DSpace at VNU: Nghiên cứu tổng hợp khả năng ức chế ăn mòn kim loại Benzpylhidrazo

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TAP CHI KHOAHgC DHQGHN,KHTN & CN, T.XXil],S6 1,2007

NGHIENctltr tdxc Hdp vA rrTA NANCUCCHfr

alv tvroNKrMLoAr ctia uOr sd nnNzoyLHIDRAZoNoHit*o"taoroPHENoN
Nguy6n

Minh Thio,

Ph4m Vin

Nhi6u,

Nguydn Thi Thu Hrtong, Hd Thi Vdn, Vfr Phuong Li€n
Khoa H6a hgc,TnrirngDqi hpel{hoa hqc TVNhidn, DHQGHN
Trong thdi gian gdn d6y c6c nhi H6a hgc Nam Hin c6 mQt th6ng b6o [1]vd khA
nlng rlc chd in mdn kim logi cira mQt sd hidrazon di tr] o- hidroxiaxetophenon v]r
hidrazit ctra c6c axit benzoic thd. Chfng t6i da m6 rQng vi ph6t tridn phrrong htr6ng
nghiOn crlu niry vi dd c6 mQt sd c6ng bd 12,3, 41. Trong bdi b6o niry chfng t6i tidp t+c
th6ng b6o sqr dng hgp c6c hidrazon hldng tg, di tr} cdc metyl o-hidroxiaxetophenon v6i
hidrazit cria c6c axit benzoic thd:

+H2N-Mr-""€"
s -q;*_*_TOl

*q;
(I 1,2)

(II1-5)

0II1-8)

d d6y: I: 1) 4-CHg;2) 3-CH3
II: R: H, m-CH3,o-NO2,m-NO2vh p-NO2
C6c hgp chdt Ir, , dugc di6li chd trl m-crezolvi o-crezol th6ng qua phAn rlng este
h6a rdi chuydn vi Fries 6 nhiQt dQcao (160-1800C)v6i nh6mclorua khan lim xric t6c [5].
Hgp phdn hidrazit (II1j nh{n dugc tfi c6c axit benzoicthd qua phin rlng este h6a
th6ng thrrdng rdi tidp theo ld phin rlng gifla estevdi hidrazin hidrat 86% I2l.
TrI hai hgp phdn tr6n v6i ti lQ mol 1:1 khi dun s6i hdi lttu tt 3 - 5 gid trong etandl
tuy6t d6i s€ nh{n drrgc sin phdm cu6i cring (IIIr. J, md chring d6-utAch ra drr6i d4ng
tinh thd ngay khi dun s6i h6n hgp phin rlng. Kdt qui ttugc gi6i thiQu 6 bing 1.

Bing 1. C6c benzoylhidrazon o- hidroxiaxetophenon (lll r.!)

:;.-*."*

68


69

Nghi€ncriutdnghgpvd khi ntng rlc chdtn mbnkim loqi...

STT

Vitrf
CHt

Vitri R

1

3_CH3

H

2

3_CH3

3

3_CH3

4

5

6

7

8

3_CH3

3_CH3

Higu
sudt,

ton", oc

Phdhdngngoqi,cm'l

To

Vox

Vrn

Vc=H.

vco

168-169

85

3243

3028

1602

1643

m_CH.

148-149

85

3228

3070

1602

1644

o_NO,

120-12',1

70

3213

3086

1604

1651

m_NO2

196-197

75

3213

3122

1606

1646

't91-192

82

3262

3108

1602

1650

P-Noz

4_CH3

o_NO,

123-124

70

3298

3213

1614

1659

4_CH3

m_NO2

269-270

75

3202

3029

1609

1643

220-221

82

3209

3009

1599

1647

4_CH3

P-Noz

Vruoz

1528
1349
1526
1346
1518
1345
1564
1348
1529
1348
1519
1354

Tr0n phd h6ng ngo4i cria cdc hidrazon nhfln drrgcd6:uthdy xudt hign cdc v4ch d{c
trdng cho dao dQngh6a tri cira nh6m OH phenol E 3202"8298cm'l, cfra nh6m NH amit 6
3009.-3213
cm'r, cria C=N 6 L599-1614cm-r,cria nh6m CO amit 6 f0+g-f059 cm'l, vA
crianh6m nitro 6 1518-1564cm'r vA 1345-1354
cm'l.
TrOn phd IH-NMR th{y xudt hiQn cic tfn hiQu irng v6i chuydn dich h6a hgc cira
c6c proton trong phAn t&: 6*1: 13,15- 13,67ppm; 6es: IL,23 - 11,60ppm; 6gH3:2,2! 3,30 pfm; cdn c6c proton thom c6 chuydndlch h6a hgc 6 6,80 - 8,?4ppm.Birig'3 ehi lai
c6c drl kiQn vd ptrd rH-MvIR cria mQt sdhidrazontdnghgp drrgc.
Blng 2. Phd TH.NMR
cia mQtsdhidrazon

?:N-*H-co
cHr

Tqtpchi Khoa lwc DHQGI I N, RHTN & CN, T.nil il, Sd I, 2N7

70

ill

Nguy€n Minh Thio, Phlm Vln Nhi0u...

Vitrf CH3

R

Phd rH-NMR (6 pp,)

2,48(3H,C-CH.);3,30(3H,CH.);6,81(1H,Cu_H);
7,2O(1H,
1

3-CH3

H

Ca_H);7,48(1H,C-H); 7,55(2H,C-H vA Crt_H);7,63(1H,
OH);13,67(1H,_NH).
C,o_H);7,94(2H,
C-H vi C,-H); 11,28(1H,
2,41(3H,C-GH.); 2,48(3H,CHr);6,81(1H,
2,21(3H,Ce_GH3);

2

3-CH3

m-CH.

7,49(1H,'
Cu_H);
7,20(1H,C-H);7,44(2H,Cn_HvA C,o_H);
C,,_H);7,75 (2H,C-H vi C,-H); 11,23(1H,OH);13,67(1H,_NH).
2,22(3H,G-CH.); 2,52(3H,CH.);6,82(1H,CrH); 7,22(1H,

4

3-CH3

m-NO,

(1H,Co_H);8,38(1H,C,n_H);8,47
C-H);7,50 (1H,C.'.,_H);7,86
(1H,C-H); 11,60(1H,OH);13,56(1H,_NH).
2,22(3H,C-CHJ;2,51(3H,CH.);6,82(1H,Cu_H);7,22(1H,

5

3-CH3

P-Noz

C.-H);7,52('lH,C-H);8,19 (2H,C-H vi C,'z_H);8,37(2H,CLH
vAC',_H);11,61(1H,OH);13,55(1H,_NH).

2,29(3H,C-CH); 2,50(3H,CH.);6,85(2H,CLH vd C-H); 7,55

7

4-CH3

m-NO,

(1H,Cu_H);7,83(1H,C'_H); 8,40(2H,C*H vA Cto_H);8,74(1H,
C,-H); 11,58(1H,OH);13,20(1H,-NH).
2,29(3H,C-CHr); 2,50(3H,CH.);6,75(2H,Ca-Hvit C-H); 7,54

8

4-CH3

P-Noz

(1H,Co_H);8,17(2H,C-H vi C.,z_H);8,38(2H,C-H vAC,,_H);
11,57(1H,OH);13,18(1H,_NH).

TrOn phd khdi luOng cria mQt sd hidrazon thdy xudt hiQn pic ion phAn trl c6 sd
khdi phrl hgp v6i phdn trl khdi vi c6c pic kh6c c6 sd khdi phi hgp vdi cic ion minh
trong so dd phAn minh:
+ Hgp chdt III2 (mlz\:282 (M), 267,163,148,133, 720 (100%),119, 105,91,77,
65, 51.
+ Hgp chdt IIIa (mlz):313(M), 298,296,165,163,150 (100%), 148,134,133,1.19,
105,104,76,50.
+ Hqp chdt 1116
(mlz):313(M*), 298,296,179,163,150,148, 134,120 (100%),105,

104,92,69,55, 50.
Tr) cic sdliQu tr6n, c6 thd d6n ra so dd phAn minh chfnh cria c6c hidrazon nhu sau:

Tqpchi KhoahocDHNH N, KI{TN & CN, Tffi II, SdI, 2007


Nghi0ncfu t6nghqp vl khi nangrlc chdin mbnkim loqi...

7l

d\(o'

"'t\l\f

:N-M.."-[fuil+
cHr

\/

M*
(\(""
u^
H'c-\l\;-,.-.

,/"

v 't:v-*"-.-@*-h".

ILco.
.,

k*,

",.\l\
;

'f:n-i'"

.

I""'-.
|

oH
..N
t-un

*

r

1"",""
-A(*

"'\l\

r{r

l * ,
ft1*

,S-r-

'_.o.-

\

|

1

+

_O
-z

,

\

-@'

,^","{'lL__-N-l+
tr-!---q

\:zNl*

*

v
H

"g

l "o

l'*

'fr' -,-*fil ",.fi--rl
Nhu vfy, c6c dfl kiQn v6'pfrd da x6c nhsn cdu t4o c&a c6c hidrazon tdng hqp drrQc
ld dring vA hoin toirn pht hgp v6i c6c kdt quA nghiQncrlu dd dtrqccdng bd. t2l
Od ntao s6t khi ning itc chd trn mdn kim logi cria c6c hidrazon tdng hgp dtrgc,
theo phrtong ph6p kh6i lrrgng, ddi vdi th6p CT-3, nghia lh cho
' chfng t6i de thrl nghiQm
th6p CT-3 vio dung dich axit HCI 2M kh6ng c6 (m5u so s6nh) vA co chdt rlc chd trong
ctng mQt thbi gian, rdi x6c dinh mrlc eiim khdi lrrgng cira c6c tdm th6p, til d6 rrit ra
drrgckdt lu{n v6'khi n[ng r1cchd 6n mdn kim lo4i ctra c6c ch{t nghidn cilu, d{a tren str
tfnh to6n theo cic c0ng th0c sau d6y:
+TdcdQinmdn: y =(m,-m) - L^

s.r

s.t

Trong d6: me,m: khd lrrqng t{m th6p CT-3 tuu6cvi sau khi thf nghiem [g]
S: tdng diQntfch c6c b6'm{t t{m th6p CT-3 [cm2]
t: thdi gian thi nghiQmbhftl

Tsp chi KhoahpcDHQGHN,KHTN & CN, nffill,

SdI, 2Un

Nguy6nMinh Thio, PhamVen Nhi€u...

72

+ HO sdin mdn: = Y * tooyo
' y o
"
Trong d6: V6, V : tdc d0 dn mdn trong trddng hgp kh6ng c6 vi c6 (tuong fing) ch{t .
tlc chd
+ HiGusudt bio vQ:F/o =Vo-]-V *I00o/o= (l0o - y)%

vo

Kdt qui thrl nghiQm drrgcddn ra & bing 3 sau diy:
chdngln mdnth6pCT-3trongm6itrudngHCI2Mc0acic hidrazon
Blng 3. Kdtqul thfi nghiQm

\a,

DeiluglSV

"t
Po/o

0

1

2

3

4

5

6

7

29,40

5,76

4,26

9,00

8,28.

7,80

6,70

3,86

5,52

100

19,59

14,19

30,60 2 8 , 1 6 26,53

23,08

13,28

17,02

80,41

85,51

69,40

73,47

76,92

86,72

82,98

0

71,84

I

Nhrr v{y, t{t cA c6c hidrazon tdng hgp drrgcd6luc6 khi ning itc chd dn mdn kim
Io4i v6i mrlc dQkh6c nhau (hiQusudt b6o vQtt 69,4- 86,7%).

Th{c nghiQm
* Tdng hqp S-vi 4- metyl - 2- hidroxi axetophenon( ILz )[5]
Di til o-cresolvi m-cresol qua phin rlng este h6a bing anhidrit axetic rdi chuydn
vi Fries tidp theo [5] v6i Alcls khan lhm x6c tdc.
HiQusudt: gO-g4%
t!:2l|oC
o-cresylaxetat
m-cresylaxetat

HiQusudt: 9Q- 94o/o

t! :2l0oC

3-metyl-2-hidroxiaxetophenon

HiQu sudt:75%

t! :1750C

4-metyl-2-hidroxiaxetophenon

HiQusudt: 71%

r! :1600C

* Tdng hep c6c hidrazit

cia c6c axit benzoic thd ( IIr . E) [2]

C6c hidrazit drrgc tdng hqp tr] axit benzoic thd qua hai brr6c: este h6a th6ng
thudng (t6c dgng v6i aniol c6 xric t6c axit) rdi tidp theo cho este phin itng v6i hidrazin
hidrat 85% khi dun s6i trong etanol.
Nh4n dugc:
1) Etylbenzoat

HiQusudt:82%

t!:212-2140C

Tsp chiKhoa hpcDHQGHN, KIIT N & CN, T.)Wil, SdI, 2007


fc chd nn mbnkim

2) Metyl m-toluat ,

HiQusudt: 65%

t!:2l5oC

3) Etyl o-nitrobenzoat

HiQusudt: 72%

t!:2L5oC

4) Metyl m,nitrobenzoat

HiQusudt:65%

t!:78-790C

5) Metyl p-nitrobenzoat

Hi6u sudt: 65%

to,296-97oC

1) Hidrazit ctra axit benzoic

HiQu sudt: 80%

-l
{ : 109 lOoC

2) Hidrazit cria axit m-toluic

HiQu su{t: 93%

t! :90-910C

3) Hidrazit cira axit o-nitrobenzoic

Hi0u su{t: 80%

t! :120 -l2lo C

4) Hidrazit cfra axit m-nitrobenzoic

Hii.,.rrft, OOX

tl :165-16dC

5) Hidrazit cria axit p-nitrobenzoic

HiQu sudt: 82%

t!:215-2l6oc

CAcHidrazit:

* Tdng hQp c6c hidrazon di tfi 3-(hoic 4.) metyl-2-hidroxiaxetophenon
c6c hidrazit cta c6c axit benzoic thd (IIIr,8)

vdi

Dun s6i hdi luu hdn hqp cria 0,025 mol 3- (ho{c -) metyl-2-hidroxi axetophenon
v6i 0,025 mol cria hidrazit axit benzoic thd trong etanol tuyQt d6i. Ldc ddu h6n hgp
phin rlng tan hdt. Sau d6 sAn phdm phin rlng hinh thAnh vi t6ch ra 6 dqng chdt rdn
tinh thd ngay trong khi dun n6ng. Lgc n6ng, rrla bing mQt it etanol n6ng. Dd kh6 ngoli
khdng khf, cAn vi tinh hiQu su{t. Kdt qui dugc trinh bny 6 bAng 1.

Kdt luQn

Dd tdng hqp duo.cmQt ddy hidrazon di tt c6c metyl o-hidroxiaxetophenon v(n che
hidrazit cria e6c axit benzoic thd. Cdu t4o cria cdc sin phdm di du-o.cx6c clinh nhi phd
hdng ngoqi, cQnghtr8ng tt pr6ton vi phdkhd lugng. T{t ci c6c hidrazon nhgn dugc ttdu
c6 khA ning rlc chdin m6n th6p CT-3 trong mOitrudng HCI 2M.
u

TAr LrSU THAL KHAO
1.

A. S. Fouda, M. M. Gauda, S. I. Abd El-Ratimarr, Bull. Korean Chem, Soc., Vol.21, 1f11,
(2000), 1085.
Nguy6n Minh Th6o, Vfr Minh TAn, Phqm Vdn Nhitu, Tgp chi H6a hgc,T.42, If3(2004), tr.
3 11 .
Ph4m VIn Nhi6u, Vfr Minh Tdn, Nguy6n Minh Thho, Tg.p chi Ph6n tich H6a, L! vd Sinh
hgc, T. 9, lf2(2004), tr. 42.

Tqpchi Khoaho.c DHQGHN, KHTN & CN, T)N II, SdI, 2M7


Nguy€nMinhThio,PhemVnnNhiOu...

74

4.

NguySn Minh Th6o, Phgm Vin Nhi€u, Nguy6n Mgnh Cuing, Tqp chi H6a hgc vd tng
dVng, T{7 (2005), tr. 35.

5.

Nguy6n Minh Thio, Ng.,y6tr Dinh Thinh, Dlng Nhrr Tgi, D[ng Quttc Thanh, Nguy6n ViQt
Ttr{ng, Hoing Kim Vdn, Nguy6n Thu Lan, Phan Vin Cu,Ta.pchi H6a hQc,T.}l, No8(1997),
tr.17.
VNU. JOURNALOF SCIENCE,Nai.,Sci., & Tech.,TJqlll, Nol, 2007

STUDYON SYNTHESTSAI{D METALLIC CORROSIONINHIBITION
OF SOIUEBENZOYLHYDRAZONESO.
TIYDRO)ffACETOPHBNONES
Nguyen Minh Thao, Ph4m Van Nhieu, Nguyen Thi Thu Huong,
Ho Thi Van, Vu Phuong Lien
Department of Chemistry, Collcge of Sci,ence,VNU

Some hydrazones from hydrazides of substituted benzoic acids with ohidroxyacetophenones have been prepared by the condensation of hydrazides of
substituted benzoic acids vrith o - hidroxyacetophenones.
IH-NMR and MS
The structure of these products have been determined by IR,
spectroscopies.

Tqpchi KhoahqcDHQGHN, KI{TN & CN, T)Oilil, Si I, 2N7


VIETNAM
NATIONAL
UNIVERSITY,
HANOI
JOURNAL OF SCIENCE
NATUMLSCIENCES
& TECHNOLOGY
T. XXIII, No1- 2OO7

CONTENTS
l .

Vu Duc Minh. Some new experiment results applying combination
of the electrical souriding methods in order to discover old
vestiges

2,

Le Duc Manh, Nguyen Thi Huong Giang. Appiication of PCR
techniquefor detectionof Salrnonellain polluted surfacewater
Lz

3.

Pham Ngoc Lan, Luu Van Boi. Amphiphilic polyurethanes with a
novel peg-containing chain extender part
I: Synthesis and

characterization)
4.

Hoang Thu Ha, Pham Thi Tran Chau. Study on trypsin inhibitor
(tI) and chymotrypsin inhibitor (KI) from seeds of blue dragon
(Hylocereus
undatus (Haw.)Britton & Rose).....

D .

Mai Trong Nhuanr, Tran Dang Quy, Nguyen Tai Tue, Dao

Manh Tien, Nguyen Thi Hong Hue, Nguyen Thi Hoang Ha.
Study characteristics of sediment environmental geochemistry of
Phan Thiet - Ho Tram near-shoreZonef.orsustainableuse of natural
resources..

19

Q A
da

6.

Nguyen Kien Cuong. Plasma-InducedGraft Polymerization of
Acrylic Acid onto Poiy(ethylene terephthalate) Films: Hydrophilic
Modification
47

7.

Tran Minh Hanh, Nguyen Quoc Tuan, Luu Cam Loc.
Photooxidationof p-xyieneon TiO2and modified-TiO, catalysts..,,...,, o t

8.

Nguyen Minh Thao, Pham Van Nhieu, Nguyen Thi Thu
Huong, Ho Thi Van, Vu Phuong Lien, Study on synthesisand
metallic corrosion inhibition of some benzoyl hydrazonesohydroxyacetophenones,...,......,.....