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

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.. C5u true dien

DAI HOC QUOC GIA H A Npi

TRirdNG DAI HOC KHOA HOC Tl/ NHIEN

CHUA Dl VONG PIRIDIN, THAM DO HOAT

TINH KHANG KHUAN VA KHA NANG (fC CHE

AN MON KIM LOAI CUA CHIJNG

M A 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

B PHAN NOI DUNG CHINH ^

} TONG QVAN VE AZOMETIN VA HOP CHAT THIAZOLIDlNON-4 6

1.1 TONG QUAN VE AZOMETIN 6

i.1.1 C4u true dien tir ddng phan hinh hoc, tinh baza cua azometin b

1.1.2 Cac phuang phap tong hop azometin 6

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 : t)

1.2.1 Tong quan: ^

1.2.2 Cac phuang phap t6ng hgrp thiazolidinon-4 [17]: 10

1.3 U'NG DUNG CUA AZOMETIN: 12

1.3.1 Hoat tinh sinh hoc cua cac azometin: 12

1.3.2 Tinh chit Ore ch6 an mon kim loai cua cac azometin: 12

1.4 PHUONG PHAP NGHIEN CUU CUA DE TAI 15

2 KET QUA VA Tl-JAO LUAN /^

2.1 TONG HOP AZOMETIN: 15

2.1.1 Pl|ian tich kha nang phan img ciia cac amin va andehit chua di vong piridin: 15

2.1.2 K6t qua tong hop azometin: 17

2.1.3 Ph6 h6ng ngoai ciJa azometin: 20

2.1.4 Pho tCr ngoai cua cac azometin: 22

2.1.5 Ph6 kh6i lugng cua cac azometin: 26

2.1.6 Pho cong huang tir proton cua cac hgp chat ( ' H - N M R ) : 30

2.2 TONG HOP B I S - A Z O M E T I N 34

2.2.1 Ket qua tong hgp bis-azometin 34

2.2.2 Pho hong ngoai cua bis-azometin: 38

2.2.3 Pho tu ngoai cua cac bis-azometin 38

2.2.5 Ph6 cong huong tu hat nhan'lI-NMR: 44

2.3 TONG HOP CAC DAN XUAT CUA THIAZOLIDIN-4-ON VA BIS-THlAZOLlDlN-4-ON 46

2.3.1 Tong hgp cac lhiazolidin-4-on va bis-thiazolidin-4-on: 46

2.3.2 Pho hong ngoai ciia thiazolidin-4-on va bis- thiazolidin-4-on 46

2.3.3 Pho khoi lugng ciia cac thiazolidin-4-on va bis-thiazolidin-4-on: 49

2.3.4 Pho cong huong tu hat nhan 1 H-NMR ciia cac thiazolidin-4-on va bis-thiazolidin-4-on 52

2.4 KHU'HOA AZOMETIN 57

2.4.1 Khu hoa azometin 57

2.4.2 Pho hong ngoai 57

2.4.3 Plli6 cong huong tu hat nhan 'H-NMR: 58

2.5 HOATTJNH SINH HOC CUA CAC AZOMETIN: 60

2.6 KHAO SAT TINH U'C CHE AN MON THEP CT-3 CUA CAC AZOMETIN TRONG MOI

TRUONG AXIT HCl 2M 63

3 THUC NGHIEM 6S

3.1 TONG HOP AMINOPIRIDIN 68

3.2 TONG HOP AZOMETIN; 68

3.3 TONG HOP CAC BIS-AZOMETIN: 68

3.4 TONG HOPTHIAZONLIDINON-4: 68

3.5 KHU'HOA AZOMETIN: 68

3.6 HOAT TiNH SINH HOC CUA CAC AZOMETIN: 68

3.7 KHAO SAT KHA N A N G U C CHE A N MON THEP CT-3 CUA CAC AZOMETIN: 69

-/ KfynuAN ~o TAt LIEU THAM KHAO ^/

C PHU LUC 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:

- 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

n SUMMARY

a Reaserching Project: "Synthesis and investigation of anti-bacterial and metallic

corrosion inhibition activity of some compounds containing pyridine ring"

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 bacterial and metallic corrosion inhibition activity

anti-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 andehit

piridin-4-• 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 A Z O M E T I N v A HOP C H A T T H I A Z O L I D I N O N - 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]

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:

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

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:

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

I SnCl., CI

4 0-CH3-C6H4-CH-N-C6H5 (62-70%)

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:

^ t° cao CH3-N=N-C6H5 + CH3-C6H5 • CfeHs-N^CH-CftHs

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]

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%)

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%)

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 420-480nm 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:

S-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, a-hydroxiankanoic, cdc axit Ojp- khong no hoac este cda cdc axit do:

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:

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 :

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 ^^CgHs NHCS S CHR COOH ^

-> K : 6 H 5 - N — CO

I 1

s c 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

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

Co che phan img theo F.C.Brawn dugc mo ta nhu sau:

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:

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]

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 v d h d l 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 = ^ — 1 0 0 %

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]:

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

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 b l 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 Q U A 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:

1 O©

(2)

R - C H - N H R ^ > R - C H = N R -f H2O

OH

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:

fl.OfS

D I7B

o.i;i

.3: Mat dd dien trong phan tir anilin

Hinh 2.1: Mat do dien tich Hinh 2.2: Mat do dien

trong phan tir tfch trong phan tir

3-aminopiridin 2-aminopiridin

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:

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

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

Trang

Vang

Vang

Trang vang Vang

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 v l phd H ' - NMR, va MS

Bang 2.1b: Ket quS t6ng hop azometin Ar'-CH=N-Ar di tir piridin-2-andehit, andehit, piridin-4-andehit

Nau

dd

Da cam Xanh

Da cam

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

dit

Xanh luc Vang sang Vang

Vang

Vang nhat Vang nhat Nau

dit

Nau dit

Hieu suat

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

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

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

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

va DoH chan rdng trong khoang 2726 ^ 3261 cm

Hinh 2.8: Pho hong ngoai cua 2-((piridin-3-yIimino)met>i]phenol (T9)

D a l e 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''

Dale Tue Ap 21 22 52.30 2009

Vlv li \' ii''> :1

2&00 2000 Wavenumbers (cm-l)

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

0801

1330 Description

Hinh 2.12: Pho tu* ngoai cua

202 80

255 20 211.00

Abs, 1.263 2.784

1898

0 562

1630 Description

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

0201 Description

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

0 553

0 078

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 T 5 x u a t 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

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

828 (P) 816,713 (m)

Bang 2.2b: Ph6 hSng ngoai va tir ngoai ciia cac azometin di tir piridin-2-andehit,

834 (P)

823 (P)

825 (P) 841.756

(m)

758 (0)

836 (P)

830 (P)

830 (P)

822 (P)

739,810 (m)

832 (P)

827 (P)

Nhom chuc Chan rong VQH- 2900-

3600 Chan rong VQH' 2900-

c6 the chung minh rang cac phan umg ngung tu tao azometin da xay ra va cac san pham thu dugc

trung vdi cdng thuc'dir kien

2.1.5 Pho khoi luong ciia cac azometin:

De khang dinh mot each chinh xac hon nua cau tao cua cac hgp chat, chung tdi tien hanh ghi phd khdi lugng cua cac san pham tao thanh

Khao sat phd khoi lugng 4-clo-A'^-(piridin-4-ylmetyliden)anilin (T34) Ta thSy phan tir azometin T34 co chua nhom the CI nen trong phd khdi lugng cua no ta nhan thay co 2 pick la

216 va 218 ung vdi cac ddng vi ''^Cl va ''^Cl vai ti le la 7/4 Manh 215 va 217 la manh M' tuang ung (Hinh 2.17)

r i i o u e Ttil DefalctD D O A V A T U E C - K h o a I l o a b o f TniOOK DU KHTN DH QG UN

T«ii m * u niarUi Tra TN

Nguoi (to 0 ( S '^Fii N h u n g

Ngat d o Oft D o c p m b B i £ 0 0 8

/ V u i t o B i s ^ o P i - ^ i x i l o r

T c n u i H j ' N.-oc 5 « n Bjai U S *

( •

: - M i , <\\\'- , i i M i i | , •:, I

i'j 5 b

r^i-oo 165 170 " 5 iBC' 1BL •Vu

Hinh 2.17: Pho khoi luong cua 4-clo-A^-(piridin-4-ylmetyliden)anilin (T34)

Co so dd phan manh nhu sau: (Sa dd 2.1)

Khao sat phd khdi lugng cua 7V^-(4-clo ben2yliden)piridin-3-amin (TI 1) Ta thay azometin

Tl 1 va T34 cd cung cdng thuc phan tu la C12H9N2CI, trong cdng thuc cau tao cd su trao ddi hgp ph4n amin va hgp phan andehit cho nhau:

77 0 4 M G3 03O5 I

Phong Khoi pho

21 May 109 10:15 am using AcqMethod N-DIP 59B9B MS

So-do 2.3: So' do phan manh cua 4-metyl-A^-(piridin-3-yl metyliden)anilin (T25)

Cac azometin dugc tong hop tu cac dan xuat amin chua dj vong piridin khac nhau vcri cung 1 andehit thooii tren pho khoi se co cac pick dac trung tuong tu nhau cho nen sa d6 phan manh luong tu nhau (hinh 22 va hinh 24)

N:

v\ /^'""-"^ //

CH-Ten mau T h « « i ' l a T M

"4l^aj" on Oaa •>>• Nnunn

Ngay dc 00 D£ceoO«<, 20V8

.en mat A.utcrSi>^<3 I>»-oia:i.l*

Nuoc son njSI ' VISA

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^lAX^ , i i , i l i i i l i l

'^ so M K 6i ' W IPS ' ' 0 1 ' * '^^ " * '^^ ' " IS! IBO 165 ITO ITS lBO 1«; >90 1SS 7P0

Hinh 2.20: Pho khoi luong cua 4-metyl-A^-(piridin-4-yl metyliden)anilin (T35)

m/e= 181

So' do 2.4: So- do phan manh cua 4-metyl-7V-(piridin-4-yl met> liden)anilin (T35)

Tren hinh 2.19 va hinh 2.20 ta thay pho khoi cua T25 va T35 co cung cong thuc phan tu

la C13H12N2 nen co chung cac pick dac trung m/z: 196; 195; 181; 118; 105; 91; 79 Tuy nhien cucmg do cac pick la khac nhau: (Bang 2.3)

Bang 2.3: Cu'ong do pick cua T25 va T35 trong pho MS;

195

92.4%

78%

181 5.9%

5.0%

118

11.8%) 46.4%)

105

5.9%) 5.0%)

Bang 2.4: Pho khoi lu-gng cua cac azometin STT

227(M"), 210, 180, 154, 127, 79, 51 227(M^), 210, 181, 168, 121 94, 78 183(M'), 182, 105,94,79

184 (M"" + H), 182, 155, 105, 94 79, 78 L97(M"'), 196, 195, 103, 91, 78, 77 196(M''), 182, 179, 149, 127,78 216(M^), 215, 105,89,78,77 227(M''), 226, 181, 127, 105, 78, 77 221(M"'), 220, 145, 144, 116, 89, 78, 73

196 (M""), 195, 118,91,79

2.1.6 Pho cong huong tir proton cua cac hop chat (*H-NMR):

De xac dinh mot each chinh xac cau true cua cAc azometin chung toi tien hanh ghi ph6 H-NMR, day la phpong phap hiru hieu nliat, chung toi tien hanh ghi pho cua mot s6 azometin

da tong hgp dugc Ket qua cho thay tren phd xuat hien day du cac tin hieu cua cac proton c6 mat trong phan tu Viec qui ket cac tin hieu cong huong cho cac proton, chung toi dua vao cuong do tuong doi cua van pho do chuyen djch hoa hpc trong tai lieu tham khao va dua vao sir tuong tac

spin-spin giua cac proton

Hinh 2.21: Pho ' H - N M R cua N-(3-nitrobenzyliden)piridin-2-amin (T4)

Phan tich pho ' H - N M R cuaN-(3-nitrobenzyliden)piridin-2-amin (T4) ta thu dugc bang sau:

I: Bang 2.5: Tin hieu *H-NMR cua H3

7.92 8.450

J

4.7 4.8 8.0 7.9

7.67 7.60 7.8 7.91 7.96 8.10

Tu bang tin hieu tren ta thay:

- Cac proton H| Hi H3 va H4 la cac proton cua vong benzen co do dich chuyen tu 7.36 ppm den 9,327ppm Trong do ta thay H| co do dich chuyen Ion nhat vai 6 = 9,327ppm do H| bi anh hirong manh cua cac nhom -NO2 va -CH-N- lam giam mat do electron do do H| di chu\'^n

ve truang yeu va ta thu dugc tin hieu a dang singlet Con H3 chiu it anh huang cua nhom -NO2

va -CH=N- CO do fjich chuyen nho nh4t 5 = 7,36ppm H3 tuong tac gin vai II2 vai J - 4.8 (J2 = 4,7) va H4 vai J = 8,0 (J4 = 7,9) Do do ta thu dugc tin hieu duai dang triplet Proton I I.i co

dp djch chuyen 6 = 7.43ppm, thu dugc tin hieu duai dang duplet do tuang tac vai H3 Vai Proton

H2 ta thu dugc tin hieu duai dang duplet do tuong tac vai H3 va co dp dich chuyen hoa hoc

a gan nguyen t6 N am dien han Tin hieu a dang douplet do tuang tac vai Hg voi hang so tuong

lac J = 8,l(Jfi = 7,96) Proton H7 co dp dich chuyen la nho nhat 5 = 7.84ppm thu dugc tin hieu a dang triplet do tuong tac voi He vai hing so tuong tac J = 7,6 (Je = Ifil) va tuong tac vai Hs voi

J = 7,8 (Jg = 7,91) Ta thu dugc tin hieu triplet vai proton Hg do Hg tuong tac voi H9 va H7 va co

dp dich chuyen hoa hpc 5 = 7,92 Vai proton He do 6 gan nh6m -CH=N do do dp djch chuyin hoa hpc tuong d6i cao 5 = 8,4ppm, thu dugc tin hieu duoi dang douplet do tuong tac vai H7

Ph6 ' H - NMR cua N-(4-clo benzyliden)piridin-3-amin (Tl 1) (Hinh 2.22) Nhin vao bang 2.6 ta thay:

- Proton H3 CO dp chuyen djch hoa hpc lan nhat 5 = 8,716 ppm va 6 dang singlet Nguyen nhan la do proton nay chiu anh huong bai hai nhom hut electron 6 ben canh lam cho no di chuyen ve truong yeu

- H|, Hr, H2 va H2- la cac proton cua vong thom co dp chuyen djch hoa hpc trong khoang

6-9ppm Trong do Hi va Hp co dp dich chuyen ldn hon (5 = 7,984 ppm) H2 va H2- (5 = 7.615

ppm) do anh huong cua nhom CH=N va Cl lam cho mat dp electron a vi tri Hi va H r kem hon 6

vj tri H2 va H2- Dong thoi Hi va H2 co su tuong tac spin-spin voi hang so tuong tac Ji = J2 (Ji ^ 8,491 va I2 = 8,454) Thu dugc tin hieu a dang duplet

- H4 do nam gan di to nito va chju anh huong cua nhom CH=N manh hon so voi cac prion khac trong vong piridin do do dp dich chuyen ve phia truang yeu hon cua H| va H2 (5 = 8,509 ppm) Dong thoi tin hieu 6 dang duplet do tuong tac xa voi He vai hang s5 tuong tac J4 = 2,398 (J6 = 2,370)

Ket qua qui ket tin hieu ph6 ' H - NMR cua Tl 1 nhu sau:

Bang 2.6: Cac tin hieu ' H - NMR cua T i l

7.456

7.718

J 8.491 8.459

2.389 4.669 4.654 2.370 8.016 8.014

2 H gan nhau

Tuong tac xa voi He

2 H gan nhau Tuong tac xa voi H4

2 H gan nhau

- Voi proton H5 ciang chju anh huong cua nguyen to N do do, dp dich chuyen nam a truang yeu 5 = 8,465 ppm Tin hieu a dang duplet do tuong tac voi prton He voi h4ng s6 tuong

lac J5 = 4,669 (Je = 4,645)

- Vai proton He cijng bj anh huong cua nguyen to N va nhom CH=N nhung chiu anh

huang it hon va tuong tac gan voi H5 voi Je = 4,645 (J5 = 4,669) va voi H7 voi Je = 8,016 (J7 = 8,041) Dong thai tuong tac xa voi H4 vai hkng s6 tuong tac Je = 2,37 (J4 = 2,398) Do do

tin hieu cua He a dang mutile

-Proton H7 cjo dp dich chuyen 5 = 7,718 ppm, tuong tac gin voi He ta thu dugc dang tin hieu la duplet

Bang 2.7: Cac tin hieu ' H - NMR ciia T27

N /

J 5.946 5.98

7.423 7.313

2 H gan nhau

2 H gan nhau

2.2 TONG HOP BIS-AZOMETIN

' •

2.2.1.Ket qua tong hop bis-azometin

Phuang phap tong hgp cac bis-azometin hoan toan tuong tu nhu phuong phap tong hgp cac azometin trinh bay o tren, do la phuang phap ngung tu giija andehit va diamin bac mpt theo vai ty le moi 2:1 trong etanol khan c6 xuc tac la bazo piperdin theo so do sau :

trong qua trinh chpn he dung moi dk kit tinh lai

Cung giong nhu qua trinh tong hgp azometin, muc do cua qua trinh tdng hgp bis-azometin cung phu thugc vao ban chdt cua cac andehit va cac diamin tham gia phan ung Nhu da phan tich klia nang tham gia phan ung cua cac andehit chua di vong piridin khong khac nhieu so vai cac andehit thom khac

Trong qua trinh tong hgp ta can luu y tai piridin-2-andehit vi no de dang bi keo san phdm bai tac dong nhiet gay kho khan cho viec tong hgp cac bis-azometin tuang ung nen chung toi chi tong hgp va ket tinli lai dugc 3 bis-azometin tuong ung

Ngoai ra cac diamin khac nhau ciing anh huong tai kha nang phan ung tao bis-azoniein Chung toi da tiln hanh t6ng hgp cac bis-azomedn xuat phat tu 9 diamin, nghien cuu mat do dien tich am tren nguyen tu N bing phin mem hyperChem cho ket qua nhu sau: (Bang 2.8)

Bang 2.8: Ket qua phan tich mat do dien tich tren nguyen t u N cua diamin

Cong thuc cau tao

-0.363 -0.360

-0.395

-0.321 -0.320

-0.396

•0 1B7 iN-il

0.220 0.223 ' 12

0 222 0.129

NV D 4 0 7

-u t,« - ^ 0.222 0.137

0.137 0.137 0.069

T 0 1 4 0

0.129 -0 1 B 0 - ° - ' " * ° 0.033 0.131

290 -0.319

0.203 D.135

N

,1:0.395 D.235 0.227

Hinh 2.30: Mat do dien tich A6 Hinh 2.31: Mat do dien tich A7

-0.172 -0.08B

X J O l B l 0.03Z

0.127

H i n h 2.33: M a t do dien

Dira vao ca che phan ung tong hop azometin ta thay rang mat dp dien tich tren nguyen tir

N cua diamin cang am thi phan ung xay ra cang de dang hon Tren nguyen tu N cua Al mat dp dien tich am la 1cm nhat (bang 2.8) nen kha nang phan ung cua Al la tot nhat, cac san pham tao thanh co hieu suat cao va de dang tinh che, da tien hanh tong hop duac 3 bis-azometin xuat phat

tu Al va 3 andehit tuong ung Tuy nhien, yeu to khong gian cijng anh huong mpt phan lan toi kha nang phan ung:

• A4 va A8 tu^ co mat dp dien tich am tren nguyen t u N la -0.407 va -0.321 khong ion lam nhung kha nang phan ung cua A4 va A8 rat tot do hieu ung khong gian giua 2 nhom NH2

Bang 2.9: Ket qua t6ng hop bis-azometin Ar-CH=N-Ar'-N=CH-Ar

i

Tir 3 andehit chira di vong piridin va 9 diamin chung toi da tien hanh tong hprp dupe 19

bis-azometin (Bang 2.9) tit ca d^u la chat rkn co mau tir vang nhat den nau den, co nhiet dp nong

chay tir 120-300*^0 Da s6 khong tan trong nuac, kho tan trong etanol, benzen, toluen

C4u true cua cac bis-azometin duac khing dinh nho ghi pho IR, UV, MS, HI-NMR

2.2.2 Ph6 hong ngoai cua bis-azometin:

Tuang tu nhu cac azometin tren ph6 h6ng ngoai cua cac bis-azometin thay xuat hien dinh hap thu cua lien ki^t C=N nim trong viing 1585-1624cm"' tuy theo tiing chat; khong tha\ xual hien tren ph6 cac pick dac trung cua amin va andehit tuang img

Ngoai viec can cu vao cac pick dac trung cho dao dong hoa tri ciia lien ket C=N thi chung ta con c6 th§ can cu vao nhom chirc dinh vao vong benzen tren hprp phan diamin ciia cac bis-azometin; vi du nhu thiy xuit hien dao dong hoa tri dac trung cho lien ket C=N a 1623 cm"'

va C-O-C a 1240,13cm"' ciia 4,4'-oxi bis[7V-(piridin-2-yl metyliden) anilin] (Hinh 2.34)

4000 3500 3000 2500 2000 1500 1000 500

Wavenumbers (cm-1)

Dale Mon Nov 03 23 19 39 2008 TBN4-1 KBr

Hinh 2.34: Pho hong ngoai cua 4,4'-oxi bis[A^-(piridin-2-yl metyliden) anilin] (TB2) 2.2.3 Pho tu' ngoai cua cac bis-azometin

Tuong tu su hinh thanh cac azometin, cac bis-azometin dupe tong hgp tir andehit va diamin bac 1 la mpt su keo dai mach lien hpp TC—>-7i* va n->7r*, su lien hgp nay lam cho nang lugng giam xuong dan den ^^max ciia azometin va bis-azometin dich chuyen ve phia buoc song dai hon so voi andehit va amin, diamin tuong img nhung cuong dp hap thu lai giam xuong Can cir vao su dich chuyen ve phia buac song dai ciia bis-azometin so vai andehit va diamin tuong img chiing ta co the khang dinh su hinh thanh cua cua bis-azometin

Duoi day la bang tong ket pho hong ngoai va tir ngoai ciia cac azometin va bis-azometin

ma chiing toi da tong hgp dugc (Bang 2.10):

839 (P)

844 (P)

817 (P)

839 (P)

846 (P)

785 (P)

tir ngoai cua cac bis-azometin

vcnbh 2862;3034

NH:3156 vc-o-c

1255 NH: 3229

vcHbh 2910,3031

UV (nm)

243.207

240.250

265.259.202 326.205

382.283.245

366.253.203

Nhu vay, cac bis-azometin ma chiing toi tong hgp dugc co nhiet dp nong chay, pho hong ngoai, tir ngoai xac dinh va kliac xa so voi chat dau Dieu nay co the chirng minh rang cac phan irng ngung tu lao azometin va bis-azometin da xay ra

2.2.4 Pho lihoi luoTig ciia cac bis-azometin

Cung giong nhu cac azometin, phuang phap pho khoi lugng la mpt trong nhung phuong phap hihi hieu nhat de nghien cinj cau triic ciia bis-azometin Can cir vao cac manh phan lap dugc chiing ta se xac dinh dugc cau true va chirng minh dugc su hinh thanh ciia bis-azomclin