CN86103679A - 菲类衍生物的制备方法 - Google Patents
菲类衍生物的制备方法 Download PDFInfo
- Publication number
- CN86103679A CN86103679A CN198686103679A CN86103679A CN86103679A CN 86103679 A CN86103679 A CN 86103679A CN 198686103679 A CN198686103679 A CN 198686103679A CN 86103679 A CN86103679 A CN 86103679A CN 86103679 A CN86103679 A CN 86103679A
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- Prior art keywords
- compound
- general expression
- phenyl
- phenanthrene
- oxime
- Prior art date
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- 239000000203 mixture Substances 0.000 claims abstract description 38
- 239000000470 constituent Substances 0.000 claims abstract description 23
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 17
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 13
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 7
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/12—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reactions not involving the formation of oxyimino groups
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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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
- A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
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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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group; Thio analogues thereof
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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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
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- A—HUMAN NECESSITIES
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- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/26—Phenanthrenes; Hydrogenated phenanthrenes
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Abstract
本发明是关于菲类新的衍生物(式I),其中
R代表C1-10烷氨基,C1-10烷硫基;C1-5烷氧基;苯基或苯基氨基,后二个基团的苯环上可选择性地有一个或多个相同或不同的C1-4烷基、C1-4烷氧基、硝基、氨基、氰基和/或卤素取代基。
本发明可以作为杀菌剂或抗菌剂组合物的有效成分应用在农业、园艺以及人的疾病的治疗上。
具有一般式I的化合物可以由酰化9,10-菲二酮-9-肟或它的碱金属盐或碱土金属盐制得。
Description
本发明是关于新的菲类衍生物,它的制备方法,以及含有它的杀菌组合物,该组合物可用于农业、园艺上,并且还可应用于人和兽医治疗。
本发明提供了具有一般式Ⅰ的新的菲衍生物
其中
R代表C1-10烷氨基、C1-10烷硫基、C1-5烷氧基、苯基或苯基氨基,苯基或苯基氨基的苯环上可选择地被一个或者多个相同或者不同的C1-4烷基、C1-4烷氧基、硝基、氨基、氰基和/或囟素取代。
本说明书中自始至终应用的术语“烷基”是与直链的或带支链的烷基(如甲基、乙基、正-丙基、异-丙基、正-丁基、异-丁基)有关。术语“烷氧基”是与直链的或带支链的烷氧基(如甲氧基、乙氧基、丙氧基或异-丙氧基)有关。术语“囟素”是指氟、氯、溴和碘原子。
作为C1-10烷氨基的R,最好是甲氨基,乙氨基、正-丙氨基或正-丁氨基。
作为C1-10烷硫基的R,最好是硫基、乙硫基、正-丙硫基、正-丁硫基或正-辛硫基。
作为C1-5烷氧基的R,最好是甲氧基或乙氧基。
R作为有选择性取代的苯基,最好是有一个或者二个相同或不同的甲基、乙基、甲氧基、乙氧基、氰基、氯和/或溴取代基。
R作为有选择性取代的苯氨基,最好是有一个或者二个相同或不同的甲基、乙基、甲氧基、乙氧基、氰基、氯和/或溴取代基。
具有一般式(Ⅰ)的特别好的化合物是下述衍生物:9,10-菲-二酮-9-(甲氨基羰基)-肟和9,10-菲-二酮-9-(正-丁氨基羰基)-肟。
具有一般式(Ⅰ)的新化合物显示出有杀菌作用。根据我们进行的广泛试验,本发明的新化合物具有抗各种使人致病的丝状皮真菌(发癣菌属、表皮癣菌属、小孢子菌属)的作用,并且对许多使植物致病的真菌(镰孢霉属,长蠕孢霉属核盘菌属、黑孢霉属等)也有效。式Ⅰ化合物可以成功地应用于叶上以及水中和土壤里。
式Ⅰ化合物具有广泛作用〔例如,类似于N-(三氯甲硫基)-邻苯二甲酰亚胺和双(二甲基-硫代氨基甲酰基)-二硫化物的作用〕。体外作用的效果与上述商品产物约为同一数量级,但是体内试验时,式Ⅰ化合物优于这些已知的药物。
当喷雾有效成分含量为0.05~0.1%的药剂时,最好的式Ⅰ化合物在体内试验中,抗谷类植物、黄瓜、欧芹和甜菜的白粉病显示出非常好的并且是安全的保护作用。作用的效果与苯菌灵〔甲基1-(正-丁基氨基甲酰基)-2-苯并咪唑-氨基甲酸酯〕为同一数量级。喷雾含0.05%的式Ⅰ化合物对疣顶单胞锈菌(菜豆锈病菌)也是有效的。
抗疣顶单胞锈菌的效果,式Ⅰ化合物约与商品产物“代森锌M-45”{有效成分:锰+〔1,2-亚乙基双(硫代氨基甲酸)〕锌}相同。
式Ⅰ化合物在应用的浓度下对于栽培植物无植物毒性作用。
在体外,式Ⅰ化合物的杀菌作用通过下述方法测定:
制备试验化合物的0.5%乙醇溶液,并且取1.0、0.4、0.2和0.1毫升量的溶液分别与50毫升萨布罗氏类型(Sabouraud-type)的培养基混合均匀。使培养基固化,随后在表面上用受试真菌属的芽孢悬浮液接种。
下述真菌和细菌属用于试验:
石膏状发癣菌 细支链孢霉
发癣菌(Simii) 多主枝孢
表皮癣菌(longifusum) 胡萝卜黑斑匐柄霉
石膏状小孢霉 甜菜尾孢霉
禾木科镰孢 黄萎轮枝霉
大刀镰孢 立枯丝核菌
麦根腐长蠕孢 蚕、豌豆深褐斑菌
罂粟长蠕孢 密西根棒状杆菌
稻黑孢 黄单胞杆菌(Vesicatoria)
核盘病菌 欧文氏菌(Carotovora)
核果链核盘菌 丁香翰癌极毛杆菌
灰葡萄孢 滕黄细球菌
墨色刺盘孢 植物肥大病菌(tumefaciens)
在陪替氏培养皿(Petri-dishes)中有效成分的浓度分别为100、40、20和10微克/毫升,于28℃孵育5天后沉淀其活性
结果发现,在体外试验中有效成分浓度为10~20微克/毫升的最有效的式Ⅰ化合物(按实例1、4、5、7和8制备的化合物),对于大多数试验真菌(尤其是对发癣菌属、念珠菌属和长蠕孢属)显示出抑制真菌的作用。另一方面,已知的商品杀菌剂,如N-(三氯甲硫基)-邻苯二甲酰亚胺和双-(二甲基硫代氨基甲酰基)二硫化物只是在40~1000微克/毫升高浓度下才具有同样的作用。
进行了抗谷类植物白粉病的体内试验。
在Conviron植物盒内于20℃、相对湿度为90%和光照强度为9000勒克司条件下,测定化合物抗小麦白粉病的体内活性。应用经过正式鉴定的优良种子MV-4小麦品种生长的谷物作为宿主植物。将小麦植物栽培在含有沙和珍珠岩(1∶1)混合物的栽培盘(直径11厘米)内6天。每盘含160株植物,开始处理时植物高5~6厘米。制备高度分散的试验化合物的水悬浮液或丙酮溶液,并且用氮气控制的喷雾器将8毫升水悬浮液或丙酮溶液分别喷雾在植物上。在用杀菌剂处理后,孵育24天。在人工气候室里,试重复三次并且随机分组。在孵育后第8天测定感染率。分别观察50~60株植物,根据Hinfner和Pa PP所述的方法用数字进行评价试验结果。
未处理的对照组感染率是很高的,大多数植物被感染,约30~40%植物的外表由于感染而受到影响。
商业上有出售的杀菌剂,如1-丁基-氨基甲酰基-苯并咪唑-2-甲基-氨基甲酸酯和6-(1-甲基-庚基)-2,4-二硝基苯基-巴豆酸酯,在相同的试验条件下与最有效的新化合物(实例7和8的产物)相比,显示出较低的活性。
试验结果以受试化合物的ED50值和ED90值表示,ED50和ED90是根据效果与浓度的相互关系应用数字-生物统计学的方法计算而得的。E和E值分别表示与未经处理的对照组相比,能减少50%或90%试验植物感染白粉病所喷雾的有效成分的浓度(以ppm表示)。
试验结果总结于表Ⅰ。
表Ⅰ
试验化合物 ED50(ppm) ED50(ppm)
实例8 357 1336
实例7 346 1101
参照化合物*410 1455
*:参照化合物为苯菌灵〔甲基1-(正-丁基氨基甲酰基)-2-苯并咪唑-氨基甲酸酯〕
此外还在斑豆属上进行了抗菜豆锈病菌(疣顶单胞锈菌)的试验。在每个栽培盘中将3粒种子播种在由沙、珍珠岩和优质堆肥组成的混合物(1∶1∶0.035)里。经过7~9天温室予先栽培的二叶阶段的豆类植物用试验化合物处理,并将处理过的植物进行人工接种。孢子悬浮液的浓度为0.1克/10毫升,并将每个栽培盘用2.5毫升孢子悬浮液接种。接种后于20℃在相对湿度100%的条件下孵育48小时。在感染后7~8天出现症状。试验重复三次,试验中有未经处理的对照组,商品产物“代森锌M-45”用作为参照物。
结果表明,当应用喷雾的浓度为500ppm时,代森锌M-45抑制70~80%的豆锈病菌感染,而在相同条件下用本发明实例7和8的化合物可得到100%的抑制。
另一方面,本发明还提供了杀菌剂组合物,该组合物包括由至少一个有效量的式Ⅰ化合物(其中R同上所述)和合适的固体或液体载体以及另外经选择的添加剂组成的混合物。
式Ⅰ化合物的有效成分可以配制成通常可用于农业和园艺的杀菌剂组合物,以保护植物,例如可配制成粉剂、可湿性粉剂、喷雾剂、油喷雾剂、气溶胶、乳油、颗粒剂、微粒剂等。
本发明的杀菌剂组合物包括普通的和常规的固体载体或稀释剂。为此,下述物质可以优先选用:粉状或颗粒状的矿物(如滑石、膨润土、蒙脱土、陶土、高岭土、高度分散的硅胶、硅藻土、云母、磷灰石、蛭石、石膏、石灰石、叶蜡石、丝云母、浮石、硫、活性炭、风化的石灰、珍珠岩等),来源于植物(如大豆茎、小麦茎、木材、坚果外壳、锯屑、麸、皮层、树皮、植物萃取的残余物、淀粉、结晶纤维素)的粉末,粉状多聚物(如聚氯乙烯、玛树脂,酮的树脂等),纤维物质(如纸,瓦楞纸、破布),化肥(如硫酸铵、磷酸铵、硝酸铵、尿素、氯化铵等),以及矾土或蜡。
组合物还可以含有常规的和普遍的液体稀释剂,例如醇类(如甲醇、乙醇、异丙醇、乙二醇、聚乙二醇、苄醇);芳香族烃类(如苯、二甲苯、甲苯、甲基萘基);脂肪族烃类(如煤油、己烷);氯代烃类(如氯仿、四氯化碳、氯苯、三氯乙烯、二氯甲烷等);醚类(如二乙基醚、二异丙基醚、二恶烷、四氢呋喃、乙二醇***);酮类(如丙酮、甲基乙基酮、环己酮);酯类(如醋酸乙酯、乙二醇醋酸酯);酰胺类(如N,N-二甲基甲酰胺);腈类(如乙腈)或亚砜类(如二甲基亚砜)。
此外,本发明的杀菌剂组合物也可含有添加剂,如粘合剂和/或分散剂(如明胶、Ca Seine、藻酸钠、羧甲基纤维素、淀粉、磺化油、膨润土、聚氧丙二醇醚、聚乙烯醇、石蜡)稳定剂(如异丙基磷酸酯、三甲苯基磷酸酯、妥尔油、环氧化油、表面活性剂、脂肪酸、脂肪酸醚),乳化剂(如烷基磺酸酯、聚氧乙烯烷基磺酸酯、烷基芳基磺酸酯、聚乙二醇烷基醚或聚氧乙烯烷基芳基醚等),湿润剂(如十二烷基苯磺酸酯、月桂基磺酸酯、烷基萘磺酸盐)。
本发明的杀菌剂组合物除含有一般式Ⅰ的菲衍生物之外,还可以含有一种或多种其它具有生物活性的药物,如可含有促进生长的物质和/或其它杀菌剂如铝-三(乙基磷酸酯)、2-氨基丁烷、4,6-二氯-2-(2-氯代苯胺基)-1,3,5-三嗪、2-碘代-N-苯甲酰苯胺、甲基-1-(丁基氨基甲酰基)-2-苯并咪唑-氨基甲酸酯、1,4-苯醌-1-苯甲酰基腙-4-肟、2-仲丁基-4,6-二硝基-苯基-3-甲基巴豆酸酯、β-〔(1,1′-二苯基)-4-氧〕-α-(1,1-二甲基乙基)-1H-1,2,4-***-1-乙醇、1,2,3,6-四氢-N-(1,1,2,2-四氯乙硫基)-邻苯二甲酰亚胺、1,2,3,6-四氢-N-(三氯甲硫基)-邻苯二甲酰亚胺、2-(甲氧基羰基氨基)-苯并咪唑、5,6-二氢-2-甲基-1,4-氧硫杂环己二烯-3-N-甲酰苯胺、多氧霉素、有效霉素、链霉素、十二烷基胍醋酸酯、1-(4-氯苯氧基)-1-(咪唑-1-基)-3,3-二甲基-丁酮、四氢-3,5-二甲基-1,3,5-噻二嗪-2-硫酮、N-二氯-氟-甲硫基-N′,N-二甲基-N-苯基磺酰胺、2,3-二氯-1,4-萘醌、5-丁基-2-二甲氨基-4-羟基-6-甲基-嘧啶、2-或4-(1-甲基-庚基)-4,6-(或2,6)-二硝基-苯基-巴豆酸酯、2,3-二氰基-1,4-二硫代-蒽醌、5-丁基-2-乙氨基-4-羟基-6-甲基嘧啶、2-甲基呋喃-3-N-甲酰苯胺、N-(三氯甲硫基)-邻苯二甲酰亚胺、2-十七基-2-咪唑啉醋酸酯、7-溴-5-氯-喹啉-8-基丙烯酸酯、8-羟基喹啉及它的盐、1-(β-烯丙氧基-2,4-二氯苯基乙基)-咪唑、N-(2-甲氧基乙酰基)-N-(2,6-二甲苯基)-DL氨基丙酸甲酯、2,4,5-三甲基-N-苯基-3-呋喃羧酸酰胺、2-(4-噻唑基)-1H-苯并咪唑、1,2-双-(3-乙氧基羰基)-2-(硫脲基)-苯、1-(4-氯苯氧基)-3,3-二甲基-1-(1,2,4-***-1-基)-丁醇等。
本发明的组合物除含有式Ⅰ化合物作为有效成分之外,还可含有一种或多种杀虫剂,如2-甲氧基-4H-1,3,2-苯并二噁磷英-2-硫、(5-苄基-3-羟基-甲基-呋喃)-d-反式-菊酸酯、3-苯氧基苄基-菊酸酯、O,O-二乙基-1-(2,4-二氯苯基)-2-氯乙烯基磷酸酯、2,2-二甲基-3-(2,2-二氯乙烯基)-环丙烷羧酸-α-氰基-2-苯氧基苄基酯、O,O-二乙基-O-(2-异丙基-4-甲基嘧啶基)-硫代磷酸酯、2,3-二氢-2,2-二甲基-7-苯并呋喃基-N-甲基-氨基甲酸酯等。
在上述组合物中,各个农药的活性并不降低,因此上述复方可以同时杀灭二种或二种以上的病虫害(真菌、昆虫)。此外,本发明的组合物还可以含有用于于农业上和园艺上的药物,如可以含有对丝状昆虫和蛾有效的杀虫剂(如琥珀酸2,2-二甲基酰肼、氯化2-氯乙基三甲基铵、2-氯乙基磷酸、氯化1,1-二甲基哌啶)。本发明的组合物中还可以加入化肥。
本发明组合物中含有的有效成分的量可以在较大的范围内变动,按重量计通常可为0.001~95.0%,最好为5~80%(按重量计)。有效成分的用量最好是100~1000克/公顷,所用组合物的浓度按重量计约为0.01(20~60%)的形式。但是上述的变动范围只是提供点资料,实际的用量和使用浓度要根据不同的因素(如配方的类型、施药的方式和现场的情况、真菌病害的严重程度以及要给施药的农作物的情况等)决定,可以低于或高于上述变动范围。
本发明的具有杀菌作用的组合物可以用农药产业已知的方法制备。
此外,本发明还提供了具有抗菌作用的药用组合物,该组合物含有至少一个式Ⅰ化合物作为有效成分,并且与合适的惰性固体液体药用载体组成混合物。
上述药用组合物可以用制药产业本身已知的方法制备。
另一方面,本发明也提供了制备一般式Ⅰ的菲类衍生物(其中R同上述)的方法,该方法包括
a)为了制备具有一般式Ⅰ的化合物,其中R代表C1-10烷氨基,或代表在苯环上有选择地被一个或多个相同或者不同的C1-4烷基、C1-4烷氧基、硝基、氨基、氰基和/或囟素取代的苯基氨基,
可使菲-9,10-二酮-9-肟(式Ⅱ)
与具有一般式Ⅳ的异氰酸酯反应,
其中R1代表C1-10烷基,或代表有选择地被一个或多个相同或者不同的C1-4烷基、C1-4烷氧基、硝基、氨基、氰基和/或囟素取代的苯基;
b)为了制备具有一般式Ⅰ的化合物,其中R代表C1-4烷氧基或C1-4烷硫基,
可使菲-9,10-二酮-9-肟(式Ⅱ)或它的碱金属或碱土金属盐(式Ⅲ)
(其中M为1价的碱金属或碱土金属)
与具有一般式Ⅴ的化合物反应,
(其中R2代表C1-10烷基;Y代表氧或硫,并且HIg为囟素);或
c)为了制备具有一般式Ⅰ的化合物,其中R代表有选择地被一个或多个相同或不同的C1-4烷基、C1-4烷氧基、硝基、氨基、氰基和/或囟素取代的苯基,
可使菲-9,10-二酮-9-肟(式Ⅱ)或它的碱金属或者碱土金属盐(式Ⅲ,其中M同上述)
与具有一般式Ⅵ的化合物反应,
(其中R3代表有选择地被一个或多个相同或不同的C1-4烷基,C1-4烷氧基、硝基、氨基、氰基和/或囟素取代的苯基,并且X代表离去基团)。
按照本发明的制备方法,方法a)是使9,10-菲-二酮-一肟(式Ⅱ)与具有一般式Ⅳ的异氰酸酯反应。该反应可在惰性有机溶剂中进行。可以应用的反应介质为芳香烃(如苯或二甲苯),醚(如四氢呋喃、二噁烷),囟代烃类(如氯仿、二氯甲烷或四氯化碳)。在无水条件下进行反应是有利的。还可将亲核催化剂加到反应混合物中。为此,可从应用叔胺(如N-乙基-哌啶三乙胺)。反应可在0℃~35℃之间进行,在室温下进行反应是有利的。反应需进行约0.5~6小时;在室温下反应,反应时间为约1~3小时。
按照方法b),最好应用其中HIg为氯的一般式Ⅴ为起始原料。可以用式Ⅱ的碱金属(如钠或钾)盐或碱土金属(如钙或镁)盐(式Ⅲ)代替9,10-菲-二酮-肟(式Ⅱ)。最好是用钠盐。反应可在惰性有机溶剂(如丙酮、二噁烷或二甲基甲酰胺)中进行。反应可在0℃~100℃之间进行,最好是在10℃~70℃之间进行。
按照完成方法b)优先选用的方式,使9,10-菲-二酮-肟(式Ⅱ)与Ⅴ化合物的反应可在偶极性的非质子传递溶剂(如乙腈、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜)中,在经选择的较小极性的非质子传递溶剂(如吡啶、二恶烷或苯)存在下进行,反应约需0.5~10小时,特别是1.5~3小时。
按照方法c),可使9,10-菲二酮-一肟(式Ⅱ)或它的碱金属(如钠或钾)盐或碱土金属(如钙或镁)盐(式Ⅲ)与具有一般式Ⅵ的酰化剂反应。最好是应用具有一般式Ⅲ的钠盐。在具有一般式Ⅵ的酰化剂中,X最好为囟素(如氯或溴)、烷基磺酰氧基(如甲基磺酰氧基)或芳基磺酰氧基(如苯基、对-甲基苯基或对-溴苯基磺酰氧基)。反应可在惰性有机溶剂中进行。选择反应介质应考虑X离去基团的特点。为此,可以应用非极性的非质子传递介质(如二噁烷、苯、氯仿、四氯化碳)或具有质子活性的溶剂(如甲酰胺、醋酸或乙醇)。反应可在0℃~120℃之间进行,最好在20℃~25℃之间进行。反应时间约为0.5~10小时,最好1~2小时。
应用的起始原料可用先有技术中已知的方法制得,例如可按照下述刊物所述的方法制备:
9,10-菲-醌〔J.Am.Chem.Soc64,2023(1942)〕;
9,10-菲-醌-9-肟〔Ber.22,(1889)〕;
后-化合物的钠盐〔J.Am Chem.Soc 76,124~127(1954)〕。
在下述实例中将进一步详述本发明,但该实例并不限制本发明要求保护的范围。
实例1
24.6克(0.1摩尔)9,10-菲-二酮-9-肟的钠盐悬浮于100毫升丙酮中,随后在搅拌下将15.4克(0.11摩尔)苯甲酰氯和50毫升丙酮的溶液加入,产生轻微的放热反应,析出氯化钠沉淀,约在1小时内形成深棕色溶液。反应完成后,将反应混合物加热至沸腾15分钟,并在减压下蒸发。得到28.2克9,10-菲-二酮-9-苯甲酰基-肟,产率86.2%,熔点为148~149℃。
元素分析:C21H13NO3
计算值:C%=77.06;H%=3.98;N%=4.28
实测值:C%=77.15;H%=3.96;N%=4.32
实例2
在搅拌下将22.3克(0.1摩尔)9,10-菲二酮-9-肟溶于200毫升二甲基甲酰胺和乙腈的混合液(1∶1)中,然后加入16毫升吡啶。在搅拌下向反应混合物中滴入氯代甲酸甲酯和30毫升乙腈组成的溶液,反应混合物先在室温下搅拌1小时,然后在沸点温度下搅拌15分钟。冷却反应混合物,并倾入700毫升冰水中。冷却中析出的油状产品固化,得到22.9克9,10-菲-二酮-9-甲氧基羰基肟,为赭黄色产品。产率81.5%,熔点为142~143℃。
元素分析:C16H11NO4
计算值:C%=68.32;H%=3.91;N%=4.98
实测值:C%=68.29;H%=3.90;N%=4.92
实例3~6
除了应用相应的起始原料外,可以按实例2的方法制备下列化合物:
3)9,10-菲-二酮-9-(乙氧基羰基)-肟
元素分析:C17H13NO4
计算值:C%=69.15;H%=4.41;N%=4.75
实测值:C%=69.00;H%=4.39;N%=4.71
4)9,10-菲-二酮-9-(乙基硫代羰基)-肟
元素分析:C17H13NO3S
计算值:C%=65.59;H%=4.18;N%=4.50;S%=10.29
实测值:C%=65.49;H%=4.13;N%=4.13;S%=10.29
5)9,10-菲-二酮-9-(正-丙基硫代羰基)-肟
元素分析:C18H15NO3S
计算值:C%=66.46;H%=4.61;N%=4.30;S%=9.84
实测值:C%=66.41;H%=4.60;N%=4.28;S%=9.92
6)9,10-菲-二酮-9-(正-辛基硫代羰基)-肟
元素分析:C23H25NO3S
计算值:C%=69.87;H%=6.33;N%=3.54;S%=8.10
实测值:C%=69.79;H%=6.30;N%=3.49;S%=8.18
实例7
22.3克(0.1摩尔)9,10-菲-贰酮-9-肟在0.2毫升三乙胺存在下,与12毫升(0.11摩尔)异氰酸正-丁酯在100毫升氯仿中的溶液反应1小时,反应混合物加热至沸腾半小时,并在减压下蒸发。得到32克9,10-菲-二酮-9-(正-丁氨基羰基)-肟,为淡黄棕色油状物,产率99%,该产品可经层析纯化。
元素分析:C19H18N2O3
计算值:C%=70.81;H%=5.59;N%=8.69
实测值:C%=70.01;H%=5.51;N%=8.71
实例8~10
除了应用相应的起始原料外,可以按实例7的方法制备下列化合物:
8)9,10-菲-二酮-9-(甲氨基羰基)-肟
元素分析:C16H12N2O3
计算值:C%=68.57;H%=4.29;N%=10.0
实测值:C%=68.40;H%=4.23;N%=9.89
9)9,10-菲-9-(4-氯代苯基-氨基-羰基)-肟
元素分析:C21H13ClN2O3
计算值:C%=67.02;H%=3.46;N%=7.44;Cl%=9.31
实测值:C%=67.08;H%=3.41;N%=7.39 Cl%=9.33
10)9,10-菲-二酮-9-(3,4-二氯代苯基-氨基-羰基)-肟
元素分析:C21H12Cl2N2O3
计算值:C%=61.46;H%=2.93;N%=6.82;Cl%=17.07
实测值:C%=60.99;H%=2.90;N%=6.73 Cl%=17.01
实例11
粉剂组合物
将2份重量的实例1化合物和98份重量的陶土充分混匀,得到含2%有效成分的粉剂组合物。
实例12
可湿性粉剂
将50份重量的实例3化合物、2.5份重量的十二烷基苯磺酸盐(湿润剂)、2.5份重量的木素磺化钠(分散剂)和45份重量的硅藻土充分掺和并混匀,得到含50%有效成分的可湿性粉剂,该可湿性粉剂经水稀释后可用于喷雾。
实例13
可湿性粉剂
将90份重量的实例6化合物,2.5份重量的十二烷基苯磺酸盐、2.5份重量的木素磺化钠和5份重量的硅藻土充分掺和并混匀,得到含90%有效成分的可湿性粉剂,该可湿性粉剂经水稀释后可用于喷雾。
实例14
粉剂
将0.2份重量的实例5化合物,1份重量的石蜡油和98.8%重量的陶土充分掺和并混匀,得到含0.2%有效成分的可随时应用的粉剂组合物。
实例15
浓乳剂
将20份重量的实例8化合物、30份重量的二甲基亚砜、40份重量的二甲苯和10份重量的聚(氧乙烯)-十二烷基酚醚(乳化剂)充分混合,得到含20%有效成分的浓乳剂,该浓乳剂经水稀释后可用于喷雾。
实例16
粒剂
将15份重量的实例10化合物、81.5份重量的陶土和3.5份重量的聚乙烯醇型粘合剂掺和,粉碎并充分混匀,混合物与水一起捏和,制成颗粒并干燥,该颗粒含有15%有效成分,可以颗粒剂的形式应用,或与泥土掺和应用。
实例17
可悬浮的粒剂
将10份重量的实例7化合物施在85份重量的浮石(颗粒大小为0.5~1毫米)上,使有效成分渗入载体,然后再将5份重量的液体石蜡喷到浮石上,得到含10%有效成分的可随时应用的悬浮粒剂。
实例18
包衣粒剂
将20份重量的实例4化合物施在64份重量的石英砂(颗粒大小为0.5~1毫米)上,并向颗粒上喷撒6份重量10%的聚乙烯醇水溶液,该颗粒与10份重量的白炭黑掺和,得到含有20%有效成分的可随机应用的包衣粒剂。
实例19
粒剂
将10份重量的实例9化合物、30份重量的膨润土、1份重量的木素磺化钙、0.1份重量的十二烷基硫酸钠和58.9份重量的陶土混匀。混合物与水一起捏和,并通过合适筛目的筛子而制成颗粒,颗粒经干燥,得到含10%有效成分的粒剂,该粒剂可以粒剂形式应用,也可以作为稀释的水溶液应用。
Claims (20)
1、制备具有一般式Ⅰ的菲-二酮衍生物的方法,
其中
R代表C1-10烷氨基;C1-10烷硫基;C1-5烷氧基;苯基或苯基氨基,后二个基团的苯基上可选择性地有一个或多个相同或不同的C1-4烷基、C1-4烷氧基、硝基、氨基、氰基和/或囟素取代基,
该方法包括
a)为了制备具有一般式Ⅰ的化合物,其中R代表C1-10烷氨基或在苯环上有一个或多个相同或不同的C1-4烷基、C1-4烷氧基、硝基、氨基、氰基和/或囟素有选择取代的苯基氨基,可使菲-9,10,二酮-9-肟(式Ⅱ)
与具有一般式Ⅳ的异氰酸酯反应,
R1-NCO (Ⅳ)
其中R1代表C1-10烷基或由一个或多个相同或不同的C1-4烷基、C烷氧基、硝基、氨基、氰基和/或囟素有选择取代的苯基;或者
b)为了制备具有一般式Ⅰ的化合物,其中R代表C1-5烷氧基或C1-10烷硫基,
可使菲-9,10-二酮-9-肟(式Ⅱ)或它的碱金属盐或碱土金属盐(式Ⅲ)
(其中M是一价碱金属或碱土金属)
与具有一般式Ⅴ的化合物反应,
R2-Y-CO-HIg (Ⅴ)
(其中R2代表C1-10烷基;Y代表氧或硫,HIg代表囟素);或者
c)为了制备具有一般式Ⅰ的化合物,其中R代表由一个或多个相同或不同的C1-4烷基,C1-4烷氧基、硝基、氨基、氰基和/或囟素有选择取代的苯基,
可使菲-二酮-9-肟(式Ⅱ)或它的碱金属盐或碱土金属盐(式Ⅲ,其中M同上述)与具有一般式Ⅵ的化合物反应,
R3-CO-X (Ⅵ)
其中R3代表由一个或多个相同或不同的C1-4烷基、C1-4烷氧基、硝基、氨基、氰基和/或囟素有选择取代的苯基,并且X代表离去基团。
2、按照权利要求1a所述的方法,该方法包括在惰性有机溶剂中进行该反应。
3、按照权利要求1a或10所述的方法,该方法包括在亲核催化剂存在下进行该反应。
4、按照权利要求3所述的方法,该方法包括应用叔胺,最好是N-乙基-哌啶或三乙胺作为亲核催化剂。
5、按照权利要求1b所述的方法,该方法包括应用具有一般式Ⅴ的化合物作为起始原料,其中H/g代表氯。
6、按照权利要求1b或5所述的方法,该方法包括应用9,10-菲-二酮-肟的钠盐(式Ⅲ化合物,其中M为钠)。
7、按照权利要求6所述的方法,该方法包括在惰性溶剂中进行该反应。
8、按照权利要求1c所述的方法,该方法包括应用具有一般式Ⅵ的化合物作为起始原料,其中X代表囟素,烷基磺酰氧基或芳基磺酰氧基。
9、按照权利要求8所述的方法,该方法包括应用具有一般式Ⅵ的化合物作为起始原料,其中X代表氯、溴、甲基磺酰氧基、苯基磺酰氧基、对-甲基苯基磺酰氧基或对-溴苯基磺酰氧基。
10、按照权利要求8或9所述的方法,该方法包括应用具有一般式Ⅲ的化合物作为起始原料,其中M是钠。
11、按照权利要求8~10中任何一项所述方法,该方法包括在惰性有机溶剂中进行该反应。
12、按照权利要求1a所述的方法制备9,10-菲二酮-9-(甲氨基羰基)-肟,该方法包括应用具有一般式Ⅳ的化合物作为起始原料,其中R代表甲基。
13、按照权利要求1a所述的方法制备9,10-菲二酮-9-(正-丁氨基羰基)-肟,该方法包括应用具有一般式Ⅳ的化合物作为起始原料,其中R代表正-丁基。
14、以至少一个有效量的式Ⅰ化合物(其中R的定义同权利要求1所述)作为有效成分,并与合适的固体或液体载体以及另外选择的添加剂混合组成的杀菌剂组合物。
15、按照权利要求14所述的杀菌剂组合物,该组合物包括以9,10-菲-二酮-9-(甲氨基羰基)-肟或9,10-菲二酮-9-(正-丁氨基羰基)-肟作为有效成分。
16、按照权利要求14所述的制备杀菌剂组合物的方法,该方法包括使至少一个式Ⅰ化合物与合适的惰性固体或液体载体混合。
17、杀灭农业或园艺的真菌病害的方法,该方法包括将有效量的权利要求1所述的化合物或权利要求14所述的组合物施在植物上、植物的某部位上、土壤中以及需保护的目的物上或病害上。
18、制备用于治疗人类疾病的抗菌剂组合物的方法,该方法包括使至少一个式Ⅰ化合物与合适的惰性固体或液体药用载体混合。
19、按照权利要求1~13中任何一项所述方法制备的式Ⅰ化合物。
20、其中根据实例已经详细叙述的方法。
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HU2194/85 | 1985-06-04 | ||
HU852194A HU196288B (en) | 1985-06-04 | 1985-06-04 | Fungicides containing as active substance new derivatives of fenantren and process for production of the active substance |
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US (1) | US4746678A (zh) |
JP (1) | JPS6248661A (zh) |
KR (1) | KR870011083A (zh) |
CN (1) | CN86103679A (zh) |
AU (1) | AU589637B2 (zh) |
BE (1) | BE904865A (zh) |
BR (1) | BR8602608A (zh) |
CH (1) | CH667645A5 (zh) |
CS (1) | CS411386A2 (zh) |
DD (2) | DD248357A5 (zh) |
DE (1) | DE3618715A1 (zh) |
DK (1) | DK262286A (zh) |
ES (1) | ES8707711A1 (zh) |
FI (1) | FI862382A (zh) |
FR (1) | FR2582647B1 (zh) |
GB (1) | GB2176186B (zh) |
GR (1) | GR861451B (zh) |
HU (1) | HU196288B (zh) |
IL (1) | IL79029A0 (zh) |
IT (1) | IT1204376B (zh) |
NL (1) | NL8601435A (zh) |
NO (1) | NO862231L (zh) |
PL (1) | PL147246B1 (zh) |
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SE (1) | SE8602525L (zh) |
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CN106565536A (zh) * | 2016-07-15 | 2017-04-19 | 广西民族大学 | 异长叶烯酮肟醚衍生物及其制备方法和应用 |
CN110156867A (zh) * | 2019-06-27 | 2019-08-23 | 南京神奇科技开发有限公司 | 一种氨基甲酸黄柏酮肟酯及其制备方法与应用 |
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DE3708320A1 (de) * | 1987-03-14 | 1988-09-22 | Bayer Ag | Benzaldoxim-derivate |
JP2003518039A (ja) * | 1999-12-21 | 2003-06-03 | アストラゼネカ アクチボラグ | Cd45阻害剤 |
DE60023744T2 (de) * | 1999-12-21 | 2006-09-21 | Astrazeneca Ab | Cd45 inhibitoren |
KR20090104877A (ko) * | 2007-01-23 | 2009-10-06 | 후지필름 가부시키가이샤 | 옥심 화합물, 감광성 조성물, 컬러 필터, 그 제조방법 및 액정표시소자 |
AR108745A1 (es) * | 2016-06-21 | 2018-09-19 | Syngenta Participations Ag | Derivados de oxadiazol microbiocidas |
GB202014840D0 (en) * | 2020-09-21 | 2020-11-04 | Syngenta Crop Protection Ag | Microbiocidal compounds |
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US3547621A (en) * | 1967-05-29 | 1970-12-15 | Gulf Research Development Co | Method of combating weeds |
GB1180846A (en) * | 1967-08-08 | 1970-02-11 | Agfa Gevaert Nv | Photopolymerisation of Ethylenically Unsaturated Organic Compounds |
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- 1986-05-31 CN CN198686103679A patent/CN86103679A/zh active Pending
- 1986-06-03 BE BE0/216735A patent/BE904865A/fr not_active IP Right Cessation
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- 1986-06-04 CS CS864113A patent/CS411386A2/cs unknown
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- 1986-06-04 JP JP61130007A patent/JPS6248661A/ja active Pending
- 1986-06-04 SU SU864027579A patent/SU1450737A3/ru active
- 1986-06-04 PT PT82713A patent/PT82713B/pt unknown
- 1986-06-04 DE DE19863618715 patent/DE3618715A1/de not_active Withdrawn
- 1986-06-04 NL NL8601435A patent/NL8601435A/nl not_active Application Discontinuation
- 1986-06-04 IT IT20666/86A patent/IT1204376B/it active
- 1986-06-04 IL IL79029A patent/IL79029A0/xx unknown
- 1986-06-04 DD DD86290957A patent/DD248357A5/de not_active IP Right Cessation
- 1986-06-04 DD DD86301000A patent/DD261083A5/de not_active IP Right Cessation
- 1986-06-04 GB GB8613531A patent/GB2176186B/en not_active Expired
- 1986-06-04 BR BR8602608A patent/BR8602608A/pt unknown
- 1986-06-04 DK DK262286A patent/DK262286A/da not_active Application Discontinuation
- 1986-06-04 US US06/870,402 patent/US4746678A/en not_active Expired - Fee Related
- 1986-06-04 SE SE8602525A patent/SE8602525L/ not_active Application Discontinuation
- 1986-06-04 ES ES555709A patent/ES8707711A1/es not_active Expired
- 1986-06-04 GR GR861451A patent/GR861451B/el unknown
- 1986-06-04 FI FI862382A patent/FI862382A/fi not_active IP Right Cessation
- 1986-06-04 KR KR1019860004449A patent/KR870011083A/ko not_active Application Discontinuation
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106565536A (zh) * | 2016-07-15 | 2017-04-19 | 广西民族大学 | 异长叶烯酮肟醚衍生物及其制备方法和应用 |
CN106565536B (zh) * | 2016-07-15 | 2018-05-08 | 广西民族大学 | 异长叶烯酮肟醚衍生物及其制备方法和应用 |
CN110156867A (zh) * | 2019-06-27 | 2019-08-23 | 南京神奇科技开发有限公司 | 一种氨基甲酸黄柏酮肟酯及其制备方法与应用 |
CN110156867B (zh) * | 2019-06-27 | 2022-03-25 | 南京神奇科技开发有限公司 | 一种氨基甲酸黄柏酮肟酯及其制备方法与应用 |
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