CN113698378B - 一类萘醌类化合物及其制备与杀螨、杀菌用途 - Google Patents

一类萘醌类化合物及其制备与杀螨、杀菌用途 Download PDF

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CN113698378B
CN113698378B CN202111172271.1A CN202111172271A CN113698378B CN 113698378 B CN113698378 B CN 113698378B CN 202111172271 A CN202111172271 A CN 202111172271A CN 113698378 B CN113698378 B CN 113698378B
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郝双红
王红梅
林琎
余海涛
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Qingdao Agricultural University
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Abstract

本发明（名称为：一类萘醌类化合物及其制备与杀螨、杀菌用途）涉及15种2,3‑取代的萘醌衍生物及其制备方法，以及在杀螨、抑菌方面的用途。15种2,3‑取代的萘醌衍生物，通过2‑羟基‑1,4萘醌与不同醛加成得化合物1‑6，再与不同酰氯或磺酰氯在碱催化下缩合成得化合物7‑15。这些化合物可作为杀螨剂防治作物害螨，也可作为杀菌剂防治番茄灰霉病菌、苹果腐烂病菌、黄瓜枯萎病菌、小麦全蚀病菌。

Description

一类萘醌类化合物及其制备与杀螨、杀菌用途
技术领域
本发明涉及一类萘醌类化合物及其制备与杀螨、杀菌用途，具体的涉及农用杀螨剂及杀菌剂领域。
背景技术
萘醌类化合物是天然醌类化合物中的重要一类，具有多种生物活性，在杀虫、抑菌、抗肿瘤等领域均有应用；萘醌类衍生物有较高的活性，对哺乳动物毒性很小，其杀虫、抑菌作用值得深入研究。
灭螨醌是商品化杀螨剂，对灭螨醌脱乙酰基代谢物作用机制的研究表明：该代谢物可以抑制电子传递链中复合物III的线粒体呼吸作用，键合点为复合物III辅酶氧化作用点。
萘醌类化合物已被证实是有效的抗真菌药物，其中二噻农是商品化的优秀杀菌剂品种，具有广谱、低毒、低抗性的优点；可用于仁果、核果的多种病害防治，可以治疗苹果、梨的黑星病；樱桃叶斑病；桃杏缩叶病，特别对龙眼，荔枝褐斑病、霜霉病有很好的防治效果。
综上信息，该专利以天然活性2-羟基-1,4-萘醌为先导，将不同取代基引入其2位及3位进行结构修饰，设计合成了一类萘醌类化合物，并筛选了该类化合物的杀螨及杀菌活性。
发明内容
本发明的目的在于提供一类萘醌类化合物及制备方法，它可应用于作物杀螨及病害防治。
本发明的技术方案如下：
本发明提供的萘醌类化合物，其结构通式如下：
Figure 886685DEST_PATH_IMAGE001
1--6：R1选自十二烷基、4-三氟甲基苯基、2,4,5-三甲氧基苯基、4-氰基苯基、
Figure 7087DEST_PATH_IMAGE002
、
Figure 114721DEST_PATH_IMAGE003
；
7--12：R1选自十二烷基、4-三氟甲基苯基、4-氰基苯基、
Figure 854138DEST_PATH_IMAGE004
，R2选自4- 甲基-苯基、4-三氟甲基-苯基、6-氯-3吡啶基；
13--15：R1选自十二烷基、4-三氟甲基苯基、2,4,5-三甲氧基苯基，R2选自4-甲基-苯基、2-吡啶基。
萘醌类化合物合成反应式：
Figure 137351DEST_PATH_IMAGE005
式中R1、R2及R3定义如上；
通式化合物制备方法：在适当溶剂中，适当温度下，使用适当催化剂，2-羟基-1,4-萘醌与不同醛反应可生成化合物1~6。然后在适当溶剂中，适当温度下，使用适当催化剂，化合物1、2、4、5与不同的酰氯发生反应，即得化合物7~12，化合物1、2、3与不同的磺酰氯 发生反应，即得化合物13~15；
适当溶剂可选自二氯甲烷、三氯甲烷等；
适当温度指0 ℃至溶剂的沸点温度；
适当催化剂指N-甲基吗啉、汉斯酯、L-脯氨酸、2-甲基吡啶等；
反应时间为2小时至30小时；
本发明的化合物对朱砂叶螨具有优异杀螨作用，部分化合物对番茄灰霉病菌、黄瓜枯萎病菌、苹果腐烂病菌、小麦全蚀病菌也有良好抑制作用。
具体实施方式
实例1 化合物6及12的制备：
Figure 553289DEST_PATH_IMAGE006
干燥条件下，0.17 g（1 mmoL）的2-羟基-1,4-萘醌，0.35 g（2 mmol）色酮-3-甲醛，0.28 g（1.1 mmol）的汉斯酯，0.023 g（0.2 mmol）的L-脯氨酸，10 mL的二氯甲烷，30 ℃下反应17 h，TLC检测反应结束后，通过硅胶柱层析纯化，层析液用乙酸乙酯：石油醚 = 1:3，得红褐色固体中间体，即化合物6；
干燥条件下，0.066 g（0.2 mmol）的中间体1，0.070 g（0.4 mmol）的6-氯-烟酰氯，33.7 ul（0.3 mmol）的N-甲基吗啉，10 mL的三氯甲烷，50 ℃下反应12 h，TLC检测反应结束后，通过硅胶柱层析纯化，层析液用乙酸乙酯：石油醚 = 1:2，得黄色固体目标产物，即目标化合物12；
化合物1-5按照与6相似的方法合成，化合物7- 12、13-15按照与12相似的方法合成。
合成化合物1H NMR、13C NMR及质谱数据如下；
Figure 289164DEST_PATH_IMAGE007
1. 1HNMR (500 MHz, CDCl3) δ 8.09 (dd, 2H), 7.70 (dt, 2H), 7.39 (s, 1H), 2.60 (t, 2H), 1.53 (d, 2H), 1.25 (s, 18H), 0.87 (t, 3H). 13CNMR (126 MHz, CDCl3) δ 145.17, 140.17, 134.01, 133.77, 132.23, 131.07, 130.61, 129.57, 126.59, 125.42, 31.94, 30.06, 29.56, 29.56, 29.34, 29.24, 29.16, 28.55, 24.41, 22.70, 21.84, 14.12. HRMS (ESI): calcd for C22H29O3, ([M- H]+), 341.2117, found, 341.2122.
Figure 829342DEST_PATH_IMAGE008
2. 1HNMR (500 MHz, CDCl3) δ 8.10 (dd, 2H), 7.76 (td, 1H), 7.69 (td, 1H), 7.50 (s, 4H), 7.48 (s, 1H), 4.00 (s, 2H). 13CNMR (126 MHz, CDCl3)δ 184.00, 177.80, 162.52, 151.85, 141.11, 137.19, 134.53, 134.26, 131.86 (d,J = 272.52 Hz),130.94, 130.87 (d,J = 3.65 Hz), 129.32 (d,J = 3.69 Hz), 127.08, 126.90, 125.89, 125.64 (d,J = 32.56 Hz), 125.62, 30.19. HRMS (ESI): calcd for C18H10F3O3, ([M-H]+), 331.0590, found, 331.0588.
Figure 967063DEST_PATH_IMAGE009
3. 1HNMR (500 MHz, CDCl3) δ 8.1 (m, 2H), 7.88 (s, 1H), 7.70 (t, 2H), 6.87 (s, 1H), 6.51 (d, 1H), 3.90 (s, 2H), 3.88 (s, 3H), 3.85 (s, 3H), 3.80 (s, 3H). 13CNMR (126 MHz, CDCl3)δ 184.53, 181.43, 153.88, 150.89, 148.33, 143.35, 134.67, 132.93, 132.71, 129.80, 126.75, 126.12, 123.18, 118.26, 114.64, 97.95, 56.95, 56.73, 56.20, 22.60. HRMS (ESI): calcd for C20H17O6, ([M-H]+),353.1034, found, 353.1039.
Figure 288323DEST_PATH_IMAGE010
4. 1HNMR (500 MHz, CDCl3) δ 8.10 (dd, 2H), 7.77 (td, 1H), 7.72 (d, 1H), 7.55 (d, 2H), 7.49 (d, 2H), 3.99 (s, 2H). 13CNMR (126 MHz, CDCl3) δ 184.12, 181.35, 153.36, 144.47, 135.25, 133.25, 132.65, 132.27, 129.98, 129.34, 127.01, 126.36, 121.49, 118.94, 110.29, 29.32. HRMS (ESI): calcd for C18H10NO3, ([M-H]+), 288.0668, found, 288.0666.
Figure 511494DEST_PATH_IMAGE011
5. 1HNMR (500 MHz, CDCl3) δ 8.11 (dd, 2H), 7.75 (dt, 2H), 3.87 (s, 2H), 2.64 (m, 2H), 1.65(m, 2H), 1.36 (dd, 2H), 0.91 (t, 3H). 13CNMR (126 MHz, CDCl3) δ184.44, 181.57, 156.99, 134.96, 133.64, 132.60, 130.51, 126.31, 125.67, 121.51, 118.90, 118.74, 30.17, 27.59, 27.43, 22.01, 18.29, 14.38. HRMS (ESI): calcd for C18H17ClN2O3, ([M-H]+), 343.0856, found, 343.0854.
Figure 592713DEST_PATH_IMAGE012
6.1HNMR (500 MHz, CDCl3) δ 11.05 (s, 1H), 8.34 (s, 1H), 8.26 (dd, 8.1, 1H), 8.08 (dd, 2H), 7.68 (m, 3H), 7.47 (m, 2H), 3.75 (s, 2H). 13C NMR (126 MHz, CDCl3) δ 184.90, 181.11, 180.02, 156.71, 156.52, 155.91, 134.52, 134.07, 133.12, 132.25, 130.81, 126.39, 126.15, 125.96, 125.70, 122.75, 121.67,121.53, 118.25, 20.05. HRMS (ESI): calcd for C20H11O5, ([M-H]+), 331.0613, found, 331.0612.
Figure 850519DEST_PATH_IMAGE013
7. 1HNMR (500 MHz, CDCl3) δ 8.2 (m, 4H), 7.79 (m, 2H), 7.37 (m, 2H), 2.62 (t, 2H), 2.46 (d, 3H), 1.56 (dd, 2H), 1.36 (m, 18H), 0.87 (t, 3H). 13CNMR (126 MHz, CDCl3)δ 182.27, 178.53, 177.70, 145.53, 144.24, 140.75, 134.46, 131.49, 129.53, 129.38, 129.12, 128.87, 127.33, 125.62, 125.17, 123.01, 120.85, 35.69, 33.77, 31.94, 30.25, 29.56, 28.55, 24.41, 22.70, 21.84, 19.98, 16.72, 16.61, 14.12. HRMS (ESI): calcd for C30H36O4Na, ([M +Na]+), 483.2503, found, 483.2506.
Figure 873839DEST_PATH_IMAGE014
8. 1HNMR (500 MHz, CDCl3) δ 8.15 (m, 2H), 7.77(m, 2H), 7.51 (dd, 4H), 4.23 (s, 2H), 1.26 (s, 10H), 1.20 (s, 13H). 13CNMR (126 MHz, CDCl3) δ 182.27, 178.53, 177.70, 145.53, 144.24, 140.75, 134.46, 134.23, 131.49, 131.28, 129.45 (d,J= 33.41 Hz), 129.45, 129.12, 128.87, 127.28, 125.62 (d,J = 3.7 Hz), 125.59 (d,J = 3.64 Hz)124.08 (d,J = 274.21 Hz), 123.01, 120.85, 35.69, 33.77, 31.43, 30.20, 29.71, 23.61, 22.69, 22.63, 19.98, 16.72, 16.67, 14.16. HRMS (ESI): calcd for C30H33F3O4Na, ([M+Na]+), 537.2321, found, 537.2323.
Figure 584306DEST_PATH_IMAGE015
9. 1HNMR (500 MHz, CDCl3) δ 8.13(m, 2H), 8.04 (d, 2H), 7.75 (m, 2H), 7.50 (d, 2H), 7.42 (d, 2H), 7.34 (d, 2H), 4.03 (s, 2H), 2.48 (s, 3H). 13CNMR (126 MHz, CDCl3) δ 184.23, 178.15, 163.72, 152.24, 145.58, 141.42, 137.02, 134.31, 134.09, 131.91, 130.97, 130.65, 129.05 (d,J = 32.27 Hz), 129.60, 129.41, 129.18, 128.93, 126.87, 125.61 (d, J = 3.67 Hz), 125.57, 125.35 (d,J = 3.69 Hz), 125.22, 125.35 (d,J = 272.52 Hz), 124.99, 123.04, 123.12, 30.13, 21.87. HRMS (ESI): calcd for C26H16F3O4, ([M-H]+), 449.1009, found, 449.1006.
Figure 203637DEST_PATH_IMAGE016
10. 1HNMR (500 MHz, CDCl3) δ 8.25 (d, 2H), 8.14 (m, 2H), 7.81 (m, 4H), 7.50 (d, 2H), 7.40 (d, 2H), 4.05 (s, 2H). 13CNMR (126 MHz, CDCl3)δ 184.00, 177.80, 162.52, 151.85, 141.11, 137.19, 136.01, 135.86 (q,J= 30.69 Hz), 134.53, 134.26, 131.86, 131.02, 130.94, 130.81, 130.60, 129.34, 129.23 (q,J = 32.84 Hz), 129.09, 127.08, 126.90, 125.96 (q,J= 3.57 Hz), 125.91 (q,J = 3.66 Hz), 125.69 (q,J = 3.66 Hz), 125.64 (d,J = 3.81 Hz), 125.15, 124.51, 124.05 (q,J = 271.8 Hz), 123.39 (q,J = 277.28 Hz), 122.98, 122.34, 30.19. HRMS (ESI): calcd for C26H13F6O4, ([M-H]+), 503.0726, found, 503.0724.
Figure 315950DEST_PATH_IMAGE017
11. 1HNMR (500 MHz, CDCl3) δ 8.11 (d, 2H), 8.03 (d, 2H), 7.75(m, 2H), 7.53 (d, 2H), 7.41 (d, 2H), 7.34 (d, 2H), 4.02 (s, 2H), 2.48 (s, 3H). 13CNMR (126 MHz, CDCl3)δ 184.11, 177.99, 163.67, 152.38, 145.69, 142.86, 136.50, 134.37, 134.17, 132.41, 131.75, 130.87, 130.62, 129.85, 129.62, 126.87,126.84, 124.81 , 118.74, 110.63, 30.36, 21.88. HRMS (ESI): calcd for C26H16NO4, ([M-H]+), 406.1086, found, 406.1085.
Figure 244591DEST_PATH_IMAGE018
12. 1HNMR (500 MHz, CDCl3) δ9.15(d,1H), 8.41(dd, 1H), 8.14(dd,1H), 8.09 (dd, 2H), 8.05(s, 1H), 7.78 (m, 2H), 7.62 (t, 1H), 7.49(d,1H), 7.35 (dd,2H), 3.87(s, 2H). 13CNMR (126 MHz, CDCl3)δ 184.31, 177.68, 176.58, 161.85, 156.70, 156.22, 154.56, 152.01, 151.32, 140.32, 136.49, 134.40, 134.19, 133.63, 131.93, 130.79, 126.95, 126.82, 125.85, 125.18, 124.45, 123.62,123.48, 120.27, 118.02, 20.27. HRMS (ESI): calcd for C26H13ClNO6,([M-H]+), 470.0440 , found, 470.0437.
Figure 442355DEST_PATH_IMAGE019
13. 1HNMR (500 MHz, CDCl3) δ 8.12 (m, 2H), 8.02 (d, 2H), 7.76 (m, 2H), 7.43 (d, 2H), 2.64 (t, 2H), 2.50 (s, 3H), 1.5 (m, 2H), 1.25 (m, 18H), 0.88 (t, 3H). 13CNMR (126 MHz, CDCl3)δ184.59, 178.66, 149.26, 145.69, 142.98,134.29, 134.21,134.05, 133.99, 132.01, 130.78, 129.80, 128.68, 128.52, 126.89, 126.69, 32.56, 30.95, 29.82, 29.70, 29.64,29.56, 29.39, 29.07, 28.62, 25.34, 22.73, 21.85, 14.16. HRMS (ESI): calcd for C29H36O5SNa, ([M+Na]+), 519.2177, found, 519.2176.
Figure 865377DEST_PATH_IMAGE020
14. 1HNMR (500 MHz, CDCl3) δ 8.09 (m, 2H), 8.03 (d, 2H), 7.75 (m, 2H), 7.50 (d, 2H), 7.43 (d, 4H), 4.11 (s, 2H), 2.51 (s, 3H). 13CNMR (126 MHz, CDCl3) δ 184.19, 178.62, 149.73, 146.09, 141.12, 139.66, 134.47, 134.32, 133.55, 133.11, 131.71, 130.70, 129.90, 129.54, 129.12 (d,J = 33.5 Hz), 128.68, 128.62, 127.01, 126.82, 125.56 (d,J = 3.53 Hz), 125.50 (d,J = 3.8 Hz), 125.22 (d,J = 271.49 Hz), 30.54, 21.85. HRMS (ESI): calcd for C25H16F3O5S, ([M-H]+), 485.0680, found, 485.0676.
Figure 832196DEST_PATH_IMAGE021
15. 1HNMR (500 MHz, CDCl3) δ 9.27 (d,1H), 8.94 (q, 1H), 8.41 (m, 1H), 8.08 (m, 2H), 7.75 (m, 2H), 7.58 (q, 1H), 6.89 (s, 1H), 6.46 (s, 1H), 4.03 (s, 2H), 3.85 (s, 3H), 3.83 (s, 3H), 3.74 (s, 3H). 13CNMR (126 MHz, CDCl3)δ 183.83, 178.60, 154.62, 151.58, 149.10,149.03, 148.61, 142.90, 141.56, 136.17, 134.46, 134.08, 133.92, 131.94, 130.48, 127.02, 126.67, 123.62, 116.41, 114.85, 97.68, 56.73, 56.47, 56.10, 25.41. HRMS (ESI): calcd for C25H21NO8SNa, ([M+Na]+), 518.0878, found, 518.0880。
实例2 杀螨活性测定
称取2.5 mg化合物溶于0.5 mL丙酮，加水至50 mL，配制成50 mg/L浓度的药液，再利用二倍稀释法配制25.00、12.50、6.25、3.13、1.56、0.78 mg/L浓度的药液。将双面胶剪成3cm长, 贴在载玻片的一端, 用镊子揭去胶带上的纸片, 用零号毛笔挑选事先准备好的、健康活泼、整齐一致的朱砂叶螨雌成螨。将其背部粘在双面胶带上, 每片3行, 每行10只左右。26 ℃、70 %湿度、光照条件L：D=14：10条件下放置4h后, 用双目镜观察, 剔除死亡或不活泼的个体, 记载实际的活螨的个数, 作为供试基数。将粘有活螨的载玻片在配好的药液中均匀沾湿后取出。在上述条件下放置48 h, 每12 h检查1次结果, 以毛笔轻触螨体, 螨鳌肢不动者为死亡, 设置溶剂对照。根据对照组及处理组螨虫存活率计算杀螨率，再根据杀螨率及浓度，利用软件回归毒力方程。
表1 目标化合物杀螨活性（%）
Figure 197318DEST_PATH_IMAGE022
a：置信区间。
实例3 抑菌活性测定
称取20 mg 化合物溶于1 mL丙酮，配制成20 mg/mL浓度的药液，取0.05 mL不同浓度的药液分别加入到10 mL熔融的马铃薯琼脂培养基中，然后趁热倒入培养皿，冷却形成带毒平板培养基，接种测试病菌，对照用等量丙酮，每个处理设置三个重复。放置25 ℃下培养，十字交叉法量取菌落直径，求取平均值，计算抑制率。
表2 目标化合物抑菌活性初筛（100 mg/L，抑制率（%））
Figure 616798DEST_PATH_IMAGE023
。
实例4 抑菌活性活体实验
以番茄灰霉病菌为例，测其对活体番茄叶片的治疗及保护作用。分别称取2.5 mg的药物，溶于1 mL丙酮，加蒸馏水稀释至50 mL，配置成50 mg/L的药液。预防作用：将药液均匀的喷洒在番茄叶子叶片背面，晾干24 h后接菌，72 h后观察菌斑大小。治疗作用：将菌饼接在叶片背部，培养24 h后将药物均匀的喷洒于叶片背部，72 h后观察菌斑大小。设置空白对照，每个处理设置三个重复。放置25 ℃下培养，十字交叉法量取菌斑直径，求取平均值，计算防治效果。
表3 目标化合物对于番茄灰霉病菌活体实验的抑制率（%）
Figure 840581DEST_PATH_IMAGE024

Claims (5)

1.一类萘醌类化合物结构如通式所示：
Figure 32788DEST_PATH_IMAGE001
，
通式所述的结构为以下化合物中的任意一种：
Figure 356453DEST_PATH_IMAGE002
、
Figure 339452DEST_PATH_IMAGE003
、
Figure 241DEST_PATH_IMAGE004
、
Figure 17875DEST_PATH_IMAGE005
、
Figure 246862DEST_PATH_IMAGE006
、
Figure 779475DEST_PATH_IMAGE007
、
Figure 181637DEST_PATH_IMAGE008
、
Figure 991461DEST_PATH_IMAGE009
、
Figure 515984DEST_PATH_IMAGE010
。
2.根据权利要求1所述化合物，其特征在于：选自以下化合物：
Figure 473575DEST_PATH_IMAGE004
、
Figure 631760DEST_PATH_IMAGE005
、
Figure 420725DEST_PATH_IMAGE006
、
Figure 53831DEST_PATH_IMAGE007
、
Figure 701982DEST_PATH_IMAGE009
、
Figure 508264DEST_PATH_IMAGE010
。
3.根据权利要求1所述化合物，其特征在于：选自以下化合物：
Figure 292680DEST_PATH_IMAGE002
、
Figure 831109DEST_PATH_IMAGE003
、
Figure 91189DEST_PATH_IMAGE008
。
4.如权利要求2所述化合物在防治害螨的用途，所述用途为非用于疾病的治疗或诊断方法的用途。
5.如权利要求3所述化合物在防治植物病害的用途，所述的植物病害为番茄灰霉病菌、苹果腐烂病菌、黄瓜枯萎病菌、小麦全蚀病菌。
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