CN115197134A - 一类樟脑磺酸酯类化合物的制备方法及其应用 - Google Patents
一类樟脑磺酸酯类化合物的制备方法及其应用 Download PDFInfo
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- CN115197134A CN115197134A CN202210833033.9A CN202210833033A CN115197134A CN 115197134 A CN115197134 A CN 115197134A CN 202210833033 A CN202210833033 A CN 202210833033A CN 115197134 A CN115197134 A CN 115197134A
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- compound
- triethylamine
- dimethylaminopyridine
- acid ester
- chloride intermediate
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
- C07D215/22—Oxygen atoms attached in position 2 or 4
- C07D215/233—Oxygen atoms attached in position 2 or 4 only one oxygen atom which is attached in position 4
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- A—HUMAN NECESSITIES
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- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/04—Sulfonic acids; Derivatives thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
- A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
- C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D309/36—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
- C07D309/40—Oxygen atoms attached in positions 3 and 4, e.g. maltol
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- C—CHEMISTRY; METALLURGY
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Abstract
Description
技术领域
本发明属于农药合成技术领域,具体涉及到一类樟脑磺酸酯类化合物的制备方法及其应用。
背景技术
辣椒疫霉病是近年来流行的一种危害辣椒生长的毁灭性病害,是世界性的土传病害,在各辣椒产区均有发生。其病原菌除危害辣椒外,也可侵染番茄、茄子、黄瓜、西瓜、南瓜等作物。近年来,随着辣椒在各主产区的连茬种植,病害有逐渐加重的趋势,危害较为显著。
目前,在化学防治辣椒疫霉病菌领域,当田间零星发生时,选用75%百菌清可湿性粉剂兑水600倍液;53%金雷多米尔粒剂兑水600~800倍液;58%雷多米尔粉剂兑水600~800倍液;80%乙磷铝可湿性粉剂兑水500倍液,每隔7~10天任选一种轮换喷施一次。防治疫霉病关键技术是大雨前后及时用药防治,在雨季到来之前连续防治3次,每7天防治一次;施药方法采用灌根与喷雾相结合。药剂可选用53.8%可杀得可湿性粉剂600倍液,或72%杜邦克露可湿性粉剂600倍液,或64%杀毒矾可湿性粉剂600倍液,每隔5~7天进行喷施一次。但如上品种大量使用,药效大幅降低,已不再是防治辣椒疫霉病菌的有效品种。
因此,寻找高效、低毒、环境友好且具全新作用机制的新型化合物来代替现有的辣椒疫霉病菌的高抗性品种是一个长期存在的重大难题。辣椒疫霉病作为辣椒产区的重要病害,也需要寻找高新靶点的品种。
在另一方面,近年来,萜类化合物在医用或者农用领域的研究备受广泛关注,作为林产重要资源的樟脑,是一种具有双环单萜结构的非木质林产品,天然存在于樟科植物中,是我国的可再生天然优势生物质资源,其IUPAC名称为1,7,7-三甲基二环[2.2.1]庚烷-2-酮,化学式为C10H16O。室温下为白色或透明的蜡状固体,可用于驱虫。樟脑提炼自樟树干中,树龄越老的的樟树所富含樟脑比例越多。提炼方法为将树干切成小块用水蒸馏,樟脑油受热后随着水蒸汽上升,在接触到预先放置在上方的陶缸冷却后便可形成樟脑。在中药成方制剂中主要利用其具有清凉、芳香及温散止痛的功效。常入橡胶膏剂、酊剂、膏药、油剂、软膏剂。因此,樟脑在医药中间体、环境友好型防虫蛀剂、香料、熏香、工业原料等领域内得到了广泛的应用。
目前,樟脑磺酸酯类化合物的制备方法与杀菌方面的应用尚未报道。
发明内容
本部分的目的在于概述本发明的实施例的一些方面以及简要介绍一些较佳实施例。在本部分以及本申请的说明书摘要和发明名称中可能会做些简化或省略以避免使本部分、说明书摘要和发明名称的目的模糊,而这种简化或省略不能用于限制本发明的范围。
鉴于上述和/或现有技术中存在的问题,提出了本发明。
因此,本发明的目的是,克服现有技术中的不足,提供一类樟脑磺酸酯类化合物。
为解决上述技术问题,本发明提供了如下技术方案:一类樟脑磺酸酯类化合物,所述樟脑磺酸酯类化合物结构式如下所示:
其中:R为-CF3、-Br、-COCH3、-CH3、-CH(CH3)2或-OCH3;
X为-CH3或-CH2CH3。
本发明的再一个目的是,克服现有技术中的不足,提供一类樟脑磺酸酯类化合物的制备方法。
为解决上述技术问题,本发明提供了如下技术方案:一类樟脑磺酸酯类化合物的制备方法,包括,L-10-樟脑磺酸与氯化亚砜反应合成L-10-樟脑磺酰氯中间体;
L-10-樟脑磺酰氯中间体与取代4-羟基喹啉、三乙胺和4-二甲氨基吡啶反应,合成樟脑磺酸酯类化合物I;
L-10-樟脑磺酰氯中间体与取代苯酚类、三乙胺和4-二甲氨基吡啶反应,合成樟脑磺酸酯类化合物II;
L-10-樟脑磺酰氯中间体与7-羟基香豆素、三乙胺和4-二甲氨基吡啶反应,合成樟脑磺酸酯类化合物III;
L-10-樟脑磺酰氯中间体与取代麦芽酚、三乙胺和4-二甲氨基吡啶反应合成樟脑磺酸酯类化合物IV;
L-10-樟脑磺酰氯中间体与羟基蒽醌、三乙胺和4-二甲氨基吡啶反应合成樟脑磺酸酯类化合物V。
作为本发明所述樟脑磺酸酯类化合物的制备方法的一种优选方案,其中:所述L-10-樟脑磺酰氯中间体,其制备方法包括,
将L-10-樟脑磺酸并加入氯化亚砜中溶解,升温至回流温度反应,冷却,浓缩除去大部分溶剂和HCl,得白色固体L-10-樟脑磺酰氯,产物未经进一步处理直接投下一步;其中,
L-10-樟脑磺酸与氯化亚砜的摩尔比以mmol:mmol计为3.0:3.3;
反应时间为5~6h。
作为本发明所述樟脑磺酸酯类化合物的制备方法的一种优选方案,其中:所述合成樟脑磺酸酯类化合物I,包括,
将取代4-羟基喹啉、4-二甲氨基吡啶和三乙胺溶解于无水二氯甲烷中,降温至0℃,分批加入L-10-樟脑磺酰氯中间体,升至常温反应1~5h;
TLC监测原料反应完全,有机层以水洗涤3次,饱和食盐水洗涤3次,干燥,抽-滤,浓缩除去二氯甲烷,粗品经柱层析CH2Cl2:MeOH=20:1得目标化合物I;
其中,取代4-羟基喹啉包括2,8-二三氟甲基-4-羟基喹啉、2-三氟甲基-4-羟基喹啉和2-三氟甲基-8-溴-4-羟基喹啉;
取代4-羟基喹啉、4-二甲氨基吡啶和三乙胺与L-10-樟脑磺酰氯中间体的比例为1mmol:0.1mmol:1.1mmol:1.2mmol。
作为本发明所述樟脑磺酸酯类化合物的制备方法的一种优选方案,其中:所述合成樟脑磺酸酯类化合物II,包括,
将取代苯酚、4-二甲氨基吡啶和三乙胺溶解于无水二氯甲烷中,降温至0℃,分批加入L-10-樟脑磺酰氯中间体,升至常温反应1~5h;
TLC监测原料反应完全,有机层以水洗涤3次,饱和食盐水洗涤3次,干燥,抽-滤,浓缩除去二氯甲烷,粗品经柱层析CH2Cl2:MeOH=20:1得目标化合物I;
其中,取代苯酚包括2-甲基-5-异丙基苯酚、2-异丙基-5-甲基苯酚、2-羟基-4-甲氧基苯乙酮和2-羟基苯乙酮;
取代苯酚、4-二甲氨基吡啶和三乙胺与L-10-樟脑磺酰氯中间体的比例为1mmol:0.1mmol:1.1mmol:1.2mmol。
作为本发明所述樟脑磺酸酯类化合物的制备方法的一种优选方案,其中:所述合成樟脑磺酸酯类化合物III,包括,
将7-羟基香豆素、4-二甲氨基吡啶和三乙胺溶解于无水二氯甲烷中,降温至0℃,分批加入L-10-樟脑磺酰氯中间体,升至常温反应1~5h;
TLC监测原料反应完全,有机层以水洗涤3次,饱和食盐水洗涤3次,干燥,抽-滤,浓缩除去二氯甲烷,粗品经柱层析CH2Cl2:MeOH=20:1得目标化合物I;
其中,7-羟基香豆素、4-二甲氨基吡啶和三乙胺与L-10-樟脑磺酰氯中间体的比例为1mmol:0.1mmol:1.1mmol:1.2mmol。
作为本发明所述樟脑磺酸酯类化合物的制备方法的一种优选方案,其中:所述合成樟脑磺酸酯类化合物IV,包括,
将取代麦芽酚、4-二甲氨基吡啶和三乙胺溶解于无水二氯甲烷中,降温至0℃,分批加入L-10-樟脑磺酰氯中间体,升至常温反应1~5h;
TLC监测原料反应完全,有机层以水洗涤3次,饱和食盐水洗涤3次,干燥,抽-滤,浓缩除去二氯甲烷,粗品经柱层析CH2Cl2:MeOH=20:1得目标化合物I;
其中,取代麦芽酚包括甲基麦芽酚、乙基麦芽酚;
取代麦芽酚、4-二甲氨基吡啶和三乙胺与L-10-樟脑磺酰氯中间体的比例为1mmol:0.1mmol:1.1mmol:1.2mmol。
作为本发明所述樟脑磺酸酯类化合物的制备方法的一种优选方案,其中:所述合成樟脑磺酸酯类化合物V,包括,
将羟基蒽醌、4-二甲氨基吡啶和三乙胺溶解于无水二氯甲烷中,降温至0℃,分批加入L-10-樟脑磺酰氯中间体,升至常温反应1~5h;
TLC监测原料反应完全,有机层以水洗涤3次,饱和食盐水洗涤3次,干燥,抽-滤,浓缩除去二氯甲烷,粗品经柱层析CH2Cl2:MeOH=20:1得目标化合物I;
羟基蒽醌、4-二甲氨基吡啶和三乙胺与L-10-樟脑磺酰氯中间体的比例为1mmol:0.1mmol:1.1mmol:1.2mmol。
本发明的另一个目的是,克服现有技术中的不足,提供所述樟脑磺酸酯类化合物在防治农业或林业的植物真菌的应用,其中,所述植物真菌为辣椒疫霉病菌和油菜菌核病菌。
本发明有益效果:
(1)本发明所述樟脑磺酸酯类化合物,分子结构新颖,均为新化合物;化学结构特征鲜明,结构式中含有酯基,其中羟基喹啉,苯酚,香豆素,麦芽酚或蒽醌基团与樟脑磺酸中间体通过磺酸酯键相连接;所述的化合物的制备方法简便,原料易得,反应条件易控,尤其在合成樟脑磺酸酯类化合物这步反应中,产物经柱层析即可得到。
(2)本发明所述的化合物是一种在农业或林业领域的防治植物真菌的药剂,这种药剂对于辣椒疫霉病菌和油菜菌核病菌有较好的防治效果。
附图说明
为了更清楚地说明本发明实施例的技术方案,下面将对实施例描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动性的前提下,还可以根据这些附图获得其它的附图。其中:
图1为本发明实施例中樟脑磺酸酯类化合物I,II,III,IV和V制备方法示意图。
图2为本发明实施例中樟脑磺酸酯类化合物IV-1辣椒疫霉活体实验示意图。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂,下面结合说明书实施例对本发明的具体实施方式做详细的说明。
在下面的描述中阐述了很多具体细节以便于充分理解本发明,但是本发明还可以采用其他不同于在此描述的其它方式来实施,本领域技术人员可以在不违背本发明内涵的情况下做类似推广,因此本发明不受下面公开的具体实施例的限制。
其次,此处所称的“一个实施例”或“实施例”是指可包含于本发明至少一个实现方式中的特定特征、结构或特性。在本说明书中不同地方出现的“在一个实施例中”并非均指同一个实施例,也不是单独的或选择性的与其他实施例互相排斥的实施例。
樟脑磺酸酯类化合物的制备:
于单口瓶中加入L-10-樟脑磺酸(3.0mmol)并加入氯化亚砜(3.3mmol)溶解,升温至回流温度反应5h,冷却,浓缩除去大部分溶剂和HCl,得白色固体L-10-樟脑磺酰氯,产物未经进一步处理直接投下一步。
具体樟脑磺酸酯类化合物I,II,III,IV和V制备方法示意图,见图1。
实施例1
将中间体2,8-二三氟甲基-4-羟基喹啉(1.0mmol),4-二甲氨基吡啶(0.1mmol),三乙胺(1.1mmol)溶解于无水二氯甲烷中,降温至0℃,分批加入L-10-樟脑磺酰氯(1.2mmol),升至25℃反应2h。
TLC监测原料反应完全,有机层以水洗涤3次(8ml*3),饱和食盐水洗涤3次(8mL*3),干燥,抽滤,浓缩除去二氯甲烷,粗品经柱层析(CH2Cl2:MeOH=20:1)得目标化合物I-1,白色固体,m.p.135–137℃,收率72%;
1H NMR(600MHz,CDCl3)δ8.47(d,J=8.5Hz,1H),8.24(d,J=7.2Hz,1H),7.99(s,1H),7.82(t,J=7.9Hz,1H),4.06(d,J=14.9Hz,1H),3.44(d,J=14.9Hz,1H),2.56–2.45(m,2H),2.22(t,J=4.5Hz,1H),2.17–2.12(m,1H),2.03(d,J=18.6Hz,1H),1.86–1.82(m,1H),1.55–1.51(m,1H),1.18(s,3H),0.96(s,3H);13C NMR(150MHz,CDCl3)δ213.61,154.09,149.69,149.45,149.21,148.97,145.37,130.10(q,J=5.4Hz),128.94(q,J=30.6Hz),128.65,128.12,126.19,124.12,123.40,121.54,120.62(q,J=274.1Hz),108.95,58.23,49.90,48.26,42.85,42.41,26.87,25.27,19.69,19.67.
实施例2
将中间体2-三氟甲基-4-羟基喹啉(1.0mmol),4-二甲氨基吡啶(0.1mmol),三乙胺(1.1mmol)溶解于无水二氯甲烷中,降温至0℃,分批加入L-10-樟脑磺酰氯(1.2mmol),升至25℃反应3h。TLC监测原料反应完全,有机层以水洗涤3次(8ml*3),饱和食盐水洗涤3次(8mL*3),干燥,抽滤,浓缩除去二氯甲烷,粗品经柱层析(CH2Cl2:MeOH=20:1)得目标化合物I-2,白色固体,m.p.150–151.5℃,收率79%;1H NMR(600MHz,CDCl3)δ8.26(t,J=8.2Hz,2H),7.91–7.88(m,2H),7.77(t,J=7.6Hz,1H),4.05(d,J=14.9Hz,1H),3.43(d,J=14.9Hz,1H),2.58–2.53(m,2H),2.21–2.11(m,2H),2.03(d,J=18.6Hz,1H),1.85–1.80(m,1H),1.54–1.50(m,1H),1.19(s,3H),0.95(s,3H);13C NMR(150MHz,CDCl3)δ213.62,154.00,149.16,131.75,130.17,129.39(q,J=32.5Hz),122.73,121.73,119.17(q,J=270Hz),107.95(q,J=4.8Hz),58.21,49.62,48.17,42.87,42.41,26.87,25.24,19.78,19.70.
实施例3
将中间体2-三氟甲基-8-溴-4-羟基喹啉(1.0mmol),4-二甲氨基吡啶(0.1mmol),三乙胺(1.1mmol)溶解于无水二氯甲烷中,降温至0℃,分批加入L-10-樟脑磺酰氯(1.2mmol),升至25℃反应3.5h。TLC监测原料反应完全,有机层以水洗涤3次(8ml*3),饱和食盐水洗涤3次(8mL*3),干燥,抽滤,浓缩除去二氯甲烷,粗品经柱层析(CH2Cl2:MeOH=20:1)得目标化合物I-3,白色固体,m.p.98–99.9℃,收率85%;1H NMR(600MHz,CDCl3)δ6.83(d,J=2.1Hz,1H),6.79–6.76(m,2H),6.01(s,2H),3.80(d,J=15.0Hz,1H),3.17(d,J=15.0Hz,1H),2.57–2.52(m,1H),2.44–2.40(m,1H),2.14(t,J=4.5Hz,1H),2.11–2.07(m,1H),1.98(d,J=18.5Hz,1H),1.74–1.69(m,1H),1.48–1.44(m,1H),1.16(s,3H),0.91(s,3H);13C NMR(150MHz,CDCl3)δ214.08,148.26,146.54,143.22,114.91,108.10,104.32,102.02,58.10,47.91,47.23,42.82,42.42,26.83,25.09,19.93,19.68.
实施例4
将中间体2-甲基-5-异丙基苯酚(1.0mmol),4-二甲氨基吡啶(0.1mmol),三乙胺(1.1mmol)溶解于无水二氯甲烷中,降温至0℃,分批加入L-10-樟脑磺酰氯(1.2mmol),升至25℃反应5h。TLC监测原料反应完全,有机层以水洗涤3次(8ml*3),饱和食盐水洗涤3次(8mL*3),干燥,抽滤,浓缩除去二氯甲烷,粗品经柱层析(CH2Cl2:MeOH=20:1)得目标化合物II-1,无色油状物,收率80%;
1H NMR(600MHz,CDCl3)δ7.18(dd,J=8.6,4.7Hz,2H),7.06(dd,J=7.8,1.5Hz,1H),3.88(d,J=15.0Hz,1H),3.24(d,J=15.0Hz,1H),2.92-2.87(m,1H),2.62–2.57(m,1H),2.45–2.41(m,1H),2.33(s,3H),2.15(d,J=4.4Hz,1H),2.12–2.05(m,1H),1.98(d,J=18.5Hz,1H),1.75–1.71(m,1H),1.48–1.44(m,1H),1.24(d,J=6.9Hz,6H),1.18(s,3H),0.93(s,3H);13C NMR(150MHz,CDCl3)δ214.19,148.46,147.83,131.48,128.41,125.07,120.01,58.15,48.10,47.86,42.83,42.43,33.54,29.65,26.83,25.06,23.82,19.96,19.68,16.36.
实施例5
将中间体2-异丙基-5-甲基苯酚(1.0mmol),4-二甲氨基吡啶(0.1mmol),三乙胺(1.1mmol)溶解于无水二氯甲烷中,降温至0℃,分批加入L-10-樟脑磺酰氯(1.2mmol),升至25℃反应2-5h。TLC监测原料反应完全,有机层以水洗涤3次(8ml*3),饱和食盐水洗涤3次(8mL*3),干燥,抽滤,浓缩除去二氯甲烷,粗品经柱层析(CH2Cl2:MeOH=20:1)得目标化合物II-2,无色油状物,收率75%;
1H NMR(600MHz,CDCl3)δ7.23(d,J=7.9Hz,1H),7.15(s,1H),7.07(d,J=7.9Hz,1H),3.88(d,J=15.0Hz,1H),3.35-3.31(m,1H),3.26(d,J=15.0Hz,1H),2.62–2.57(m,1H),2.44–2.41(m,1H),2.33(s,3H),2.14–2.06(m,2H),1.98(d,J=18.5Hz,1H),1.75-1.70(m,1H),1.48–1.43(m,1H),1.23(t,J=7.3Hz,6H),1.18(s,3H),0.93(s,3H);13C NMR(150MHz,CDCl3)δ214.17,146.36,138.38,136.97,128.15,126.96,122.35,58.17,48.36,47.86,42.87,42.43,26.83,26.71,25.06,23.35,23.19,20.80,19.97,19.69.
实施例6
将中间体2-羟基-4-甲氧基苯乙酮(1.0mmol),4-二甲氨基吡啶(0.1mmol),三乙胺(1.1mmol)溶解于无水二氯甲烷中,降温至0℃,分批加入L-10-樟脑磺酰氯(1.2mmol),升至25℃反应4h。TLC监测原料反应完全,有机层以水洗涤3次(8ml*3),饱和食盐水洗涤3次(8mL*3),干燥,抽滤,浓缩除去二氯甲烷,粗品经柱层析(CH2Cl2:MeOH=20:1)得目标化合物II-3,黄色油状物,收率90%;
1H NMR(600MHz,CDCl3)δ7.79(d,J=8.8Hz,1H),6.99(d,J=2.4Hz,1H),6.88(dd,J=8.8,2.4Hz,1H),3.91(d,J=15.0Hz,1H),3.88(s,3H),3.43(d,J=15.0Hz,1H),2.61(s,3H),2.54–2.49(m,1H),2.45–2.41(m,1H),2.15(t,J=4.5Hz,1H),2.11–2.07(m,1H),1.98(d,J=18.5Hz,1H),1.78–1.73(m,1H),1.49–1.45(m,1H),1.16(s,3H),0.94(s,3H);13C NMR(150MHz,CDCl3)δ213.91,196.13,163.42,148.34,132.24,124.92,112.86,108.84,77.00,58.16,55.90,48.73,48.03,42.86,42.46,30.00,26.88,25.24,19.83,19.71.
实施例7
将中间体2-羟基苯乙酮(1.0mmol),4-二甲氨基吡啶(0.1mmol),三乙胺(1.1mmol)溶解于无水二氯甲烷中,降温至0℃,分批加入L-10-樟脑磺酰氯(1.2mmol),升至25℃反应2h。TLC监测原料反应完全,有机层以水洗涤3次(8ml*3),饱和食盐水洗涤3次(8mL*3),干燥,抽滤,浓缩除去二氯甲烷,粗品经柱层析(CH2Cl2:MeOH=20:1)得目标化合物II-4,无色油状物,收率83%;1H NMR(600MHz,CDCl3)δ7.98(d,J=7.8Hz,1H),7.58(t,J=7.8Hz,1H),7.44(d,J=8.2Hz,1H),7.38(t,J=7.6Hz,1H),3.93(d,J=16.2Hz,4H),3.45(d,J=15.0Hz,1H),2.57–2.49(m,1H),2.45–2.40(m,1H),2.14(t,J=4.6Hz,1H),2.11–2.05(m,1H),1.97(d,J=18.5Hz,1H),1.74–1.70(m,1H),1.48–1.43(m,1H),1.18(s,3H),0.94(s,3H);13C NMR(150MHz,CDCl3)δ214.02,164.89,147.61,133.64,132.05,126.97,124.74,123.88,77.00,58.11,52.41,48.52,47.86,42.84,42.41,26.81,25.17,19.87,19.64.
实施例8
将中间体4-甲基-7-羟基香豆素(1.0mmol),4-二甲氨基吡啶(0.1mmol),三乙胺(1.1mmol)溶解于无水二氯甲烷中,降温至0℃,分批加入L-10-樟脑磺酰氯(1.2mmol),升至25℃反应2-5h。TLC监测原料反应完全,有机层以水洗涤3次(8ml*3),饱和食盐水洗涤3次(8mL*3),干燥,抽滤,浓缩除去二氯甲烷,粗品经柱层析(CH2Cl2:MeOH=20:1)得目标化合物III,白色固体,m.p.100–101.5℃,收率45%.1H NMR(600MHz,CDCl3)δ7.65(d,J=8.4Hz,1H),7.35–7.29(m,2H),6.31(s,1H),3.85(d,J=15.0Hz,1H),3.25(d,J=15.0Hz,1H),2.55–2.50(m,1H),2.45–2.41(m,4H),2.17(t,J=4.5Hz,1H),2.12–2.08(m,1H),1.99(d,J=18.6Hz,1H),1.78–1.73(m,1H),1.51–1.47(m,1H),1.16(s,3H),0.92(s,3H);13C NMR(150MHz,CDCl3)δ213.78,160.04,154.14,151.60,151.05,125.94,118.88,118.16,115.11,110.77,77.00,58.10,48.30,48.02,42.80,42.40,26.83,25.14,19.84,19.67,18.70.
实施例9
将中间体甲基麦芽酚(1.0mmol),4-二甲氨基吡啶(0.1mmol),三乙胺(1.1mmol)溶解于无水二氯甲烷中,降温至0℃,分批加入L-10-樟脑磺酰氯(1.2mmol),升至25℃反应2h。TLC监测原料反应完全,有机层以水洗涤3次(8ml*3),饱和食盐水洗涤3次(8mL*3),干燥,抽滤,浓缩除去二氯甲烷,粗品经柱层析(CH2Cl2:MeOH=20:1)得目标化合物IV-1,白色固体,m.p.108–109℃,收率51%;1H NMR(600MHz,CDCl3)δ7.68(s,1H),6.43(s,1H),4.12(d,J=15.0Hz,1H),4.05(d,J=15.0Hz,1H),2.45–2.40(m,5H),2.13(t,J=4.4Hz,1H),2.10–2.05(m,1H),1.97(d,J=18.5Hz,1H),1.84–1.79(m,1H),1.48–1.44(m,1H),1.15(s,3H),0.95(s,3H);13C NMR(150MHz,CDCl3)δ213.62,172.68,163.13,154.22,138.66,117.44,77.00,58.24,50.86,48.18,42.84,42.52,26.94,25.30,19.71,19.68,15.84.
实施例10
将中间体乙基麦芽酚(1.0mmol),4-二甲氨基吡啶(0.1mmol),三乙胺(1.1mmol)溶解于无水二氯甲烷中,降温至0℃,分批加入L-10-樟脑磺酰氯(1.2mmol),升至25℃反应3h。TLC监测原料反应完全,有机层以水洗涤3次(8ml*3),饱和食盐水洗涤3次(8mL*3),干燥,抽滤,浓缩除去二氯甲烷,粗品经柱层析(CH2Cl2:MeOH=20:1)得目标化合物IV-2,红色固体,m.p.105–107.5℃,收率56%;1H NMR(600MHz,CDCl3)δ7.72(d,J=5.7Hz,1H),6.42(d,J=5.7Hz,1H),4.12(q,J=15.0Hz,2H),2.81(q,J=7.6Hz,2H),2.46–2.40(m,2H),2.13(t,J=4.5Hz,1H),2.11–2.05(m,1H),1.96(d,J=18.5Hz,1H),1.83–1.78(m,1H),1.48–1.44(m,1H),1.29(t,J=7.6Hz,3H),1.15(s,3H),0.95(s,3H);13C NMR(150MHz,CDCl3)δ213.66,172.93,166.92,154.33,137.79,117.32,77.00,58.28,50.83,48.19,42.86,42.55,26.96,25.33,22.73,19.74,19.70,10.69.
实施例11
将中间体1-羟基蒽醌(1.0mmol),4-二甲氨基吡啶(0.1mmol),三乙胺(1.1mmol)溶解于无水二氯甲烷中,降温至0℃,分批加入L-10-樟脑磺酰氯(1.2mmol),升至25℃反应2-5h。TLC监测原料反应完全,有机层以水洗涤3次(8ml*3),饱和食盐水洗涤3次(8mL*3),干燥,抽滤,浓缩除去二氯甲烷,粗品经柱层析(CH2Cl2:MeOH=20:1)得目标化合物V,黄色固体m.p.133-135℃,收率50%;
1H NMR(600MHz,CDCl3)δ8.35(d,J=8.5Hz,1H),8.27–8.26(m,2H),8.15(d,J=2.5Hz,1H),7.80(dd,J=7.1,3.1Hz,2H),7.73(dd,J=8.5,2.5Hz,1H),3.92(d,J=15.0Hz,1H),3.33(d,J=15.0Hz,1H),2.57–2.43(m,1H),2.46–2.43(m,1H),2.18(t,J=4.5Hz,1H),2.15–2.03(m,1H),2.01(d,J=18.5Hz,1H),1.82–1.78(m,1H),1.53–1.49(m,1H),1.18(s,3H),0.95(s,3H);13C NMR(150MHz,CDCl3)δ213.61,181.68,181.66,153.33,135.34,134.38,134.21,133.19,133.07,129.78,127.47,127.26,120.10,58.05,48.59,48.01,42.74,42.34,26.80,25.10,19.76,19.62.
实施例12
杀菌活性(离体)实验:
本实验中所用的植物真菌为实验室4℃保存的菌种,为茶树炭疽病菌、葡萄座腔病菌、马铃薯晚疫病菌、辣椒疫霉病菌、油菜菌核病菌、苹果轮纹病菌和番茄灰霉病菌。
采用的培养基为马铃薯琼脂葡萄糖培养基(简称PDA)。PDA培养基配方:马铃薯(去皮)200g,葡萄糖20g,琼脂15g,蒸馏水1000mL,配制方法:将马铃薯洗净去皮,称200g切成小块,加水煮烂(煮沸20-30分钟,能被玻璃棒戳破即可),用八层纱布过滤于烧杯中,根据实验需要加15–20g琼脂,加入20g葡萄糖,搅拌均匀,充分溶解后稍冷却,补足水至1000mL,分装后121℃灭菌15分钟,冷却后备用。
实验方法:采用生长速率法。
(1)先将7种植物真菌在PDA平板上25℃培养3-6d左右待用;
(2)将PDA培养基加热溶化,冷却至45–50℃,加入250μL的10g/L浓度的待测化合物制成含50mg/L药液的培养基,并分别倒入培养皿中冷却,萎绣灵(carboxin)和氟唑菌酰羟胺作为阳性对照;
(3)以无菌操作,用打孔器在培养6d的各菌株菌丝边缘(生长状况尽量一致)打取圆形菌饼(直径0.50cm),再用接种针挑至含药平板中央,然后将培养皿倒置于培养箱(28℃)中培养;
(4)于处理后不同时间观察测定菌丝的生长情况,并采用十字交叉法测得直径并处理数据,计算抑制率;
(5)抑制率(%)=(对照菌丝直径-处理菌丝直径)/(对照菌丝直径-0.5)×100;
(6)每个处理重复3次。
表1樟脑磺酸酯类化合物对七种农业致病真菌的抑制活性试验结果
a注:试验中每个处理设三次重复,表中数据为三次重复的平均值。
表2部分化合物的EC50值
由表1和表2的结果可见,50mg/L浓度时,化合物I,II,III,IV和V对7种植物真菌显示出不同程度的杀菌活性,部分化合物对辣椒疫霉病菌和油菜菌核病菌有较好的抑制活性;其中,化合物IV-1和IV-2在50mg/L浓度下对辣椒疫霉病菌的抑制率达96.7%和87.8%,与阳性对照萎锈灵相当。
鉴于目标化合物对几种植物病菌具有较好的抑制活性,测试了普筛抑制率较高的化合物IV-1的EC50值。化合物的EC50列于表2,可以看出,化合物IV-1对辣椒疫霉病菌的EC50值为0.059mg/L,优于阳性对照萎锈灵(0.163mg/L)。该系列化合物对几种真菌均有较好的抑制活性,具有开发抗真菌剂的潜力。
实施例13
辣椒疫霉菌种在马铃薯葡萄糖琼脂培养基(PDA)上培养5天。用蒸馏水水冲洗琼脂中的孢子。通过两层纱布过滤得孢子悬浮液,将孢子数调整为1×105个孢子/毫升。首先,将化合物IV-1和阳性对照萎锈灵溶于200μL二甲基亚砜中,用0.2%吐温-80稀释,得到浓度为200mg/L的供试品溶液。然后将均匀喷洒在辣椒叶上。自然干燥后,孢子悬浮液由DeVilbiss喷雾器喷洒在辣椒植株的叶子上。将接种的植株放置36小时(25℃,相对湿度>80%)中。感染期结束后,将辣椒植株置于人工气候培养箱中培养7天,并评价病情指数。
表3化合物IV-1对辣椒疫霉病菌的活体实验(辣椒植株)
图2为本发明实施例中化合物IV-1对辣椒疫霉病菌的活体实验示意图(植株法)。从结果可以看到,化合物IV-1对辣椒疫霉菌侵染的辣椒植株的保护活性为80%,接近阳性对照萎锈灵的保护活性。
本发明所述含有磺酸酯基的樟脑类化合物,结构区别明显,化学结构特征鲜明,对于防治辣椒疫霉病菌显示出较好的效果。可用于防治农业或林业植物真菌病害。所述化合物的制备方法简便,收率较高,产物性质稳定。
应说明的是,以上实施例仅用以说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的精神和范围,其均应涵盖在本发明的权利要求范围当中。
Claims (10)
2.权利要求1所述樟脑磺酸酯类化合物的制备方法,其特征在于:包括,
L-10-樟脑磺酸与氯化亚砜反应合成L-10-樟脑磺酰氯中间体;
L-10-樟脑磺酰氯中间体与取代4-羟基喹啉、三乙胺和4-二甲氨基吡啶反应,合成樟脑磺酸酯类化合物I;
L-10-樟脑磺酰氯中间体与取代苯酚类、三乙胺和4-二甲氨基吡啶反应,合成樟脑磺酸酯类化合物II;
L-10-樟脑磺酰氯中间体与7-羟基香豆素、三乙胺和4-二甲氨基吡啶反应,合成樟脑磺酸酯类化合物III;
L-10-樟脑磺酰氯中间体与取代麦芽酚、三乙胺和4-二甲氨基吡啶反应合成樟脑磺酸酯类化合物IV;
L-10-樟脑磺酰氯中间体与羟基蒽醌、三乙胺和4-二甲氨基吡啶反应合成樟脑磺酸酯类化合物V。
3.如权利要求2所述樟脑磺酸酯类化合物的制备方法,其特征在于:所述L-10-樟脑磺酰氯中间体,其制备方法包括,
将L-10-樟脑磺酸并加入氯化亚砜中溶解,升温至回流温度反应,冷却,浓缩除去大部分溶剂和HCl,得白色固体L-10-樟脑磺酰氯,产物未经进一步处理直接投下一步;其中,
L-10-樟脑磺酸与氯化亚砜的摩尔比以mmol:mmol计为3.0:3.3;
反应时间为5~6h。
4.如权利要求2所述樟脑磺酸酯类化合物的制备方法,其特征在于:所述合成樟脑磺酸酯类化合物I,包括,
将取代4-羟基喹啉、4-二甲氨基吡啶和三乙胺溶解于无水二氯甲烷中,降温至0℃,分批加入L-10-樟脑磺酰氯中间体,升至常温反应1~5h;
TLC监测原料反应完全,有机层以水洗涤3次,饱和食盐水洗涤3次,干燥,抽-滤,浓缩除去二氯甲烷,粗品经柱层析CH2Cl2:MeOH=20:1得目标化合物I;
其中,取代4-羟基喹啉包括2,8-二三氟甲基-4-羟基喹啉、2-三氟甲基-4-羟基喹啉和2-三氟甲基-8-溴-4-羟基喹啉;
取代4-羟基喹啉、4-二甲氨基吡啶和三乙胺与L-10-樟脑磺酰氯中间体的比例为1mmol:0.1mmol:1.1mmol:1.2mmol。
5.如权利要求2所述樟脑磺酸酯类化合物的制备方法,其特征在于:所述合成樟脑磺酸酯类化合物II,包括,
将取代苯酚、4-二甲氨基吡啶和三乙胺溶解于无水二氯甲烷中,降温至0℃,分批加入L-10-樟脑磺酰氯中间体,升至常温反应1~5h;
TLC监测原料反应完全,有机层以水洗涤3次,饱和食盐水洗涤3次,干燥,抽-滤,浓缩除去二氯甲烷,粗品经柱层析CH2Cl2:MeOH=20:1得目标化合物I;
其中,取代苯酚包括2-甲基-5-异丙基苯酚、2-异丙基-5-甲基苯酚、2-羟基-4-甲氧基苯乙酮和2-羟基苯乙酮;
取代苯酚、4-二甲氨基吡啶和三乙胺与L-10-樟脑磺酰氯中间体的比例为1mmol:0.1mmol:1.1mmol:1.2mmol。
6.如权利要求2所述樟脑磺酸酯类化合物的制备方法,其特征在于:所述合成樟脑磺酸酯类化合物III,包括,
将7-羟基香豆素、4-二甲氨基吡啶和三乙胺溶解于无水二氯甲烷中,降温至0℃,分批加入L-10-樟脑磺酰氯中间体,升至常温反应1~5h;
TLC监测原料反应完全,有机层以水洗涤3次,饱和食盐水洗涤3次,干燥,抽-滤,浓缩除去二氯甲烷,粗品经柱层析CH2Cl2:MeOH=20:1得目标化合物I;
其中,7-羟基香豆素、4-二甲氨基吡啶和三乙胺与L-10-樟脑磺酰氯中间体的比例为1mmol:0.1mmol:1.1mmol:1.2mmol。
7.如权利要求2所述樟脑磺酸酯类化合物的制备方法,其特征在于:所述合成樟脑磺酸酯类化合物IV,包括,
将取代麦芽酚、4-二甲氨基吡啶和三乙胺溶解于无水二氯甲烷中,降温至0℃,分批加入L-10-樟脑磺酰氯中间体,升至常温反应1~5h;
TLC监测原料反应完全,有机层以水洗涤3次,饱和食盐水洗涤3次,干燥,抽-滤,浓缩除去二氯甲烷,粗品经柱层析CH2Cl2:MeOH=20:1得目标化合物I;
其中,取代麦芽酚包括甲基麦芽酚、乙基麦芽酚;
取代麦芽酚、4-二甲氨基吡啶和三乙胺与L-10-樟脑磺酰氯中间体的比例为1mmol:0.1mmol:1.1mmol:1.2mmol。
8.如权利要求2所述樟脑磺酸酯类化合物的制备方法,其特征在于:所述合成樟脑磺酸酯类化合物V,包括,
将羟基蒽醌、4-二甲氨基吡啶和三乙胺溶解于无水二氯甲烷中,降温至0℃,分批加入L-10-樟脑磺酰氯中间体,升至常温反应1~5h;
TLC监测原料反应完全,有机层以水洗涤3次,饱和食盐水洗涤3次,干燥,抽-滤,浓缩除去二氯甲烷,粗品经柱层析CH2Cl2:MeOH=20:1得目标化合物I;
羟基蒽醌、4-二甲氨基吡啶和三乙胺与L-10-樟脑磺酰氯中间体的比例为1mmol:0.1mmol:1.1mmol:1.2mmol。
9.权利要求1所述樟脑磺酸酯类化合物在防治农业或林业的植物真菌的应用。
10.如权利要求9所述应用,其特征在于:所述植物真菌为辣椒疫霉病菌和油菜菌核病菌。
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