CN1048483C - N-丙酮基苯甲酰胺及其杀真菌组合物和控制致植物真菌的方法 - Google Patents

N-丙酮基苯甲酰胺及其杀真菌组合物和控制致植物真菌的方法 Download PDF

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CN1048483C
CN1048483C CN93120097A CN93120097A CN1048483C CN 1048483 C CN1048483 C CN 1048483C CN 93120097 A CN93120097 A CN 93120097A CN 93120097 A CN93120097 A CN 93120097A CN 1048483 C CN1048483 C CN 1048483C
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E·L·米切劳迪
D·H·扬
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Abstract

本发明涉及下式新型N-丙酮基苯甲酰胺化合物或其农(艺)学上可受盐及其在控制植物真菌中的应用，式中R1，R3，R2，R4，R5，X定义见说明书，
此化合物在控制致植物病真菌，尤其是控制卵菌纲类真菌有效，并且表现出强的杀真菌活性和相对低的植物毒性。重要的卵菌纲类真菌包括疫霉属，单轴霉属，霜霉属和假霜霉属，它们能引起诸如土豆和西红柿的后期枯萎病及葡萄和其它作物的丘陵起伏的霉病之类的病害。

Description

N-丙酮基苯甲酰胺及其杀真菌组合物和控制致植物真菌的方法
本发明涉及某些N-丙酮基取代的苯甲酰胺及其在控制真菌，尤其是致植物病真菌方面的应用。
已知N-(1，1-二烷基-3-氯丙酮基)取代的苯甲酰胺类的苯甲酰胺具有杀菌活性，例如见美国专利3,661,991和3,751,239。这些化合物在治疗植物真菌感染方面的实用性受到了这些化合物产生的实际植物毒性的限制。人们已认识到，通过把末端碳原子上的取代基改变为不同于氢或氯，能降低这些N-丙酮基取代的苯甲酰胺的植物毒性，例如见美国专利4,822,902和4,863,940。
应用杀菌有效量的通式(I)化合物可以控制致植物病真菌：
Figure C9312009700041
其中：
R1和R3相互独立，各为卤素或(C1-C4)烷基；
R2是(C1-C4)烷基，(C2-C4)烯基，(C2-C6)炔基，(C1-C4)烷氧基或氰基；
R4和R5独立为氢或(C1-C4)烷基，假设至少R4和R5之一为(C2-C4)烷基；且
X是卤素，硫氰基或异硫氰基；或它们的农〔艺〕学上可受的盐。
(C1-C4)烷基是每个基团上含有1-4个碳原子的直链或支链烷基，包括甲基，乙基，正丙基，异丙基，正丁基，异丁基，仲丁基和叔丁基。
(C2-C4)烯基是每个基团上含有2-4个碳原子的直链或支链烯基，例如包括乙烯基，2-丙烯基，2-丁烯基，1-甲基乙烯基，2-甲基-2-丙烯基。
(C2-C6)炔基是每个基团上含有2-6个碳原子的直链或支链炔基，例如包括乙炔基，2-丙炔基，2-丁炔基。
卤包括氯、氟、溴和碘。
(C1-C4)烷氧基是每个基团上含有1-4个碳原子的直链或支链烷氧基，例如包括甲氧基，乙氧基，丙氧基，异丙氧基，丁氧基，异丁氧基，仲丁氧基和叔丁氧基。
农〔艺〕学上可受的盐包括，例如金属盐，如钠、钾、钙和镁盐，铵盐，如异丙基铵盐，和三烷基锍盐，如三乙基锍盐。
在优选的实施例中，R1和R3相互独立各为氯、氟或溴，R2是(C1-C4)烷基，(C1-C4)烷氧基或氰基且X为氯。
在高度优选的实施例中，R1和R3各为氯，R2为(C1-C4)烷基，(C1-C4)烷氧基或氰基，R4为乙基，R5为甲基，且X为氯。
本发明化合物在控制致植物病真菌，尤其是控制卵菌纲类真菌方面有效，并具有高的杀菌活性和相对低的植物毒性。重要的卵菌纲类包括疫霉属，单轴霉属，霜霉属和假霜霉属，它们能引起诸如土豆和西红柿的晚期枯萎病及葡萄和其它作物的丘陵起伏的霉病之类的病害。
本发明化合物可按常用的方法被用作杀菌喷雾剂，如常用的高加仑量液压喷雾剂，低加仑量的喷雾剂，气流，气雾剂和粉剂。所用的稀度和比率将取决于所用设备的类型、方法和要求应用的频度及所控制的病害，典型的有效量是每公顷约0.01kg-约20kg化合物，较可取的是约0.1kg-约5kg化合物，更可取的是约0.125kg-约0.5kg化合物。
本发明化合物用于控制作物的致植物病真菌，也可用作种子保护剂，土壤杀菌剂和/或叶子杀真菌剂。用作种子保护剂时，在种子上涂一层本发明的一种化合物，剂量是每50kg种子约10g-约20g化合物。用作土壤杀菌剂时，将本发明的的一种化合物混合到土壤中或在土壤表面上应用，剂量是每公顷土地约0.5kg-约20kg化合物，较可取的是约1kg-约5kg。用作叶子杀菌剂时，将本发明的一种化合物施于生长着的植物上，配比剂量是每公顷约0.1kg-约5kg化合物，较可取的是约0.125kg-约0.5kg化合物。
为上述目的，这些化合物可以工业方式或形成制备的纯态的形式用作溶液或组合物。通常该化合物由载体携带或组合，以使其适于随后用作杀菌剂。例如，这些化合物可配制成可湿粉，干粉，可乳化的浓缩物，粉尘剂，粒状制剂，烟雾剂，或可流动的乳剂浓缩物。在这些组合物中，该化合物与一种液体或固体载体掺杂在一起，当用干粉时，并掺入合适的表面活性剂。
通常，特别对叶子喷雾剂组合物，按照农业实际，使用诸如浸润剂，铺展剂，分散剂，粘着剂，粘合剂等的辅剂是理想的。在工艺中通常用的这些辅剂在由McCutcheon Division of MC PublishingCompany(NewJersey)每年出版的下列出版物中查到：Mc-Cutcheon′s Emulsifiers和Detergents，Mclutcheon′s Emulsifiers和Detorgents/Functional Materials和McCutcheon′s FunctionalMaterials。
一般地，本发明所用的化合物能溶于适当的溶剂中，如丙酮，甲醇，乙醇，二甲基甲酰胺或二甲亚砜，并且这些溶液能与水互溶。该溶液浓度的变化范围为1％-90％，较可取的是5％-50％。
为了制备可乳化的浓缩物，将本发明所用的化合物与使杀菌剂分散在水中的乳化剂一起溶于适当的有机溶剂或混合溶剂中。此浓缩物中活性组分的浓度通常为10％-90％，在可流动的可乳化浓缩物中，活性组分的浓度可高达75％。适于喷洒的可湿粉可通过把本发明化合物与细粒状的固体，如粘土、无机硅酸盐和碳酸盐，和硅石混合，并在混合物中掺入润湿剂、粘着剂，和/或分散剂而制得。在该组合物中，活性组分的浓度范围通常为20-98％，尤其是40％-75％。
粉尘剂是通过把本发明化合物的盐及其络合物与细粒状的有机或天然无机惰性固体混合而制得的。所用的惰性物质包括植物粉末，硅石，硅酸盐，碳酸盐和粘土。制备粉尘剂的一种方便方法是用细粒状的载体稀释可湿粉。通常能制得含有20％-80％活性组分的粉尘剂，随后稀释到1％-10％的使用浓度。
本发明化合物也可与其它杀菌剂联合使用，如：
(a)二硫代氨基甲酸盐和衍生物，如：二甲基二硫代氨基甲酸铁(福美铁)，二甲基二硫代氨基甲酸锌(福美锌)，亚乙基双二硫代氨基甲酸锰(maneb)及其与锌离子的配位产物(mancozeb)，亚乙基双二硫代氨基甲酸锌(zineb)，亚丙基双二硫代氨基甲酸锌(propineb)，甲基二硫代氨基甲酸钠(metham)，二硫化四甲基秋兰姆(thiram)，亚乙基双二硫代氨基甲酸锌与二硫化多亚乙基秋兰姆的配合物，3，5-二甲基-1，3，5-2H-四氢硫杂二嗪-2-硫酮(dazomet)，和它们的混合物及与铜盐的混合物；
(b)硝基苯酚衍生物如：二硝基-(1-甲基庚基)苯基的丁烯酸酯(dinocap)，2-仲丁基-4，6-二硝基苯基-3，3-二甲基丙烯酸酯(binapacryl)，和2-仲丁基-4，6-二硝基苯基异丙基碳酸酯；
(c)杂环化合物如：N-三氯甲基硫代四氢苯邻二甲酰亚胺(Capten)，N-三氯甲基硫代苯邻二甲酰亚胺(folpet)，2-十七烷基-2-咪唑乙酸酯(glyo-dine)，2-辛基异噻唑酮-3，2，4-二氯-6-(邻-氯苯胺基)-三嗪，二乙基苯邻二甲酰亚氨基硫代磷酸盐，4-丁基-1，2，4-三唑，5-氨基-1-〔双(二甲基氨基)氧膦基〕-3-苯基-1，2，4-三唑，5-乙氧基-3-三氯甲基-1，2，4-硫杂二唑，2，3-二氰基-1，4-二硫杂蒽醌(dithionon)，1，3-二硫杂环戊二烯并-〔4，5-b〕喹喔啉-2-硫酮(thioquinox)，1-(丁基氨基甲酰基)-2-苯并咪唑碳酸乙酯(benomyl)，2，4′-(噻唑基)苯并咪唑(thiabendazole)，4-(2-氨苯基亚肼基)-3-甲基-5-异噁唑酮，3-(3，5-二氯苯基)-5-乙烯基-5-甲基-2，4-噁唑烷二酮(vinolozolin)；3-(3，5-二氯苯基)-N-(1-甲基乙基)-2，4-二氧-1-咪唑烷甲酰胺(iprodione)；N-(3，5-二氯苯基)-1，2-二甲基环丙烷-1，2-二甲酰亚胺(procymidone)；β-(4-二氯苯氧基)-α-(1，1-二甲基乙基)-1H-1，2，4-三唑-1-乙醇(triadimenol)；1-(4-氯苯氧基)-3，3-二甲基-1-(1H-1，2，4-三唑-1-基)-2-丁酮(triadimefon)；β-〔1，1′-联苯基)-4-基氧基〕-α-(1，1-二甲基乙基)-1H-1，2，4-三唑-1-乙醇(bitertanol)；2，3-二氯-N-(4-氟苯基)马来酰亚胺(fluorimide)；1-〔2-(2，4-二氯苯基)-4-丙基-1，3-二氧戊环-2-基甲基〕-1H-1，2，4-三唑；吡啶-2-硫羟基-1-氧化物；8-羟基喹啉硫酸酯及其金属盐；2，3-二氢-5-N-甲酰苯胺基-6-甲基-1，4-氧硫杂环己二烯-4，4-二氧化物，2，3-二氢-5-N-甲酰苯胺基-6-甲基-1，4-氧硫杂环己二烯，α-(苯基)-α-(2，4-二氯苯基)-5-嘧啶基甲醇(triarimol)，顺-N-〔(1，2，2-四氯乙基)硫代〕-4-环己烯-1，2-二甲酰亚胺，3-〔2-(3，5-二甲基-2-氧基环己基)-2-羟基〕戊二酰亚胺(cycloheximide)，脱氢乙酸，N-(1，1，2，2-四氯乙基硫代)-3a，4，7，7a-四氢苯邻二甲酰亚胺(captafol)，丁基-2-乙基氨基-4-羟基-6-甲基嘧啶(ethirimol)，4-环癸基-2，6-二甲基吗啉的乙酸酯(dodemonph)，4-〔3-(4-氯苯基)-3-(3，4-二甲氧基苯基)丙烯酰基〕吗啉(dimethomorph)和6-甲基-2-氧代-1，3-二硫杂环戊二烯并〔4，5-b〕-喹喔啉(quinomethion-ate)。
(d)混杂的卤代杀菌剂如：四氯-对苯醌(chloranil)，2，3-二氯-1，4-萘醌(dichlone)，1，4-二氯-2，5-二甲氧基苯(chloroneb)，3，5，6-三氯-O-对甲氧基苯甲酸(tricamba)，2，4，5，6-四氯异邻苯二甲腈(TCPN)，2，6-二氯-4-硝基苯胺(dichloran)，2-氯-1-硝基丙烷，多氯硝基苯如五氯硝基苯(PC-NB)和四氟二氯丙酮；
(e)杀真菌的抗生素如：灰黄霉素，春日霉素和链霉素；
(f)基于铜的杀真菌剂如：氢氧化铜，氧化亚铜，碱式氯化铜，碱式碳酸铜，三邻苯二甲酸铜，环烷酸铜和酸性枣红(Bordeaux)混合物；且
(g)混杂的杀真菌剂如：联苯，砜，十二烷基胍乙酸酯(dodine)，三-O-乙基膦酸铝(fosetyl-al)，N-(2，6-二甲基苯基)-N-(甲氧基乙酰基)丙氨酸甲酯(methoxyl)和其它的碱性杀真菌剂，乙酸苯基汞，N-乙基汞-1，2，3，6-四氢-3，6-桥亚甲基-3，4，5，6，7，7-六氯苯邻二甲酰亚胺，苯基汞单乙醇乳酸铵，对-二甲基氨基苯磺酸钠，异硫氰酸甲酯，1-硫氰基-2，4-二硝基苯，1-苯基硫代氨基脲，含镍的化合物，氰氨基钙石灰硫，1，2-双(3-甲氧基羰基-2-硫脲基)苯(thiophanate-methyl)，和2-氰基-N-(乙基氨基)羰基-2-(甲氧基亚胺)乙酰胺(cymoxanil)。
本发明的苯甲酰胺化合物可用常规的合成方法制得，如图A所示。例如，式(I)化合物可以这样制得：在-20℃下，在如二氯甲烷之类的溶剂存在下，用一种卤或卤源处理炔属酰胺(II)得到中间体噁唑啉(III)，此中间体在40-50℃的温度下，用氢氯酸和甲醇或四氢呋喃作为溶剂，在酸性条件下，容易水解。原料炔属酰胺可这样制得：在如氢氧化钠，三乙胺或吡啶之类的碱存在下，用水，二氯甲烷或乙醚作溶剂，在室温下，通过相应的芳香酰氯(IV)和炔属胺(V)反应。
Figure C9312009700121
图A
炔属胺(V)可从相应的商品化的炔属醇(VI)制得，如图B所示。
Figure C9312009700131
图B
制备典型的苯甲酰氯起始原料(IV)的合成方法概括如下图C和D)。
Figure C9312009700132
R＝CH3 or CH2CH3图C图D实施例1：N-〔3′-(1′-氯-3′-甲基-2′-氧代戊烷〕-3，5-二氯-4-甲基苯甲酰胺步骤a)3，5-二氯-4-甲基苯甲酸的制备：
向对-甲苯甲酸95.0g，0.698mol)的二氯甲烷(1升)溶液中分批加入氯化铝(260，0g，1.948mol)，并保持反应温度低于10℃。加完后，通入氯气并控制通气速度以保持反应温度低于10℃。用气液色谱跟踪反应。大约4小时后大多原料转变成了预想的化合物。将所得混合物倒入冰和浓盐酸中，然后用乙酸乙酯萃取数次。合并有机层，用水洗并用无水硫酸钠干燥。旋转蒸发除去溶剂得到白色固体状粗产物。用丙酮/水重结晶得115.4g含有少量杂质的3，5-二氯-4-甲基苯甲酸(81％收率)。步骤b)3，5-二氯-4-甲基苯甲酰氯的制备：
慢慢加热3，5-二氯-4-甲基苯甲酸(230g，1.12mol)，亚硫酰氯(204g，1.71mol)，和二甲基甲酰胺(30ml)的甲苯(1升)混合物至70℃，并在此温度下搅拌2小时。旋转蒸除甲苯得到276g 3，5-二氯-4-甲基苯甲酰氯，此化合物就这样用于下一步中。步骤c)3-甲基-1-戊炔-3-胺的制备
在2000ml四口圆底烧瓶上，装有一温度计，其侧面接口连接洗气系统、一机械搅拌棒，一500ml加料漏斗和一与氯化氢气体细压缩气瓶相连的导气管，向烧瓶中加入350ml浓盐酸，冷至5℃，通入氯化氢气体直到气泡大小不变为止。加入醇，控制加入速度保持温度低于0℃，同时向反应混合物中通入氯化氢气体。加醇需要2-2.5小时。加完醇后所得混合物于-5℃下继续搅拌30-45分钟。得到的混合物分层后分离，有机层用冰水洗涤直至洗涤液的pH为7。所得浅黄色可流动的油状物无需进一步纯化直接用于下一步骤中。步骤d)3-氨基-3-甲基-1-戊炔的制备
在3000ml四口圆底烧瓶上，装有一温度计其侧面接口连有洗气系统，一机械搅拌器，一500ml加斗漏半和一与氨气细压缩气瓶相连的导气管，向瓶中加入1000ml浓氢氧化铵。冷却氢氧化铵溶液至-5℃，并通入氨气直至气泡大小不变为止。通过加料漏斗向瓶中加入氯化物(600g)和50％的NaOH并且控制向氨溶液中加入的速度使每一种化合物以相等的化学计量加入反应瓶中，并保持反应液温度低于0℃。加料需要2至3小时，加完后，反应混合物在5℃下搅拌1小时。分离混合物，有机相用冰-水洗一次。得到浅黄色油状物在大气压下与水共沸蒸馏，分出四种级分：组分1(bp71-79℃)包含胺与低沸点链烯烃。组分2和3(bp80-85℃和85-89℃)1H-NMR表明为纯胺(总量220g)组分4(bp90-99℃)为胺与醇原料的混合物。合并级分1和4并溶于无水醚中，冷却下通入氯化氢气体，用此法可得90g纯胺盐酸盐。按醇计算总收率57％。步骤e)N-〔3′-(3′-甲基-1′-戊炔基)〕-3，5-二氯-4-甲基苯甲酰胺的制备：
在2升的三口圆底烧瓶上，装有一机械搅拌器，氮气入口管和温度计，向瓶中加入142g3-甲基-1-戊炔-3-胺盐酸盐，300ml四氢呋喃和350ml二甲基甲酰胺。充分搅拌后，向混合物中慢慢加入212ml三乙胺，保持温度为5-10℃之间。向所得混合物中加入221g前述酰氯，控制加入速度使反应温度保持在5-10℃之间。加完后，室温下搅拌反应混合物3小时，然后倒入2升水中并用乙酸乙酯(3×400ml)萃取。合并有机层并用水洗涤(1×300ml)，然后用5％的盐酸水溶液(2×300ml)洗涤，再用水(1×300ml)，最后再用5％的碳酸钠水溶液(2×300ml)洗涤，然后用无水硫酸钠干燥。旋转蒸除溶剂得266g N-〔3′-(3′-甲基-1′-戊炔基)〕-3，5-二氯-4-甲基苯甲酰胺。步骤f)2-(3，5-二氯-4-甲基苯基)-4-甲基-4-乙基-5-氯亚甲基噁唑啉的制备：
在3升三口圆底烧瓶上，装一机械搅拌器，一温度计和一100ml加料漏斗，向瓶中加入溶于750ml二氯甲烷中的143g，0.503mol N-〔3′-(3′-甲基-1′-戊炔基)〕-3，5-二氯-4-甲基苯甲酰胺。冷却所得混合物至-50℃，慢慢加入氯的二氯甲烷冷溶液(800ml，0.528M)。加完后，在-65℃下搅拌反应混合物30分钟。旋转蒸发反应混合物得到168.5g 2-(3，5-二氯-4-甲基苯基)-4-甲基-4-乙基-5-氯亚甲基噁唑啉粗产品，此浅黄色固体粗产品用于下一步中。步骤g)N-〔3′-(1′-氯-3′-甲基-2′-氧代戊烷)〕-3，5-二氯-4-甲基苯甲酰胺的制备，
将上一步中制备的168g，0.473mol 2-(3，5-二氯-4-甲基苯基-4-甲基-4-乙基-5-氯亚甲基噁唑啉溶于1.6升四氢呋喃，250ml水和60ml浓盐酸中，加热至55℃并在此温度下搅拌4小时。冷却反应混合物并倒入冰水混合物中，然后用二氯甲烷(4×400ml)萃取。合并有机层并用盐水洗，然后干燥。旋转蒸除溶剂得到N-〔3′-(1′-氯-3′-甲基-2′氧代戊烷)〕-3，5-氯-4-甲基苯甲酰胺。实施例2：N-〔3′-(1′-氯-3′-甲基-2′氧代戊烷)〕-3，5-二氯-4-甲基苯甲酰胺。
此化合物按上述实施例1中的方法用4-乙基苯甲酸为起始原料制备。实施例3：N-〔3′-(1′-氯-3′-甲基-2′氧代戊基)〕-3，5-氯-4-甲基苯甲酰胺，和实施例4：N-〔3′-(1′-氯-3′-甲基-2′氧代戊基)〕-3，5-氯-4-甲基苯甲酰胺
通过上面实施例1的方法，用3，5-二氯-4-羟基-苯甲酸作原料，先制得其乙基和甲基醚衍生物，可制备实施例3和实施例4的化合物。实施例5：N-〔3′-(1′-氯-3′-甲基-2′氧代戊基)〕-3，5-氯-4-甲基苯甲酰胺步骤a)：4-氰基-3，5-二氯苯甲酸的制备
用一100ml圆底烧瓶中加25ml浓硫酸，冷至5％。充分搅拌后，加入3.82g(0.055mol)亚硝酸钠。加热所得混合物到50℃直至形成溶液(约30分钟)。将所得溶液冷至0℃(冰浴)。剧烈搅拌下，用45分钟以上的时间，分批加入10.0g(0.049mol)4-氨基-3，5-二氯苯甲酸，并始终保持温度为3到5℃之间。加完后，将所得混合物热至15℃并在此温度下搅拌90分钟。然后在15℃剧烈搅拌下将此混合物倒入17.3g(0.26mol)氰化钾的50ml水溶液中。加热所得混合物至35-40℃并保持40分钟，然后冷至室温，并用乙酸乙酸萃取。合并有机相，用水洗涤，并且无水硫酸镁干燥。然后在旋转蒸发器上蒸除溶剂，得4.07g，N-〔3′-(1′-氯-3′-甲基-2′-氯代戊基)〕-4-氰基-3，5-二氯苯甲酰胺。此化合物就这样用于下一步中。步骤b)，4-氰基-3，5-二氯苯甲酰氯
用4-氰基-3，5-二氯苯甲酸(4.07g，0.019mol)的100ml无水甲苯溶液中加入亚硫酰氯(1.4ml，0.019mol)和二甲基甲酰胺(2滴)。回流所得混合物3小时，冷至室温并旋转蒸发蒸除溶剂。残余物真空干燥后就这样用于下列步骤中。步骤c)N-〔3′-甲基-1′-戊炔基〕-4-氰基-3，5-二氯苯甲酰胺
在0℃(冰-水浴下，向充分搅拌好的4-氰基-3，5-二氯苯甲酰氯(4.0g，0.017mol)和水(100ml)的混合物中，加入3-氨基-3-甲基-1-戊炔的盐酸盐和50％重量的NaOH水溶液(10ml)。在0℃下搅拌所得混合物1小时，加热至室温并用乙酸乙酯(3×50ml)萃取，合并有机相，并用水洗涤(3×50ml)，然后用无水硫酸钠干燥。旋转蒸发除去溶剂，得一黄油状(2.79g)粗产品，用装有Merck(60级)硅胶的Michel-Miller色谱柱纯化粗产品，用乙酸乙酯作溶剂，得0.75gN-〔 3′-甲基-1′-戊炔基〕-4-氰基-3，5-二氯苯甲酰胺。步骤d)2-(4-氰基-3，5-二氯苯基)-4-甲基-4-乙基-5-氯亚甲基噁唑啉的制备
向一装有电磁搅拌器，温度计和10ml加料漏斗的50ml三颈圆底烧瓶中，加入溶解于25ml二氯甲烷中的0.5g(1.7mmol)N-〔3′-(3′-甲基-1′-戊炔基)〕-4-氰基-3，5-二氯苯甲酰胺。冷却所得混合物至-50℃并慢慢加入冷的氯的二氯甲烷溶液(1.7ml，1.0M)。加完后，在-65℃时搅拌反应混合物30分钟，旋转蒸发除去相反应混合物中的溶剂，得淡黄色固体2-(4-氰基-3，5-二氯苯基)-4-甲基-4-乙基-5-氯-亚甲基噁唑啉，此化合物就这样用于下一步中。步骤e)N-〔3′-(1′-氯-3′-甲基-2′-氧代戊基)〕-4-氰基-3，5-二氯苯甲酰胺的制备
将上一步的粗产品溶于50ml甲醇，2ml水和3ml浓盐酸中，加热至55℃并在此温度下搅拌4小时。冷却反应物，并倒入冰水混合物中，然后用饱和碳酸氢钠水溶液中和并用二氯甲烷(4×50ml)萃取。合并有机相，用盐水洗涤并干燥。旋转蒸发除去溶剂得粗产品，用柱色谱纯化得120mg N-〔3′-(1′-氯-3′-甲基-2′-氧代戊基)〕-4-氰基-3，5-二氯苯甲酰胺。
本发明的典型化合物列于表1中。
表1
N-丙酮基苯甲酰胺的结构式为
Figure C9312009700211
Ex No.R1   R2    R3    R4    R5    X1    Cl    CH3    Cl   CH2CH3 CH3   Cl2    Cl  CH2CH3  Cl   CH2CH3 CH3   Cl3    Cl  OCH2CH3 Cl   CH2CH3 CH3   Cl4    Cl    OCH3   Cl   CH2CH3 CH3   Cl5    Cl    CN      Cl   CH2CH3 CH3   Cl与实施例1-5每一化合物特征有关的NMR光谱数据列于下表2中。实施例号，    200MHz  数字单位  ppm
         四甲基硅烷(TMs)内标，溶剂CDI31
          7.70(2，s)，6.80(1，s)，4.40(2，d)，2.50(3，s)，1.65
          (2，s)，1.60(3，s)，0.90(3，t)2.
          7.70(2，s)，6.75(1，bs)，4.35(2，c)，2.95(2，c)，
          2.40-2.10(1，m)，2.10-1.80(1，m)，1.65(3，s)
          1.20(3，t)，0.85(3，t)3
          7.70(2，s)，6.90(1，bs)，4.40(2，c)，4.15(2，c)，
          2.40-2.10(1，m)，2.1-1.80(1，m)，1.60(3，s)，
          1.45(3，t)，0.90(3，t)4
          7.75(2，s)，6.90(1，bs)，4.40(2，c)，3.95(3，s)，
          2.40-2.10(1，m)，2.10-1.80(1，m)，1.65(3，s)，
          0.90(3，t)5.
          7.85(1，s)，7.15(1，bs)，4.40(2，c)，2.50-2.30
          2.00-1.80(1，m)，1.70(3，s)，0.90(3，t)
实施例6
对实施例1-5化合物进行了杀真菌活性和植物毒性测试，并与下表3中所列的对比实施例C1-C4的化合物的测试结果进行比较。
表3结构式为
Figure C9312009700221
的N-丙酮基苯甲酰胺实施例号    R1   R2   R3    R4     R5    XCl          Cl    OH    Cl      CH3    CH3   ClC2          Cl    CH3  Cl      CH3    CH3   ClC3          Cl    H     Cl      CH2CH3CH3   ClC4          Cl    Cl    Cl      CH2CH3CH3   Cl抗级极腐霉真菌毒性测定
用二甲亚砜配制实施例1-5和对比实施例C1-C4化合物的稀溶液系列，向装有19.9ml液体天冬酰胺-蔗糖介质(见Erwin，D.C.和Katznelson，K.，1971，Can.J.Microbiol.7，15)的直径为9cm的陪替氏培养皿中加每份稀释液0.1ml，得到测试化合物所要求的浓度。从在土豆葡萄糖琼脂上生长的终极腐霉的培养基生长边缘取一直径7mm的菌丝塞放入培养皿中培养。每份实验用两个同样的培养皿。在25℃下生长并且gyrotary振荡器以每分种60转的频率振动48小时，然后测出菌丝干重量的增加，得到腐霉属EC50值随剂量的响应曲线。这里用的术语“EC50”意思是与不加测试化合物的对照相比抑制生长50％所需测试化合物的浓度。植物毒性测定
用二甲亚砜配制实施例1-5和C1-C4化合物的系列稀溶液，取每份溶液20微升(μl)加到20ml熔融营养介质中，此介质中含有Murashige和Skoog盐基，2％的蔗糖和1％琼脂，得到测试化合物预想浓度，迅速将此混合物倒入直径为9cm的陪替氏培养皿中。将表面经过防菌处理的烟草种子放在每一培养皿中(每一培养皿20粒种子)，并且所有培养皿竖直于27℃的培养器中培养，此培养器上有一16小时光周期，7天后计算出平均根长度。确定出烟草EC50值随剂量的响应曲线。
计算出每一化合物的腐霉属EC50与烟草EC50的比值，此比值用作每一化合物杀真菌活性相对于植物毒性指标。
真菌毒性和植物毒性的测试结果以“腐霉属EC50”和“烟草EC50”的形式列于表4中，各自的单位是微克/毫升(μl/ml)并且“(腐霉属EC50/烟草EC50)”即为所得的每一化合物的腐霉属EC50相对于烟草EC50的比值。
                       表4实施例号  腐霉属EC50 烟草EC50 (腐霉属EC50   烟草EC50)
      (μg/ml)    (μg/ml)1         0.02       0.05       0.42         0.12       0.22       0.553         0.49       1.58       0.314         0.14       0.25       0.565         0.11       0.48       0.23C1        10.7       ＞20     ＜0.53C2        0.09       0.03       3C3        0.011      0.004      2.75C4        0.08       0.05       1.6
实施例1-5的化合物都同时表现出了高杀真菌活性和相对低的植物毒性，而对比实施例C1-C4的每个化合物要么具有低植物毒性和低杀真菌活性，例如对比实施例C1，要么具有高杀真菌活性和相对高的植物毒性，例如对照实施例C4。

Claims (12)

1.一种通式为
Figure C9312009700021
的化合物其中：
R1和R3各自独立是卤原子或C1-C4的烷基；
R2是卤原子，C1-C4的烷基，C2-C4的烯基，C2-C6的炔基，C1-C4的烷氧基，或氰基；
R4和R5各自独立是C1-C4的烷基，假设至少R4，R5之一是C2-C4的烷基；并且
X是卤原子，硫氰基或异硫氰基；或其一种农艺学上的可受盐。
2.权利要求1的化合物，其中R1和R3各自独立为氯，氟或溴；R2是C1-C4的烷基，C1-C4的烷氧基或氰基；并且X是氯。
3.权利要求2的化合物，其中R1和R3分别是氯，氟或溴。
4.权利要求3的化合物，其中R1和R2分别是氯。
5.权利要求4的化合物，其中R4是乙基并且R5是甲基。
6.权利要求4的化合物，其中R2是C1-C4的烷基。
7.权利要求6的化合物，其中R2是甲基或乙基。
8.权利要求4的化合物，其中R2是C1-C4的烷氧基。
9.权利要求8的化合物，其中R2是甲氧基或乙氧基。
10.权利要求4的化合物，其中R2是氰基。
11.一种杀真菌的组合物，其包含一种农艺学上可受的载体和杀真菌有效量的权利要求1到10中的任何一种化合物。
12.一种控制致植物病真菌的方法，其包括向植物叶子，植物的种子或向植物生长的媒质中施用杀真菌有效量的权利要求1到10中的任何一种化合物。
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