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CN1216885C - 一种具有生物活性的杂环取代的稠杂环衍生物 - Google Patents

一种具有生物活性的杂环取代的稠杂环衍生物 Download PDF

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CN1216885C
CN1216885C CN 02139609 CN02139609A CN1216885C CN 1216885 C CN1216885 C CN 1216885C CN 02139609 CN02139609 CN 02139609 CN 02139609 A CN02139609 A CN 02139609A CN 1216885 C CN1216885 C CN 1216885C
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triazole
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CN1401648A (zh
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侯仲轲
王晓光
任叶果
雷满香
臧开保
张立杰
黄明智
柳爱平
刘光辉
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Hunan Research Institute of Chemical Industry
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • 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
    • A01N43/74—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 one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

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Abstract

本发明公开了通式(I)所示的杂环取代稠杂环衍生物及其制备方法。Het为：见右下式。本发明化合物具有优异的除草活性，在18.75ga.i/ha的低剂量施用时，对阔叶杂草的防效≥95%，对小麦、玉米、水稻和大豆安全。同时对由真菌引起的疫霉、霜霉有保护和治疗作用。

Description

一种具有生物活性的杂环取代的稠杂环衍生物
技术领域：本发明涉及一种具有生物活性的杂环取代的稠杂环衍生物及其制备方法。
背景技术：我们知道1，2，4，5-四取代苯类化合物是一种原卟啉原氧化酶抑制剂，具有除草活性。其中稠杂环四取代苯类化合物更具生物活性，国外已有不少专利报导。例如：EP420194、USP5084084、USP5127935、USP5322835、USP6323154、DE3922107、JP03,47180、USP5232898、WO96/28442和WO0130782等报导了下列通式的化合物具有除草活性：
Het为2，4-(1H，3H)嘧啶二酮、1，3，4-噻二唑烷酮、1，2，4-三唑啉酮、吡唑、噁(咪)唑烷二酮、酞酰亚胺等。
其中下列化合物(flumioxazin)具有很好的除草活性(20-50ga.i/ha)，已经商品化(Sumisoya)。
flumioxazin
上述各种取代稠杂环衍生物虽具有不同程度的除草活性，但有的对阔叶草的选择性除草效果较差，用于水稻、小麦、玉米、大豆等作物除草时，会对作物本身造成一定的伤害；有的仅适用于作物的芽前处理，对生长期内杂草防效较差；还有的内吸传导作用较差，对大龄杂草防效较差。
发明内容：本发明的目的是提供一种杂环取代的稠杂环衍生物及其制备方法。
本发明的化合物用结构通式(I)表示：
Figure C0213960900091
其中：n＝0，1；X为碳、氮；Y、Z为氧或硫；
R为氢、烷基、烯基、炔基、卤炔基、烷羰基、烷氧羰基、烷胺羰基、磺酰基、氰基、氨基；
R1为氢、卤素、氰基、硝基、氨基、烷基、烷氧基、烷硫基；
Het为2，4-(1H，3H)嘧啶(二)酮时化合物结构式用通式(II)表示；为1，3，4-噻二唑烷酮时化合物结构式用通式(III)表示；为1，2，4-三唑啉酮时化合物结构式用通式(IV)表示；为酞酰环状亚胺时化合物结构式用通式(V)表示；为非环状酞酰亚胺时化合物结构式用通式(VI)表示；
式(II)中：n、X、Y、Z、R、R1同上所述。
R2＝氢、烷基、烯基、炔基、烷氧基、烷硫基、烷羰基、烷氧羰基、氰基、氨基、氰基；较好是烷基和氨基；
R3＝氢、卤素、氰基、氨基、羧基、羟基、烷基、烷氧基、烷氧羰基、甲酰基、氨基甲酰基、肟基甲基、磺酰基；较好是氨基；
Figure C0213960900101
式(III)中：n、X、Y、Z、R、R1同前所述。
Figure C0213960900102
式(IV)中：n、X、Y、Z、R、R1同上所述。
R4＝氢、烷基、烯基、炔基、烷氧基、烷氧羰基、烷胺羰基、烷基磺酰基、三唑基、三唑亚甲基、三唑磺酰基；较好是烷基、炔基、烷胺羰基；
R5＝氢、烷基、烯基、炔基、卤素；较好是烷基；
式(V)中：n、X、Y、Z、R、R1同上所述。
式(VI)中：n、X、Y、Z、R、R1同上所述。
R6＝氢、烷基、烷羰基、烯羰基、炔羰基、芳基羰基；较好是烷羰基、芳基羰基；
R7＝羟基、烷氧基、烷硫基、烷胺基；较好是烷氧基、烷胺基；
经过生物筛选测定，发现本发明通式(I)的杂环取代的稠杂环衍生物具有非常好的生物活性，除草活性优于目前使用的常规除草剂，在18.75ga.i/ha的低剂量施用时，对阔叶杂草有大于95％的优良防效，对玉米、小麦、大豆及水稻安全。式(IV)类化合物还具有优良的杀菌活性，在100ppm浓度下，对霜霉、疫霉等病菌有大于90％的保护和治疗效果。
本发明是通过如下方法来制备的。
1本发明中化合物(II)的制备方法如下：
Figure C0213960900111
中间体(A)在适当溶剂中，加入相应的取代氨基链烯酸酯，加热至30～150℃，搅拌反应1～12h得到(D)。其中较好的溶剂是乙酸；较好的摩尔比为1∶1；较佳的温度是溶剂回流温度；较优的反应时间为3h。
化合物(D)在适当溶剂中加入缚酸剂和卤化物反应得到(II)。其中较好的溶剂是DMF；较好的缚酸剂是K2CO3；较好的摩尔比是(D)∶卤化物∶K2CO3＝1∶2∶3；较佳的温度25℃；较优的反应时间24h。
化合物(D)在上述溶剂和缚酸剂体系中，加入氨化剂得到(II)。其中较好的氨化剂是1-氨基氧基-2，4-二硝基苯。
2本发明中化合物(III)的制备方法如下：
Figure C0213960900121
中间体(A)在适当溶剂中，用硫光气处理得到(H)。较好条件是：在甲苯中用过量一倍的硫光气加热回流4h。
化合物(H)在适当溶剂中，与六氢哒嗪混合，室温搅拌反应1～24h，然后在适当缚酸剂存在下，加入过量的20％光气甲苯或硫光气处理，得到通式(III)化合物。其中，较好溶剂为二氯甲烷；较好摩尔比(H)∶六氢哒嗪＝1∶1；室温搅拌12h；较优缚酸剂为吡啶。
3本发明中化合物(IV)的制备方法如下：
Figure C0213960900131
中间体(A)经重氮化、还原制得肼(K)，较好的条件是：在0℃下用NaNO2重氮化，SnCl2/HCl还原。
化合物(K)在适当溶剂中，先后用醛、异硫氰酸钠及次氯酸钠处理得到(L)其中用醛处理时较好条件是在含12％水的叔丁醇中，使用等摩尔的醛，室温搅拌反应4h；用异硫氰酸钠处理的较优条件是在同样体系中，用等摩尔的异硫氰酸钠，室温搅拌4h；用次氯酸钠处理的较优条件是用两倍的6％的次氯酸钠水溶液处理，室温搅拌18h。
化合物(L)在适当溶剂中，加入缚酸剂，用相应的卤代物处理得到通式(IV)化合物。较好条件是在丙酮中，用K2CO3作缚酸剂，用等摩尔的溴化物处理，加热回流12h。
当化合物(IV)中R为烯基和炔基时，在适当溶剂和催化剂存在下，用N-碘代丁二酰亚胺处理可得到R为碘烯基和碘炔基的通式(IV)化合物。其中较好的溶剂是丙酮，较好的催化剂是AgNO3。
4本发明中化合物(V)的制备方法如下：
中间体(A)在适当溶剂中，用3，4，5，6-四氢邻苯二甲酸酐处理得到(V)，即为通式(V)化合物。较好条件是：在冰乙酸中，用等摩尔的3，4，5，6-四氢邻苯二甲酸酐加热回流4h。
5本发明中化合物(VI)的制备方法如下：
中间体(A)在适当溶剂中用2，3，4，5-四氢邻苯二甲酸酐处理得到(O)，然后酯化/酰胺化得到(P)，最后酰化得到通式(VI)化合物。制备(O)较好条件是在丙酮中，室温搅拌24h；酯化较好条件是用H2SO4作催化剂，加热回流，共沸脱水；酰化较好条件是在催化剂DMAP存在下，用酰卤反应。
依据上述制备方法，合成了一系列本发明的杂环取代的稠杂环衍生物，具体见表1到表5。
Figure C0213960900151
表1
    No     n     X     Y     Z     R     R1     R2     R3
    123456789101112131415161718192021222324     000000000000000000000000     CCCCCCCCCCCCCCCCCCCCCCCC     OOOOOOOOOOOOOOOOOOOOOOOO     OOOOOOOOOOOOOOOOOOOOOOOO   CH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3     HClFCNHClFCNHClFCNHClFCNHClFCNHClFCN     HHHHCH3CH3CH3CH3NH2NH2NH2NH2HHHHCH3CH3CH3CH3NH2NH2NH2NH2     CF3CF3CF3CF3CF3CF3CF3CF3CF3CF3CF3)CF3)CF3CF3CF3CF3CF3CF3CF3CF3CF3CF3CF3)CF3)
  252627282930313233343536373839404142434445464748495051525354555657   000000000000000000000000111111111   CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC   OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO   OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO     NH2NH2NH2NH2NH2NH2NH2NH2NH2NH2NH2NH2CH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CI     HClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCNH     HHHHCH3CH3CH3CH3NH2NH2NH2NH2HHHHCH3CH3CH3CH3NH2NH2NH2NH2HHHHCH3CH3CH3CH3NH2     CF3CF3CF3CF3CF3CF3CF3CF3CF3CF3CF3)CF3)CF3CF3CF3CF3CF3CF3CF3CF3CF3CF3CF3)CF3)CF3CF3CF3CF3CF3CF3CF3CF3CF3
    585960616263646566676869707172737475767778798081828384858687888990     111111111111111111111111111111111     CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC     OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO     OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO   CH2C≡CICH2C≡CICH2C≡CICH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3NH2NH2NH2NH2NH2NH2NH2NH2NH2NH2NH2NH2CH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CH     ClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHCl     NH2NH2NH2HHHHCH3CH3CH3CH3NH2NH2NH2NH2HHHHCH3CH3CH3CH3NH2NH2NH2NH2HHHHCH3CH3     CF3CF3)CF3)CF3CF3CF3CF3CF3CF3CF3CF3CF3CF3CF3)CF3)CF3CF3CF3CF3CF3CF3CF3CF3CF3CF3CF3)CF3)CF3CF3CF3CF3CF3CF3
    919293949596     111111     CCCCCC     OOOOOO     OOOOOO     CH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CH     FCNHClFCN     CH3CH3NH2NH2NH2NH2     CF3CF3CF3CF3CF3)CF3)
表2
    No.     n     X     Y     Z     R     R1
    979899100101102103104105106107108109110111112113114115116117118119120     000000000000000000000000     CCCCCCCCCCCCCCCCCCCCCCCC     OOOO0OOOOOOOOOOOOOOOSSSS     OOOOOOOOOOOOOOOOSSSSOOOO     HHHHCH3CH3CH3CH3CH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHHCH3CH2C≡CICH2C≡CHHCH3CH2C≡CICH2C≡CH     HClFCNHClFCNHClFCNHClFCNFFFFFFFF
    121122123124     0000     NNNN     OOOO     OOOO     HCH3CH2C≡CICH2C≡CH     FFFF
    125126127128129130131132133134135136137138139140141142143144145146147148149150151152     1111111111111111111111111111     CCCCCCCCCCCCCCCCCCCCCCCCNNNN     OOOOOOOOOOOOOOOOOOOOSSSSOOOO     OOOOOOOOOOOOOOOOSSSSOOOOOOOO     HHHHCH3CH3CH3CH3CH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHHCH3CH2C≡CICH2C≡CHHCH3CH2C≡CICH2C≡CHHCH3CH2C≡CICH2C≡CH     HClFCNHClFCNHClFCNHClFCNFFFFFFFFFFFF
Figure C0213960900211
表3
  No.     N   X   Y   Z     R   R1     R4     R5
  153154155156157158159160161162163164165166167168169170171172173174175176177178     00000000000000000000000000   CCCCCCCCCCCCCCCCCCCCCCCCCC   OOOOOOOOOOOOOOOOOOOOOOOOOO   OOOOOOOOOOOOOOOOOOOOOOOOOO     HHHHHHHHHHHHHHHHHHHHHHHHCH3CH3   HClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHCl     CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CH2C≡CICH2C≡CICH2C≡CICH2C≡ClCH2C≡CICH2C≡CICH2C≡CICH2C≡CI1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基CHF2CHF2   CH3CH3CH3CH3C3H7-nC3H7-nC3H7-nC3H7-nCH3CH3CH3CH3C3H7-nC3H7-nC3H7-nC3H7-nCH3CH3CH3CH3C3H7-nC3H7-nC3H7-nC3H7-nCH3CH3
  179180181182183184185186187188189190191192193194195196197198199200201202203204205206207208209210211     000000000000000000000000000000000   CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC   OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO   OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO     CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3NH2NH2NH2NH2NH2NH2NH2NH2NH2NH2NH2   FCNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHClF     CHF2CHF2CHF2CHF2CHF2CHF2CH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CI1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CH2C≡CICH2C≡CICH2C≡CI   CH3CH3C3H7-nC3H7-nC3H7-nC3H7-nCH3CH3CH3CH3C3H7-nC3H7-nC3H7-nC3H7-nCH3CH3CH3CH3C3H7-nC3H7-nC3H7-nC3H7-nCH3CH3CH3CH3C3H7-nC3H7-nC3H7-nC3H7-nCH3CH3CH3
 212213214215216217218219220221222223224225226227228229230231232233234235236237238239240241242243244     000000000000000000000000000000000   CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC   OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO   OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO     NH2NH2NH2NH2NH2NH2NH2NH2NH2NH2NH2NH2NH2CH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CH   CNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCN   CH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CI1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CI1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基   CH3C3H7-nC3H7-nC3H7-nC3H7-nCH3CH3CH3CH3C3H7-nC3H7-nC3H7-nC3H7-nCH3CH3CH3CH3C3H7-nC3H7-nC3H7-nC3H7-nCH3CH3CH3CH3C3H7-nC3H7-nC3H7-nC3H7-nCH3CH3CH3CH3
  245246247248249250251252253254255256257258259260261262263264265266267268269270271272273274275276277     000000000000111111111111111111111   CCCCCCCCCNNNCCCCCCCCCCCCCCCCCCCCC   OOOOOOOSSOOOOOOOOOOOOOOOOOOOOOOOO   OOOOSSSOOOOSOOOOOOOOOOOOOOOOOOOOO  CH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHNH2CH3CH2C≡CHNH2CH2C≡CHCH3CH2C≡CHHHHHHHHHHHHHHHHHHHHHH   HClFCNFFFFFFFFHClFCNHClFCNHClFCNHClFCNHClFCNH 1.2.4-三唑磺酰基1.2.4-三唑磺酰基1 2.4-三唑磺酰基1.2.4-三唑磺酰基CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CI1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基  C3H7-nC3H7-nC3H7-nC3H7-nCH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3C3H7-nC3H7-nC3H7-nC3H7-nCH3CH3CH3CH3C3H7-nC3H7-nC3H7-nC3H7-nCH3CH3CH3CH3C3H7-n
  278279280281282283284285286287288289290291292293294295296297298299300301302303304305306307308309310     111111111111111111111111111111111   CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC   OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO   OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO     HHHCH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3NH2NH2NH2NH2NH2NH2   ClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHCl 1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CI1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1 2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基CHF2CHF2CHF2CHF2CHF2CHF2  C3H7-nC3H7-nC3H7-nCH3CH3CH3CH3C3H7-nC3H7-nC3H7-nC3H7-nCH3CH3CH3CH3C3H7-nC3H7-nC3H7-nC3H7-nCH3CH3CH3CH3C3H7-nC3H7-nC3H7-nC3H7-nCH3CH3CH3CH3C3H7-nC3H7-n
  311312313314315316317318319320321322323324325326327328329330331332333334335336337338339340341342343     111111111111111111111111111111111   CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC   OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO   OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO     NH2NH2NH2NH2NH2NH2NH2NH2NH2NH2NH2NH2NH2NH2NH2NH2NH2NH2CH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CI   FCNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHClF     CHF2CHF2CH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CI1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1 2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.3.4-三唑磺酰基CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2CH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CI  C3H7-nC3H7-nCH3CH3CH3CH3C3H7-nC3H7-nC3H7-nC3H7-nCH3CH3CH3CH3C3H7-nC3H7-nC3H7-nC3H7-nCH3CH3CH3CH3C3H7-nC3H7-nC3H7-nC3H7-nCH3CH3CH3CH3C3H7-nC3H7-nC3H7-n
  344345346347348349350351352353354355356357358359360     11111111111111111   CCCCCCCCCCCCCCNNN   OOOOOOOOOOOOSSOOO   OOOOOOOOOSSSOOOOS   CH2C≡CICH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHNH2CH3CH2C≡CHNH2CH2C≡CHCH3CH2C≡CH   CNHClFCNHClFCNFFFFFFFF     CH2C≡CI1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基1.2.4-三唑磺酰基CHF2CHF2CHF2CHF2CHF2CHF2CHF2CHF2  C3H7-nCH3CH3CH3CH3C3H7-nC3H7-nC3H7-nC3H7-nCH3CH3CH3CH3CH3CH3CH3CH3
Figure C0213960900281
表4
No. n X Y Z R R1
    361362363364365366367368369370371372373374375376377378379380381382383384     000000000000000000000000     CCCCCCCCCCCCCCCCCCCCCNNN     OOOOOOOOOOOOOOOOOOOSSOOO     OOOOOOOOOOOOOOOOSSSOOOOS     HHHHCH3CH3CH3CH3CH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH3CH2C≡CHCH2C≡CHCH3CH2C≡CHCH3CH2C≡CH     HClFCNHClFCNHClFCNHClFCNFFFFFFFF
    385386387388389390391392393394395396397398399400     1111111111111111     CCCCCCCCCCCCCCCC     OOOOOOOOOOOOOOOO     OOOOOOOOOOOOOOOO     HHHHCH3CH3CH3CH3CH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CH     HClFCNHClFCNHClFCNHClFCN
Figure C0213960900301
表5
  No.   n   X   Y   Z     R   R1     R6       R7
  401402403404405406407408409410411412413414415416417418419420421422423424425426   0O000000000000000000000000   CCCCCCCCCCCCCCCCCCCCCCCCCC   OOOOOOOOOOOOOOOOOOOOOOOOOO   OOOOOOOOOOOOOOOOOOOOOOOOOO     HHHHHHHHHHHHCH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH2C≡CICH2C≡CI   HClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHCl     C2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5CO     OCH3OCH3OCH3OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3HNC3H7-iHNC3H7-iHNC3H7-iHNC3H7-iOCH3OCH3OCH3OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3HNC3H7-iHNC3H7-iHNC3H7-iHNC3H7-iOCH3OCH3
  427428429430431432433434435436437438439440441442443444445446447448449450451452453454455456457458459  00000000000000000000O000000000000  CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC  OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO  OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO  CH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHHHHHHHHHHHH   FCNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHClF   C2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO     OCH3OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3HNC3H7-iHNC3H7-iHNC3H7-iHNC3H7-iOCH3OCH3OCH3OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3HNC3H7-iHNC3H7-iHNC3H7-iHNC3H7-iOCH3OCH3OCH3OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3HNC3H7-iHNC3H7-iHNC3H7-i
 460461462463464465466467468469470471472473474475476477478479480481481483484485486487488489490491492  000000000000000000000000000000000  CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC  OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO  OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO     HCH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CH   CNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCN   3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO     HNC3H7-iOCH3OCH3OCH3OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3HNC3H7-iHNC3H7-iHNC3H7-iHNC3H7-iOCH3OCH3OCH3OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3HNC3H7-iHNC3H7-iHNC3H7-iHNC3H7-iOCH3OCH3OCH3OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3
  493494495496   0000   CCCC   OOOO   OOOO  CH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CH   HClFCN   3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO     HNC3H7-iHNC3H7-iHNC3H7-iHNC3H7-i
  497498499500501502503504505506507508509510511512513514515516517518519520521522   11111111111111111111111111   CCCCCCCCCCCCCCCCCCCCCCCCCC   OOOOOOOOOOOOOOOOOOOOOOOOOO   OOOOOOOOOOOOOOOOOOOOOOOOOO     HHHHHHHHHHHHCH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH2C≡CICH2C≡CI   HClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHCl   C2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5CO     OCH3OCH3OCH3OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3HNC3H7-iHNC3H7-iHNC3H7-iHNC3H7-iOCH3OCH3OCH3OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3HNC3H7-iHNC3H7-iHNC3H7-iHNC3H7-iOCH3OCH3
  523524525526527528529530531532533534535536537538539540541542543544545546547548549550551552553554555   111111111111111111111111111111111   CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC   OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO   OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO   CH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHHHHHHHHHHHH   FCNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHClF   C2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5COC2H5CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO     OCH3OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3HNC3H7-iHNC3H7-iHNC3H7-iHNC3H7-iOCH3OCH3OCH3OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3HNC3H7-iHNC3H7-iHNC3H7-iHNC3H7-iOCH3OCH3OCH3OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3HNC3H7-iHNC3H7-iHNC3H7-i
 556557558559560561562563564565566567568569570571572573574575576577578579580581582583584585586587588   111111111111111111111111111111110   CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC   OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO  OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO     HCH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CICH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CH   CNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCNHClFCN  3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO     HNC3H7-iOCH3OCH3OCH3OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3HNC3H7-iHNC3H7-iHNC3H7-iHNC3H7-iOCH3OCH3OCH3OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3HNC3H7-iHNC3H7-iHNC3H7-iHNC3H7-iOCH3OCH3OCH3OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3OCH2CH2OCH3
  589590591592   1111   CCCC   OOOO   OOOO   CH2C≡CHCH2C≡CHCH2C≡CHCH2C≡CH   HClFCN  3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO3-F-C6H4CO     HNC3H7-iHNC3H7-iHNC3H7-iHNC3H7-i
具体实施方式：
以下结合制备和应用实施例，对本发明做进一步说明：
实施例一：制备本发明除草剂3-(5-氟-3-炔丙基-1，3-苯并噁唑酮-6-基)-6-三氟甲基-1，-甲基-2，4(1H，3H)嘧啶二酮(NO.43)。
化学反应式：
取3-炔丙基-5-氟-6-氨基苯并噁唑酮2.06g，(N，N-二甲胺羰基)胺基4，4，4-三氟甲基丁烯酸乙酯2.54g，冰乙酸20ml于反应瓶中，加热至回流，搅拌反应2h。冷却，倒入到200ml冰水中，析出固体，过滤，水洗，干燥得中间体。将此中间体溶于20mlDMF中，加入2,76gK2CO3和2.13g碘甲烷，室温搅拌12h。然后倒入到20ml冰水中过滤出固体，水洗，干燥，柱分，得到(NO.43)2.53g，收率66％。
NMR：3.02(m，1H，嘧啶环H)  3.47(S，3H，N-CH3)  4.75(d，2H，CH2)6.37(S，1H，C≡CH)  7.34(d，2H，苯环H)
同法可制备3-(5-氟-3-甲基-1，3-苯并噁唑酮-6-基)-6-三氟甲基-1-甲基-2，4(1H，3H)嘧啶二酮(NO.19)及其类似化合物。
实施例二：制备本发明除草剂9-(5-氟-3-炔丙基-1，3-苯并噁唑酮-6-基)-8-硫-1，6-二氮双环[4，3，0]壬酮(NO.111)
反应式：
取3-炔丙基-5-氟-6-氨基苯并噁唑酮2.06g，溶于20ml甲苯中，慢慢加入2.30g硫光气，加热回流2h。冷却，用N2赶尽余气，脱溶得硫异氰酸酯。
在另一个反应瓶中加入0.86g六氢哒嗪溶于10ml无水乙醇中，10度以下，慢慢缓加上述硫异氰酸酯溶于15ml二氯甲烷中，滴加完毕，室温搅拌4h。用二氯甲烷稀释，水洗，干燥，脱溶，残物溶于20ml二氯乙烷中，室温下慢慢滴加20％光气甲苯10ml。然后室温搅拌12h。加二氯乙烷稀释，水洗，干燥，脱溶，柱分，得到NO.111 2.42g，收率68％。
NMR：1.76(m，4H)  2.32(m，4H)  4.70(d，2H)  6.39(S，1H)  7.35(d，2H)
实施例三：制备本发明除草剂N-(5-氟-3-炔丙基-1，3-苯并噁唑酮-6-基)环己-1-烯-1，2-二羧酰亚胺(NO.375)。
反应式：
Figure C0213960900381
取3-炔丙基-5-氟-6-氨基苯并噁唑酮2.06g，溶于20ml冰乙酸中，加入1.67g3，4，5，6-四氢邻苯二甲酸酐，然后加热回流4h。冷却，倾入到200ml冰水中，过滤出固体，水洗，干燥，脱溶得(NO.375)3.00g，收率88％。
NMR：3.68(m，4H)  3.79(m，4H)  4.72(d，2H)  6.31(S，1H)  7.30(d，2H)
实施例四：制备本发明杀菌剂1-(5-氟-3-碘炔丙基-1，3-苯并噁唑酮-6-基)-3-正丙基-4-碘丙炔基三唑啉酮(NO.239)。
反应式：
Figure C0213960900382
取3-炔丙基-5-氟苯并噁唑酮肼2.21g，溶于40ml叔丁醇∶水＝88∶12的混合溶剂中，10度以下慢慢滴加0.72g正丁醛，然后室温搅拌2h。接着往反应瓶中慢慢加入0.97gNaSCN溶于2ml水的浆状物，加完后，室温搅拌4h。接着往反应中慢慢滴加20ml 6％NaClO水溶液，滴加完毕，室温搅拌反应12h。倾入到500ml冰水中，析出固体，过滤，水洗，干燥，脱溶，残物溶于20ml丙酮中，加入4.5gN-碘代丁二酰亚胺，0.2g AgNO3，室温搅拌24h。过滤，脱溶，柱分，得到(NO.239)2.18g，收率34％。
NMR：0.98(m，3H)  1.21(m，2H)  2.06(m，2H)  4.70(d，2H)  7.32(d，2H)
应用实施例
例一：盆栽除草试验
(1)试剂
准确称取样品，用适宜的溶剂溶解后，加少量乳化剂，再加蒸馏水定容至10ml采用适当喷雾机喷洒，折合单位面积药量为18.75ga.i/ha。
(2)试材
双子叶选用藜(Chenopodium album)、苘麻(Abutilon theophrast)i、凹头苋(Amaranthus ascedense)，单子叶选用马唐(Digitaria sanguinalis)、稗草(Echinochloa crus-galli)、狗尾草(Setaria viridis)。
(3)试材植株的培育
在截面积64cm2的塑料盆钵中定量装土，压平，浇  透水，选取籽粒饱满、大小一致的马唐、稗草、狗尾草、苘麻、藜、凹头苋种子，分单、双子叶植物分钵栽种，各占钵面积的1/3，覆1cm厚细土并淋水，置于温室培养。待单子叶试材长至1叶1心期、双子叶试材长至2片真叶期，用药液进行苗后茎叶喷雾处理，试材播种次日进行苗前土壤处理。随后放回温室。
(4)测试
15天后目测地上部生长情况，计算生长抑制率，生长抑制率(％)＝100(对照株高-处理株高)/对照株高。根据生长抑制率进行除草活性分级：A级生长抑制率＞90％  B级  生长抑制率75～90％  C级  生长抑制率50～75％  D级  生长抑制率  小于50％。
本发明的部分化合物如化合物NO.43 19 111 375等分别以18.75gai./ha的施用量对盆栽试材植株芽后茎叶处理，抑制毒力效果见表11。
                    表11：盆栽除草试验
样品      马唐     稗草    狗尾草      藜      苘麻    凹头苋
NO.43      D        D        D         C        B        A
19         D        D        D         A        A        A
111        D        D        D         B        B        A
375        D        D        D         C        B        B
如表11可知：测试的四个化合物在18.75ga.i/ha的低剂量下对阔叶杂草均有一定的防效，其中化合物NO.19在18.75ga.i/ha的低剂量下对阔叶杂草有很好的防效。但在18.75ga.i/ha的低剂量下对禾本科杂草无效。
例二：作物安全性试验。
选取籽粒饱满、大小一致的水稻Oryza sativa、小麦Triticum aestivum、玉米Zea mays、高粱sorghum vulgare、大豆Glycine max和油菜Brassicacampestris种子，用0.1％HgCl2消毒5min，后用蒸馏水浸种12h，滤出放入小瓷盘(内放润湿吸水纸)中在25℃植物生长箱内催芽24h，取大小和芽长一致的种子10粒，播于64cm2定量装土的塑料盆钵中，覆1cm厚细土并淋水，置于温室培养。待单子叶试材长至1叶1心期、双子叶试材长至2片真叶期，用150、75、37.5、18.75、9.375、4.6875ga.i./ha药液进行苗后茎叶喷雾处理，试材播种次日进行苗前土壤处理，分别以喷雾溶剂和清水为对照，两次重复，处理试材置于温室培养，15d后观察作物受害症状，目测地上部生长抑制率。生长抑制率(％)＝100(对照株高-处理株高)/对照株高，根据生长抑制率估测作物1C’10值，并结合杂草IC90值，按IC’10/IC90计算选择性指数(Z)，安全性等级标准：A∶Z＞4 B 2＜Z＜4  C Z＜2，B级以上可视为安全。
本发明的化合物(NO.19)对作物的安全性实验结果见表12
                             表12：安全性实验
样品    剂量ga.i/ha    水稻     小麦     油菜     玉米     高梁     大豆
            150         C        A        C        A        C        C
            75          C        A        C        A        C        C
NO.19       37.5        B        A        C        A        C        B
            18.75       A        A        C        A        C        A
            9.375       A        A        C        A        C        A
            4.6875      A        A        B        A        C        A
如表12可见：化合物NO.19在150ga.i/ha的高剂量下对小麦和玉米安全。在18.75ga.i/ha的较低剂量下对水稻和大豆安全。但对油菜和高梁甚至在4.6875ga.i/ha的低剂量下也不安全。
例三：杀菌试验。
在温室盆栽植物试材，生长至一定时期备用。待测化合物原药用一定量的DMF溶解，用水稀释至一定浓度。喷雾施药到植物试材上，以喷清水的试材为对照，喷药完毕后，将植物试材置于阴凉处风干，24小时后进行病害接种。接种后，将植物试材放在恒温恒湿的培养箱中，使病原菌的以继续侵染。接种数天后，当对照充分发病时，进行病害的发病调查。杀菌活性等级如下：A级：抑菌率＞90％；B级：抑菌率75～90％；C级：抑菌率50～75％；D级：抑菌率小于50％。
本发明的部分化合物如化合物NO.239以100ppm浓度对盆栽试材植株芽后茎叶处理，抑菌效果见表13。
                        表13：抑菌实验
样品    烟草疫霉  辣椒疫霉  黄瓜疫霉  番茄晚疫  马铃薯晚疫  葡萄霜霉
NO.239    A          A          A         A          A         A
由表13可知：新化合物NO.239对各种真菌病害如疫霉霜霉有较好的抑菌作用。

Claims (4)

1 一种杂环取代的稠杂环衍生物，其特征在于它具有如下结构通式(I)
Figure C021396090002C1
Het为：
Figure C021396090002C2
n＝0；X为碳；Y、Z为氧；
R为氢、烷基、烯基、炔基、卤炔基；
R1为卤素；
R4＝氢、炔基；
R5＝烷基；
其中通式(I)中当Het是：
Figure C021396090003C1
时所得的化合物用通式(III)表示：
Figure C021396090003C2
当Het是：
时所得的化合物用通式(IV)表示：
Figure C021396090003C4
当Het是：
时所得的化合物用通式(V)表示：
2 根据权利要求1所述的杂环取代的稠杂环衍生物的制备方法，其特征在于用如下合成路线得到；
通式(III)化合物的反应路线是：
中间体(A)在甲苯溶剂中，用过量一倍的硫光气加热回流4h得到(H)；化合物(H)在二氯甲烷溶剂中，与六氢哒嗪混合，摩尔比(H)∶六氢哒嗪＝1∶1，室温搅拌反应1～24h，然后在适当缚酸剂吡啶存在下，加入过量的20％光气甲苯或硫光气处理，得到通式(III)化合物；
通式(IV)化合物的反应路线是：
Figure C021396090005C2
中间体(A)经重氮化、还原制得肼(K)；化合物(K)在含12％水的叔丁醇中，使用等摩尔的醛，室温搅拌反应4h；再加入等摩尔的异硫氰酸钠室温搅拌4h；再用两倍的6％的次氯酸钠水溶液处理，室温搅拌18h，得到化合物(L)；化合物(L)在丙酮溶剂中，加入缚酸剂K2CO3，用等摩尔的溴化物处理，加热回流12h，得到通式(IV)化合物；
通式(V)化合物的反应路线是：
Figure C021396090006C1
中间体(A)在冰乙酸溶剂中，用等摩尔的3，4，5，6-四氢邻苯二甲酸酐加热回流4h得到通式(V)化合物。
3 一种稠杂环化合物，其结构式如下：
4 根据权利要求1和3所述的杂环取代的稠杂环衍生物，其特征在于具有除草活性，在18.75ga.i/ha的剂量下，对阔叶杂草的防效≥95％，并对小麦、玉米、水稻、大豆作物安全；同时对由真菌引起的疫霉、霜霉有保护和治疗作用。
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