CN112898222B - 噁二唑类化合物及其制备方法与应用 - Google Patents
噁二唑类化合物及其制备方法与应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- -1 Oxadiazole compound Chemical class 0.000 title claims description 77
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- 238000000034 method Methods 0.000 claims description 17
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
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- 238000006243 chemical reaction Methods 0.000 claims description 2
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 4
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 3
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
- C07D271/113—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
-
- 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
- A01N43/82—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 five-membered rings with three ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
Description
技术领域
本发明涉及新化合物的制备方法与应用,具体是噁二唑类化合物及其在制备杀菌剂中的应用。
背景技术
用于农业方面的有杀虫剂噁虫酮和除草剂噁草酮及丙炔噁草酮等。
叶姣等[CN104592216B,2017.2.15授权]描述了5-苯基-1,3,4-噁二唑衍生物(A)的制备方法。5-苯基-1,3,4-噁二唑衍生物作为杀稻纹枯病菌、油菜菌核病菌、黄瓜灰霉病菌、小麦白粉病菌和辣椒疫霉病菌的杀菌剂。
2006年,Li等[Bioorganic&Medicinal Chemistry Letters,2006,16(8):2278-2282]报道了15种新颖的Strobilurin衍生物(B)的杀菌活性。
R=H,4-OCH3,4-OCH2C6H5,3-Cl,2,3-Cl2,2,4-Cl2,2,5-Cl2,2,4-Cl2-5-F,2-F,4-F,2-F-4-Br,2,3-F2,4-CF3,2-I,4-NO2
其中化合物B(R=4-F,2-F-4-Br,2,3-F2,50mg/L)对轮纹病菌和灰霉病菌的抑制率均为100%。
本发明拟开发新型结构的噁二唑类化合物杀菌剂。
发明内容
本发明解决的技术问题是提供一类噁二唑类化合物及其制备方法与作为杀菌剂的用途。
为解决本发明的技术问题,本发明提供如下技术方案:
本发明技术方案的第一方面是提供了一类如结构式Ⅰ所示的噁二唑类化合物:
R选自:氢,2-甲基,4-甲基,4-氟,2-氯,4-氯,4-溴,4-碘,4-甲氧基,4-叔丁基,2-硝基,4-硝基,2,4-二氯,2-甲基-4氯;R1~R2选自:R1~R2选自:C1~C2烷基、C3~C4直链烷基或C3~C5烯丙基。
本发明技术方案的第二方面是提供了噁二唑类化合物的制备方法,其中式Ⅰ所示的化合物的制备反应如下:
R选自:氢,2-甲基,4-甲基,4-氟,2-氯,4-氯,4-溴,4-碘,4-甲氧基,4-叔丁基,2-硝基,4-硝基,2,4-二氯,2-甲基-4氯;X选自:氯、溴或碘。R1~R2选自:R1~R2选自:C1~C2烷基、C3~C4直链烷基或C3~C5烯丙基。
本发明技术方案的第三方面是提供本发明所述噁二唑类化合物在制备杀菌剂方面的应用。
本发明技术方案的第四方面是提供了化学结构式Ⅰ9所示的化合物的单晶体;单晶结构原子编号如下:
化合物Ⅰ9单晶体属于三斜晶系,空间群为P-1,每个晶胞中含有2个分子。晶胞参数为:α=88.615(4)°;β=81.736(5)°;γ=65.629(5)°;Z=2,Dc=1.451g/cm3,F(000)=462,μ=0.200mm-1,287个可观测点[I>2σ(I)],可观测点精修最终偏离因子R=0.0748,wR=0.2147,S=1.06,
有益技术效果:
本发明的噁二唑类化合物是一类具有杀菌活性或杀虫活性的化合物。
附图说明
图1是化合物Ⅰ9单晶体的分子结构。
图2是化合物Ⅰ9单晶体的晶体堆积图。
具体实施方式
以下实施例旨在说明本发明而不是对本发明的进一步限定。
实施例1
(E)-2-(甲氧基亚氨基)-2-(2-(((5-(苯氧基甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)乙酸甲酯(Ⅰ1)的制备
1.0mmol 5-(苯氧甲基)-2-巯基-1,3,4-噁二唑,1.1mmol碳酸钾,5mL乙腈,0.6mmol碘化钾,室温搅拌下分批加入1.05mmol(E)-2-溴甲基-α-甲氧亚胺基苯乙酸甲酯,升温至回流,反应3h,减压脱溶,乙酸乙酯萃取,水洗,无水硫酸钠干燥,脱溶,柱层析分离(V石油醚:V乙酸乙酯=10:1)得(E)-2-(甲氧基亚氨基)-2-(2-(((5-(苯氧基甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)乙酸甲酯(Ⅰ1),收率70.0%;白色固体,m.p.60~62℃;1H NMR(400MHz,CDCl3)δ:7.58~6.98(m,9H,苯环氢),5.20(s,2H,OCH2),4.35(s,2H,SCH2),4.07(s,3H,NOCH3),3.88(s,3H,OCH3);13C NMR(101MHz,CDCl3)δ:165.65,163.42,163.22,157.50,149.02,133.78,130.58,130.21,129.86,129.73,128.67,128.14,122.23,114.85,63.92,59.76,53.17,34.69。
实施例2
(E)-2-(甲氧基亚氨基)-2-(2-(((5-((2-甲苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)乙酸甲酯(Ⅰ2)的制备
按照实施例1方法制备,1.0mmol 5-((邻甲苯氧基)甲基)-2-巯基-1,3,4-噁二唑和1.05mmol(E)-2-溴甲基-α-甲氧亚胺基苯乙酸甲酯回流反应3h,得(E)-2-(甲氧基亚氨基)-2-(2-(((5-((2-甲苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)乙酸甲酯,收率73.4%,粘稠液体;1H NMR(400MHz,CDCl3)δ:7.60~6.90(m,8H,2×C6H4),5.20(s,2H,OCH2),4.36(s,2H,SCH2),4.07(s,3H,NOCH3),3.89(s,3H,OCH3),2.23(s,3H,CH3);13C NMR(101MHz,CDCl3)δ:165.59,163.66,163.23,155.76,149.03,133.81,131.14,130.57,130.20,129.87,128.67,128.14,127.40,126.95,122.00,111.70,63.92,60.03,53.16,34.69,16.13。
实施例3
(E)-2-(甲氧基亚氨基)-2-(2-(((5-((4-甲苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)乙酸甲酯(Ⅰ3)的制备
按照实施例1方法制备,1.0mmol 5-(4-甲基苯氧甲基)-2-巯基-1,3,4-噁二唑和1.05mmol(E)-2-溴甲基-α-甲氧亚胺基苯乙酸甲酯回流反应3h,得到(E)-2-(甲氧基亚氨基)-2-(2-(((5-((4-甲苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)乙酸甲酯(Ⅰ3),收率74.0%;白色固体,m.p.82~84℃;1H NMR(400MHz,CDCl3)δ:7.59~7.15(m,4H,C6H4),7.10(d,J=8.2Hz,2H,C6H23,5-H),6.88(d,J=8.2Hz,2H,C6H22,6-H),5.17(s,2H,OCH2),4.35(s,2H,SCH2),4.07(s,3H,NOCH3),3.89(s,3H,OCH3),2.29(s,3H,CH3);13C NMR(101MHz,CDCl3)δ:165.58,163.56,163.22,155.44,149.02,133.79,131.62,130.58,130.21,130.14,129.86,128.66,128.13,114.78,63.92,60.02,53.17,34.68,20.50。
实施例4
(E)-2-(2-(((5-((4-氟苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)-2-(甲氧基亚氨基)乙酸甲酯(Ⅰ4)的制备
按照实施例1方法制备,1.0mmol 5-(4-氟苯氧甲基)-2-巯基-1,3,4-噁二唑和1.05mmol(E)-2-溴甲基-α-甲氧亚胺基苯乙酸甲酯回流反应3h,得到(E)-2-(2-(((5-((4-氟苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)-2-(甲氧基亚氨基)乙酸甲酯(Ⅰ4),收率78.9%;白色固体,m.p.114~116℃;1H NMR(400MHz,CDCl3)δ:7.60~7.14(m,4H,C6H4),7.03~6.91(m,4H,C6H4),5.16(s,2H,OCH2),4.35(s,2H,SCH2),4.06(s,3H,NOCH3),3.88(s,3H,OCH3);13CNMR(101MHz,CDCl3)δ:165.72,163.23,159.28,156.89,153.60,153.58,149.01,133.74,130.58,130.19,129.86,128.69,128.16,116.31,116.28,116.22,116.05,63.92,60.53,53.16,34.69。
实施例5
(E)-2-(2-(((5-((4-氯苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)-2-(甲氧基亚氨基)乙酸甲酯(Ⅰ5)的制备
按照实施例1方法制备,1.0mmol 5-((4-氯苯氧基)甲基)-2-巯基-1,3,4-噁二唑和1.05mmol(E)-2-溴甲基-α-甲氧亚胺基苯乙酸甲酯反应3h,得到(E)-2-(2-(((5-((4-氯苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)-2-(甲氧基亚氨基)乙酸甲酯(Ⅰ5),收率67.5%;黄色固体,m.p.92~94℃;1H NMR(400MHz,CDCl3)δ:7.59~7.15(m,4H,C6H4),7.26(d,J=9.0Hz,2H,C6H43,5-2H),6.92(d,J=9.0Hz,2H,C6H42,6-2H),5.17(s,2H,OCH2),4.35(s,2H,SCH2),4.06(s,3H,CH3),3.88(s,3H,CH3);13C NMR(101MHz,CDCl3)δ:165.35,164.12,163.25,150.67,149.03,134.67,133.79,130.74,130.59,130.22,129.90,128.76,128.22,127.42,125.51,124.99,63.96,53.20,34.84,20.37。
实施例6
(E)-2-(2-(((5-((2-氯苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)-2-(甲氧基亚氨基)乙酸甲酯(Ⅰ6)的制备
按照实施例1方法制备,1.0mmol 5-((2-氯苯氧基)甲基)-2-巯基-1,3,4-噁二唑和1.05mmol(E)-2-溴甲基-α-甲氧亚胺基苯乙酸甲酯反应3h,得到(E)-2-(2-(((5-((2-氯苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)-2-(甲氧基亚氨基)乙酸甲酯(Ⅰ6),收率72.6%,粘稠液体;1H NMR(400MHz,CDCl3)δ:7.60~6.95(m,8H,Ar-H),5.28~5.18(m,2H,OCH2),4.35(s,2H,SCH2),4.06(s,3H,NOCH3),3.88(s,3H,CH3);13C NMR(101MHz,CDCl3)δ:165.88,163.22,162.97,153.16,149.02,133.74,130.74,130.20,129.87,128.68,128.16,127.93,123.37,116.25,114.99,114.84,63.93,60.97,53.18,34.70。
实施例7
(E)-2-(2-(((5-((4-溴苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)-2-(甲氧基亚氨基)乙酸甲酯(Ⅰ7)的制备
按照实施例1方法制备,1.0mmol 5-((4-溴苯氧基)甲基)-2-巯基-1,3,4-噁二唑和1.05mmol(E)-2-溴甲基-α-甲氧亚胺基苯乙酸甲酯反应3h,得到(E)-2-(2-(((5-((4-溴苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)-2-(甲氧基亚氨基)乙酸甲酯(Ⅰ7),收率40.7%;黄色固体,m.p.93~95℃;1H NMR(400MHz,CDCl3)δ:7.58~7.14(m,4H,C6H4),7.40(d,J=9.0Hz,2H,C6H43,5-2H),6.88(d,J=9.0Hz,2H,C6H42,6-2H),5.17(s,2H,OCH2),4.35(s,2H,SCH2),4.06(s,3H,NOCH3),3.88(s,3H,OCH3);13C NMR(101MHz,CDCl3)δ:165.80,163.22,163.00,156.56,149.00,133.72,132.58,130.57,130.19,129.87,128.69,128.17,116.71,114.63,63.93,59.93,53.17,34.70。
实施例8
(E)-2-(2-(((5-((4-碘苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)-2-(甲氧基亚氨基)乙酸甲酯(Ⅰ8)的制备
按照实施例1方法制备,1.0mmol 5-((4-碘苯氧基)甲基)-2-巯基-1,3,4-噁二唑和1.05mmol(E)-2-溴甲基-α-甲氧亚胺基苯乙酸甲酯反应3h,得到(E)-2-(2-(((5-((4-碘苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)-2-(甲氧基亚氨基)乙酸甲酯(Ⅰ8),收率33.4%;黄色固体,m.p.110~112℃;1H NMR(400MHz,CDCl3)δ:7.58(d,J=8.7Hz,2H),7.56~7.14(m,4H,C6H4),6.77(d,J=8.7Hz,2H),5.16(s,2H,OCH2),4.35(s,2H,SCH2),4.06(s,3H,NOCH3),3.88(s,3H,OCH3);13C NMR(101MHz,CDCl3)δ:165.79,163.20,162.98,157.32,148.98,138.52,133.69,130.55,130.17,129.85,128.67,128.16,117.19,84.70,63.92,59.74,53.17,34.69。
实施例9
(E)-2-(甲氧基亚氨基)-2-(2-((((5-(4-甲氧基苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)乙酸甲酯(Ⅰ9)的制备
按照实施例1方法制备,1.0mmol 5-((4-甲氧基苯氧基)甲基)-2-巯基-1,3,4-噁二唑和1.05mmol(E)-2-溴甲基-α-甲氧亚胺基苯乙酸甲酯反应3h,得到(E)-2-(甲氧基亚氨基)-2-(2-((((5-(4-甲氧基苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)乙酸甲酯(Ⅰ9),收率58.3%;白色固体,m.p.73~75℃;1H NMR(400MHz,CDCl3)δ:7.60~7.12(m,4H,C6H4),6.93(d,J=9.1Hz,2H,C6H42,6-H),6.83(d,J=9.1Hz,2H,C6H43,5-H),5.14(s,2H,OCH2),4.35(s,2H,SCH2),4.07(s,3H,NOCH3),3.89(s,3H,COOCH3),3.76(s,3H,OCH3);13CNMR(101MHz,CDCl3)δ:165.57,163.60,163.21,154.93,151.63,149.02,133.79,130.58,130.21,129.86,128.66,128.13,116.22,114.81,63.92,60.76,55.69,53.16,34.68。
实施例10
(E)-2-(甲氧基亚氨基)-2-(2-((((5-((4-叔丁基苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)乙酸甲酯(Ⅰ10)的制备
按照实施例1方法制备,1.0mmol 5-((4-叔丁基苯氧基)甲基)-2-巯基-1,3,4-噁二唑和1.05mmol(E)-2-溴甲基-α-甲氧亚胺基苯乙酸甲酯反应3h,得到(E)-2-(甲氧基亚氨基)-2-(2-((((5-((4-叔丁基苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)乙酸甲酯(Ⅰ10),收率48.9%,稠状液体;1H NMR(400MHz,CDCl3)δ:7.60~7.14(m,4H,C6H4),7.32(d,J=8.7Hz,2H,C6H43,5-H),6.93(d,J=8.7Hz,2H,C6H42,6-H),5.18(s,2H,OCH2),4.35(s,2H,SCH2),4.07(s,3H,NOCH3),3.89(s,3H,OCH3),1.29(s,9H,3×CH3);13C NMR(101MHz,CDCl3)δ:165.58,163.58,163.22,155.29,149.03,145.01,133.80,130.58,130.22,129.86,128.66,128.13,126.51,114.35,63.92,59.89,53.16,34.68,34.17,31.47。
实施例11
(E)-2-(甲氧基亚氨基)-2-(2-(((5-((4-硝基苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)乙酸甲酯(Ⅰ11)的制备
按照实施例1方法制备,1.0mmol 5-((4-硝基苯氧基)甲基)-2-巯基-1,3,4-噁二唑和1.05mmol(E)-2-溴甲基-α-甲氧亚胺基苯乙酸甲酯反应3h,得到(E)-2-(甲氧基亚氨基)-2-(2-(((5-((4-硝基苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)乙酸甲酯(Ⅰ11),收率73.9%,稠状液体;1H NMR(400MHz,CDCl3)δ:8.22(d,J=9.2Hz,2H,C6H43,5-H),7.60~7.14(m,4H,C6H4),7.09(d,J=9.2Hz,2H,C6H42,6-H),5.30(s,2H,OCH2),4.35(s,2H,SCH2),4.06(s,3H,NOCH3),3.89(s,3H,OCH3);13C NMR(101MHz,CDCl3)δ:166.16,163.21,162.21,162.05,148.98,142.64,133.63,130.58,130.18,129.87,128.72,128.22,126.03,114.92,63.94,59.92,53.18,34.73。
实施例12
(E)-2-(甲氧基亚氨基)-2-(2-((((5-((2-硝基苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)乙酸甲酯(Ⅰ12)的制备
按照实施例1方法制备,1.0mmol 5-((2-硝基苯氧基)甲基)-2-巯基-1,3,4-噁二唑和1.05mmol(E)-2-溴甲基-α-甲氧亚胺基苯乙酸甲酯反应3h,得到(E)-2-(甲氧基亚氨基)-2-(2-((((5-((2-硝基苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)乙酸甲酯(Ⅰ12),收率24.7%,稠状液体;1H NMR(400MHz,CDCl3)δ:7.87~7.13(m,8H,2×C6H4),5.35(s,2H,OCH2),4.35(s,2H,SCH2),4.06(s,3H,NOCH3),3.88(s,3H,CH3);13C NMR(101MHz,CDCl3)δ:166.23,163.21,162.28,150.60,149.00,140.67,134.24,133.66,130.59,130.21,129.88,128.68,128.18,125.85,122.48,115.95,63.94,61.27,53.19,34.72。
实施例13
(E)-2-(2-(((5-((2,4-二氯苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)-2-(甲氧基亚氨基)乙酸甲酯(Ⅰ13)的制备
按照实施例1方法制备,1.0mmol 5-((2,4-二氯苯氧基)甲基)-2-巯基-1,3,4-噁二唑和1.05mmol(E)-2-溴甲基-α-甲氧亚胺基苯乙酸甲酯反应3h,得到(E)-2-(2-(((5-((2,4-二氯苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)-2-(甲氧基亚氨基)乙酸甲酯(Ⅰ13),收率52.3%,粘稠液体;1H NMR(400MHz,CDCl3)δ:7.57~7.00(m,7H,Ar-H),5.24(s,2H,OCH2),4.35(s,2H,SCH2),4.07(s,3H,NOCH3),3.89(s,3H,OCH3);13C NMR(101MHz,CDCl3)δ:166.04,163.22,162.61,151.96,149.00,133.68,130.59,130.47,130.19,129.87,128.70,128.19,127.97,127.84,124.71,115.86,63.94,61.18,53.18,34.72。
实施例14
(E)-2-(2-(((5-((4-氯-2-甲基苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)-2-(甲氧基亚氨基)乙酸甲酯(Ⅰ14)的制备
按照实施例1方法制备,1.0mmol 5-((4-氯-2-甲基苯氧基)甲基)-2-巯基-1,3,4-噁二唑和1.05mmol(E)-2-溴甲基-α-甲氧亚胺基苯乙酸甲酯反应3h,得到(E)-2-(2-(((5-((4-氯-2-甲基苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)-2-(甲氧基亚氨基)乙酸甲酯(Ⅰ14),收率72.5%;白色固体,m.p.148~150℃;1H NMR(400MHz,CDCl3)δ:7.60~7.15(m,4H,C6H4),7.14~6.84(m,3H,C6H3),5.18(s,2H,OCH2),4.35(s,2H,SCH2),4.06(s,3H,NOCH3),3.88(s,3H,OCH3),2.19(s,3H,CH3);13C NMR(101MHz,CDCl3)δ:165.74,163.27,163.23,154.31,149.01,133.75,130.92,130.57,130.18,129.87,129.35,128.69,128.17,126.84,126.56,112.89,63.93,60.24,53.17,34.71,16.06。
实施例15
噁二唑类化合物的杀菌活性测定
1试验目的
在室内测定了新化合物在供试浓度下对各种病原菌的毒力,初步评价其杀菌活性。
2试验条件
2.1供试靶标
黄瓜灰霉病菌(Botrytis cinerea)、烟草赤星病菌(Alternaria alternata)、小麦赤霉病菌(Gibberella zeae)、油菜菌核病菌(Sclerotonia sclerotiorum)和辣椒疫霉病菌(Phytophythora capsici),以上菌种均保存在冰箱(4-8℃)内,试验前2-3天从试管斜面接种到培养皿内,在适宜温度下培养供试验用。实验用培养基均为马铃薯琼脂培养基(PDA)。
2.2培养条件
供试靶标及试验后靶标的培养条件为温度25±5℃,相对湿度65±5%
2.3仪器设备
烧杯、移液管、量筒、培养皿、高压灭菌锅、恒温生化培养箱等。
3试验设计
3.1试验药剂:实施例化合物。
3.2试验浓度
离体药剂浓度设25mg/L;玉米锈病病菌和小麦白粉病菌药剂浓度设500mg/L。
3.3药剂配制
原药:用万分之一电子天平称取所需量;溶剂:N,N-二甲基甲酰胺(DMF),0.2%;乳化剂:Tween 80,0.1%;
普筛测定:准确称取0.0500g样品,用0.20mLDMF溶解,加入含0.1%Tween80乳化剂的无菌水98.8mL,搅拌均匀,配制成500mg/L浓度溶液备用。
4试验方法
参照《农药生物活性评价SOP》。
黄瓜灰霉病菌、烟草赤星病菌、小麦赤霉病菌、油菜菌核病菌和辣椒疫霉病菌:参照生测标准方法NY/T1156.2-2006,采用含药培养基法:取各500mg/L化合物药液2mL,加入冷却至45℃的38mL的PDA中,制成终浓度为25mg/L的含药培养基平板。然后从培养好的试验病菌菌落边缘取6.5mm直径菌丝块,移至含药培养基上,每处理4次重复。处理完毕,置于28℃的恒温生化培养箱中培养,4天后测量菌落直径,计算生长抑制率。
5杀菌剂活性评价
处理后定期观察记录叶片、植株的发病情况和菌丝生长情况,根据病情指数和菌丝直径,计算防效和抑制率。
噁二唑类化合物的离体杀菌活性(25μg/mL)和活体杀菌活性(500mg/L)如下表1-2所示:
表1-2化合物Ⅰ1~Ⅰ14(25μg/mL)的杀菌活性
化合物Ⅰ14(500mg/L)对小麦白粉病菌和玉米锈病病菌的活体杀菌活性(防效)分别为80%和90%。
活性结果显示:噁二唑类化合物具有良好的杀菌活性,可作为制备杀菌剂在农业上应用。
实施例16
化合物Ⅰ9的单晶的制备
将适量(E)-2-(甲氧基亚氨基)-2-(2-((((5-((4-甲氧基苯氧基)甲基)-1,3,4-噁二唑-2-基)巯基)甲基)苯基)乙酸甲酯(Ⅰ9)溶于乙醇/水(V乙醇:V水=3:1)中,室温下经微孔滤膜过滤后使其缓慢挥发,约6天之后,析出白色晶体。
实施例17
化合物Ⅰ9的单晶测定(化合物Ⅰ9的单晶X衍射)
选取大小为0.12×0.11×0.1mm3的单晶体,在BRUKER SMCRT APEX-Ⅱ1000CCD衍射仪上收集衍射数据,利用石墨单色器单色化了的Mo Kα射线,在273.15K下以ω-扫描方式收集衍射数据,在2.36≤θ≤28.33范围收集9597个数据,其中独立衍射点4931个,可观测点287个。然后运用Bruker的SAINTPLUS程序将数据还原,同时运用SADABS程序进行经验吸收校正。运用SHELXS.97和SHELXL.97程序对晶体结构进行解析和精修。采用全矩阵最小二乘法对所有的非氢原子进行各向异性精修,并对理论加氢及氢原子各向同性热参数进行修正。化合物Ⅰ9的单晶衍射图见图1,分子堆积图见图2,晶体数据与结构参数列入表3,非氢原子坐标和热参数列入表4,部分键长和键角列入表6和7。
表3化合物Ⅰ9的晶体数据和结构参数
由表3可知,化合物Ⅰ9属于三斜晶系,空间群为P-1,每个晶胞中含有2个分子。晶体结构图(图2)表明,整个分子以S-C(11)为中心分布。由键长键角表(表6和表7)可知,C(18)=N(3)双键键长为符合常见碳氮双键键长,其余数据均符和常见键长键角数据。苯环平面C(3)—C(4)—C(5)和噁唑环平面N(1)—C(7)—O(1)通过C(7)—C(4)相连,二面角为9.687°。C(13)—C(12)—C(17)平面和N(2)—O(2)—C(10)平面二面角为87.883°。
表6化合物Ⅰ9的部分键长
表7化合物Ⅰ9的部分键角
表8化合物Ⅰ9的晶体扭转角
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