1-(4-氯苯基)-2-环丙基酮肟醚的设计、 合成及杀虫活性

doi:10.7503/cjcu20190582

摘要/Abstract

摘要：

采用中间体衍生化方法, 以环唑醇中间体1-(4-氯苯基)-2-环丙基丙酮作为基本骨架, 引入肟醚活性片段, 合成了32个新的1-(4-氯苯基)-2-环丙基酮肟醚类化合物, 其化学结构经核磁共振波谱和质谱等确认. 单晶X衍射分析表明, 化合物2n属于单斜晶系, 空间群为P2₁/c. 生物活性筛选结果表明, 化合物1i在200 mg/L浓度下对蚜虫的致死率为78.57%; 化合物1g在200 mg/L浓度下对红蜘蛛的致死率为69.95%; 化合物1i在200和12.5 mg/L浓度下对黏虫的致死率分别为100%和85%.

关键词: 1-(4-氯苯基)-2-环丙基酮肟醚, 合成, 单晶, 杀虫活性

Abstract:

Based on the intermediate derivatization method, the active fragment of oxime ether was introduced into 1-(4-chlorophenyl)-2-cyclopropylpropan-1-one as a basic skeleton, and 32 novel compounds were designed and synthesized with the fragment of 1-(4-chlorophenyl)-2-cyclopropylpropan-1-one. Their chemical structures were confirmed by nuclear magnetic resonance spectroscopy and mass spectrometry. Single crystal X-ray diffraction of compound 2n was carried out. The result showed that compound 2n belonged to the monoclinic system and space group of 2n was P2₁/c. The initial screening activity showed that the mortality rate of compound 1i and 1g against aphids and red spiders were 78.57% and 69.95% at the concentration of 200 mg/L, respectiviely, while the mortality rate of compound 1i were 100% and 85% against aphids at the concentration of 200 and 12.5 mg/L, respectiviely. The results showed that compound 1i had the value of further development.

Key words: 1-(4-Chlorophenyl)-2-cyclopropylpropan-1-oneoxime ether, Synthesis, Single crystal, Insecticidal activity

中图分类号:

O622.4

TrendMD:

李康明,陈佳,易阳杰,闫忠忠,叶姣,龙楚云,柳爱平,胡艾希,李建明. 1-(4-氯苯基)-2-环丙基酮肟醚的设计、合成及杀虫活性. 高等学校化学学报, 2020, 41(5): 1026.

LI Kangming,CHEN Jia,YI Yangjie,YAN Zhongzhong,YE Jiao,LONG Chuyun,LIU Aiping,HU Aixi,LI Jianming. Design, Synthesis and Insecticidal Activity of 1-(4-Chlorophenyl)-2-cyclopropylpropan-1-one Oxime Ether ^†. Chem. J. Chinese Universities, 2020, 41(5): 1026.

图/表 6

参考文献 31

[1]	Fan L., Cui J. G., Wei Y. L., Huang Y. M., Modern Agrochemicals, 2008,7(2), 6—11
	( 范磊, 崔建国, 韦英亮, 黄燕敏 . 现代农药, 2008,7(2), 6—11)
[2]	Dai H., Chen J., Li G., Ge S. S., Shi Y. J., Fang Y., Ling Y., Bioorg. Med. Chem. Lett., 2017,27, 950—953 doi: 10.1016/j.bmcl.2016.12.083 URL pmid: 28108247
[3]	Liang J. H., Lv W., Li X. L., An K., Cushman M., Wang H., Xu Y. C., Bioorg. Med. Chem. Lett., 2013,23(5), 1387—1393 doi: 10.1016/j.bmcl.2012.12.070 URL pmid: 23375796
[4]	Luo Y. P., Gong Q., Chen Q., Yang G. F., Chin. J. Org. Chem., 2008,28(9), 1561—1565
	( 骆焱平, 龚青, 陈琼, 杨光富 . 有机化学, 2008,28(9), 1561—1565)
[5]	Bull M. J., Davies J. H., Searle R. J., Henry A. C., Pestic. Sci., 1980,11, 249—253
[6]	Wang Y. S., Wei Y. T., Zheng Q. L., Pesticides, 1997,36(10), 14—15
	( 王银淑, 魏云亭, 郑巧兰 . 农药, 1997,36(10), 14—15)
[7]	Sun R. F., Wang Z. W., Li Y. Q., Xiong L. X., Liu Y. X., Wang Q. M., J. Agric. Food Chem., 2013,61(3), 517—522 doi: 10.1021/jf304468b URL pmid: 23305601
[8]	Ruth B. K., Khoon M. C., Neil L., Pest Manag. Sci., 2002,58(3), 261—267 doi: 10.1002/ps.443 URL pmid: 11975172
[9]	Liu A. P., Ou X. M., Huang M. Z., Wang X. G., Liu X. P., Wang Y. J., Chen C., Yao J. R., Pest. Manage. Sci., 2005,61(2), 166—170 doi: 10.1002/ps.947 URL pmid: 15619716
[10]	Liu A. P., Wang X. G., Ou X. M., Liu S. D., Mo H. B., Liu X. P., Wang T. J., He H. J., Hu L., Huang M. Z., Liu Z. J., Yao J. R., Chin. J. Org. Chem., 2008,43(6), 827—840
	( 柳爱平, 王晓光, 欧晓明, 刘曙东, 莫洪波, 刘兴平, 王婷瑾, 何海军, 胡礼, 黄明智, 刘钊杰, 姚建仁 . 有机化学, 2008,43(6), 827—840)
[11]	Hu Z. B., Luo H. A., Wang X. G., B. Korean Chem. Soc., 2014,35(4), 1073—1076
[12]	Wang S. D., Yang C. M., Liu X. P., Chen C., Yu K., Liu A. P., J. Nat. Sci. Hunan Normal Univ., 2005,28(1), 56—59
	( 王胜得, 杨春明, 刘兴平, 陈灿, 喻快, 柳爱平 . 湖南师范大学自然科学学报, 2005,28(1), 56—59)
[13]	Xu Y., Yuan L. P., Cao J., Ni C. C., Shen Z., Chen L., Zhang Y. B., Chin. J. Pest. Sci., 2007,9(1), 19—24
	( 许艳, 袁莉萍, 曹瑾, 倪长春, 沈宙, 陈亮, 张一宾 . 农药学学报, 2007,9(1), 19—24)
[14]	Philip A. C., Thomas G. C., Plainsboro J., Insecticidal Substituted-biphenylmethyl Oximethers, US 4434182, 1984-02-28
[15]	Liu C., Zhang J. F., Zhou Y. Y., Wang B. L., Xiong L. X., Li Z. M., Chem. Res. Chinese Universities, 2014,30(2), 228—234
[16]	Song H. J., Liu Y. X., Xiong L. X., Li Y. Q., Yang N., Wang Q. M., J. Agric. Food Chem., 2012,60(6), 1470—1479 doi: 10.1021/jf204778v URL pmid: 22304385
[17]	Guan A., Qin Y., Wang J., Li B ., J. Fluorine Chem., 2013,156, 120—123
[18]	Bhanu P. T., Dinneswara R. G., Padmaja A., Padmavathi V., Eur. J. Med. Chem., 2014,82, 347—354 doi: 10.1016/j.ejmech.2014.06.001 URL pmid: 24929288
[19]	Qian C. W., Huang H. J., Fei Z. H., Zhang Y. Q., Wang D., Zong Q. S., Chin. J. Appl. Chem., 2015,32(4), 399—404
	( 钱存卫, 黄海军, 费正皓, 张愉晴, 王栋, 宗乾收 . 应用化学, 2015,32(4), 399—404)
[20]	Li Y., Ma L. F., Wang X. J., Lei B. W., Zhao Y., Yang J. N., Li Z. Y., Chin. J. Org. Chem., 2017,37(5), 1213—1219
	( 李瑶, 马丽芳, 王晓姣, 雷搏文, 赵怡, 杨嘉宇, 李子元 . 有机化学, 2017,37(5), 1213—1219)
[21]	Andrade S. F., Oliveira B. G., Pereira L. C., Ramos J. P., Joaquim A. R., Steppe M., Souza-Fagundes E. M., Alves R. J., Eur. J. Med. Chem., 2017,138, 13—25 doi: 10.1016/j.ejmech.2017.06.022 URL pmid: 28641157
[22]	Shi Y. J., Du X. C., Wang X. L., Chen Q. W., Li L., Dai H., Xu C. C., Zhang J. Y., Ling Y., Chin. J. Org. Chem., 2018,38(7), 1772—1778
	( 石玉军, 杜显超, 王祥龙, 陈庆文, 李玲, 戴红, 徐蔡芹, 张敬远, 凌勇 . 有机化学, 2018,38(7), 1772—1778)
[23]	Wang S. L., Shi Y. J., He H. B., Li Y., Li Y., Dai H., Chin.Chem. Lett., 2015,26(6), 672—674
[24]	Hua X. W., Liu C., Zhou S., Chen M. G., Xiong L. X., Li Y. Q., Li Z. M., Chem. Res. Chinese Universities, 2017,33(6), 882—889
[25]	Liu J. B., Li Y. X., Chen Y. W., Wu C. C., Wan Y. Y., Wei W., Xiong L. X., Zhang X., Yu S. J., Li Z. M., Chem. Res. Chinese Universities, 2016,32(1), 41—48
[26]	Yan Z. Z., Liu A. P., Huang M. Z., Liu M. H., Pei H., Huang L., Yi H. B., Liu W. D., Hu A. X., Eur. J. Med. Chem., 2018,149, 170—181 doi: 10.1016/j.ejmech.2018.02.036 URL pmid: 29501939
[27]	Liu A. P., Yu W. Q., Liu M. H., Bai J. J., Liu W. D., Liu X. P., Pei H., Hu L., Huang M. Z., Wang X. G., J. Agric. Food Chem., 2015,63(34), 7469—7475 doi: 10.1021/acs.jafc.5b02279 URL pmid: 26208876
[28]	Sheldrick G. M., SADABS Program for the Absorption Correction, University of Göttingen, Göttingen, 2004
[29]	Sheldrick G. M., SHELXS-97 Program for the Solution of Crystal Structure, University of Göttingen, Göttingen, 1997
[30]	Sheldrick G. M., SHELXL-97 Program for the Refinement of Crystal Structure, University of Göttingen, Göttingen, 1997
[31]	Chen S. Z., Hu A. X., Li L. X., Yao Z. X., Ma Y. C., Guo R., Development and Design of Chemical Process, Chemical Industry Press, Beijing, 2005, 73—74
	( 陈声宗, 胡艾希, 李立新, 姚志湘, 马银承, 郭睿 . 化工过程开发与设计, 北京: 化学工业出版社, 2005, 73—74)

Compd.	t/h	Appearance	m. p./℃	Yield(%)	ESI-HRMS(calcd.), m/z[M+1]
1a	4.0	Yellow liquid	—	73.3	314.1208(314.1032)
1b	1.0	Yellow liquid	—	76.8	328.1436(328.1509)
1c	1.0	Yellow liquid	—	46.0	332.1116(332.1327)
1d	0.5	Yellow liquid	—	53.1	348.0807(348.1019)
1e	0.5	Yellow liquid	—	72.8	392.0325(392.0517)
1f	8.0	Yellow liquid	—	40.6	359.1102(359.1309)
1g	4.0	Yellow liquid	—	74.9	339.1207(339.1026)
1h	10.0	Yellow liquid	—	47.3	359.1125(359.1234)
1i	10.0	Colorless liquid	—	78.5	406.1502(406.1316)
1j	10.0	Yellow liquid	—	78.6	328.1409(328.1531)
1k	8.0	Yellow liquid	—	77.6	348.0826(348.1039)
1l	16.0	Yellow liquid	—	80.3	382.1102(382.0995)
1m	4.0	Yellow liquid	—	73.1	382.0509(382.0738)
1n	4.0	Yellow liquid	—	38.6	350.1016(350.1103)
2a	5.0	Yellow liquid	—	71.9	349.0817(349.1008)
2b	5.0	Yellow liquid	—	68.0	343.1608(343.1816)
2c	5.0	Yellow liquid	—	78.7	373.1615(373.1804)
2d	5.0	Yellow liquid	—	65.0	355.0432(355.0619)
2e	5.0	Yellow liquid	—	54.4	397.1108(397.1001)
2f	5.0	Colorless liquid	—	45.5	415.1015(415.1207)
2g	5.0	Yellow liquid	—	47.6	431.1014(431.1226)
2h	5.0	Yellow solid	41—43	48.5	465.1005(465.1034)
2i	5.0	Yellow solid	52—54	46.1	411.1026(411.1204)
2j	5.0	Yellow liquid	—	50.1	465.1119(465.1205)
2k	5.0	Yellow liquid	—	46.9	411.1047(411.1234)
2l	5.0	Colorless liquid	—	64.3	381.1008(381.0914)
2m	5.0	Colorless liquid	—	62.3	399.1207(399.1025)
2n	5.0	White solid	60—62	62.2	415.1029(415.1212)
2o	5.0	White solid	54—56	54.9	449.1219(449.1222)
2p	5.0	White solid	71—73	53.2	395.1025(395.1215)
2q	5.0	Yellow liquid	—	57.4	449.1008(449.0910)
2r	5.0	Colorless liquid	—	52.7	395.1416(395.1213)

Compd.	t/h	Appearance	m. p./℃	Yield(%)	ESI-HRMS(calcd.), m/z[M+1]
1a	4.0	Yellow liquid	—	73.3	314.1208(314.1032)
1b	1.0	Yellow liquid	—	76.8	328.1436(328.1509)
1c	1.0	Yellow liquid	—	46.0	332.1116(332.1327)
1d	0.5	Yellow liquid	—	53.1	348.0807(348.1019)
1e	0.5	Yellow liquid	—	72.8	392.0325(392.0517)
1f	8.0	Yellow liquid	—	40.6	359.1102(359.1309)
1g	4.0	Yellow liquid	—	74.9	339.1207(339.1026)
1h	10.0	Yellow liquid	—	47.3	359.1125(359.1234)
1i	10.0	Colorless liquid	—	78.5	406.1502(406.1316)
1j	10.0	Yellow liquid	—	78.6	328.1409(328.1531)
1k	8.0	Yellow liquid	—	77.6	348.0826(348.1039)
1l	16.0	Yellow liquid	—	80.3	382.1102(382.0995)
1m	4.0	Yellow liquid	—	73.1	382.0509(382.0738)
1n	4.0	Yellow liquid	—	38.6	350.1016(350.1103)
2a	5.0	Yellow liquid	—	71.9	349.0817(349.1008)
2b	5.0	Yellow liquid	—	68.0	343.1608(343.1816)
2c	5.0	Yellow liquid	—	78.7	373.1615(373.1804)
2d	5.0	Yellow liquid	—	65.0	355.0432(355.0619)
2e	5.0	Yellow liquid	—	54.4	397.1108(397.1001)
2f	5.0	Colorless liquid	—	45.5	415.1015(415.1207)
2g	5.0	Yellow liquid	—	47.6	431.1014(431.1226)
2h	5.0	Yellow solid	41—43	48.5	465.1005(465.1034)
2i	5.0	Yellow solid	52—54	46.1	411.1026(411.1204)
2j	5.0	Yellow liquid	—	50.1	465.1119(465.1205)
2k	5.0	Yellow liquid	—	46.9	411.1047(411.1234)
2l	5.0	Colorless liquid	—	64.3	381.1008(381.0914)
2m	5.0	Colorless liquid	—	62.3	399.1207(399.1025)
2n	5.0	White solid	60—62	62.2	415.1029(415.1212)
2o	5.0	White solid	54—56	54.9	449.1219(449.1222)
2p	5.0	White solid	71—73	53.2	395.1025(395.1215)
2q	5.0	Yellow liquid	—	57.4	449.1008(449.0910)
2r	5.0	Colorless liquid	—	52.7	395.1416(395.1213)

Compd.	¹H NMR(400 MHz, CDCl₃), δ
1a	7.44—7.12(m, 9H, C₆H₅, C₆H₄), 5.17(s, 1H, OCH₂), 5.04(s, 1H, OCH₂), 1.85—1.80(m, 1H, CH), 1.27(d, J=7.0Hz, 1.5H, CH₃), 1.15(d, J=7.0Hz, 1.5H, CH₃), 0.92—0.07(m, 5H, Cyclo-C₃H₅)
1b	7.44—7.13(m, 8H, C₆H₄, C₆H₄), 5.18(s, 1H, OCH₂), 5.05(s, 1H, OCH₂), 2.64—2.59(m, 1H, CH), 2.36(s, 1.5H, CH₃), 2.34(s, 1.5H, CH₃), 0.90—0.10(m, 5H, Cyclo-C₃H₅)
1c	7.44—6.98(m, 8H, C₆H₄, C₆H₄), 5.22(s, 1.33H, OCH₂), 5.11(s, 0.67H, OCH₂), 1.88—1.77(m, 1H, CH), 1.26(d, J=6.8Hz, 2H, CH₃), 1.15(d, J=7.2Hz, 1H, CH₃), 0.96—0.07(m, 5H, Cyclo-C₃H₅)
1d	7.47—7.14(m, 8H, C₆H₄, C₆H₄), 5.27(s, 2H, OCH₂), 2.69—2.61(m, 1H, CH), 1.30(d, J=7.2Hz, 3H, CH₃), 0.96—0.17(m, 5H, Cyclo-C₃H₅)
1e	7.56—7.10(m, 8H, C₆H₄, C₆H₄), 5.24(s, 1.4H, OCH₂), 5.12(s, 0.6H, OCH₂), 1.85—1.78(m, 1H, CH), 1.31(d, J=7.2Hz, 2.1H, CH₃), 1.16(d, J=6.8Hz, 0.9H, CH₃), 0.97—0.12(m, 5H, Cyclo-C₃H₅)
1f	8.08—7.21(m, 8H, C₆H₄, C₆H₄), 5.57(s, 1.33H, OCH₂), 5.44(s, 0.67H, OCH₂), 1.78—1.73(m, 1H, CH), 1.34(d, J=7.2Hz, 2H, CH₃), 1.27(d, J=6.8Hz, 1H, CH₃), 1.10—0.15(m, 5H, Cyclo-C₃H₅)
1g	7.67—7.15(m, 8H, C₆H₄, C₆H₄), 5.34(s, 2H, OCH₂), 2.69—2.62(m, 1H, CH), 1.29(d, J=7.2 Hz, 3H, CH₃), 0.97—0.11(m, 5H, Cyclo-C₃H₅)
1h	8.24—7.17(m, 8H, C₆H₄, C₆H₄), 5.25(s, 2H, OCH₂), 2.68—2.61(m, 1H, CH), 1.30(d, J=7.2Hz, 3H, CH₃), 0.94—0.17(m, 5H, Cyclo-C₃H₅)
1i	7.36—6.87(m, 13H, C₆H₅, C₆H₄, C₆H₄), 5.10, 5.00(2×s, 2H, OCH₂), 1.83—1.75(m, 1H, CH), 1.22, 1.12(2×d, J₁=7.1 Hz, J₂=7.0 Hz, 3H, CH₃), 0.89—0.07(m, 5H, Cyclo-C₃H₅)
1j	7.40—7.10(m, 8H, C₆H₄, C₆H₄), 5.12(s, 1.36H, OCH₂), 5.00(s, 0.64H, OCH₂), 2.35(s, 2H, CH₃), 2.33(s, 1H, CH₃), 1.87—1.79(m, 1H, CH), 1.26(d, J=7.2Hz, 2H, CH₃), 1.15(d, J=6.8Hz, 1H, CH₃), 0.92—0.13(m, 5H, Cyclo-C₃H₅)
1k	7.37—7.11(m, 8H, C₆H₄, C₆H₄), 5.11, 4.98(2×s, 2H, OCH₂), 2.68—1.74(m, 1H, CH), 1.26, 1.14(2×d, J₁=7.0 Hz, J₂=7.0 Hz, 3H, CH₃), 0.89—0.03(m, 5H, Cyclo-C₃H₅)
1l	7.60—7.16(m, 8H, C₆H₄, C₆H₄), 5.21(s, 1.35H, OCH₂), 5.07(s, 0.65H, OCH₂), 1.83—1.78(m, 1H, CH), 1.30(d, J=7.2Hz, 2H, CH₃), 1.16(d, J=7.2Hz, 1H, CH₃), 0.96—0.07(m, 5H, Cyclo-C₃H₅)
1m	7.38—7.15(m, 7H, C₆H₄, C₆H₃), 5.10, 4.47(2×s, 2H, OCH₂), 1.87—1.79(m, 1H, CH), 1.16(d, J=7.0 Hz, 3H, CH₃), 0.72—0.08(m, 5H, Cyclo-C₃H₅)
1n	6.92—7.87(m, 7H, C₆H₄, C₆H₃), 5.20(s, 1.35H, OCH₂), 5.08(s, 0.65H, OCH₂), 1.83—1.81(m, 1H, CH), 1.29(d, J=7.2Hz, 2H, CH₃), 1.16(d, J=6.8Hz, 1H, CH₃), 0.95—0.09(m, 5H, Cyclo-C₃H₅)

Compd.	¹H NMR(400 MHz, CDCl₃), δ
1a	7.44—7.12(m, 9H, C₆H₅, C₆H₄), 5.17(s, 1H, OCH₂), 5.04(s, 1H, OCH₂), 1.85—1.80(m, 1H, CH), 1.27(d, J=7.0Hz, 1.5H, CH₃), 1.15(d, J=7.0Hz, 1.5H, CH₃), 0.92—0.07(m, 5H, Cyclo-C₃H₅)
1b	7.44—7.13(m, 8H, C₆H₄, C₆H₄), 5.18(s, 1H, OCH₂), 5.05(s, 1H, OCH₂), 2.64—2.59(m, 1H, CH), 2.36(s, 1.5H, CH₃), 2.34(s, 1.5H, CH₃), 0.90—0.10(m, 5H, Cyclo-C₃H₅)
1c	7.44—6.98(m, 8H, C₆H₄, C₆H₄), 5.22(s, 1.33H, OCH₂), 5.11(s, 0.67H, OCH₂), 1.88—1.77(m, 1H, CH), 1.26(d, J=6.8Hz, 2H, CH₃), 1.15(d, J=7.2Hz, 1H, CH₃), 0.96—0.07(m, 5H, Cyclo-C₃H₅)
1d	7.47—7.14(m, 8H, C₆H₄, C₆H₄), 5.27(s, 2H, OCH₂), 2.69—2.61(m, 1H, CH), 1.30(d, J=7.2Hz, 3H, CH₃), 0.96—0.17(m, 5H, Cyclo-C₃H₅)
1e	7.56—7.10(m, 8H, C₆H₄, C₆H₄), 5.24(s, 1.4H, OCH₂), 5.12(s, 0.6H, OCH₂), 1.85—1.78(m, 1H, CH), 1.31(d, J=7.2Hz, 2.1H, CH₃), 1.16(d, J=6.8Hz, 0.9H, CH₃), 0.97—0.12(m, 5H, Cyclo-C₃H₅)
1f	8.08—7.21(m, 8H, C₆H₄, C₆H₄), 5.57(s, 1.33H, OCH₂), 5.44(s, 0.67H, OCH₂), 1.78—1.73(m, 1H, CH), 1.34(d, J=7.2Hz, 2H, CH₃), 1.27(d, J=6.8Hz, 1H, CH₃), 1.10—0.15(m, 5H, Cyclo-C₃H₅)
1g	7.67—7.15(m, 8H, C₆H₄, C₆H₄), 5.34(s, 2H, OCH₂), 2.69—2.62(m, 1H, CH), 1.29(d, J=7.2 Hz, 3H, CH₃), 0.97—0.11(m, 5H, Cyclo-C₃H₅)
1h	8.24—7.17(m, 8H, C₆H₄, C₆H₄), 5.25(s, 2H, OCH₂), 2.68—2.61(m, 1H, CH), 1.30(d, J=7.2Hz, 3H, CH₃), 0.94—0.17(m, 5H, Cyclo-C₃H₅)
1i	7.36—6.87(m, 13H, C₆H₅, C₆H₄, C₆H₄), 5.10, 5.00(2×s, 2H, OCH₂), 1.83—1.75(m, 1H, CH), 1.22, 1.12(2×d, J₁=7.1 Hz, J₂=7.0 Hz, 3H, CH₃), 0.89—0.07(m, 5H, Cyclo-C₃H₅)
1j	7.40—7.10(m, 8H, C₆H₄, C₆H₄), 5.12(s, 1.36H, OCH₂), 5.00(s, 0.64H, OCH₂), 2.35(s, 2H, CH₃), 2.33(s, 1H, CH₃), 1.87—1.79(m, 1H, CH), 1.26(d, J=7.2Hz, 2H, CH₃), 1.15(d, J=6.8Hz, 1H, CH₃), 0.92—0.13(m, 5H, Cyclo-C₃H₅)
1k	7.37—7.11(m, 8H, C₆H₄, C₆H₄), 5.11, 4.98(2×s, 2H, OCH₂), 2.68—1.74(m, 1H, CH), 1.26, 1.14(2×d, J₁=7.0 Hz, J₂=7.0 Hz, 3H, CH₃), 0.89—0.03(m, 5H, Cyclo-C₃H₅)
1l	7.60—7.16(m, 8H, C₆H₄, C₆H₄), 5.21(s, 1.35H, OCH₂), 5.07(s, 0.65H, OCH₂), 1.83—1.78(m, 1H, CH), 1.30(d, J=7.2Hz, 2H, CH₃), 1.16(d, J=7.2Hz, 1H, CH₃), 0.96—0.07(m, 5H, Cyclo-C₃H₅)
1m	7.38—7.15(m, 7H, C₆H₄, C₆H₃), 5.10, 4.47(2×s, 2H, OCH₂), 1.87—1.79(m, 1H, CH), 1.16(d, J=7.0 Hz, 3H, CH₃), 0.72—0.08(m, 5H, Cyclo-C₃H₅)
1n	6.92—7.87(m, 7H, C₆H₄, C₆H₃), 5.20(s, 1.35H, OCH₂), 5.08(s, 0.65H, OCH₂), 1.83—1.81(m, 1H, CH), 1.29(d, J=7.2Hz, 2H, CH₃), 1.16(d, J=6.8Hz, 1H, CH₃), 0.95—0.09(m, 5H, Cyclo-C₃H₅)

Compd.	¹H NMR(400 MHz, CDCl₃), δ	¹³C NMR(100 MHz, CDCl₃), δ
2a	8.46—7.07(m, 3H, Pyridine-H), 7.41—7.23(m, 4H, C₆H₄), 5.14, 5.01(2s, 2H, OCH₂), 2.58—1.72(m, 1H, CH), 1.25, 1.13(2d, J₁=7.0 Hz, J₂=7.0 Hz, 3H, CH₃), 0.97—0.03(m, 5H, Cyclo-C₃H₅)
2b	8.25(s, 1H, Pyridine 6-H), 7.41—7.39(m, 2H, C₆H₄ 3,5-H), 7.31—7.29(m, 3H, Pyridine 4-H, C₆H₄ 2,6-H), 5.26(s, 2H, OCH₂), 2.64—2.58(m, 1H, CH), 2.38(s, 3H, CH₃), 2.30(s, 3H, CH₃), 1.22(d, J=7.2 Hz, 3H, CH₃), 0.85—0.10(m, 5H, Cyclo-C₃H₅)	162.78, 151.95, 147.01, 138.81, 134.62, 134.45, 132.83, 132.69, 129.30, 128.23, 76.34, 38.87, 18.18, 18.04, 17.41, 14.77, 5.24, 4.29
2c	8.23(s, 1H, Pyridine-H), 7.40(d, J=8.4 Hz, 2H, C₆H₄ 3,5-H), 7.30(d, J=8.4 Hz, 2H, C₆H₄ 2,6-H), 5.26(s, 2H, OCH₂), 3.77(s, 3H, OCH₃), 2.64—2.56(m, 1H, CH), 2.32(s, 3H, CH₃), 2.26(s, 3H, CH₃), 1.22(d, J=7.2 Hz, 3H, CH₃), 0.85—0.10(m, 5H, Cyclo-C₃H₅)	164.15, 162.90, 154.82, 149.10, 134.57, 134.48, 129.31, 128.24, 126.49, 126.16, 76.57, 59.83, 38.87, 17.41, 14.77, 13.36, 11.09, 5.24, 4.29
2d	7.48—7.35(m, 4H, C₆H₄), 7.11(s, 1H, Thiazole-H), 5.23, 5.09(2s, 2H, OCH₂), 2.59—1.78(m, 1H, CH), 1.25, 1.20(2d, J₁=7.2 Hz, J₂=7.0 Hz, 3H, CH₃), 0.93—0.08(m, 5H, Cyclo-C₃H₅)
2e	7.96—7.95(m, 2H, C₆H₅), 7.43—7.41(m, 5H, Ph, C₆H₄ 3,5-H), 7.33(d, J=8.0 Hz, 2H, C₆H₄ 2,6-H), 7.21(s, 1H, Thiazole-H), 5.36(s, 2H, OCH₂), 2.72—2.64(m, 1H, CH), 1.31(d, J=6.8 Hz, 3H, CH₃), 0.96—0.20(m, 5H, Cyclo-C₃H₅)	168.20, 163.44, 154.75, 134.64, 134.51, 133.63, 130.03, 129.29, 128.93, 128.34, 126.60, 115.92, 72.00, 39.33, 17.33, 14.83, 5.29, 4.35
2f	7.95—7.10(m, 4H, C₆H₄), 7.42(d, J=8.4 Hz, 2H, ClC₆H₄ 3,5-H), 7.32(d, J=8.4 Hz, 2H, ClC₆H₄ 2,6-H), 7.20(s, 1H, Thiazole-H), 5.33(s, 2H, OCH₂), 2.71—2.64(m, 1H, CH), 1.31(d, J=7.2 Hz, 3H, CH₃), 0.97—0.19(m, 5H, Cyclo-C₃H₅)	166.96, 165.10, 163.47, 162.61, 154.81, 134.67, 134.47, 130.00, 129.28, 128.52, 128.44, 128.34, 116.11, 115.89, 71.93, 39.32, 17.33, 14.82, 5.29, 4.35
2g	7.88(d, J=8.0 Hz, 2H, C₆H₄), 7.42—7.39(m, 4H, C₆H₄, C₆H₄), 7.32(d, J=8.4 Hz, 2H, C₆H₄), 7.22(s, 1H, Thiazole-H), 5.34(s, 2H, OCH₂), 2.71—2.63(m, 1H, CH), 1.31(d, J=7.2 Hz, 3H, CH₃), 0.95—0.19(m, 5H, Cyclo-C₃H₅)	166.79, 163.50, 155.00, 135.97, 134.68, 134.46, 132.14, 129.28, 129.16, 128.35, 127.76, 116.20, 71.90, 39.33, 17.33, 14.83, 5.31, 4.35
2h	8.07(d, 2H, J=8.4 Hz, C₆H₄ 3,5-H), 7.69(d, 2H, J=8.0 Hz, C₆H₄ 2,6-H), 7.42(d, J=8.0 Hz, 2H, ClC₆H₄ 3,5-H), 7.33(d, J=8.4 Hz, 2H, ClC₆H₄ 2,6-H), 7.29(s, 1H, Thiazole-H), 5.36(s, 2H, OCH₂), 2.71—2.64(m, 1H, CH), 1.31(d, J=7.2 Hz, 3H, CH₃), 0.96—0.19(m, 5H, Cyclo-C₃H₅)	166.22, 163.59, 155.42, 136.70, 134.72, 134.42, 131.62, 129.27, 128.36, 126.76, 125.97, 125.93, 125.26, 122.56, 117.00, 71.85, 39.35, 17.32, 14.82, 5.31, 4.35
2i	7.85(d, J=7.6 Hz, 2H, C₆H₄), 7.43(d, J=8.4 Hz, 2H, ClC₆H₄ 3,5-H), 7.33(d, J=8.4 Hz, 2H, ClC₆H₄ 2,6-H), 7.24(d, J=7.6 Hz, 2H, C₆H₄), 7.17(s, 1H, Thiazole-H), 5.35(s, 2H, OCH₂), 2.72—2.64(m, 1H, CH), 2.40(s, 3H, CH₃), 1.31(d, J=7.2 Hz, 3H, CH₃), 0.97—0.20(m, 5H, Cyclo-C₃H₅)	168.39, 163.39, 154.56, 140.26, 134.63, 134.54, 131.02, 129.61, 129.30, 128.33, 126.51, 115.45, 72.04, 39.32, 21.43, 17.34, 14.84, 5.30, 4.36
2j	7.81—7.56(m, 4H, C₆H₄), 7.42(d, J=8.0 Hz, 2H, ClC₆H₄ 3,5-H), 7.37(s, 1H, Thiazole-H), 7.33(d, J=8.0 Hz, 2H, ClC₆H₄ 2,6-H), 5.37(s, 2H, OCH₂), 2.71—2.63(m, 1H, CH), 1.30(d, J=7.2 Hz, 3H, CH₃), 0.96—0.19(m, 5H, Cyclo-C₃H₅)	164.22, 163.50, 154.13, 134.64, 134.54, 132.34, 131.61, 129.67, 129.29, 128.34, 126.67, 118.08, 71.83, 39.39, 17.28, 14.79, 5.25, 4.31
2k	7.72—7.70(m, 1H, C₆H₄), 7.44(d, J=8.4 Hz, 2H, ClC₆H₄ 3,5-H), 7.35—7.29(m, 5H, ClC₆H₄ 2,6-H, C₆H₄), 7.27(s, 1H, Thiazole-H), 5.38(s, 2H, OCH₂), 2.72—2.64(m, 1H, CH), 2.58(s, 3H, CH₃), 1.32(d, J=7.2 Hz, 3H, CH₃), 0.98— 0.20(m, 5H, Cyclo-C₃H₅)	167.72, 163.32, 153.98, 136.55, 134.65, 134.57, 133.02, 131.40, 129.96, 129.42, 129.29, 128.36, 126.05, 116.54, 72.11, 39.41, 21.35, 17.34, 14.84, 5.31, 4.39
2l	7.68(s, 1H, Oxazole-H), 8.05—7.45(m, 5H, C₆H₅), 7.42(d, J=8.4 Hz, 2H, C₆H₄ 3,5-H), 7.33(d, J=8.4 Hz, 2H, C₆H₄ 2,6-H), 5.17(s, 2H, OCH₂), 2.69—2.62(m, 1H, CH), 1.28(d, J=6.8 Hz, 3H, CH₃), 0.92—0.19(m, 5H, Cyclo-C₃H₅)	163.54, 161.79, 139.07, 136.47, 134.64, 134.49, 130.41, 129.30, 128.77, 128.33, 127.45, 126.42, 68.17, 39.18, 17.32, 14.83, 5.27, 4.31
2m	8.05—7.12(m, 4H, C₆H₄), 7.66(s, 1H, Oxazole-H), 7.41(d, J=8.4 Hz, 2H, ClC₆H₄ 3,5-H), 7.32(d, J=8.4 Hz, 2H, ClC₆H₄ 2,6-H), 5.15(s, 2H, OCH₂), 2.68—2.61(m, 1H, CH), 1.27(d, J=7.2 Hz, 3H, CH₃), 0.91—0.18(m, 5H, Cyclo-C₃H₅)	165.34, 163.59, 162.84, 160.98, 139.09, 136.50, 134.66, 134.44, 129.29, 128.58, 128.50, 128.33, 123.81, 116.08, 115.86, 68.08, 39.16, 17.31, 14.82, 5.26, 4.30
2n	7.97(d, J=8.4 Hz, 2H, C₆H₄), 7.67(s, 1H, Oxazole-H), 7.44—7.40(m, 4H, C₆H₄, C₆H₄), 7.32(d, J=8.0 Hz, 2H, C₆H₄), 5.15(s, 2H, OCH₂), 2.68—2.60(m, 1H, CH), 1.27(d, J=7.2 Hz, 3H, CH₃), 0.91—0.17(m, 5H, Cyclo-C₃H₅)	163.61, 160.86, 139.28, 136.67, 136.53, 134.68, 134.43, 129.28, 129.10, 128.33, 127.68, 125.93, 68.06, 39.17, 17.31, 14.82, 5.27, 4.31
2o	8.16—7.72(m, 4H, C₆H₄), 7.70(s, 1H, Oxazole-H), 7.41(d, J=8.0 Hz, 2H, ClC₆H₄ 3,5-H), 7.32(d, J=8.4 Hz, 2H, ClC₆H₄ 2,6-H), 5.17(s, 2H, OCH₂), 2.69—2.61(m, 1H, CH), 1.28(d, J=7.2 Hz, 3H, CH₃), 0.92—0.18(m, 5H, Cyclo-C₃H₅)	163.67, 160.36, 139.66, 137.22, 134.71, 134.41, 131.98, 130.55, 129.27, 128.34, 126.63, 125.81, 125.78, 125.19, 122.49, 68.00, 39.21, 17.28, 14.81, 5.27, 4.30
2p	7.94—7.27(m, 4H, C₆H₄), 7.65(s, 1H, Oxazole-H), 7.41(d, J=8.0 Hz, 2H, ClC₆H₄ 3,5-H), 7.33(d, J=8.0 Hz, 2H, ClC₆H₄ 2,6-H), 5.15(s, 2H, OCH₂), 2.69—2.61(m, 1H, CH), 2.40(s, 3H, CH₃), 1.27(d, J=7.2 Hz, 3H, CH₃), 0.91—0.18(m, 5H, Cyclo-C₃H₅)	163.53, 162.02, 140.71, 138.87, 136.15, 134.62, 134.50, 129.48, 129.30, 128.32, 126.39, 124.76, 68.20, 39.16, 21.52, 17.31, 14.82, 5.25, 4.29
2q	8.02—7.57(m, 4H, C₆H₄), 7.77(s, 1H, Oxazole-H), 7.41(d, J=8.4 Hz, 2H, ClC₆H₄ 3,5-H), 7.33(d, J=8.0 Hz, 2H, ClC₆H₄ 2,6-H), 5.19(s, 2H, OCH₂), 2.68—2.60(m, 1H, CH), 1.28(d, J=6.8 Hz, 3H, CH₃), 0.92—0.18(m, 5H, Cyclo-C₃H₅)	163.70, 159.75, 139.19, 137.71, 134.67, 134.46, 131.83, 131.62, 130.31, 129.29, 128.34, 126.85, 68.07, 39.28, 17.27, 14.79, 5.25, 4.27
2r	7.99—7.28(m, 3H, C₆H₄), 7.70(s, 1H, Oxazole-H), 7.42(d, J=8.4 Hz, 2H, ClC₆H₄ 3,5-H), 7.34—7.32(m, 3H, ClC₆H₄ 2,6-H, C₆H₄), 5.19(s, 2H, OCH₂), 2.69(s, 3H, CH₃), 2.67—2.61(m, 1H, CH), 1.29(d, J=7.2 Hz, 3H, CH₃), 0.94—0.19(m, 5H, Cyclo-C₃H₅)	163.45, 162.22, 138.76, 137.48, 136.02, 134.64, 134.54, 131.56, 129.99, 129.28, 128.95, 128.34, 126.56, 125.93, 68.31, 39.28, 21.87, 17.30, 14.82, 5.27, 4.33