Synthesis of New Multinuclear Schiff Bases and Oxidation of Ascorbic Acid by TheirCopper(II) Complexes

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2003, Vol. 47, No. 2

Printed in the Republic of Korea

Cu(II)

*

(2003. 3. 7 )

Synthesis of New Multinuclear Schiff Bases and Oxidation of Ascorbic Acid by Their Copper(II) Complexes

Sun Deuk Kim*and Jin Dong Kim

Department of Material Science, Daegu University, Gyeongsan 712-714, Korea (Received March 7, 2003)

: , , Cu(II)

Keywords: Multinuclear Schiff base, Oxidation of Ascorbic acid, Copper(II) Complexe

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,@ AB ,

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$ 6 ; 2D H IB JK LM .N ?OPB QRE STU.^10-134 VE W

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"#$ N, N, N',N'-Tetrasalicylidene-3,3'-diamino-benzidine (H4TSDB) AB N, N, N', N'-Tetrasalicylidene-3,3'4,4'- tetraamino-diphenyl-methane(H4TSTM) Cu(II)

[Cu2(TSDB)] + [Cu²(TSTM)]6

,@ =>E F14. & ]Cu(II) =>^

6 ; [Cu(salen)]8 & =>

^& _` ?OaN bcde.¹⁴A4 ;

[salenCr-N3]f & [(salenCr-N³)2] ghY 8 i &7 & TMSN³(Me3SiN3)2 4 2j$

kl 0" mn 2D =>E F1o ] &

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"#$ ) VB

I.

 2DB Scheme2 ?O f &  - ! ; |" "#$f N, N'- Bis(salicylidene)-(2-aminoethyl)-ethane-1,2-diamine (H2SED)L RE \ m " & + m

| " "#$Y )de. A4

&7 "#$ Cu(II) [Cu(SBD)], [Cu²(TSED)], [Cu2(TSBD)] + [Cu³(HSED)]Y )d0, & Cu(II)

7& ,@(p2 B

N vde.

 . 2 v14 ethylamine, ethylene- diamine, diethylenetriamine, 1,4-diaminobutane,

6 Fluka .N dM 0 /E v

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1de. tris(2-aminoethyl)amine, 1,10-phenanthroline + 6 Aldrich .N /E v1deR,

1>f 4-toluenesulfonyl chloride, + 2- aminoethanol6 JunseiY dM 0 /E v1 de. % ¡¢6 Shimadzu UV-160A , --p!E £deR, *¤ ¡¢6 Shimadzu IR-470 ,--p!Y &1de. ¹H-NMR,

13C-NMR ¡¢6 Varian Mercury 300 NMR ,-

Y &1de0, C. H. N ¥ ,¦6 Carlo Erbav

Instrument 1106N &1de0, § ¡¢6 JEOL v §,- JMS 700N v1de.

4-benzyldiethylenetriamine2HCl . 50 ml

2{¨2 diethylenetriamine(5.2 g,0.05 mol) benzaldehyde (14.6 g, 0.12 mol)N LdJ 6#<© ª «, &

1¬2 benzyl chlolide(8.8 g, 0.07 mole) LdJ 6®

<© ¯X ° ±¡/(50:50)N LdJ ²

³%N z. z ³%N 2{¨2 ´

&0 N LdJ µ¶ ²N ·¸.

Yield: 78%. IR(KBr, cm⁻¹): 3416(vN-H), 1476, 1602(vC=C).

1H NMR(D2O): δ 2.69(2H, methylene), 3.26(4H, C1-H), 3.46(4H, C2-H), 7.18(5H, benzene). ¹³C NMR(DMSO):

δ 30.54, 40.26, 46.72, 124.67, 124.69, 126.32, 130.27.

N,N-Bis(salicylidene)-(2-aminoethyl)-benzyl-ethane- 1,2-diamine(H2SBD) . 50 ml 2{¨2 4- benzyldiethylenetriamine¹2HCl(1.93 g, 0.01 mol)N ´

&0 60^oC2D DDG salicylaldehyde(2.8 g, 0.22 mol) N L4 « & º)¬N 5 #<© ¯X »i

¼½¶N ¾. & 1¬2 N § LdJ ¿À0 2 d<© Zi ¼½¶ \ H2SBD& ².

Yield: 69%. Anal. Calcd. C25H27N3O2: C, 74.78; H, 6.77;

N, 10.47. Found: C, 72.57; H, 6.92; N, 10.26(%). UV/

Vis(70% dioxane), λmax, nm(ε, M⁻¹cm⁻¹): 254(19,940), 324(5,620). IR(KBr, cm⁻¹): νC=N 1638, νC=C 1580, 1460, νO-H 3480. ¹H NMR(DMSO): δ 2.72(2H, C2-H), 3.62(2H, methylene), 3.65(2H, C3-H), 6.76(1H, phenol), 6.85(1H, phenol), 7.06(2H, benzene), 7.07(1H, benzene), 7.12(1H, phenol), 7.14(2H, benzene), 7.45(1H, phenol), 8.11(1H, C=N). ¹³C NMR(DMSO): δ49.02, 50.32, 53.96, 116.23, 118.32, 121.84, 127.21, 128.14, 129.31, 130.73, 131.62, 132.12, 137.82, 165.82. Mass(GC-mass), m/e:

401(M⁺), 91(base).

N-(p-toluenesulfonyl)aziridine(Ts-aziridine) . Á$"ÂY )o ] N-ÃÄ ¥ÅL 9B N-(p- toluenesulfonyl)aziridineB & ÆÇ2 80 ÈÉR E )de.^16,17 Yield: 79%. ¹H NMR(DMSO): δ 2.38 (4H, C1-H), 2.41(3H, methyl), 7.37(2H, benze ne), 7.82 (2H, benzene). ¹³C NMR(DMSO):δ18.9, 25.4, 126.6, 129.3, 135.1, 148.9.

Scheme 1.

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N,N,N',N'-Tetrakis(2-aminoethyl)-ethane-1,2-diamine (TAED)4HBr . 50 ml ethylenediamine(3.4 g, 0.05 mol) Ts-aziridine(43.3 g, 0.22 mol)N 2 #

<© ¯X ª « 50 ml 2{¨N LdJ d<© ª. &] ² ³%N z

« 2{¨ 2ÊY &1dJ Ë0 & ³%2 ±¡

/(70:30 v/v) 100 mlf 3 mlY LdJ 90^oC2D 24#<© ¯X dJ µ¶ TAED¹ 4HBrN ·¸. ·6 TAED¹4HBrN Ì 2{¨E Í ËÎ ÏÐ « v1de. Yield: 35%. IR(KBr, cm⁻¹): 3420(νN-H), 1110(νC-N). ¹H-NMR(D2O):δ 2.86(1H, C1-H), 3.29(2H, C2-H), 3.33(2H, C3-H). ¹³C NMR(DMSO): δ 12.10, 44.52, 52.61.

N,N,N',N'-Tetra(salicylidene)-tetrakis(2-aminoethyl)- ethane-1,2-diamine(H4TSED) . TAED¹4HBr (5.1 g, 0.01 mol)Y 2{¨ 50 ml2 ´&0 ?¡

Ñ(1.6 g, 0.04 mole)N LdJ Òª « salicylaldehyde (4.5 g, 0.4 mole)N LdJ 5#<© ¯X »i

¼½¶N ¾. & 1¬2 N § LdJ pH 4.5

p 1¬N Ó7Î ¿À02 d<© Zi

¼½¶ m " & H⁴TSEDL ·Î Ô

. Yield: 52%. Anal. Calcd. for C38H44N6O4: C, 70.35;

H, 6.84; N, 12.95. Found: C, 69.25; H, 6.82; N, 12.99(%).

UV/Vis(70% dioxane), λmax, nm(ε, M⁻¹cm⁻¹): 404 (8.710).

IR(KBr, cm⁻¹): 1632(νC=N), 1472, 1604(νC=C), 3424 (νO-H). ¹H NMR(DMSO): δ 2.73(2H, C2-H), 3.39(1H, C1-H), 3.55(2H, C3-H), 6.87(2H, phenol), 7.28(2H, phenol), 8.37(1H, C=N). ¹³C NMR(DMSO): δ 52.87, 54.92, 56.79, 116.45, 118.09, 118.38, 131.32, 132.01, 160.84, 165.94. Mass(GC-mass), m/e: 648(M⁺), 324(base).

N,N,N',N'-Tetrakis(2-aminoethyl)-butane-1,4-diamine (TABD)4HBr . 50 ml 2{¨2 1,4- diaminobutane(5.1 g, 0.05 mole) Ts-aziridine (43.3 g, 0.22 mole)N LdJ TAED¹4HBr )ÈÉ 6 ÈÉRE TABD¹4HBrN ·¸. Yield: 32%. IR(KBr, cm⁻¹): 3430(νN-H), 1120(νC-N). ¹H NMR(D2O): δ 2.86(1H, C1-H), 3.29(2H, C2-H), 3.33(2H, C3-H). ¹³C NMR(DMSO):δ 12.10, 44.52, 52.61.

N,N,N',N'-Tetra(salicylidene)-tetrakis(2-aminoethyl)- butane-1,4-diamine(H4TSBD) . 2{¨ 50 ml 2 TABD¹4HBr(5.5 g, 0.01 mol)Y ´&0 ?¡Ñ (1.6 g, 0.04 mol)N LdJ Òª « salicylaldehyde

(4.5 g, 0.4 mol)N LdJ H4TSEDf 6 ÈÉRE )

dJ m" & H4TSBDY ·¸.

Yield: 50%. Anal. Calcd. for C40H48N6O4: C, 70.98; H, 7.15; N, 12.42. Found: C, 70.86; H, 7.31; N, 12.34(%).

UV/Vis(70% dioxane), λmax, nm(ε, M⁻¹cm⁻¹): 405(8.630).

IR(KBr, cm⁻¹): 1635(νC=N), 1597, 1475(νC=C), 3480 (νO-H). ¹H NMR(DMSO): δ 1.16(1H, C1-H), 2.19(1H, C2-H), 2.38(2H, C3-H), 3.40(2H, C4-H), 6.87(2H, phenol), 7.28(2H, phenol), 8.38(1H, C=N). ¹³C NMR (DMSO): δ 24.68, 53.74, 54.35, 56.65, 116.38, 118.04, 118.34, 131.27, 131.92, 160.79, 165.88. Mass(GC-mass), m/

e: 677(M⁺), 84(base).

N,N-(2-amino-ethyl)-[2-(bis-2-[bis-(2-aminoethyl)- amino]-ethylamino)-ethyl]-ethane-1,2-diamine(AAED) 6HBr . 2{¨ 50 ml2 tris(2-aminoethyl) amine(7.8 g, 0.05 mol) Ts-aziridine(69 g, 0.35 mol) N LdJ TAED¹4HBr )ÈÉ 6 ÈÉRE AAED¹6HBrY ·¸. Yield: 32%. IR(KBr, cm⁻¹):

3430(νN-H), 1120(νC-N). ¹H NMR(D2O):δ 2.82(2H, C1-H), 3.02(2H, C2-H), 3.09(2H, C3-H). 3.31(2H, C4-H).

13C NMR(DMSO): δ 31.82, 42.21,46.05, 52.54 ppm.

N,N,N,N',N',N'-Hexa(salicylidene)-N,N-(2-amino- ethyl)-[2-(bis-2-[bis-(2-aminoethyl)-amino]-ethylamino)- ethyl]-ethane-1,2-diamine(H6HSED) . 2{

¨ 50 ml2 AAED¹6HBr(8.9 g, 0.01 mol)Y ´&0 ?¡Ñ(2.4 g, 0.06 mol)N LdJ Òª « salicylaldehyde(6.8 g, 0.6 mol)N LdJ H⁴TSEDf 6 ÈÉRE )dJ m | " H6HSED Y ·¸. Yield: 42%. Anal. Calcd. C60H72N10O6: C, 70.01; H, 7.05; N, 13.61. Found: C, 69.87; H, 7.15; N, 13.82(%). UV/Vis(70% dioxane), λmax, nm(ε, M⁻¹cm⁻¹):

402(9.410). IR(KBr, cm⁻¹): 1632(νC=N), (νC=C) 1579, 1465(νC=C), 3472(νO-H). ¹H NMR(DMSO): δ1.97 (2H, C3-H), 2.23(1H, C1-H), 3.08(1H, C2-H), 3.62(2H, C4-H), 6.76(1H, phenol), 6.93(1H, phenol H), 7.15(1H, phenol), 7.25(1H, phenol), 8.55(1H, C=N). ¹³C-NMR (DMSO): δ 51.04, 53.82, 54.77, 56.20, 117.51, 118.19, 118.21, 131.29, 132.01, 160.13, 165.07. Mass(GC-mass), m/e: 1029(M⁺), 338(base).

Cu(II)- . H2SBD, H4TSED, H4TSBD + H6HSED "#$f Cu(NO3)2¹ 3H2OY ÕÕ JK ÖkE ×{¨ 1>2 ´&0

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X ¯XÀ2D 60^oCE d<© ° Ø´

¶ + ØÙ¶ N )de. A4 ;

[Cu(SED)], & [Cu²(TSDB)] f [Cu²(TSTM)]

6 & 80 ÚÆ^13,14 & )dJ v1de.

Cu(II)&Û ) "#$L N ²o ] \) kB DMSO 1>2 ´c Cu(NO³)2¹3H²O 1¬ )

4 "#$7Y ÖkÉ2 yÜ JK ktRE Ý6 «2 d<© ÈdJ [Cu(SBD)]B 590 nm2D, [Cu2(TSED)]

f [Cu²(TSBD)]B 603 nm2D, [Cu³(HSED)]B 589 nm 2D -pY £dJ de.

[Cu(SBD)]H2O. Yield: 32%. Anal. Calcd. for C25H25-

CuN3O2¹H²O; C, 60.17; H, 5.05; N, 8.42. Found: C, 59.07;

H, 4.97; N, 8.13(%). UV/Vis(DMSO), λmax, nm(ε, M⁻¹cm⁻¹):

590(186). IR(KBr, cm⁻¹): 1632(νC=N), 1579, 1462(νC=C), 3472(νO-H). FAB-MS, m/e: 463(M⁺), 359(base).

[Cu2(TSED)]2H2O. Yield: 35%. Anal. Calcd. for C38H40Cu2N6O4¹2H2O; C, 56.49; H, 4.99; N,10.40. Found:

C, 55.36; H, 5.05; N, 10.18(%). UV/Vis(DMSO), λmax, nm(ε, M⁻¹cm⁻¹): 603(404). IR(KBr, cm⁻¹): 1625(νC=N), 1580, 1452(νC=C), 3424(νO-H). FAB-MS, m/e: 772 (M⁺), 338(base).

[Cu2(TSBD)]2H2O. Yield: 31%. Anal. Calcd. for C40H44- Cu2N6O4¹2H2O: C, 57.48; H, 5.79; N, 10.05. Found:

C, 56.29; H, 5.68; N, 9.85(%). UV/Vis(DMSO), λmax, nm(ε, M⁻¹cm⁻¹): 603(397). IR(KBr, cm⁻¹): 1632(νC=N), 1596, 1478(νC=C), 3470(νO-H). FAB-MS m/e: 800(M⁺), 338(base).

[Cu3(HSED)]4H2O. Yield: 23%. Anal. Calcd. for C60H66Cu3N10O6¹4H2O: C, 56.05; H, 5.17; N,10.89.

Found: C, 55.36; H, 5.32; N, 10.92(%). UV/Vis(DMSO), λmax, nm(ε, M⁻¹cm⁻¹): 589(521). IR(KBr, cm⁻¹): 1635 (νC=N), 1594, 1472(νC=C), 3440(νO-H). FAB-MS, m/e: 1214(M⁺), 307(base).

 . (pY £

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Cu(II) àpE ¯dJ 5.0×10⁻⁶ M& 9p de.

1>B 70% DMSO/waterN v1de. 25^oC2D

#2 4 á§6 OnishiÉRE £

de0 âã äåN Xd2D äåde.¹⁸

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#$Y DE \»? AB JK " ®ï ð

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& "#$ )2DB Lød?

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"#$ )p Lød.^14,17,18 yÜD

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[Cu(SBD)], [Cu2(TSED)], [Cu2(TSBD)] + [Cu3(HSED)]

6 ×{¨ 1>2 )4 Õ "#$f Cu(II)&Û N ÕÕ JK ÖkE ûÎ ° Ø´¶ + ØÙ¶

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N )de. ) Õ %

¡¢ \Y 8i 590-603 nm üú2D ý L ? Oþ. & \Eê ) Cu(II)6 ÿrú v ÕY &0 :N o :.^8,19)

Cu(II)6 *¤, L, § ¡¢ + ¥ ,

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) Cu(II)N =>E v1o ]

,@(pB Cu(II)2 @ ,@

90 a:B àpY Onishi ÈÉ2 yÜ -pY £dJ de.¹⁸/ \B Fig. 1 + Table 12 ?OP¸. &] Fig. 1 + Table 1 \

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salen Cu(II) Z [L \ &

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®ï (p kY de. Table 1 \Y 8 i ,@ (p B ;

c [Cu(SED)]f [Cu(SBD)] gh 6 tN ? OP¸. & ghB W " [Cu2(TSDB)] + [Cu2(TSTM)] 8 | " [Cu²(TSED)] [Cu²(TSBD)]

L s (p Y ?OP¸0, &] (p

B ; 8 10r & tN ?Ou. /"0

& { vwx& ~L2 yÜDp

,@ (pL ~LôN Ã.

[Cu3(HSED)] ghB & 8p s

(p tN ?OP¸. \2D % (p

t _ DB [Cu(SED)] [Cu(SBD)]<<[Cu2(TSDB)]

<[Cu2(TSTM)]<[Cu2(TSED)]<[Cu2(TSBD)]<[Cu3(HSE D)]&¸. &f & ; 8 & &1 ] => ^& ~9Î

(pL 10r & G s tN ?ON Ã :

. / &B Cu(II)&

,@ 2D ,P Cu(II)L DE <N ô RE (pL ~L40 ²Õ. / VE ;

[salenCr-N³]f & [(salenCr-N³)2] g h TMSN32 4 2j$ kl 0" mn =>

2D + vwx&2 yÜD =>^

~L D \f ®de.¹⁵yÜD

2D v1 H2SED ; Co(II)6 &

&<=>2, Cu(II)6 ,@2

&190 :.^6,9RE 2D )

"#$ H4TSED, H4TSBD + H6HSED JK

%&'( 76 ,@ &¤2 JK =>ED 1& .

B 2001p P k M¥2

dJ 9¸R &2 v$.

1. Molina, R. H.; Mederos, A.; Gili, P.; Dominguez, S.;

Nuricz, P. Polyhedron 1997, 16, 4191.

2. Kim, S. D.; Jang, G. H.; Kim, J. K.; Lee, S. W.; Jung, J. J. Anal. Sci. & Tech. 1996, 14, 346.

Fig. 1. Plots of log(Co/C) against time t for oxidation of ascorbic acid in the presence of Cu(II) complexes in 70%

DMSO/water.

Table 1. Rate constants of the oxidation of ascorbic acid by Cu(II) complexes in 70% DMSO/watera

Complex k×10⁴, min⁻¹

none 0.28

[Cu(SED)] 0.33

[Cu(SBD)] 0.37

[Cu2(TSDB)] 3.56(14.20)^b

[Cu2(TSTM)] 4.22(17.00)^b

[Cu2(TSED)] 4.56

[Cu2(TSBD)] 4.64

[Cu3(HSED)] 5.26

aAcetate buffer pH 4.6; [Cu(II)]=5.0×10⁻⁶ M.

bRef 12, ([Cu(II)]=1.0×10⁻³ M in DMSO)

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3. Yearwood, B.; Parkin, S.; Atwood, D, A. Inorg. Chim.

Acta 2002, 333, 124.

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5. Brewer.G.; Brewer. C. T.; Kamaras, P.; Prytkov, S.;

Shang, M.; Scheidt, W. R. Inorg. Chim. Acta 2001, 321, 175.

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Chem. 1984, 23, 275.

7. (a) Chen, D.; Martell, A. E. Inorg. Chem. 1987, 26, 1026.

(b) Chen, D.; Martell, A. E.; Sun, Y. Inorg. Chem.

1989, 28, 2647.

8. Kim, S. D.; Joung. M. S.; Jin, G. R.; Kim, C. S. J.

Korean Chem. Soc. 1995, 39, 932.

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11. Chen, H.; Cronin, J. A.; Archer, R. D. Macromolecules 1994, 27, 2174.

12. Archer, R. D.; Chen, H.; Thompson, L. C. Inorg. Chem.

1998, 37, 2089.

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P. J. Korean Chem. Soc. 1992, 36, 709.

14. Kim, S. D.; Lee, Y. S.; Park, J. E. Anal. Sci. & Tech.

2000, 13, 558.

15. (a) Konsler, S.; Karl, R. G.; Jacobsen. E. N. J. Am.

Chem. Soc. 1998, 120, 10780. (b) Martinez, L. E.;

Leighton. J. L.; Carsten. D. H.; Jacobsen. E. N. ibid.

1995, 117, 5897.

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18. Onishi, I.; Hara, T. Bull. Chem. Soc. Jpn. 1964, 1314.

19. (a) Hathaway, B. J.; Dudley, R. U.; Nicholls, P. J. Chem.

Soc. 1969, 1845. (b) Hathaway, B. J.; Procter, L. M.;

Slad, R. C.; Romlinson, A. A. J. Chem. Soc. 1969, 2219.

Synthesis of New Multinuclear Schiff Bases and Oxidation of Ascorbic Acid by TheirCopper(II) Complexes 

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Synthesis of New Multinuclear Schiff Bases and Oxidation of Ascorbic Acid by Their Copper(II) Complexes

Synthesis of New Multinuclear Schiff Bases and Oxidation of Ascorbic Acid by TheirCopper(II) Complexes

Cu(II)