Tổng hợp một số hợp chất hữu cơ chứa dị vòng piridin, thăm dò hoạt tính kháng khuẩn và khả năng ức chế ăn mòn kim loại của chúng

DAI HOC QUOC GIA H A Npi
TRirdNG DAI HOC KHOA HOC Tl/ NHIEN
*

«!# •!# ftf^ *!« 9S0 * 1 * ^ 1 * ^t#

* ^ *J» rj* *J» »J* *J» *J» *J»

yv-^

TEN DE TAI
^

TONG HdP MOT SO HCfP CHAT HUU CCf
•

•

•

CHUA Dl VONG PIRIDIN, THAM DO HOAT
TINH KHANG KHUAN VA KHA NANG (fC CHE
AN MON KIM LOAI CUA CHIJNG

MA SO: QG-08-08

x^

CHU TRI DE TAI: PGS. TS. TRAN THACH VAN
CAC CAN Bp THAM GIA: ThS. TRAN THI THANH VAN
TS. NGUYEN VAN NGOC

OAI H O C feJUOC ^ i M f^A NOI
TRUNG TAM THONG TIN THU VIEN_

UKim.
HA NOI - 2009


MUC LUC
•

•

I. BAO CAO TOM TAT
n. SUMMARY

2
-*

A. L C > I M 6 D A U

5

B. PHAN NOI DUNG CHINH
}. TONG QVAN VE AZOMETIN VA HOP CHAT THIAZOLIDlNON-4
1.1 TONG QUAN VE AZOMETIN
i.1.1. C4u true dien tir. ddng phan hinh hoc, tinh baza cua azometin
1.1.2 Cac phuang phap tong hop azometin
1.1.3. Pho cua azometin:
1.2. TONG 9 U A N V E HOP CHAT T H I A Z O L I D I N O N - 4 :
1.2.1. Tong quan:

1.2.2. Cac phuang phap t6ng hgrp thiazolidinon-4 [17]:
1.3. U'NG DUNG CUA AZOMETIN:
1.3.1. Hoat tinh sinh hoc cua cac azometin:
1.3.2. Tinh chit Ore ch6 an mon kim loai cua cac azometin:
1.4. PHUONG PHAP NGHIEN CUU CUA DE TAI
2. KET QUA VA Tl-JAO LUAN
2.1. TONG HOP AZOMETIN:
2.1.1. Pl|ian tich kha nang phan img ciia cac amin va andehit chua di vong piridin:
2.1.2 K6t qua tong hop azometin:
2.1.3. Ph6 h6ng ngoai ciJa azometin:
2.1.4. Pho tCr ngoai cua cac azometin:
2.1.5. Ph6 kh6i lugng cua cac azometin:
2.1.6. Pho cong huang tir proton cua cac hgp chat ( ' H - N M R ) :
2.2. TONG HOP B I S - A Z O M E T I N

2.2.1 .Ket qua tong hgp bis-azometin
2.2.2. Pho hong ngoai cua bis-azometin:
2.2.3. Pho tu ngoai cua cac bis-azometin
2.2.5. Ph6 cong huong tu hat nhan'lI-NMR:
2.3. TONG HOP CAC DAN XUAT CUA THIAZOLIDIN-4-ON VA BIS-THlAZOLlDlN-4-ON
2.3.1 Tong hgp cac lhiazolidin-4-on va bis-thiazolidin-4-on:
2.3.2 Pho hong ngoai ciia thiazolidin-4-on va bis- thiazolidin-4-on
2.3.3 Pho khoi lugng ciia cac thiazolidin-4-on va bis-thiazolidin-4-on:
2.3.4 Pho cong huong tu hat nhan 1 H-NMR ciia cac thiazolidin-4-on va bis-thiazolidin-4-on
2.4. KHU'HOA AZOMETIN
2.4.1. Khu hoa azometin
2.4.2. Pho hong ngoai
2.4.3. Plli6 cong huong tu hat nhan 'H-NMR:
2.5. HOATTJNH SINH HOC CUA CAC AZOMETIN:
2.6. KHAO SAT TINH U'C CHE AN MON THEP CT-3 CUA CAC AZOMETIN TRONG MOI

TRUONG AXIT HCl 2M
3. THUC NGHIEM
3.1. TONG HOP AMINOPIRIDIN
3.2. TONG HOP AZOMETIN;
3.3 TONG HOP CAC BIS-AZOMETIN:
3.4. TONG HOPTHIAZONLIDINON-4:
3.5. KHU'HOA AZOMETIN:
3.6. HOAT TiNH SINH HOC CUA CAC AZOMETIN:
3.7. KHAO SAT KHA N A N G U C CHE A N MON THEP CT-3 CUA CAC AZOMETIN:
-/. KfynuAN
TAt LIEU THAM KHAO
C. PHU LUC

\-

^
6
6
b
6
^
t)
^
10
12
12
12
15
/^
15

15
17
20
22
26
30
34

34
38
38
44
46
46
46
49
52
57
57
57
58
60
63
6S
68
68
68
68
68
68

69
~o
^/
73


I. BAO CAO TOM T A T
a. Ten de tai: " Tong hap mot so hgp chdt hiru ca chira di vdng piridin, thdm dd hoat tinh
khdng khudn vd khd ndng itc che dn mdn kim loai cua chung"
Ma so: QG-08-08
b. Chij tn de tai:

PGS. TS. Tran Thach Van

c. Can bg tham gia:
- ThS. Tran Thi Thanh Van
- TS. Nguy6n Van Ngoc
d. Muc tieu va npi dung nghien cuu:
- Muc tieu:
•

Tong hop duac aminopiridin.

•

Tong hop cac azometin chua vong piridin.

•

Chuyen hoa cac azometin thanh thiazolidinon-4 hoac amin bac 2.

•

Khao sat hoat tfnh khang khuan, khang nam va kha nang uc che an mon ciia chiing.

- Npi dung:
•

Tong quan tinh hinh nghien cuu cac chat chua vong piridin theo huang tren.

•

Tong hgp 2-azometinpiridin va 3-azometinpiridin.

•

Tong hgp cac azometin chua vong piridin roi nghien cij*u cau true ciia chiing. Khao sat kha
nang khang khuan, khang nam ma cac ca quan phoi hgp co Xht h6 trg dugc. Khao sat kha
nang irc che an mon kim loai ciia cac azometin.

•

Chuyen hoa azometin thanh thiazolidinon-4 va amin bac 2 roi khao sat cac hoat tfnh kt
tren.

e. Ket qua dat dugc:
+ Ket qud khoa hpc:
•

Da tong hgp dugc 37 azometin va 19 bis-azometin

•

Tong hgp dugc 11 thiazolidinon-4-on va 4 bis-thiazolidin-4-on tu cac azometin va
bis-azometin tuong ung.

•

Da khiY hoa dugc 9 azometin va 2 bis-azometin ve amin bac 2 bang NaBH4

•

Cau tao cua cac azometin, bis-azometin, thiazolidinon-4 va san pham khu hoa dugc
chirng minh bang pho hong ngoai. tu ngoai. pho cgng huong ' H-NMR va pho khoi
lugng.

•

Da thir hoat tinh sinh hgc cua 43 azometin va bis-azometin.

•

Tien har^i khao sat kha nang ire che an mon kim loai theo phuang phap ton hao khoi
lugng dugc 25 mau azometin va bis-azometin.

+ Ket qud cdng bd: Vai ket qua do da cong bo cong trinh sau day:
2


-

Tran Thach Van, Tran Thi Thanh Van, Le Thi Thanh Tra, 2009. "Tong hgp.
nghien cuu cau tao mot so hgp chat azometin va bis-azometin chira di vong
I'
' ,
piridin". Tap chi Hoa hoc, T.47, so 2A, tr. 126-131.

-

Tran Thach Van, Tran Thi Thanh Van, Le Thi Thanh Tra. Cao Thi Huang. Chu
Thi Lanh, 2009. "Tong hgp, nghien cuu cau tao va hoat tinh sinh hgc ciia mot so
azometin chua di vong piridin". Tap chi Hoa hgc, T.47, so 4A. tr.269-274.

-

Tran Thach Van, Tran Thj Thanh Van, Le Thi Thanh Tra, 2009. ''Tong hgp.
nghien cim cau tao va hoat tinh sinh hgc ciia mot so bis-azometin chira di vong
piridin". Tap chi Hoa hgc, T.47, s5 4A, tr.778-782.

•

Dua tren 66 tai nay da gop phan dao tao dugc: Da gop phan dao tao 01 thac sy (Le Thi
Thanh Tra, CH K18), 02 sinh vien K50S (Cao Thj Huang va Chu Thi Lanh) bao ve
thanh cong khoa luSn tot nghiep va 02 sinh vien K51S (Nguyen Thi Nga va Nguydn
Thi Phuong) lam nghien cuu khoa hgc.

f. Tmh hinh su dung kinh phi:
Tong kinh phi dugc cap cho viec thuc hien de tai la 90 trieu dong chii yeu dugc diing de
mua hoa chat thi nghiem. Mot phan khac dugc dimg de thue mudn chuyen mon va lao dong.
Hd noi, ngdy 10 thdng 12 ndm 2009

KHOA HOA HOC

CHU NHIEM DE TAI

P6S-,7^t^H U^^ v'o^t^ll^'
PGS. TS. Tran Thach Van

T R l / d N G DAI HOC KHOA H O C TlT N H I E N

•HO Hif u naoNe

^c.]iY^\.y&^f^'^ ^)l^^^^'^^^^


n. SUMMARY
a. Reaserching Project:
"Synthesis and investigation of anti-bacterial
corrosion inhibition activity of some compounds containing pyridine ring"

and

metallic

Code: QG. 08-08
b. Director:

Tran Thach Van, Prof.Ph.D

c. Members:
- Tran TIiiTlianh Van, M.S

- Nguyen Van Ngoc, Ph.D.
d. Researching Attitudes and Contents:
- Researching

Attitudes:

•

Synthesis of aminopyridine

•

Synthesis of some azomethines containing pyridine ring

•

Transform sofctie azometines into thiazolidinon-4 or amine

• Investigation of anti-bacterial and metallic corrosion inhibition activity of them
- Researching Contents:
•

Synthesis of 2-aminopyridine and 3-aminopyridine pyridinandehid

•

Synthesis of some azomethines containing pyridine ring then determining the
constitutions of the products. Investigation of anti-bacterial and metallic corrosion
inhibition activity of azometines

•

Transform some azometines into thiazolidinon-4 or amine then investigation of antibacterial and metallic corrosion inhibition activity

e. Results:
•

37 azometines and 19 bis-azometines have been synthesized.

•

11 thiazolidinon-4 and 4 bis-thiazolidinon-4 have been synthesized.

•

9 azomethines and 2 bis-azomethines have been disposed.

•

Tlie constitutions of the products have been determined by using IR-, UV-VIS, MS and
NMR spectroscopies

•

Anti-bacterial of 43 azomethines and bis-azomethines have been surr\'aied

•

Metallic corrosion inliibition activity of 25 azomethines and bis-azomethines have been
surrvaied

•

Three reaserching paper has been submitted.

•

The reaserching project has contributed to the graduations of one master two baciielors
and the researchs of two juniors.


A. LCJI MO DAU
Cac azometin con dugc ggi la baza Schiff la nhCmg hgp chat trong phan tu chiia nhom
lien ket azometin ~C=N- kieu R-CH^N-R', trong do R va R' la cac g6c ankyl. ar\i hoac
hetaryl.
Nguoi ta biet den loai hgp chat nay tir lau song chi vai chuc nam gan da\. chiing moi
dugc nghien cuu nti'ieu, nhat la tir khi phat hien thay chung va cac san pham chuyen hoa tir
chiing CO nhieu boat tinh sinh hgc quy gia; nhu tfnh khang kliuan, cliong \icm, dicl nam \a
khang virul. Dac biet la tinh chat ire che an mon rat cao vai nhieu loai kim loai va hgp kim trong
cac moi truang khac nhau.
Cac azometin co kha nang phan img cao, co the tham gia vao nhieu qua trinh sinh hoa va
chuyen hoa hoa hgc khac nhau tao ra nhieu hgp chat c6 the umg dung trong dugc pham. trong
bien tinh cao su, trong hoa phan tich va trong ITnh vuc phong chong an mon va bao ve kim loai...
NhijTig nam gan day, nhieu cong trinh nghien cim ve azometin chira nhan tham. di vong
da dugc cong bo. Nhung vai cac azometin chira dj vong piridin it dugc de cap den. Chfnh vi \ a>
de tai dat ra mot so nhiem vu sau:
•

Tong hgp cac azometin di tir 2-aminopiridin, 3-aminopiridin.

•

Tong hgp cac bis-azometin di tir piridin-2-andehit, piridin-3-andehit va piridin-4andehit.

•

Chuyen hoa cac azometin va bis-azometin thanh cac dan xuat thiazolidinon-4
tuang irng.

•

Khir hoa cac azometin va bis-azometin thanh cac amin bac 2 tuang img.

•

Thii' hoat tfnh sinh hgc ciia cac azometin va bis-azometin da tong hgp dugc.

•

Kliao sat kha nang ire che an mon kim loai ciia cac azometin va bis-azometin.


V

B. PHAN NOI DUNG CHINH
1. TONG QUAN VE AZOMETIN v A HOP CHAT THIAZOLIDINON-4
1.1 TONG QUAN VE AZOMETIN
1.1.1. C5u true dien tu, d6ng phan hinh hoc, tinh baza cua azometin
Phan tir azometin co thi t6n tai a hai dang dong phan cis (syn) va trans (anti).[25.26]
R t .

^ H

R 1

c is ( s y n )

^

H

trans ( a m i )

t-

C.H. Waren va cgng su [25] da nghien cuu cau triic cua N-benzylidenanilin, tinh dugc
goc R2NC va thdy ring dang syn co gia tri goc 253^ va dang anti co gia tri 117^. Momen luang
cue ciia cac phan tu nay la 1,57 D.
V.A.Izmailski va cgng sir [23] da chi ra rang a cac azometin tham co hai kieu he lien
hgp: Su lien hgp nha cac dien tir n (lien hgp TZ-K) va su lien hgp giira cac cap dien tir khong chia
se tren nguyen tir nita ciia azometin va he thong dien tir n trong nhan tham amin (lien hgp n-n).
Chinh sir lien hgp n-Ti nay lam cho nhan tham amin quay mot goc nao do ra khoi mat phang cua
phan tir azometin.
V.I. Minkin va cgng su [13] da co mot loat nhirng cong trinh nghien cuu ve tfnh dong
phang cua azometin. Cac tinh toan ly thuyet cho thay goc khong dong phang la 40-90', con tinh
toan bang phuang phap pho tir ngoai thi goc khong dong phang la 45-60 .
Nguyen tir nita ciia lien ket azometin co cap dien tir khong chia se, do vay nita la trung
tam baza Lewis. Su lien hgp n, 71 co anh huang nhat djnh den lire baza ciia azometin, cac nhom
the a nhan tham hgp phan amin co anh huang ro ret den lire baza ciia phan tir azometin, con cac
nhom the a nhan tham hgp phan andehit co anh huong khong dang ke den tfnli baza cua phan tir

azometin. Cac gia tri pKb cua cac benzylidenanilin nam trong khoang 9-13.
De xac dinh hang s5 pKb tuang doi cua cac baza azometin, nguai ta thuong diing phuang
phap chuan do do the trong axetonitrin hay trong etanol-nuac (1 : 1). Cac gia tri pKb nhan dugc
CO mot su tuong quan tuyen tfnh tot vai cac hang so nhom the Hammelt. Thong so phan irng p
ciia su tuong quan tren luon duang (p>0) chimg to su co mat ciia cac nhom the hut dien tir trong
nhan tham se lam giam mat do dien tir a tren nguyen tir nita va lam giam lire baza cua phan tir
azometin va ngugc lai.
1.1.2 Cac phuong phap tong hop azometin
Cac azometin co the dugc tdng hgp bang cac phuang phap kliac nhau. Sau day la nhung
phuang phap chinh:
1.1.2.1. Phdn ung giua andehit vd amin bac mat
Day la phuang phap thuan Igi nhat de tong hgp cac azometin xuat phat tir chat dau de
kiem, cho hieu suat cao. Phan img nhu sau:
R'-CHO

+R'-NH2

-^

R'CH=NR-

+H2O

Trong do: R va R co the la goc ankyl, aryl hay di vong.


Noi chung, cac azometin beo dieu che tir andehit beo va amin beo khong ben. cac
azometin tham ben vung han. Dac biet cac azometin tham hoan toan thi rat ben virng.
CO che cua phan ung giura andehit va amin bac mot dugc bieu dien bang so do tong qual
sau: [7]

!:

(1)
^ ^

1
*
2
R—CH-NHj—R

^

O"
1

2

R—CH-NH
OH

{2)

R

1

^ >

2

R—CH=N-R

+

HnO

(1)

Khao sat mot so lan phan ung loai nay bang quang pho nguai ta nhan thay vach hap thu
ciia nhom C ^ O bien di rat nlianh, tham chi co khi bien het truac khi xuat hien vach hap thu ciia
nhom C = N; dieu nay chimg to sinh ra hgp chat trung gian (I).
Xuc tac cho phan ung la axit hoac baza cho ca hai giai doan tan cong nucleophin ciia
amin vao nhom cacbpnyl (1) va giai doan tach nuac de tao thanh azometin (2). Khi diing xiic tac
axit, CO che phan img dien ra nhu sau:
1^

^ ^

+

1

R—NHn

1

+

2

I

OH
1

c

>

i^-

2

R—Chf-NH

-^2^

R

1

^

+

2

"^^

R—ChF^Nhf-R

1

^

2

R-LCH=N-R

^oti (D
Con khi sir dung baza lam xuc tac, ca che dien ra nhu sau:
R-NH2

1 ^

+

B"

^

'

R-CH^^O

^

2

+

R-NH"

-

R-NH

1

=s=^

2

R1_CI-HNH

R'^

+B^

-^

O

^
-^

1

r>.

,

R—ChH—NH-R
-V OH

-Ufl
<

^

R—CH=N-R^

Dac trung cua phan ung la sir thay d6i ca ch§ theo sir thay d6i pH ciia phan img [13]. Khi
tang tinh axit, pH giam, toe do tach nuac tang nhung tang ndng do amin a dang proton hoa, l6c
do phan img cgng giam. Giai doan quyet djnh toe do la giai doan cgng nucleophin. Klii tang gia
tri pH. giam tinh axit, su proton hoa hgp chdt cgng giam, giai doan tach nuac cham va tra thanh
giai doan quyet dinh toe do phan img.
1.1.2.2. Phdn dng khfrhod amit the [lj
0-CH3-C6H4-CO-NH-C6H5

SnCl.,.
4

- ^ ^

0-CH.-C6H4-C-N-C0H5

0-CH3-C6H4-CH-N-C6H5 (62-70%)

I

CI


Han che cua phuong phap nay la viec khir hoa khong chgn lgc, dong thai cac san pham
trung gian de bi thuy phan.
1.1.2.3. Di tir hpp chdt azo vd metylaren
Phan une dien ra nhu sau:
^
CH3-N=N-C6H5 + CH3-C6H5

t° cao

•

CfeHs-N^CH-CftHs

-QH5NH3
/. 1.2.4. Di tir hpp chdt tham cd nhdm metyl hoat ddng vd hcrp chdt nitrozo
/—\
(H3C)2N-Hf V N O +

O2N.
/—\
HgC-^f V N O 2

0
Na2C03, t
^

O^N

(HaQjN—^

' ^ N = C H ^ ^

^

H2O

OoN

1.1.2.5. Bdng phdn Ung giUa andehit tham vd hap chdt nitro tham
Phan irng ciia andehit tham va hgp chat nitro tham trong cacbon oxit vai sir co mat ciia
hgp chat chira paladi va cac hgp chat c6 chira nita, photpho va Fe2Mo7024 cho san pham
azometin. Thi du hon hgp cua benzandehit, nitrobezen, phuc Cb-piridin va CO trong benzen a
150 atm, 230"C trong 5 gia cho benzyliden vai hieu suat 7 1 % [10].
CftHs - CHO + C6H5NO2
^^Q^^"^-^h
C6H5CH=N-C6H5
1.1.2.6. Ngung tu cdc hpp chat nitro beo hay thorn beo cd nhdm a-metylen vai cdc nitrozoaren
Phan img nay xay ra vai su co mat cua natri hidroxit hay natri xianua [19].
Cf,H5CH2NO^'+ HO

//

NaCN

\s—K\(ru^\.
N(CH3)2

^^ uH ^nC R —n C—= M

N
's'-e

//

\s

N{CH3);

70

1.1.2.7. Bdng phdn ung giCta nitroaren vd cdc

a-hetarylaxetonitrin.

Phan img xay ra khi co mat kiem, hieu suat dat tir 50-80%).
O7N
~N

CH2-CN

w/ 4

+ C2H5OH
CH2-CH2-C1

KOH

CH3

N
CH3

CH=N

(\
\

^/

/)—N-f-CH2-CH2-CI
^
'2

1.1.2.8. Di td' cdc di vdng chua nita cd nhdm metyl hoat ddng vd cdc nitrozoaren.
Phuang phap nay dat hieu suat tir 50-70%).
+

O.N

•N-(-CH2-CI-l2-OH

\\

//

CH=N

•N-(-

\\

CH2-CH2-OH j

//

Trong cac phuang phap tong hgp azometin da neu tren thi phuang phap di tir andehit va
amin bac 1 la thuan Igi va pho bien hon ca.


1.1.3. Pho cua azometin:
1.1.3.1. Pho hdng ngoai cda azometin:
Trong pho hong ngoai cua cac azometin co dinh hap thu nam trong vimg 1590-1690 c m '
dac trung cho dao dgng hoa tri ciia nh6m lien ket azometin. Vi tri vach hap thu nay phu thugc
vao ban chat ciia cac nhom gan vai nhom lien ket azometin. Thuong thi cac azometin beo co
vach vc=N nam a so song cao han cac azometin beo tham va tham. Dung moi anh huong kliong
dang ke den cuong do va vi tri cua vach nay, nhung khi thay doi nhom the hut dien tir thi cucmg
do cua vach DC-N giam di va ngugc lai. Tinh dong phang cua phan tir cung co anh huang den
cuong do ciia vach nay.
1.1.3.2. Phd tir ngoai cua azometin:
Pho tir ngoai CLia azometin cung phu thugc rat nhieu vao ban chat ciia cac nhom the gan
vai lien ket azometin, vao tfnh dong phang ciia phan tir va vao ban chat ciia dung moi. So dai hap
thu CO the la 2, 3 hoac 4 dai tuy theo timg day azometin, song thuong chi co tir 2-3 cue dai hap
thu nam trong viing 210-230, 240-270 va 320-390nm, cue dai hap thu thir 4 nam trong vimg 420480nm vai cuong do yeu va doi khi xuat hien dang diem uon va dac trung cho buac nhay dien tir
n-7c . Cue dai hap thu a viing 240-270nm doi khi tach thanh hai dai.
1.1.3.3. Phd khdi luang cua cdc azometin:
Pho khoi lugng ciia cac azometin thuong cho pick ion phan tir rat manh, chfnli vi vay pho
khoi lugng la phuang phap phan tfch hieu qua nhat trong viec chimg minh cau triic ciia cac
azometin. Ngoai ra dua vao ty le chieu cao giira cac pick trong pho do chung ta c6 the de dang
tinh dugc cong thirc cgng cua azometin va ket qua nay la mot yeu to gop phan khdng dinh cdu

triic phan tir chat da tong hgp.
/. 1.3.4. Phd cdng hudng tir hat nhdn ^H-NMR cua cdc azometin:
Pho H-NMR la phuang phap chirng minh chfnh xac nhat cau triic ciia azometin. 1 rC-n
pho H-NMR ciia cac azometin thuong thay xuat hien tfn hieu cgng huang ndm trong khoang lii'
8-9 ppm, dac trung cho proton a lien ket -CH=N-. Thong thuong proton nay cho tfn hieu a dang
singlet voi cuong do manh, tuy thugc vao nhom th§ trong_phan tir azometin ma do dich chuyan
hoa hgc cua proton nay co su khac nhau chut it.
1.2. TONG QUAN VE HOP CHAT THIAZOLIDINON-4:
1.2.1. Tong quan:
Thiazolidinon^ la dan xuat ciia thiazolidin co nhom (C=0) 6 vi tri s6 4. Co cong thirc
nhu sau:
•N-H

Sthiazolidinon-4

r
Nhieu hgp chat di vong thiazolidinon-4 da dugc h\k d§n nho nhung hoat tinh sinh hgc da
dang. Su co mat cua nhom chuyin nguyen t6 N-C-S va nhom C - 0 trong loai hgp chdt nay da
quyet dinli hang loat tinh chat sinh hgc quy gia nhu gay me, gay te, kliang amip, ch6ng co gifit.
chong lao, chong nhiem kliuan, tdy giun va diet ndm. Viec t5ng hgp va nghien ciru \h cac hgp
chat mai co chira he vong thiazolidinon-4 luon dugc nhiiu nguoi quan tam \ a no giu mot \'i tri
quan trgng trong ITnh vuc nghien ciiu vk. cac hgp chdt di vong.


1.2.2. Cac phirong phap t6ng hop thiazolidinon-4 [17]:
1.2.2.1. Tong hpTfi thiazolidinon-4 tir cdc axit a-halogen,
Ojp- khong no hoac este cda cdc axit do:

a-hydroxiankanoic,

cdc axit

a. Phan ung voi dithiocacbamat:
Trong phan img nay nguai ta cho amin bac mot tac dung vai eacbondisunfua khi co mat
bazo, sau do cho san phdm dithiocacbamat thu dugc tac dung vai axit tuang img. Thf du:
R. NH, . CS2 ^ ^ ^

R-NH-C-SNHR3' C^CH^COONa

R ~ N H - C - S — CH2C00Na

«- R N — (TO
SC
CH.

I

Phan img thong thuong dugc tien hanh trong etanol thu dugc cac dan xuat
2-thionthiazolidinon- 4 the a vi tri 3.
b. Phan irng vai thidure:
Cac dan xuat 2-iminothiazolidinon-4 dugc dieu che bang phan ung cua axit cloaxetic,
este hoac amit ciia no voi thioure, thioure doi xung hoac bat doi xung :
R,-N =C
Q

•HX, -H 2O

N - R-,
p Q

S

/

II

•

•

N H - C - N H - R 2 ^ R-CH-COOH
X
-HX,-H 2O
H
R

Ngudi ta CO the diing etanol khan, benzen khan de lam dung moi phan ung vi cac iniin dc
bi thuy phan trong moi truong axit. Do vay nguoi ta hay dimg axetat natri CHsCOONa hoac
amin bac ba nhu piridin de loai bo axit HCl tao thanh trong phan img.
1.2.2.2. Bdng phdn irng ciia di (a-cacboxylankyl)-trithiocacbamat

vdi amin bac mat

Phan img xay ra nhu sau:
C^Hs NH. + SC(SCHRCOOH) 2
> K : 6 H 5 - N —

I
sc

^^CgHs NHCS- S- CHR- COOH ^ CO

1
CHR

1.2.2.3. Phdn irng chuyen hod cua azometin vdi axit

a-thiocacboxylic:

Do cac nguyen tir nita va cacbon co do am dien khac nhau (C= 2,5; N - 3,0) nen lien ket
-CH=N- luon bi phan cue ve phia nguyen tir N lam cho mat do electron tren nguyen tir N cao
hon tren nguyen tir C. Cac tfnh toan lugng tir cho thay dien tfch hieu dung tren nguyen tir C va N
ciia lien ket azometin la khac nhau: nguyen tir N mang dien tich am con nguyen tir C mang dien
tich duong.
-0.1446

f) ,^7-^

l^-CgHs

N-C4H9

CgHj-CH

C(,H,-CH

-0.0285

^ - +0 1703

10


Nhu vay trong phan tir azometin xuat hien hai trung tam phan ung kliac nhau: trung tam
electrophin tren nguyen tir C va trung tam nucleophin tren nguyen tir N. Vi vay cac azometin co
the tham gia vao nhieu loai phan ung khac nhau. Cac azometin phan img voi axit
a-thiocacboxylic cho cac thiazolidinon-4 chua cac nhom the o vi trf so 2 va 3 ciia vong. Phan
img dugc tien hanh trong ete khan hoac benzen khan. Muon tao ra thiazolidinon-4 khong co
nhom the a vi tri so 5 nguoi ta cho axit thioglycolic phan irng vai azometin.
R - CH = N - R^ + HSCH2COOH

Co che cua phan img tong hgp thiazolidinon-4 tir bazo Schiff va axit thioglicolic lan dau
tien dugc Brawn dua ra vao nam 1961 nhu sau :
Co so ciia CO che Brawn la sir phan li cua nhom thiol SH.
HSCH2COOH ^ H+ + -SCH2COOH
V
Giai doan (1) anion thiolat SCH2COOH cgng hgp vao nguyen tir cacbon-zometin tao ra
kien ket C-S va trung tam dien tfch am tren nguyen tir nito-azometin. Giai doan (2) la sir ket hgp
voi proton tao thanli hgp chat trung gian va cuoi ciing la sir loai nuoc dong vong.
Co che phan img theo F.C.Brawn dugc mo ta nhu sau:
0A©
R^-CH-N

R2 +

cham
'^"- ^

SCH^COGH

®
Ri-CH-N
R2
SCH2COOH

H^
^

>

nhanh
«- Ri-CH-NH—R2
SCH2COOH

^
'"2^

R.-HC—N
Ro
^
c^o

Vao nam 1977, khi nghien cim tong hgp mot so thiazolidinon-4 co chua he v6ng
2,2'-dithienyl, Lipkin lai dua ra mot co che khac cho phan ung tren :
D fS^^
Ri-
D
H*
r. %. .u,

r.
R2—^^^—»- R i - C H - N H — R 2

SCHXCOH
^

(1)

Ri-CH-NH—R2
SCH2C00H

(2)

(3) 3, R^_HC—N
-np

s

R2

c=o

Hai CO che do Lipkin va Brawn de ra hoan toan trai ngugc nhau. Theo Lipkin thi co ch§
la cgng hgp ai dien tir (proton H"" tan cong truoc), con Bravm thi cho ring co ch§ la cgng hap ai
nhan (anion "SCH2COOH tan cong truoc). So sanh hai co chi tren nay chiing ta thdy rdng co chi
cgng hgp ai nhan do Brawn de ra co phdn hgp li hon vi anion •SCH2COOH tuy co kich thuoc Ion
hon proton H^ song no co tfnh nucleophin lan hon so voi nito mang dien tich am phdn trong lien
ket azometin. Do do anion "SCH2COOH tdn cong vao cacbon mang dien tich duong de han la
proton H"" tan cong vao nito mang dien tich am.
A.R. Surrey [16] cung tan thanh co che do Brawn de ra. Ong cho rdng giai doan ddu ciia

phan irng la sir tdn cong ciia anion "SCH2COOH va co kem theo hien tugng phat nhiet, tilp sau
do la loai nuac va dong vong. Ong da tach dugc san phdm (A) khi tiln hanh dun axit
N-benzylidenantrannilic voi axit thioglicolic trong benzen khan:

11


COOH

COOH
HSCH,COOH

CH^
SCH; COOff
(A)

Theo Erlenmeyer va Oberiin [20] thi cac san pham (A) co the chuyen thanh
thiazolidinon-4 bdng each dun nong chung trong dung moi dioxan voi sir co mat ciia P2O5 trong
khoang thoi gian ia 30 phut.
Voi nhirng co ehi da dl cap a tren thi se co nhieu yeu to anh huong toi klia nang phan
irng ciia bazo azometin va do do anh huong toi hieu suat phan ung.
•

Theo Brawn [21] khi dien tfch duong phan cua cacbon nhom azometin cang lan thi anion
'SCH2COOH tdn cong cang de va ngugc lai. Do do, nhom the hut dien tii" lien ket voi
cacbon nhom metin se thuc day phan img xay ra thuan Igi, nhom the day dien tii" sc gay
kho khan cho phan ung. Cac nhom thi lien ket voi nito chi anh huong toi dien tfch duong
phdn ciia cacbon metin nho hieu img lien hgp hoac sieu lien hgp do do it gay anh huang
den qua trinh va hieu suat ciia phan img.

•

Theo Lipkin^su co mat ciia nhom the day dien tir lien ket voi nito ciia bazo azometin lam
tang tfnh bazo ciia azometin do do lam tang kha nang cgng hgp proton H"^, hieu suat phan
irng lang. Ngugc lai, nhom hut dien tir lien ket voi nito se lam giam hieu suat phan img vi
lam giam tfnh bazo ciia nito.

•

v l lilu lugng axit thioglicolic da so cac ket qua thirc nghiem cho thay rang khong anh
huong nhilu idm tien trinh phan img. Nhung G.Ferech [22] da chi ra rang neu diing qua
du (khoang 5-6 ldn so voi lieu lugng tfnh theo If thuyet) thi lai thu dugc thioaxetan va
mecaptan.
HSCH2COOH
/SCH2COOH ,
R,- CH= N - R.
'
«- R,- CH<
^
+ R.NH.HSCH.COOH
^SCH2C00H
Ngoai ra con mot so yeu to khac anli huong den phan img nhu nhiet do, dung moi va thai
gian phan img. Thdng thuong hay diing dung moi la benzen khan, dun hoi liru each thuy
va thai gian thi tuy thugc vao cac chat dau c6 the tir 4- 6gia.

•

v.
1.3. UTNG DUNG CUA AZOMETIN:
1.3.1. Hoat tinh sinh hoc ciia cac azometin:

Cac azometin tham gia vao qua trinh trao doi aminoaxit, chung cung la san pham trung
gian trong qua trinh tong hgp trong cac qua trinh tong hgp cac peptit. Cac azometin cung co hoat
tinh sinh hgc quy nhu: hoat tinh khang khuan, khang virut, chong viem, khang lao, chong loan
nhjp tim, chong co that, lam gian mach mau, chong viem phoi, giam dau, hoat tfnh iic che enzini,
diet nam...
1.3.2. Tinh chat uc che an mon kim loai cua cac azometin:
1.3.2.1. Sir dn mon [4]:
Hien tugng an mon kim loai la sir pha buy kim loai do cac tac nhan hoa ligc cua moi
truang gay ra (trong nghTa rgng nen quan niem la sir an mon vat lieu). Ngay nay, trong mot ngliTa
tuong doi su pha hu\; kim loai do tac nhan hoa hgc ciia moi truang gay ra xa\' ra theo hai ca che:
an mon hoa hgc va an mon dien hoa, an mon sinh hgc [5].
12


An mon theo ca che hoa hgc (eon ggi la sir an mon hoa hgc) la su pha huy kim loai bai
phan img hoa hgc di the khi be mat kim loai tiep xuc vai moi trudng gay an mon. khi do kim loai
bi chuyen thanh ion kim loai di vao moi truong trong ciing mot giai doan.
An mon dien hoa hgc-la su phan huy kim loai bdi qua trinh tuong tac ciia moi truong an
mon voi bl mat kim loai theo co chi dien hoa. Qua trinh pha huy kim loai theo co che nay khong
phai xay ra Irong mot giai doan va lai nhieu vi trf khac nhau tren be mat kim loai.
Theo cac tai lieu cong bo tren the giai gan day nguoi ta khang dinh rang sir an mon kim
loai ve tong the gay thiel hai dang ke cho nen kinh te quoc dan |6|. sir thiet hai na\' chicm khtiang
gan 4% tong thu nhap qu6c dan doi voi nhirng nuoc cong nghiep phat trien. Vi vay. vice nghien
ciru hien tugng an mon va cac bien phap ngan ngira han che su pha buy kim loai. vat lieu tren
cac cau kien: Cac tau tren bien, cau, cac cong trinh xay dung ven bien, cac thiet bi san xuat hoa
chdt v.v...lamgt vdhdl rat co y ngliTa ve mat khoa hgc cung nhu thuc tien.
1.3.2.2. Cdc phuang phdp xac dinh tdc dp dn mdn kim loai :
1.3.2.2.1. Phuang phdp tdn hao khdi luang [2].
Phuong phap ton hao khoi lugng la phucrng phap ngam mau thir trong mot dung dich an
mon, la mot phep thir don gian. Tuy nhien cac dieu kien an mon ciia thi nghiem phai dugc khong

che chat che de dam bao kit qua lap di lap lai. Phuang phap nay dua tren su thay doi khoi lugng
mau kim loai sau mot thai gian ngam trong moi trudng an mon. Kfch thuoc mau cung c6 vai tro
quan trgng, ti le giira dien tfch be mat va khoi lugng mau thir cang cao thi cang tot. Chgn ti le
nay cue dai sc cho phep tien hanh thf nghiem trong thdi gian ngan nhat.
Co cac chi so dinh lugng khac nhau danh gia hieu qua tac dung ire che nhu do bong ciia
be mat, chieu sau ciia cac vet an mon, do thay doi khoi lugng ciia mau...nhirng clii so quan Irong
nhat la toe do an mon ki hieu la P. Toe do an mon la do thay doi khoi lugng ciia mau kim loai
sau mot dem vi thdi gian, tfnh cho mot don vi dien tfch be mat:
^ P=Am/S.t
Trong do:
+ Am la su thay doi khoi lugng ciia mau sau thdi gian ngam t (g)
+ S la dien tfch be mat ciia mau tiep xiic vdi moi trudng ngam
Kha nang ire che ciia chat ire che dugc danh gia bang hieu qua ire che y hay mire do bao
ve Z.
Hieu qua ire che cho biet chat ire che lam cham toe do an mon bao nhieu lan va dugc tfnh
theo cong thirc sau:
7= P/Po
Trong do: P: la toe do an mon kim loai khi co chat ire che.
Po: la toe do an mon kim loai klii khong c6 chat ire che.
N4irc do bao ve Z dac trung day dii cho su ire che an mon va dugc tinh theo cong thiic sau:
t:
'

P -P
Z=^—100%

I lien na\' phuong phap ton hao khoi lugng van la phuong phap re tien nhat \ix dugc su
dung rgng rai trong nghien ciai chat ire che. TUN' nhien, ban che ciia phuang phap nay la a cho
kho giai ihfch dugc co che tac dung ciia chat ire che.
1.3.2.2.2. Phuang phdp the tich [3]:

13


Sir an mdn dien hoa luon luon co hai phan ung gan lien vdi nhau, dd la su hoa tan kim
loai (tai anot) va kem theo phan ung giai ph6ng hidro hoac tieu thu oxi tren catot ciia pin an mon.
Vi vay, ngoai viec diing phuong phap trgng lugng danh gia toe do an mdn bang sir hao
tin trgng lugng cdn c6 thi danh gia tdc do an mdn thong qua the tfch khf hidro thoat dugc giai
phdng ra hoac the tich khi oxi bi tieu thu.
1.3.2.2.3. Cdc phuang phdp phdn tich [3J:
DQ xac dinh toe do an mon kim loai ngudi ta xac djnh nong do ion kim loai bi hoa tan
vao moi trudng xam thuc. tir do suy ra tic do an mon. Co the diing cac phuang phiip plian lich
dinh lugng, vf du phuong phap quang phi, phuong phap hap phu nguyen tir, phuang phap cue
pho...
1.3.2.2.4. Phuang phdp dien hod [3]:
Mot uu dilm quan trgng ciia phuong phap dien hoa la cho phep xac dinh dugc toe do an mon
kim loai trong mot thdi gian ngdn va chinh xac vdi dieu kien thf nghiem dugc tien hanh mot each
than trgng va dung quy each. Co thi dimg phuang phap do dien hoa de xac dinh toe do an mon kim
loai trong dilu kien gia tic dl so sanh vdi nhung thf ngliiem trong dieu kien tu nhien. Phuong phap
nay se dem lai kit qua kha phii hgp vdi dieu kien tu nhien neu chgn dung dich va dieu kien mo
phong phan anh dugc nhimg ylu t l gdn sat thuc tl hien trudng. Trong trudng hgp ngugc lai, neu
dieu kien do dien hoa khong phii hgp vdi dieu kien thuc te gay ra su sai sot tram trgng.
Trong qua trinh an mon kim loai xay ra chi gan vdi sir khir ion H"^ trong dung dich hoac
la su tieu thu oxi trong dung djch, thi viec do dien hoa se dem lai ket qua kha phii hgp vdi dieu
kien thuc te .
1.3.2.3. Khd ndng ire che dn mdn cua azometin:
Gdn day, cac cong trinh nghien cim da chi ra cac azometin ciang co boat tfnh ire che an
mon kim loai.
Nam 1986, azometin N-(2-mecaptophenyl) salixylidenimin (BBS) ciing vdi cac amin
tuong img dugc thir nghiem lam chat ire che an mon cho dong trong dung djch NaCl 0,1M vdi

dung moi la nirdc-etanol 25% ve the tfch d 30"C [23,24]. Cac ket qua nghien cim cho thay toe do
an mon giam dang ke khi co mat cua BBS. Ngoai ra, ket qua nghien cuu cdn cho thay cac
azometin co kha nang ire che an mon cao ban cac andehit va amin tuong irng .
Nam 1991, Abon-El- Wafa va H.M.Moustafa [23] da nghien cuu kha nang ire che an
mon ding thau 70/30 cua 2-(o-OH, p-OH, ;?-0CH3, va ;;-N(CH3)2
bezylliden)
hydrozonbenzothiazol. Ket qua ehi ra azometin chua nhdm the o-OH tren phan andehit co kha
nang ire che an mon ldn nhat trong khoang nong do (1.10'^ M ^ 7.10'^ M), trong khi cac
azometin chira nhomp-OH lai c6 kha nang ire che cao d nong do 0,7. lO"'^ ^ 7.10""^ M. Cac yeu
to anh hudng den kha nang ire che an mon nhu: nong do, cau true, nh6m chirc, vi trf, anh hudng
khong gian ciing nhu ban chat va do ben ciia cac phirc dugc tao thanh giiJa cac azometin vdi kim
loai cung da dugc nghien cim va thao luan.
Nam 1996, M.A.Elmorci va M.Gaber [25] da nghien cim tong hgp cac phirc chat ciia
azometin thu dugc tir sunphamethazin va salixylandehit vdi cac ion Co(II), Ni(II), Cu(II) theo ti le
1:1. Sir ire che an mdn dong khi co, khong co azometin va cac phirc chat dugc nghien ciru trong
dung dich HNO3 0,3M. Ket qua cho thay, d nong do nho cac phirc chat ciia azometin vdi Cu (II) la
chat ire che tot hon d nong do cao. Hieu qua ire che an mon cao nliat thu dugc ldn ban 90%.
Nam 1997, mot so tac gia vien kien triic va xay dung thugc \'ien Han lam khoa hoc Quoc
gia Ucraina da nghien ciru 31 azometin la dan xuat the mot lan ciia benz}iidenanilin. Cac lac gia
14


da nghien cuu va danh gia kha nang ire che an mon thep cua cac azometin, moi lien quan giua
kha nang ire chi an mdn vdi cac nhdm the va tfnh bazo cua cac azometin. Ket luan dugc riit ra la
cac azometin chua nhom vinyl la c6 hieu qua uc che cao nhat.
Nam 1998, S.L.Li va cac cgng sir [26] da nghien cim kha nang an mon Cu trong moi
trudng c r cua azometin N,N'-o-phenylen-bis (3-metoxi salixylandenimin) va dua ra kei luan
rdng: kha nang ire ehi Cu trong dung dich NaCl IM cao hon nhieu so vdi trong dung dich HCl
IM. Kha nang ire chi tang cimg vdi su tang cua nong do chat ire che va nhiet do. Chat ire che
nghien cim tao thanh phirc bin vdi ion Cu"^ trong dung dich NaCl IM. HCl 1 M va phirc na\ tao

kit tiia tren bl mat Cu tao thanh lap mang co tfnh bao ve cao hon. Tac gia da dua ra co che ire
chi an mon kim loai cua azometin bang viec tao phirc khdng tan, ben, cd chira 4 phoi tir giua
Cu(ll) vdi nguyen tir N ciia nhom azometin va nguyen tir O ciia nhdm o-hidroxi.
C) nude ta ciing da cd mot so cong trinh nghien cim ve tinh ire che an mon ciia mot so
azometin thugc day 5-aminobenzothiazol va mot so azometin thugc day 5,6-benzoquinolin. Ket
qua cho thay, cac azometin la chat uc che an mon dong va thep trong moi trudng CI" rat hieu
qua. Dac biet khi nghien ciru sir uc che an mon dong va thep trong moi trudng NaCl ciia mot so
azometin thugc dayl5-aminobenzothiazol, cac tac gia da dua ra co che ire che va tim each chiing
minh bang viec sir dung ket hgp cac phuong phap do phan cue the dgng va do tong trd dien hoa
ciing vdi ket qiia tinh toan cac tham so cau true cua phan tir.
Nhu vay, cac ket qua nghien cim da ehi ra kha nang ire che an mon kim loai ciia cac
azometin la tuong doi cao va co the dugc img dung trong thyc te lam chat ire che an mon kim loai.
1.4. PHUONG PHAP NGHIEN ClTU CUA DE TAI
- Sir dung phuong phap tdng hgp hiru co de tong hgp cac chat dau va san pham (azometin,
thiazoIidinon-4, amin bac 2...)
- Sir dung cac phuong phap ket tinh lai, sac ky lap mdng de tinh che va kiem tra do tinh khiet
ciia san pham.
- Sir dung cac phucrng phap vat ly hien dai de chirng minh cau tao ciia san pham.
- Sir dung phuang phap ton hao khoi lugng de khao sat kha nang uc che an mon ciia cac
azometin, cac andeliil va amin ban dau, cac san pham chuyen hda eiia azometin.
2. K E T QUA VA T H A O LUAN
2.1. T O N G HOP AZOMETIN:
2.1.1. Phan tich kha nang phan ung cua cac amin va andehit chiia di vong piridin:
2.1.1.1. Khd ndng phdn img cda 2-aminopiridin vd

3-aminopiridin:

Ca che phan ung tao azometin nhu sau:

R-CH = 0

+

R-CH-NHR

R'—>]H2

—ii^

(2)
^ >

OH

15

©

R-CH=NH2R
1
O©

R-CH=NR

-f

H2O


Kha nang phan img cua cac amin thom phu thudc vao mat do dien tfch am do doi

electron chua chia tren nguyen tir N quyet dinh: Neu mat do dien tfch am tren ngu\'en tir N cang
cao thi kha nang phan ung cang tdt va ngugc lai.
Sir dung phuong phap tinh toan HyperChem ta co the tinh toan dugc mat do dien tich
tren nguyen tir N cua 2-aminopiridin va 3-aminopyrdin nhu sau:

I.:
i,'
N:,

N^-.

11"

D I7B

4.179
0.13S

fl.OfS

tl77
41)?

N

S.Dl

t.m

Hinh 2.1: Mat do dien tich
trong phan tir
3-aminopiridin

Hinh 2.2: Mat do dien
tfch trong phan tir
2-aminopiridin

o.i;i

Hinh 2 .3: Mat dd dien
tich trong phan tir
anilin

Dua vao tfnh toan tren ly thuylt ta thay kha nang phan img vdi ciing 1 andehit thom ciia
3-aniinopiridin la clo ban 2-aminopiridin. Khi tien hanh thuc nghiem ta ciing thu dugc ket qua
phii hgp tinh toan:
•

Khi tien hanh phan img 3-aminopiridin thu dugc hieu suat cao hon

•

San pham tong hgp tir 3-aminopiridin de dang tach va tinh che hon

•

Thdi gian phan img tdng hgp tir 3-aminopiridin ngan hon

Day cac hgp chat azometin da dugc nghien cuu va tdng hgp tir rat lau, tuy nhien theo ciic

tai lieu mdi chi cd cac azometin tdng hgp tir andehit thom va amin thom. Cac nghien ciru tong
hgp azometin tir cac di vong thom con dang rat ban che.
Khi tien hanh nghien cuu tdng hgp cac azometin chira di vdng piridin chung tdi gap 1 sd
kho klian ban dau do klia nang phan img ciia cac amin chira di vdng piridin thap hon rat nhieu so
vdi cac amin thom khac.
Theo tinh toan HyperChem mat do dien tfch am tren N cua anilin la -0.412 thap hon rat
nhieu so vdi 2-aniinopiridin la -0.392. Chfnh vi nguyen nhan nay nen phan img tdng hgp
azometin tir cac amm thoni chi can dun hdi luu 2-4h, trong khi do phan ung tdng hgp azometin
lir amin chira di vdng piridin can den 16h.
2.1.1.2 Khd ndng phdn irng cda piridin-2-andehity piridin-3-andehit,
piridin~4-andehit.
Ngugc lai vdi cac amin thi kha nang phan img ciia andehit phu thudc vao mat do dien
tich duong tren nguyen tir C ciia nhdm CHO. Neu mat do dien tich ducnig tren nguyen tir C cang
cao thi kha nang phan irng cang cao va ngugc lai.
Theo tinh toan HyperChem ta thu dugc mat do dien tfch tren cac nguyen tir nhu sau:


TRUN^TAMIHi^QTlNJMUVlg^

DII m
N,
N"^'?

.0.195
0.0<3

0.15)

Hinh 2.5: Mat do dien tich trong phan
tir piridin-3-andehit

Hinh 2.4: Mat do dien tich trong phan
tir piriain-2-andehit

N

Hinh 2.7: Mat do dien tich trong phan
tir benzandehit

Hinh 2.6: Mat do dien tich trong phan
tir piridin-4-andehit

Su kliac nha^ive mat do dien tich tren nguyen tir C ciia nhom cacbonyl eiia cac andehit chira
di vdng piridin vdi benzandehit la khdng nhieu, kha nang phan ung la nhu nhau dan den klii tien
hanh tdng hgp azometin xuat phat tir cac andehit chua di vdng piridin ta chi can dun hdi km 4h.
2.1.2 Ket qua tong hop azometin:
Cac azometin dugc tdng hgp theo phuong phap: ngung tu giira andehit thom va amin bac
mot theo ti le 1: 1 trong etanol theo phan ung sau:
•

Di tir cac amin thom chua di vdng piridin: 2-aminopiridin va 3-aminopiridin
^ ^

• CHO

+

piperidin

NH'

^

^

^^CH=:Nr^

t°. 16h

Di tir cac andehit thorn chira di vdng piridin: piridin-2-andehit, piridin-3-andehit, piridin4-andehit
piperidin

CHO

N'

\ ^

•HC=N

t°, 16h

Trong do: R: m-N02;/7-Cl,/?-CH3....
Hoa lan a moi amin trong etanol, sau dd cho them 2-3 gigt piperidin de tao mdi irudng
kiem yeu. Tiep den cho vao hdn hgp phan irng a moi andehit. Hdn hgp phan irng dugc dun hdi
luu trong vdng 4-16h. San pham thu dugc cho vao cdc, de ngudi thu dugc cac linh the \a lam
lanh, Igc tach lay ket tiia. Cac azometin dugc ket tinli lai trong dung mdi ctanol-nudc.
17

Dua theo phan ung va quy trinh tren chung tdi da tdng hgp dugc 37 azometin trong dd cd
13 azometin dugc tdng hgp tir 2-aminopiridin va 3-aminopiridin va 24 azometin dugc tdng hgp
tir piridin-2-andehit, piridin-3-andehit, piridin-4-andehit (Bang 2.1a va bang 2.1b)
Bang 2.1a: Ket qua t6ng hop azometin Ar -CH=N-Ar
di tu- 2-aminopiridin,
3-aminopiridin
TT

Ki hieu

Ar'

Ar^

1

Tl

V_/

cy

2

T2

cy
^ ^'^C^ Qb- Q"

I nc

Mau
sac

Hieu
sual

96-98

Trang
nga

75%

180-182

Vang
xanh

40%

88-90

Trang

72%)

84-86

Trang

80%)

128-130

Vang

72%o

120-122

Vang

87%o

112-114

Trang
vang

65%o

130-132

Vang

80%o

75-77

Trang

35%o

85-87

Vang

85%

182-184

Trang

80%o

110-112

Trang

72%

220-222

Vang

10%

OH

3

T3

4

T4

5

T5

a
NO2

6

T6

0
N — ^

7

T7

0
^

8

T8

9

T9

N

^ '^C^
OH

10

11

TIO

Til

"'"^y

^'^0^
O^N

12

T12

13

T13
H

0-

a
0a
^

N

N

^

a
a
o
N

^

\

1


Cac azometin dugc tdng hgp deu la cac chat ran d dang tinh the hinh kim, cd mau tir
tring nga tdi mau vang nau, nhiet do ndng chay tir 50°C den tren 300 '^C. Cau true ciia cac

azometin da tdng hgp dugc xac dinh bing cac phuang phap phd nhu IR, UV-VIS, va mot so dai
dien da dugc khao sat ki vl phd H ' - NMR, va MS.
Bang 2.1b: Ket quS t6ng hop azometin Ar'-CH=N-Ar
andehit, piridin-4-andehit
TT

Ki
hieu

1

T14

-yO
' nc

Mau
sac

Hieu
suat

270

Nau
dd

56%

50-52

Da
cam

75%

150-152

Xanh

80%o

65-67

Trang

82%

50-52

Trang

70%o

>300

Dd

55%o

>300

Dd

63%o

>300

Vang
nau

68%o

CC^

90-92

Da
cam

83%)

cycy

128-130

Vang

80%o

70-72

Trang

70%o

50-52

Trang

62%o

Ar^

Ar*

^^—N

2

T15

3

T16

4

T17

(y

5

T18

6

T19

7

T20

OH

OJ

o- cyo\^—N

di tir piridin-2-andehit, piridin-3-

"'^y
"^'^cy
"°^cy
HO

8

9

T21

o

T22
N — ^

10

T23
N — ^

11

T24

cy
N—^

12

T25

T26

^'^y
H

N

13

OH

3

C

^

^

^

"°^y
19

>300

Nau

dk

60%.


Bang 2.1b (ti€p theo): Ket qua t6ng hop azometin Ar*-CH=N-Ar^ di tir piridin-2-andehit,
piridin-3-andehit, piridin-4-andehit
TT

Ki
hieu

14

T27

15

T28

16

T29

17

T30

18

T31

19

T32

20

T33

21

T34

22

T35

23

T36

24

T37

Ar^

Ar'

"Cy

^ o'

vJ^
HOOC^Q^

"Zy

. ""Cy

'Cy
""Cy

Hieu
suat

70-72

Vang
nhat

67%

290-291

Vang
nhat

80%o

OH

o ob
• "Cy

Mau
sac

255-257

^

'Cy
""Zy

* nc

"T-O

Nau

dit

60%o

110-120

Xanh
luc

80%

OJ

85-87

Vang
sang

75%o

CX5-

120-122

Vang

83%

128-130

Vang

75%o

80-82

Vang
nhat

70%

105-107

Vang
nhat

75%

02N

""^y
"''~^cy
"°^y

>300

Q-

>300

Nau

dit
Nau
dit

60%o

62%o

HO

2.1.3. Pho hong ngoai ciia azometin:
Tren phd hdpg ngoai cua cac azometin da thiy xuit hien cac pick dac trmig cho dao ddng
hoa tri ciia lien kit C-N thay thi cho pick dao ddng DC^O= 1680-1800 cm'" ciia nhdm CHO dac
trung cho andehit. Sd sdng dac trung cho dao ddng ciia lien kit nay la DC^N = 1590-1630 cm"',
cac pick nay thudng cd cudng do ldn va chan rdng. Dilu nay da chimg td hinh thanh cac hgp

chat azometin.
Ngoai viec can cir vao cac pick dac trung DC=N chung ta cdn cd ihl can cir vao nhdm chirc
dugc dinh vao vdng benzen trong cac azometin dl xac dinh sir hinh thanh ciia azometin.
Tren phd chat T9 (hinh 2.8): cac pick dao ddng ciia nlidm NH2 trong 2-aminopiridin \a
nhdm CHO eiia a -hydroxylbenzandehit da biln mit va xuit hien cac pick dao dgng cua cac

20


nhdm: 1)C=N =1614 cm'' va DQH chan rdng trong khoang 2644 ^ 3061 cm*' . Chinh su xuat hien
cac pick nay da khing djnh sir hinh thanh ciia cac azometin nhu mong mudn.
Xuit phat tir ciing 1 andehit la o-hidroxibenzandehit nhung vdi 2-amino piridin (hinh 2.9)
va 3-amino piridin (hinh 2.8) thi cac azometin thu dugc cd dang phd hdng ngoai gan gidng nhau.
Gidng nhu tren phd chit T9 thi tren phd chat T2 cung khdng thay xuat hien cac pick dao dgng
ciia andehit va amin ban diu ma thay vao do la sir xual hien ciia pick dao ddng : UC=N = 1604cm''
va DoH chan rdng trong khoang 2726 ^ 3261 cm

Hinh 2.8: Pho hong ngoai cua 2-((piridin-3-yIimino)met>i]phenol (T9)
Dale. 8/1.1/2008

Hinh 2.9: Pho hong ngoai cua 2-[(pindin-2-ylimino)met> l|phenol (T2)
Xuat phat tir ciing 1 amin la 2-aminophenol nhung vdi piridin-2-andehit (hinh 2.10) va
piridin-3-andehit (hinh 2.11) tren phd ta diu thiy xuit hien pick dao ddng ciia UC-N = 1590cm''
va 1587 cm"' uon chan rdng trong khoang 2726 - 3261 cm''

21


CH=N

\

//

i 1 "r'

I h

HO

li

Vlv

00

2&00

IOOO

\'

ii''> :1

2000

Wavenumbers (cm-l)
Dale Tue Ap. 21 22 52.30 2009

Resolutioo 4 OOO

Hinh 2.10: Ph6 hong ngoai cua 2-[(piridin-2-ylraetyliden)amino]phenol (T14)
J

y

V

.y

V

^
r-^

\ Kn
I
if} an

11

N:^
CH=N

^

//

\

^

/

HO

r-ii ^Jo:^ ffc i

Hinh 2.11: Pho hong ngoai cua 2-[(piridin-3-yImethylidene)amino]phenol (T21)
2.1.4. Pho tu* ngoai cua cac azometin:
Ta thay tren phd tir ngoai cua cac azometin xuat hien 3 cue dai hap thu ciia azometin
vdng tliain[l]: \x = 293,00-260,00 nm (dai K); Xj = 231,00-249,00 nm (dai B) va dai E:
Xl = 202,00-205 nm
Dai hap thu sdng X\ (dai K) tuong ung vdi budc nhay dien tir n^Ti , dac trmig cho su lien
hgp loan thanh phan ciia phan tir azometin. Dai nay kha nhay vdi sir thay ddi cua nhdm the d
nhan thom benzen-andchit. IChi thay the nguyen tir hidro bang cac nhdm khac nhau thi vi tri ciia
cue dai hap phu nay|bi xe dich.

22


"I

'

:i50O

r

:PHCH-N^Q).

h'

1

1

1

IN

—

,1 ^ '%-//-

0=

\
i

II

1

V"" '
A

K

1.623

-CH:N—

.

I

\y

i

i \

-ft'

=0

\
•

'
1

295 00

No.
1
2
3
4

5

295.00

P/V

Wavelength

(i>
®
®
0
0

25880

No.

Description

Abs.

1
2
3
4
5

0.803

232 20

1.917

20260

1.446

25680

0801

21160

1330

Hinh 2.12: Pho tu* ngoai cua N-(3nitrobenzyliden)piridin-2-amin (T4)

PA^

Wavelength

®
®
®
0
0

295.40

1.263

231.80

2.784

Abs,

Description

202 80

1898

255 20

0 562

211.00

1630

Hinh 2.13: Pho tii' ngoai cua 7V-(2nitrobenzyliden)pindin-2-amin (T5)
m

1

1
-N

1

,

1

,

—c^i=N—<^

\

1
1

)) '

HO

1

1
OJ74
It

'^ .1
J._
\,
:"j^

'-.'[XI

190.00

mo}

No.
1
2
3

Hinh 2.14: Pho tir ngoai
ciia 2-|(piridin-3ylimino)nietyl]phenol (T9)

-005;
150.00

PW

Wavelength

®
®
0

28350

0.225

20150

0.909

26650

0201

AtB.

Description

Hinh 2.15: Pho tir ngoai
ciia 2-|(piridin-2ylimino)metyl]phenol (T2)

,

.

1

-^

1

"^""
•

:

1

,

1

,

l^i.OO

Uo
1
2
3
4
5

PN

Wavelength

®
®
®
0
0

43100

mii)
Abs.

233 50

CH1
CM7

207 00

0 553

3M00

0 078

232 00

0 257

DKCtiplion

Hinh 2.16: Pho tir ngoai cua
2-[(piridin-2-

yImet>'Iiden)amino]phenol (T14)

Dira vao hinh 2.12 va hinh 2.13 chung ta nhan thiy sir dich chuyen ve phia song dai han
cua azometin T4 va T5 vai cac buac song hip thu nhu sau:
•

T4:X, = 2 5 8 n m a 2 = 232nm, ;^3 = 203nm.

•

T5:X] = 295nm, A.2-231nm, X3-203nm.

Ta thay cac dao dong nay da chuyen ve phia song dai so vai amin va andehit ban dhu.
Azometin T4 va T5xuat phat tu cung amin la 2-amino piridin vai o-u\[ro benzen va /;7-nitro
benzen nen dang pho cua chung gdn giong nhau a 2 cue dai 2 va 3 nhung a cijc dai thu 1 do \'i
tri cua nhom the NO2 la khac nhau nen kliac nliau.
23


Tren hinh 2.14, 2.15 va 2.16 la cac azometin co cung cong thuc phan tu nhung cong thuc
cAu tao la khac nhau cho nen dang pho la khac nhau.
Dual day la bang tdng kk ph6 hdng ngoai va tu ngoai cua cac azometin da tong hop
dugc (Bang 2.2a va bang 2.2b)
Bang 2.2.a: Ph6 hSng ngoai va tu* ngoai cua cac azometin di tir 2-aminopiridin.
3-aminopiridin

\-

TR ( cm ')
SI

Ki

T

hieu

V\ (nm)

vc=c
S c H benzen

VC=N

N h o m chiic

benzen

1550

1

Tl

1595

2

T2

1604

3
4
5
6

T3
T4
T5
T6

293.235.203

1441
1505

761

1456

(0)

1553

825

1463

(P)

1518

810J85

1461

(m)

1531

773

1459

(0)

Chan rong UOH: 27443500

1621

Dc-ci: 788

1620
11599

283.201

DN02: 1578, 1354

258.232.202

DN02: 1578, 1354

295.231.202

1529

296.234.202

1604
1471

7

T7

1520
1604
1475

8

TS

1517
1596
1479

9
10
11
12
13

T9
TIO
Til

T12
T13

1613

756

Chan rong UOH: 2644-

(0)

3061

1472
1510

793

1469

(P)

1564

828

1486

(P)

1573

816,713

1417

(m)

1620

249.205

vcHbh: 2910, 3074

1623

i)c-ci: 709

1615

DN02:1572,1353

1572
1610

vuH. 3098

1452

24

297.241.206