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CN1049344A - 氮杂环戊烷衍生物及其制备方法和农业园艺作物杀真菌剂 - Google Patents

氮杂环戊烷衍生物及其制备方法和农业园艺作物杀真菌剂 Download PDF

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CN1049344A
CN1049344A CN90106933A CN90106933A CN1049344A CN 1049344 A CN1049344 A CN 1049344A CN 90106933 A CN90106933 A CN 90106933A CN 90106933 A CN90106933 A CN 90106933A CN 1049344 A CN1049344 A CN 1049344A
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杉浦久雄
田中敏房
西村孝
横山修司
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Abstract

本文介绍式I氮杂环戊烷衍生物及其制备方法 和含有该衍生物作为活性成分的农业、园艺作物的杀 真菌剂，所述式(I)如下：

Description

氮杂环戊烷衍生物及其制备 方法和农业园艺作物杀真菌剂
本发明涉及氮杂环戊烷衍生物及其制备方法，还涉及含有这类氮杂环戊烷衍生物作为活性成分的农业、园艺作物的杀真菌剂。
本发明的氮杂环戊烷衍生物作为农业、园艺作物的杀真菌剂是相当新的化合物，尚不曾发现有类似的化合物。
本发明的目的是提供能有效用作农业、园艺作物杀真菌剂的新的氮杂环戊烷衍生物。
式(I)即是本发明的氮杂环戊烷衍生物：式中：
R1代表氢原子，含1至10个碳原子的烷基或环烷基；R2代表氢原子，含1至18个碳原子的烷基，链烯基，炔基，烷氧基烷基，链烯基氧基烷基，烷硫基烷基，烷氧基羰基，呋喃基或噻嗯基，或苯基烷基，苯氧基烷基，苯硫基烷基，苯基烷氧基烷基，吡啶氧基烷基，苯氧基苯氧基烷基，苄氧基苯氧基烷基或吡啶氧基苯氧基烷基，上述苯环或吡啶环可被卤素原子、烷基烷氧基、卤代烷基或卤代烷氧基取代；或者R1和R2可彼此和与之键合的碳原子结合形成由式(II)代表的基团：
Figure 9010693300082
式中R6代表氢原子，卤素原子或低级烷基；R7代表氢原子，烷基，链烯基，烷氧基，链烯氧基或烷硫基，或苯基，苯氧基，苄氧基或吡啶硫基，这些苯环或吡啶环可被囟素原子、烷基、烷氧基或卤代烷基取代；n是整数1至3；
R3代表氢原子或低级烷基；
R4代表氢原子，低级烷基，苯基或苄基，或R和R可彼此和与之键合的碳原子结合形成由下式代表的基团：
Figure 9010693300091
式中m是整数4或5；
R5代表氢原子，低级烷基或苯基，或者R4和R5可彼此和与之键合的碳原子结合形成由下式代表的基团：
Figure 9010693300092
式中1代表整数3或4；以及
Z代表氧原子或硫原子。
在式(I)中，由R1代表的烷基包括含1至10个碳原子的烷基、例如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基和癸基，这些基团中优选的是甲基。环烷基包括含有3至6个碳原子的环烷基，例如环丙基、环戊基和环己基。
除上述R1定义的烷基外，由R2代表的烷基可包括含有1至18个碳原子的直链或支链烷基，例如十一基、十二基、十四基、十六基、十八基、1-乙基戊基和3-甲基己基，这些基团中，优选的是含有5至12个碳原子的直链烷基。链烯基可包括含有1至8个碳原子的链烯基，例如烯丙基、2-丁烯基、2-戊烯基和1-丁基-2-丁烯基。炔基可包括2-丙炔基。烷氧基烷基可包括甲氧基乙基、乙氧基甲基和十二氧基甲基。链烯基氧基烷基可包括烯丙氧乙基。烷硫基烷基可包括甲硫基乙基和十二硫基甲基。烷氧基羰基可包括甲氧基羰基和乙氧基羰基。苯基烷基、苯氧基烷基、苯硫基烷基、苯基烷氧基烷基、吡啶氧基烷基、苯氧基苯氧基烷基、苄氧基苯氧基烷基和吡啶氧基苯氧基烷基的所有烷基部分是含有1至5个碳原子的烷基，在苯基烷基中最优选者是C3烷基。当用卤素原子取代苯环或吡啶环时，可提及的卤素原子是氯、溴、氟和碘，烷基可包括含有1至6个碳原子的烷基，例如甲基、乙基、丙基、异丙基、丁基、戊基和己基。烷氧基可包括含有1至4个碳原子的烷氧基，例如甲氧基、乙氧基、丙氧基、异丙氧基和丁氧基。卤代烷基可包括三氟甲基。卤代烷氧基可包括2，2，2-三氟乙氧基。
当R6代表卤素原子时，最优选者是氯，当代表低级烷基时，最好是甲基。
当R7代表烷基时，最好是含有1至6个碳原子的烷基，例如甲基、乙基、丙基、丁基、戊基和己基。链烯基可包括烯丙基和2-丁烯基。烷氧基可包括含有1至6个碳原子的烷氧基，例如甲氧基、乙氧基、丙氧基、丁氧基、戊氧基和己氧基。链烯基氧基可包括烯丙氧基。烷硫基可包括甲硫基、乙硫基和戊硫基。苯基、苯氧基、苄氧基和吡啶氧基的苯环或吡啶环上的取代基可包括上述R2所定义的那些取代基。
式(I)化合物的优选基团如下所述：R1是氢原子或甲基，R2是含有5至12个碳原子的直链烷基，其中烷基部分是1至5个碳原子的苯基烷基，最好是在苯基的对位含有氯或溴原子以及含有3碳烷基的苯基烷基，或苯氧基烷基，所述苯基可以未被取代或被低级烷基或烷氧基取代。由R1、R2和与之键合的碳原子结合形成的式(II)基团中，R6是氢原子或氯原子，R7是氢原子、含有4至6个碳原子的烷基、含有4至6个碳原子的烷氧基、烯丙氧基，或者可被卤素原子取代的苯基、苯氧基或苄基，n是2，R3和R4各自为甲基或由R3、R4和与之键合的碳原子结合形成的或 R5是氢原子，Z是氧原子。
表1中举例说明本发明式(I)所包括的化合物。表1
Figure 9010693300113
                               表1化合物
    R1     R2                  R3       R4        R5     Z      物理性质No.1       H    C6H13-n                CH3      CH3       H       O    nD 27  1.48302       H    C7H15-n                CH3      CH3       H       O    nD 26  1.47783       H    C8H17-n                CH3      CH3       H       O    nD 26  1.48354       H    C9H19-n                CH3      CH3       H       O    nD 26  1.47685       H    C10H21-n               CH3      CH3       H       O6       H    C11H23-n               CH3      CH3       H       O    nD 27  1.48147       H                  CH3       CH3       H       O    nD 26  1.51038       H    
Figure 9010693300122
             CH3       CH3       H       O    nD 25  1.48739       H    -CH(C2H5)C4H9     CH3       CH3       H       O    nD 26  1.482810      H      CH3      CH3       H       O化合物
   R1        R2                         R3       R4        R5     Z     物理性质No.11    CH3    C6H13-n                       CH3       CH3       H       O    nD 26  1.486912    CH3    C7H15-n                       CH3       CH3       H       O    nD 26  1.488013    CH3    C8H17-n                       CH3       CH3       H       O    nD 27  1.487214    CH3    C9H19-n                       CH3       CH3       H       O    nD 26  1.486415    CH3    C10H21-n                      CH3       CH3       H       O    nD 26  1.483316    CH3    C12H25-n                      CH3       CH3       H       O17    C2H5  C7H15-n                      CH3       CH3       H       O    nD 26  1.494518  C5H11-n  C5H11-n                      CH3       CH3       H       O    nD 27  1.490219  C7H15-n  C7H15-n                      CH3       CH3       H       O    nD 26  1.482220    CH3    
Figure 9010693300131
           CH3      CH3        H       O    nD 26  1.526421    CH3    
Figure 9010693300132
          CH3      CH3        H       O    nD 20  1.510322    CH3    
Figure 9010693300133
  CH3      CH3        H       O    nD 20  1.5196化合物
   R1           R2               R3   R4   R5 Z    物理性质No.23    CH3          CH3  CH3  H   O  nD 25  1.515224    CH3  
Figure 9010693300142
        CH3  CH3  H   O  nD 25  1.504425    CH3          CH3  CH3  H   O  nD 24  1.518226    CH3  
Figure 9010693300144
      CH3  CH3  H   O  nD 24  1.509627    CH3  
Figure 9010693300145
       CH3  CH3  H   O  nD 23  1.504628    CH3  
Figure 9010693300146
     CH3  CH3  H   O  nD 25  1.513529    CH3      CH3  CH3  H   O  nD 27  1.524630    CH3     CH3  CH3  H   O  nD 24  1.494531    CH3  
Figure 9010693300149
  CH3  CH3  H   O  nD 25  1.509232    CH3  
Figure 90106933001410
  CH3  CH3  H   O  nD 24  1.516733    CH3  
Figure 90106933001411
  CH3  CH3  H   O  nD 24  1.503834    CH3  
Figure 90106933001412
      CH3  CH3  H   O  nD 24  1.5092化合物
  R1            R2                     R3   R4    R5  Z     物理性质No.35    CH3  
Figure 9010693300151
             CH3  CH3    H    O36    CH3  
Figure 9010693300152
         CH3  CH3    H    O   nD 29  1.540637    CH3  
Figure 9010693300153
         CH3  CH3    H    O   nD 26  1.529338    CH3           CH3  CH3    H    O   nD 25  1.501639    CH3             CH3  CH3    H    O   nD 20  1.500340    CH3        CH3  CH3    H    O   nD 20  1.494341    CH3          CH3  CH3    H    O   nD 24  1.526942    CH3  
Figure 9010693300158
   CH3  CH3    H    O   nD 24  1.512143    CH3  
Figure 9010693300159
         CH3  CH3    H    O   nD 25  1.516444    CH3  
Figure 90106933001510
         CH3  CH3    H    O   nD 25  1.502145    CH3            CH3  CH3    H    O   nD 25  1.517846    CH3  
Figure 90106933001512
         CH3  CH3    H    O   nD 25  1.5172化合物
   R1                  R2                       R3  R4   R5 Z    物理性质No.47    CH3       
Figure 9010693300161
       CH3  CH3   H  O  nD 24  1.505148    CH3       
Figure 9010693300162
          CH3  CH3   H  O  nD 21  1.510249    CH3       
Figure 9010693300163
          CH3  CH3   H  O  nD 25  1.501650    CH3       
Figure 9010693300164
                CH3  CH3   H  O  m.p   91-93℃51    CH3                        CH3  CH3   H  O  m.p   123～125℃52    CH3           -CH2-S-C12H25-n              CH3  CH3   H  O  nD 25  1.505053    CH3       
Figure 9010693300166
          CH3  CH3   H  O  nD 27  1.526354    CH3       
Figure 9010693300167
              CH3  CH3   H  O  nD 25  1.539255    CH3                      CH3  CH3   H  O  nD 25  1.536456                              CH3  CH3   H  O  nD 20  1.489257    
Figure 90106933001610
                         H      CH3   H  O  nD 25  1.498058    CH3         
Figure 90106933001611
         H      C2H5 H  O  nD 28  1.5457化合物
   R1        R2                       R3     R4     R5  Z   物理性质No.59    CH3    C8H17-n                     H       C2H5   H    O  nD 28  1.487660    CH3    C6H13-n                     H       C3H7-n  H    O  nD 26  1.487061    CH3    C6H13-n                     H          H   O  nD 28  1.529562    CH3    C9H19-n                          O  nD 26  1.513563    CH3    C8H17-n                                 H  O  nD 20  1.490164    CH3           H  O  m.p    146～150℃65  
Figure 9010693300175
                 
Figure 9010693300176
       H  O nD 26  1.516466  
Figure 9010693300177
                  CH3    CH3      H  O  nD 26  1.483667  
Figure 9010693300178
                     CH3    CH3       H  O  nD 24  1.548968  
Figure 9010693300179
                   CH3    CH3       H  O  nD 25  1.510469  
Figure 90106933001710
        CH3    CH3       H  O  nD 25  1.497070  
Figure 90106933001711
            CH3    CH3       H  O  m.p     130～133℃化合物
     R1        R2                    R3     R4     R5Z      物理性质No.71  
Figure 9010693300181
             CH3    CH3     H  O   m.p    105～106℃72   
Figure 9010693300182
               CH3    CH3     H  O   nD 26 1.496773  
Figure 9010693300183
               CH3    CH3     H  O   nD 24 1.515274  
Figure 9010693300184
               CH3    CH3     H  O75  
Figure 9010693300185
                  CH3    CH3     H  O   nD 26 1.487276  
Figure 9010693300186
                CH3    CH3     H  O   nD 20 1.518177  
Figure 9010693300187
            CH3    CH3     H  O   nD 22 1.543978  
Figure 9010693300188
                          H    H  O   m.p    93～94℃79                        H   C3H7-n      H  O   nD 26 1.520880                      
Figure 90106933001812
 O   nD 22  1.552581                                   H  O  m.p    155～158℃82                     
Figure 90106933001816
            H  O  nD 21 1.5116化合物
   R1           R2                     R3    R4     R5 Z      物理性质No.83    CH3                     H      H       H    S    nD 22  1.571484    CH3      --COOC2H5                 H      H       H    S    nD 22  1.530385    
Figure 9010693300192
       CH3   CH3   H    S86             
Figure 9010693300193
                H       H      H    S   m.p     90～93℃87    CH3                   CH3   CH3    H    O  nD 25   1.505488    CH3     -(CH2)2CH(CH3)C3H7      CH3   CH3   H    O   nD 26   1.485089    CH3    
Figure 9010693300195
      CH3   CH3   H    O  nD 24   1.514090    CH3    
Figure 9010693300196
        CH3   CH3    H    O  m.p     78～81℃91    CH3    
Figure 9010693300197
  CH3    O  nD 24   1.501192    CH3      C8H17-n                     CH3        O  nD 25   1.516693    CH3    
Figure 90106933001910
   CH3   CH3      H   O   nD 25  1.514494    CH3    
Figure 90106933001911
   CH3   CH3      H   O   nD 22  1.5287化合物
    R1          R2              R3      R4    R5Z        理性质No.95     CH3  
Figure 9010693300201
       CH3    CH3   H   O    nD 22 1.541996     CH3         CH3    CH3   H   O   m.p    124～126℃97     CH3  
Figure 9010693300203
      CH3    CH3   H   O   nD 28  1.534898     CH3  
Figure 9010693300204
       CH3    CH3   H   O  m.p     68～70℃99     CH3          CH3    CH3   H   O  m.p     88～90℃100    CH3  
Figure 9010693300206
       CH3    CH3   H   O  m.p     98～100℃101    CH3  
Figure 9010693300207
     CH3    CH3   H   O  m.p     81～83℃102    CH3  
Figure 9010693300208
    CH3    CH3   H   O  m.p     62～65℃103    CH3  
Figure 9010693300209
    CH3    CH3   H   O   nD 26  1.5215104    CH3       CH3    CH3   H   O   nD 25  1.5020105    CH3     CH3    CH3   H   O   0nD 25 1.5147106    CH3             CH3    CH3   H   O   0nD 25 1.4988化合物
     R1              R2              R3     R4     R5Z    物理性质No.107     CH3  
Figure 9010693300211
     CH3     CH3    H  O     m.p72～74℃108    
Figure 9010693300212
  CH3     CH3   H  O     m.p67～70℃109           
Figure 9010693300213
          CH3     CH3    H  O     m.p115～116℃110                   CH3     CH3    H  O     m.p53～56℃111        
Figure 9010693300215
     CH3     CH3    H  O     m.p174～176℃112                  CH3     CH3    H  O     m.p.178～180℃113           
Figure 9010693300217
       CH3     CH3    H  O     m.p177～179℃114           
Figure 9010693300218
      CH3     CH3    H  O     m.p100～102℃
上述化合物中，最优选的是：2-甲基-2-(对氯苯基丙基)-3-(1-咪唑基羰基)-5，5-二甲基-1，3-噁唑烷(化合物No.22)和2-甲基-2-(对溴苯基丙基)-3-(1-咪唑基羰基)-5，5-二甲基-1，3-噁唑烷(化合物No.23)。
本发明式(I)化合物的制备方法：在碱存在下，使式III化合物与咪唑反应，反应路线如下所示：
Figure 9010693300221
本反应可采用的反应介质，例如甲苯，丙酮，甲基乙基酮，乙腈，二甲基甲酰胺，二甲亚砜和二噁烷。
所采用的碱，例如碳酸钾，碳酸钠，氢氧化钠，三乙胺和吡啶。
本反应中每mole氨基甲酰基氯所用的咪唑量优选为0.5至5.0mole，最好为1.0至2.0mole。反应温度优选为20至150℃，最好为50至100℃。反应时间优选为10分钟至8小时，最好为1至3小时。使仲胺(IV)与碳酰氯(V)或三氯甲基氯甲酸酯(VI)反应可得到式(III)化合物，反应式如下：
Figure 9010693300222
式(I)化合物显示出极佳的杀真菌作用，还对因植物病原菌引起作物病害的预防和治疗显示出极佳的效果。例如，对下述病害特别有效：白粉病，锈斑，眼点病，水稻条纹叶枯病，稻瘟病，胡麻斑病，黑斑病，“恶苗病”和斑点病。此外，它们防治对由现有农业化学药品耐药菌引起的病害也极有效，因此，它们具有许多优点。
当本发明的式(I)化合物用作农业、园艺作物杀真菌剂时，可采用下述剂型：粉剂，湿润剂，乳化剂，颗粒，细粒和其它通常采用的剂型。本发明所采用的载体可以是固体或液体，并未规定特殊载体，可采用的适宜载体包括固体载体(如各种粘土，高岭土，白土，硅藻土，滑石粉和硅石)和液体载体，所述液体载体包括用于本发明化合物的溶剂和即使不是溶剂，但加入后可分散或溶解化合物的有效成分的那些载体。例如这类液体载体可包括苯，二甲基，甲苯，煤油，醇类，酮类，二甲亚砜和二甲基甲酰胺。适宜的表面活性剂和其它辅剂(例如分散剂和固定剂)经过混合，可以用作水溶液或乳化剂。另外，本发明化合物可以混合其它杀菌剂、杀虫剂，除莠剂和节省劳力的植物生长调节剂，获得可靠的预防效果。实施例
以下实施例用来说明本发明并非限制本发明。制备实施例中简单提及“份”，意即“按重量计的份”。实施例1
2-甲基-2-正己基-3-(1-咪唑基羰基)-5，5-二甲基-1，3-噁唑烷(化合物No.11)
将2.6g(0.01mole)2-甲基-2-正己基-3-氯羰基-5，5-二甲基-1，3-！唑烷，1.0g(0.015mole)咪唑和2.1g(0.015mole)碳酸钾的混合物与30ml作为溶剂的二甲基甲酰胺(DMF)于50至60℃搅拌1小时，反应完成后，加入水，然后用甲苯提取该混合物，用水洗涤甲苯层，干燥缩合，然后用柱层析纯化，由此得到2.7g浅黄色的标题化合物。实施例2
2，2-二-正庚基-3-(1-咪唑基羰基)-5，5-二甲基-1，3-！唑烷(化合物No.18)
将3.0g(0.01mole)2，2-二-正庚基-3-氯羰基-5，5-二甲基-1，3-！唑烷，1.0g(0.015mole)咪唑和2.1g(0.015mole)碳酸钾的混合物与30ml作为溶剂的DMF于60至70℃搅拌3小时，反应完成后，加入水，然后用甲苯提取该混合物，用水洗涤甲苯层，干燥缩合，然后用柱层析纯化，由此得到2.8g浅黄色的标题化合物。实施例3
将10份化合物NO.13的化合物、69.75份高岭土、18.00份白碳、1.80份NEOPELEX(商品名)和0.45份DEMOL EP(商品名)均匀混合，磨碎，得到细粒湿润剂。当这一物料用作叶用涂铺剂时，应稀释200至2000倍后涂铺到植物上。此外，当用作种子消毒剂时，应稀释至20至1000倍，并且稻种要浸渍处理10分钟至48小时。实施例4
将60份化合物NO.21的化合物、23份甲基乙基酮、17份聚氧乙烯壬基苯基醚混合并溶解，得到乳化液。当这一乳化液用作叶用涂铺剂时，应稀释500至4000倍后涂铺到植物上。此外，当用作种子消毒剂时，应稀释到10至400倍，并且稻种要浸渍处理10分钟至48小时，或者用0.5至1％(以稻种重量计)的量撒粉处理。实施例5
将2份No.22的化合物和98份白土均合混合，磨碎，得到粉剂。实施例6
将15份水加到5份No.23的化合物、25份膨润土和27份白碳的混合物中，捏和，制粒，然后用流化床干燥器干燥，得到颗粒。实施例7
对稻瘟病的控制活性试验(预防效果)
采用一个直径5cm塑料缽，对温室土壤培育的1.5叶发育阶段稻(稻种：Nipponbare)，每次涂铺10ml按实施例3制备的并已稀释到预定浓度的湿润剂，一天后，喷雾接种稻瘟病孢子混悬液，5天后，测定每片有病害叶的稻瘟病孢子数。
测定结果以5至0共计6个等级表示。无斑点的为5，患斑点表面积计10％或与未处理区域比较稍少的为4，计20％左右的为3，计40％左右的为2，计60％左右的为1，而全部叶子落下病害的为0。化学药品损害的测定指标为：5：非常大量，4：大量，3：许多，2：少量，1：微量，0：无。试验结果列于表2。
                       表2化合物            浓度           效果              化学药品损害
No           (ppm)                                damage
4             200              5                    0
20            200              5                    0
30            200              5                    0
36            200              5                    0
58            200              5                    0
59            200              5                    0
61            200              5                    0
80            200              5                    0对照物化学药品EDDP          200              4                    0未处理的                           0                    -
Figure 9010693300261
实施例8
对大麦白粉病的控制活性试验(预防效果)
采用一个直径5cm塑料缽，对温室土壤培育的第1叶发育阶段大麦(麦种：Kuromugi)，每次涂铺10ml按实施例3制备的并已稀释到预定浓度的湿润剂，一天后，轻微喷雾接种大麦白粉病孢子，并抖散在叶上，7天后，测定每片有病害叶的大麦白粉病孢子数。
化学药品损害的测定指标与实施例7相同。试验结果列于表3。
                               表3化合物             浓度            效果              化学药品损害
No            (ppm)
4              200              5                      0
14             200              5                      0
18             200              5                      0
22             200              5                      0
23             200              5                      0
24             200              5                      0
25             200              5                      0
26             200              5                      0
29             200              5                      0
37             200              5                      0
42             200              5                      0
49             200              5                      0
63             200              5                      0
66             200              5                      0
67             200              5                      0
71             200              5                      0
73             200              5                      0
82             200              5                      0对照物化学药品               200              5                      0Triazimehon未处理的                            0                      -Triazimehon实施例9
对小麦锈斑的控制活性试验(预防效果)
采用一个直径5cm塑料缽，对温室土壤培育的第1叶发育阶段小麦(麦种：Kobushikomugi)，每次涂铺10ml按实施例3制备的并已稀释到预定浓度的湿润剂，一天后，喷雾接种小麦锈斑孢子混悬液，7天后，测定每片有病害叶的小麦锈斑孢子数。
化学药品损害的测定指标与实施例7相同。试验结果列于表4。
                           表4化合物             浓度           效果              化学药品损害
No.           (ppm)
14             200             5                      0
15             200             5                      0
21             200             5                      0
22             200             5                      0
23             200             5                      0
24             200             5                      0
25             200             5                      0
26             200             5                      0
27             200             5                      0
36             200             5                      0
49             200             5                      0
53             200             5                      0
54             200             5                      0
58             200             5                      0
63             200             5                      0
66             200             5                      0
67             200             5                      0
68             200             5                      0
69             200             5                      0
71             200             5                      0
72             200             5                      0
77             200             5                      0
82             200             5                      0对照物化学药品Triazimehon    200             4                      0未处理的                           0                      -实施例10
对小麦眼点病的控制活性试验(预防效果)
采用一个直径5cm塑料缽，对温室土壤培育的第3叶发育阶段小麦(麦种：Kobushikomugi)，每次涂铺10ml按实施例3制备的并已稀释到预定浓度的湿润剂，一天后，喷雾接种小麦眼点病孢子混悬液，8天后，测定每片有病害叶的小麦眼点病孢子数。
化学药品损害的测定指标与实施例7相同。试验结果列于表5。
                           表5化合物            浓度          效果         化学药品损害
No           (ppm)
22            200            5                 0
23            200            5                 0
对照物
苯菌灵        200            5                 0
未处理的                     0                 -
苯菌灵
Figure 9010693300301
实施例11
对稻“恶苗病”的控制活性试验(预防效果)
将稻“恶苗病”菌缩合孢子混悬液喷雾到成熟稻(稻种：Nipp-onbare)上，接种形成被染“恶苗病”菌稻，用作试验稻。通过按实施例3制备的湿润剂用来制备预定浓度的稀释溶液，将上述试验稻于20℃浸渍在该稀释溶液中24小时，使稻种子消毒，所述试验稻与稀释液之比(V/V)为0∶1。消毒后，将试验稻于20℃浸渍于水中3天，然后，在30℃下发芽24小时，根据苗箱培养法，将其播种在土中呈鸡胸形栽培。此后，在玻璃暖房里栽培和管理禾苗。25天(4叶发育阶段)后，拔出每一试验区的所有禾苗，调查病害侵袭情况，计算稻恶苗病的病苗数，得到病害侵袭禾苗的比率(％)，由此计算出预防值(％)。另外，按本实施例的同一标准调查化学药品对稻的损害。按每区5垄进行这一试验，测定稻种子的平均消毒比率(％)。试验结果列于表6。
Figure 9010693300311
                              表6化合物          浓度         种子消毒剂比率         化学药品损害
No         (ppm)                   (％)
13         1000                100                    0
20         1000                100                    0
23         1000                100                    0
26         1000                100                    0
66         1000                100                    0
对照物
苯菌灵     1000                98                     0
未处理的                       0                      -

Claims (13)

1.式(I)表示的氮杂环戊烷衍生物：式中R1代表氢原子，含1至10个碳原子的烷基或环烷基；
R2代表氢原子，含1至18个碳原子的烷基，链烯基，炔基，烷氧基烷基，链烯基氧基烷基，烷硫基烷基，烷氧基羰基，呋喃基或噻嗯基或苯基烷基，苯氧基烷基，苯硫基烷基，苯基烷氧基烷基，吡啶氧基烷基，苯氧基苯氧基烷基，苄氧基苯氧基烷基或吡啶氧基苯氧基烷基，上述苯环或吡啶环可被囟素原子、烷基烷氧基、卤代烷基或卤代烷氧基取代；或者R1和R2可彼此和与之键合的碳原子结合形成由式(II)代表的基团：式中R6代表氢原子，卤素原子或低级烷基；R7代表氢原子，烷基，链烯基，烷氧基，链烯氧基或烷硫基，或苯基，苯氧基，苄氧基或吡啶硫基，这些苯环或吡啶环可被卤素原子、烷基、烷氧基或卤代烷基取代；n是整数1至3；
R3代表氢原子或低级烷基；
R4代表氢原子，低级烷基，苯基或苄基，或R3和R4可彼此和与之键合的碳原子结合形成由下式代表的基团：
Figure 9010693300031
式中m是整数4或5；
R5代表氢原子，低级烷基或苯基，或者R4和R5可彼此和与之键合的碳原子结合形成由下式代表的基团：式中1代表整数3或4；以及
Z代表氧原子或硫原子。
2.按权利要求1的氮杂环戊烷衍生物，其中所述R1是氢原子或甲基。
3.按权利要求1的氮杂环戊烷衍生物，其中所述R2是含有5至12个碳原子的直链烷基。
4.按权利要求1的氮杂环戊烷衍生物，其中所述R2是苯氧基甲基，其中苯基可具有取代基。
5.按权利要求1的氮杂环戊烷衍生物，其中所述R2是含有C3烷基，并且所述苯基可具有取代基。
6.按权利要求1的氮杂环戊烷衍生物，其中所述R6是氯原子或甲基。
7.按权利要求1的氮杂环戊烷衍生物，其中所述R1是氢原子或甲基，R2是含有5至12个碳原子的直链烷基，其中烷基部分是1至5个碳原子的苯基烷基，或苯氧基烷基，所述苯基可以未被取代或被低级烷基或烷氧基取代；当R1、R2和与之键合的碳原子结合形成式(II)的基团时，所述R6是氢原子或氯原子，R7是氢原子、含有4至6个碳原子的烷基、含有4至6个碳原子的烷氧基、烯丙氧基，或者可被卤素原子取代的苯基、苯氧基或苄基；n是2；所述R3和R4各自为甲基或由所述R3、R4和与之键合的碳原子结合形成的或 R5是氢原子，Z是氧原子。
8.按权利要求1的氮杂环戊烷衍生物，其中所述化合物选自2-甲基-2-正己基-3-(1-咪唑基羰基)-5，5-二甲基-1，3-！唑烷(化合物No.11)和2，2-二-正庚基-3-(1-咪唑基羰基)-5，5-二甲基-1，3-噁唑烷(化合物No.18)。
9.制备式I的氮杂环戊烷衍生物的方法，所述式(I)如下：
Figure 9010693300043
式中R1代表氢原子，含1至10个碳原子的烷基或环烷基；
R2代表氢原子，含1至18个碳原子的烷基，链烯基，炔基，烷氧基烷基，链烯基氧基烷基，烷硫基烷基，烷氧基羰基，呋喃基或噻嗯基，或苯基烷基，苯氧基烷基，苯硫基烷基，苯基烷氧基烷基，吡啶氧基烷基，苯氧基苯氧基烷基，这些苄氧基苯氧基烷基或吡啶氧基苯氧基烷基，苯环或吡啶环可被卤素原子、烷基、烷氧基、卤代烷基或卤代烷氧基取代；或者R1和R2可彼此和与之键合的碳原子结合形成由式(II)代表的基团：式中R6代表氢原子，卤素原子或低级烷基；R7代表氢原子，烷基，链烯基，烷氧基，链烯氧基或烷硫基，或苯基，苯氧基，苄氧基或吡啶硫基，这些苯环或吡啶环可被卤素原子、烷基、烷氧基或卤代烷基取代；n是整数1至3；
R3代表氢原子或低级烷基；
R4代表氢原子，低级烷基，苯基或苄基，或R3和R4可彼此和与之键合的碳原子结合形成由下式代表的基团：式中m是整数4或5；
R5代表氢原子，低级烷基或苯基，或者R4和R5可彼此和与之键合的碳原子结合形成由下式代表的基团：
Figure 9010693300052
式中1代表整数3或4；以及
Z代表氧原子或硫原子；该方法包括式(III)化合物与咪唑反应，所述式(III)如下：
Figure 9010693300053
式中R1、R2、R3、R4、R5和Z的定义同上。
10.按权利要求9的方法，其中所述反应在碱存在下，于20至150℃进行10分钟至8小时。
11.按权利要求10的方法，其中所述碱选自碳酸钾、碳酸钠、氢氧化钠、三乙胺和吡啶。
12.按权利要求9的方法，其中每摩尔式(III)化合物的咪唑用量为0.5至5.0摩尔。
13.一种农业、园艺杀真菌剂，它包括有效量的式(I)氮杂环戊烷衍生物和农业和园艺作物上可接受的载体，式(I)为：
Figure 9010693300061
式中R1代表氢原子，含1至10个碳原子的烷基或环烷基；
R2代表氢原子，含1至18个碳原子的烷基，链烯基，炔基，烷氧基烷基，链烯基氧基烷基，烷硫基烷基，烷氧基羰基，呋喃基或噻嗯基，或苯基烷基，苯氧基烷基，苯硫基烷基，苯基烷氧基烷基，吡啶氧基烷基，苯氧基苯氧基烷基，苄氧基苯氧基烷基或吡啶氧基苯氧基烷基，这些苯环或吡啶环可被卤素原子、烷基、烷氧基、卤代烷基或卤代烷氧基取代；或者R1和R2可彼此和与之键合的碳原子结合形成由式(II)代表的基团：式中R6代表氢原子，卤素原子或低级烷基；R7代表氢原子，烷基，链烯基，烷氧基，链烯氧基或烷硫基，或苯基，苯氧基，苄氧基或吡啶硫基，这些苯环或吡啶环可被卤素原子、烷基、烷氧基或卤代烷基取代；n是整数1至3；
R3代表氢原子或低级烷基；
R4代表氢原子，低级烷基，苯基或苄基，或R3和R4可彼此和与之键合的碳原子结合形成由下式代表的基团：式中m是整数4或5；
R5代表氢原子，低级烷基或苯基，或者R4和R5可彼此和与之键合的碳原子结合形成由下式代表的基团：
Figure 9010693300072
式中1代表整数3或4；以及
Z代表氧原子或硫原子；
CN90106933A 1989-08-08 1990-08-08 氮杂环戊烷衍生物的制备方法 Expired - Lifetime CN1026700C (zh)

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