JOURNAL OF SCIENCE OF HNUE Natural Sci., 2014, Vol. 59, No. 4, pp. 69-75 This paper is available online at http://stdb.hnue.edu.vn
TONG H O P VA XAC 0 I N H CONG THtTC CAU TAO PHUTC CHAT CUA Ni{n), Co(II), C o ( n i ) V 6 l AXIT 6-HYDROXY-3-SUNFOQUINOLIN-7-YLOXYAXETIC
L c T h i H o n g H a i \ T r § n T h i Da^ v a N g u y e n T h i N g o c V i n h ^
^Khoa Hda hoc, Trudng Bai hoc Su pham Hd Ndi
^Khoa Hda hoc. Trudng Dai hoc Hdng DUc, Thanh Hda
Tom tat. Tir eugenol trong Unh dau huong nhu, chiing toi da tong hdp dUdc mot dan xuat cua quinolin la axit 6-hydroxy-3sunfoquinol-7-yloxyaxetic (Q). TU dung dich CO chUa muoi ciia cac ion kim loai va phoi tU Q, tai pH = 6 -;- 7, da tim dUdc dieu kicn thich hdp de tach 3 phUc chat cua NiCII), Co(II}, Co{riI). DUa tren cac ket qua do EDX, phan tich nhiet, pho hap thu hong ngoai, pho kh6i ESI-MS, chiing toi da de nghi cong thUc phan tU, cong thUc cau tao cac phUc chat tong hdp dUdc: Na[Ni(Q-3H)(H20)2]-H20 (NiQ); NalCo(Q-3H)(H.20)2].2H20 {CoQD; Na2[Co(Q-3H)(Q-2H)(H20)2]4H20 (CoQ2). Cac du kien vg pho cho thay trong cac phUc chit ph6i tii Q lien k6t vdi nguyen tU kim loai trung tam qua nguyen tif O ciia nhom COO" hoac nguyen tU oxi ciia nhom phenolat.
Tif khoa: Tong hdp, cau triic, dan xuat ciia quinolin. phUc chat ciia Ni(II). Co(U).
Co(IlI), axit 6-hydroxyl-3sunfoquinol-7yloxyaxetic.
1. Md dau
TO lau, quinolin va cac dan xuat da thu hut dUdc sU quan tam nghien cUu cua cac nha khoa hpc do chung co nhieu Ung dung quan trpng trong hoa dUdc va hda phan tich.
Cac hdp chat co chUa vong quinolin da dUdc sU dung lam thuoc chfla benh s6t ret, chdng lao phoi. thudc chira ung thU,... [1,2], mot so thuoc thii' hiru cd co vong quinolin da dUdc diing lam chat chi ihi kim loai [3]. Ben canh do phUc ch4t cua cac hdp chdt co chUa vong quinolin cung thu hut dUdc sU quan lam nghien cUu ca ve mat c5u true cung nhu Ung dung 14,5].
Gan day, nhom chung toi khi khur dan xuat dinitro ciia axit eugenoxy axetic bang Na2S20.i da khep vong nhanh anlyl tao ra dan xudt mdi cua quinolin la axit 6-hydroxy-3-.sunfoquinolin-7-yloxyacelic (ki hieu la Q) [6]. Trong bai bao nay chung tdi trinh bay quy trinh tong hdp phoi tuf Q va ket qua nghien cUu tong hdp, cSu true, tinh chat phUc chat ciia phoi tii: nay vdi mot s6 kim loai chuyen tiep nhom d (Co, Ni).
Ngiiy nhiin bai' 11/5/2014 Ngiiy nhan dang: 6/6/2014.
Tac i-ia lien lac: Le Thi Hong Hiii. dia chi e-mail: [email protected].
Le Thi Hong Hai, Tran Thi Da va Nguyen Thj Ngoc Vinh 2. No! dung nghien ciiu
2.1. Tong h«p phoi tuT
Chung toi tien hanh long help ph6i tii Q theo each thtic da dUdc trinh bay trong [6], / \ ^ ^ ^ l - l 1)CICH,C0,N. ^ ' \ . ^ ^ ' , ' HNUj.AcOH U O T c ^ ^.f ^ f llNa,S,0,
•ro
If | [ • ^ n .1 , _ 11 II 1
•OCH2CO2H NO,'^ j f ^ ^ t f 2)H*
cT OH CHjCOill tH.CO,H
eugenol (Al) (A2) (Q)
2.2. Tong hop phiic chat cua coban, niken v6i phoi tuf Q
Chung toi da nghien cUu IUdng lac ciia phoi tOl Q vdi cac ion kim loai Ni-^+, C o "
Irong cac di£u kien khac nhau ve dung moi phan irng (dung moi nudc, DMSO, DMF), ciich lien hanh phan ling, ti le cac chat tham gia phan dng (ti le moi ciia ion kim loai: ph6i lii la I; I va 1:2), nong dp, nhiet dp, moi trudng va each tach san pham. Qua thiTc nghiem da tim duoc dieu kien thich hdp de tach duoc 3 philc chat ciia Ni(ll), Co(ll), Co(III) vdi phoi Hi Q.
Tong hop phUc chat C o Q l : Cho 0,3g Q (I mmol) vao ,"5 mL H2O, them tii til 2 mL dung dich NaOIl 0,5 M khuay cho Q tan hoan toan, thu dutic dung dich 1 co pH ^ 7. Nho tif tii 4 mL dung djch CoClj 0,25 M (1 mmol) viio dung dich 1, khuiiy 2h 6 nhiet do phong Ihu duoc dung dich mau xanh den. Them etanol 96° (Veianoi =2V dung djch), thay xuat hien ket tua mau xiim nau. Loc kel tiia, riia bang ruou, say d 50 °C. Ket tinh lai trong dung moi etanol - nUdc ti le 1. 5, Ihu dUdc bpl mau den, ki hieu C o Q l , hieu suat 4 5 % .
Tong hap phiic chat CoQ2: Cho 0,5 g Q (2 mmol) vao 50 mL B^O, khuSy d 50 °C thu duoc dung dich Q. Cho dung dich Q vao I mmol Co(OI 1)3 trong 5 mL 11-,0. Khu§y 30 phiit d 50 °C thu duoc dung dich trong su6t, khuay tiep 2h. Them rUOu etylic (V,ij„„i
= 2 V dung dich), thay xu^t hien ket tua mau niiu. Loc ket tiia, riia bang rUOu, say d 50
°C. Ket linh lai trong dung moi elanol - nUdc (ti Ic 1:2), Ihu duOc bol mau den, ki hieu la CoQ2, hieu siiai 50%.
Tdng hgp phiic chat NiQ: Cho 0,3g Q (I mmol) vao 5 mL H.,0, them lit tir 2 mL dung dich NaOH 0,5 M khuSy cho Q lan hoan toim, Ihu dugc dung dich 1 co pH « 7. Nho lif 111 4 mL dung dich NiCb 0,25 M (1 mmol) vao dung dich I, khuay 2h 6 nhiet do phong Ihu duoc dung dich mau xanh hoi den. Them etanol 96° (Va,„„,i = 2 V dung dich), Ihay xuat hien k6l tiia mau xanh reu. Lgc thu kel tiia, riia bang etanol, say d 50 °C. KSt tinh lai irong hon hgp dung moi elanol nUdc ti le 1:5, thu dUdc tinh the miiu xanh reu, ki hieu NiQ, hieu suSl 50%.
2.3. Nghien ciiu thanh phan cau tao, tinh chat cua cac phiic chat Pho EDX ciia ciic phiic chat dugc do lai Vien Khoa hpc vat lieu - Viijn Han lam Khoa hoc va Cong nghe Viet Nam. Kel qua do EDX cho Ihiy sU co mat ciia cac nguyen l i
Tong hap vd xdc dinh cdng thdc cdu tao phifc chdt cua Ni(/l). Codl). Co(IIl)...
trong phan tiJr va ti le tUdng d6i giUa chiing. Trong cac phiic chit NiQ, CoQl ti le nguyen K\i kim loai trung tam M (Ni, C o ) : S «; I: I, vi vay trong cac phiic ch4t nay ti le nguyen tU kim loai trung tam (Ni, Co): Q la 1:1. Con trong phiic chdt CoQ2, ti le nay la I : 2. DUa vao ket qua do EDX, kit hdp vdi cac diJ kien thuc nghiem khac nhu pho ESI-MS, phan lich nhiet chung toi sd bp de nghi cong thUc phan ui cua cac phiic chat nhu c) Bang 1,
Bdng 1. Ket qua phan tich ti le nguyen td stt
1 2 3
Kl hieu NiQ CoQl CoQ2
Cdng thdc phan tii Na[Ni(CiiH6OTNS)(H20)2l.H20 Na[Co(CiiH,,07NS)(H20)2].2H20
Na2[Co(CiiHr,07NS)(ClIH707NS)(H20)2].4H20
Tl le nguyen tiif (TN/LT) Na(K):M:S
4,32:4,47:5,73/1:1:1 5,32:5,50:5,89/1:1:1 3,80:2,14:3,95/2:1:2 Gian dd phan tich nhiet cua cac phUc chat dUdc do tai Bp mon Hoa Li, Khoa Hda hpc. TrUdng Dai hpc Su Pham Ha Noi, trong kbi quyen trd, tdc dp nang nhiet la 10 °C/
phiit, nhiet dp tii 30 °C den 800 °C. K6t qua phan tich nhiet ciia 3 phUc chat dUdc trinh bay cf bang 2. Tren gian dd phan hiiy nhiet cua cac phUc chSt NiQ, CoQ I, CoQ2 xual hien hai hieu Ung d4u tien la hieu Ung thu nhiet, kem theo su giam khdi lUdng tren dUdng TOA trong khoang nhiet dp 80 -f 250 °C do vay trong cac phUc chat nay cd chUa ca nUdc ket tinh va nUdc ph6i tri. Ham lUdng nUdc ket tinh, phoi tri theo cong thUc de ngbj cua cac phUc chat kha phii hdp vdi dp giiim khoi lUdng tren dUdng TGA (Bang 2). Cac giai doan sau chung toi chUa co diSu kien nghien cUu ki, chi sd bp de nghi san pham ran con lai sau khi phan hiiy d 800 °C. K£t qua cho thay ham lUdng chdt ran con lai tinh theo cdng thUc de nghi kha phCi hdp vdi % chat ran cdn lai tinh theo dp giam khdi lUdng tren dudng TGA.
Ki hieu
NiQ CoQl CoQ2
Bdng 2. Ket qud phan tich nhiet cua cdc phu
Cling thiic ciia hop chat
Na[Ni(CiiHi,07NS) ( H 2 0 ) J 1 . H 2 0 Na(Co(CuH(i07NS) (H20)2J 2H2O Nii2[Co(CiiH|,07NS) (C„H707NS)(H20)2].
4H2O
Mat nudc kilt tinh va nu6c phoi tri Al°C 80-250 80-250 80-240
Am,%
TN/LT 14,1/12.5 15,3/16,0 15,4/13,4
c chdt Phan hiiy, oxi hoa khuf At°C
250-800 250-800 240-800
San pham con lai
NiO, l/2Na2CO-,
CoO, l/2Na2CO,
CoO, Na2C0:s
Am,5i TN/LT 30,5/29,6 31,6/31,1 23,0/22,5
Phfi khoi lugng cua cac phiic chat theo phUOng phap ESI - IVIS (Electro Spray Ionization Mass Spectrometry) dUdc do Iren may 1100 Series LC-MSD-Trap-SL tai Vien Hoa hgc, Vien Han lam Khoa hgc va Cong nghe Viet Nam. Cac phdc chat nghien cdu deu la nhiing phiic chat dien li, tan trong nUdc, do do khi ghi pho theo phUOng phap ESI MS, tren phti cac cum pic phan lii khong xuat hien hoac cd cudng do thap, ma xuat hicn 71
1^ Thi Hong Hai. Tran Thi Da va Nguyin Thj Ngoc Vinh
cac cum pic manh idn hoac cac cum pic cua cac cation, anion dUdc tao ra khi cac phan lii phiic chat k6t hdp vdi cac ion am hoac ion dUdng co trong dung dich mlu hoac trong cac giptmu(Na+,K+, H+...), nU6c ket tinh (mot so trUdng hdp keca nUdc phdi tri) khong c6 trong thanh phSn cac ion phUc khi do pho (cac cum pic nay dUdc gdi la cac cum pic ion phan t^ gia). Tit gia tri m/Z cua pic co trong cum pic phan tur gia, chiing toi xac djnh dUdc khoi lUdng phan tii phiic chat tUdng dng. Cac gia tri do dUdc goi la phan tuf kh6i cua phiic chat xac dinh dUdc dUa vao thUc nghiem nen ki bieu la MTN. Dua vao cac dong vi ciia cac nguyen td, chiing toi tinh dUdc phan tii khdi cua cac phUc chat cd gia tri nho nh3t (ki hieu la Mmm) va phan td khoi cd gia tri 16n nhat (ki hieu la Mmjix) (Bang 3, Hinh la). Mot so pic chinh tren pho ESI-MS cua cac phiic chat da dUdc quy ket va trinh bay cf Bang 3.
K8t qua cho thiy cd sU phu hdp giUa cdng thUc phan tiJf de nghi vdi gia tri ciia cac pic tren pho ESI-MS (Bang 3).
Bdng 3. DU kien chinh tren pho MS cda cdc phiic chdt stt
1
2
3 Kl hieu
NiQ
CoQl
CoQ2
Cong thiic phan tii
NalNi(Q-3H)(H20)2].H20
Na[Co(Q-3H)(H20)2].2H20 Na2[Co(Q-3H)(Q-2H)(H20)2 4H2O
Mm|„, Mma«
MTN 413,418
414 450,453
450 806,812
806
Cac pic trong cum pic ion phan tuf gia tren ph(> m/Z;
quy ket 397 = 396 -t 1 = (Na[Ni(Q-3H)(ll20)]-l-H)+
499 = 373-1- 126 = ([Ni(Q-3H)(H2O)] + 7H20)- 414= (Na[Co(Q-3H)(H20)2]|
437 = 414-1-23
=(Na[Co(Q-3l-l)(Il20)2]-l-Na) + 753 = 698 -r 54 -1- 1
=(Na2[Co(Q-3H)(Q-2H)(H20)2l -l-3H20-i-H) +
a) Mot phan pho'ESI-1\4S cuaphiic chdt NiQ
Hinh L
b) Phd hdp thu hong ngoai cua phUc chat CoQ2 72
Tdng hap vd xdc dinh cdng ihifc cdu tao phiic chdt cua Ni(II). Co(II). Co(lII)...
P h o h a p t h u h o n g n g o a i c u a c a c phUc c h a t dUdc d o t r e n m a y I M P A C K - 4 1 0 N I C O L E T , tai V i e n H d a h p c , V i e n H a n l a m K h o a h o c v a C d n g n g h e V i e t N a m . C a c v a n h a p t h u c h i n h t r e n p h o h o n g n g o a i d u p c t r i n h b a y d B a n g 4 . T r e n p h o h d n g n g o a i c u a h a u h6t c a c p h U c c h a t m a c h u n g tdi t d n g h d p dUdc x u a t h i e n 2 v a n h a p t h u m a n h d tan s o k h o a n g 1 6 0 0 v a 1 4 0 0 c m ' , tUdng Ung vdi tSn s 6 d a o d p n g k h o n g d d i xUng v a d o i xUng c u a n h o m C O O " . Sif t h a y d o i t a n s o c u a U^Q^J. va U'^'IJQ- S O vdi p h 6 i tii t u d o , chUng to n h o m C O O " d a t h a m g i a l i e n k i t p h o i tri v d i n g u y e n tut k i m loai t r u n g t a m . Ci v u n g tan sd t h a p ( k h o a n g 5 0 0 c m " ' ) x u a t h i e n n h i e u v a n hSp t h u vdi cUtlng d p m a n h d o x u a t h i c n t h e m d a o d o n g h o a tri ciia l i e n k e t k i m l o a i v d i n g u y e n t d o x i . C a c dU k i e n t r e n p h o h o n g n g o a i c h o t h a y t r o n g c a c p h i i c c h a t , p h d i tii Q lien ket vdi n g u y e n lU k i m loai t r u n g t a m q u a n g u y e n tiV O c u a n h d m C O O " h o a c n g u y e n tii oxi ciia n h o m O H p h e n o l h o a c n g u y e n tU o x i cQa n h d m 8 0 7 .
Stt
1
2 3 4
Ki hicu
Q N i Q
C o Q l
C o Q 2
-—
Bdng 4. Cdc van hap thu cliiiih tren phij hdng ngoai (cm ~ ^
I'm!.
3700 - 2830 3 6 1 0 - 2 9 0 0 3650 - 3010 3 6 8 9 - 2 9 5 0
l^CHihifii
Bi che lap Bi che
lap Bi Clio
lap B i c h e
liip '^OHno
Bi che lap B i c h e
lap 2930
2858 '^c:oo-
1632
1608
1622
1618
..
'-"(•-c.
"C-K
(A)_
1503
1526 Bi che
lap 1523
„dx
^coo-
1405 1458 1482- 1421 1458
..
'-•c-o
1 2 7 7 - 1222 1 5 2 9 - 1203 1 2 6 0 - IIKI 1203
'^SOi
1353
1341
1310
1341 i^M o
476 543 509
D u a t r e n c a c k e l q u a d o E D X , p h o k h d i E S I - M S , p h a n lich n h i e t , p h d h a p thu h d n g n g o a i , c h i i n g tdi b u d c d d u d c n g h i c o n g thiic c 5 u l a o c u a c a c phUc c h a t n h u s a u :
.H2O Ni
Phiic chdt NiQ
H2O O H ,
X •
PhUc chat CoQl
o
\
.aHjOLe Thi Hong Hai, Trin Thi Dii va Nguyen Thi Ngoc Vinh
Vo^i/°-<'
^/ V
H,C jr . ^ CH2
SO3- SOj- PhUc chdt CoQ2
3. Ket luan
- Qua khao sat, chung toi da lim dugc dieu kien thich hgp de long hop 3 phdc chSl ciia Ni(ll), Co(II), Co(III) vdi phdi lif Q.
- Difa tren cac kel qua do EDX, phan tich nhiet, phi) hSp thu hdng ngoai, pho khdi ESI-MS biidc dau da d6 nghi cong thiic phan lii, cong Ihiic cau lao ciic phiic chat long hgp dugc: Na[Ni(Q-3H)(H20)2|.H20 (NiQ); Na[Co(Q-3H)(H20)2].2H20 (CoQl);
Na2[Co(Q-3H)(Q-2H)(H20)2].4H20(CoQ2).
- Cac du kien ve pho cho thay ion kim loai Ni^+, Co^^ tao phiic vdi phoi tuf Q theo li le ion trung tam:pht)i lii la 1:1; con Co(lll) lao phiic vdi phdi td Q theo ti le la 1:2. Trong ciic phdc chat phoi Hi Q lien kSl vdi nguyen tut kim loai trung tam qua nguyen Hi O cda nhdm COO" hoac nguyen td oxi ciia nhdm phenolat.
Lili cdm an: Cdng trinh dugc hoiin thanh vdi stt giup dd cua Quy Phat trien Khoa hgc va Cdng nghe Quoc gia (NAEOSTED).
TAX LIEU T H A M KH/VO
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| 2 | A. Nayyar, A Maldc, H. Coulinho el al., 2006. Synthesis, anti-luhercidosis activity.
and 3D-QSAR study of ring-sub.stinited-2/4-quinolinecarbaldehyde derivatives.
Bioorg. Med .Chem, 14(21), 7302-7310.
| 3 | l-rank John Welcher, 2012. Organic Analytical reagents. Literary Licensing (LLC).Pub. Vol.3.
Tdng hop vd xdc dinh cdng iliitc cdu tao phdc chdt cua NHII). Co(II). Co(IIl)...
[4] Celine Deraeve, Christophe Boldron et al., 2008. Preparation and Study of New Poly-8-Hydroxyquinoline Chelators for an anti- Alzheimer Strategy. Chem. Hur. J, Vol 14, pp. 682-696.
[5] Lifcn Xiao, Yuan Liu, Qian Xiu, Lirong Zhang et al., 2010. Novel polymeric metal complexes as dye sensitizers for Dye-sensitized solar cells based on polythiophene amlaining complexes of 8-hydroxyquinoline with Zn(Il), Cu(II) and Eu(Il) in the side chain. Tetrahedron Vol 66 (15), pp. 2835-2842.
[6] Nguyen Huu Dinh, L.V. Co, N.M. Tuan, L.TH. Hai. L.V Meervelt. 2012. New route to novel polysubsiituted quinolines starting with eugenol, the main constituent of Ocinium sanctum L. oil. Heterocycles, Vol. 85, No. 3, pp. 627-637.
ABSTRACT
Synthesis and structure complexes of Ni(Il), Co(II), Co(III) with 6-hydroxy -3-sulfoquinolin-7-yloxyacetic acid
A derivative of quinolinc, 6-hydroxy-3-sulfoquinolinc-7-yloxyacelic acid quinolinc (Q) was synthesized starting with eugenol, the main constituent of Ocimum sanctum L.
oil. Three complexes of Ni(II), Co(ll), Co(lll) with ligand Q: Na|Ni(Q-3H)(H20),|.H20 (NiQ); Na[Co(Q-3H)(H20)2].2H20 (CoQl); Na^[Co(Q-3H)(Q-2ll)(H.20).2|.4H.2O (CoQ2) were isolated from aqueous solution of M""', Q ai pH = 6 -:- 7. The structure of the complexes was suggested on basis of EDX, thermal decomposition, liSI-MS, IR spectroscopy. Experimental data showed that in those complexes ligand Q coordinates with metal atoms through oxygen atoms of the carboxylatc and phenolatc groups.
