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Chuyn bi dng HSG Ha hu c

Trng THPT chuyn L Qu n



1

CHNG I: AMIN V MUI IAZONI
Bi: AMIN
I.KHI NIM
1.nh ngha
Amin l dn xut th H ca NH
3
, bng cc gc hirocacbon bo hay thm.
Amin loi bo: gc hirocacbon l gc ankyl hay xicloankyl
CH
3
-CH
2
CH
2
-NH
2

Amin thm, gc hyrocacbon l nhn thm:

NH
2

2.Bc amin:
Amin bc 1, c nhm chc amin -NH
2
nh vi 1 gc hirocacbon
Amin bc 2, c nhm chc amin NH nh vi hai gc hirocacbon
Amin bc 3, N nh vi 3 gc hirocacbon
RNH
2
(CH
3
)
2
CNH
2
R
2
NH CH
3
CH
2
NHCH
3
R
3
N (CH
3
)
3
N
amin bc nht amin bc hai amin bc ba
II.DANH PHP
Amin thng c gi theo tn thng thng hn l IUPAC

Tn gc hirocacbon+amin
(vit lin 1 ch)
X-amino + tn hirocacbon


Tn thng thng Tn IUPAC
CH
3
NH
2

(CH
3
)
2
NH
(CH
2
CH
2
CH
2
)
3
N
CH
3
CH
2
CH-NH
2
CH
3

CH
3
CH
2
CH - N - CH
2
CH
3
CH
3
CH
3

NH
2

N(CH
3
)
2

NH
2
C H
3

metylamin
imetylamin
tri-n-propylamin
sec-butylamin


metyletyl-sec-butylamin





phenylamin,anilin



imetylphenylamin
imetylanilin

p-toluiin
aminometan
N-metylaminometan
N,N-ipropylaminopropan
Amino-2-butan


N, N-etylmetylamino-2-butan





aminobenzen(benzenamin)



N, N-imetylbenzenamin
N, N-imetylanilin

p-aminotoluen

III.PHNG PHP TNG HP
1. Ankyl ha trc tip amoniac hay amin
NH
3
tc dng vi RX to thnh mui:
Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

2
NHR NR
2
CH
3
NH
2
CH(CH
3
)
2
CH
3
NO
2
CH(CH
3
)
2
CH
3
NH
2
NH
2
CH
3
NO
2
NO
2
CH
3
CH
2
-Br + NH
3
CH
3
CH
2
NH
3
+
Br
-

NaOH
CH
3
CH
2
NH
2

2.Phn ng kh
a, Kh hp cht nitro
Nhm nitro b kh thnh amin bc nht. Phn ng ch yu dng iu ch amin thm. Tc nhn
kh c th l hiro ha xc tc hay tc nhn kh ha hc trong dung dch.


[H]
p, t
o






Fe
C
2
H
5
OH, HCl, t
o




b,Kh hp cht nitrin
Nitrin b kh bng hiro trn xc tc hoc bng LiAlH
4
trong dung dch to thnh amin bc
nht:
H
2/
Ni
R-CN R-CH
2
-NH
2

hay LiAlH
4

IV.CU TRC
Amin l sn phm th ca NH
3
, nn ni chung c cu trc ging cu trc ca NH
3
:
NH
3
R-NH
2
R-NH-R R-N-R
|
R
V.TNH CHT HA HC
1. Tnh baz
Amin l baz Lewis do amin c cp electron n khng lin kt N tng t nh ancol, ete.
Khi xt mt amin c tnh baz, cn so snh tnh n nh ca amin so vi mui amoni. Nu ion
amoni n nh hn amin th amin c tnh baz. Khi so snh tnh baz ca amin bo, cn ch
hai nhn t: nhn t phn cc v nhn t solvat ha.
Nu xt theo nhn t phn cc, khi tng gc R s lm tng mt electron N, va lm
tng kh nng kt hp proton, va lm tng tnh n nh ca ion amoni. Do tnh baz gim
theo th t:
R
3
N > R
2
NH > RNH
2

Nu xt theo nhn t solvat ha ca ion amoni, s lng proton ion amoni cng nhiu
th kh nng solvat ha ca ion cng ln, do , tnh baz thay i theo th t:
RNH
3
+
> R
2
NH
+
2
> R
3
NH
+
Tng hp c hai nhn t trn, s thay i tnh baz ca cc amin c bc khc nhau nh sau:
RNH
2
< R
2
NH > R
3
N
Tnh baz ca cc amin thm bo cng thay i theo th t nh trn:

< >


NH
2
Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

3
2. S to mui
Do c tnh baz, amin c kh nng to mui vi axit:
C
6
H
5
NH
2
+ HCl C
6
H
5
NH
3
+
Cl
-

(CH
3
)
2
NH + HNO
3
(CH
3
)
2
NH
2
+
.NO
3
-

C
6
H
5
N(CH
3
)
2
+ RCOOH C
6
H
5
NH
+
(CH
3
)
2
.RCOO
-

Cc ion amoni c kh nng tan tt trong nc hn l amin:
CH
3
(CH
2
)
9
NH
2
+ HCl CH
3
(CH
2
)
9
NH
3
+
NH
3
+
Cl
-

( khng tan) (tan tt)
3.Phn ng ca hir ca N-H
3.1. Phn ng ankyl ha
Hiro nh vi N c th b th bi gc hirocacbon khi amin tng tc vi halogenua ankyl
bc 1, 2, 3 hay thm. Nu ankyl ha hon ton th thu c mui amoni bc 4:
RX RX RX
RNH
2


RRNH RR
2
N [RR
3
N]
+
X
-
Mui amoni bc 4 l hp cht inoic, c nhit nng chy cao v d tan trong nc
Ch : Cc dn xut thn ch tham gia phn ng khi c nhm ht electron v tr ortho v
pa ra, th d nh 2, 4-(NO
2
)C
6
H
3
F
3.2. Phn ng axyl ha
Amin bc nht v amin bc hai phn ng vi halogenua axit hay anhirit axit to thnh amit:
2CH
3
NH
2
+ CH
3
COCl CH
3
NH-CO-CH
3
+ CH
3
NH
3
+
Cl
-

CH
3
NH
2
+ (CH
3
CO)
2
O CH
2
NH-COCH
3
+ CH
3
COOH
Tng qut: R - NH
2
+ Cl - CO - R
+ tach cng
R - NH - COR + HCl
R - NH
2
+ RCOO - CO - R
+ tach cng
R - NH - COR + RCOOH
Nu dng clorua axit th cn 1 lng tng ng trung ha axit clohiric to thnh.
ng dng: bo v nhm -NH
2
trong tng hp hu c
Nh phn ng axetyl ho (dng axetyl clorua hoc anhirit axetic ngi ta bo v nhm amino
trong tng hp hu c ).
bo v nhm amino ca aminoaxit v peptit trong qua trnh tng hp peptit, khng dng
phn ng axetyl ho c, v khi mun gii phng nhm -NH
2
ra khi -NHCOCH
3
phi thu
phn, do lm t lun c lin kt peptit - CO - NH -. Tt hn ht nn dng C
6
H
5
CH
2
OCOCl
(benzyl oxicacbonyl clorua) v khi cn gii phng nhm - NH
2
c th dng phn ng kh bng
H
2
/Pd (khng nh hng ti lin kt peptit). Th d tng hp ipeptit Ala-Gly theo s :
C
6
H
5
CH
2
OCOCl H
2
NCH(CH
3
)-COOH
C
6
H
5
CH
2
OCO HNCH(CH
3
)-COOH
H
2
NCH
2
COOCH
2
C
6
H
5
DDC
C
6
H
5
CH
2
OCO HNCH(CH
3
)-CO HNCH
2
COOCH
2
C
6
H
5
H
2
/Pd/C
C
6
H
5
CH
3
CO
2
H
2
NCH(CH
3
)-CO HNCH
2
COOCH
2
C
6
H
5
+
2 + +

(DCC: ixiclohexylcacboiimit).
3.3. Phn ng vi axit nitr:
Axit nitr HONO gn nh khng tc dng vi amin bc 3, tr phn ng nitroso ho nhn
thm.
Axit nitr tc dng vi amin bc hai sinh ra nitrosoamin(N - nitrosoamin) c mu vng, nh
vy c th phn bit amin bc hai vi amin cc bc kh. Th d:
(C
2
H
5
)
2
NH + HONO
+) (
H
(C
2
H
5
)
2
N N = O + H
2
O
(Cht lng mu vng)
Amin bc mt tc dng HONO sinh ra mui iazoni RN
) (+
NX
(-)
(t RNH
2
) hoc
Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

4
) ( +

ArN
) (+
NX
(-)
(t ArNH
2
). C ch phn ng ca amin bc mt tng t trng hp amin bc
hai ch lc u cng to ra hp cht nitroso, sau phn ng tip nh sau:

R - N = NOH
2
N
R- NH - N = O
H
R- NH = NOH
+
H -
+
R - N = NOH
H
+
+
R - N


ng ch l mui iazoni dy bo RN N khng bn nn chuyn ho ngay thnh ancol gii
phong kh nit. Trong khi y, mui iazoni dy thm li bn nhit thp v ch phn hu
thnh phenol ng thi gii phng N
2
khi un nng. Th d:

C
2
H
5
- NH
2
NaNO
2
C
2
H
5
- N NCl

OH
2
N
2
C
2
H
5
OH
HCl, 0
0
C
+
-
+ + HCl


C
6
H
5
- NH
2
NaNO
2
OH
2
N
2
C
6
H
5
OH
C
6
H
5
- N NCl
HCl, 0
0
C
+
-
+ + HCl
un

Mui iazoni thm ArN
2
(+)
X
(-)
c dng rng ri trong tng hp hu c.
3.4. Phn ng th nhn thm:
Cc nhm -NH
2
, -NHR v - NR
2
(R = ankyl) u hot ho nhn thm v nh hng ortho -
para.
a, Halogen ho
Nc brom d dng phn ng vi anilin cho 2, 4, 6 - tribromoannilin (kt ta trng), vi p -
toluidin p - CH
3
C
6
H
4
NH
2
cho 2,6 - ibrom - 4 - metylanilin.
Brom lng tc dng vo v tr para ca N - axetylanilin (hay axetanilit) C
6
H
5
NH -
COCH
3
; thu phn sn phm sinh ra s c p - bromanilin.
Iot trong hn hp vi NaHCO
3
( trung ho HI sinh ra trong phn ng) tc dng vi anilin
cho ta p - Iotanilin.
b, Nitro ho
Khng th trc tip nitro ho anilin bng HNO
3
, v khi y amin b proton ho tr thnh mui
amoni; nhm -
3
) (
H N
+
sinh ra s phn hot ho rt mnh v nh hng th vo v tr meta, mun
mononitro ho anilin phi bo v nhm - NH
2
ri mi nitro ho, sau gii phng - NH
2
.
NH
2 NHCOCH
3
NHCOCH
3
NO
2
NH
2
NO
2
(CH
3
CO)
2
O
HNO
3
, H
2
SO
4
H
3
O+
OH-
1)
2)

Nu mun a nhm nitr vo v tr ortho phi kho v tr para ri mi nitro ho:
Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

5
NH
2 NHCOCH
3
NHCOCH
3
SO
3
H
(CH
3
CO)
2
O
H
2
SO
4
HNO
3
, H
2
SO
4
NHCOCH
3
SO
3
H
HNO
3
, H
2
SO
4
NHCOCH
3
SO
3
H
NO
2
H
2
SO
4
OH
2
NHCOCH
3
NO
2




Bi: MUI IAZONI

I.CU TRC CA CATION IAZONI
Ion iazoni c nhm N
2
hay NN mang in tch dng phn b trn c hai nit nhng tp
trung N nh vi phn t benzen nhiu hn:


N N N N

(Ar-N
2
)
hay
+ +
+

trong h lin hp, mt lin kt lin hp c vi h ca nhn benzen cn mt lin kt nm
thng gc vi mt phng ny
II.TNH CHT HA HC
Mui iazoni thm ArN
2
(+)
X
(-)
c th ng vai tr l cht phn ng trong cc phn ng
thay th nhm - N
2
(+)
, mt khc c th l tc nhn electrophin tham gia phn ng th electrophin
nhn thm, l phn ng ghp.
1. Phn ng th nhm -N
2
(+)

1.1. Th -N
2
(+)
bng -OH v bng -I

Ar - N N
-N
2
Ar - Y
+
Ar
+
Y
-

Khi un nng dung dch ArN
2
(+)
, H
2
SO
4
(-)
trong nc s sinh ra ArOH theo c ch nu trn
(H
2
SO
4
(-)
c tnh nucleophin km H
2
O). Phn ng ny c dng tng hp phenol t amin
thm. Th d:
m - NO
2
C
6
H
4
NH
2
NaNO
2
, H
2
SO
4
, H
2
O
m - NO
2
C
6
H
4
N
2
HSO
4
OH
2
m - NO
2
C
6
H
4
OH
N
2
+ -
t
0
+

Khc vi H
2
SO
4
(-)
c tnh nucleophin km nc, anion I
(-)
c tnh nucleophin cao hn nc
nhiu, nn d tc dng vi mui iazoni sinh ra ArI. Th d:

C
6
H
5
NH
2
NaNO
2
, HCl
C
6
H
5
N
2
Cl
KI
C
6
H
5
I
0 - 5
0
C
25
0
C
+
-

1.2.Th -N
2
(+)
bng - Cl, -Br v -CN (phn ng Sandmeyer)
Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

6
Nh tng git huyn ph ca Cu
2
X
2
(X = Cl, Br hoc CN) vo dung dch ArN
2
(+)
X
(-)
lnh s
xy ra phn ng th -N
2
(+)
bng -X. Th d:

C
6
H
5
NH
2
NaNO
2
, HCl
C
6
H
5
N
2
Cl
KI
C
6
H
5
I
0 - 5
0
C
25
0
C
+
-


o-ClC
6
H
4
NH
2
NaNO
2
, HBr
o-ClC
6
H
4
N
2
Br
Cu
2
Cl
2
o-ClC
6
H
4
Br
0 - 5
0
C
+
-


p-CH
3
C
6
H
4
NH
2
NaNO
2
, HCl
p-CH
3
C
6
H
4
N
2
Cl
Cu(CN)
2
p-CH
3
C
6
H
4
CN
0 - 5
0
C
+
-
-

1.3. Th -N
2
(+)
bg -F v -NO
2

Sau khi iu ch mui areniazoni tetrafluoroborat ArN
2
(+)
BF
4
(-)
em nhit phn s c ArF
hoc cho tc dng vi NaNO
2
/Cu s c ArNO
2
. Th d:

p-NO
2
C
6
H
4
NH
2
NaNO
2
HBF
4
p-NO
2
C
6
H
4
N
2
BF
4
-N
2
, -BF
3
NaNO
2
/Cu
p-NO
2
C
6
H
4
F
p-(NO
2
)
2
C
6
H
4
+ -
t
o


1.4. Th -N
2
(+)
bng -H. Phn ng kh:
Dng axit hipophotphor(H
3
PO
2
) hoc etanol c th kh c mui iazoni ArN
2
(+)
thnh ArH:

ArNH
2
NaNO
2
, H
ArN
2
H
3
PO
2
C
2
H
5
OH
+
0 - 5
0
C
+
hoc
ArH

Nh phn ng ny ngi ta c th loi b nhm amino trong vng thm v do tng hp
c nhng dn xut th khng th iu ch bng phn ng th trc tip. Th d t toluen tng
hp m - bromotoluen:

CH
3
NHCOCH
3
Br
CH
3
CH
3
NH
2
Br
CH
3
N
2
(+)Cl-
Br
CH
3
Br
CH
3
NO
2
CH
3
NH
2
CH
3
NHCOCH
3
HNO
3
Sn, HCl (CH
3
CO)
2
O Br
2
H
3
PO
2
-H
3
PO
3
NaNO
2
OH
2
xt
HCl
2. Phn ng ghp:
Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

7
Ion arenddiazoni ArN
2
(+)
l nhng tc nhn electrophin khng mnh, thng ch tc dng vi
nhng cht thm giu mt electron nh amin, phenol,...theo c ch electronphinin:

R - N N
Y H Y R-N=N
S
+
+
E
2

Cu t iazo Cu t azo Hp cht azo
2.1.Phenol v dn xut
Nu cu t azo l phenol, phn ng ghp xy ra v tr para v pH ti u l 9 - 10
chuyn -OH thnh -O
(-)
c hiu ng +C mnh hn. pH cao hn ArN
) (+
N s chuyn thnh ArN
= NOH v Ar - N = N-O
(-)
khng cn tnh electrophin. Th d:

C
6
H
5
- N N
O C
6
H
5
-N=N
S
O
+
+
E
2
(-) (-)

2.2.Amin thm
Nu cu t azo l amin thm bc 3 nh C
6
H
5
- NR
2
pH thun li l 5-9, phn ng cng xy
ra v tr para. Th d:

C
6
H
4
-N N
N(CH
3
)
2
N(CH
3
)
2
C
6
H
5
-N=N
+
+
Phn ng mui iazoni vi amin thm bc mt xy ra nguyn t nit. Th d:

C
6
H
5
- N N
C
6
H
5
-N=N - NH - C
6
H
5
H
2
N - C
6
H
5
+
+

i vi amin thm bc hai nh C
6
H
5
NHCH
3
phn ng xy ra c nit ln v tr para ca
vng thm. Th d:


C
6
H
5
- N N
NHCH
3
C
6
H
5
- N=N NHCH
3
C
6
H
5
- N=N - N(CH
3
)
2
+
+
Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

8

CHNG II: AMINOAXIT - PROTIT

Bi: AMINOAXIT
I. NH NGHA-CU TRC - DANH PHP
1.nh ngha: Aminoaxit l cc HCHC tp chc, phn t c cha ng thi
nhm chc -NH
2
(amino) v -COOH (-cacboxyl)
2.Cng thc tng qut:
CT chung: (NH
2
)
x
R (COOH)
y

x = y hoc x > y hoc y > x
Khi x=1, y= 1, R: no, mch h th CT l
NH
2
- C
n
H
2n
- COOH
VD: C
3
H
7
O
2
N ng phn aa?(2 p)
3.Cu trc: a s cc aa thin nhin l cc , dy L
trng thi rn tn ti ion lng cc, trong dung dch tn ti dng cn bng
V d 1: Cu hnh R/S v D/L ca hu ht cc amino axit l g ? (b) Vit cu hnh tuyt i ca (i) L-
cystein v (ii) L-serin.
(a) S v L
(b) (i)
COO
CH
2
SH
H H
3
N
(ii)
COO
CH
2
OH
H H
3
N



V d: (a) Vit tt c cc ng phn lp th ca threonin (dng cng thc Fischer).
(b) Xc nh L-threonin v cho bit danh php R/S ca n.
(a)
COO
-
CH
3
H
OH
H
3
N
+
H

COO
-
CH
3
+
NH
3
H
H
HO

COO
-
CH
3
H
H
H
3
N
+
HO

COO
-
CH
3
+
NH
3
OH
H
H

racemat-1 (threo) racemat-2 (erythro)

(b) Cc cu hnh tng ng vi racemat-1 l L- v D-threonin, vi racemat-2 l L- v D-
allothreonin, L- c xc nh theo cu hnh ca C

. Nu c mt C bt i trong nhm R, cu
hnh ca n khng lin quan n k hiu D,L hay R,S ca amino axit. L-threonin l (2S,3R). ng
phn lp th dia - (2S,3S)-threonin- c gi l L-allothreonin
4.Danh php:

a,Tn thng:
Axit +K hiu v tr (-NH
2
) [(,,,...)]+ amino + tn thng thng ca axit tng ng

b,Tn quc t:
Axit+v tr nhm -NH
2
+amino+tn quc t ca axit HC.


5.Tnh axit , baz ca aa
Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

9

Tn K hiu Cng thc
Monoaminomonocacboxylic
Glixin Gly H
3
N
+
CH
2
COO
-
Alanin Ala H
3
N
+
CH(CH
3
)COO
-

Valin
*
Val H
3
N
+
CH(i-Pr)COO
-

Leuxin
*
Leu H
3
N
+
CH(i-Bu)COO
-

Isoleuxin
*
ILeu H
3
N
+
CH(s-Bu)COO
-

Serin Ser H
3
N
+
CH(CH
2
OH)COO
-

Threonin
*
Thr H
3
N
+
CH(CHOHCH
3
)COO
-

Monoaminodicacboxylic v dn xut amit
Axit aspatic Asp HOOC-CH
2
-CH(
+
NH
3
)COO
-
Asparagin Asp(NH
2
) H
2
NOC-CH
2
-CH(
+
NH
3
)COO
-

Axit glutamic Glu HOOC-(CH
2
)
2
-CH(
+
NH
3
)COO
-

Glutamin Glu(NH
2
) H
2
NOC-(CH
2
)
2
-CH(
+
NH
3
)COO
-

Diaminomonocacboxylic
Lysin
*
Lys H
3
N
+
-(CH
2
)
4
-CH(NH
2
)COO
-

Hydroxylizin Hylys H
3
N
+
-CH
2
-CHOH-CH
2
-CH
2
-CH(NH
2
)COO
-

Arginin
*
Arg H
2
N
+
=C(NH
2
)-NH-(CH
2
)
3
-CH(NH
2
)COO
-
Aminoaxit cha lu hunh
Systein CySH H
3
N
+
CH(CH
2
SH)COO
-
Cystin CySSCy
-
OOC-CH(
+
NH
3
)CH
2
S-SCH
2
CH(
+
NH
3
)COO
-
Methionin
*
Met CH
3
SCH
2
CH
2
CH(
+
NH
3
)COO
-
Aminoaxit thm
Phenylalanin
*
Phe PhCH
2
CH(
+
NH
3
)COO
-
Tyrosin Tyr p-C
6
H
4
CH
2
CH(
+
NH
3
)COO
-
Aminoaxit d vng

Histidin
*

His
N
HN
CH
2
CH
+
NH
3
COO
-


Prolin

Pro
N
H H
H
COO
-



Hydroxyprolin


Hypro
N
H H
H
COO
-
H
HO



Tryptophan
*


Try
N
H
CH
2
CH
+NH
3
COO
-


Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

10


II. Tnh cht vt l:
Cht rn, khng mu, a s tan tt, c nhit nc tng i cao.

III. Tnh cht ho hc:
1. Tnh cht axit-baz: im ng in
Tnh lng tnh


baz tnh



axit tnh


OH
-
+ H
3
N
+
CHRCOOH H
3
N
+
CHRCOO
-
+
H
2
O
H
2
NCHRCOO
-
+ H
3
O
+
cation A ion lng tnh B anion C
(+1) (0) (-1)
Gi tr pH m ti phn t aminoaxit tn ti dng ion lng cc (I) cn bng v in tch
v khng di chuyn v mt in cc no c c gi l im ng in v k hiu l pH
1
.
Gi tr v im ng in ca cc aminoaxit thin nhin c gii thiu bng 17.1.
im ng in ca cc axit monoaminomonocacboxylic tnh c theo biu thc:

2
2 1
1
a a
pK pK
pH
+
=
Gi tr pK
a1
ng vi nhm -COOH, pK
a2
ng vi nhm .
3
H N
+
V d i vi glyxin, pK
a1
=
9,6 tnh c pH
1
= (2,34 + 9,6) : 2 = 5,97.
Cc aminoaxit c gi tr pH
1
khc nhau nn mt gi tr pH xc nh cc aminoaxit s dch
chuyn v catot hoc anot vi nhng vn tc khc nhau. Da vo c tnh ny ngi ta xy
dng phng php in di phn tch aminoaxit t hn hp ca chng.
2. Tnh cht ca nhm cacboxyl:
a, Phn ng este ho:
Tng t axit cacboxylic, aminoaxit phn ng vi ancol c axit v c xc tc cho este ( dnh
mui). V d:

H
3
N - CH(R) - COO C
2
H
5
OH H
3
N - CH(R) - COOC
2
H
5

OH
2
Cl
+
bo ha kh HCl
+
+ -
+

Ra sn phm bng dung dch NH
3
s thu c este:
H
2
N

- CH(R) - COOC
2
H
5
.
b, Phn ng ecacbolxyl ho:
Phn ng tch CO
2
t nhm cacboxyl xy ra trong c th nh enzim ecacboxyllaza:
H
2
N - CH(R) - COOH
za decaboxyla
R - CH
2
- NH
2
+ CO
2

3. Tnh cht ca nhm amino:
a, Phn ng vi axit nitr HNO
2

Tng t cc amin bc mt, aminoaxit phnu ng vi axit nitr gii phng ra N
2
v to thnh
hiroxiaxxit:
O H N COOH R CH HO HONO O CO R CH N H
2 2 3
) ( ) ( + + +
+

Da vo th tch N
2
thot ra c th tnh c lng aminoaxit trong dung dch.
b, Phn ng eamino ho (tch nhm amino)
Phn ng xy ra trong c th nh enzim, aminoaxit chuyn thnh xetoaxit v NH
3
. V d:
CH
3
- CH(NH
2
) - COOH
[ ]

enzim O ,
CH
3
- C - COOH + NH
3

O
Alamin Axit

piruvic
c, Phn ng ankyl ho hoc aryl ho
Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

11
Nhm amino ca aminoaxit c ankyl ho hoc aryl ho bng dn xut halogen to ra dn
xut N-ankyl hoc N - aryl tng ng. V d :

CH
3
I H
3
N - CH
2
- COO N
H
H
C H
3
CH
2
-COO + +
HI
- +
+
-

F O
2
N
NO
2
H
3
N - CH
2
- COO
O
2
N
NO
2
NH-CH
2
-COOH
- +
+
+ HF
N-(2,4-dinitrophenyl) glyxin
d, Phn ng axyl ho:
Nhm amino ca phn t aminoaxit c axyl ho dng bi halogenua axit trong mi
trng kim. Vd:

O
C
6
H
5
- C - Cl H
3
N - CH(R) - COO
OH /H
2
O
H
O
C
6
H
5
- C - NH(R) - COOH + HCl
- +
+
1)
-
2)
+

Cng c th axyl ha bng anhirit axetic:
Cng c th axyl ha bng anhirit axetic:

O
(CH
3
- CO)
2
O H
3
N - CH(R) - COO
O
CH
3
- C - NH(R) - COOH + CH
3
COOH
+
- +
t
0

e, Phn ng ngng t vi anehit fomic (Phn ng sorenxen)
Aminoaxit phn ng d dng vi anehit fomic to thnh dn xut cha nhm metylenamino:
O H COOH R CH N CH O HCH O CO R CH N H
2 2 3
) ( ) ( + = = +
+

Do nhm amino b kho nn c th chun nhm cacboxyl bng kim. y l phn
ng quan trng dng nh lng aminoaxit v nh gi mc thu phn protein.
4. Tnh cht ca c phn t:
a, Tc dng ca nhit
Cc -aminoaxit (hoc este cachng) khi un nng to thnh iamitvng 6 cnh c gi l
ixetopiperazin, do hai phn t aminoaxit b tch hai phn t nc (hoc hai phn t ancol). V
d:

O
C H
2
N H
NH
CH
2
O
OH
2
NH
3
C H
2
O
C
O
H
3
N-CH
2
C = O O
Dixetpiperazin
+
t
0
+
+
-
-
+



Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

12
NH
2
R - C OC
2
H
5
C
O
H
2
N- CH - R
C = O C
2
H
5
O
O
R-CH
N H
NH
CH-R
O
C
2
H
5
OH
+
+
+
t
0
Diankyldixetopiperazin

Tng t cc amit, cc i xetopiperazin b phn hu trong mi trng axit hoc baz, trc
ht m vng tao thnh hai phn t aminoaxit:

O
C H
2
N H
NH
CH
2
O
H
2
O, H
O
H
3
N CH
2
- C - NH - CH
2
- COOH
H
2
O, H
H
3
N - CH
2
- COO
+
+
(nhm peptit) Dipeptit
+
- +
2

Khi un nng, ipeptit li khp vng to thnh ixetopiperazin.
Cc -aminoaxit b tch NH
3
bi nhit to thnh axit , -khng no:

H
3
N - CH
2
- CH
2
- COO CH
2
=CH-COOH +NH
3
-
+
t
0

Cc va , -aminoaxit di tc dng cuat nhit b tch nc to thnh amit vng, thng
gi l lactam:

CH
2
- CH
2
- CH
2
C = O O NH
3
C=O
C
H
2
C
H
2
C H
2
NH
OH
2
- +
t
o
+
Butirolactam

b, Phn ng to hp cht phc
Cc -aminoaxit phn ng c vi mt s ion kim loi nng cho hp cht phc kh tan,
thng c mu c trng. V d hp cht phc ca glyxin vi Cu
2+
:

OH
2 Cu
O C
1
C H
2
NH
2
O
O C
1
CH
2
N H
2
O
CH
2
- COO
NH
3
Cu(OH)
2
+
-
+
2
+
Kt ta mu xanh
2

5. Phn ng mu ca aminoaxit:
a, Phn ng vi ninhirin
Cc -aminoaxit phn ng vi ninhirin (cn gi l trixeto hirinen hirat) cho sn phm
mu tm xanh tan trong nc (ring prolin cho sn phm mu vng):

Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

13

OH
OH
O
O
R - CH - C O OH
NH
2
OH
H
O
O
NH
3
C O
2
RCH= O
O
O
N
O
O
NH
3
+
+ + +
t m xa n h
+ Nin h id r in
+

Phn ng rt nhy, c th pht hin n microgam -aminoaxit, v vy phn ng ny c
dng phn tch nh tnh v inh lng cc -aminoaxit. nh lng -aminoaxit c th
dng phng php so mu o cng mu dung dch phn ng, hoc dng phng php o th
tch CO
2
.
b, Phn ng xangtoproteic
Cc aminoaxit c gc hirocacbon thm (Phe, Tyr, Trp...) phn ng vi HNO
3
c nng cho
sn phm mu vng.
c, Phn ng vi thuc th Milon
Cc aminoaxit c gc phenol (Tyr...) phn ng vi thuc th Milon (hn hp Hg(NO
3
)
2
v
HNO
3
c) khi un nng cho sn phm mu .
d, Phn ng Pauli
Phn ng Pauli c trng cho tryptophan. Tryptophan phn ng vi axit iazobenzensunfonic
trong dung dch kim cho sn phm c mu anh o.
e, Phn ng Aamkevic v Hopkin
Phn ng c trng cho aminoaxit cha vng inol nh tryptophan. Tryptophan phn ng vi
axit gloxilic (O=CH-COOH) c mt H
2
SO
4
c cho sn phm c mu tm.
g, Phn ng Sacaguchi
Phn ng c cho arginin. Arginin phn ng vi hn hp natri -naphtolat v natri hipobromat
cho sn phm mu .
IV-IU CH AMINOAXIT
1. Thu phn protein
Thu phn protein nh xc tc axit, hoc kim hay enzim thu c hn hp cc L-aminoaxit:

H
2
N-CH
R
CO NH -CH CO -
R'
HN-CH
R"
CO - ...
H
2
O/H
H
2
N-CH
R
COOH H
2
N-CH
R'
CO HN-CH
R"
COOH
+ + ....

Nh cc phng php thch hp (sc, k, in li...) c th tch ring r tng aminoaxit.
2. Amin ho axit -halogencacboxylic (phong php Peckin)
Cho axit -halogencacbylic tc dng vi dung dch amoniac c nhit phng thu c
-aminoaxit.

H
2
N-CH
X
COOH NH
3
H
2
N-CH
NH
3
COO
-
NH
4
Br
+
2
+
+

3. Ankyl ho cc este ca axit aminomalonic N-th
Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

14
Este ca axit aminomolonic N-th (III) c iu ch t ietyl monobrommalonat (I) v kali
phtalimiat (II):

O
O
N
-
BrCH(COOC
2
H
5
)
2
O
O
N
CH(COOC
2
H
5
)
2
K
+
+
-KBr
DietylN-phtalimitmalonat
(I)
(II)
(III)
ietyl N-phtalimit malonat (III) c ankyl ho bi ankyl halogenua hoc hp cht caconyl
, -khng no, sau un nng sn phm ankyl ho trong mi trng axit xy ra qua qu trnh
thu phn este v ecacboxyl ho thu c -aminoaxit:

O
O
N
CH(COOC
2
H
5
)
2
O
O
N
CR(COOC
2
H
5
)
2
H
3
O+
-CO
2
R-CH - COO
NH
3
COOH
COOH
C
2
H
5
OH
(III)
1)Bazo
RX 2)
(III)
-
+
+
+

Phng php ny c dng iu ch nhiu a-aminoaxit, v d methionin, axit glutanic...:

O
O
N
CH(COOC
2
H
5
)
2
C
2
H
5
ONa
C
2
H
5
ONa
CH
3
SCH
2
CH
2
Cl
CH
2
=CH-COOC
2
H
5
H
2
O/H+
H
2
O/H+
CH
3
SCH
2
CH
2
-CH - COO
NH
3
HOOCCH
2
CH
2
-CH - COO
NH
3
(III)
1)
2)
2)
1)
t
o
t
o
-
+
+
-
Me thionin
Axit glutamic
4. Tng hp Streck (Strecker)
Cc -aminoaxit cng c tng hp bng cch thu phn cc -aminnonitrin theo s
phn ng:

RCH=O +NH
3
+ HCN
R-CH-N
N
NH
2
H
2
O/H
R-CH
NH
3
COO
-
+
+
+

5. iu ch v -aminoaxit
Axit - aminocaproic v axit - aminoenantoic (u khng c trong thin nhin) l nguyn
liu quan trng sn xut t capron v t enang.
Axit - aminocaproic c iu ch t oxim ca xiclohexanon. Khi un nng oxim ny vi
H
2
SO
4
c thu c caprolactam, sau thu phn thnh axit -aminocaproic:
Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

15

O
H
2
N-OH
OH
2
N-OH
H
2
SO
4
C
H
2
C
H
2
C=O
C H
2
NH
C
H
2
C
H
2
H
2
O/H
H
2
N-(CH
2
)
5
-COOH
Oxim ca xiclohexanon
c
+

Axit -aminoenantoicc iu ch t etilen v cacbon tetraclorua nh phn ng telome ho
to thnh 1, 1, 1, 7 - tetraclohepan, sau thu phn v amin ho:

CH
2
=CH
2
CCl
4
ClCH
2
-(CH
2
)
5
-CCl
3
H
2
O/H
2
SO
4
ClCH
2
-(CH
2
)
5
-COOH
NH
3
NH
2
CH
2
-(CH
2
)
5
-COOH
3



Bi: PEPTIT
I - Trng thi thin nhin:
Mt s cht peptit c trong c th ngi. V d nh trong m c c cacnozin v anserin (u l
ipeptit), gan v no c glutation (tripeptit). Glutation cn c trong mm la m v mt s loi
nm. Mt s peptit l hormon trong c th sinh vt nh insulin, oxytoxin...
II - Cu trc v danh php:
1. Cu trc
Peptit thin nhin l hp cht polime ca cc oaxit a min , gm t 2 n khong 50 n v
oaxit a min kt hp vi nhau nh cc lin kt peptit.
Lin kt peptit

... - HN-CH
R
CO NH-CH
R1
CO - ...

Nhm peptit
Tu thuc vo s n v (2, 3, 4, ..., n) aminoaxit trong phn t ngi ta phn chia thnh
ipeptit, tripeptit, tetrapeptit...polipeptit. Theo quy c mt peptit c phn t khi trn 10000
c gi l polipeptit; nhng peptit c phn t khi thp hn c gi l oligopeptit.
Trong phn t peptit, u mch cha n v aminoaxit cn nhm -NH
2
(
+
NH
3
) c gi l
u N, cn u mch kia cha n v aminoaxit cn nhm -COOH (hay COO
--
) c gi l
ui C. Theo quy c, u mch c nhm -NH
2
c vit pha bn tri, cn u c nhm -
COOH c vit pha bn phi:

-CH
R
CO NH
H
2
N-CH
R
CO
NH - CH
R
COOH
Aminoaxit u N Aminoaxit u C

Nhm peptit -CO -NH- c cu trc phng, nguyn t H ca nhm -NH- nm v tr anti i
nguyn t O ca nhm cacbonyl. Lin kt peptit C-N mang mt phn c im ca lin kt i
C=N
Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

16
Do vy lin kt peptit kh quay t do xung quanh trc C-N, trong khi kh nng quay t do
ca cc lin kt n gia C

vi nhm peptit l rt ln. l nguyn nhn dn n cu trc xon


ca mch polipeptit (xem bi protein).
Tng t aminoxit, phn t peptit cng tn ti dng ion lng cc, peptit l hp cht
lng tnh.
*Tnh axit v baz
V d: C mt hn hp protit gm pepsin (pH
I
= 1,1), hemoglobin (pH
I
= 6,8) v prolamin
(pH
I
= 12,0). Khi tin hnh in di dung dch protit nu trn pH = 7,0 thi c ba vt cht (xem
hnh)
Xut pht
Cc (+) Cc (-)
A B C

Cho bit mi vt cht c trng cho protit no ? Gii thch.
Bi gii :Vt A l pepsin, vt B l hemoglobin v vt C l prolamin.
Gii thch : Pepsin l protit c tnh axit mnh (pH
I
= 1,1) nn tn ti dng anion khi pH =7,
di tc dng ca in trng s chuyn v cc dng (anot). Hemoglobin (pH
I
= 6,8) hu
nh tn ti lng cc vi in tch bng khng khi pH = 7, do gn nh khng chuyn
dch. Prolamin l protit c tnh baz mnh (pH
I
= 12,0) nn tn ti dng cation khi pH =7,
di tc dng ca in trng s chuyn v cc m (catot).

2. Danh php
Tn ca cc peptit c gi theo quy tc sau:
- Ghp tn cc aminoaxit to nn phnt peptit theo trt t sp xp ca chng trong mch.
- Nhng aminoaxit c nhm cacboxyl tham gia to lin kt peptit c gi tn bng cch i
ui in thnh ui yl (xem bi 17.1), aminoaxit ng cui mch cn nhm cacboxyl (ui C)
c gi nguyn tn. V d:
H
2
N CH
2
CO NH CH(CH
3
) COOH Glyxylalanin (Gly Ala)

H
2
N CH(CH
3
) CO NH CH
2
COOH Alanyl glyxin (Ala Gly)

H
2
N CH
2
CO NH CH CO NH CH
2
COOH Glyxyl phenylalanylglyxin
C
6
H
5
CH
2
(Gly-Phe-Gly)
III- Tnh cht:
1. Tnh cht vt l:
Nhng peptit c phn t khi thp l nhng cht kt tinh tan tt trong nc. Cc peptit c phn
t khi ln l nhng cht v nh hnh, to thnh dung dch keo vi nc.
2. Tnh cht ho hc:
a, Phn ng thu phn:
Cc peptit b thu phn hon ton trong dung dch axit nng hoc dung dch kim nng cho sn
phm cui cng l hn hp cc aminoaxit. Thng thu phn bng dung dch HCl 2N 110
0
C
trong khong 24 - 72 gi. V d: H
+
, t
0


H
2
N-CH
R
CO NH-CH CO -
R'
HN-CH
R"
CO - ... nH
2
O
H
2
N-CH
R
COOH H
2
N-CH
R'
COOH
H
2
N-CH
R"
COOH
+
+ + + ....

Cc peptit c th c thu phn khng hon ton nhng on peptit ngn hn nh cc enzim
c hiu:
Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

17
- Aminoaxit N -u mch c tch ra khi mch nh enzim aminopeptiaza. V d:
aminopeptiaza

H
2
N-CH
R
CO NH-CH CO -
R'
HN-CH
R"
CO - ... nH
2
O
H
2
N-CH
R
COOH H
2
N-CH
R'
CO HN-CH
R"
COOH
+
+ + ....

- Aminoaxit C-u mch c tch ra khi mch nh enzim cacboxipeptiaza.
cacboxipeptiaza
... - HN-CH
R
CO NH-CH CO -
R'
HN-CH
R"
COOH nH
2
O
... - HN-CH
R
CO HN-CH
R'
COOH
H
2
N-CH
R"
COOH
+
+ + ....




- phn cch mt s lin kt peptit xc nh trong phn t peptit (hoc protein) c th dng
cc enzim proteaza nh tripsin, chimotri-psin, pepsin... . Trpin xc tc cho s phn ct lin kt
peptit sau gc lysin hoc arginin. Chimotripsin xc tc cho s phn ct lien kt peptit sau cc
gc phenylalanin, tryptophan, tyrosin, leuxin, axit aspactic hoc axit glu tamic. V d:

NHCHCO-...
...-NHCHCO
R
...-NHCHCOO
R
-
H
3
NCHCO-...
R
1
enzim
R
1
+
+


Enzim Aminoaxit u N
Tripsin Lys, Arg
Chi motripsin Phe, Trp, Tyr
Pepsin Phe, Trp, Tyr, Leu, Asp, Glu

b, Phn ng vi 2,4 - initroflobenzen:
Tng t aminoaxit, nhm -NH
2
ca n v aminoaxit N-u mch phn ng c vi
2,4-initroflobenzen cho dn xut 2,4-initro-phenyl (DNP) mu vng :

O
2
N
F
NO
2
H
2
NCH-CONH-CH-CO-
O
2
N
NO
2
NHCHCONH-CHCO-
R R
R R
+HF +


Phn ng ny c dng xc nh trt t sp xp cc n v aminoixit trong phn t peptit
(Phng php Sanger).
c, Phn ng mu biure
Phn ng mu biure c trng cho lin kt peptit, tt c c peptit c t hai lin kt peptit tr ln
u phn ng vi dung dch CuSO
4
long trong mi trng kim cho dung dch hp cht phc c
mu tm hoc tm .
Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

18
Phn ng biure c dng phntch nh tnh (nhn bit) v phn tch nh lng peptit v
prrotein.
IV - Tng hp peptit:
Khc vi nhiu loi hp cht hu c khc, cc phn ng tng hp (iu ch) peptit rt phc tp.
Khng th tng hp c peptit mong mun nh phn ng trng ngng cc phn t aminoaxit
khc nhau, v s to ra hn hp cc peptit. V d trng hp n gin nht l ngng t hai phn t
aminoaxit khc nhau s to ra 4 ipeptit:

Glixin + Alanin
-H
2
O
Gly-Gly
Ala-Ala
Gly-Ala
Ala-Gly

Do vy tng hp mt peptit c trt t xc nh cc n v aminoaxit trong phn t cn phi
bo v nhm amino hay nhm cacboxyl no khi khng cn chngs tham gia phn ng to ra
lin kt peptit. Nhm bo v cn tho mn mt s tiu chun sau:
- D gn vo phn t aminoaxit.
- Bo v c nhm chc trong iu kin hnh thnh cc lin kt peptit.
- D loi ra m khng nh hng n s tn ti ca cc lin kt peptit.
1. Bo v nhm amino:
Nhm amino thng c bo v bi nhm benzyloxicacbonyl (C
6
H
5
- CH
2
O - C -, cn gi l
O
cacbobenzonxi v c k hiu l C
bz
) bng cch cho aminoaxit phn ng vi benzyl clofomiat
(C
6
H
5
-CH
2
-O-CO-Cl, cacbonbenzoxi clorua) trong dung dch. V d:

C
6
H
5
CH
2
OCOCl H
3
NCH
2
COO
-
C
6
H
5
CH
2
OCONHCH
2
COO
H
3
O
C
6
H
5
CH
2
OCONHCH
2
COOH
+
+ -
dd NaOH
5
o
C 30 pht
-
+
Benzyloxicacbonylglyxyl

Sau khi tng hp c peptit nhm bo v s c loi ra khi phn t peptit nh phn ng
hiro phn:
NHCHCO-...
C
6
H
5
CH
2
-OCONHCHCO
R
H
2
/Pd
C
6
H
5
CH
3
NHCHCO-...
HOCONHCHCO
R
CO
2
NHCHCO-...
H
2
NCHCO
R
R
1
+
R
1
+
R
1

2. Bo v nhm cacboxyl:
Nhm cacbonxyl thng c bo v bng cch chuyn thnh metyl hay etyl hoc benzyl este.
Nhm este d thu phn hn nhm peptit nn c loi ra khi phn t peptit bng cch thu
phn bi dung dch kim:
Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

19

C
6
H
5
CH
3
NHCHCO-...
HOCONHCHCO
R
CO
2
NHCHCO-...
H
2
NCHCO
R
...- C-NHCH(R)-COOCH
3
O
OH/H
2
O
H
3
O+
...- C-NHCH(R
1
)-COOH
O
CH
3
OH
+
R
1
+
R
1
-
+

Ring nhm benzyloxi (C
6
H
5
CH
2
O-) cn c loi nh phn ng hiro phn:

...- C-NHCH-CO(R)OCH
2
C
6
H
5
O
H
2
/Pd
...- C-NH(R)CH-COOH
O
C
6
H
5
CH
3 +

3. Ngng t cc aminoaxit c bo v
Thc hin phn ng ngng t cc aminoaxit c nhm chc c bo v s thu c peptit
mong mun. V d tng hp i peptitthreonylalanin:

C
6
H
5
CH
2
OCONHCH-COOH
H
2
NCHCOOCH
2
C
6
H
5
DDC
-H
2
O
CH
3
CHOH CH
3
C
6
H
5
OCONHCH-CO
CH
3
CHOH
HNCHCOOCH
2
C
6
H
5
CH
3
-NH
2
DDC
-H
2
O
-CH
2
C
6
H
5
H
2
/Pd/C
CH
3
COOH
H
3
NCH-CO
CH
3
CHOH
HNCHCOO
CH
3
C
6
H
5
CH
3
CO
2
+
Alanin bo v -COOH
Cbz-Thr-Ala-
+
_
2
+
+
Threonin bo v

V XC NH CU TRC
xc nh cu trc ca peptit thng thc hin cc bc c bn sau:
1. Xc nh thnh phn cc aminoaxit trong phn t peptit:
Thu phn hon ton peptit thnh hn hp cc aminoaxit (thng thu phn bng dung dch
HCl 6N 110
0
C trong khong 24-72 gi). Sau khi lm sch dung dch thu phn, tch ring tng
aminoaxit nh phng php sc k. nhn bit tng aminoaxit cn tin hnh sc k thm mt
dung dch chun cha hn hp cc aminoaxit bit v c nng xc nh. So snh cc sc k
ca dung dch chun s bit c thnh phn v t l tng aminoaxit trong phn t peptit.
2. Xc nh trnh t sp xp cc n v aminoaxit trong phn t peptit:
2.1. Xc nh aminoaxit u N
- Phng php Sanger
Cho peptit phn ng vi 2,4-initro-flobenzen thu c dn xut 2,4-initrophenyl ca peptit.
Thu phn dn xut ny trong mi trng axit thu c hn hp cc aminoaxit v 2,4-
initrophenyl ca aminoaxit u N, dn xut DNP ca aminoaxit c th nhn bit c bng
cc phng php sc k, t suy ra n v aminoaxit u N:
Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

20
Ph
C=S
NH
CH R
C=O
NH
CH R'
C=O
NH
CH R''
C=O
Ph
N=C=S
NH
2
CH R
C=O
NH
CH R'
C=O
NH
CH R''
C=O
phenyl iso thioxyanat
+
CH R'
C=O
NH
CH R''
C=O
N
O=C
CH
C=S
NH R
Ph
NH
2
phenyl thiohydantoin
+
O
2
N
F
NO
2
O
2
N
NO
2
NHCHCONH-CHCO-
O
2
N NHCHCOOH
NO
2
H
3
N CH-COO
H
2
NCH-CONH-CH-CO-
R R
R
R
+
R R
+
2,4-dinitroflobenzen
HCl, t
o
+
-

N-(2,4-initrophenyl) aminoaxit
- Phng php Edman
Cho peptit tc dng vi phenylosothioxionat C
6
H
5
N=C=S, nhm NH
2
ca n v aminoaxit
u N phn ng to ra dn xut penylisothicacbamonyl peptit (dn xut phenyl thioure ca
peptit), sau cho dn xut thu c tc dng vi HCl trong mitrometan s xy ra s phn ct
lin kt peptit gc aminoaxit u N, to thnh peptit ngn hn v phenylthiohiantoin:






HCl
H
2
O













peptit phenylthiocacbamoylpeptit peptit ngn hn
Sn phm phenylthiohiantoin c nhn bit nh phng php sc k, trn c s so snh vi
cht chun bit c th suy ra aminoaxit u N, peptit ngn hn c tinh ch v li tip tc
thc hin phng php Edman nhn ra n v aminoaxit u N ca n...
2.2. Xc nh aminoaxit u C
Thu phn peptit nh enzim cacboxipeptiaza

-NH-CHR
3
-CO-NH-CHR
2
-CO-CHR
1
-COO
-

tidz cacboxypep
-NH-CHR
3
-CO-NH-CHR
2
-COO
-

+-NH
3
+

CHR
1
-COO
-

Aminoaxit xut hin u tin trong dung dch chnh l aminoaxit u C. Hn ch ca phng
php ny l enzim cacboxipeptidata khng tch c cc aminoaxit ui C l prolin hoc
hiroxiprolin ra khi mch peptit.
2.3. Thu phn tng phn mch peptit
Thu phn peptit nh cc enzim proteaza (tripsin, chimotripsin, pepsin...) thu c hn hp
cc peptit c mch ngn hn; cc peptit ny c tch ring nh phng php sc k, tinh ch
Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

21
N
CH
CH
2
CH
2
SCH
3
H
N
H
C
CH
R
O
O
C
N
H
C H
2
CH
2
O
CO
CH
CH
R
CO
N H
2
CH
3
SCN
+
+
sch r xc nh trnh t sp xp cc n v aminoaxit trong phn t ca chng theo cc phng
php nu trn.
phn ct peptit thnh cc peptit c mch ngn hn cn dng cc tc nhn xian bromua
BrCN. Tc nhn ny ch phn ct mch peptit sau gc methiomin:



BrCN





homoserin lacton
i vi mt mch peptit, nu dng cc xc tc phn ct mch khc nhau s thu c nhng phn
on khc nhau. Chng hn phn ct on mch sau:
Phn ct bng trypsin

Ala Leu Gly Met Lys Trp Phe Arg Ala Ala Ser Met Ala Phe Lys

Phn ct bng BrCN

Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

22

MT S BI TP V HP CHT CA NIT

Cu 1: ( thi HSG quc gia nm 2000-2001)
Xut pht t Brombenzen cha
14
C v tr 1 v cc ha cht v c cn thit khng cha
14
C,
hy iu ch cc hp cht thm cha
14
C v tr 3:
a) anilin b) Iotbenzen c) Axit benzoic
Cu 2: So snh tnh baz ca cc hp cht sau y: R
3
N, R
2
NH, RNH
2

Gii thch v sao c s sp xp ?
Cu 3: (Chn i HSG Tnh 2006- 2007)
Mt pentapeptit (A) khi thu phn hon ton cho 2 mol Gly, 1 mol Ala, 1 mol Val v
1mol Phe. Trong s thu phn tng phn (A) thy c Ala-Gly, Gly-Ala. A tc dng vi HNO
2

khng thy gii phng N
2
. Xc nh cng thc cu to ca A.
Cu 4: Mui C
6
H
5
N
2
+
Cl
-
(phenyliazoni clorua) c sinh ra khi cho C
6
H
5
-NH
2
(anilin) tc
dng vi NaNO
2
trong dung dch HCl nhit thp (0-5
o
C). iu ch c 14,05 gam
C
6
H
5
N
2
+
Cl
-
(vi hiu sut 100%), lng C
6
H
5
-NH
2
v NaNO
2
cn dng va l
A. 0,1 mol v 0,4 mol. B.0,1 mol v 0,2 mol. C.0,1 mol v 0,1 mol. D.0,1 mol v 0,3 mol.
Cu 5: Cho 8,9 gam mt hp cht hu c X c cng thc phn t C
3
H
7
O
2
N phn ng vi
100 ml dung dch NaOH 1,5M. Sau khi phn ng xy ra hon ton, c cn dung dch thu c
11,7 gam cht rn. Cng thc cu to thu gn ca X l
A. HCOOH
3
NCH=CH
2
. B. H
2
NCH
2
CH
2
COOH.
C. CH
2
=CHCOONH
4
. D. H
2
NCH
2
COOCH
3
.
( thi H 2008)
Cu 6: C cc dung dch ring bit sau y:
C
6
HH
5
NH
3
Cl(phenylamoniclorua, H
2
N-CH
2
-CH
2
-CH(NH
2
)-COOH, ClH
3
N-CH
2
-COOH,
HOOC-CH
2
-CH
2
-CH(NH
2
)-COOH, H
2
N-CH
2
-COONa.
S lng cc dung dch c pH <7 l:
A.2 B.5 C.4 D.3
( thi H 2008)
Cu 7: Cho hn hp X gm hai cht hu c c cng cng thc phn t C
2
H
7
NO
2
tc dng va
vi dung dch NaOH v un nng, thu c dung dch Y v 4,48 lt hn hp Z ( ktc) gm
hai kh (u lm xanh giy qu m). T khi hi ca Z i vi H
2
bng 13,75. C cn dung dch
Y thu c khi lng mui khan l (cho H = 1, C = 12, N = 14, O = 16, Na = 23)
A. 16,5 gam. B. 14,3 gam. C. 8,9 gam. D. 15,7 gam.
( thi H 2007)
Cu 8: Bit axit glutamic[ HOOC-CH
2
-CH
2
-

CH(NH
2
)-COOH ] c cc gi tr pK
a
(4,3; 9,7; 2,2)
1. Vit phng trnh in ly ca axit glutamic v tnh im ng in ca n.
2. Vit tn IUPAC v cng thc Fis pH
I
v trn cng thc hy ghi ( trong ngoc) gi
tr pK
a
bn cnh nhm chc thch hp v gii thch v sao.
Cu 9: Tng hp cc aminoaxit cha ng v trong nghin cu sinh hc c ngun
14
C t Ba
14
CO
3

v Na
14
CN v tc nhn etri ho l D
2
O, LiAlD
4
hay D
2
.
(Cho php dng mt s cht khc nh: SOCl
2
, N-phtalimidomalonic este, axetamidomalonic
este, C
2
H
5
ONa...)

+
NH
3

+
NH
3

1. CH
3
-
14
CH COO
-
2. CH
2
CDCOO
-



+
NH
3

+
NH
3

3. (CD
3
)
2
CHCHCOO
-
4. HOO
14
CCH
2
CHCOO
-

Hy vit s iu ch cc cht trn
Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

23
Cu 10: ( thi HSG quc gia - 1997)
Khi thy phn hon ton 1 mol polipeptit X thu c 2 mol CH
3
CH(NH
2
)COOH (Alanin
hay vit tt l Ala), 1 mol HOOC(CH
2
)
2
CH(NH
2
)COOH (Axit glutamic hay Glu), 1 mol
H
2
N(CH
2
)
4
CH(NH
2
)COOH (Lysin hay Lys)
v 1 mol (Histidin hay His)


Nu cho X phn ng vi 2,4-dinitroflobenzen (k hiu ArF) ri mi thy phn th thu c Ala,
Glu, Lys v hp cht :


Mt khc nu thy phn X nh enzim cacboxipeptidaza th thu c Lys v mt tetrapeptit.
Ngoi ra khi thy phn khng hon ton X cho ta cc dipeptit Ala-Glu, Ala-Ala v His-Ala.
1.Xc nh cng thc cu to v tn ca polipeptit X.
2.Sp xp cc amino axit trn theo trt t tng dn pH
I
, bit cc gi tr pH
I
l 3,22; 6,00;
7,59 v 9,74.
3.Vit cng thc cu to dng ch yu ca mi aminoaxit trn cc pH bng 1 v 13.
4.Di tc dng ca enzim thch hp aminoaxit c th b decacboxyl ha (tch nhm
cacboxyl). Vit cng thc cu to cc sn phm decacboxyl ha Ala v His. So snh tnh baz
ca cc nguyn t N trong phn t gia hai sn phm . Gii thch.
Cu 11: ( thi HSG quc gia - 2000)
t chy 0,2 mol hp cht A thuc loi tp chc thu c 26,2 gam kh CO
2
; 12,6 gam hi
H
2
O v 2,24 lt kh N
2
(ktc). Nu t chy 1 mol A cn 3,75 mol O
2
.
1.Xc nh cng thc phn t ca A .
2.Xc nh cng thc cu to v tn A. Bit rng A c tnh cht lng tnh, phn ng vi
axit nitr gii phng nit; vi ancol etylic c axit lm xc tc to thnh hp cht c cng thc
C
5
H
11
O
2
N. Khi un nng A chuyn thnh hp cht vng c cng thc C
6
H
10
N
2
O
2
. Hy vit y
cc phng trnh phn ng xy ra v ghi iu kin (nu c). A c ng phn loi g?
Cu 12: ( thi HSG quc gia - 2001)
1.C mt hn hp protit gm pepsin (pH
I
= 1,1), hemoglobin (pH
I
= 6,8) v prolamin (pH
I

= 12,0). Khi tin hnh in di dung dch protit nu trn pH = 7,0 thi c ba vt cht (xem hnh)
Xut pht
Cc (+) Cc (-)
A B C

Cho bit mi vt cht c trng cho protit no ? Gii thch.
2.Khi thy phn hon ton 1 mol tripeptit X thu c 2 mol axit glutamic
(HOOC(CH
2
)
2
CH(NH
2
)COOH), 1 mol alanin (CH
3
CH(NH
2
)COOH) v 1 mol NH
3
. X khng
phn ng vi 2,4-dinitroflobenzen v X ch c mt nhm cacboxyl t do. Thy phn X nh enzim
cacboxipeptidaza thu c alanin v mt dipeptit Y. Vit cng thc cu to ca X, Y v gi tn
chng.
Cu 13: ( thi HSG quc gia - 2002)
Thu phn mt protein (protit) thu c mt s aminoaxit c cng thc v pK
a
nh sau:
Ala : CH
3
CH(NH
2
)COOH (2,34; 9,69; Ser : HOCH
2
CH(NH
2
)COOH (2,21; 9,15)
Asp : HOOCCH
2
CH(NH
2
)COOH (1,88; 3,65;9,60)
Orn : H
2
N[CH
2
]
3
CH(NH
2
)COOH (2,10; 8,90; 10,50)
Arg : H
2
NC(=NH)NH[CH
2
]
3
CH(NH
2
)COOH (2,17; 9,04; 12,48)
N
N
H
CH
2
CH COOH
NH-Ar
N
N
H
CH
2
CH COOH
NH
2
Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

24
Pro
N
H
COOH
(1,99; 10,60)
1.Vit tn IUPAC v cng thc Fisher pH
I
ca Arg, Asp, Orn. Trn mi cng thc
hy ghi (trong ngoc) gi tr pK
a
bn cnh nhm chc thch hp. Bit nhm -NHC(=NH)NH
2
c
tn l guanidino.
2.Ala v Asp c trong thnh phn cu to ca aspactam (mt cht c ngt cao hn
saccaroz ti 160 ln). Thu phn hon ton aspactam thu c Ala, Asp v CH
3
OH. Cho
aspactam tc dng vi 2,4-dinitroflobenzen ri thu phn th c dn xut 2,4-dinitrophenyl ca
Asp v mt sn phm c cng thc C
4
H
9
NO
2
. Vit cng thc Fisher v tn y ca aspactam,
bit rng nhm -COOH ca Asp khng cn t do.
3.Arg, Pro v Ser c trong thnh phn cu to ca nonapeptit bradikinin. Thu phn
bradikinin sinh ra Pro-Pro-Gly ; Ser-Pro-Phe ; Gly-Phe-Ser ; Pro-Phe-Arg ; Arg-Pro-Pro ; Pro-
Gly-Phe ; Phe-Ser-Pro. (a) Dng k hiu 3 ch ci (Arg, Pro, Gly,...), cho bit trnh t cc
aminoaxit trong phn t bradikinin. (b) Vit cng thc Fisher v cho bit nonapeptit ny c gi
tr pH
I
trong khong no ? ( 6; <6; << 6; > 6; >> 6).
Cu 14: ( thi HSG quc gia - 2003)
1.Hp cht A (C
5
H
11
O
2
N) l mt cht lng quang hot. Kh A bng H
2
c xc tc Ni s
c B (C
5
H
13
N) quang hot. Cho B tc dng vi axit HNO
2
thu c hn hp gm ancol C
quang hot v ancol tert-amylic (2- metyl-2-butanol).
Xc nh cng thc cu to ca A. Dng cng thc cu to, vit phng trnh cc phn
ng to thnh B, C v ancol tert-amylic t A.
2.Hp cht A (C
5
H
9
OBr) khi tc dng vi dung dch it trong kim to kt ta mu vng.
A tc dng vi dung dch NaOH to ra 2 xeton B v C cng c cng thc phn t C
5
H
8
O. B, C
u khng lm mt mu dung dch kalipemanganat lnh, ch c B to kt ta mu vng vi
dung dch it trong kim. Cho B tc dng vi CH
3
MgBr ri vi H
2
O th c D (C
6
H
12
O). D tc
dng vi HBr to ra hai ng phn cu to E v F c cng thc phn t C
6
H
11
Br trong ch c
E lm mt mu dung dch kalipemanganat lnh.
Dng cng thc cu to, vit s phn ng t A to thnh B, C, D, E, F. Vit tn A v
D theo danh php IUPAC.

Cu 15: ( thi HSG quc gia - 2005)
L-Prolin hay axit (S)-piroliin-2-cacboxylic c pK
1
= 1,99 v pK
2
= 10,60. Piroliin
(C
4
H
9
N) l amin vng no nm cnh.
1. Vit cng thc Fis v cng thc phi cnh ca L-prolin. Tnh pH
I
ca hp cht ny.
2. Tnh gn ng t l dng proton ho H
2
A
+
v dng trung ho HA ca prolin
pH = 2,50.
3. Tnh gn ng t l dng eproton ho A

v dng trung ho HA ca prolin
pH = 9,70.
4. T metylamin v cc ho cht cn thit khc (benzen, etyl acrilat, natri etylat v cc
cht v c), hy vit s iu ch N-metyl-4-phenylpiperiin.
Bi 16: ( thi HSG quc gia, Vit Nam - 2007)
1. Thy phn hon ton mt hexapeptit M thu c Ala, Arg, Gly, Ile, Phe v Tyr. Cc
peptit E (cha Phe, Arg) v G (cha Arg, Ile, Phe) c to thnh trong s cc sn phm thy
phn khng hon ton M. Dng 2,4-dinitroflobenzen xc nh c amino axit Ala. Thy phn M
nh tripsin thu c tripeptit A (cha Ala, Arg, Tyr) v mt cht B.
a. Xc nh th t lin kt ca cc amino axit trong M.
b. Amino axit no c pH
I
ln nht v amino axit no c pH
I
nh nht?
Bit cu to chung ca cc amino axit l H
2
N-CHR-COOH
AA: Ala Arg Gly Ile Phe Tyr
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R : CH
3
(CH
2
)
3
NHC(=NH)NH
2
H CH(CH
3
)C
2
H
5
CH
2
C
6
H
5
p-HOC
6
H
4
CH
2

2. Isoleuxin c iu ch theo dy cc phn ng sau (A, B, C, D l k hiu cc cht cn
tm):

A B C D
3
NH
Isoleuxin
C
2
H
5
ONa 2. HCl
Hy cho bit cng thc ca cc cht A, B, C, D v Isoleuxin.
Cu 17: ( chon i tuyn QT 2006)
Ala, Val, Leu l ch vit tt tn cc aminoaxit thin nhin, cng thc ln lt l
CH
3
CH(NH
2
)COOH, (CH
3
)
2
CHCH(NH
2
)COOH, (CH
3
)
2
CHCH
2
CH(NH
2
)COOH.
1. Vit cc phng trnh phn ng tng hp tripeptit Leu-Ala-Val t cc cht:
Ala, Val, Leu, photpho pentaclorua, BOC-Cl (tert-butyloxicacbonyl clorua), ancol
benzylic, DCC (ixiclohexylcacboiimit), axit trifloaxetic, axit axetic, hiro, palai v cacbon.
2. C bao nhiu tripeptit c to thnh m mi tripeptit c 3 aminoaxit trn, nu
khng s dng nhm bo v.
3. Biu din cng thc phi cnh ca tripeptit Leu-Ala-Val.
4. Ghi gi tr pK
a
vo nhm tng ng v tnh pH
I
ca tripeptit ny, bit rng pK
a1
= =
3,42; pK
a2
= 7,94.

CH
Br
CH
3
CH
2
CH
3

2 2 5 2
CH OOC) H (C

KOH . 1

2
Br

0
t
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COO
CHNH
2
CH
2
COO
COOH
CHNH
3
(CH
2
)
3
CH
2
NH
3
OH
H
COO
CHNH
3
(CH
2
)
3
CH
2
NH
3
OH
H

MT S BI TP C LI GII

V d 1: Di tc dng ca in trng, aminoaxit di chuyn v pha in cc no khi
pH < pI, (b) pH > pI v pH = pI ? Gii thch.
Bi gii:
pH < pI: cation A chim u th, nn di chuyn v pha catot, (b) pH > pI : anion C chim u
th nn di chuyn v pha anot v (c) khi pH = pI in tch cn bng nn amino axit khng chuyn
dch.
V d 2: Vit cn bng in ly ca lysin (mt baz) v tnh im ng in ca n.
Xem gi tri pK
a
trong bng
Bi gii:

COO
CHNH
2
(CH
2
)
3
CH
2
NH
3
OH
H

COO
CHNH
2
(CH
2
)
3
CH
2
NH
2

(+2) (+1) (0) (-1)
in tch tng cng ca mi dng c ghi trong ngoc n trn, dng c in tch bng khng
tn ti gia hai dng c pK
a
tng ng l 8,95 v 10,53. Nh vy pI = (8,95+10,53)/2 = 9,74.

V d 3: Vit cn bng in ly ca axit aspatic v tnh im ng in ca n.
Bi gii:

COOH
CHNH
3
CH
2
COOH
OH
H

COO
CHNH
3
CH
2
COOH
OH
H

COO
CHNH
3
CH
2
COO
OH
H


(+1) (0) (-1) (-2)
Dng c in tch bng khng tn ti gia hai dng c pK
a
tng ng l 1,88 v 3,65.
Nh vy pI = (1,88 + 3,65)/2 = 2,77.
V d 4: Khi thy phn hon ton 1 mol tripeptit X thu c 2 mol axit glutamic
[HOOC(CH
2
)
2
CH(NH
2
)COOH], 1 mol alanin [CH
3
CH(NH
2
)COOH] v 1 mol NH
3
. Cht X
khng phn ng vi 2,4-dinitroflobenzen v X ch c mt nhm cacboxyl t do. Thy phn X
nh enzim cacboxipeptidaza thu c alanin v mt dipeptit Y.
Vit cng thc cu to ca X, Y v gi tn chng.
Bi gii:
Xc nh cu to X v Y :
-Thy phn X nh enzim cacboxipeptidaza thu c alanin v mt dipeptit Y aminoaxit C-
u mch l Ala v nh vy tripeptit X c cu to theo trt t : Glu-Glu-Ala.
-X khng phn ng vi 2,4-dinitroflobenzen v X ch c mt nhm cacboxyl t do nhm -
NH
2
ca aminoaxit N-u mch to lactam vi nhm cacboxyl ca Glu th nht.
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27
-Khi thy phn hon ton 1 mol tripeptit X thu c 1 mol NH
3
nhm cacboxyl ca Glu
th hai tn ti dng amit -CONH
2
.
Vy X v Y l :
O C
CH
2
NH CH
CH
2
CO NH CH CO
(CH
2
)
2
CONH
2
NH CH
CH
3
COOH
X :
Glutamolactamylglutaminylalanin

Y :
Glutamolactamylglutamin
O C
CH
2
NH CH
CH
2
CO NH CH COOH
(CH
2
)
2
CONH
2

V d 5: Xc nh cng thc cu to v tn ca A(C
3
H
7
O
2
N). Bit rng A c tnh cht lng tnh,
phn ng vi axit nitr gii phng nit; vi ancol etylic c axit lm xc tc to thnh hp cht c
cng thc C
5
H
11
O
2
N. Khi un nng A chuyn thnh hp cht vng c cng thc C
6
H
10
N
2
O
2
. Hy
vit y cc phng trnh phn ng xy ra v ghi iu kin (nu c). A c ng phn loi g ?

Bi gii:
a) Cng thc cu to ca A :
A phn ng vi axit nitr gii phng nit A cha nhm -NH
2

A phn ng vi ancol etylic to C
5
H
11
O
2
N A cha nhm -COOH
un nng A to hp cht vng C
6
H
10
N
2
O
2
A l -aminoaxit
Cng thc cu to ca A : CH
3
CH(NH
2
)COOH (alanin)
b) Phng trnh phn ng :


2 2 2 2 2 7 3
N
2
1
O H
2
7
CO 3 O
4
15
N O H C + + +

CH
3
CH
NH
2
COOH + HONO CH
3
CH
OH
COOH + N
2
+ H
2
O


CH
3
CH
NH
2
COOH + C
2
H
5
OH CH
3
CH
NH
3
Cl
COOC
2
H
5
+ H
2
O
HCl

CH
3
CH
NH
3
Cl
COOH + NH
3
CH
3
CH
NH
2
COOC
2
H
5
+ NH
4
Cl

CH
3
CH
NH
2
COOH + H
2
O
t
o
2
HN
NH
CH
3
O
CH
3
O

(c) A c ng phn quang hc do phn t c nguyn t cacbon bt i :
H C
CH
3
NH
2
COOH
H
2
N C
CH
3
H
COOH

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V d 6: Xut pht t brombenzen cha
14
C v tr 1 v cc ho cht v c cn thit khng cha
14
C, hy iu ch cc hp cht thm cha
14
C v tr 3 :
a) Anilin ; b) Iotbenzen ; c) Axit benzoic.
Bi gii:
a,

C
14
Br
Mg
ete khan
C
14
MgBr
C
14
MgBr
CO
2
COOMgBr
COOMgBr
H
3
O
COOH
C
14
COOH
HNO
3
H
2
SO
4
C
14
COOH
NO
2
HOH
+
(1)
+
(2)
+
+
(3)
+
+ (4)

C
14
COOH
NO
2
Na
2
CO
3
C
14
NO
2
COONa
HOH
CO
2
C
14
NO
2
COONa
CaO
C
14
NO
2
Na
2
CO
3
C
14
NO
2
C
14
NH
3
Cl
FeCl
3
HOH
C
14
NH
3
Cl
NaOH
C
14
NH
2
NaCl HOH
+
+ + (5)
+ NaOH rn +
(6)
2
2
+ 3 Fe
+ 7 HCl +
3 +
2 (7)
+
+ + (8)

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29
b,
C
14
NH
2
NaNO
2
C
14
N N

C
14
I
N
2 KCl
-
C
14
N N

-
+ +
2 HCl
+
+ NaCl +
2HOH
+ KI
+ +
(9)
(10)
Cl
+
Cl

c,
C
14
N N

C
14
C
N
N
2
CuCl
H
+
C
14
COOH
NH
4
C
14
C
N
+
+
CuCN
-
+
+
2HOH +
+
+
2
Cl
(11)
(12)


V d 7:( thi HSG quc gia 1997)
Thu phn hon ton 1mol polipeptit X cho ta:
2mol CH
3
- CH(NH
2
) - COOH (Alanin hay vit tt l Ala).
1mol (HOOC - CH
2
- CH
2
- CH(NH
2
) - COOH (axit gluconic hay Glu).
1mol H
2
N-(CH
2
)
4
-CH(NH
2
)-COOH (Lizin hay Lis)
1mol (Histidin hay His)


Nu cho X tc dng vi 2,4 (NO
2
)
2
C
6
H
3
F (k hiu ArF) ri mi thy phn th tm c
Ala, Glu, Lys v hp cht


Mt khc nu thu phn X nh enzim cacboxipetidaza th thu c Lys v mt tetrapeptit.
Ngoi ra khi thu phn khng hon ton X cho ta cc ipeptit Ala - Glu, Ala-Ala v His- Ala.
1. Xc nh cng thc cu to v tn ca poliptit X.
2. Sp xp cc aminoaxit trn theo th t tng dn pH
I
(pH
I
c gi l im ng in,
ti pH d aminoaxit tn ti dng ion tng cc trung ho v in tch v khng di chuyn v
mt din cc no c). Bit gi tr pH
I
l 3,22 ; 6,0; 7,59; 9,74.
3. Vit cng thc cu to dng ch yu ca mi aminoaxit trn cc pH bng 1v 13.
N
H
N CH
2
CH
NH
2
COOH
N
H
N CH
2
CH COOH
NH Ar
Chuyn bi dng HSG Ha hu c



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30
H
2
N - CH - C - NH - CH - C - NH - CH - C - NH - CH - C - NH - CH - COOH
CH
3
CH
3 O O O O
N
N
CH
2
H
(CH
2
)
2
COOH
(CH
2
)
2
NH
2
CH
3
- CH - COOH
+NH
3
CH
3
- CH - COO-
NH
2
HOOC - (CH
2
)
2
- CH - COOH
+NH
3
-OOC - (CH
2
)
2
- CH - COO-
NH
2
N
N
CH
2
-CH-COOH
H
H
+NH
3
+
N
N
CH
2
-CH-COO-
H
NH
2
H
3
N - (CH
2
)
4
- CH - COOH
+NH
3
+
H
2
N - (CH
2
)
4
- CH - COO-
NH
2
4. Di tc dng ca enzim thch hp aminoaxit c th b decacboxyl ho (tch nhm
cacboxyl). Vit cng thc cu to ca cc sn phm ecacboxyl ho Ala v His. So snh tnh
baz ca cc nguyn t nit trong phn t gia hai sn phm . Gii thch.

Bi gii:
1. T s mol v cng thc cu to ca cc aminoaxit suy ra X l mt pentapeptit.
T kt ta thu phn sn phm phn ng gia X v ArF suy ra u N (u cha nhm -
NH
2
t do) ca X l His.
T sn phm thu phn X nh enzim cacboxipeptitdaza suy ra u C (u cha nhm -
COOH t do) ca X l Lys.
Khi thu phn khng hon ton X cho cc ipeptit His-Ala, Ala-Ala, Ala-Glu.
Trt t sp xp cc aminoaxit trong mch: His - Ala - Ala - Glu Lys.
Cng thc cu to ca X:






(Th sinh c th vit cng thc trong nhm - CO NH - gia Glu v Lys c to ra bi
nhm COOH v tr ca Glu vi nhm NH
2
v tr ca Lys.
1. Th t tng dn pH
I
:
Glu < Ala < His < Lys
pH
I
3.22 6.00 7.59 9.74
Gii thch: tnh axit ca aminoaxit cng ln th gi tr pH
I
cng nh, tnh baz cng ln th
pH
I
cng ln.
- Glu c pH
I
nh nht (3.22) v s nhm COOH nhiu hn s nhm NH
2
. Mun tn ti
dng HOOC - (CH
2
)
2
CH - COO phi thm H
+
(a v pH thp) nhm -COOH th hai
khng phn li.
NH
2

- Lys c pH
I
ln nht (9.74) v s nhm -NH
2
nhiu hn s nhm -COOH.
- Ala c pH
I
= 6.00 v c mt nhm -COOH v mt nhm -NH
2
.
- His c pH
I
trung gian gia Ala v Lys, v tuy c s nhm -COOH v - NH
2
bng nhau
nhng d vng cha N cng l trung tm baz (tuy yu hn -NH
2
).
3. pH = 1 pH = 13
Ala :



Glu :


His :




Lys:


Chuyn bi dng HSG Ha hu c



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31
CH
3
- CH - COOH
NH
2
enzim
-CO
2
N
N
CH
2
-CH-COOH
H
NH
2
enzim
-CO
2
N
N
CH
2
-CH
2
-NH
2
H
4.
CH
3
CH
2
NH
2

(c)





(d)

- Tnh baz gim dn: N
(a)
> N
(b)
> N
(c)
> N
(d)
.
Gii thch: Tnh baz nguyn t N tng khi mt electron trn n tng. Mt electron
N
(a)
> N
(b)
v N
(a)
lin kt vi gc C
2
H
5
y e, trong khi N
(b)
nh hng bi gc d vng ht
e. Mt e N
(c)
< N
(b)
v N
(c)


trng thi lai ho sp
2
(c m in ln hn nguyn t N
(b)
lai
ho sp
3
). V N
(c)
li lin kt vi nhng nguyn t C lai ho sp
2
(kh nng ht e ca C lai ho sp
2

mnh hn C lai ho sp
3
). N
(d)
khng c tnh baz v khng cn cp electron t do (do tham gia
to h lin kt trong vng thm).

V d 8: ( thi HSG quc gia 2008)
1. a, HSCH
2
CH(NH
2
)COOH (xistein) c cc pKa: 1,96; 8,18; 10,28. Cc cht tng ng
vi n l HOCH
2
CH(NH
2
)COOH (serin), HseCH
2
CH(NH
2
)COOH (selenoxistein), C
3
H
7
NO
5
S (axit
xisteic). Hy xc nh cu hnh R/S i vi serin v axit xisteic.
B, Hy qui kt cc gi tr pKa cho tng nhm chc trong phn t xistein. Vit cng thc
ca xistein khi Ph = 1,5 v 5,5.
2. Sp xp 4 amino axit trn theo th t tng dn gi tr Ph
I
v gii thch s sp xp .
3. Thy phn hon ton mt nonapeptit X thu c Arg, Ala, Met, Ser, Lys, Phe
2
, Val, v
Ile. S dng phn ng ca X vi 2,4-initroflobenzen xc nh c Ala. Thu phn X vi
trypsin thu c pentapeptit (Lys, Met, Ser, Ala, Phe), ipeptit (Arg, Ile) v ipeptit (Val, Phe).
Thu phn X vi BrCN dn n s to thnh mt tripeptit (Ser, Ala, Met) v mt hexapeptit.
Thu phn vi cacboxypeptiaza c X v hexapeptit u cho Val.
Xc nh th t cc amino axit trong X.
Bi gii:
1. a.Xc nh cu hnh
Axit L-xisteic (cu hnh R)
COOH
CH
2
SO
3
H
H
3
N
L-Serin

(cu hnh S)
COO
CH
2
OH
H
H
3
N

b. Gi tr Ph v cng thc ca xistein
pKa (xistein): 1,96 (COOH) ; 8,18 (SH) ; 10,28 (NH
2
)
Ph
I
(xistein) = (1,96 + 8,18) / 2 = 5,07
Ph = 1,5 : HS CH
2
CH (NH
3
) COOH
Ph = 5,5 : HS CH
2
CH (NH
3
) COO
-

2.Trt t Ph
I
Trnh t tng dn Ph
I
: Axit xisteic < selenoxistein < xistein < serin
+
+
Chuyn bi dng HSG Ha hu c



Trng THPT chuyn L Qu n

32
NH CH
3 CH
2
NH
2
NH
2
CH
2
NH
2
O
2
N ,
,
,
3.Xc nh cng thc cng thc ca X
Theo bi xc nh c u N l Ala; u C l Val.
Thy phn vi trypsin thu c: Ala-(Met, Ser, Phe)-Lys
Ile-Arg v Phe-Val
Da vo kt qu thy phn vi BrCN, suy ra: Ala-Ser-Met-Phe-Lys
Vy X l: Ala-Ser-Met-Phe-Lys-Ile-Arg-Phe-Val

V d 9: Sp xp s tng dn tnh baz (c gii thch) ca cc cht trong tng dy sau:
Sp xp s tng dn tnh baz (c gii thch) ca cc cht trong tng dy sau:
1. CH
3
-CH(NH
2
)-COOH , CH
2
=CH-CH
2
-NH
2
, CH
3-
CH
2
-CH
2
-NH
2
, CHC-CH
2
-NH
2
.
2.




Bi gii:
Tnh baz tng theo th t:
1.CH
3
-CH(NH
3
)
+
-COO
-
< CHC-CH
2
-NH
2
< CH
2
=CH-CH
2
-NH
2
< CH
3-
CH
2
-CH
2
-NH
2


Tn ti dng m in C
SP
> C
SP
2 > C
SP
3
ion lng cc

2.

NH
2
O
2
N
CH
2
-NH
2
CH
2
-NH
2
-CH
3
NH
< <
<

Nhm p-O
2
N-C
6
H
4
- Nhm C
6
H
4
-CH
2
- Nhm C
6
H
11
-CH
2
- - Nhm C
6
H
11
-
ht e mnh do c ht e yu y e, lm tng v -CH
3
y e,
nhm -NO
2
(-I -C) mt e trn - Amin bc II
lm gim nhiu mt nhm NH
2

e trn nhm -NH
2













Chuyn bi dng HSG Ha hu c



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33

TI LIU THAM KHO
1.C s ha hc hu c-Thi Don Tnh - NXB GD-Nm 2008
2.Bi tp ha hc hu c-Thi Don Tnh - NXB GD-Nm 2008
3. thi HSG Quc gia cc nm
4.Bi tp ha hc hu c Ng Th Thun - NXB KHKT-Tp 2-Nm 2007
5.Bi tp ha hc hu c Ng Th Thun - NXB KHKT-Tp 2-Nm 2007
6.Bi tp ha hc hu c Triu Qu Hng - NXB GD-Nm 2007
7.Ha hc hu c Hu nh, nh Rng - NXB GD-Nm 2007
8.C ch phn ng ha hc hu c-Trn Quc Sn NXB GD-Nm 2002
9. thi HSG tnh Qung Tr.
10.Mt s vn chn lc ca ha hc Tp 3 NXBGD Nguyn Duy i, Trn
Quc Sn, Nguyn Tnh Dung, Trn Thnh Hu, Nguyn Vn Tng