CN1019667B - 苯并噻嗪酮衍生物的制备方法 - Google Patents
苯并噻嗪酮衍生物的制备方法Info
- Publication number
- CN1019667B CN1019667B CN87104156A CN87104156A CN1019667B CN 1019667 B CN1019667 B CN 1019667B CN 87104156 A CN87104156 A CN 87104156A CN 87104156 A CN87104156 A CN 87104156A CN 1019667 B CN1019667 B CN 1019667B
- Authority
- CN
- China
- Prior art keywords
- group
- compound
- pvp
- hydrogen atom
- atom
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
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- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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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
- A01N43/86—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 1,3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/04—1,3-Thiazines; Hydrogenated 1,3-thiazines
- C07D279/08—1,3-Thiazines; Hydrogenated 1,3-thiazines condensed with carbocyclic rings or ring systems
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- Chemical & Material Sciences (AREA)
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- Zoology (AREA)
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- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
Abstract
本发明提供了含有化学式为
(其中X为O，S或NH；R2为氢原子或烷基，R1为任意取代的烷基，链烯基，杂环或芳基)的苯并噻嗪酮衍生物的杀真菌组合物；某些新的苯并噻嗪酮化合物，制备这些化合物的方法及利用这些组合物或化合物杀灭植物病原真菌的方法。
Description
本发明涉及的是含有苯并噻嗪酮衍生物的杀真菌组合物、新的苯并噻嗪酮化合物、制备这些化合物的方法以及利用此类组合物或化合物消灭植物病原真菌的方法。
英国专利1，065，920中介绍了2位取代的苯并噁嗪酮
此化合物中，R2-R5最好为氢、卤素、烷基，y为OR6、SR8或NR7R8，这里的R6-R8为各烃基。此专利中还公开了这些化合物具有抗某些真菌的活性。德国公开说明书1302657描述了其中的R2、R3、R4和R5均为氢原子，y为苯氧基、萘氧基或-OCH2CCl3基团，此杂环氧原子变为硫原子的上述结构的衍生物，然而在该文献中并未公开有关化合物的任何杀真菌活性。
现已发现某些2位取代的苯并噻嗪酮具有有用的杀真菌活性，此类噻嗪酮中有一些是新的。因此，本发明提供了一种杀真菌组合物，该组合物包括载体和作为活性成分的2位取代的苯并噻嗪酮，它的通式为Ⅰ：
其中：X代表氧原子或硫原子或NH基团，R2代表氢原子或烷基，R1为任意取代的烷基、链烯基、杂环或芳基，优选的为苯基。
当任何上述取代基可以任意取代时，这些任意存在的取代基可为任何一个或多个通常用于研制杀虫剂化合物的基团、和/或用于这类物质的改良以影响其结构/活性、持久性、渗透性或其它性质的基团。这类取代基的典型例子有：卤素（尤其是氟、氯或溴原子）、硝基、氰基、烷基、卤代烷基（尤其是三氟甲基）、烷氧基、烷硫基、链烷酰基、烷基亚硫酰基、烷基磺酰基、烷氧基羰基烷氧基及被一个或多个卤原子或卤代烷基任意取代的苯氧基。如果上述的任一取代基代表或含有烷基或链烯基取代基，则它可以是直链的或支链的，所含碳原子数最多为12。优选的碳原子数量多为6，而最好的碳原子数量多为4，甲基、乙基、丙基、丁基和丙烯基则是其典型的例子，如果这些取代基代表芳基，则优选的为苯基，如果为杂环，则优选的
为吡啶基。
优选的情况是：X代表氧原子或硫原子;R2代表氢原子或甲基;R1代表其碳原子数为1-4的烷基、烯丙基、吡啶基、或被选自下述基团中的一个或两个取代基任意取代的苯基：氟、氯、硝基、氰基、甲基、丙基、三氟甲基、甲氧基、甲硫基、乙酰基、甲基亚硫酰基、甲基磺酰基、甲氧基羰基乙氧基和氢代-三氟甲基苯氧基。
式Ⅰ中的许多化合物是新的，因此这些新的化合物也在本发明的范围之列。这些新的化合物是其中的取代基定义同上的苯并噻嗪酮，而其条件是当R1是苯基、萘基或2，2，2-三氯乙基，且R2是氢时，X是硫或NH。
本发明也提供了一种制备定义如上的通式为Ⅰ的化合物的方法，该方法包括：将化合物Ⅱ与通式为Ⅲ的化合物R1X-Q反应，
其中：X、R1和R2的定义同上，P1代表基团OR3（R3代表氢原子或烷基），P2表示氢原子，Q表示氰基;或P1和P2一起表示基团-N＝
（Hal代表卤原子）、Q代表一个氢原子。此反应可方便地在诸如乙醚或二氯甲烷这类惰性有机溶剂中、于室温至回流温度下进行。如P1和P2一道代表基团-N＝
-Hal，Q代表氢原子，优选的情况是此反应在碱存在下进行，如三烷基胺是适宜的有机碱，最好选用三乙胺。
化学式为Ⅱ，其中P1和P2一起代表-N＝
-Hal基团的起始化合物可方便地由氨茴酸来制备，其具体方法是，将其与酸或亚硝酸盐反应，接着与硫氰酸盐反应生成2-氰硫基-苯甲酸，此酸再与五氯化磷反应，适宜的情况是此反应在诸如乙醚之类的有机溶剂中进行。
化学式为Ⅲ其中的Q代表氰基的起始化合物可方便地用下述方法制备：将化学式为R1XOH（其中的R1和X定义同上）的化合物与溴化氰进行反应，适宜的情况是在如丙酮这类有机溶剂中进行，优选的是在诸如三乙胺的有机碱存在下进行。
本发明也包括制备如上述定义的杀真菌组合物的方法，该方法包括将化合物Ⅰ与至少一种载体合并起来。
本发明组合物中的载体为任何能与活性成分一道配制成便于现场，例如植物，种子或土壤、使用的物质，或有利于贮存、运输或处理的物质。其载体可以是固体或液体，这包括在一般情况下为气相，但经压缩可以成为液体的物质，可以使用配制除草剂组合物所用的任何载体。按重量计，本发明组合物中活性组分的优选的含量为0.5%-95%。
适宜的固体载体包括：天然的、合成的粘土及硅酸盐，例如，硅藻土之类的天然的氧化硅、如滑石这类的硅酸镁、如硅镁土和蛭石这类硅铝酸镁，如高岭土、蒙脱土和云母这类硅酸铝;碳酸钙;硫酸钙;硫酸铵;合成的水合氧化硅和合成的硅酸钙或硅酸铝;如碳或硫这类元素;如苯并呋喃树脂，聚氯乙烯、苯乙烯聚合物和共聚物这类合成树脂;固体的多氯代苯酚;沥青;石蜡;固体化学肥料（例如过磷酸钙）。
适宜的液体载体有：水;如异丙醇、1，2-亚乙基二醇这类的醇;如丙酮、甲乙酮、甲异丁基酮和环己酮这类的酮;醚类;如苯、甲苯和二甲苯这类芳族的或脂族的烃类;如煤油及轻质矿物油之类的石油馏份;如四氯化碳、全氯乙烯、三氯乙烷这类氯代烃。经常使用的是各种液体的混合物。
经常配制、运输的农用组合物都为浓缩形式，在其施用前由用户稀释。作为表面活性剂存在的少量载体对稀释有利。因此优选的是在组合物中至少有一种载体是表面活性剂，例如，此组合物可能含有至少两种载体，则其中至少有一种载体为表面活性剂。
表面活性剂可以是乳化剂、分散剂或湿润剂，可以是非离子的或离子的，适宜的表面活性剂的例子有：聚丙烯酸的钠盐或钙盐及木素磺酸;其分子中至少含有12个碳原子的脂肪酸或脂族胺或酰胺与环氧乙烷和或环氧丙烷的缩合物;丙三醇、山梨糖醇、蔗糖或季戊四醇的脂肪酸酯类，这些酯与环氧乙烷和/或环氧丙烷的缩合物;脂肪醇或烷基酚（如对一辛基苯酚或对-辛基甲酚）与环氧乙烷和/或环氧丙烷的缩合产物;分子中碳原子数至少为10的硫酸或磺酸酯的碱金属或碱土金属盐（优选
的为钠盐），如：十二烷基硫酸钠、仲烷基硫酸钠、磺化蓖麻油的钠盐，烷基芳基磺酸钠，如十二烷基苯磺酸盐;环氧乙烷聚合物及环氧乙烷和环氧丙烷共聚物。
本发明的组合物可以配制成可湿性粉剂、粉剂、颗粒剂、溶液、可乳化的浓缩物，乳化液、悬浮浓缩物和烟雾剂。按重量计，可湿性粉剂通常含有25、50、或75%的活性组分，此外一般还含有固体惰性载体、3-10%的分散剂、如有必要，还可以含有0-10%的稳定剂（一种或多种）和/或其他诸如渗透剂或粘结剂之类的添加剂。粉剂一般配制成粉状浓缩物，其组成与可湿性粉剂相似，只是无分散剂，在使用现场再用其它的固体载体稀释以配制成一般含活性成分1/2-10%（按重量计）的组合物。颗粒剂通常制成的大小为10-100目（英国标准）（1.676～0.152毫米），可采用凝聚技术或浸渍技术来制备。按重量计，颗粒剂一般含1/2-75%活性成分和0-10%诸如稳定剂、表面活性剂、缓慢释放调节剂、粘合剂之类的添加剂。所说的“干的可流动的粉剂”是由较小的含活动组分浓度较高的颗粒组成。可乳化的浓缩物通常含有某种溶剂，必要时，可含潜溶剂，活性成分的含量为10-50%（重量/体积）、乳化剂含量为2-20%（重量/体积）及如稳定剂、渗透剂、防腐剂之类的其它添加剂0-20%（重量/体积）。悬浮浓缩物一般需经化合以制得稳定的、不沉淀的可流动产品，按重量计，一般含活性成分10-75%，分散剂0.5-15%，如保护胶体及触变剂一类的悬浮剂0.1-10%，如消泡剂、渗透剂、稳定剂、粘着剂和防腐剂之类的其他添加剂0-10%，此活性成分基本上不溶于其中的水或有机液体，将某些有机固体或无机盐溶解在制剂中以用于防止制剂的沉淀或用作水的防冻剂。
根据本发明，用水稀释可湿性粉剂或浓缩物而得到的分散水液及悬浮水液属本发明的范围之列，所说乳化液既可为油包水型也可为水包油型的，其稠度可类似稠的“蛋黄酱”。
本发明的组合物也可含其他成分，例如具有除草、杀虫或杀真菌性能的其他化合物。
特别有利的是所用载体要能提高本发明保护剂的活性期，此种载体将使本发明的杀真菌化合物缓慢释放于所要保护的植物的周围，例如可将这种缓慢释放的制剂插于藤本植物根部周围的土壤中，这种缓慢释放的制剂还可含某种具有粘附力的化合物以使之能直接施用于藤本植物的茎部。
本发明还提供了通式为Ⅰ（定义同上）的苯并噻嗪酮作为杀真菌剂的用途和将其用于病害现场的方法，该方法包括用其衍生物处理其场所（例如植物易遭受或已遭受真菌侵袭的场所）、易遭受或已遭受真菌侵袭的植物的种子或此类植物生长或将要在其中生长的介质。
在保护作物免受真菌的侵害方面，本发明具有广泛的适用性，可以保护的典型的作物有：藤本植物、谷类作物（如小麦、大麦）、水稻、豆科植物和苹果树。保护期一般取决于选用的具体的化合物，还取决于各外因的变化（例如气候），但通过使用适宜的制剂可以减轻这些外因的影响。
用下述实施例来说明本发明。
实施例1
A）.2-氰硫基苯甲酸的制备
将亚硝酸钠（16.5克，0.2摩尔）在水（20毫升）中的溶液滴加于搅拌下的氨茴酸（30克，0.2毫升）在盐酸水溶液（浓盐酸∶水＝1∶1，90毫升）中的悬浮液中，用冰浴冷却此混合物。在70℃下，将所得的棕色溶液逐滴加入到搅拌下的硫氰酸钾（63克，0.65摩尔）和硫氰酸铜（Ⅰ）（21.3克，0.18摩尔）在水（50毫升）中的混合物中。将所得棕色混合物冷却、过滤、残余物用丙酮萃取。于真空中除去丙酮得到所需的棕/黄色固体产物，熔点152～153℃。
B）.2-氯-1，3-苯并噻嗪-4-酮的制备
于70℃、在氮气下，将如A）中制备的2-氰硫基苯甲酸（33.6克，0.19毫升）同在二-正-丁基醚（200毫升）中的五氯化磷（40克，0.192毫升）一同搅拌6小时。冷却此混合物，过滤该棕色固体并用乙醚洗涤得到所需的产品，熔点112℃。
C）.2-（4-氯苯氧基）-1，3-苯并噻嗪-4-酮的制备
于4-氯苯酚（2.56克，0.20毫升）的二氯甲烷溶液中加入三乙胺（2.8毫升，0.02摩尔）制备溶液，将所制溶液滴加入搅拌下的2-氯-1，3-苯并噻嗪-4-酮（4克，0.20摩尔）在二氯甲烷中的悬浮液中，将其搅拌18小时后加入水，有机
层用硫酸镁干燥，再经旋转蒸发器浓缩，用快速色谱纯化所得棕色固体，用3%甲醇的二氯甲烷中的溶液洗脱，制得所要的最终产品，熔点114-115℃。
分析结果：计算值：C58.0;H2.8;N4.8%
测定值：C58.0;H2.9;N5.1%
实施例2
A）氰酸2-甲基-4-氯苯酯的制备
将4-氯-2-甲基苯酚（10克，0.07摩尔）和溴化氰（7.4克，0.07摩尔）于丙酮中，0℃下进行搅拌，再滴加三乙胺（9.7毫升，0.07摩尔）。所得混合物于0℃下再搅拌2小时，然后过滤，滤液用旋转蒸发器浓缩，得到所要的淡黄色固体产物，使用时不再进一步纯化，经乙酸乙酯/己烷重结晶后测得其熔点为60℃。
分析结果：计算值：C57.3;H3.6;N8.4%
测定值：C57.6;H3.3;N7.6%
B）2-（4-氯代-2-甲基）苯氧基苯并噻嗪酮的制备
将氰酸2-甲基-4-氯苯酯（1.8克，0.01摩尔）和2-巯基苯甲酸乙酸（2克，0.01摩尔）于乙醚（30毫升）中回流72小时。由过滤即得所要的白色固体产物，熔点144℃（经乙醇重结晶）。
分析结果：计算值：C59.3;H3.3;N4.6%
测定值：C59.8;H3.2;N4.4%
实施例3-43
按类似于实施例1和2所述的步骤来制备另一类2位取代的苯并噻嗪酮，其中用适宜的硫酚或苯胺代替了实施例1C中的氯苯酚或实施例2A中的4-氯代-2-甲苯酚，它们的物理性质和分析结果列于下表Ⅰ中，参照化合物Ⅰ的取代基来定义这些化合物
实施例44
用下述试验说明本发明有代表性的化合物的杀真菌活性：
a）抗藤本植物霜霉病（plasmopara viticola;p.v.p）的直接保护剂活性。
该实验为一直接保护剂实验，用叶喷雾来进行的。将所有藤本植物（CV Cabernet Sauvignon）叶的下表面喷以实验化合物在水/丙酮（1∶1）溶液[含0.04%“吐温20”（商品名，为聚氧乙烯的梨糖醇酯表面活性剂）]中的溶液。所用喷雾器为活动履带式的，其用量为1千克/公顷，于普通温室条件下，24小时后对其叶的下表面以喷雾的方式注射含游动孢子囊的水溶液（104/毫升）进行接种。接种后的植物放于高湿度的室中24小时，一般温室条件下5天，再置于高湿度室中24小时。再将孢子形成复盖的叶面积的百分率同对照植物的叶进行比较以作出评价。
b）抗藤苯植物灰霉病（Botrytis cinerea;BCP的直接保护剂活性
该实验为一直接保护剂实验，用叶喷雾来进行。将藤苯植物（CV cabernet sauvignon）落叶的下表面用如a）中喷雾器按1公斤/公顷的剂量喷上实验化合物。喷雾后24小时，对此叶喷含105分生孢子/毫升的悬浮水液进行接种，再于高湿度下5天后，评定病害复盖叶的百分率。
c）抗大麦白粉病（Erysiphe graminis f.sp.borbei;Eg）的活性
本实验为直接治疗实验，用叶喷雾来进行。对大麦苗（CV.Gol-den promise）叶喷以霉变的分生孢子粉进行接种后一天，再用实验化合物对其处理。处理前将接种的植物放于室温和环境潮湿的温室中过夜，再用a）中所述的喷雾器对接种的植物按1公斤活性物质/公顷的剂量进行喷雾。干后将其放于温度为20-25℃、湿度中等的室中最多7天，然后进行评价。其评价是按孢子形成复盖的叶面积的百分率同对照物的叶进行比较作出的。
d）抗西红柿早疫病（落叶病）（Alternaria solani;AS）的活性
本实验是测定试验化合物在叶喷雾应用中的接触预防活性。
当西红柿幼苗（CV Outdoor Girl）长到第二真叶张开的阶段，将其用a）所述的喷雾器进行喷雾处理，所用的实验化合物为含表面活性剂（“吐温20”-商标）0.04%的在丙酮和水（50∶50体积/
体积）的混合物中的溶液或悬浮液。
处理后一天，对西红柿苗叶的上表面喷以含104孢子/每毫升的落叶病分生孢子（A，solani）悬浮液进行接种，接种后，将其在相对湿度为100%或将近100%的温室中，21℃下保持潮湿3天。其后将它保持在潮湿但并非饱和的条件下。
接种后7天根据病变的密度和速度对病害作出评价。
e）在试管内抗小麦眼状色斑（Pseudocercos porella herpotrichoides;phI）的活性
本实验用以测定化合物抗真菌引起的小麦眼状色斑在试管内的活性。
将实验化合物溶解或悬浮于丙酮中，再将其加于熔融的半固化的马铃薯葡萄糖琼酯中使最终化合物浓度为100ppm，丙酮3.5%。琼脂凝固后，用P.herpotrichoides经14天培养后所得的直径为6毫米的琼脂/菌丝塞接种平板。
将接种后的平板在20℃下培养12天，测定从接种塞径向生长的平板。
f）在试管内抗镰孢属（Fusarium species;FSI）的活性
本实验用来测定化合物在试管内抗引起茎和根腐烂的镰孢属的活性。
将化合物溶于或悬浮于丙酮中，加入到熔融的半固化的马铃薯葡萄糖琼脂中以使最终的化合物浓度为100ppm，丙酮为3.5%。待琼脂凝固后用经7天培养镰孢属所得的直径为6毫米的琼脂/菌丝接种平板。
接种后的平板在20℃下培养5天后测定从接种塞的径向生长。
g）抗叶稻瘟（稻瘟病菌：pyricularia oryzae po）的活性
本实验为直接治疗实验，喷雾在叶上进行。将稻秧（每盆约30株）叶喷以含105孢子/毫升的悬浮水液，24小时后再用实验化合物处理。将接种后植物在高湿度下放置过夜，让其干燥后再用a）中所述喷雾器按1公斤活性物质/公顷的剂量喷以实验化合物。处理后，将植物放于25-30℃，高湿度的稻室中，处理后4-5天与对照物进行比较，按其每片叶的坏死病变密度进行评价。
h）抗小麦叶锈病（Puccinia recondita;pr隐匿柄锈）的活性
本实验为直接保护剂实验，采用的是叶喷雾，在生长到1-1 1/2 阶段的小麦苗上（CV Brigand）。用a）中所述喷雾器按1公斤/公顷的剂量喷以实验化合物。所用的实验化合物为在丙酮和水（50/50，体积/体积）混合物中的水溶液或悬浮液，含表面活性剂（“吐温20”-商标）0.04%。
处理后18-24小时，对其叶各面喷以约含105孢子/毫升的悬浮孢子水液以接种所说的小麦苗。接种18小时后，将此植物置于高湿度和20-22℃条件下，然后再将其放在具有如下温室条件的环境中，即相对湿度适中，温度为20℃的温室。
接种后10天将其与对照植物进行比较，按产孢色点复盖的植物百分率进行评价。
上述各实验的病害抑制程度是与未处理的对照或经稀释剂喷雾的对照进行比较按下述标准的等级表示的：
0＝病害抑制小于50%
1＝病害抑制约50-80%
2＝病害抑制大于80%
上述实验结果列于下表Ⅱ中：
表Ⅱ
实施例号 杀真菌活性
1 类同2;Pvp 1
2 Pr 1
3 Pvp 1
4 Pvp 1
5 As 2;Pvp 1
6 Pvp 2;Bcp 1;类同1
7 Pvp 2
8 Pvp 1;类同2;Eg 1
9 Pvp 2;类同2
10 Pvp 2;类同1
11 Pvp 1;类同2
12 Pvp 2
13 Bcp 1;ph 1
16 Pvp 1;Fs 1
18 Pvp 2;Fs 1
19 Po 2
20 Pvp 1;类同2
22 Ph 1;Fs 1
23 As2
25 Pvp2;Eg 1;Ph 2
26 Pvp1
30 As 2
32 As 1
续表Ⅱ
实施例号 杀真菌活性
35 PVP 1;类同1;Fs 1
36 Eg 1
37 Pvp 2;pr 1;Ph 1;Fs 1
38 Pvp 1;类同2;Ph 1;Fs 1
39 Pvp 1;Fs 1
40 Pvp 2;Ph 1;Fs 1
41 Bcp 1
42 Pvp 2;类同2;Fs 1
43 Pvp 2;类同2;Po 1
Claims (2)
1、一种通式Ⅰ苯并噻嗪酮化合物的制备方法，
其中R2为氢或甲基；X为氧原子时，R1为任意取代的苯基；吡啶基；X为硫原子时，R1为被卤素、低级烷基或硝基取代的苯基；当X为NH时，R1为低级烷基(此时R2为甲基)，烯丙基、被卤素、低级烷基、三氟甲基或取代的苯氧基取代的苯基，该方法包括将通式(Ⅱ)化合物
Ⅱ
与通式(Ⅲ)化合物反应，
R1X-Q (Ⅲ)
其中X1、R1和R2的定义同上，P1为OR3基团(R3为氢原子或烷基)，P2为氢原子，并且Q为氰基；或P1与P2一起为-N=C(HAL)-基团(其中HAL为卤原子)，并且Q为氢原子。
2、如权利要求1所述的方法，其中该方法是在有机碱存在的情况下于惰性有机溶剂中进行的。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB868611618A GB8611618D0 (en) | 1986-05-13 | 1986-05-13 | Fungicides |
| GB8611618 | 1986-05-13 |
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| Publication Number | Publication Date |
|---|---|
| CN87104156A CN87104156A (zh) | 1987-12-16 |
| CN1019667B true CN1019667B (zh) | 1992-12-30 |
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| CN87104156A Expired CN1019667B (zh) | 1986-05-13 | 1987-05-11 | 苯并噻嗪酮衍生物的制备方法 |
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| Country | Link |
|---|---|
| US (1) | US4833137A (zh) |
| EP (1) | EP0245902A3 (zh) |
| JP (1) | JPS62267277A (zh) |
| KR (1) | KR940011460B1 (zh) |
| CN (1) | CN1019667B (zh) |
| AR (1) | AR244503A1 (zh) |
| AU (1) | AU612573B2 (zh) |
| BR (1) | BR8702379A (zh) |
| CA (1) | CA1315782C (zh) |
| CS (1) | CS270566B2 (zh) |
| DK (1) | DK237887A (zh) |
| EG (1) | EG18164A (zh) |
| GB (1) | GB8611618D0 (zh) |
| HU (1) | HU200894B (zh) |
| IL (1) | IL82477A0 (zh) |
| PH (1) | PH23453A (zh) |
| PL (1) | PL150125B1 (zh) |
| PT (1) | PT84854B (zh) |
| SU (1) | SU1528318A3 (zh) |
| TR (1) | TR24935A (zh) |
| ZA (1) | ZA873340B (zh) |
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| US5126449A (en) * | 1989-06-26 | 1992-06-30 | Hoechst-Roussel Pharmaceuticals Inc. | (1,2,3,4-Tetrahydro-9-acridinimino)cyclohexane carboxylic acid and related compounds |
| NZ258570A (en) * | 1992-12-02 | 1996-06-25 | Shell Int Research | Azoxycyanobenzene derivatives and plant fungicidal compositions |
| ATE159934T1 (de) * | 1993-08-18 | 1997-11-15 | Shell Int Research | Azoxycyanobenzol-derivate und ihre verwendung als fungizide |
| EP0645384A1 (en) * | 1993-08-18 | 1995-03-29 | Shell Internationale Researchmaatschappij B.V. | Azoxycyanobenzodioxane derivatives and their use as fungicides |
| EP0644184B1 (en) * | 1993-08-18 | 1997-11-05 | Shell Internationale Researchmaatschappij B.V. | Azoxycyanobenzene derivatives and their use as fungicides |
| AU3704400A (en) * | 1999-03-04 | 2000-09-21 | E.I. Du Pont De Nemours And Company | Fused bicyclic oxazinone and thiazinone fungicides |
| DE50203896D1 (de) * | 2001-05-21 | 2005-09-15 | Basf Ag | Oxazin(thi)onverbindungen als fungizide |
| EP2208728A4 (en) * | 2007-09-19 | 2011-12-21 | Inst Med Molecular Design Inc | HETEROCYCLIC DERIVATIVE DERIVATIVE DERIVATIVE TO 11 -? - HYDROXYSTEROIDDEHYDROGENASE TYPE I |
| CN102367239B (zh) * | 2011-07-20 | 2015-10-28 | 沈阳药科大学 | 2-芳基-2,3-二氢-4h-1,3-苯并噻嗪-4-酮衍生物及其用途 |
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| DE1302657B (zh) * | 1970-11-26 | |||
| BE572200A (zh) * | 1957-10-24 | |||
| DE1445742A1 (de) * | 1963-11-06 | 1968-12-19 | Bayer Ag | Verfahren zur Herstellung von 2-Stellung substituierten Benzoxazinonen |
| DE1545807A1 (de) * | 1965-04-24 | 1969-11-27 | Bayer Ag | Verfahren zur Herstellung von 2-Halogen-1,3-benzothiazinonen-4- |
| US3470168A (en) * | 1967-03-31 | 1969-09-30 | American Home Prod | 2-substituted-4h-1,3-benzothiazin-4-one derivatives |
| US3853876A (en) * | 1972-03-06 | 1974-12-10 | American Home Prod | Ortho-mercaptoaroylamides and salts thereof abstract of the disclosure |
| US3881019A (en) * | 1972-03-06 | 1975-04-29 | American Home Prod | O-Mercapto-benzamides as hypoglycemia agents |
| US3928590A (en) * | 1972-03-06 | 1975-12-23 | American Home Prod | Ortho-mercaptoaroylamides and salts thereof as hypoglycemic agents |
| US3829488A (en) * | 1972-03-06 | 1974-08-13 | American Home Prod | Bis-(o-n-substituted-carbamylphenyl)disulfide and mercapto reduction product |
| JPS591267B2 (ja) * | 1976-03-11 | 1984-01-11 | 関東医師製薬株式会社 | チアジン誘導体およびその製造法 |
| US4436739A (en) * | 1978-10-16 | 1984-03-13 | Eli Lilly And Company | Substituted 1-thia-3-aza-4-ones |
-
1986
- 1986-05-13 GB GB868611618A patent/GB8611618D0/en active Pending
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1987
- 1987-04-29 EP EP87200819A patent/EP0245902A3/en not_active Withdrawn
- 1987-05-08 PH PH35236A patent/PH23453A/en unknown
- 1987-05-11 SU SU874202583A patent/SU1528318A3/ru active
- 1987-05-11 ZA ZA873340A patent/ZA873340B/xx unknown
- 1987-05-11 CA CA000536854A patent/CA1315782C/en not_active Expired - Fee Related
- 1987-05-11 EG EG272/87A patent/EG18164A/xx active
- 1987-05-11 IL IL82477A patent/IL82477A0/xx not_active IP Right Cessation
- 1987-05-11 JP JP62112652A patent/JPS62267277A/ja active Pending
- 1987-05-11 AR AR87307520A patent/AR244503A1/es active
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- 1987-05-11 PL PL1987265624A patent/PL150125B1/pl unknown
- 1987-05-11 PT PT84854A patent/PT84854B/pt not_active IP Right Cessation
- 1987-05-11 CS CS873352A patent/CS270566B2/cs unknown
- 1987-05-11 DK DK237887A patent/DK237887A/da not_active Application Discontinuation
- 1987-05-11 KR KR1019870004594A patent/KR940011460B1/ko not_active Expired - Fee Related
- 1987-05-11 CN CN87104156A patent/CN1019667B/zh not_active Expired
- 1987-05-11 AU AU72700/87A patent/AU612573B2/en not_active Ceased
- 1987-05-11 BR BR8702379A patent/BR8702379A/pt active Search and Examination
- 1987-05-13 US US07/049,245 patent/US4833137A/en not_active Expired - Fee Related
- 1987-05-13 TR TR87/0336A patent/TR24935A/xx unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0245902A3 (en) | 1989-02-15 |
| PH23453A (en) | 1989-08-07 |
| PT84854B (pt) | 1990-02-08 |
| SU1528318A3 (ru) | 1989-12-07 |
| CA1315782C (en) | 1993-04-06 |
| AU7270087A (en) | 1987-11-19 |
| PT84854A (en) | 1987-06-01 |
| PL265624A1 (en) | 1988-08-18 |
| BR8702379A (pt) | 1988-02-17 |
| JPS62267277A (ja) | 1987-11-19 |
| CN87104156A (zh) | 1987-12-16 |
| ZA873340B (en) | 1987-11-02 |
| IL82477A0 (en) | 1987-11-30 |
| GB8611618D0 (en) | 1986-06-18 |
| PL150125B1 (en) | 1990-04-30 |
| TR24935A (tr) | 1992-07-27 |
| HU200894B (en) | 1990-09-28 |
| HUT44694A (en) | 1988-04-28 |
| CS335287A2 (en) | 1989-11-14 |
| DK237887A (da) | 1987-11-14 |
| AU612573B2 (en) | 1991-07-18 |
| EG18164A (en) | 1992-08-30 |
| EP0245902A2 (en) | 1987-11-19 |
| CS270566B2 (en) | 1990-07-12 |
| AR244503A1 (es) | 1993-11-30 |
| US4833137A (en) | 1989-05-23 |
| KR940011460B1 (ko) | 1994-12-15 |
| DK237887D0 (da) | 1987-05-11 |
| KR870011116A (ko) | 1987-12-21 |
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