28 3 ( ) Vol128 No13 38 2010 5 Journal of Beijing Technology and Business University(Natural Science Edition) May 2010 : 167121513 (2010) 0320038206 4 /Ti 2 2La 2 3 1, 1, 1, 1, 2 (1., 435002; 2., 430072) : 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 < - 11194.,,. 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 ( ). 1 111 1, 22 Til 4 H 2 S 4 : 2010-03 - 16 : (2005ABA053) ;. : (1964 ),,,,,.
28 3 : 4 /Ti 2 2La 2 3 39,. ; PKW 2 ; Abbe; XRD26000 X,,, K 1, 40 kv,30 ma, 2 5 70 ; N icolet 5DX, ; MERURY2VX 300 (Dl 3, TMS). 112 La 2 3 3. 0 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 ), 105. 018 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 ]. 114 114. 1 ( ), 4 /Ti 2 2La 2 3,.,,,,. IR 1 HNMR. 114. 2( ) 100mL ( ) ( ) ( 1, 22),,,,,. Nal,MgS 4,,,,. 114. 3 4 /Ti 2 2La 2 3, 160 164, n 20 D = 11407 0, [ 13 ] ( n 20 D 11407 5),. ( IR,) : 2 963, 2 876 cm - 1 ( H ), 1 738 cm - 1 ( ), 1 182 cm - 1 ( ),. 1 H NMR ( Dl 3, 300 MHz ) H : 4102 ( 2H, H 2 ), 2123 ( 2H, H 2 2 ), 1130 1164 ( 6H, 3 2H 2 2), 0192 (6H, 2 2H 3 ). IR 1 H NMR [ 14 ]. 2 2. 1 4 /T i 2 2La 2 3 4 /Ti 2 2La 2 3 FT2IR : 1 379, 1 132, 1 043 cm - 1, [ 15 ],, [ 16 ] 4 /M x y., 4 /M x y FT2IR 900 1 300 cm - 1 1 300 1 400 cm - 1. S, S. FT2IR 1 636 cm - 1 3 415 cm - 1, H. 1 383 cm - 1, 4,, 1 630 1 620 cm - 1. XRD, 4 /Ti 2 2La 2 3 4 /Ti 2, XRD 2, 4 / Ti 2 2La 2 3 XRD La 2 3, La 2 3,, La 2 3, La 2 3
40 ( ) 2010 5, XRD La 2 3 [ 17 ]. EDTA 4 / Ti 2 2La 2 3 La 2 3 0170%. Hammett2, 42 (H o = - 13. 75) 2, 42 (H o = - 14152) 1, 3, 52 (H o = - 16. 40), 2, 42, 2, 42, 1, 3, 52,, - 16140 < H o < - 14. 52. 2. 2 2. 2. 1 n (La 3 + ) n ( Ti 4 + ) 115%, n ( ) n ( ) =113 1, 94 112 110 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 + ) 0 1 136 1 68 1 34 1 17 w ( S 3 ) / % 1160 6. 33 8. 31 9. 48 7. 35 /% 7516 87. 5 88. 1 94. 7 7112 1, 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 + ) = 1 34. 2. 2. 2 n (La 3 + ) n ( Ti 4 + ) = 1 34, 480, 115%, n ( ) n ( ) = 113 1, 94 112 110 h,,, 2. 2 Tab. 2 Effect of soaked time of H 2 S 4 on catalytic activity / h 8 16 24 32 w ( S 3 ) / % 9. 23 9. 27 9. 48 10136 /% 84. 8 88. 3 94. 7 92. 6 2,. :,.,, ;,.,,,., Ti 2,,.,24 h. 2. 2. 3 n (La 3 + ) n ( Ti 4 + ) = 1 34, 018 mol L - 1, 24 h, 115%, n ( ) n ( ) = 113 1, 94 112 110 h,,, 3. 3 Tab. 3 Effect of calcination temperature on catalytic activity / 280 380 480 580 w ( S 3 ) / % 11143 11115 9. 48 4. 34 /% 76. 3 87. 8 94. 7 82. 5 3,, 480,.,,.,,, 480. 2. 2. 4 n (La 3 + ) n ( Ti 4 + ) = 1 34, 018 mol L - 1, 24 h, 480, 115%,
28 3 : 4 /Ti 2 2La 2 3 41 n ( ) n ( ) = 113 1, 94 112 110 h,,, 4. 4 Tab. 4 Effect of burnt time on catalytic activity / h 1 2 3 4 w ( S 3 ) / % 10198 10156 9. 48 8. 39 /% 77. 1 83. 7 94. 7 88. 2 4,,,, 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 2 4 - /Ti 2 2La 2 3 113 1 60 114 94. 7 H 2 S 4 110: 1 120 158 72. 1 H 3 PW 12 40 110: 1 113 140 62. 5 5, 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 2 3 10( ),. 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, ( ),,
42 ( ) 2010 5,,,,., 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 126 128 /6. 7 kpa 11432 5 84. 7 1 738, 1 375, 1 244, 1 188, 1 047 H 2 H 3 H 3 H 2 (H) H 2 H 150 154 /6. 7 kpa 11427 5 88. 6 1 740, 1 377, 1 244, 1 188, 1 043 3c H (H 2 ) 2 H 174 180 11458 0 84. 3 2 937, 2 863, 1 163, 1 104 3d H 3 H 2 (H) H 2 H 172 176 11449 3 84. 6 2 937, 2 864, 1 163, 1 103 3e H 3 H 2 H 3 H (H 2 ) 2 H 116 119 11410 5 4114 3 1 254, 1 215, 1 194, 1 130 3f H 3 H 2 H 3 H 3 H 2 (H) H 2 H 126 130 11410 2 64. 6 3 1 250, 1 218, 1 194, 1 157 3g H 3 H 2 H 2 H H (H 2 ) 2 H 130 134 11419 0 9513 1 146, 1 123, 1 023, 946 3h H 3 H 2 H 2 H H 3 H 2 (H) H 2 H 139 144 11415 0 9518 1 150, 1 123, 1 024, 970 3 i 6 H 5 H H (H 2 ) 2 H 226 230 11526 4 8010 1 096, 1 071, 1 028, 947 3 j 6 H 5 H H 3 H 2 (H) H 2 H 218 222 11509 4 8018 1 097, 1 067, 1 011, 976 3, 2 h, 5811%, 1, 22 6817%. : [ 1 ],. [ J ]., 2001, 16 (2) : 19-24. [ 2 ] Anastas P T, W arner J. Green hem istry Frontiers in Benign hem ical Synthesis and Processes [M ]. xford: xford University Press, 1998. [ 3 ] Loader E, Anderson Hugh J. Pyrrole chem istry part XX: synthesis of pyrrole acetals [ J ]. Synthesis, 1978, (3) : 295-297. [ 4 ],. [M ]. :. 1981: 319. [ 5 ],. [ J ]., 1994, 23 (3) : 166-169. [ 6 ],,. 4 /Zr 2 [ J ]., 1994, 52 (1) : 36-411 [ 7 ],,. Zr 2 / 4 [ J ]., 1992, 13 (12) : 1498-1502. [ 8 ],,,. 4 /Mxy [ J ]., 2003, 23 (3) : 243-248. [ 9 ]. 4 /Ti 2 /La 3 + [ J ]., 2000, 20 (5) : 805-807. [ 10 ],. [ J ]., 2002, 22 (7) : 13-17, 211 [ 11 ],. 4 2Ti 2 2Mo 3 [ J ]., 2001, 21 (12) : 1153-1156. [ 12 ],. W 3 2Ti 2 2 4 [ J ]., 2002, 19 ( 1) : 36-38. [ 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 12 40 /Ti 2 [ J ]., 2003, 23 (11) : 1294-1298. [ 15 ],,. 4 /Ti 2 2A l 2 3 2Sn 2 [ J ]., 1996, 17 (1) : 83-86. [ 16 ],,,. 4 / ( Zr 2 2Ti 2 2 Sn 2 ) [ J ]., 1994, 23 (1) : 22-26. [ 17 ],. X [ J ]., 2001, 16 (3) : 36-39. [ 18 ],,. [ J ]., 1993 (1) : 51-53.
28 3 : 4 /Ti 2 2La 2 3 43 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 435002, hina; 2. ollege of hem istry and M olecular Sciences, W uhan U niversity, W uhan 430072, 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 100048, h ina; 2. Pha rm aceutical ollege, Heilongjiang U niversity of h inese M edicine, Harbin 150040, 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 = 61423 667 + 011613 X 1 + 01684 253 X 2-01523 753 X 3-01660 0833 X 1 3 X 1 + 01174 53 X 1 3 X 2-01657 53 X 1 3 X 3-01534 5833 X 2 3 X 2-01013 53 X 2 3 X 3 time 3170 h, - 11527 5833 X 3 3 X 3, and the op timum conditions were ratio of material to solvent 1 13176, and temperature 93137. 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 ( :)