH
C OH
C
C
C
OH
OH
HO
H
H
CH2OH
H
H
++
D -Glucosazon D (+)-Galactose D -(-) - Acid gluconic
Acid LactobionicLactosazon
Thuy phanThuy phan
O
H
H
H
HH
CH2OH
OHHO
OH
O
H
HOOH
CH2OH
H H
HCOOH
OH
O
H
H
H
HH
CH2OH
OHHO
OH
O
H
HO
CH2OH
H
H
CC=NNHC6H5
OH
NNHC6H5
H
O
H
H
H
HH
CH2OH
OH
HO
OH
O
H
HOOH
CH2OH
HH
H
OH
H
O
C6H5NHNH2 Br2 ,H2O+ +
Lactose ( -Anomer ) Lactose c ng phn v l do s chuyn quay.
S chuyn quay ca lactose c th minh ha nh sau:
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(dang )
O
OOHHO
OH
HO H
CH2OH
OH
O
CH2OH OH+
O
OOHHO
OH
HO H
CH2OH
OH
OH
CH2OH OH2
H +(dang)
+O
OOHHO
OH
HO OH2
CH2OH
OH
OH
CH2OHO
OOHHO
OH
HO OH
CH2OH
OH
O
CH2OHban acetal chuyen quay
2.2. Disaccharid khng kh. ng khng kh
ng khng kh l ng khng cn nhm OH bn acetal chuyn thnhaldehyd. Do ng khng kh khng tc dng vi thuc th Fehling v thuc
th Tollens.
2.2.1. Saccharose hay-Glucopyranosido--D-fructofuranosid:ng ma.Saccharose c gc quay cc (+),c trong ng ma, ng c ci.
Saccharose c cng thc phn t C12H22O11. Khc vi cc disaccharid khc,saccharose khng tc dng vi cc thuc th Tollens v Fehling cho nn saccharosel ng khng kh.
(+)-Saccharose khng to osazon, khng c ng phn anomer v cngkhng c hin tng bi quay trong dung dch.
Nhng tnh cht trn chng t (+)-saccharose khng c chc aldehyd trongphn t. Saccharose b thy phn to thnh D -(+)-glucose v D -(-)-fructose.
(+)-Saccharose c cng thc cu to nh sau:
3
6
5 O
OHHO
HO
CH2OH
HH
H
H
O
HO
CH2OH
H
H
H
CH2OH
OH
HO
4
2
D-Glucopyranse
D-Fructofuranose
Thy phn saccharose bng dung dch acid long hay enzym invertase sto thnh hn hp D -(+)-glucose v D -(-)-fructose c khi lng nh nhau. Sthy phn ny dn n s thay i gc quay cc ban u ca saccharose. Gcquay cc t (+)chuyn thnh (-). Hin tng gi l s nghch quay (o quay)ca (+)saccharose. Hn hp thy phn trn gi l "ng nghch quay". Mt ongl ng nghch quay.
S nghch quay l do s b tr gc quay cc ca D -(+)-glucose v D -(-)-
fructose. Gc quay cc ca (+) saccharose +66,5, ca D -(+)-glucose +52,7 v ca
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D -(-)-fructose 92,4. Kt qu l dung dch saccharose sau khi thy phn c gcquay cc (-).
V vy D -(+)-glucose cn gi lDextrose v D -(-)-fructose gi lLevulose.
3. Polysaccharid
Polysaccharid l nhng hp cht bao gm hng trm n hng nghn gcmonosaccharid kt hp vi nhau bng lin kt glycosid.
Cc polysaccharid quan trng hay gp l tinh bt v cellulose. Chng u ccng thc phn t l (C6H10O5) n. Cc polysaccharid l nhng thnh phn quantrng trong th gii ng vt v thc vt. Polysaccharid c hnh thnh do qutrnh quang hp trong t nhin. Di tc dng ca nh sng, CO2 v H2O tothnh monosaccharid. Cc monosaccharid mt nc to thnh polysaccharid.
h6CO2 + 6 H2O C6H12O6 + 6O2
+ n H2O(C6H10O5)nnC6H12O6
Tinh bt v cellulose l nhng cht quan trng i vi con ngi. Thc phmchng ta dng hng ngy, o ta mc, vt dng ta dng trong gia nh u cngun gc t tinh bt v cellulose.
3.1. Tinh bt
Tinh bt c cu to dng ht v kch th
c khc nhau.Tinh bt c 20% amylose v 80% amylopectin. Amylose c cu trc mch
thng v tan c trong nc. Amylopectin c cu trc phn nhnh v khng tantrong nc. Di tc dng ca acid hoc enzym, tinh bt b thy phn dn thnhcc phn t c phn t lng nh hn l dextrin, maltose v glucose.
3.1.1. Cu trc ca amylose
Amylose c cu trc mch thng do cc phn t -glucose lin kt vi nhaubng lin kt -[1,4]-glucosid.
Amylose dang cong thc Haworth
D-Glucose
n
O
OOH
OH
CH2OH
H
H
H
HH
O
HH
H
H
H
CH2OH
OH
OH
O
O
O
O
OH
OH
CH2OH
H
H
H
HH
O
HH
H
H
H
CH2OH
OH
OH
O
D-Glucose (+)Maltose
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O
O
HO
O
H
H
H
H
HH
H
HH H
CH2OH
O
OH
OH
O
O
OH
OH
CH2OH
CH2OH
HHH
H
HH
H
H
H
H
O
HO
O
O
HO
HO
14
14
14
14
D-Glucose
D-Glucose
D-Glucose
n
Amylose dang cong thc cau dang
(+) Maltose
D-Glucose
CH2OH
Cc phn ng chng minh cu to amylose:Methyl ha amylose bng dimethylsulfat v NaOH. Sn phm methyl ha
em thy phn to thnh 2,3,4,6-tetra-O-methyl -D-glucose v 2,3,6-tri-O-metyl--D-glucose. iu chng t trong amylose c lin kt [1-4]-glucosid.
n
O
O
CH3O
O
H
H
H
H
HH
H
HH H
CH2OCH
3
CH2OCH
3
CH3O
OCH3
OCH3
O
OCH3
OCH3
CH2OCH3
CH2OCH3
HHH
H
H H
H
H
H
H
O
CH3O
O
O
OCH3
CH3O
CH3O
HCl
2,3,6-Tri-O-metyl- -D-gluccose( n+1) phan t
2,3,4,6-Tetra-O-metyl- -D-gluccosehieu suat 0,5%
va
HO
OCH3
CH2OCH
3
HH
H
H
H
O
O
CH3O
O
OH
H
H
H
HH
CH2OCH3
CH3O
OCH3CH3O
3.1.2. Cu trc ca amylopectin
Amylopectin cng gm cc phn t -D-glucose to thnh bng lin ktglucosid v tr [1-4] v [1-6].
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D-Glucose
D-Glucose
O
O
HO
O
H
H
H
H
HH
H
HH H
CH2OH
CH2OH
O
OH
OH
O
CH2 O
O
HO
O
H
H
H
H
HH
H
HH H
CH2OH
OH
OH
O
HO
HO
1
4
6
1
1
4
D-Glucose
D-GlucoseLien ket glucosid 1,4
Lien ket glucosid 1,4
Lien ket glucosid 1,6
Cong thc cau dang cua amylopectin
Cc phn ng chng minh cng thc cu to ca amylopectin:Methyl ha amylopectin sau em thy phn trong mi trng acid th
thu c 2,3,6-tri-O-methyl--D-glucose (chim 90%), 2,3,4,6-tetra-O-methyl--D-glucose (chim khong 5%) v 2,3-di-O-methyl--D-glucose (chim khong 5%).
11
2
2,3,6-Tri-O-methyl- D-Glucose
(90%)
2,3,-Di-O-methyl- D-Glucose
( Khoang 5% )
2,3,4,6-Tetra-O-methyl- D-Glucose
( Khoang 5%)
2
66
44
33
6
1
4
312
OCH3
CH2OH
HH
H
H
H
OHOCH3O
OHCH3O
OH
H
HH H
CH2OCH3
OCH3
CH3O
OH
O
H
H
H
HH
CH2OCH3HO
OCH3 OH
CH3O
3.1.3. Glycogen
L hp cht c cu to gn ging vi amylopectin nhng phn t glycogen cmch phn nhnh nhiu hn v c s n v glucose (12-18 n v glucose) t hnamylopectin. Glycogen l hydrat carbon d tr ca c th.
3.2. Cellulose3.2.1. Cu to
Cellulose l thnh phn ch yu ca g v si thc vt. Bng c xem lcellulose nguyn cht. Cellulose khng tan trong nc. Cellulose khng c tnhkh. Phn t lng ca cellulose rt ln (250.000 - 1.000.000) bao gm trn 1500n v glucose. Cellulose c cng thc phn t (C6H10O5)n. Thy phn hon toncellulose bng acid ch thu c -D-(+)-glucose.
Trong phn t cellulose, cc phn t -D-(+)-glucose lin kt vi nhau bnglin kt -[1-4]-D-glucosid.
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O
HOOH
OH
CH2OH
H
H
H
HO
O
HOH
OH
CH2OH
H
H
H
HO
H
H
H
H
CH2OH
OH
OH
H
O O
O
OH
OH
CH2OH
H
H
H
HO
D-Glucose
D-Glucose
D-Glucose
D-Glucose
Cong thc cau tao cua cellulose dang Haworth
O
H
O
H
HH
CH2OH
OHHO
O
H
HOOH
CH2OH
HH
H H
O
H
O
H
HOOH
CH2OH
HH
H H
O
OO
H
O
H
HH
CH2OH
OHHO
H
Lien ket 4- -Glucosid Lienke t 4- -Glucosid Lienke t 4- -Glucosid
Cellobiose CellobioseCong thc cau dang cua cellulose
2 41
1
1
14
4
42
2
2
Cellulose c cu trc mch thng, do cellulose d ko thnh si.
3.2.2. Cc phn ng ca cellulose
Trn mi mt xch D -glucose c 3 nhm OH t do. Chnh cc nhm OH nytham gia cc phn ng ester ha v phn ng to ether...
a. Nitrat cellulose
Cellulose tc dng vi hn hp acid nitric v acid sulfuric to nitratcellulose. Nitrat cellulose nh l mt ester. Tnh cht v lnh vc s dng canitrat cellulose ty thuc vo mc nitrat ha. Nitrat cellulose c ng dnglm cc mng phim, lm cht do, cht keo dn, thuc sng khng khi...
b. Acetat cellulose
Cellulose tc dng vi hn hp anhydrid acetic v acid acetic c mt t acidsulfuric to ra hn hp triacetat cellulose. Acetat cellulose km bn hn nitratcellulose. Acetat cellulose c s dng lm phim nh. Ho tan acetat cellulosetrong aceton sau c th ko thnh si gi l t acetat.
c. Ether cellulose
Alkyl ha cellulose bng alkyl halogenid trong mi trng kim to ra ethercellulose. Cc ether methyl, benzyl ca cellulose c s dng trong cng nghipdt, to mng mng, to nguyn liu cht do. Carboxy Methyl Cellulose (CMC)cng thuc loi ether ca cellulose.
etCarboxy M hyl Cellulose(CMC)
n
O
HOOCH
2COOH
OH
CH2OH
H
H
H
HO
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d. T visco v Cellophan
Cellulose tc dng vi carbor disulfid CS2 v NaOH to dung dchXanthogenat cellulose c nht rt cao gi l visco. Ko visco qua khe nh vqua b ng acid thu c si cellulose gi l t visco.
Mng mng visco c cht do ho l glycerin gi l cellophan. Cellophanthng c gi l giy bng knh, dng gi hng ha.
C th hnh dung cu to ca cc loi polysaccharid nh hnh v di y:
Polysaccharid mach thang
Polysaccharid mach nhanh
Polysaccharid mach vong
3.3. Pectin
Pectin c ngun gc t thc vt,
c to thnh t acid -D-galacturonic vmt s methylester. Acid -D-galacturonic lin kt vi nhau to acid pectic. Acidpectic l khung c bn ca pectin.
O
OH
OH
COOH
O
O
OH
OH
COOH
O
O
OH
OH
COOH
O
O O
OH
OH
COOHO
O
OH
OH
COOHO
Acid pectic
Acid D - galacturonic
3.4. Acid alginic
Acid alginic c trong mt s loi rong bin. Tn ti dng t do hoc dngmui calci. Thy phn acid alginic thu c acid D -mannuronic.
3.5. Chitin
Chitin l mt loi polysaccharid c trong v tm, cua.... Thy phn chitinthu c acid acetic v D -glucosamin (chitosamin, 2-aminoglucose). Thy phnchitin bng enzym s thu c N -acetylglucosamin.
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Cu to ca chitin cng ging cu to ca cellulose. N -methyl-L-glucosaminl thnh phn ca streptomycin.
Streptomycin
N-Methyl-L-glucosamin
NH
NH2CNH
OH
OH
OH
H
H H
H
H
NH C NH
NH
HO
HO
CHO
O
H H
H
CH3
H
O
HH
H
H
OH
OH O
CH3NH
CH2OH
Bi tp
Monosaccharid
1- Phn t (-)-fructose c bao nhiu nguyn t carbon khng i xng?
2- Phn t 2-cetohexose c bao nhiu cp i quang? V cng thc chiu Fischerv cng thc Haworth i vi mt cp i quang ca D -(-)-Fructose.
3- Vit phn ng to osazon ca cc cht sau, cc osazon c cu hnh th no?
a ) D-glucose; b) D-Mannose; c ) D-Fructose.
4- C bao nhiu aldotetrose thu c khi xut pht t D -(+)-aldehyd glyceric.
5- Vit cc phng trnh phn ng theo s sau:
Vit cng thc cu to ca cc cht A E.(+)Gulose thuc loi cu hnh no, D hay L ?
Disaccharid
D-(+)-Glucose Acid(+)-Saccharic
A
HNO3
( Lacton ) D-(+)-Glucose
- H2O A va B (eu la Lacton)
Na ( Hg) - H2O Na ( Hg)
E ( Lacton ) (+)-GuloseNa ( Hg) - H2O Na ( Hg)B
C ( Acid gluconic )
C ( Acid gluconic )
6- Vit phng trnh phn ng oxy ha, methyl ha v thy phn ca cc cht:
(+)- Lactose, (+)-Maltose, (+)-Saccharose.
7- Vit cng thc cu hnh ca:
(+)- Lactose, (+)-Maltose,(+)- Saccharose v (+)- Cellobiose.
8- Gii thch s nghch quay ca (+)-saccharose.
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Chng 29
ACID AMIN, PEPTID V PROTID
Mc tiu
1.Gi c tn v xc nh c cu hnh ca acid amin.
2.Trnh by c ha tnh ca acid amin.
3.Nm c cc kiu cu to ca protid.
1.Acid amin
1.1.nh ngha
Acid amin l nhng hp cht tp chc, c hai nhm nh chc khc nhau l:chc amin (NH2) v chc acid (COOH).
C 2 loi acid amin:
H2N-R-COOH: R l gc hydrocarbon no, cha no, vng khng thm, d vng
H2N-Ar-COOH: Ar l gc hydrocarbon thm
1.2. Cu to
1.2.1. Cc acid amin thin nhin: l nhng -aminoacid
Cng thc chung:
H2N CH COOH
R
Trong gc R
Alkyl (mch h hay nhnh)
Cycloalkyl, Ar -, gc d vng
Cha hoc khng cha mt s nhm chc ( -SH, -OH)(Nhng nhm chc ny thng u mch ca gc R)
S nhm chc ca mi loi c th mt hoc hai nhm:
A
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