Formation of α,α'-Bis(substituted benzylidene)cycloalkanones from Masked Aldehydes Promoted by Samarium(III) Triiodide
Formation of α,α'-Bis(substituted benzylidene)cycloalkanones from Masked Aldehydes Promoted by Samarium(III) Triiodide
摘要
Diacetates 1 and N-[(1-benzotriazol-l-yl)alkyl]amides 2, both masked forms of aldehydes, could undergo deprotection and condensation with cycloalkanones in a one-pot procedure promoted by samarium(III) iodide (SmI3) to afford α,α'-bis(substituted benzylidene) cycloalkanones in good yields.
Diacetates 1 and N-[(1-benzotriazol-l-yl)alkyl]amides 2, both masked forms of aldehydes, could undergo deprotection and condensation with cycloalkanones in a one-pot procedure promoted by samarium(III) iodide (SmI3) to afford α,α'-bis(substituted benzylidene) cycloalkanones in good yields.
参考文献13
-
1[1](a) H. B. Kagan, Chem. Rev., 2002, 102, 1805; (b) G. A. Molander, Chem. Rev., 1992, 92, 29;(c) G. A. Molander, C. R. Harris, Chem. Rev., 1996, 96, 307; (d) G. A. Molander, Acc. Chem. Res., 1998, 31, 603; (e) H. B. Kagan, J. Chem. Soc. Perkin Trans. 1, 2001, 2727; (f) P. G. Steel, J. L. Namy, Tetrahedron, 1986, 42, 6573. 被引量：1
-
2[2]Y. P. Yu, R. H. Lin, Y. M. Zhang, Tetrahedron Lett., 1993, 34, 4547. 被引量：1
-
3[3]T. K. Ying, W. L. Bao and Y. M. Zhang, Synth. Commun., 1996, 26, 2905. 被引量：1
-
4[4](a) S. H. Wu, Synth Commun, 24, 1994, 2173.(b) Y. Ukaji, N. Koumoto ( T. Fujiaawa, Chem. Lett., 1989, 1255. 被引量：1
-
5[5](a) Y. P. Yu, Y. M. Zhang ( R. H. Lin, Synth. Commun., 1993, 23, 1973(b) W. L. Bao ( Y. M. Zhang, Org. Prep. Proced. Int., 1997, 29, 335. 被引量：1
-
6[6]W. L. Bao, Y. M. Zhang, T. K. Ying, Synth. Commun., 1996, 26, 503. 被引量：1
-
7[7]General procedure for the synthesis of (,('-bis(substituted benzylidene)cycloalkanones (4): Under nitrogen atmosphere, samarium powder (0.15 g, 1.0 mmoL) and iodide (0.39 g, 1.55 mmol) in dry THF (10 mL) were stirred for 1 hour at room temperature to obtain a yellow suspension, to which was added a solution of 1 mmol of 1,1-diacetates or N-[(1-benzotriazol-1-yl)alkyl]amides and 1 mmol of cycloalkanone in 2 mL of THF, the resulting mixture was then refluxed till the starting materials disappeared (monitored by TLC). After evaporating most of the THF, 3 mL of hydrochloric acid (0.2 mol/L) was added. Usually the products were precipitated, subsequent filtration and recrystallization from methanol afforded the pure products. If no precipitate was produced after the adding of hydrochloric acid, the mixture was extracted with diethyl ether (3 × 15 mL). The combined extracts were washed with saturated solution of Na2S2O3, then a saturated solution of NaCl and dried over anhydrous Na2SO4. After evaporating the solvent under reduced pressure, the crude solid products were obtained. Recrystallization from 95% EtOH or MeOH afforded the products in pure form. 被引量：1
-
8[8]Physical data: 3a. m.p. 184~186(C, (lit.9 188~189(C); 3b. m.p. 227~229(C, (lit.10 231(C); 3c. m.p. 242~244(C, (lit.10 245~246(C); 3d. m.p. 213~215(C, (lit.10 219~220(C); 3e. m.p. 182-188(C (accompanied by decomposition); 1H NMR (CDCl3, 400 MHz) δ(ppm): 7.52 (s, 2H), 7.36~7.38 (m, 4H), 7.21~7.25 (m, 2H), 2.62 (s, 4H); IR (KBr) ((cm-1): 3060, 2933, 1704, 1633, 1578, 1554; MS (70eV) m/z (%): 361 (M+-35, 100), 363 (95.86), 325 (12.72), 291 (6.49), 255 (5.49), 226 (8.46), 202 (18.47), 161 (13.98), 149 (38.26), 113 (47.65); Anal. Calcd for C19H12Cl4O: C 57.32, H 3.04; Found C 57.21, H 3.14; 3f. m.p.247-249(C; 1H NMR (CDCl3, 400 MHz) δ(ppm): 7.36 (s, 2H), 7.23~7.25 (d, 4H, J = 8.8 Hz), 7.03~7.05 (d, 2H, J = 7.6 Hz), 6.11 (s, 4H), 3.04 (s, 4H); IR (KBr) ((cm-1):2909, 1682, 1632, 1612, 1597; MS (70eV) m/z (%):349 (M++1, 22.58), 348 (M+, 100), 347 (91.49), 102 (97.96); Anal. Calcd for C21H16O5: C 72.41, H 4.63; Found C 72.36, H 4.65; 3g. m.p.216-218(C (lit.6 215-216(C); 3h. m.p. 150-152(C (lit.11 152.3~152.6(C); 3i. m.p. 208-210(C; 1H NMR (CDCl3, 400 MHz) δ(ppm): 7.74 (s, 2H), 7.52~7.53 (m, 6 H), 7.33 (t, 2 H, J = 8.0 Hz), 3.13 (s, 4 H); IR (KBr) ((cm-1): 3059, 2920, 1687, 1623, 1603, 1554, 1180; MS (70 eV) m/z (%): 420 (M+, 19.30), 419 (25.69), 418 (41.02), 417 (42.56), 416 (M+, 20.91), 339 (71.48), 337 (72.44), 129 (42.56), 115 (100); Anal. Calcd for C19H14Br2O: C 54.58, H 3.38; Found C 54.52, H 3.43; 4a. m.p. 115-116(C (lit.12 116~117(C); 4b. m.p. 144-147(C (lit.13 146~148 (C); 4c. m.p. 171-173(C (lit.13 171~173(C). 被引量：1
-
9[9]M. Zheng, L. Wang, J. Shao, Q. Zhong, Synth. Commun., 1997, 27, 351. 被引量：1
-
10[10]H. Frey, G. Behmann, G. Kaupp, Chem. Ber., 1987, 120, 387. 被引量：1
-
1陈小原,钟为慧,张永敏.三碘化钐促进的β-氨基酸的简便合成[J].合成化学,2001,9(2):145-147.
-
2孙国香,石延霞,翟志文,杨明艳,翁建全,谭成侠,刘幸海,李宝聚.Synthesis,Crystal Structure and Biological Activity of(E)-3-Chloro-2-(2-(2-methylbenzylidene)-hydrazinyl)pyridine[J].Chinese Journal of Structural Chemistry,2016,35(4):640-644.
-
3YOU Wen-Wei,ZHAO Pei—Liang,DUAN An-Na,WU Shu-Guang.Synthesis and Crystal Structure of(E)-Ethyl 2-(4-(2,4-dimethoxybenzylideneamino)-5-(3,4,5-trimethoxyphenyl)-4H-1,2,4-triazol-3-ylthio)acetate[J].Chinese Journal of Structural Chemistry,2011,30(4):600-603.
-
4张丽,汪洪,赵承光,唐琴琴,熊伟,蔡跃飘,陈高帜,胡杰,梁广.Synthesis and Crystal Structure of(2E,6E)-2,6-bis(2,3-dimethoxybenzylidene)cyclohexanone[J].Chinese Journal of Structural Chemistry,2011,30(2):278-283.
-
5Xin Ying ZHANG, Xue Sen FAN, Hong Ying NIU, Jian Ji WANGSchool of Chemical and Environmental Sciences, Henan Normal University, Key Laboratory ofEnvironmental Science and Engineering of Henan Education Department,Xinxiang 453002.A Novel Green Preparation of a, a'-Bis (substituted benzylidene)-cycloalkanones Promoted by FeCl_3 6H-2O in Ionic Liquid[J].Chinese Chemical Letters,2003,14(10):1005-1007. 被引量：5
-
6Dan Feng HUANG,Jin Xian WANG,Yu Lai HU.A New Solvent-free Synthesis of a, a'-Dibenzylidenecycloalkanones from Acetals with Cycloalkanones under Microwave Irradiation[J].Chinese Chemical Letters,2003,14(4):333-334. 被引量：1
-
7Gui Sheng DENG,Tie Gang REN.InCl_3·4H_2O Catalyzed Aldol Condensation of Cycloalkanones with Aromatic Aldehydes[J].Chinese Chemical Letters,2001,12(10):859-860.
-
8XU Liang-Zhong SHANG Yu-Qing YU Guan-Ping LI Kai SI Guo-Dong.Synthesis and Crystal Structure of 5-[(1H-1,2,4-Triazol-1- yl)methyl]-4-(2,3-dimethoxybenzylideneamino)-2-2H-1,2,4-triazole-3(4H)-thione Monohydrate[J].Chinese Journal of Structural Chemistry,2006,25(6):673-676.
-
9邬继荣,陈巍峰,罗蒙贤,贺小林,李志芳.三碘化钐催化的一锅法合成α-胺基腈化合物[J].有机化学,2010,30(10):1497-1501. 被引量：2
-
10钟为慧,张永敏.三碘化钐促进的芳胺与α,β-不饱和腈(酯)的共轭加成[J].有机化学,2000,20(5):747-749. 被引量：4
