CN117049967A - 2,6-二硝基-3,4-二甲基苯酚衍生物的制备方法及活性应用 - Google Patents
2,6-二硝基-3,4-二甲基苯酚衍生物的制备方法及活性应用 Download PDFInfo
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- CN117049967A CN117049967A CN202310835432.3A CN202310835432A CN117049967A CN 117049967 A CN117049967 A CN 117049967A CN 202310835432 A CN202310835432 A CN 202310835432A CN 117049967 A CN117049967 A CN 117049967A
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- dimethylphenol
- dinitro
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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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
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-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
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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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
-
- A—HUMAN NECESSITIES
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- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
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- A—HUMAN NECESSITIES
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C205/20—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C07C205/21—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to carbon atoms of six-membered aromatic rings having nitro groups and hydroxy groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
- C07C205/23—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to carbon atoms of six-membered aromatic rings having nitro groups and hydroxy groups bound to carbon atoms of the same non-condensed six-membered aromatic ring having two nitro groups bound to the ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
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- C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
- C07C205/37—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明公开了2,6‑二硝基‑3,4‑二甲基苯酚衍生物的制备方法及活性应用,其中2,6‑二硝基‑3,4‑二甲基苯酚衍生物包括了五种化合物,该类衍生物与R‑X在碳酸盐和有机溶剂,温度为50℃~100℃的情况下进行反应而得到。2,6‑二硝基‑3,4‑二甲基苯酚衍生物具有很好的抑制植物生长和抑制AHAS酶活性的作用,可用作除草剂。
Description
技术领域
本发明涉及化工技术领域,尤其涉及2,6-二硝基-3,4-二甲基苯酚衍生物的制备方法及活性应用。
背景技术
二硝基苯胺类除草剂在化学除草中占有重要地位,此类除草剂为播前土壤处理剂施用时与土壤拌匀,埋于土层,被杂草的胚芽鞘吸收,破坏杂草的偶联反应,抑制ATP形成,干扰植物分生组织细胞分裂而使杂草死亡。二硝基苯胺类除草剂主要品种为氟乐灵、二甲戊乐灵和双丁乐灵等,至今已有十几个品种,2,6-二硝基苯胺的结构通式如下:
二甲戊灵作为世界上销量最大的选择性除草剂,其合成方法已经受到了广泛的研究与注意,根据所采用的起始原料来划分,二甲戊乐灵的合成主要有三条路线:(1)3,4-二甲基硝基苯路线;(2)3,4-二甲基卤苯路线;(3)3,4-二甲基苯酚(醚)路线。二甲戊灵结构式的结构式如下:
其中,第一种合成路线会产生N-亚硝胺副产物,第二种合成路线原料来源复杂,而3,4-二甲基苯酚为起始原料的胺化法工艺是一种无N-亚硝胺产生的新合成方法。该路线反应主要以3,4-二甲基苯酚为原料,经硝化、甲基化、胺化反应,得到目标产物N-(1-乙基-丙基)-2,6-二硝基-3,4-二甲基苯胺(反应路线如下式所示)。
早期,该路线中中间体2,6-二硝基-3,4-二甲基苯酚的合成比较困难,因为酚类在硝化时极易被氧化,形成粘稠油状物,难以分离,反应硝化选择性不高,使得其反应收率不高。1981年,Lawrence J等采用60%浓硝酸直接硝化3,4-二甲基苯酚,获得的二硝化产物收率不足60%;1997年,Sarel等通过对上述方法进行改进,使二硝化收率提高到75%;1998年,萨比拉等提出采用ZnCl2做催化剂,无机酸做辅助催化剂,在有机溶剂中可使二硝化收率达到90%;2003年,张之行等人报道用二氯乙烷作溶剂,用盐酸稀释硝酸后硝化3,4-二甲基苯酚,二硝化收率达到90%。
美国专利5475148已经提出利用中间体2,6-二硝基-3,4-二甲基苯酚经过连续步骤:在两相介质中使用硝酸将3,4-二烷基苯酚二硝化,将获得的2,6-二硝基-3,4-二烷基苯酚进行烷基化,在相转移催化剂存在下,将形成的3,4-二烷基-2,6-二硝基烷氧基苯与不同胺反应,制备二甲戊灵和其他N-烷基-3,4-二烷基取代的二硝基苯胺化合物。法国专利EP870756也提出对3,4-二甲基苯酚进行二硝基化,然后利用二硝基衍生物的O-烷基化,以及3,4-二烷基-2,6-二硝基-烷氧基苯的胺化,胺化试剂包括N-甲基-2-环丙胺、N-2-甲基-2-乙基丙胺、N-甲基-2-环丙胺等,这样一个方法来制备更多的N-烷基-3,4-二甲基取代的二硝基苯胺化合物,而且所得到的化合物基本对植物细胞分裂有抑制作用。
综上所述,从中间体2,6-二硝基-3,4-二甲基苯酚出发,用不同的烷基化试剂,包括烷基卤化物、多卤代烷基、卤代醇等进行O-烷基化,然后用其他不同伯胺或仲胺对前一步制备的3,4-二甲基-2,6-二硝基烷氧基苯进行胺化,可以得到更多3,4-二甲基-2,6-二硝基苯胺衍生物,而这些化合物在结构上与已知除草剂二甲戊灵相似,有希望成为新的二硝基苯胺类除草剂。
发明内容
本发明的目的在于提供2,6-二硝基-3,4-二甲基苯酚衍生物的制备及活性应用,此类衍生物对植物的生长有较好的抑制作用,可以用作除草剂。
为实现本发明的目的,本发明拟提供2,6-二硝基-3,4-二甲基苯酚衍生物的制备方法,反应路线如下:
所述R-X选自
所述有机溶剂选自MeCN、DMF;
所述碳酸盐选自碳酸铯、碳酸钾、碳酸镁、碳酸钙。
本发明中,3,4-二甲基-2,6-二硝基苯酚与碳酸盐的摩尔比为(1~5):(2~10);优选(1.4~3):(3.4~8.9)。
本发明中,3,4-二甲基-2,6-二硝基苯酚与R-X的摩尔比为(1~3):(2~5),优选为(1.4~3):(2.8~3.6)。
在一些实施方案中,所述R-X为任意一种;其反应路线如下:
其中,3,4-二甲基-2,6-二硝基苯酚与R-X摩尔比为(1~3):(2~4),优选为3:3.6。
其中,3,4-二甲基-2,6-二硝基苯酚与CsCO3的摩尔比为(1.4~3):(3.4~8.9),优选为3:8.9。
进一步地,所述2,6-二硝基-3,4-二甲基苯酚衍生物为 任意一种。
在一些实施方案中,所述R-X为其反应路线如下:
其中,其中,3,4-二甲基-2,6-二硝基苯酚与R-X摩尔比为(1~3):(2~4),优选为1.4:2.8。
其中,3,4-二甲基-2,6-二硝基苯酚与CsCO3的摩尔比为(1.4~3):(3.4~8.9),优选为1.4:3.4。
在一些实施方案中,所述R-X为更进一步地,其反应路线如下:
其中,其中,3,4-二甲基-2,6-二硝基苯酚与R-X摩尔比为(1~3):(2~4),优选为3.0:3.3。
其中,3,4-二甲基-2,6-二硝基苯酚与CsCO3的摩尔比为(1.4~3):(3.4~8.9),优选为3.0:6。
本发明中,2-(2-羟基乙氧基)乙基-4-甲基苯磺酸盐的合成方法如下:
其总路线如下:
本发明还提供了2,6-二硝基-3,4-二甲基苯酚衍生物在制备杀菌剂和/或除草剂产品中的应用。
其中,所述产品为AHAS酶抑制剂。
AHAS酶(乙酰羟酸合成酶),是由细胞核编码的叶绿体酶;它完成两种平行反应,第一,乙酰羟酸合成酶浓缩二分子的丙酮酸合成产生乙酰乳酸,称之为乙酰乳酸合成酶,在反应体系中最终可合成缬氨酸和亮氨酸;第二,乙酰羟酸合成酶催化一分子丙酮酸和一分子2-丁酮酸,产生乙酰羟丁酸,乙酰羟丁酸的最终产物为异亮氨酸,缬氨酸和亮氨酸为支链氨基酸。AHAS酶存在于植物所有部位,但它的活性在不同的植物的不同器官不同的发育阶段是不同的,一般植物分生组织的活性最高,而黄化部分活性降低。
其中,所述产品为抑制植物生长的产品。
其中,所述产品为抑制植物根部生长的产品。
本发明的有益效果:
本发明以2,6-二硝基-3,4-二甲基苯酚为原料合成2,6-二硝基-3,4-二甲基苯酚衍生物,其方法简单易操作,且产物收率高;本发明中合成的衍生物2,6-二硝基-3,4-二甲基苯酚衍生物对植物的生长有很好的抑制作用,可用作除草剂,同时对AHAS酶活性有抑制作用。
2,6-二硝基-3,4-二甲基苯酚是硝基邻二甲苯生产过程中的主要副产物,产率约2%,在年产万吨的硝基邻二甲苯生产线中年产量约200吨。在硝基邻二甲苯的生产中,该化合物在现阶段被作为废药进行处理。但其无害化处置过程复杂,处置成本高。同时,该废药在一定条件下具有燃爆性,在生产运输、贮存、处置过程中存在较大的安全隐患。将其作为原料制备得到具有一定生物活性的产品,不但提高了安全性,同时,还能废物利用,进一步降低了废物处理成本,带来了一定的收益。
附图说明
图1为化合物1的核磁H谱图;
图2为化合物1的核磁C谱图;
图3为化合物2的核磁H谱图;
图4为化合物2的核磁C谱图;
图5为化合物3的核磁H谱图;
图6为化合物3的核磁C谱图;
图7为化合物4的核磁H谱图;
图8为化合物4的核磁C谱图;
图9为化合物5的核磁H谱图;
图10为化合物5的核磁C谱图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例和试验例1,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。另外,如果没有明确说明,在下面的实施例中所采用的所有试剂均为市场上可以购得的,或者可以按照本文或已知的方法合成的,对于没有列出的反应条件,也均为本领域技术人员容易获得的。实施例1 1-(2-(3,4-二甲基-2,6-二硝基苯氧基)乙基)吡咯烷的合成
将3,4-二甲基-2,6-二硝基苯酚(630mg,3.0mmol)和碳酸铯(2.9g,8.9mmol)溶于乙腈(20ml)中,室温下搅拌30min后,向混合物中加入N-(2-氯乙基)吡咯烷盐酸盐(606.2mg,3.6mmol),反应液置于80℃油浴锅中回流8h。反应完全后将反应液减压蒸馏后,用二氯甲烷萃取,有机层水用饱和食盐水洗涤(1*5mL),然后用无水硫酸钠干燥后减压蒸馏除去溶剂。得到1-(2-(3,4-二甲基-2,6-二硝基苯氧基)乙基)吡咯烷251.7mg。其核磁数据如下:
1H NMR(400MHz,DMSO-d6):δ(ppm)8.11(s,1H),4.10(t,J=5.7Hz,2H),2.73(t,J=5.7Hz,2H),2.44(t,J=5.9Hz,4H),2.36(s,3H),2.21(s,3H),1.67–1.63(m,4H)。
13C NMR(101MHz,DMSO-d6)δ147.67,142.49,140.63,135.99,135.82,127.71,75.92,54.99,54.02,23.60,19.36,15.04。
实施例2 1-(2-(3,4-二甲基-2,6-二硝基苯氧基)乙基)哌啶的合成
将3,4-二甲基-2,6-二硝基苯酚(630mg,3.0mmol)溶于乙腈(20ml),加入碳酸铯(2.9mg,8.9mmol),室温下搅拌30min后,向混合物中加入1-(2-氯乙基)哌啶盐酸盐(656.2mg,3.6mmol),并置于80℃油浴锅中回流8h。反应完全后减压浓缩。然后用DCM(15ml)和水(10ml)萃取。有机相用无水硫酸钠干燥后,用PE:EA:DCM=7:1:1的混合体系作洗脱剂进行柱层析得到1-(2-(3,4-二甲基-2,6-二硝基苯氧基)乙基)哌啶380mg。其核磁数据如下:
1H NMR(400MHz,DMSO-d6):δ(ppm)8.09(s,1H),4.09(t,J=5.6Hz,2H),2.57(t,J=5.6Hz,2H),2.35(s,3H),2.33(t,J=5.1Hz,4H),2.20(s,3H),1.44–1.39(m,4H),1.35–1.28(m,2H)。
13C NMR(101MHz,DMSO-d6)δ147.67,142.54,140.53,135.94,135.57,127.68,74.27,57.97,54.42,25.75,24.16,19.33,15.01。
实施例3 4-(2-(3,4-二甲基-2,6-二硝基苯氧基)乙基)吗啉的合成
将3,4-二甲基-2,6-二硝基苯酚(630mg,3.0mmol)溶于乙腈(20ml),加入碳酸铯(2.9g,8.9mmol),室温下搅拌30min后,向混合物中加入4-(2-氯乙基)吗啉盐酸盐(669.9mg,3.6mmol),反应置于80℃油浴锅中回流8h。反应完全后将反应液减压蒸馏,然后用DCM(15ml)和水(10ml)萃取。有机相用无水硫酸钠干燥后,用PE:EA:DCM=8:1:1的混合体系作洗脱剂进行柱层析即可得4-(2-(3,4-二甲基-2,6-二硝基苯氧基)乙基)吗啉450mg。其核磁数据如下:
1H NMR(400MHz,DMSO-d6):δ(ppm)8.11(s,1H),4.11(t,J=5.4Hz,2H),3.50(t,J=4.6Hz,4H),2.59(t,J=5.5Hz,2H),2.36(s,3H),2.34(t,J=4.6Hz,4H),2.21(s,3H)。
13C NMR(101MHz,DMSO-d6)δ147.67,142.52,140.57,135.99,135.67,127.70,74.20,66.51,57.76,53.71,19.82,15.02。
实施例4 2-(2-(3,4-二甲基-2,6-二硝基苯氧基)乙氧基)乙烷-1-醇的合成
向3,4-二甲基-2,6-二硝基苯酚(300mg,1.4mmol)和乙腈(10ml)的混合物中加入B(737.0mg,2.8mmol),K2CO3(468.9mg,3.4mmol),反应置于80℃油浴锅中回流8h。反应完全后,用PE:EA=3:1的混合体系作洗脱剂进行柱层析得到2-(2-(3,4-二甲基-2,6-二硝基苯氧基)乙氧基)乙烷-1-醇263.1mg。其核磁数据如下:
1H NMR(400MHz,DMSO-d6):δ(ppm)8.10(s,1H),4.56(t,J=5.4Hz,1H),4.16–4.12(m,2H),3.63(t,J=4.6Hz,2H),3.47(q,J=5.3Hz,2H),3.39(t,J=5.0Hz,2H),2.36(s,3H),2.21(s,3H)。
13C NMR(101MHz,DMSO-d6)δ147.58,142.49,140.55,136.00,135.76,127.70,76.50,72.68,69.59,60.50,19.35,15.03。
实施例5 2-(十二烷氧基)-4,5-二甲基-1,3-二硝基苯的合成
将3,4-二甲基-2,6-二硝基苯酚(636.6mg,3.0mmol)溶于(20ml)DMF,加入碳酸铯(2.0mg,6mmol),室温下搅拌30min后,向反应液中加入一溴十二烷(822.5mg,3.3mmol),然后将反应置于100℃油浴锅中回流8h左右。反应完全后用乙酸乙酯和水萃取。有机相用饱和食盐水洗涤,无水硫酸钠干燥后。用纯PE作洗脱剂进行柱层析得到2-(十二烷氧基)-4,5-二甲基-1,3-二硝基苯。其核磁数据如下:
1H NMR(400MHz,DMSO-d6):δ(ppm)8.10(s,1H),3.99(t,J=6.4Hz,2H),2.36(s,3H),2.20(s,3H),1.62(p,J=6.5Hz,2H),1.24(s,18H),0.88–0.82(m,3H)。
13C NMR(101MHz,DMSO-d6)δ147.69,142.41,140.63,135.92,135.75,127.68,77.71,31.77,29.65,29.47,29.38,29.33,29.17,28.97,25.34,22.56,19.33,14.97,14.39。试验例1 2,6-二硝基-3,4-二甲基苯酚衍生物对AHAS酶活性的抑制作用1 试验方法
1.1 样本制备
取0.3g烟草叶片,加入1mL提取液,进行冰浴匀浆,4℃×12000rpm离心15min,取上清液待使用。
1.2样品配置
称取药品将其配置成10mmol/L和1mmol/L的DMSO溶液,再分别取5μL加入到500μL烟草蛋白提取液中(即检测浓度分别为:100μM和10μM),混匀待测。
1.3上机检测
先将酶标仪预热30min,调节波长为525nm。将试剂盒中的所有试剂在25℃预热10min,设置样本管和对照管。在1mL离心管中依次加入试剂一(样本管20μL,对照管0),试剂二(样本管100μL,对照管120μL),样品溶液(样本管80μL,对照管80μL),在35℃暗反应1h。再加入试剂三(样本管20μL,对照管20μL),在60℃条件下水浴脱羧15min,加入试剂四(样本管100μL,对照管100μL),试剂五(样本管100μL,对照管100μL),继续60℃条件下水浴显色15min。最后于12000rpm离心5min,分别取200μL澄清液体至96孔板中,于525nm处读值,得到ΔA,ΔA=A样品管-A对照管,每组设置两个平行。
1.4抑制率计算
公式:酶活抑制率=1-(ΔA样品/ΔA空白对照)。
2结果分析
结果如表1所示:化合物1在100μM时的抑制率为79.9%,其他化合物2、3、4、5在100μM时对AHAS活性基本没有抑制效果。
表1 2,6-二硝基-3,4-二甲基苯酚衍生物在100uM浓度下对AHAS酶的抑制活性
注:抑制率分级如下:
A:75%<抑制率≤100%;B:50%<抑制率≤75%;C:25%<抑制率≤50%;D:0%≤抑制率≤25%。
试验例2 2,6-二硝基-3,4-二甲基苯酚衍生物对小球藻生长的抑制作用1 实验方法
1.1 药液配置
称取药品5mg,加入100μL DMSO溶液,再加入2滴吐温80,混匀,加入无菌水定容至5mL。
1.2藻的生长
量取药液4mL,加入14mL OD值在0.4的小球藻液,再加入2mL50%蔗糖溶液,加入25mL锥形瓶中,在27℃摇床中震荡培养(最终浓度为0.2mg/mL)。
1.3上机检测
在0、24、48、72h时取200μL藻液,用酶标仪在670nm处测量特征吸收峰值,每组3个平行,设置空白对照组。
1.4抑制率计算
公式:酶活抑制率=1-(Δ样品/Δ空白对照)。
2结果分析
为了进一步验证2,6-二硝基-3,4-二甲基苯酚衍生物对植物生长的抑制效果,我们选取小球藻来进行了生长抑制实验,结果如表2所示:2,6-二硝基-3,4-二甲基苯酚衍生物对小球藻普遍具有抑制效果,抑制率最高的化合物为1和2(100%),其他3个化合物3、4、5抑制效果率都比较差,抑制率分别为34%、27%、22%。化合物1不仅对小球藻的抑制率达到了100%,并且对AHAS酶活性也有较好的抑制率。
表2 2,6-二硝基-3,4-二甲基苯酚衍生物对小球藻生长的抑制率
注:抑制率分级如下:
A:75%<抑制率≤100%;B:50%<抑制率≤75%;C:25%<抑制率≤50%;D:0%≤抑制率≤25%。
Claims (10)
1.2,6-二硝基-3,4-二甲基苯酚衍生物的制备方法,其特征在于,反应路线如下:
所述R-X选自
所述有机溶剂选自MeCN和DMF;
所述碳酸盐选自碳酸铯、碳酸钾、碳酸镁、碳酸钙。
2.根据权利要求1所述的方法,其特征在于,所述R-X为 任意一种;进一步地,其反应路线如下:
3.根据权利要求2所述的方法,其特征在于,所述2,6-二硝基-3,4-二甲基苯酚衍生物为任意一种。
4.根据权利要求1所述的方法,其特征在于,所述R-X为进一步地,其反应路线如下:
5.根据权利要求1所述的方法,其特征在于,所述R-X为进一步地,其反应路线如下:
6.根据权利要求4所述的方法,其特征在于,所述2-(2-羟基乙氧基)乙基-4-甲基苯磺酸盐的合成方法如下:
7.权利要求1~6任意一项所述方法制备得到的2,6-二硝基-3,4-二甲基苯酚衍生物在制备杀菌剂和/或除草剂产品中的应用。
8.根据权利要求7所述的应用,其特征在于,所述产品为AHAS酶抑制剂。
9.根据权利要求7所述的应用,其特征在于,所述产品为抑制植物生长的产品。
10.根据权利要求9所述的应用,其特征在于,所述产品为抑制植物根部生长的产品。
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