新型含苯基取代嘧啶基磺酰脲衍生物的设计、 合成及生物活性

doi:10.7503/cjcu20140955

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (4): 672.doi: 10.7503/cjcu20140955

新型含苯基取代嘧啶基磺酰脲衍生物的设计、合成及生物活性

陈伟¹, 魏巍¹, 周莎¹, 李永红¹, 张晓¹, 童军², 李玉新¹(), 李正名¹()

1. 南开大学元素有机化学国家重点实验室, 化学化工协同创新中心(天津)
2. 农药国家工程研究中心, 天津 300071

收稿日期:2014-10-27 出版日期:2015-04-10 发布日期:2015-03-27
作者简介:联系人简介: 李正名, 男, 博士, 教授, 中国工程院院士, 主要从事有机化学和农药化学研究.E-mail: nkzml@vip.163.com. 李玉新, 女, 博士, 副研究员, 主要从事绿色农药化学和有机合成化学研究. E-mail: liyx128@nankai.edu.cn
基金资助:
国家自然科学基金(批准号: 21272129)和“十二五”国家科技支撑计划项目(批准号: 2011BAE06B05)资助

Design, Synthesis and Biological Activity of Novel Sulfonylurea Derivatives Containing Phenyl-substituted Pyrimidine Moiety^†

CHEN Wei¹, WEI Wei¹, ZHOU Sha¹, LI Yonghong¹, ZHANG Xiao¹, TONG Jun², LI Yuxin^1,^*(), LI Zhengming^1,^*()

1. State Key Laboratory of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering(Tianjin)
2. National Pesticide Engineering Research Center, Nankai University, Tianjin 300071, China

Received:2014-10-27 Online:2015-04-10 Published:2015-03-27
Contact: LI Yuxin,LI Zhengming E-mail:liyx128@nankai.edu.cn;nkzml@vip.163.com
Supported by:
† Supported by the National Natural Scinece Foundation of China(No.21272129) and the National Key Technologies Research and Development Program of China(No.2011BAE06B05)

摘要/Abstract

摘要：

将苯基引入到嘧啶环的4位, 设计、合成了2个系列共24个结构新颖的磺酰脲类衍生物, 并对其生物活性进行了研究. 抑菌实验结果表明, 目标化合物对苹果轮纹病菌和小麦纹枯病菌表现出优异的抑制率, 其中化合物9f对5种病菌的抑制率均超过65%. 进一步研究发现, 化合物9f对苹果轮纹病菌的EC₅₀值为8.63 mg/L, 略高于对照药百菌清(7.33 mg/L); 化合物8k和9k对小麦纹枯病菌的EC₅₀值分别为5.48和6.09 mg/L, 与百菌清(4.26 mg/L)接近. 同时, 盆栽法除草测试结果表明, 在75 g/ha剂量下, 化合物8d和9d对油菜具有较好的芽前除草活性, 分别为86%和73%; 化合物9h对反枝苋的土壤处理抑制活性为100%, 优于对照药氯磺隆(96%).

关键词: 磺酰脲, 乙酰乳酸合成酶, 苯基取代嘧啶, 抑菌活性, 除草活性

Abstract:

Acetolactate synthase(ALS) has been regarded as an attractive target for fungicide and herbicide discovery. Furthermore, sulfonylurea(SU) as one of the most active ALS inhibitors were used as herbicides in crops protect. In order to discuss the multi-biological activity of SU, two series of novel SU derivatives containing phenyl-substituted pyrimidine moiety were designed, synthesized and their antifungal activity and herbicidal activity were evaluated. The bioassay results indicated that some title compounds showed excellent antifungal activity against Physalospora piricola and Rhizoctonia cerealis in vitro at the dosage of 50 mg/L. Particularly, compound 9f exhibited more than 65% inhibitory activity against five phytopathogens. On the basis of advanced screening test, the EC₅₀ value of compound 8f against P. piricola was 8.63 mg/L, which was a little higher than Chlorothalonil(EC₅₀=7.33 mg/L), the EC₅₀ value of compounds 8k(5.48 mg/L) and 9k(6.09 mg/L) against R. cerealis were similar to Chlorothalonil(EC₅₀=4.26 mg/L). In addtion, the title compounds showed favorable pre-emergence treatment herbicidal activity against Brassica napus and Amaranthus retroflexus at the dosage of 75 g/ha. For example, compounds 8d and 9d showed 86% and 73% inhibition activity respectively against Brassica napus; compound 9h exhibited 100% herbicidal activity against Amaranthus retroflexus, which was better than that of Chlorsulfuron(96%). The results provided useful information for designing new SU with highly fungicidal activity and herbicidal activity.

Key words: Sulfonylurea, Acetolactate synthase, Phenyl-subsituted pyrimidine, Antifungal activity, Herbicidal activity

中图分类号:

O625.7

TrendMD:

陈伟, 魏巍, 周莎, 李永红, 张晓, 童军, 李玉新, 李正名. 新型含苯基取代嘧啶基磺酰脲衍生物的设计、合成及生物活性. 高等学校化学学报, 2015, 36(4): 672.

CHEN Wei, WEI Wei, ZHOU Sha, LI Yonghong, ZHANG Xiao, TONG Jun, LI Yuxin, LI Zhengming. Design, Synthesis and Biological Activity of Novel Sulfonylurea Derivatives Containing Phenyl-substituted Pyrimidine Moiety^†. Chem. J. Chinese Universities, 2015, 36(4): 672.

图/表 10

参考文献 34

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Compd.	m.p.(ref.)/℃	Compd.	m.p.(ref.)/℃	Compd.	m.p.(ref.)/℃
7a	103—104(108—110^[26])	7e	73—74(70—72.5^[29])	7j	140—141(140—141^[27])
7b	123—125(121—123^[26])	7f	146—147(151—153^[26])	7k	103—104(102—104^[31])
7c	99—100(97—98^[27])	7h	162—163(160—164^[30])	7l	137—139(143—144^[27])
7d	151—152(153—155^[28])	7i	124—125(122—125^[30])

Compd.	m.p.(ref.)/℃	Compd.	m.p.(ref.)/℃	Compd.	m.p.(ref.)/℃
7a	103—104(108—110^[26])	7e	73—74(70—72.5^[29])	7j	140—141(140—141^[27])
7b	123—125(121—123^[26])	7f	146—147(151—153^[26])	7k	103—104(102—104^[31])
7c	99—100(97—98^[27])	7h	162—163(160—164^[30])	7l	137—139(143—144^[27])
7d	151—152(153—155^[28])	7i	124—125(122—125^[30])

Compd.	Appearance	Yield (%)	m.p./℃	HRMS(calcd.) m/z, [M+H]⁺	Compd.	Appearance	Yield (%)	m.p./℃	HRMS(calcd.) m/z, [M+H]⁺
8a	White solid	80.3	208—209	368.0946(368.0943)	9a	White solid	81.2	210—211	368.0942(368.0943)
8b	White solid	81.4	214—216	382.1093(382.1100)	9b	White solid	80.7	200—201	382.1099(382.1100)
8c	White solid	76.1	173—174	442.1310(442.1311)	9c	White solid	73.2	188—190	442.1311(442.1311)
8d	White solid	75.2	206—207	414.0872(414.0874)	9d	White solid	73.7	203—205	414.0871(414.0874)
8e	White solid	63.1	204—206	427.1076(427.1076)	9e	White solid	72.1	185—187	427.1077(427.1076)
8f	White solid	74.7	207—209	403.0632(403.0633)	9f	White solid	71.4	189—190	403.0632(403.0633)
8g	White solid	67.9	233—235	448.0482(448.0482)	9g	White solid	70.1	203—205	448.0484(448.0482)
8h	White solid	54.2	187—189	441.1346(441.1345)	9h	White solid	68.7	202—203	441.1346(441.1345)
8i	White solid	74.3	157—158	462.0903(462.0906)	9i	White solid	74.7	160—161	462.0903(462.0906)
8j	White solid	75.4	168—169	468.0953(468.0953)	9j	White solid	71.3	168—169	468.0950(468.0953)
8k	White solid	80.3	191—193	445.1291(445.1294)	9k	White solid	79.7	188—189	445.1290(445.1294)
8l	White solid	78.7	210—211	501.1007(501.1015)	9l	White solid	79.4	183—184	501.1011(501.1015)

Compd.	Appearance	Yield (%)	m.p./℃	HRMS(calcd.) m/z, [M+H]⁺	Compd.	Appearance	Yield (%)	m.p./℃	HRMS(calcd.) m/z, [M+H]⁺
8a	White solid	80.3	208—209	368.0946(368.0943)	9a	White solid	81.2	210—211	368.0942(368.0943)
8b	White solid	81.4	214—216	382.1093(382.1100)	9b	White solid	80.7	200—201	382.1099(382.1100)
8c	White solid	76.1	173—174	442.1310(442.1311)	9c	White solid	73.2	188—190	442.1311(442.1311)
8d	White solid	75.2	206—207	414.0872(414.0874)	9d	White solid	73.7	203—205	414.0871(414.0874)
8e	White solid	63.1	204—206	427.1076(427.1076)	9e	White solid	72.1	185—187	427.1077(427.1076)
8f	White solid	74.7	207—209	403.0632(403.0633)	9f	White solid	71.4	189—190	403.0632(403.0633)
8g	White solid	67.9	233—235	448.0482(448.0482)	9g	White solid	70.1	203—205	448.0484(448.0482)
8h	White solid	54.2	187—189	441.1346(441.1345)	9h	White solid	68.7	202—203	441.1346(441.1345)
8i	White solid	74.3	157—158	462.0903(462.0906)	9i	White solid	74.7	160—161	462.0903(462.0906)
8j	White solid	75.4	168—169	468.0953(468.0953)	9j	White solid	71.3	168—169	468.0950(468.0953)
8k	White solid	80.3	191—193	445.1291(445.1294)	9k	White solid	79.7	188—189	445.1290(445.1294)
8l	White solid	78.7	210—211	501.1007(501.1015)	9l	White solid	79.4	183—184	501.1011(501.1015)

Compd.	¹H NMR(400 MHz), δ	¹³C NMR(101 MHz), δ
8a^a	12.79(s, 1H, SO₂NH), 9.72(br, 1H, CONH-Pyrim), 8.61(s, 1H, Pyrim-H), 8.12(d, J=7.4 Hz, 2H, Ph-H), 7.67—7.63(m, 2H, Ph-H), 7.60(d, J=7.4 Hz, 1H, Ph-H), 7.57—7.51(m, 5H, Ph-H), 2.39(s, 3H, Pyrim-CH₃)	165.10, 160.65, 155.11, 149.64, 139.37, 136.41, 133.59, 130.55, 128.89, 128.84, 128.72, 128.27, 122.61, 16.64
8b^a	12.90(s, 1H, SO₂NH), 10.52(br, 1H, CONH-Pyrim), 8.66(s, 1H, Pyrim-H), 8.23(d, J=7.9 Hz, 1H, Ph-H), 7.66(d, J=5.1 Hz, 2H, Ph-H), 7.57—7.54(m, 3H, Ph-H), 7.48(t, J=7.4 Hz, 1H, Ph-H), 7.37(t, J=7.6 Hz, 1H, Ph-H), 7.25(d, J=7.0 Hz, 1H, Ph-H), 2.55(s, 3H, Ph—CH₃), 2.38(s, 3H, Pyrim-CH₃)	165.14, 160.66, 155.16, 149.37, 137.33, 137.30, 136.37, 133.62, 132.35, 130.93, 130.49, 128.81, 128.72, 126.31, 122.63, 20.01, 16.54
8c^a	12.78(s, 1H, SO₂NH), 10.14(br, 1H, CONH-Pyrim), 8.66(s, 1H, Pyrim-H), 8.14(d, J=7.5 Hz, 1H, Ph-H), 7.75(d, J=6.1 Hz, 2H, Ph-H), 7.62—7.49(m, 4H, Ph-H), 7.10(t, J=7.5 Hz, 1H, Ph-H), 6.98(d, J=8.1 Hz, 1H, Ph-H), 4.01(t, J=4.7 Hz, 2H, OCH₂), 3.25(t, J=4.7 Hz, 2H, OCH₂), 3.01(s, 3H, OCH₃), 2.40(s, 3H, Pyrim-CH₃)	164.85, 160.82, 156.21, 155.30, 149.60, 136.53, 135.43, 131.78, 130.53, 129.01, 128.89, 127.20, 122.35, 120.84, 113.81, 70.04, 68.52, 58.87, 16.68
8d^b	13.39(br, 1H, SO₂NH), 10.93(s, 1H, CONH-Pyrim), 8.69(s, 1H, Pyrim-H), 8.28(d, J=2.6 Hz, 1H, Ph-H), 8.05—7.96(m, 3H, Ph-H), 7.73—7.55(m, 5H, Ph-H), 2.32(s, 3H, Pyrim-CH3)	160.05, 155.52, 148.08, 136.96, 135.95, 133.94, 133.05, 132.93, 130.54, 129.28, 128.95, 128.51, 125.32, 124.73, 123.12, 16.46
8e^b	12.84(br, 1H, SO₂NH), 10.78(s, 1H, CONH-Pyrim), 8.68(s, 1H, Pyrim-H), 8.19(d, J=6.8 Hz, 1H, Ph-H), 7.85—7.68(m, 5H, Ph-H), 7.73—7.55(m, 3H, Ph-H), 3.63(s, 3H, COOCH₃), 2.32(s, 3H, Pyrim-CH₃)
8f^b	13.22(br, 1H, SO₂NH), 10.76(s, 1H, CONH-Pyrim), 8.66(s, 1H, Pyrim-H), 7.71—7.46(m, 9H, Ph-H), 2.31(s, 3H, Pyrim-CH₃)	166.52, 157.82, 155.85, 152.00, 139.75, 133.30, 133.02, 131.54, 129.26, 128.75, 127.50, 127.12, 125.32, 124.73, 123.12, 18.76
Compd.	¹H NMR(400 MHz), δ	¹³C NMR(101 MHz), δ
8g^b	10.89(s, 1H, CONH-Pyrim), 8.78(s, 1H, Pyrim-H), 8.64—8.50(m, 3H, Ph-H, SO₂NH), 8.03—7.98(m, 1H, Ph-H), 7.70—7.57(m, 5H, Ph-H), 2.31(s, 3H, Pyrim-CH₃)	166.52, 155.26, 146.37, 139.75, 137.73, 134.07, 130.59, 129.26, 128.99, 128.75, 127.50, 127.12, 125.32, 124.73, 123.12, 16.43
8h^b	13.00(br, 1H, SO₂NH), 10.78(s, 1H, CONH-Pyrim), 8.72(s, 1H, Pyrim-H), 7.75—7.53(m, 8H, Ph-H, Py-H), 2.94[s, 3H, 1/2 N(CH₃)₂], 2.82[s, 3H, 1/2 N(CH₃)₂], 2.31(s, 3H, Pyrim-CH₃)	167.12, 166.12, 160.83, 160.21, 155.73, 155.06, 150.20, 149.90, 149.70, 137.27, 129.29, 129.02, 128.51, 127.19, 123.09, 38.71, 34.76, 16.49
8i^a	9.29(s, 1H, CONH-Pyrim), 8.67(d, J=2.8 Hz, 1H, Py-H), 8.55(s, 1H, Pyrim-H), 8.19(d, J=7.3 Hz, 1H, Py-H), 7.68(d, J=5.4 Hz, 2H, Ph-H), 7.49—7.32(m, 4H, Ph-H, Py-H, SO₂NH), 7.16—7.08(m, 1H, Ph-H), 3.26(q, J=7.2 Hz, 2H, CH₂), 2.37(s, 3H, Pyrim-CH₃), 1.31(t, J=7.2 Hz, 3H, CH₃)	166.27, 159.94, 156.84, 154.03, 151.34, 142.08, 139.99, 137.72, 129.55, 129.01, 128.38, 122.23, 119.78, 117.27, 49.14, 16.61, 7.15
8j^b	13.03(s, 1H, SO₂NH), 10.80(s, 1H, CONH-Pyrim), 8.60(s, 1H, Pyrim-H), 8.41(d, J=4.4 Hz, 1H, Py-H), 7.66(d, J=6.0 Hz, 2H, Ph-H), 7.56—7.50(m, 4H, Ph-H, Py-H), 7.46(d, J=8.3 Hz, 1H, Ph-H), 4.42(q, J_HF=7.9 Hz, 2H, OCH₂CF₃), 2.39(s, 3H, Pyrim-CH₃)
8k^a	13.12(s, 1H, SO₂NH), 10.58(s, 1H, CONH-Pyrim), 8.63(s, 1H, Pyrim-H), 7.86(s, 1H, Pyrazole-H), 7.80(d, J=5.4 Hz, 2H, Ph-H), 7.54—7.50(m, 3H, Ph-H), 4.33(s, 3H, NCH₃), 4.08(d, J=6.8 Hz, 2H, OCH₂), 2.39(s, 3H, Pyrim-CH₃), 1.15(t, J=6.7 Hz, 3H, CH₃)	165.60, 160.66, 160.30, 154.88, 150.29, 140.28, 138.56, 136.45, 130.41, 129.10, 128.70, 122.84, 116.16, 60.86, 41.54, 16.69, 14.10
8l^b	13.43(br, 1H, SO₂NH), 10.88(s, 1H, CONH-Pyrim), 9.19(d, J=7.0 Hz, 1H, Py-H), 8.65(s, 1H, Pyrim-H), 8.11—7.92(m, 2H, Py-H), 7.84—7.71(m, 3H, Ph-H, Py-H), 7.58—7.40(m, 3H, Ph-H), 3.63(q, J=7.1 Hz, 2H, SO₂CH₂), 2.44(s, 3H, Pyrim-CH₃), 1.20(t, J=7.2 Hz, 3H, CH₃)	165.11, 160.14, 155.34, 144.66, 143.74, 137.00, 130.50, 129.93, 129.42, 129.00, 128.92, 128.54, 127.77, 122.97, 118.90, 116.86, 49.15, 16.46, 7.12
9a^a	13.12(s, 1H, SO₂NH), 8.16(d, J=7.5 Hz, 2H, Ph-H), 8.02(dd, J=6.5, 3.1 Hz, 2H, Ph-H), 7.67—7.50(m, 7H, CONH-Pyrim, Ph-H), 7.30(s, 1H, Pyrim-H), 2.57(s, 3H, Pyrim-CH₃)	169.70, 164.93, 156.64, 149.27, 139.21, 135.16, 133.65, 131.86, 129.30, 128.86, 128.41, 127.22, 111.35, 24.26
9b^a	13.24(s, 1H, SO₂NH), 8.24(d, J=7.9 Hz, 1H, Ph-H), 8.19—7.95(m, 3H, CONH-Pyrim, Ph-H), 7.60—7.44(m, 4H, Ph-H), 7.36(t, J=7.6 Hz, 1H, Ph-H), 7.31(s, 1H, Pyrim-H), 7.27(d, J=7.6 Hz, 1H, Ph-H), 2.66(s, 3H, Ph—CH₃), 2.57(s, 3H, Pyrim-CH₃)	169.41, 165.25, 156.73, 149.12, 137.34, 137.13, 135.08, 133.72, 132.38, 131.90, 131.20, 129.29, 127.22, 126.32, 111.35, 24.25, 20.17
9c^a	13.08(s, 1H, SO₂NH), 8.16(dd, J=7.9, 1.4 Hz, 1H, Ph-H), 8.08(dd, J=6.5, 2.9 Hz, 2H, Ph-H), 7.59—7.52(m, 5H, CONH-Pyrim, Ph-H), 7.33(s, 1H, Pyrim-H), 7.12(t, J=7.7 Hz, 1H, Ph-H), 7.00(d, J=8.3 Hz, 1H, Ph-H), 4.12(t, J=4.7 Hz, 2H, OCH₂), 3.40(s, 2H, OCH₂), 2.97(s, 3H, OCH₃), 2.59(s, 3H, Pyrim-CH₃)	169.96, 164.28, 156.84, 156.19, 149.12, 135.50, 135.16, 132.11, 131.86, 129.35, 127.29, 126.95, 120.81, 113.59, 111.10, 70.18, 68.41, 58.72, 24.31
9d^c	13.81(br, 1H, SO₂NH), 9.64(s, 1H, CONH-Pyrim), 8.43(d, J=7.3 Hz, 1H, Ph-H), 8.22(d, J=7.0 Hz, 2H, Ph-H), 8.05—7.96(m, 3H, Ph-H), 7.73(s, 1H, Pyrim-H), 7.64—7.54(m, 3H, Ph-H), 2.63(s, 3H, Pyrim-CH₃)	164.44, 158.07, 149.80, 149.29, 136.47, 136.20, 134.16, 133.20, 132.53, 132.39, 129.93, 128.27, 127.06, 125.69, 112.07, 24.02
9e^b	13.37(br, 1H, SO₂NH), 10.81(s, 1H, CONH-Pyrim), 8.19—8.03(m, 3H, Ph-H), 7.69—7.55(m, 6H, Ph-H), 7.44(s, 1H, Pyrim-H), 3.69(s, 3H, COOCH₃), 2.30(s, 3H, Pyrim-CH₃)	168.18, 163.65, 157.37, 149.43, 137.52, 134.51, 131.88, 131.41, 130.89, 129.72, 129.53, 129.11, 127.74, 127.22, 111.79, 105.73, 53.30, 23.92
Compd.	¹H NMR(400 MHz), δ	¹³C NMR(101 MHz), δ
9f^a	13.46(br, 1H, SO₂NH), 8.26(d, J=7.5 Hz, 1H, Ph-H), 7.96(d, J=6.8 Hz, 2H, Ph-H), 7.67(br, 1H, CONH-Pyrim), 7.46—7.44(m, 3H, Ph-H), 7.40—7.37(m, 3H, Ph-H), 7.24(s, 1H, Pyrim-H), 2.50(s, 3H, Pyrim-CH₃)	168.18, 163.65, 157.37, 156.57, 149.02, 136.38, 134.67, 132.89, 131.92, 131.65, 129.29, 127.27, 127.20, 111.45, 105.73, 24.24
9g^b	14.18(br, 1H, SO₂NH), 10.98(s, 1H, CONH-Pyrim), 8.80(d, J=2.6 Hz, 1H, Ph-H), 8.52(dd, J=8.7, 2.5 Hz, 1H, Ph-H), 8.16(d, J=6.8 Hz, 2H, Ph-H), 8.02(d, J=8.7 Hz, 1H, Ph-H), 7.62—7.56(m, 3H, Ph-H), 7.47(s, 1H, Pyrim-H), 2.52(s, 3H, Pyrim-CH₃)	157.67, 156.42, 146.46, 137.62, 135.26, 134.14, 133.95, 133.35, 132.45, 129.64, 129.12, 127.70, 127.23, 111.77, 105.72, 23.89
9h^b	13.49(br, 1H, SO₂NH), 10.84(s, 1H, CONH-Pyrim), 8.76(d, J=7.3 Hz, 1H, Py-H), 8.15—8.04(m, 2H, Py-H), 7.77—7.59(m, 5H, Ph-H), 7.37(s, 1H, Pyrim-H), 2.96[s, 3H, 1/2 N(CH₃)₂], 2.85[s, 3H, 1/2 N(CH₃)₂], 2.44(s, 3H, Pyrim-CH₃)
9i^a	9.31(s, 1H, CONH-Pyrim), 8.66(dd, J=4.7, 1.8 Hz, 1H, Py-H), 8.19(dd, J=7.8, 1.8 Hz, 1H, Py-H), 8.10(br, 2H, SO₂NH, Py-H), 7.53(d, J=6.4 Hz, 2H, Ph-H), 7.43(dd, J=7.8, 6.4 Hz, 2H, Ph-H), 7.27(s, 1H, Pyrim-H), 7.12(d, J=7.8 Hz, 1H, Ph-H), 3.26(q, J=7.4 Hz, 2H, SO₂CH₂), 2.57(s, 3H, Pyrim-CH₃), 1.31(t, J=7.4 Hz, 3H, CH₃)	166.27, 159.94, 156.84, 154.03, 151.34, 142.08, 139.99, 137.72, 129.55, 129.01, 128.38, 122.23, 119.78, 117.27, 49.14, 16.61, 7.15
9j^c	13.37(s, 1H, SO₂NH), 9.47(s, 1H, CONH-Pyrim), 8.31(d, J=7.1 Hz, 1H, Py-H), 8.20(d, J=6.5 Hz, 2H, Py-H), 7.74—7.69(m, 2H, Ph-H), 7.58—7.55(m, 4H, Ph-H, Pyrim-H), 4.92(q, J_HF=8.0 Hz, 2H, OCH₂CF₃), 2.58(s, 3H, Pyrim-CH₃)	169.72, 164.34, 157.45, 151.65, 149.47, 145.10, 141.97, 135.60, 131.57, 129.11, 129.05, 127.25, 124.84, 123.88, 110.90, 66.24, 23.24
9k^a	13.58(s, 1H, SO₂NH), 8.09(br, 3H, CONH-Pyrim, Ph-H), 7.88(s, 1H, Pyrazole-H), 7.55—7.54(m, 3H, Ph-H), 7.32(s, 1H, Pyrim-H), 4.36(s, 3H, NCH₃), 4.17(q, J=7.0 Hz, 2H, OCH₂), 2.64(s, 3H, Pyrim-CH₃), 1.22(t, J=7.0 Hz, 3H, CH₃)	169.49, 165.24, 160.62, 156.42, 150.24, 140.25, 138.66, 135.36, 131.69, 129.15, 127.51, 116.21, 111.71, 60.83, 41.53, 24.05, 14.11
9l^b	13.95(s, 1H, SO₂NH), 10.91(s, 1H, CONH-Pyrim), 9.22(d, J=7.0 Hz, 1H, Py-H), 8.21—7.99(m, 3H, Py-H), 7.78(d, J=7.2 Hz, 2H, Ph-H), 7.61—7.56(m, 3H, Ph-H), 7.48(s, 1H, Pyrim-H), 3.64(q, J=7.1 Hz, 2H, OCH₂), 2.53(s, 3H, Pyrim-CH₃), 1.18(t, J=7.2 Hz, 3H, CH₃)	169.68, 163.96, 156.93, 151.81, 145.71, 144.69, 135.47, 132.20, 130.83, 129.51, 128.84, 127.84, 118.91, 118.35, 117.10, 111.73, 49.13, 23.91, 7.11

新型含苯基取代嘧啶基磺酰脲衍生物的设计、合成及生物活性

Design, Synthesis and Biological Activity of Novel Sulfonylurea Derivatives Containing Phenyl-substituted Pyrimidine Moiety^†

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Compd.	P. piricola	F. graminearum	F. moniliforme	S. sclerotiorum	P. capsici	R. cerealis	C. lagenarium	B. Cinerea
8a	51	27	20	14	25	57	35	11
8b	18	41	25	16	16	61	38	14
8c	46	16	45	12	32	46	46	11
8d	93	56	25	7	66	78	42	20
8e	78	61	25	7	50	46	16	65
8f	78	28	33	11	47	81	21	20
8g	89	50	25	7	47	57	21	5
8h	59	28	33	7	38	54	11	20
8i	47	27	31	14	13	47	23	14
8j	35	47	19	14	10	63	26	56
8k	42	49	50	86	13	94	48	75
8l	50	27	19	20	10	41	21	14
9a	67	39	45	24	19	64	54	14
9b	65	33	65	18	23	66	58	14
9c	58	36	50	14	16	64	50	17
9d	96	61	33	13	34	57	21	45
9e	96	61	33	7	25	62	26	10
9f	100	72	42	48	66	87	42	80
9g	70	50	33	22	38	70	21	65
9h	67	39	25	0	31	68	26	50
9i	37	36	27	14	10	38	16	11
9j	44	53	42	24	17	47	26	58
9k	53	64	50	21	13	91	65	56
9l	88	13	61	20	33	67	59	27
SM^a	50	18	25	46	4	47	29	18
CH^b	<50	<50	100	<50	100	100	95	100
CA^c	100	100	<50	99	<50	100	100	<50

Compd.	P. piricola			Compd.	P. piricola
Compd.	EC₅₀/(mg·L^-1)		y=ax+b	r		EC₅₀/(mg·L^-1)	y=ax+b		r
8d	9.96	y=1.9182x+3.0849	0.9847	8f	10.80		y=1.4902x+3.4594	0.9772
8g	15.70	y=2.1076x+2.4810	0.9889	8k	5.48		y=1.4748x+3.9098	0.9721
9d	14.60	y=2.4235x+2.1744	0.9449	9f	8.63		y=3.6051x+1.6250	0.9127
9e	10.20	y=2.2059x+2.7641	0.9772	9k	6.09		y=1.7018x+3.6646	0.9936
9f	8.63	y=3.6051x+1.6250	0.9127	Chlorothalonil	4.26		y=2.2706x+3.5712	0.9827
Chlorothalonil	7.33	y=1.3890x+3.7981	0.9862

Compd.	Brassica napus				Amaranthus retroflexus				Echinochloa crusgalli				Digitariasanguinalis
Compd.	Soil treatment		Foliage spray		Soil treatment		Foliage spray		Soil treatment		Foliage spray		Soil treatment		Foliage spray
8a	7		30		15		10		40		30		10		32
8b	0		0		10		0		0		0		10		0
8c	0		0		0		15		0		0		0		0
8d	89		92^*		100		95		21		15		0		10
8e	86		70^*		88		77		5		0		0		5
8f	69		36		65		48		14		5		0		0
8g	27		20		15		48		13		10		0		20
8h	22		30		34		39		20		15		0		15
8i	66		64		85		10		0		18		0		21
8j	26		9		65		5		10		0		15		21
8k	16		22		0		10		10		0		0		29
8l	15		5		39		5		0		20		5		15
9a	0		0		10		0		0		10		0		10
9b	30		70		56		79		40		28		59		25
9c	0		0		5		10		0		15		10		10
9d	88		14^*		100		86		25		10		0		25
9e	84		22		60		96		16		0		5		5
9f	65		16		30		46		13		5		0		5
9g	83		13		100		25		0		36		0		20
Compd.		Brassica napus				Amaranthus retroflexus				Echinochloa crusgalli				Digitariasanguinalis
Compd.		Soil treatment		Foliage spray		Soil treatment		Foliage spray		Soil treatment		Foliage spray		Soil treatment		Foliage spray
9h		63		28		100		61		37		0		0		0
9i		48		46		0		0		0		0		5		14
9j		26		29		15		0		5		0		0		5
9k		44		21		42		10		0		25		0		0
9l		20		45		18		0		0		0		0		25
Sulfometuron-methyl		87		85		100		100		100		100		81		100
Chlorsulfuron		100		100		100		100		99		100		100		100

Compd.	Dosage/(g·ha^-1)	Brassica napus		Amaranthus retroflexus
Compd.	Dosage/(g·ha^-1)	Soil treatment	Foliage spray	Soil treatment	Foliage spray
8d	300	98	50	74	57
	75	86	10	40	22
8e	300	87	20	50
9d	300	100		80	60
	75	73		35	5
9e	300	100			75
	75	46			26
9g	300	100		80
	75	54		10
9h	300			100
	75			100
Chlorsulfuron	75	100	100	96	100

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新型含苯基取代嘧啶基磺酰脲衍生物的设计、 合成及生物活性

Design, Synthesis and Biological Activity of Novel Sulfonylurea Derivatives Containing Phenyl-substituted Pyrimidine Moiety†

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新型含苯基取代嘧啶基磺酰脲衍生物的设计、合成及生物活性

Design, Synthesis and Biological Activity of Novel Sulfonylurea Derivatives Containing Phenyl-substituted Pyrimidine Moiety^†