不对称α-烃基-α-羟基丙二酰胺衍生物的合成新方法
收稿日期: 2013-04-17
网络出版日期: 2013-06-13
基金资助
项目受山西省留学回国人员基金(No. 0713)、山西省自然科学基金(No. 2012011046-9)、山西师范大学基金(No. SD2011CXSY-12)资助.
Novel Method for Synthesis of Unsymmetrical α-Organyl-α-hydroxymalonamide Derivatives
Received date: 2013-04-17
Online published: 2013-06-13
Supported by
Project supported by the Shanxi Province Foundation for Returness Overseas Scientists of China (No. 0713), the Natural Science Foundation of Shanxi Province of China (No. 2012011046-9), and the Foundation of Shanxi Normal University of China (No. SD2011CXSY-12).
N,N-二甲基氨甲酰基三甲基硅烷与一系列N-甲基-N-甲氧甲基α-羰基酰胺在无水无氧、105℃的条件下反应, 合成了不对称α-烃基-α-羟基丙二酰胺类化合物或不对称α-烃基-α-三甲基硅氧基丙二酰胺衍生物, 收率71%～86%, 其结构用元素分析、1H NMR、13C NMR和IR等方法进行了表征. 通过研究反应的影响因素发现, 反应底物α-羰基酰胺中与α-羰基直接相连的烃基的空间位阻是该加成反应的重要影响因素, 而α-羰基直接相连的芳环上取代基的电子效应则主要影响反应完成的时间. 并提出了可能的反应机理.
关键词： 氨甲酰基硅烷; α-羰基酰胺; 不对称α-烃基-α-羟基丙二酰胺; 加成反应; 合成
马菲 , 陈建新 . 不对称α-烃基-α-羟基丙二酰胺衍生物的合成新方法[J]. 化学学报, 2013 , 71(08) : 1118 -1120 . DOI: 10.6023/A13040417
Aldehydes may be directly converted to O-silyl-α-hydroxyamides by reaction with N-methoxymethyl-N-methyl- carbamoyl(trimethyl)silane. In an attempt to extend this chemistry, we found that N-methoxymethyl-N-methylcarbamoyl(trimethyl)silane did not react with α-ketoamides. So we started testing activity within the variety of carbonyl compounds towards N,N-dimethylcarbamoylsilane and found that the addition reaction of N,N-dimethylcarbamoyl(trimethyl)- silane with a series of N-methyl-N-methoxymethyl-α-ketoamides could afford good yields (71%～86%) of unsymmetrical α-organyl-α-hydroxymalonamide derivatives or unsymmetrical α-organyl-α-siloxymalonamide compounds. When 1.2 equiv. of a carbamoylsilane 1 was allowed to react with α-ketoamides 2 in anhydrous toluene solution under anhydrous conditions at ambient conditions or below, good yields of α-siloxyamides 3 were obtained, generally within long time. Their structures were characterized by elemental analysis, 1H NMR, 13C NMR and IR spectra. A novel method for synthesis of unsymmetrical α-organyl-α-hydroxymalonamide derivatives was provided. The experiments indicated that the steric environment was an important factor in the addition reaction since longer reaction time was needed both in case of 2b and 2c than in case of 2a, and the electronic effect influenced on the rate of the reaction since the yields were obtained about the same from a variety of aryl-α-ketoamides, the stronger donor ability of substituted group on the benzene ring of the aryl-α-ketoamides, the longer reaction time was needed. A reaction mechanism involving two intermediates is proposed, in which carbamoylsilane 1 can rearrange to its nucleophilic carbene form A, which attacked the carbonyl group of α-ketoamides to produce an unstable intermediate B, the subsequent silyl group transfer leads to corresponding the O-silylated adducts 3. The latter can be hydrolyzed to form the α-organyl-α-hydroxymalonamide derivatives 4.
[1] Wang, K.; Long, H.; Fu, M.; Yang, G.; Lu, P,-X. Opt. Lett. 2010, 35, 1560
[2] Cui, B.; Lin, H.; Zhao X.-C.; Li J.-B.; Li W.-D. Acta Phys.-Chim. Sin 2011, 27, 2411(in Chinese). (崔柏, 林红, 赵晓冲, 李建保, 李文迪,物理化学学报, 2011, 27, 2411.)
[3] Choi, J-R. Chin. Phys. B 2010, 19. 010306
[4] Todorov, Y.; Tosetto, L.; Teissier, J.; Andrews, A.-M.; Klang, P.; Colombelli, R.; Sagnes, I.; Strasser, G.; Sirtori, C. Opt. Express, 2010, 18, 13886
[5] Shen, L.-F.; Chen, X.-D.; Zhang, X.-F.; Agarwal, K. Plasmonics, 2011,6, 301
[6] Zhang, Y.-Y.; Zhang, J. Acta Chimica Sinica, 2012, 70, 2293(in Chinese). (张莹莹, 张锦, 化学学报, 2012, 70, 2293.)
[7] Fan, J.-F.; ZHAO Chen-Xing.; FAN Lou-Zhen. Acta Chim. Sinica 2012, 70, 229 (in Chinese)范建凤, 赵晨醒, 范楼珍. 化学学报 2012, 70, 229.
[8] Hibbins, A.-P.; Evans, B.-R.; Sambles, J.-R. Science, 2005, 308, 670
[9] Song, G.-F.; Wang, W.-M.; Cai, L.-K.; Guo, B.-S.; Wang, Q.; Xu, Y.;Wei, X.; Liu, Y.-T. Acta Phys. Sin.2010, 59, 5105 (in Chinese) (宋国峰,汪卫敏,蔡利康,郭宝山,王青,徐云,韦欣,刘运涛,物理学报,2010 59, 5105)
[10] Wang,Y.; Wang, X.; He, X.-J., Mei J S.; Chen, M.-H.; Yin, J.-H.; Lei, Q.-Q. Acta Phys. Sin.2012, 61, 137301 (in Chinese) (王玥,王暄,贺训军,梅金硕,陈明华,殷景华,雷清泉, 物理学报,2012, 61, 137301)
[11] Li, Y.; Lin, Z.; Li, R.-Z.; Liu, X. Acta Chim. Sinica 2012, 70, 1304 (in Chinese)(李迎, 林钊, 李蓉卓, 刘霞, 化学学报, 2012, 70, 1304.)
[12] [12] Liu, X.; Sun, Y.; Song, D.-Q.; Tian, Y.; Zhang, H.- Q.; He, Y. Acta Chim. Sinica 2007, 65, 2544 (in Chinese)(刘霞, 孙颖, 宋大千, 田媛, 张寒琦, 何彦, 化学学报, 2007, 65, 2544.)
[13] Wang, Q.; Zhu, H.-Z.; Yang, X.-H.; Wang, K.-M.; Yang, L.-J.; Ding, J. Acta Chim. Sinica 2012, 70, 1483 (in Chinese)(王青, 朱红志, 羊小海, 王柯敏, 杨丽娟, 丁静, 化学学报 2012, 70, 1483.)
[14] Quidant, R.; Girard, C. Laser & Photon. Rev. 2008, 2 47
[15] Davoyan, A.-R.; Shadriivov, I.- V.; Kivshar, Y.-S. Opt. Express, 2008, 16, 21209
[16] Zhang, R.-J.; QI, Z.-M.; Zhang, Z. Acta Phys. -Chim. Sin. 2011, 27, 1757. (张蓉君, 祁志美, 张喆,物理化学学报, 2011, 27, 1757.)
[17] Zhang, Z.-Y.; Du, J.-L.; Guo, Y.- K.; Niu, X.-Y.; Li, M.; Luo, X.-G.; Du, C,-L. Chin. Phys. Lett.2009, 26, 014211
[18] Zhang, Z.-Y.; Du, J.-L.; Guo, X.-W.; Luo, X.-G.; Du, C.-L. J. Appl.Phys.2007. 102, 074301
[19] Lv, J.-T.; Wang, F.-W.; Ma, Z.-H.; Si, G.-Y. Acta Phys. Sin.2013, 62, 057804 (in Chinese) (吕江涛,王凤文,马振鹤,司光远, 物理学报, 2013, 62, 057804)
[20] Jiang, X.-X.; Gu, Q.-C.; Wang, F.-W.; Lv, J.-T.; Ma, Z.- H.; Si, G. -Y. Materials Letters, 2013, 100, 192
[21] Si, G.-Y.; Zhao,Y.; Liu, H.; Teo, S.; Zhang, M.; Huang, T.-J.; Danner, A.-J.; Teng, J. Appl.Phys.Lett.2011, 99, 033105
[22] Hong, Q.-H.; Liu, X.-F.; Fang, Y. Acta Chimica Sinica, 2013, 71, 255. (in Chinese)(洪清华, 刘雪锋, 方云,化学学报, 2013, 71, 255.)
[23] Tan, Y.; Ding, S.-H.; Wang, Yi.; Qiang, W.-P. Acta Chim. Sinica, 2005, 63, 929 (in Chinese)(谈勇, 丁少华, 王毅, 钱卫平, 化学学报 2005, 63, 929.)
[24] Khoury, C.-G.; Norton, S.-J.; T, V.-D. ACS Nano 2009, 3, 2776
[25] Guo, B.; Shan, Wen.-Wen.; Luo, J.-S.; Tang, Y.-J.; Cheng, J.-P. Acta Chim. Sinica 2008, 66, 1435 (in Chinese)(郭斌, 单雯雯, 罗江山, 唐永建, 程建平, 化学学报, 2008, 66, 1435.)
[26] Gao, Q.; Qian, Y.; Xia, Yan.; Jiang, C.-Y. Qiang, W.-P. Acta Chim. Sinica 2011, 69, 1617 (in Chinese)(高倩, 钱勇, 夏炎, 蒋彩云, 钱卫平, 化学学报, 2011, 69, 1617.)
[27] Si, G.-Y.; Zhao, Y.-H.; Lv, J.-H.; Wang, F.-H.; Liu, H.-L.; Teng, J.-H.; Liu, Y.-J. Nanoscale. 2013, 5, 4309
[28] Ke, S.-L.; Kan, C.-X.; Mo, B.; Cong, B.; Zhu, J.-J. Acta Phys. -Chim. Sin. 2012, 28, 1275 (柯善林, 阚彩侠, 莫博, 从博, 朱杰君, 物理化学学报, 2012, 28, 1275.)
[29] Yao, J.; Liu, Z.; Liu, Y.; Wang, Y.; Sun, C.; Bartal, G.; Stacy, A.-M.; Zhang, X. Science. 2008, 321, 930
[30] Kabashin, A.-V.; Evans, P.; Pastkovsky, S.; Hendren, W.; Wurtz, G.-A.; Atkinson, R.; Pollard, R.; Podolskiy, V.-A.; Zayats, A.-V. Nat. Mater. 2009, 8, 867
[31] Lemoult, F.; Fink, M.; Lerosey, G. Nat. Commun.2012, 3, 889
[32] Wurtz, G.-A.; Pollard, R.; Hendren, W.; Wiederrecht, G.-P.; Gosztola, D.-J.; Podolskiy, V.-A.; Zayats, A.-V. Nat. Nanotech.2011, 6, 107
[33] Samuel L.-K.; Bhavya S.; Martin G.-B.; Henry A.-I.; Nicholas V.; Freeman R.-G.; Michael J.-N.; George C.- Schatz. J. Am. Chem. Soc.. 2013, 135, 301
[34] Hai N.-X.; Iain A.- L.; Smith W.- E.; Karen F.; Duncan G. J. Phys. Chem. C. 2012, 116, 8338
[35] Ehren H.; Igor I.- S.; Christopher C.-D. Nano Lett.. 2010, 10, 813
[36] Kravets, V.-G.; Schedin, F. Grigorenko, A.-N. Phys. Rev. Lett. 2008, 101, 087403
[37] Auguié, B.; Barnes, W.- L. Phys. Rev. Lett.2008, 101, 143902Atay, T.; Song, J. H.; Nurmikko, A.-V. Nano Lett. 2004, 4, 1627
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