Vol128 No13 Journal of Beijing Technology and Business University(Natural Science Edition) SO /TiO 2 2La 2 O 3 ( ), / ( 4 /TiO 2 2La 2 O 3

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1 28 3 ( ) Vol128 No Journal of Beijing Technology and Business University(Natural Science Edition) May 2010 : (2010) /Ti 2 2La 2 3 1, 1, 1, 1, 2 (1., ; 2., ) : 4 /Ti 2 2La 2 3,, n (La 3 + ) n ( Ti 4 + ) 4 /Ti 2 2La 2 3. : n (La 3 + ) n ( Ti 4 + ) = 1 34, 018 mol L - 1, 24 h, 480, 3 h. 4 /Ti 2 2La 2 3 ( ), / (, 1, 22)1 115, 015%, 1 h, 10( ) 4114% 9518%. : 4 /Ti 2 2La 2 3 ; ; ; : TQ655; TS20213: A.,,, [ 1-2 ].,, [ 3 ],, [ 4 ].,,,.,. 100%, H o < ,,. 4 2M x y, [ 5-8 ]. Zr 2 Ti 2, 4, Mo 3 W 3, [ 9-12 ]. 4 / Ti 2,, La 2 3,., n (La 3 + ) n ( Ti 4 + ) 4 /Ti 2 2La 2 3, 10 ( ) , 22 Til 4 H 2 S 4 : : (2005ABA053) ;. : (1964 ),,,,,.

2 28 3 : 4 /Ti 2 2La ,. ; PKW 2 ; Abbe; XRD26000 X,,, K 1, 40 kv,30 ma, ; N icolet 5DX, ; MERURY2VX 300 (Dl 3, TMS). 112 La mol L - 1, La 3 +, Til 4 La 3 +, NH 3 H 2 [w (NH 3 ) = 12% ], ph 8 9,, 24 h, l - ( 011 mol L - 1 AgN 3 ), mol L - 1 H 2 S 4 24 h,,110,3 h,. 113 [ 6 ], m ( Zn) m ( Na 2 3 ) = 4 1,,, S 3. Hammett [ 7 ] ( ), 4 /Ti 2 2La 2 3,.,,,,. IR 1 HNMR ( ) 100mL ( ) ( ) ( 1, 22),,,,,. Nal,MgS 4,,,, /Ti 2 2La 2 3, , n 20 D = , [ 13 ] ( n 20 D ),. ( IR,) : 2 963, cm - 1 ( H ), cm - 1 ( ), cm - 1 ( ),. 1 H NMR ( Dl 3, 300 MHz ) H : 4102 ( 2H, H 2 ), 2123 ( 2H, H 2 2 ), ( 6H, 3 2H 2 2), 0192 (6H, 2 2H 3 ). IR 1 H NMR [ 14 ] /T i 2 2La /Ti 2 2La 2 3 FT2IR : 1 379, 1 132, cm - 1, [ 15 ],, [ 16 ] 4 /M x y., 4 /M x y FT2IR cm cm - 1. S, S. FT2IR cm cm - 1, H cm - 1, 4,, cm - 1. XRD, 4 /Ti 2 2La /Ti 2, XRD 2, 4 / Ti 2 2La 2 3 XRD La 2 3, La 2 3,, La 2 3, La 2 3

3 40 ( ) , XRD La 2 3 [ 17 ]. EDTA 4 / Ti 2 2La 2 3 La %. Hammett2, 42 (H o = ) 2, 42 (H o = ) 1, 3, 52 (H o = ), 2, 42, 2, 42, 1, 3, 52,, < H o < n (La 3 + ) n ( Ti 4 + ) 115%, n ( ) n ( ) =113 1, h, n (La 3 + ) n ( Ti 4 + ),, 11 1 n (La 3 + ) n ( Ti 4 + ) Tab. 1 Effect of mole ratio of n (La 3 + ) n ( Ti 4 + ) on catalytic activity n (La 3 + ) n ( Ti 4 + ) w ( S 3 ) / % /% , La 2 3, La 2 3,,, n (La 3 + ) n ( Ti 4 + ) = 1 34,. La 2 3,,. La 2 3,, La 2 3, La 2 3. n (La 3 + ) n (Ti 4 + ) = n (La 3 + ) n ( Ti 4 + ) = 1 34, 480, 115%, n ( ) n ( ) = 113 1, h,,, 2. 2 Tab. 2 Effect of soaked time of H 2 S 4 on catalytic activity / h w ( S 3 ) / % /% ,. :,.,, ;,.,,,., Ti 2,,.,24 h n (La 3 + ) n ( Ti 4 + ) = 1 34, 018 mol L - 1, 24 h, 115%, n ( ) n ( ) = 113 1, h,,, 3. 3 Tab. 3 Effect of calcination temperature on catalytic activity / w ( S 3 ) / % /% ,, 480,.,,.,,, n (La 3 + ) n ( Ti 4 + ) = 1 34, 018 mol L - 1, 24 h, 480, 115%,

4 28 3 : 4 /Ti 2 2La n ( ) n ( ) = 113 1, h,,, 4. 4 Tab. 4 Effect of burnt time on catalytic activity / h w ( S 3 ) / % /% ,,,, 3 h. 2. 3, 4 /Ti 2 2La 2 3 n (La 3 + ) n ( Ti 4 + ) = 1 34, 018 mol L - 1, 24 h, 480, 3 h. 4 /Ti 2 2La 2 3 [ 18 ] 51 5 Tab. 5 omparison of catalytic activity of different catalysts / m in / /% S /Ti 2 2La H 2 S 4 110: H 3 PW : , 4 /Ti 2 2La 2 3,,. 4 /Ti 2 2 La 2 3,,, La 3 +,Ti 4 +, Ti 4 +, Lewis ;, Ti 2 La 3 +,, Ti 2, S 3,. 2. 4( ) 4 /Ti 2 2 La 2 3 ( ), / (, 1, 22)1 115, 015%, 1 h, 10 ( ). ( ): R 1 + R 3 H R 2 H 1 2 R 1 R 2 3a 3 j H 2 H H R 3 H 2 + H 2 4 /Ti 2 2La 2 3 cyclchexane 10 ( ). IR 6. 6, 4 /Ti 2 2La ( ),. 6,.,,, ;,,. ( ),,. 3 1) n (La 3 + ) n ( Ti 4 + ) = 1 34, 018 mol L - 1, 24 h, 480, 3 h. 2) 4 /Ti 2 2 La 2 3 ( ), / (, 1, 22)1 115, 015%, 1 h, 10( ) 4114% 9518%. ( ). 3) 4 /Ti 2 2La 2 3, ( ),,

5 42 ( ) ,,,,., 4 /Ti 2 2La 2 3 ( ),. 610( ) Tab. 6 Synthetic results of 10 classes of acetals or ketals / 1 2 / n 20 D /% /cm - 1 3a 3b H 3 H 3 H 2 H 2 H 2 H 3 H (H 2 ) 2 H /6. 7 kpa , 1 375, 1 244, 1 188, H 2 H 3 H 3 H 2 (H) H 2 H /6. 7 kpa , 1 377, 1 244, 1 188, c H (H 2 ) 2 H , 2 863, 1 163, d H 3 H 2 (H) H 2 H , 2 864, 1 163, e H 3 H 2 H 3 H (H 2 ) 2 H , 1 215, 1 194, f H 3 H 2 H 3 H 3 H 2 (H) H 2 H , 1 218, 1 194, g H 3 H 2 H 2 H H (H 2 ) 2 H , 1 123, 1 023, 946 3h H 3 H 2 H 2 H H 3 H 2 (H) H 2 H , 1 123, 1 024, i 6 H 5 H H (H 2 ) 2 H , 1 071, 1 028, j 6 H 5 H H 3 H 2 (H) H 2 H , 1 067, 1 011, 976 3, 2 h, 5811%, 1, %. : [ 1 ],. [ J ]., 2001, 16 (2) : [ 2 ] Anastas P T, W arner J. Green hem istry Frontiers in Benign hem ical Synthesis and Processes [M ]. xford: xford University Press, [ 3 ] Loader E, Anderson Hugh J. Pyrrole chem istry part XX: synthesis of pyrrole acetals [ J ]. Synthesis, 1978, (3) : [ 4 ],. [M ]. :. 1981: 319. [ 5 ],. [ J ]., 1994, 23 (3) : [ 6 ],,. 4 /Zr 2 [ J ]., 1994, 52 (1) : [ 7 ],,. Zr 2 / 4 [ J ]., 1992, 13 (12) : [ 8 ],,,. 4 /Mxy [ J ]., 2003, 23 (3) : [ 9 ]. 4 /Ti 2 /La 3 + [ J ]., 2000, 20 (5) : [ 10 ],. [ J ]., 2002, 22 (7) : 13-17, 211 [ 11 ],. 4 2Ti 2 2Mo 3 [ J ]., 2001, 21 (12) : [ 12 ],. W 3 2Ti [ J ]., 2002, 19 ( 1) : [ 13 ] Grasselli J G, R itchey W M. A tlas of Spectral Data and Physical onstants for rganic ompounds[m ]. land: R Press Inc, 1975: 598. leve2 [ 14 ],,. TiSiW /Ti 2 [ J ]., 2003, 23 (11) : [ 15 ],,. 4 /Ti 2 2A l 2 3 2Sn 2 [ J ]., 1996, 17 (1) : [ 16 ],,,. 4 / ( Zr 2 2Ti 2 2 Sn 2 ) [ J ]., 1994, 23 (1) : [ 17 ],. X [ J ]., 2001, 16 (3) : [ 18 ],,. [ J ]., 1993 (1) :

6 28 3 : 4 /Ti 2 2La PREPARAT I N AND ATALY T I AT IV ITY F 4 /T i 2 2La 2 3 YANG Shui2jin 1, HUANG Yong2kui 1, BA IA i2m in 1, YANG Yun 1, SUN Ju2tang 2 (1. ollege of hem istry and Environm ental Eng ineering, Hubei Key L abora tory of Pollutant A nalysis & R euse Technology, Hubei N orm al U niversity, Huangshi , hina; 2. ollege of hem istry and M olecular Sciences, W uhan U niversity, W uhan , hina) Abstract: 4 /Ti 2 2La 2 3, a novel solid superacid, was p repared and its catalytic activities at different synthetic conditions were analyzed w ith esterification of n2butanoic acid and n2butyl alcohol as p robing re2 action. The op timum conditions were as follow: mole ratio of n (La 3 + ) n ( Ti 4 + ) of 1 34, the soaked consistency of H 2 S 4 of 018 mol L - 1, the soaked time of H 2 S 4 of 24 h, the calcining temperature of 480, the calcining time of 3 h. The catalyzer p repared under the op timal conditions was app lied in the catalytic synthesis of ten important ketals and acetals as catalyst and exhibited high catalytic activity. yields of ketals and acetals can reach 4114% 9518% when the molar ratio of aldehyde /ketone to glycol is 1 115, the mass ratio of the catalyst used in the reactants is 015%, and the reaction time is 110 h. Key words: 4 /Ti 2 2La 2 3 ; rare earth; solid superacid; catalysis ( :) The (31 ) PTIM IZATIN N EXTRATIN ND ITINS F FLAVN IDS FRM G IN KG B ILBA LEAF USING RESPNSE SURFAE M ETHDLGY ZHA Hua 1, ZHANG Hui2m ing 1, 2, DNG Yin2mao 1, DU Xiao2wei 2, HE ong2fen 1, P INan 1 (1. B eijing Key L aboratory of P lant R esources R esea rch and D evelopm en t, B eijing Technology and B usiness U n iversity, B eijing , h ina; 2. Pha rm aceutical ollege, Heilongjiang U niversity of h inese M edicine, Harbin , h ina) Abstract: The article aim was to study the maximum extraction conditions of flavonoids from Ginkgo bi2 loba by water. W ith dried Ginkgo biloba powder as material and water as solvent, by using response sur2 face methodology, the effects of extracting temperature, extracting time and ratio of material to solvent were studied, and then the regression model was established to study the extracting condition. The result of fractional factorial design indicated that extracting time and ratio of material to solvent p layed important roles in flavonoids extracting. The regression model of extraction rate ( Y 1 ) to ethanol concentration (X 2 ) and ratio of material to solvent(x 3 ) was Y 1 = X X X X 1 3 X X 1 3 X X 1 3 X X 2 3 X X 2 3 X 3 time 3170 h, X 3 3 X 3, and the op timum conditions were ratio of material to solvent , and temperature The maximum extraction rate p redicted by the model was 61754%. Final results show that response surface methodology was a good method for op tim izing extrac2 tion conditions of flavonoids. Key words: response surface methodology; ginkgo biloba leaf; flavonoid; extraction ( :)