CN102199095B - 一种取代二苯胺类化合物及其制备与应用 - Google Patents
一种取代二苯胺类化合物及其制备与应用 Download PDFInfo
- Publication number
- CN102199095B CN102199095B CN201010129005.6A CN201010129005A CN102199095B CN 102199095 B CN102199095 B CN 102199095B CN 201010129005 A CN201010129005 A CN 201010129005A CN 102199095 B CN102199095 B CN 102199095B
- Authority
- CN
- China
- Prior art keywords
- compound
- alkyl
- acid
- formula
- halo
- 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.)
- Active
Links
- 0 Cc1cccc(O)c1Nc(c(C)c(c(*)c1)Cl)c1[N+]([O-])=O Chemical compound Cc1cccc(O)c1Nc(c(C)c(c(*)c1)Cl)c1[N+]([O-])=O 0.000 description 6
- FBAAPODRQUQJIQ-UHFFFAOYSA-N Cc(c(Nc1ccccc1)c(cc1)[N+]([O-])=O)c1Cl Chemical compound Cc(c(Nc1ccccc1)c(cc1)[N+]([O-])=O)c1Cl FBAAPODRQUQJIQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
- C07C211/56—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
-
- 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
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
- A01N33/18—Nitro compounds
-
- 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
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
- A01N33/18—Nitro compounds
- A01N33/20—Nitro compounds containing oxygen or sulfur attached to the carbon skeleton containing the nitro group
- A01N33/22—Nitro compounds containing oxygen or sulfur attached to the carbon skeleton containing the nitro group having at least one oxygen or sulfur atom and at least one nitro group directly attached to the same aromatic ring system
-
- 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
- A01N37/34—Nitriles
-
- 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
- A01N37/44—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 at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
-
- 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
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/10—Sulfones; Sulfoxides
-
- 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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
- C07C237/30—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having the nitrogen atom of the carboxamide group bound to hydrogen atoms or to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
- C07C237/40—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having the nitrogen atom of the carboxamide group bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
- C07C317/36—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atoms of the amino groups bound to hydrogen atoms or to carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
- C07C323/33—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring
- C07C323/35—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group
- C07C323/36—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group the sulfur atom of the sulfide group being further bound to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/38—Amides of thiocarboxylic acids
- C07C327/48—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
- C07D213/643—2-Phenoxypyridines; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/70—Sulfur atoms
Abstract
本发明公开了一种取代二苯胺类化合物,如通式I所示:
Description
技术领域
本发明属农用杀菌、杀虫、杀螨剂领域。具体地涉及一种取代二苯胺类化合物及其制备与应用。
背景技术
二苯胺(diphenylamine)和氟啶胺(fluazinam)是已知的杀菌剂,前者主要用于防治水果蔬菜仓储病害,后者主要用于大田作物防治多种病害。
现有技术报道了如下通式所示的化合物可以作为杀虫剂、杀螨剂、杀菌剂、除草剂、杀鼠剂或其他用途:
例如专利BR7900462、CH626323、CN1188757、DE2509416、DE2642147、DE2642148、EP26743、EP60951、GB1544078、GB1525884、JP58113151、JP64001774、JP01186849、WO2002060878、WO2005035498、WO2009037707、US3948957、US3948990、US4041172、US4152460、US4187318、US4215145、US4304791、US4316988、US4407820、US4459304、US4670596等,以及ACS Symposium Series(1992),504(Synth.Chem.Agrochem.III),336-48;Journal ofthe Chemical Society(1951),110-15等均公开了上述通式结构的化合物。
另外,杂志Chemische Berichte(1962),951711-21;Chemische Berichte(1963),96(7),1936-44;Journal of Organic Chemistry(1954),19,1641-5,Journal ofthe Chemical Society,Transactions(1913),103982-8和Journal ofthe Chemical Society,Transactions(1921),119,187-92等公开了如下化合物,但没有任何生物活性报道。
US3107263公开了如下化合物的制备方法:
发明内容
现代农业生产需要不断开发出结构新颖、性能优异的新农药。本发明的目的在于提供一种在很小的剂量下就可以控制多种病菌和害虫害螨的取代二苯胺类化合物,它可应用于农业上以防治作物的病菌和害虫害螨。
本发明的技术方案如下:
本发明提供一种取代二苯胺类化合物,如通式I所示:
式中:
R1选自氢、C1-C12烷基、C3-C12环烷基、卤代C1-C12烷基、C1-C12烷基羰基、卤代C1-C12烷基羰基、C1-C12烷氧基羰基、C1-C12烷基氨基羰基、C1-C12烷硫基、卤代C1-C12烷硫基、C1-C12烷基磺酰基、C1-C12烷氧基C1-C12烷基、C1-C12烷氧基C1-C12烷基羰基、C1-C12烷氧基羰基C1-C12烷基、C1-C12烷基氨基硫基、C2-C12二烷基氨基硫基或CO-X-CO2R4,其中X选自(CHR4)p、CR4=CR5或C6H4;
R2选自卤素、C1-C12烷基、卤代C1-C12烷基、C1-C12烷氧基、卤代C1-C12烷氧基、C1-C12烷基氨基、卤代C1-C12烷基氨基、C1-C12烷硫基、卤代C1-C12烷硫基、C1-C3烷基羰基氨基、C1-C12烷基磺酰基、C3-C12环烷基、C2-C12二烷基氨基、C3-C12烯氧基、卤代C3-C12烯氧基、C3-C12炔氧基、卤代C3-C12炔氧基、C1-C12烷基羰基氧基、C1-C12烷基磺酰基氧基、C1-C12烷氧基C1-C12烷氧基、C1-C12烷氧基羰基C1-C12烷氧基、未取代的或被1-5个R6取代的芳基氨基、杂芳基氨基、芳氧基、杂芳基氧基、芳甲基氧基或芳甲基氨基;
R3选自氢、卤素、硝基、氰基、C(=O)NR4R5、C(=S)NR4R5、C1-C12烷基氨基羰基、C1-C12烷氧基羰基、卤代C1-C12烷基或C1-C12烷基磺酰基;
R选自卤素、氰基、硝基、C(=O)NR4R5、C1-C12烷基、卤代C1-C12烷基、C1-C12烷氧基、卤代C1-C12烷氧基、C1-C12烷基氨基、卤代C1-C12烷基氨基、C1-C12烷硫基、卤代C1-C12烷硫基、C2-C12烯基、C2-C12炔基、C1-C12烷基磺酰基、C1-C12烷基羰基、C1-C12烷氧基羰基、C1-C12烷氧基C1-C12烷基、C1-C12烷氧基羰基C1-C12烷基、C1-C12烷基羰基氧基、C1-C12烷氧基羰基氧基、C1-C12烷基氨基羰基氧基、C1-C12烷基磺酰基氧基、C1-C12烷氧基C1-C12烷氧基、卤代C1-C12烷氧基卤代C1-C12烷氧基、C1-C12烷氧基羰基C1-C12烷氧基、未取代的或被1-5个R6取代的芳基、芳甲基、芳基羰基、芳甲基羰基、芳基氨基、芳氧基、杂芳基氧基、芳氧基羰基或芳基氨基羰基;
R4、R5可相同或不同,分别选自氢或C1-C6烷基;
R6选自卤素、硝基、氰基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、卤代C1-C6烷氧基、C1-C6烷硫基、C1-C6烷基羰基、C1-C6烷氧基羰基、C2-C6烯基、卤代C2-C6烯基、C3-C6烯氧基、卤代C3-C6烯氧基、C2-C6炔基、卤代C2-C6炔基、C3-C6炔氧基、卤代C3-C6炔氧基、卤代C1-C6烷硫基、卤代C1-C6烷基羰基、C1-C6烷基氨基、卤代C1-C6烷基氨基、C2-C8二烷基氨基、C1-C6烷基羰基氨基、卤代C1-C6烷基羰基氨基、C1-C6烷基氨基羰基或卤代C1-C6烷基氨基羰基;
n=1-5;p=1-6;
或通式I化合物的盐。
本发明较为优选的化合物为:通式I中
R1选自氢、C1-C6烷基、C3-C6环烷基、C1-C6烷基羰基、卤代C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷硫基、卤代C1-C6烷硫基、C1-C6烷基磺酰基、C1-C6烷氧基C1-C6烷基、C1-C6烷氧基C1-C6烷基羰基、C1-C6烷氧基羰基C1-C6烷基、C1-C6烷基氨基硫基、C2-C6二烷基氨基硫基或CO-X-CO2R4,其中X选自(CHR4)p、CR4=CR5或C6H4;
R2选自卤素、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、卤代C1-C6烷氧基、C1-C6烷基氨基、卤代C1-C6烷基氨基、C1-C6烷硫基、卤代C1-C6烷硫基、C1-C6烷基羰基氨基、C1-C6烷基磺酰基、C3-C6环烷基、C2-C6二烷基氨基、C3-C6烯氧基、卤代C3-C6烯氧基、C3-C6炔氧基、C1-C6烷基羰基氧基、C1-C6烷基磺酰基氧基、C1-C6烷氧基C1-C6烷氧基、C1-C6烷氧基羰基C1-C6烷氧基、未取代的或被1-3个R6取代的苯基氨基、吡啶基氨基、苯氧基、吡啶基氧基、苄基氧基或苄基氨基;
R3选自氢、氯、溴、氟、硝基、氰基、C(=O)NR4R5、C(=S)NR4R5、CO2CH3、三氟甲基或甲基磺酰基;
R选自卤素、氰基、硝基、C(=O)NR4R5、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、卤代C1-C6烷氧基、C1-C6烷基氨基、卤代C1-C6烷基氨基、C1-C6烷硫基、卤代C1-C6烷硫基、C2-C6烯基、C2-C6炔基、C1-C6烷基磺酰基、C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷氧基C1-C6烷基、C1-C6烷氧基羰基C1-C6烷基、C1-C6烷基羰基氧基、C1-C6烷氧基羰基氧基、C1-C6烷氧基C1-C6烷氧基、卤代C1-C6烷氧基卤代C1-C6烷氧基、C1-C6烷氧基羰基C1-C6烷氧基、未取代的或被1-4个R6取代的苯基羰基、苄基羰基、苯基氨基、苯氧基、吡啶基氧基、苯氧基羰基或苯基氨基羰基;
R4、R5可相同或不同,分别选自氢或C1-C3烷基;
R6选自卤素、硝基、氰基、C1-C3烷基、卤代C1-C3烷基、C1-C3烷氧基、卤代C1-C3烷氧基、C1-C3烷硫基、C1-C3烷基羰基、C1-C3烷氧基羰基、C1-C3烷基氨基、C2-C6二烷基氨基、C1-C3烷基羰基氨基或C1-C3烷基氨基羰基;
n=1-5。p=1-3;
或通式I化合物的盐。
进一步优选的化合物为:通式I中
R1选自氢、C1-C3烷基、C3-C6环烷基、C1-C3烷基羰基、卤代C1-C3烷基羰基、C1-C3烷氧基羰基、卤代C1-C3烷硫基、C1-C3烷基磺酰基、C1-C3烷氧基C1-C3烷基、C1-C3烷氧基C1-C3烷基羰基、C1-C3烷氧基羰基C1-C3烷基、C1-C3烷基氨基硫基、C2-C6二烷基氨基硫基或CO-X-CO2R4,其中X选自(CHR4)p、CR4=CR5或C6H4;
R2选自氯、溴、氟、C1-C3烷基、卤代C1-C3烷基、C1-C3烷氧基、卤代C1-C3烷氧基、C1-C3烷基氨基、卤代C1-C3烷基氨基、C1-C3烷硫基、卤代C1-C3烷硫基、C1-C3烷基羰基氨基、C1-C3烷基磺酰基、C2-C6二烷基氨基、C3-C4烯氧基、卤代C3-C4烯氧基、C3-C4炔氧基、C1-C3烷基羰基氧基、C1-C3烷基磺酰基氧基、未取代的或被1-3个R6取代的苯基氨基、吡啶基氨基、苯氧基、吡啶基氧基、苄基氧基或苄基氨基;
R3选自硝基;
R选自氯、溴、氟、氰基、硝基、C(=O)NR4R5、C1-C3烷基、卤代C1-C3烷基、C1-C3烷氧基、卤代C1-C3烷氧基、C1-C3烷基氨基、C1-C3烷硫基、C1-C3烷基磺酰基、C1-C3烷基羰基、C1-C3烷氧基羰基、C1-C3烷氧基C1-C2烷基、C1-C3烷基羰基氧基、C1-C3烷氧基羰基氧基、C1-C3烷氧基C1-C3烷氧基、卤代C1-C3烷氧基卤代C1-C3烷氧基、未取代的或被1-4个R6取代的苯基羰基、苄基羰基、苯基氨基、苯氧基、吡啶基氧基、苯氧基羰基或苯基氨基羰基;
R4、R5可相同或不同,分别选自氢或C1-C3烷基;
R6选自氯、溴、氟、硝基、氰基、三氟甲基、C1-C3烷基、C1-C3烷氧基、C1-C3烷硫基、C1-C3烷基羰基、C1-C3烷氧基羰基或C1-C3烷基氨基羰基;
n=1-5;p=1-3;
或通式I化合物与盐酸、硫酸、磷酸、甲酸、乙酸、三氟乙酸、甲磺酸、对甲苯磺酸、苹果酸或柠檬酸形成的盐。
更进一步优选的化合物为:通式I中
R1选自氢、甲基、乙基、环丙基、甲酰基、乙酰基、三氟乙酰基、甲氧基羰基、乙氧基羰基、三氯甲基硫基、甲基磺酰基、乙基磺酰基、甲氧基甲基羰基、甲氧基羰基甲基、甲氨基硫基、二甲氨基硫基、COCH2CO2R4、COCH2CH2CO2R4、COCHCH3CO2R4、COC6H4CO2R4或COCH=CHCO2R4;
R2选自氯、溴、氟、卤代C1-C3烷基、C1-C3烷氧基、卤代C1-C3烷氧基、C1-C3烷基氨基、C1-C3烷硫基、C1-C3烷基磺酰基、C2-C6二烷基氨基、C3-C4烯氧基、卤代C3-C4烯氧基、C3-C4炔氧基、未取代的或被1-3个R6取代的苯基氨基、苯氧基、苄基氧基或苄基氨基;
R3选自硝基;
R选自氯、溴、氟、氰基、硝基、C(=O)NR4R5、C1-C3烷基、卤代C1-C3烷基、C1-C3烷氧基、卤代C1-C3烷氧基、C1-C3烷基氨基、C1-C3烷硫基、C1-C3烷基磺酰基、C1-C3烷基羰基、C1-C3烷氧基羰基、C1-C3烷氧基C1-C2烷基、C1-C3烷基羰基氧基、C1-C3烷氧基C1-C3烷氧基、卤代C1-C3烷氧基卤代C1-C3烷氧基、未取代的或被1-4个R6取代的苯基氨基、苯氧基、吡啶基氧基、苯氧基羰基或苯基氨基羰基;
R4选自氢或C1-C3烷基;
R6选自氯、溴、氟、硝基、氰基、三氟甲基、甲基、甲氧基、甲硫基、甲氧基羰基或甲胺基羰基;
n=1-5:
或通式I化合物与盐酸、硫酸、磷酸、甲酸、乙酸、三氟乙酸、甲磺酸、对甲苯磺酸、苹果酸或柠檬酸形成的盐。
再进一步优选的化合物为:通式I中
R1选自氢、甲基、乙基、环丙基、甲酰基、乙酰基、三氟乙酰基、甲氧基羰基、乙氧基羰基、三氯甲基硫基、甲基磺酰基、乙基磺酰基、甲氧基甲基羰基、甲氧基羰基甲基、甲氨基硫基、二甲氨基硫基、COCH2CO2R4、COCH2CH2CO2R4、COCHCH3CO2R4、COC6H4CO2R4或COCH=CHCO2R4;
R2选自氯、溴、氟、C1-C3烷氧基、C1-C3烷硫基、C1-C3烷基氨基、C2-C6二烷基氨基、苯氨基、苯氧基、苄基氨基、苄基氧基、对氯苯氨基、对氯苯氧基、2-氯-4-三氟甲基苯氨基、3-氯-5三氟甲基吡啶-2-基氨基、2-氯-4-三氟甲基苯氧基或3-氯-5三氟甲基吡啶-2-基氧基;
R3选自硝基;
R选自氯、溴、氟、氰基、硝基、C(=O)NR4R5、C1-C3烷基、卤代C1-C3烷基、C1-C3烷氧基、卤代C1-C3烷氧基、C1-C3烷基氨基、C1-C3烷硫基、C1-C3烷基磺酰基、C1-C3烷基羰基、C1-C3烷氧基羰基、C1-C3烷氧基C1-C2烷基、C1-C3烷基羰基氧基、C1-C3烷氧基C1-C3烷氧基、卤代C1-C3烷氧基卤代C1-C3烷氧基、苯氨基、苯氧基、苯氧基羰基、苯氨基羰基或3-氯-5三氟甲基吡啶-2-基氧基;
R4选自氢、甲基或乙基;
n=1-5:
或通式I化合物与盐酸、硫酸、磷酸、三氟乙酸、甲磺酸或对甲苯磺酸形成的盐。
上面给出的通式I化合物的定义中,汇集所用术语一般代表如下取代基:
卤素:指氟、氯、溴或碘。
烷基:直链或支链烷基,例如甲基、乙基、丙基、异丙基或叔丁基。
环烷基:取代或未取代的环状烷基,例如环丙基、环戊基或环己基。取代基如甲基、卤素等。
卤代烷基:直链或支链烷基,在这些烷基上的氢原子可部分或全部被卤素所取代,例如,氯甲基、二氯甲基、三氯甲基、氟甲基、二氟甲基、三氟甲基等。
烷氧基:直链或支链烷基,经氧原子键连接到结构上。
卤代烷氧基:直链或支链烷氧基,在这些烷氧基上的氢原子可部分或全部被卤素所取代。例如,氯甲氧基、二氯甲氧基、三氯甲氧基、氟甲氧基、二氟甲氧基、三氟甲氧基、氯氟甲氧基、三氟乙氧基等。
烷硫基:直链或支链烷基,经硫原子键连接到结构上。
卤代烷硫基:直链或支链烷硫基,在这些烷硫基上的氢原子可部分或全部被卤原子所取代。例如,氯甲硫基、二氯甲硫基、三氯甲硫基、氟甲硫基、二氟甲硫基、三氟甲硫基、氯氟甲硫基等。
烷基氨基:直链或支链烷基,经氮原子键连接到结构上。
卤代烷基氨基:直链或支链烷基氨基,在这些烷基氨基上的氢原子可部分或全部被卤素所取代。
芳基以及芳烷基、芳氧基和芳氧基烷基中的芳基部分包括苯基或萘基等。
杂芳基是含1个或多个N、O、S杂原子的五元环或六元环。例如吡啶基、呋喃基、嘧啶基、吡嗪基、哒嗪基、三嗪基、喹啉基、吡唑基、噻唑基等。
表1和表2分别列举了部分通式I中Rn和R1具体取代基,表中Ph代表苯基,Py代表吡啶基。
表1
Rn | Rn | Rn | Rn | Rn |
2-F | 4-CH3 | 2-CH2OCH3 | 2,6-2Cl-4-CN | 2-OCF3-4-Cl-6-NO2 |
3-F | 2,3-2CH3 | 3-CH2OCH3 | 2,6-2Cl-4-COCH3 | 3-CF3-4-CN |
4-F | 2,4-2CH3 | 4-CH2OCH3 | 2,6-2Cl-4-CONH2 | 3-CN-4-CF3 |
2,3-2F | 2,5-2CH3 | 2-OCOCH3 | 2,4-2Cl-6-NO2 | 2-CF3-4-Br-6-NO2 |
2,4-2F | 2,6-2CH3 | 3-OCOCH3 | 2,4-2Cl-6-CN | 3-NO2-4-CF3 |
2,5-2F | 3,4-2CH3 | 4-OCOCH3 | 2,4-2Cl-6-CF3 | 2-NO2-4-CN-5-CF3 |
2,6-2F | 3,5-2CH3 | 2-OCOCH2CH3 | 2,4-2F-6-NO2 | 2-NO2-4-CF3-5-CN |
3,4-2F | 2-C2H5 | 3-OCOCH2CH3 | 2,6-2F-4-NO2 | 4-OCF3-2,6-2Br |
3,5-2F | 3-C2H5 | 4-OCOCH2CH3 | 2-NO2-4-F | 2-CH3-4-Cl-5-CH2CO2C2H5 |
2,3,4-3F | 4-C2H5 | 2-OCO2CH3 | 2-NO2-4-Br | 2,4-2Cl-3-CH3 |
2,3,5-3F | 2-CF3 | 3-OCO2CH3 | 2-NO2-4-CF3 | 2,4-2Cl-3-CH3-6-NO2 |
2,4,5-3F | 3-CF3 | 4-OCO2CH3 | 2-NO2-4-CN | 2-Cl-3-CH3 |
2,3,6-3F | 4-CF3 | 2-OCH2OCH3 | 2-NO2-4-COCH3 | 2-CH3-3-Cl |
2,4,6-3F | 2-OCH3 | 3-OCH2OCH3 | 2-NO2-4-CONH2 | 2-CH3-3-Cl-4,6-2NO2 |
3,4,5-3F | 3-OCH3 | 4-OCH2OCH3 | 2-NO2-4-CH3 | 2-CH3-3-Cl-4-NO2 |
2-Cl | 4-OCH3 | 2-OCF2OCF3 | 2-NO2-4-OCH3 | 2-CH3-3-Cl-6-NO2 |
3-Cl | 2-SCH3 | 3-OCF2OCF3 | 2-NO2-4-SCH3 | 2-Cl-3-CH3-4,6-2NO2 |
4-Cl | 3-SCH3 | 4-OCF2OCF3 | 2-NO2-4-NCH3 | 2-Cl-3-CH3-4-NO2 |
2,3-2Cl | 4-SCH3 | 2-COPh | 2-F-4-NO2 | 2-Cl-3-CH3-6-NO2 |
2,4-2Cl | 2-OCF3 | 3-COPh | 2-Br-4-NO2 | 2-Br-4-NO2-6-CN |
2,5-2Cl | 3-OCF3 | 4-COPh | 2-CF3-4-NO2 | 3-Cl-4-CF3-2,6-2NO2 |
2,6-2Cl | 4-OCF3 | 2-COCH2Ph | 2-CN-4-NO2 | 2NO2-4,5-2Cl |
表2
R1 | R1 | R1 |
H | CO2CH2CH2CH3 | CH2CO2CH2CH3 |
CH3 | CONHCH3 | COCH2OCH3 |
CH2CH3 | CONHCH2CH3 | COCH2OCH2CH3 |
CH2CH2CH3 | SO2CH3 | SNHCH3 |
CH2CH2CH2CH | SO2CH2CH3 | SNHCH2CH3 |
COCH3 | SCCl3 | SN(CH3)2 |
COCH2CH3 | CH2OCH3 | SN(CH2CH3)2 |
COCH2CH2CH3 | CH2CH2OCH3 | COCH2CO2H |
本发明中的部分化合物可以用表3中列出的具体化合物来说明,但并不限定本发明。
表3
编号 | R1 | R2 | R3 | Rn |
1 | H | Cl | NO2 | 2,4-2F |
2 | H | Cl | NO2 | 2,4-2Cl |
3 | H | Cl | NO2 | 2,3,4-3Cl |
4 | H | Cl | NO2 | 2,4,5-3Cl |
5 | H | Cl | NO2 | 2,4,6-3Cl |
6 | H | Cl | NO2 | 2-CN |
7 | H | Cl | NO2 | 4-CN |
8 | H | Cl | NO2 | 4-NO2 |
9 | H | Cl | NO2 | 2,4-2NO2 |
10 | H | Cl | NO2 | 2,4,6-3NO2 |
11 | H | Cl | NO2 | 2-CF3 |
12 | H | Cl | NO2 | 4-CF3 |
13 | H | Cl | NO2 | 2-OCH3 |
14 | H | Cl | NO2 | 4-OCH3 |
15 | H | Cl | NO2 | 2-SCH3 |
16 | H | Cl | NO2 | 4-SCH3 |
17 | H | Cl | NO2 | 2-OCF3 |
18 | H | Cl | NO2 | 4-OCF3 |
19 | H | Cl | NO2 | 2-COCH3 |
20 | H | Cl | NO2 | 4-COCH3 |
21 | H | Cl | NO2 | 2-SO2CH3 |
22 | H | Cl | NO2 | 4-SO2CH3 |
23 | H | Cl | NO2 | 2-CO2CH3 |
24 | H | Cl | NO2 | 4-CO2CH3 |
25 | H | Cl | NO2 | 2-CONHPh |
26 | H | Cl | NO2 | 3-CONHPh |
27 | H | Cl | NO2 | 4-CONHPh |
28 | H | Cl | NO2 | 2-CO2Ph |
29 | H | Cl | NO2 | 2-CONH2 |
30 | H | Cl | NO2 | 4-CONH2 |
31 | H | Cl | NO2 | 2-Cl-4-CF3 |
32 | H | Cl | NO2 | 2-Cl-4-NO2 |
33 | H | Cl | NO2 | 2-Cl-4-CN |
34 | H | Cl | NO2 | 2-CH3-4-Cl |
35 | H | Cl | NO2 | 2-CF3-4-Cl |
36 | H | Cl | NO2 | 2-NO2-4-Cl |
37 | H | Cl | NO2 | 2-CN-4-Cl |
38 | H | Cl | NO2 | 2,4-2Cl-6-NO2 |
39 | H | Cl | NO2 | 2,4-2Cl-6-CN |
40 | H | Cl | NO2 | 2,4-2Cl-6-CF3 |
41 | H | Cl | NO2 | 2,4-2F-6-NO2 |
42 | H | Cl | NO2 | 2,6-2F-4-NO2 |
43 | H | Cl | NO2 | 2,6-2Cl-4-NO2 |
44 | H | Cl | NO2 | 2,6-2Cl-4-CF3 |
45 | H | Cl | NO2 | 2,6-2Cl-4-CN |
46 | H | Cl | NO2 | 2,6-2Cl-4-COCH3 |
47 | H | Cl | NO2 | 2,6-2Cl-4-CONH2 |
48 | H | Cl | NO2 | 2-NO2-4-F |
49 | H | Cl | NO2 | 2-N O2-4-Br |
50 | H | Cl | NO2 | 2-NO2-4-CF3 |
51 | H | Cl | NO2 | 2-NO2-4-CN |
52 | H | Cl | NO2 | 2-NO2-4-COCH3 |
53 | H | Cl | NO2 | 2-NO2-4-CONH2 |
54 | H | Cl | NO2 | 2-NO2-4-CH3 |
55 | H | Cl | NO2 | 2-CF3-4-NO2 |
56 | H | Cl | NO2 | 2-CN-4-NO2 |
57 | H | Cl | NO2 | 2-COCH3-4-NO2 |
58 | H | Cl | NO2 | 2-CONH2-4-NO2 |
59 | H | Cl | NO2 | 2-CH3-4-NO2 |
60 | H | Cl | NO2 | 2-Cl-4-F-6-NO2 |
61 | H | Cl | NO2 | 2-Cl-4-CF3-6-NO2 |
62 | H | Cl | NO2 | 2-Cl-4,6-2NO2 |
63 | H | Cl | NO2 | 2-Cl-4-CN-6-NO2 |
64 | H | Cl | NO2 | 2-F-4-Cl-6-NO2 |
65 | H | Cl | NO2 | 2-CH3-4-Cl-6-NO2 |
66 | H | Cl | NO2 | 2-CF3-4-Cl-6-NO2 |
67 | H | Cl | NO2 | 4-Cl-2,6-2NO2 |
68 | H | Cl | NO2 | 2-CN-4-Cl-6-NO2 |
69 | H | Cl | NO2 | 4-CF3-2,6-2NO2 |
70 | H | Cl | NO2 | 4-CN-2,6-2NO2 |
71 | H | Cl | NO2 | 4-CH3-2,6-2NO2 |
72 | H | Cl | NO2 | 4-F-2,6-2NO2 |
73 | H | Cl | NO2 | 2-CF3-4,6-2NO2 |
74 | H | Cl | NO2 | 2-CN-4,6-2NO2 |
75 | H | Cl | NO2 | 2-CH3-4,6-2NO2 |
76 | H | Cl | NO2 | 2-F-4,6-2NO2 |
77 | H | Cl | NO2 | 3-CF3-4-CN |
78 | H | Cl | NO2 | 2-NO2-4-CN-5-CF3 |
79 | H | Cl | NO2 | 4-OCF3-2,6-2Br |
80 | H | Cl | NO2 | 2-CH3-4-Cl-5-CH2CO2C2H5 |
81 | H | Cl | NO2 | 2,4-2Cl-3-CH3 |
82 | H | Cl | NO2 | 2,4-2Cl-3-CH3-6-NO2 |
83 | H | Cl | NO2 | 2-Cl-3-CH3 |
84 | H | Cl | NO2 | 2-CH3-3-Cl |
85 | H | Cl | NO2 | 2-CH3-3-Cl-4,6-2NO2 |
86 | H | Cl | NO2 | 2-CH3-3-Cl-4-NO2 |
87 | H | Cl | NO2 | 2-Cl-3-CH3-4,6-2NO2 |
88 | H | Cl | NO2 | 2-Br-4-NO2-6-CN |
89 | H | Cl | NO2 | 3-Cl-4-CF3-2,6-2NO2 |
90 | H | Cl | NO2 | 2NO2-4,5-2Cl |
91 | H | Cl | NO2 | 2,5-2Cl-4-NO2 |
92 | H | Cl | NO2 | 2,5-2Cl-6-NO2 |
93 | H | Cl | NO2 | 2,3-2Cl-4NO2 |
94 | H | Cl | NO2 | 2,3-2Cl-6-NO2 |
95 | H | Cl | NO2 | 3,4-2Cl-2,6-2NO2 |
96 | H | Cl | NO2 | 2,5-2Cl-4,6-2NO2 |
97 | H | Cl | NO2 | 2,4,5-3Cl-6-NO2 |
98 | H | Cl | NO2 | 2,3,4-3Cl-5NO2 |
99 | H | Cl | NO2 | 2,3,4-3Cl-6-NO2 |
100 | H | Cl | NO2 | 2,3,5-3Cl-4,6-2CN |
101 | H | Cl | NO2 | 2,5-2Cl-4-OCF2OCF3 |
102 | H | Cl | NO2 | 3,5-2Cl-4-(3-Cl-5CF3-Pyridin-2-yloxy) |
103 | H | Cl | H | 2,4-2F |
104 | H | Cl | H | 2,4-2Cl |
105 | H | Cl | H | 2,3,4-3Cl |
106 | H | Cl | H | 2,4,5-3Cl |
107 | H | Cl | H | 2,4,6-3Cl |
108 | H | Cl | H | 2-CN |
109 | H | Cl | H | 4-CN |
110 | H | Cl | H | 4-NO2 |
111 | H | Cl | H | 2,4-2NO2 |
112 | H | Cl | H | 2,4,6-3NO2 |
113 | H | Cl | H | 4-CF3 |
114 | H | Cl | H | 2-Cl-4-NO2 |
115 | H | Cl | H | 2-Cl-4-CN |
116 | H | Cl | H | 2-CH3-4-Cl |
117 | H | Cl | H | 2-NO2-4-Cl |
118 | H | Cl | H | 2-CN-4-Cl |
119 | H | Cl | H | 2,6-2Cl-4-NO2 |
120 | H | Cl | H | 2,6-2Cl-4-CF3 |
121 | H | Cl | H | 2,6-2Cl-4-CN |
122 | H | Cl | H | 2,4-2Cl-6-NO2 |
123 | H | Cl | H | 2,4-2Cl-6-CN |
124 | H | Cl | H | 2,4-2Cl-6-CF3 |
125 | H | Cl | H | 2,4-2F-6-NO2 |
126 | H | Cl | H | 2-NO2-4-CN |
127 | H | Cl | H | 2-Cl-4-CF3-6-NO2 |
128 | H | Cl | H | 2-Cl-4,6-2NO2 |
129 | H | Cl | H | 2-Cl-4-CN-6-NO2 |
130 | H | Cl | H | 2-CH3-4-Cl-6-NO2 |
131 | H | Cl | H | 4-Cl-2,6-2NO2 |
132 | H | Cl | H | 4-CF3-2,6-2NO2 |
133 | H | Cl | H | 4-CN-2,6-2NO2 |
134 | H | Cl | H | 2-CF3-4,6-2NO2 |
135 | H | Cl | H | 2-CH3-4,6-2NO2 |
136 | H | Cl | H | 3-CF3-4-CN |
137 | H | Cl | H | 2-NO2-4-CN-5-CF3 |
138 | H | Cl | H | 4-OCF3-2,6-2Br |
139 | H | Cl | H | 2-CH3-4-Cl-5-CH2CO2C2H5 |
140 | H | Cl | H | 2,4-2Cl-3-CH3 |
141 | H | Cl | H | 2,4-2Cl-3-CH3-6-NO2 |
142 | H | Cl | H | 2-Cl-3-CH3 |
143 | H | Cl | H | 2-CH3-3-Cl |
144 | H | Cl | H | 2-CH3-3-Cl-4-NO2 |
145 | H | Cl | H | 2-Br-4-NO2-6-CN |
146 | H | Cl | H | 3-Cl-4-CF3-2,6-2NO2 |
147 | H | Cl | H | 2NO2-4,5-2Cl |
148 | H | Cl | H | 2,5-2Cl-4-NO2 |
149 | H | Cl | H | 3,4-2Cl-2,6-2NO2 |
150 | H | Cl | H | 2,5-2Cl-4,6-2NO2 |
151 | H | Cl | H | 2,4,5-3Cl-6-NO2 |
152 | H | Cl | H | 2,3,5-3Cl-4,6-2CN |
153 | H | Cl | H | 2,5-2Cl-4-OCF2OCF3 |
154 | H | Cl | CN | 2,6-2Cl-4-NO2 |
155 | H | Cl | CN | 2,6-2Cl-4-CF3 |
156 | H | Cl | CN | 2,6-2Cl-4-CN |
157 | H | Cl | CN | 4-CF3-2,6-2NO2 |
158 | H | Cl | CN | 2,4,6-3Cl |
159 | H | Cl | CN | 4-Cl-2,6-2NO2 |
160 | H | Cl | CN | 2-Br-4-NO2-6-CN |
161 | H | Cl | CN | 2-NO2-4-CN-5-CF3 |
162 | H | Cl | CN | 2,5-2Cl-4-NO2 |
163 | H | Cl | CN | 2,5-2Cl-4,6-2NO2 |
164 | H | Cl | CN | 2,4,5-3Cl-6-NO2 |
165 | H | Cl | CN | 2,4-2NO2 |
166 | H | Cl | CN | 2-Cl-4,6-2NO2 |
167 | H | Cl | CN | 2-Cl-4-CN-6-NO2 |
168 | H | Cl | CN | 2,4-2Cl-6-NO2 |
169 | H | Cl | CN | 2,4-2Cl-6-CN |
170 | H | Cl | CN | 2,4-2Cl-6-CF3 |
171 | H | Cl | Cl | 2,6-2Cl-4-NO2 |
172 | H | Cl | Cl | 2,6-2Cl-4-CF3 |
173 | H | Cl | Cl | 2,6-2Cl-4-CN |
174 | H | Cl | Cl | 4-CF3-2,6-2NO2 |
175 | H | Cl | Cl | 2,4,6-3Cl |
176 | H | Cl | Cl | 4-Cl-2,6-2NO2 |
177 | H | Cl | Cl | 2-Br-4-NO2-6-CN |
178 | H | Cl | Cl | 2-NO2-4-CN-5-CF3 |
179 | H | Cl | Cl | 2,5-2Cl-4-NO2 |
180 | H | Cl | Cl | 2,5-2Cl-4,6-2NO2 |
181 | H | Cl | Cl | 2,4,5-3Cl-6-NO2 |
182 | H | Cl | Cl | 2,4-2NO2 |
183 | H | Cl | Cl | 2-Cl-4,6-2NO2 |
184 | H | Cl | Cl | 2-Cl-4-CN-6-NO2 |
185 | H | Cl | Cl | 2,4-2Cl-6-NO2 |
186 | H | Cl | Cl | 2,4-2Cl-6-CN |
187 | H | Cl | Cl | 2,4-2Cl-6-CF3 |
188 | H | Cl | C(=O)NH2 | 2,6-2Cl-4-NO2 |
189 | H | Cl | C(=O)NH2 | 2,6-2Cl-4-CF3 |
190 | H | Cl | C(=O)NH2 | 2,6-2Cl-4-CN |
191 | H | Cl | C(=O)NH2 | 4-CF3-2,6-2NO2 |
192 | H | Cl | C(=O)NH2 | 2,4,6-3Cl |
193 | H | Cl | C(=O)NH2 | 4-Cl-2,6-2NO2 |
194 | H | Cl | C(=O)NH2 | 2-Br-4-NO2-6-CN |
195 | H | Cl | C(=O)NH2 | 2-NO2-4-CN-5-CF3 |
196 | H | Cl | C(=O)NH2 | 2,5-2Cl-4-NO2 |
197 | H | Cl | C(=O)NH2 | 2,5-2Cl-4,6-2NO2 |
198 | H | Cl | C(=O)NH2 | 2,4,5-3Cl-6-NO2 |
199 | H | Cl | C(=O)NH2 | 2,4-2NO2 |
200 | H | Cl | C(=O)NH2 | 2-Cl-4,6-2NO2 |
201 | H | Cl | C(=O)NH2 | 2-Cl-4-CN-6-NO2 |
202 | H | Cl | C(=O)NH2 | 2,4-2Cl-6-NO2 |
203 | H | Cl | C(=O)NH2 | 2,4-2Cl-6-CN |
204 | H | Cl | C(=O)NH2 | 2,4-2Cl-6-CF3 |
205 | H | Cl | C(=S)NH2 | 2,6-2Cl-4-NO2 |
206 | H | Cl | C(=S)NH2 | 2,6-2Cl-4-CF3 |
207 | H | Cl | C(=S)NH2 | 2,6-2Cl-4-CN |
208 | H | Cl | C(=S)NH2 | 4-CF3-2,6-2NO2 |
209 | H | Cl | C(=S)NH2 | 2,4,6-3Cl |
210 | H | Cl | C(=S)NH2 | 4-Cl-2,6-2NO2 |
211 | H | Cl | C(=S)NH2 | 2-Br-4-NO2-6-CN |
212 | H | Cl | C(=S)NH2 | 2-NO2-4-CN-5-CF3 |
213 | H | Cl | C(=S)NH2 | 2,5-2Cl-4-NO2 |
214 | H | Cl | C(=S)NH2 | 2,5-2Cl-4,6-2NO2 |
215 | H | Cl | C(=S)NH2 | 2,4,5-3Cl-6-NO2 |
216 | H | Cl | C(=S)NH2 | 2,4-2NO2 |
217 | H | Cl | C(=S)NH2 | 2-Cl-4,6-2NO2 |
218 | H | Cl | C(=S)NH2 | 2-Cl-4-CN-6-NO2 |
219 | H | Cl | C(=S)NH2 | 2,4-2Cl-6-NO2 |
220 | H | Cl | C(=S)NH2 | 2,4-2Cl-6-CN |
221 | H | Cl | C(=S)NH2 | 2,4-2Cl-6-CF3 |
222 | H | Cl | CO2CH3 | 2,6-2Cl-4-NO2 |
223 | H | Cl | CO2CH3 | 2,6-2Cl-4-CF3 |
224 | H | Cl | CO2CH3 | 2,6-2Cl-4-CN |
225 | H | Cl | CO2CH3 | 4-CF3-2,6-2NO2 |
226 | H | Cl | CO2CH3 | 2,4,6-3Cl |
227 | H | Cl | CO2CH3 | 4-Cl-2,6-2NO2 |
228 | H | Cl | CO2CH3 | 2-Br-4-NO2-6-CN |
229 | H | Cl | CO2CH3 | 2-NO2-4-CN-5-CF3 |
230 | H | Cl | CO2CH3 | 2,5-2Cl-4-NO2 |
231 | H | Cl | CO2CH3 | 2,5-2Cl-4,6-2NO2 |
232 | H | Cl | CO2CH3 | 2,4,5-3Cl-6-NO2 |
233 | H | Cl | CO2CH3 | 2,4-2NO2 |
234 | H | Cl | CO2CH3 | 2-Cl-4,6-2NO2 |
235 | H | Cl | CO2CH3 | 2-Cl-4-CN-6-NO2 |
236 | H | Cl | CO2CH3 | 2,4-2Cl-6-NO2 |
237 | H | Cl | CO2CH3 | 2,4-2Cl-6-CN |
238 | H | Cl | CO2CH3 | 2,4-2Cl-6-CF3 |
239 | H | Cl | CF3 | 2,6-2Cl-4-NO2 |
240 | H | Cl | CF3 | 2,6-2Cl-4-CF3 |
241 | H | Cl | CF3 | 2,6-2Cl-4-CN |
242 | H | Cl | CF3 | 4-CF3-2,6-2NO2 |
243 | H | Cl | CF3 | 2,4,6-3Cl |
244 | H | Cl | CF3 | 4-Cl-2,6-2NO2 |
245 | H | Cl | CF3 | 2-Br-4-NO2-6-CN |
246 | H | Cl | CF3 | 2-NO2-4-CN-5-CF3 |
247 | H | Cl | CF3 | 2,5-2Cl-4-NO2 |
248 | H | Cl | CF3 | 2,5-2Cl-4,6-2NO2 |
249 | H | Cl | CF3 | 2,4,5-3Cl-6-NO2 |
250 | H | Cl | CF3 | 2,4-2NO2 |
251 | H | Cl | CF3 | 2-Cl-4,6-2NO2 |
252 | H | Cl | CF3 | 2-Cl-4-CN-6-NO2 |
253 | H | Cl | CF3 | 2,4-2Cl-6-NO2 |
254 | H | Cl | CF3 | 2,4-2Cl-6-CN |
255 | H | Cl | CF3 | 2,4-2Cl-6-CF3 |
256 | H | Cl | SO2CH3 | 2,6-2Cl-4-NO2 |
257 | H | Cl | SO2CH3 | 2,6-2Cl-4-CF3 |
258 | H | Cl | SO2CH3 | 2,6-2Cl-4-CN |
259 | H | Cl | SO2CH3 | 4-CF3-2,6-2NO2 |
260 | H | Cl | SO2CH3 | 2,4,6-3Cl |
261 | H | Cl | SO2CH3 | 4-Cl-2,6-2NO2 |
262 | H | Cl | SO2CH3 | 2-Br-4-NO2-6-CN |
263 | H | Cl | SO2CH3 | 2-NO2-4-CN-5-CF3 |
264 | H | Cl | SO2CH3 | 2,5-2Cl-4-NO2 |
265 | H | Cl | SO2CH3 | 2,5-2Cl-4,6-2NO2 |
266 | H | Cl | SO2CH3 | 2,4,5-3Cl-6-NO2 |
267 | H | Cl | SO2CH3 | 2,4-2NO2 |
268 | H | Cl | SO2CH3 | 2-Cl-4,6-2NO2 |
269 | H | Cl | SO2CH3 | 2-Cl-4-CN-6-NO2 |
270 | H | Cl | SO2CH3 | 2,4-2Cl-6-NO2 |
271 | H | Cl | SO2CH3 | 2,4-2Cl-6-CN |
272 | H | Cl | SO2CH3 | 2,4-2Cl-6-CF3 |
273 | CH3 | Cl | NO2 | 2,6-2Cl-4-NO2 |
274 | CH3 | Cl | NO2 | 2,6-2Cl-4-CF3 |
275 | CH3 | Cl | NO2 | 2,6-2Cl-4-CN |
276 | CH3 | Cl | NO2 | 4-CF3-2,6-2NO2 |
277 | CH3 | Cl | NO2 | 2,4,6-3Cl |
278 | CH3 | Cl | NO2 | 4-Cl-2,6-2NO2 |
279 | CH3 | Cl | NO2 | 2-Br-4-NO2-6-CN |
280 | CH3 | Cl | NO2 | 2-NO2-4-CN-5-CF3 |
281 | CH3 | Cl | NO2 | 2,5-2Cl-4-NO2 |
282 | CH3 | Cl | NO2 | 2,5-2Cl-4,6-2NO2 |
283 | CH3 | Cl | NO2 | 2,4,5-3Cl-6-NO2 |
284 | CH3 | Cl | NO2 | 2,4-2NO2 |
285 | CH3 | Cl | NO2 | 2,4-2Cl |
286 | CH3 | Cl | NO2 | 2-Cl-4,6-2NO2 |
287 | CH3 | Cl | NO2 | 2-Cl-4-CN-6-NO2 |
288 | CH3 | Cl | NO2 | 2,4-2Cl-6-NO2 |
289 | CH3 | Cl | NO2 | 2,4-2Cl-6-CN |
290 | CH3 | Cl | NO2 | 2,4-2Cl-6-CF3 |
291 | COCH3 | Cl | NO2 | 2,6-2Cl-4-NO2 |
292 | COCH3 | Cl | NO2 | 2,6-2Cl-4-CF3 |
293 | COCH3 | Cl | NO2 | 2,6-2Cl-4-CN |
294 | COCH3 | Cl | NO2 | 4-CF3-2,6-2NO2 |
295 | COCH3 | Cl | NO2 | 2,4,6-3Cl |
296 | COCH3 | Cl | NO2 | 4-Cl-2,6-2NO2 |
297 | COCH3 | Cl | NO2 | 2-Br-4-NO2-6-CN |
298 | COCH3 | Cl | NO2 | 2-NO2-4-CN-5-CF3 |
299 | COCH3 | Cl | NO2 | 2,5-2C l-4-NO2 |
300 | COCH3 | Cl | NO2 | 2,5-2Cl-4,6-2NO2 |
301 | COCH3 | Cl | NO2 | 2,4,5-3Cl-6-NO2 |
302 | COCH3 | Cl | NO2 | 2,4-2NO2 |
303 | COCH3 | Cl | NO2 | 2-Cl-4,6-2NO2 |
304 | COCH3 | Cl | NO2 | 2-Cl-4-CN-6-NO2 |
305 | COCH3 | Cl | NO2 | 2,4-2Cl-6-NO2 |
306 | COCH3 | Cl | NO2 | 2,4-2Cl-6-CN |
307 | COCH3 | Cl | NO2 | 2,4-2Cl-6-CF3 |
308 | CO2CH3 | Cl | NO2 | 2,6-2Cl-4-NO2 |
309 | CO2CH3 | Cl | NO2 | 2,6-2Cl-4-CF3 |
310 | CO2CH3 | Cl | NO2 | 2,6-2Cl-4-CN |
311 | CO2CH3 | Cl | NO2 | 4-CF3-2,6-2NO2 |
312 | CO2CH3 | Cl | NO2 | 2,4,6-3Cl |
313 | CO2CH3 | Cl | NO2 | 4-Cl-2,6-2NO2 |
314 | CO2CH3 | Cl | NO2 | 2-Br-4-NO2-6-CN |
315 | CO2CH3 | Cl | NO2 | 2-NO2-4-CN-5-CF3 |
316 | CO2CH3 | Cl | NO2 | 2,5-2Cl-4-NO2 |
317 | CO2CH3 | Cl | NO2 | 2,5-2Cl-4,6-2NO2 |
318 | CO2CH3 | Cl | NO2 | 2,4,5-3Cl-6-NO2 |
319 | CO2CH3 | Cl | NO2 | 2,4-2NO2 |
320 | CO2CH3 | Cl | NO2 | 2-Cl-4,6-2NO2 |
321 | CO2CH3 | Cl | NO2 | 2-Cl-4-CN-6-NO2 |
322 | CO2CH3 | Cl | NO2 | 2,4-2Cl-6-NO2 |
323 | CO2CH3 | Cl | NO2 | 2,4-2Cl-6-CN |
324 | CO2CH3 | Cl | NO2 | 2,4-2Cl-6-CF3 |
325 | SO2CH3 | Cl | NO2 | 2,6-2Cl-4-NO2 |
326 | SO2CH3 | Cl | NO2 | 2,6-2Cl-4-CF3 |
327 | H | OCH3 | NO2 | 2,6-2Cl-4-CN |
328 | H | OCH3 | NO2 | 4-CF3-2,6-2NO2 |
329 | H | OCH3 | NO2 | 2,4,6-3Cl |
330 | H | OCH3 | NO2 | 4-Cl-2,6-2NO2 |
331 | H | OCH3 | NO2 | 2-Br-4-NO2-6-CN |
332 | H | OCH3 | NO2 | 2-NO2-4-CN-5-CF3 |
333 | H | OCH3 | NO2 | 2,5-2Cl-4-NO2 |
334 | H | OCH3 | NO2 | 2,5-2Cl-4,6-2NO2 |
335 | H | OCH3 | NO2 | 2,4,5-3Cl-6-NO2 |
336 | H | OCH3 | NO2 | 2,4-2NO2 |
337 | H | OCH3 | NO2 | 2-Cl-4,6-2NO2 |
338 | H | OCH3 | NO2 | 2-Cl-4-CN-6-NO2 |
339 | H | OCH3 | NO2 | 2,4-2Cl-6-NO2 |
340 | H | OCH3 | NO2 | 2,4-2Cl-6-CN |
341 | H | OCH3 | NO2 | 2,4-2Cl-6-CF3 |
342 | H | SCH3 | NO2 | 2,6-2Cl-4-CN |
343 | H | SCH3 | NO2 | 4-CF3-2,6-2NO2 |
344 | H | SCH3 | NO2 | 2,4,6-3Cl |
345 | H | SCH3 | NO2 | 4-Cl-2,6-2NO2 |
346 | H | SCH3 | NO2 | 2-Br-4-NO2-6-CN |
347 | H | SCH3 | NO2 | 2-NO2-4-CN-5-CF3 |
348 | H | SCH3 | NO2 | 2,5-2Cl-4-NO2 |
349 | H | SCH3 | NO2 | 2,5-2Cl-4,6-2NO2 |
350 | H | SCH3 | NO2 | 2,4,5-3Cl-6-NO2 |
351 | H | SCH3 | NO2 | 2,4-2NO2 |
352 | H | SCH3 | NO2 | 2-Cl-4,6-2NO2 |
353 | H | SCH3 | NO2 | 2-Cl-4-CN-6-NO2 |
354 | H | SCH3 | NO2 | 2,4-2Cl-6-NO2 |
355 | H | SCH3 | NO2 | 2,4-2Cl-6-CN |
356 | H | SCH3 | NO2 | 2,4-2Cl-6-CF3 |
357 | H | NHCH3 | NO2 | 2,6-2Cl-4-CN |
358 | H | NHCH3 | NO2 | 4-CF3-2,6-2NO2 |
359 | H | NHCH3 | NO2 | 2,4,6-3Cl |
360 | H | NHCH3 | NO2 | 4-Cl-2,6-2NO2 |
361 | H | NHCH3 | NO2 | 2-Br-4-NO2-6-CN |
362 | H | NHCH3 | NO2 | 2-NO2-4-CN-5-CF3 |
363 | H | NHCH3 | NO2 | 2,5-2Cl-4-NO2 |
364 | H | NHCH3 | NO2 | 2,5-2Cl-4,6-2NO2 |
365 | H | NHCH3 | NO2 | 2,4,5-3Cl-6-NO2 |
366 | H | NHCH3 | NO2 | 2,4-2NO2 |
367 | H | NHCH3 | NO2 | 2-Cl-4,6-2NO2 |
368 | H | NHCH3 | NO2 | 2-Cl-4-CN-6-NO2 |
369 | H | NHCH3 | NO2 | 2,4-2Cl-6-NO2 |
370 | H | NHCH3 | NO2 | 2,4-2Cl-6-CN |
371 | H | NHCH3 | NO2 | 2,4-2Cl-6-CF3 |
372 | H | N(CH3)2 | NO2 | 2,6-2Cl-4-CN |
373 | H | N(CH3)2 | NO2 | 4-CF3-2,6-2NO2 |
374 | H | N(CH3)2 | NO2 | 2,4,6-3Cl |
375 | H | N(CH3)2 | NO2 | 4-Cl-2,6-2NO2 |
376 | H | N(CH3)2 | NO2 | 2-Br-4-NO2-6-CN |
377 | H | N(CH3)2 | NO2 | 2-NO2-4-CN-5-CF3 |
378 | H | N(CH3)2 | NO2 | 2,5-2Cl-4-NO2 |
379 | H | N(CH3)2 | NO2 | 2,5-2Cl-4,6-2NO2 |
380 | H | N(CH3)2 | NO2 | 2,4,5-3Cl-6-NO2 |
381 | H | N(CH3)2 | NO2 | 2,4-2NO2 |
382 | H | N(CH3)2 | NO2 | 2-Cl-4,6-2NO2 |
383 | H | N(CH3)2 | NO2 | 2-Cl-4-CN-6-NO2 |
384 | H | N(CH3)2 | NO2 | 2,4-2Cl-6-NO2 |
385 | H | N(CH3)2 | NO2 | 2,4-2Cl-6-CN |
386 | H | N(CH3)2 | NO2 | 2,4-2Cl-6-CF3 |
387 | H | OPh | NO2 | 2,6-2Cl-4-CN |
388 | H | OPh | NO2 | 4-CF3-2,6-2NO2 |
389 | H | OPh | NO2 | 2,4,6-3Cl |
390 | H | OPh | NO2 | 4-Cl-2,6-2NO2 |
391 | H | OPh | NO2 | 2-Br-4-NO2-6-CN |
392 | H | OPh | NO2 | 2-NO2-4-CN-5-CF3 |
393 | H | OPh | NO2 | 2,5-2Cl-4-NO2 |
394 | H | OPh | NO2 | 2,5-2Cl-4,6-2NO2 |
395 | H | OPh | NO2 | 2,4,5-3Cl-6-NO2 |
396 | H | OPh | NO2 | 2,4-2NO2 |
397 | H | OPh | NO2 | 2-Cl-4,6-2NO2 |
398 | H | OPh | NO2 | 2-Cl-4-CN-6-NO2 |
399 | H | OPh | NO2 | 2,4-2Cl-6-NO2 |
400 | H | OPh | NO2 | 2,4-2Cl-6-CN |
401 | H | OPh | NO2 | 2,4-2Cl-6-CF3 |
本发明的技术方案还包括通式I化合物的制备方法,反应式如下:
式中:X和Y分别选自卤原子或氨基,但不能同时选自卤原子或氨基;即X和Y不同、分别选自卤原子或氨基;Z选自卤原子;R2、R3、R、n分别如前所述;R1如前所述,但R1≠H。
适宜的碱可选自如氢氧化钾、氢氧化钠、碳酸钠、碳酸钾、碳酸氢钠、三乙胺、吡啶、甲醇钠、乙醇钠、氢化钠、叔丁醇钾或叔丁醇钠等。
按照以上制备方法,中间体II和中间体III在碱性条件下反应得到通式I中R1=H的化合物I-a;将其与卤代烃或酰卤等反应,即可制得R1≠H的通式化合物I。
反应在适宜的溶剂中进行,适宜的溶剂可选自如四氢呋喃、乙腈、甲苯、二甲苯、苯、N,N-二甲基甲酰胺、二甲亚砜、丙酮或丁酮等。
反应温度可在室温至溶剂沸点温度之间,通常为20~100℃。
反应时间为30分钟至20小时,通常1~10小时。
中间体II多为市售商品,也可以按公知方法制备,例如参照文献Indian Journal ofChemistry,Section B:Organic Chemistry Including Medicinal Chemistry,45B(4),972-975;2006中介绍的方法或者文献Tetrahedron Letters,44(21),4085-4088;2003报道的方法,以及波兰专利PL174903中的方法等制得。
中间体III可以按公知方法制备,例如参照JP2003292476介绍的方法得到。
还可以采用其他方法制备本发明的通式I化合物,例如:可以由取代二苯胺中间体通过硝化来制得,如对通式IV、通式V化合物进行硝化均可得到含硝基的通式I化合物(制备方法参见US4041172等)。
式中:R1、R2、R分别如前所述;R3选自氢或硝基;n=1-5。
式中:R1、R2、R3、R分别如前所述;m=1-4,n=2-5;Rn中有1-3个取代基选自NO2。
还可以将通式I的Rn中不含卤原子的取代二苯胺类化合物,通过卤化得到Rn中含卤原子的通式I化合物。
本发明的通式I化合物与现有技术中公开的化合物虽然都属于二苯胺类化合物,但结构特征仍存在显著不同。并且由于这些结构上的差异而使得本发明的化合物具有很好的杀菌和杀虫杀螨活性。同时,由于合成该类化合物的原料易得、方法简便,因而同已知杀菌剂相比,本发明的化合物成本低廉,具有更广阔的应用前景。
通式I化合物对农业领域中的多种病菌显示出优异的活性。同时该类化合物表现出较好的杀虫杀螨活性。因此,本发明的技术方案还包括通式I化合物在农业和其他领域中防治病菌和害虫害螨的应用。
下面提及的病害及害虫害螨的例子仅用来说明本发明,但绝不限定本发明。
通式I化合物可用于防治下列病害:卵菌纲病害,如霜霉病(黄瓜霜霉病、油菜霜霉病、大豆霜霉病、甜菜霜霉病、甘蔗霜霉病、烟草霜霉病、豌豆霜霉病、丝瓜霜霉病、冬瓜霜霉病、甜瓜霜霉病、白菜类霜霉病、菠菜霜霉病、萝卜霜霉病、葡萄霜霉病、葱霜霉病),白锈菌(油菜白锈病、白菜类白锈病),猝倒病(油菜猝倒病、烟草猝倒病、番茄猝倒病、辣椒猝倒病、茄子猝倒病、黄瓜猝倒病、棉苗猝倒病),绵腐病(辣椒绵腐病、丝瓜绵腐病、冬瓜绵腐病),疫病(蚕豆疫病、黄瓜疫病、南瓜疫病、冬瓜疫病、西瓜疫病、甜瓜疫病、辣椒疫病、韭菜疫病、大蒜疫病、棉花疫病),晚疫病(马铃薯晚疫病、番茄晚疫病)等;半知菌病害,如枯萎病(甘薯枯萎病、棉花枯萎病、芝麻枯萎病、蓖麻枯萎病、番茄枯萎病、菜豆枯萎病、黄瓜枯萎病、丝瓜枯萎病、南瓜枯萎病、冬瓜枯萎病、西瓜枯萎病、甜瓜枯萎病、辣椒枯萎病、蚕豆枯萎病、油菜枯萎病、大豆枯萎病),根腐病(辣椒根腐病、茄子根腐病、菜豆根腐病、黄瓜根腐病、苦瓜根腐病、棉黑根腐病、蚕豆根腐病),立枯病(棉苗立枯病、芝麻立枯病、辣椒立枯病、黄瓜立枯病、白菜立枯病),炭疽病(高粱炭疽病、棉花炭疽病、红麻炭疽病、黄麻炭疽病、亚麻炭疽病、烟草炭疽病、桑炭疽病、辣椒炭疽病、茄子炭疽病、菜豆炭疽病、黄瓜炭疽病、苦瓜炭疽病、西葫芦炭疽病、冬瓜炭疽病、西瓜炭疽病、甜瓜炭疽病、荔枝炭疽病),黄萎病(棉花黄萎病、向日葵黄萎病、番茄黄萎病、辣椒黄萎病、茄子黄萎病),黑星病(西葫芦黑星病、冬瓜黑星病、甜瓜黑星病),灰霉病(棉铃灰霉病、红麻灰霉病、番茄灰霉病、辣椒灰霉病、菜豆灰霉病、芹菜灰霉病、菠菜灰霉病、猕猴桃灰霉病),褐斑病(棉花褐斑病、黄麻褐斑病、甜菜褐斑病、花生褐斑病、辣椒褐斑病、冬瓜褐斑病、大豆褐斑病、向日葵褐斑病、豌豆褐斑病、蚕豆褐斑病),黑斑病(亚麻假黑斑病、油菜黑斑病、芝麻黑斑病、向日葵黑斑病、蓖麻黑斑病、番茄黑斑病、辣椒黑斑病、茄子黑斑病、菜豆黑斑病、黄瓜黑斑病、芹菜黑斑病、胡萝卜黑腐病、胡萝卜黑斑病、苹果黑斑病、花生黑斑病),斑枯病(番茄斑枯病、辣椒斑枯病、芹菜斑枯病),早疫病(番茄早疫病、辣椒早疫病、茄子早疫病、马铃薯早疫病、芹菜早疫病),轮纹病(大豆轮纹病、芝麻轮纹病、菜豆轮纹病),叶枯病(芝麻叶枯病、向日葵叶枯病、西瓜叶枯病、甜瓜叶枯病),茎基腐病(番茄茎基腐病、菜豆茎基腐病),及其他(玉米圆斑病、红麻腰折病、稻瘟病、栗黑鞘病、甘蔗眼斑病、棉铃曲霉病、花生冠腐病、大豆茎枯病、大豆黑点病、甜瓜大斑病、花生网斑病、茶赤叶斑病、辣椒白星病、冬瓜叶斑病、芹菜黑腐病、菠菜心腐病、红麻叶霉病、红麻斑点病、黄麻茎斑病、大豆紫斑病、芝麻叶斑病、蓖麻灰斑病、茶褐色叶斑病、茄子褐色圆星病、菜豆红斑病、苦瓜白斑病、西瓜斑点病、黄麻枯腐病、向日葵根茎腐病、菜豆炭腐病、大豆靶点病、茄子棒孢叶斑病、黄瓜靶斑病、番茄叶霉病、茄子叶霉病、蚕豆赤斑病等)等;担子菌病害,如锈病(小麦条锈病、小麦杆锈病、小麦叶锈病、花生锈病、向日葵锈病、甘蔗锈病、韭菜锈病、葱锈病、栗锈病、大豆锈病),黑穗病(玉米丝黑穗病、玉米黑粉病、高粱丝黑穗病、高粱散黑穗病、高粱坚黑穗病、高梁柱黑粉病、栗粒黑穗病、甘蔗黑穗病、菜豆锈病)及其他(如小麦纹枯病、水稻纹枯病等)等;子囊菌病害,如白粉病(小麦白粉病、油菜白粉病、芝麻白粉病、向日葵白粉病、甜菜白粉病、茄子白粉病、豌豆白粉病、丝瓜白粉病、南瓜白粉病、西葫芦白粉病、冬瓜白粉病、甜瓜白粉病、葡萄白粉病、蚕豆白粉病),菌核病(亚麻菌核病、油菜菌核病、大豆菌核病、花生菌核病、烟草菌核病、辣椒菌核病、茄子菌核病、菜豆菌核病、豌豆菌核病、黄瓜菌核病、苦瓜菌核病、冬瓜菌核病、西瓜菌核病、芹菜菌核病),黑星病(苹果黑星病、梨黑星病)等。
同时,本发明的部分化合物可用于防治下列科的重要品种:叶螨科(二斑叶螨、朱砂叶螨、苹果全爪螨、柑橘全爪螨等),瘿螨科,跗线螨科等。
由于其积极的特性,上述化合物可有利地用于保护农业和园艺业重要的作物、家畜和种畜,以及人类常去的环境免于病菌、害虫和害螨的伤害。
为获得理想效果,化合物的用量因各种因素而改变,例如所用化合物、预保护的作物、有害生物的类型、感染程度、气候条件、施药方法、采用的剂型。
每公顷10克-5公斤的化合物剂量能提供充分的防治。
本发明的另一目的还涉及通过施用通式I化合物,防治农业和园艺业重要的作物和/或家畜和种畜和/或人类常去的环境中的害虫和/或植物致病性真菌的方法。尤其是,化合物的用量在每公顷10克-5公斤内变化。
为了实际应用于农业,使用含一种或多种通式I化合物的组合物通常是有益的。
因此,本发明的另外一种技术方案还包括一种杀菌杀虫杀螨组合物,含有作为活性组分的通式I化合物和农业上可接受的载体,组合物中活性组分的重量百分含量为0.5-90%。
组合物的使用形式可以是干粉、可湿性粉剂、乳油、微乳剂、糊剂、颗粒剂、溶液、悬浮剂等:组合物类型的选择取决于具体的应用。
组合物是以已知方式制备的,例如任选在表面活性剂的存在下,通过用溶剂介质和/或固体稀释剂稀释或溶解活性物质。
可用的固体稀释剂或载体是例如:二氧化硅、高岭土、膨润土、滑石、硅藻土、白云石、碳酸钙、氧化镁、白垩、粘土、合成硅酸盐、硅镁土、海泡石。
除水以外,可用的液体稀释剂是例如芳族有机溶剂(二甲苯或烷基苯的混合物、氯苯等),石蜡(石油馏分),醇类(甲醇、丙醇、丁醇、辛醇、甘油),酯类(乙酸乙酯、乙酸异丁酯等),酮类(环己酮、丙酮、苯乙酮、异佛尔酮、乙基戊基酮等),酰胺类(N,N-二甲基甲酰胺、N-甲基吡咯烷酮等)。
可用的表面活性剂是烷基磺酸盐、烷基芳基磺酸盐、聚氧乙烯烷基酚、山梨醇的聚氧乙烯酯、木质素磺酸盐等的钠、钙、三乙基胺或三乙醇胺盐。
组合物还可含特殊的添加剂用于特定的目的,例如粘合剂如阿拉伯胶、聚乙烯醇、聚乙烯吡咯烷酮等。
上述组合物中活性成分的浓度可根据活性成分、其使用目的、环境条件和采用的制剂类型而在宽范围内改变。通常,活性成分的浓度范围是1-90%,优选5-50%。
如果需要,可以向组合物中添加能与通式I化合物兼容的其他活性成分,例如其他杀真菌剂、杀螨剂/杀虫剂、植物生长调节剂、抗生素、除草剂、肥料。
几种剂型的配制方法举例如下:
悬浮剂的配制:常用配方中活性组分含量为5%-35%。以水为介质,将原药、分散剂、助悬剂和抗冻剂等加入砂磨机中,进行研磨,制成悬浮剂。
水乳剂的配制:将原药、溶剂和乳化剂加在一起,使溶解成均匀油相。将水、抗冻剂等混合一起,成为均一水相。在高速搅拌下,将水相加入到油相或将油相加入到水相,形成分散性良好的水乳剂。本发明的水乳剂活性组分含量一般为5%-15%。为制备浓乳剂,本发明的化合物可溶解于一种或数种混合溶剂,再加入乳化剂来增强化合物在水中的分散效果。
可湿性粉剂的配制:按配方要求,将原药、各种表面活性剂及固体稀释剂等充分混合,经超细粉碎机粉碎后,即得到预定含量(例如10%-40%)的可湿性粉剂产品。为制备适于喷洒用的可湿性粉剂,本发明的化合物可以和研细的固体粉末如粘土、无机硅酸盐、碳酸盐以及润湿剂、粘合剂和/或分散剂组成混合物。
水分散性粒剂的配制:将原药和粉状固体稀释剂、润湿展着剂及粘合剂等进行混合粉碎,再加水捏合后,加入装有10至100目筛网的造粒机中进行造粒,然后再经干燥、筛分(按筛网范围)。也可将原药、分散剂、崩解剂和润湿剂及固体稀释剂加入砂磨机中,以水为介质研磨,制成悬浮剂,然后进行喷雾干燥造粒,通常配制含量为20%-30%颗粒状产品。
具体实施方式
以下具体实施例用来进一步说明本发明,但本发明绝非限于这些例子。合成实施例
实例1:化合物2的制备
取60%的氢化钠0.4g(0.01mol)于反应瓶中,用石油醚洗涤后加20ml四氢呋喃搅拌,分批加入2,4-二氯苯胺0.81g(0.005mol),加完后室温下搅拌30min,将1.56g(0.006mol)2,6-二氯-3,5-二硝基甲苯溶于30ml四氢呋喃后滴入反应瓶,约30min滴加完,继续室温搅拌5小时。TLC监测反应完毕后,将反应液过滤,滤液减压脱溶,柱层析(洗脱剂为乙酸乙酯与石油醚(沸程60-90℃),体积比为1∶20)纯化得化合物2,黄色固体1.37g,熔点136-137℃。
1H-NMR(300MHz,内标TMS,溶剂CDCl3)δ(ppm):2.14(s,3H),6.53(d,1H),7.17(d,1H),7.49(s,1H),8.68(s,1H),8.93(s,1H)。
实例2:化合物38的制备
将0.56g(0.0015mol)化合物2溶于5ml浓硫酸(96%,下同)中并冷却至0℃,将0.15g发烟硝酸(95%)和3ml浓硫酸混合均匀后加入反应瓶,继续搅拌5min,TLC监测反应完毕,将反应液倒入冰水中,有固体析出,过滤,用水冲洗滤饼,干燥,得化合物38,棕色固体0.59g,熔点156-158℃。
1H-NMR(300MHz,内标TMS,溶剂CDCl3)δ(ppm):2.09(s,3H),7.66(s,1H),8.01(s,1H),8.60(s,1H),9.75(s,1H)。
实例3:化合物43的制备
取60%的氢化钠0.32g(0.008mol)于反应瓶中,用石油醚洗涤后加10ml DMF搅拌,分批加入2,6-二氯-4-硝基苯胺0.83g(0.004mol),加完后室温下搅拌30min,然后在30min内将1.20g(0.0048mol)2,6-二氯-3,5-二硝基甲苯分批加入,室温下继续反应3小时。TLC监测反应完毕后,将反应液倒入50ml饱和食盐水中,乙酸乙酯萃取,萃取液用无水硫酸镁干燥减压脱溶,柱层析(洗脱剂为乙酸乙酯与石油醚(沸程60-90℃),体积比为1∶10)纯化得化合物43,黄色固体1.20g,熔点157-158℃。
1H-NMR(300MHz,内标TMS,溶剂CDCl3)δ(ppm):2.02(s,3H),8.29(s,2H),8.65(s,1H),8.95(s,1H)。
实例4:化合物89的制备
按照实例3的方法制得中间体M,再按照实例2的方法,将M硝化得到化合物89,红棕色固体,熔点136-138℃。
1H-NMR(300MHz,内标TMS,溶剂CDCl3)δ(ppm):2.41(s,3H),8.50(s,1H),8.72(s,1H),10.10(s,1H)。
实例5:化合物285的制备
取60%的氢化钠0.10g(0.0025mol)于反应瓶中,用石油醚洗涤后,加10ml DMF和0.38g(0.001mol)化合物2,搅拌1小时,加入0.43g(0.003mol)碘甲烷,反应5小时。TLC监测反应完毕后,将反应液倒入50ml饱和食盐水中,乙酸乙酯萃取,萃取液用无水硫酸镁干燥,减压脱溶,柱层析(洗脱剂为乙酸乙酯与石油醚(沸程60-90℃),体积比为1∶10)纯化得化合物285,黄色固体0.15g,熔点142-144℃。
1H-NMR(300MHz,内标TMS,溶剂CDCl3)δ(ppm):2.54(s,3H),3.31(s,3H),7.09(d,1H),7.25(d,2H),8.04(s,1H)。
本发明的其他化合物可以参照以上实例制备。
部分化合物的物性数据及核磁数据(1HNMR,300MHz,内标TMS,ppm)如下:
化合物1:熔点136-138℃。δ(CDCl3):2.12(s,3H),7.21(m,2H),7.26(m,1H),8.72(s,1H),9.00(s,1H)。
化合物4:熔点142-143℃。δ(CDCl3):2.20(s,3H),6.59(s,1H),7.58(s,1H),8.67(s,1H),8.80(s,1H)。
化合物5:熔点160-162℃。δ(CDCl3):1.95(s,3H),7.41(s,2H),8.72(s,1H),9.19(s,1H)。
化合物7:熔点184-186℃。δ(CDCl3):2.22(s,3H),6.87(d,2H),7.62(d,2H),8.66(s,1H),8.93(s,1H)。
化合物8:熔点172-174℃。δ(DMSO):2.34(s,3H),6.83(d,2H),8.06(d,2H),8.64(s,1H),9.49(s,1H)。
化合物9:熔点185-186℃。δ(CDCl3):2.41(s,3H),6.56(d,1H),8.31(d,1H),8.52(s,1H),9.23(s,1H),10.59(s,1H)。
化合物10:红色油状物。δ(CDCl3):2.27(s,3H),8.52(s,1H),9.09(s,2H),10.93(s,1H)。
化合物12:熔点91-94℃。δ(CDCl3):2.14(s,3H),6.91(d,2H),7.21(d,2H),8.71(s,1H),9.20(s,1H)。
化合物28:熔点158-160℃。δ(CDCl3):2.10(s,3H),6.83(d,4H),7.12(m,2H),7.34(m,4H),8.56(s,1H)。
化合物32:熔点191-193℃。δ(CDCl3):2.29(s,3H),6.48(d,1H),8.06(d,1H),8.41(s,1H),8.62(s,1H),8.79(s,1H)。
化合物33:熔点206-208℃。δ(CDCl3):2.25(s,3H),6.48(d,1H),7.47(d,1H),7.77(s,1H),8.62(s,1H),8.80(s,1H)。
化合物34:熔点121-123℃。δ(CDCl3):2.02(s,3H),2.40(s,3H),6.53(d,1H),7.10(d,1H),7.27(s,1H),8.74(s,1H),9.03(s,1H)。
化合物36:熔点204-205℃。δ(CDCl3):2.31(s,3H),6.48(d,1H),7.43(d,1H),8.26(s,1H),8.54(s,1H),10.36(s,1H)。
化合物39:熔点148-150℃。δ(CDCl3):2.07(s,3H),7.53(s,1H),7.72(s,1H),8.71(s,1H),8.97(s,1H)。
化合物41:熔点154-156℃。δ(CDCl3):2.21(s,3H),7.20(m,1H),7.80(m,1H),8.59(s,1H),9.94(s,1H)。
化合物44:熔点143-144℃。δ(CDCl3):1.98(s,3H),7.66(s,2H),8.70(s,1H),9.10(s,1H)。
化合物45:熔点180-182℃。δ(CDCl3):1.99(s,3H),7.69(s,2H),8.67(s,1H),9.00(s,1H)。
化合物51:熔点259-261℃。δ(CDCl3):2.38(s,3H),6.54(d,1H),7.70(d,1H),8.50(s,1H),8.62(s,1H),10.51(s,1H)。
化合物62:熔点169-171℃。δ(CDCl3):2.26(s,3H),8.50(d,2H),8.99(s,1H),10.14(s,1H)。
化合物63:熔点204-206℃。δ(CDCl3):2.23(s,3H),7.87(s,1H),8.38(s,1H),8.51(s,1H),10.00(s,1H)。
化合物67:熔点187-190℃。δ(CDCl3):2.18(s,3H),8.23(s,2H),8.57(s,1H),10.39(s,1H)。
化合物69:熔点93-95℃。δ(CDCl3):2.19(s,3H),8.14(s,2H),8.56(s,1H),10.42(s,1H)。
化合物77:橘红色油状物。δ(DMSO):2.33(s,3H),6.92(d,1H),7.26(s,1H),7.78(d,1H),8.63(s,1H),9.54(s,1H)。
化合物78:熔点204-206℃。δ(DMSO):2.32(s,3H),7.03(s,1H),8.73(s,1H),8.86(s,1H),10.40(s,1H)。
化合物79:熔点125-127℃。δ(CDCl3):1.94(s,3H),7.53(s,2H),8.75(s,1H),9.29(s,1H)。
化合物81:熔点160-161℃。δ(CDCl3):2.13(s,3H),2.54(s,3H),6.40(d,1H),7.19(d,1H),8.68(s,1H),8.96(s,1H)。
化合物83:熔点110-112℃。δ(CDCl3):2.03(s,3H),2.50(s,3H),6.50(d,1H),7.05(t,1H),7.24(d,1H),8.73(s,1H),9.06(s,1H)。
化合物84:熔点133-135℃。δ(CDCl3):2.03(s,3H),2.50(s,3H),6.53(d,1H),7.06(t,1H),7.21(d,1H),8.74(s,1H),9.08(s,1H)。
化合物86:熔点158-161℃。δ(CDCl3):2.16(s,3H),2.61(s,3H),6.47(d,1H),7.67(d,1H),8.69(s,1H),8.85(s,1H)。
化合物88:熔点172-175℃。δ(DMSO):2.32(s,3H),8.49(s,1H),8.68(s,2H),9.50(s,1H)。
化合物90:熔点127-129℃。δ(CDCl3):2.36(s,3H),6.55(s,1H),8.40(s,1H),8.54(s,1H),10.31(s,1H)。
化合物91:熔点169-171℃。δ(CDCl3):2.32(s,3H),6.42(s,1H),8.20(s,1H),8.60(s,1H),8.62(s,1H)。
化合物96:熔点159-162℃。δ(CDCl3):2.16(s,3H),8.23(s,1H),8.63(s,1H),8.91(s,1H)。
化合物97:熔点133-135℃。δ(CDCl3):2.07(s,3H),7.70(s,1H),8.69(s,1H),9.22(s,1H)。
化合物101:熔点96-97℃。δ(CDCl3):2.21(s,3H),6.59(s,1H),7.49(s,1H),8.66(s,1H),8.78(s,1H)。
化合物102:熔点192-194℃。δ(CDCl3):2.20(s,3H),7.05(s,2H),8.04(s,1H),8.22(s,1H),9.07(s,1H),9.43(s,1H)。
化合物106:熔点112-114℃。δ(CDCl3):2.18(s,3H),6.38(s,1H),7.38(d,1H),7.50(s,1H),7.97(d,1H),8.11(s,1H)。
化合物109:熔点146-148℃。δ(CDCl3):2.19(s,3H),6.70(d,2H),7.36(d,1H),7.53(d,2H),7.96(d,1H),8.20(s,1H)。
化合物110:熔点136-138℃。δ(CDCl3):2.22(s,3H),6.70(d,2H),7.41(d,1H),8.00(d,1H),8.16(d,2H),8.22(s,1H)。
化合物113:熔点72-74℃。δ(CDCl3):2.12(s,3H),6.75(d,2H),7.12(d,2H),7.25(d,1H),7.98(d,1H),8.46(s,1H)。
化合物116:红色油状物。δ(CDCl3):2.02(s,3H),2.38(s,3H),6.34(d,1H),7.00(d,1H),7.18(m,2H),7.98(d,1H),8.30(s,1H)。
化合物120:棕色油状物。δ(CDCl3):1.92(s,3H),7.22(d,1H),7.58(s,2H),7.93(d,1H),8.39(s,1H)。
化合物126:熔点158-160℃。δ(CDCl3):2.30(s,3H),6.47(d,1H),7.59(m,2H),7.94(d,1H),8.60(s,1H),10.21(s,1H)。
化合物136:熔点136-138℃。δ(CDCl3):2.22(s,3H),6.75(d,1H),7.03(s,1H),7.45(d,1H),7.67(d,1H),7.99(d,1H),8.16(s,1H)。
制剂实施例
各组分加入量均为重量百分含量。制剂中活性组分可以选白本发明通式I中的任意化合物,经折百后计量加入。
实施例6:30%可湿性粉剂
化合物43 30%
十二烷基硫酸钠 2%
木质素磺酸钠 3%
萘磺酸甲醛缩合物 5%
轻质碳酸钙 补足至100%
将化合物及其他组分充分混合,经超细粉碎机粉碎后,即得到30%的可湿性粉剂产品。
实施例7:40%浓悬浮剂
化合物38 40%
乙二醇 10%
壬基苯酚聚乙二醇醚 6%
木质素磺酸钠 10%
羧甲基纤维素 1%
37%甲醛水溶液 0.2%
75%硅油水乳液 0.8%
水 补足至100%
化合物及其他组分充分混合,由此得到的浓悬浮剂,用水稀释所得悬浮剂可得到任何所需浓度的稀释液。
实施例8:60%水分散性粒剂
化合物38 60%
萘磺酸钠甲醛缩合物 12%
N-甲基-N-油酰基-牛磺酸钠 8%
聚乙烯吡咯烷酮 2%
羧甲基纤维素 2%
高岭土 补足至100%
将化合物及其他组分混合粉碎,再加水捏合后,加入10-100目筛网的造粒机中进行造粒,然后再经干燥、筛分(按筛网范围)。
生物活性测定
本发明化合物对农业领域中的多种病菌都表现出很好的活性,同时,还显示出较好的杀虫杀螨活性;试验结果表明本发明化合物无除草活性。
实例9:杀菌活性测定
用本发明化合物对植物的多种病害进行了试验。试验方法如下:
离体杀菌活性的测定:待测化合物原药用DMSO溶解,配制成待测液。将待测液加到96孔培养板的小孔中,再加入病原菌孢子或孢子囊悬浮液,使药液的最终浓度分别为25mg/L,8.3mg/L和2.8mg/L,处理后放置培养箱中培养。24小时后进行调查,调查时目测每个处理的孢子或孢子囊萌发情况,并根据DMSO处理的萌发情况,评价化合物抑菌率。
活体保护活性测定:采用活体盆栽测定方法。待测化合物原药用少量丙酮(丙酮与喷液量的体积比等于0.05)溶解,用含有0.1%吐温80的水稀释至所需的浓度。喷雾施药到植物试材上,24小时后进行病害接种。接种后,将植物放在人工气候室中培养,24小时后将植物试材移入温室培养。待对照充分发病后(通常为一周时间)进行化合物防病效果评估。
部分化合物的离体抑菌活性测试结果如下:
药液浓度为25mg/L时,化合物38、43、44、78对水稻稻瘟病菌的抑制率为100%,对黄瓜灰霉病菌的抑制率大于80%。
药液浓度为0.92mg/L时,化合物44对水稻稻瘟病菌的抑制率为100%。
部分化合物的活体保护活性测试结果如下:
药液浓度为400mg/L时,化合物43、44、78对黄瓜霜霉病、玉米锈病和黄瓜炭疽病的防效均为100%,对小麦白粉病的防效大于60%。
药液浓度为100mg/L时,化合物43、44、78对黄瓜霜霉病和玉米锈病的防效均为100%,对黄瓜炭疽病的防效大于90%。
药液浓度为25mg/L时,化合物44对黄瓜霜霉病的防效为100%,对玉米锈病的防效大于60%。
本发明的部分化合物、中间体及对照药剂对黄瓜霜霉病的防效测试结果如下:
药液浓度为100mg/L时,化合物5、9、10、32、38、43、44、45、62、67、69、78、88、89等的防效均达到100%;化合物77、91、96等的防效均为在95%以上;对照药剂氟啶胺和烯酰吗啉的防效为100%,中间体B的防效为20%,中间体C无防效。
药液浓度为50mg/L时,化合物9、38、43、44、67、69、78、88等的防效均达到100%;化合物62的防效为98%;化合物32、45等的防效均大于或等于70%;对照药剂氟啶胺和烯酰吗啉的防效为100%,中间体B、C及二苯胺均无防效。
药液浓度为12.5mg/L时,化合物43、78等的防效均为100%;化合物38、44、67、91等的防效均大于或等于80%;化合物45、69、88等的防效均在50%以上;对照药剂氟啶胺和烯酰吗啉的防效分别为95%和80%,中间体B、C及二苯胺均无防效。
药液浓度为3.125mg/L时,化合物43等的防效为90%;化合物38、44、45、67、69、78、91等的防效均大于或等于40%;对照药剂氟啶胺和烯酰吗啉的防效分别为40%和35%,中间体B、C及二苯胺均无防效。
以上药效数据结果可以表明本发明的部分化合物与现有技术公开的化合物相比,具有相当或更好的杀菌活性。部分效果较为突出的化合物与中间体及对照药剂防治黄瓜霜霉病的测试结果见表4(“/”表示未测试):
表4
69 | 100 | 100 | 70 | 40 |
78 | 100 | 100 | 100 | 60 |
91 | 98 | 95 | 80 | 75 |
中间体B | 20 | 0 | 0 | 0 |
中间体C | 0 | 0 | 0 | 0 |
二苯胺 | / | 0 | 0 | 0 |
氟啶胺 | 100 | 100 | 95 | 40 |
烯酰吗啉 | 100 | 100 | 80 | 35 |
实例10:杀螨活性测定
用本发明化合物对朱砂叶螨进行了活性测定试验。测定的方法如下:
待测化合物用丙酮/甲醇(1∶1)的混合溶剂溶解后,用含有0.1%吐温80的水稀释至所需的浓度。
以朱砂叶螨(Tetranychus cinnabarinus)为靶标,采用Airbrush喷雾法进行活性测定,Airbrush喷雾处理的压力为0.7kg/cm2,喷液量为0.5ml。处理后2-3日调查靶标的死亡率。
测试结果如下:
药液浓度为150mg/L时,化合物44对朱砂叶螨的致死率达100%;对照药剂氟啶胺对朱砂叶螨的致死率为90%。
药液浓度为37.5mg/L时,化合物44等对朱砂叶螨致死率为95%;对照药剂氟啶胺对朱砂叶螨的致死率为14%。
Claims (5)
2.根据权利要求1所述的化合物,其特征在于:通式I中
R2选自氯;
R3选自硝基;
R选自氯、溴、氟、氰基、硝基或CF3;
n=1-5;
或通式I化合物与盐酸、硫酸、磷酸、三氟乙酸、甲磺酸或对甲苯磺酸形成的盐。
4.一种按照权利要求1所述的通式I化合物在农业领域中防治病菌或害虫害螨的应用。
5.一种杀菌杀虫杀螨组合物,其特征在于:含有作为活性组分的通式I化合物和农业上可接受的载体,组合物中活性组分的重量百分含量为0.5-90%。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201010129005.6A CN102199095B (zh) | 2010-03-22 | 2010-03-22 | 一种取代二苯胺类化合物及其制备与应用 |
US13/578,787 US9061967B2 (en) | 2010-03-22 | 2011-03-21 | Substituted diphenylamine compounds, preparation method and use thereof |
PCT/CN2011/071983 WO2011116671A1 (zh) | 2010-03-22 | 2011-03-21 | 一种取代二苯胺类化合物及其制备与应用 |
EP11758781.6A EP2551258B1 (en) | 2010-03-22 | 2011-03-21 | Substituted diphenylamine compounds, preparation method and use thereof |
CN201180009273.7A CN102762530B (zh) | 2010-03-22 | 2011-03-21 | 一种取代二苯胺类化合物及其制备与应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201010129005.6A CN102199095B (zh) | 2010-03-22 | 2010-03-22 | 一种取代二苯胺类化合物及其制备与应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102199095A CN102199095A (zh) | 2011-09-28 |
CN102199095B true CN102199095B (zh) | 2014-04-09 |
Family
ID=44660118
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201010129005.6A Active CN102199095B (zh) | 2010-03-22 | 2010-03-22 | 一种取代二苯胺类化合物及其制备与应用 |
CN201180009273.7A Active CN102762530B (zh) | 2010-03-22 | 2011-03-21 | 一种取代二苯胺类化合物及其制备与应用 |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201180009273.7A Active CN102762530B (zh) | 2010-03-22 | 2011-03-21 | 一种取代二苯胺类化合物及其制备与应用 |
Country Status (4)
Country | Link |
---|---|
US (1) | US9061967B2 (zh) |
EP (1) | EP2551258B1 (zh) |
CN (2) | CN102199095B (zh) |
WO (1) | WO2011116671A1 (zh) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103547565B (zh) * | 2011-06-17 | 2015-05-20 | 中国中化股份有限公司 | 一种取代氰基苯胺类化合物及制备与应用 |
JP5710023B2 (ja) * | 2011-12-14 | 2015-04-30 | イハラケミカル工業株式会社 | ジフェニルアミン化合物およびその製造方法 |
EP2826474B1 (en) * | 2012-03-14 | 2021-05-26 | Sinochem Corporation | Use of substituted diphenylamine compounds in preparing anti-tumour drugs |
CN103301096B (zh) * | 2012-03-14 | 2015-05-06 | 中国中化股份有限公司 | 取代二苯胺类化合物作为制备抗肿瘤药物的应用 |
CN103539681B (zh) * | 2012-07-11 | 2016-04-20 | 沈阳中化农药化工研发有限公司 | 一种取代的二苯胺类化合物及其应用 |
CN105394061B (zh) * | 2014-09-12 | 2018-03-02 | 沈阳中化农药化工研发有限公司 | 一种杀真菌组合物及应用 |
CN105454251B (zh) * | 2014-09-12 | 2018-07-03 | 沈阳中化农药化工研发有限公司 | 一种杀真菌组合物及其用途 |
CN105724398B (zh) * | 2014-12-11 | 2018-12-14 | 沈阳中化农药化工研发有限公司 | 一种杀真菌组合物及其应用 |
CN105981728B (zh) * | 2015-03-06 | 2019-01-22 | 中化农化有限公司 | 含三唑类杀菌剂的农药组合物 |
CN105981721B (zh) * | 2015-03-06 | 2019-01-22 | 中化农化有限公司 | 一种防治土传或种传病害的杀菌组合物 |
CN105981723B (zh) * | 2015-03-06 | 2019-01-22 | 中化农化有限公司 | 一种含取代二苯胺类化合物的杀菌组合物 |
CN106561648A (zh) * | 2015-10-12 | 2017-04-19 | 陕西韦尔奇作物保护有限公司 | 一种双苯菌胺的杀菌组合物 |
CN106577702A (zh) * | 2015-10-20 | 2017-04-26 | 陕西韦尔奇作物保护有限公司 | 一种含双苯菌胺的农药组合物 |
CN106614706A (zh) * | 2015-10-30 | 2017-05-10 | 陕西韦尔奇作物保护有限公司 | 一种含双苯菌胺的增效农药组合物 |
CN108976167B (zh) * | 2017-06-02 | 2021-12-07 | 沈阳中化农药化工研发有限公司 | 一种取代苯肼类化合物及其应用 |
CN107912436A (zh) * | 2017-12-06 | 2018-04-17 | 广东中迅农科股份有限公司 | 一种含腈吡螨酯和氟啶胺的农药组合物 |
CN117378607A (zh) * | 2022-07-04 | 2024-01-12 | 沈阳中化农药化工研发有限公司 | 一种n取代苯胺类化合物及其用途 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4152460A (en) * | 1978-01-30 | 1979-05-01 | Eli Lilly And Company | 3-Chloro-2,6-dinitro-N-(substituted phenyl)-4-(trifluoromethyl)benzenamines |
US4304791A (en) * | 1980-01-08 | 1981-12-08 | Eli Lilly And Company | Benzenamines, formulations, and fungicidal method |
US4407820A (en) * | 1981-03-19 | 1983-10-04 | Eli Lilly And Company | Diphenylamine compounds |
CN1333205A (zh) * | 2000-07-10 | 2002-01-30 | 浙江省化工研究院 | 含氟取代的二苯胺衍生物 |
Family Cites Families (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3107263A (en) | 1961-01-12 | 1963-10-15 | Parke Davis & Co | Anthranilic acids |
US3948990A (en) | 1971-03-19 | 1976-04-06 | Imperial Chemical Industries Limited | Chemical compounds and compositions |
US4041172A (en) | 1972-12-20 | 1977-08-09 | Imperial Chemical Industries Limited | Compositions and methods for combating insect pests or fungal pests of plants |
GB1430046A (en) * | 1974-03-07 | 1976-03-31 | Ici Ltd | Nitrobenzene derivatives |
US4381312A (en) * | 1974-12-13 | 1983-04-26 | Eli Lilly And Company | 2,4,6-Trinitrodiphenylamines for control of foliar phytopathogens |
US3948957A (en) | 1975-06-23 | 1976-04-06 | Eli Lilly And Company | 3-Azido-2,6-dinitroanilines |
IE43715B1 (en) | 1975-09-26 | 1981-05-06 | Lilly Co Eli | Nitrotrifluoromethyl substituted diphenylamines,their preparation and rodenticidal compositions |
US4187318A (en) | 1975-09-26 | 1980-02-05 | Eli Lilly And Company | Rodenticidal N-alkyldiphenylamines |
IT1072567B (it) | 1975-09-26 | 1985-04-10 | Lilly Co Eli | Composti della difenilammina per impieghi rodenticidi |
GB1544078A (en) | 1976-02-23 | 1979-04-11 | Ici Ltd | Herbicidal process |
GB1525884A (en) | 1976-05-07 | 1978-09-20 | Ici Ltd | Coating compositions |
US4316988A (en) | 1976-07-21 | 1982-02-23 | Eli Lilly And Company | N-Alkyldiphenylamines |
DE2728536A1 (de) | 1977-06-24 | 1979-01-11 | Bayer Ag | Neue 2-arylamino-3,5-dinitro- benzotrifluoride |
DE2815290A1 (de) * | 1978-04-08 | 1979-10-18 | Bayer Ag | Neue diarylamine, verfahren zu ihrer herstellung und ihre verwendung |
US4215145A (en) | 1978-12-05 | 1980-07-29 | E. I. Du Pont De Nemours And Company | Miticidal, fungicidal, and ovicidal sulfenamides |
EP0026743B1 (de) | 1979-09-28 | 1983-05-25 | Ciba-Geigy Ag | Hochsubstituierte Diphenylamine, deren Herstellung und deren Verwendung |
IL64149A0 (en) | 1981-03-19 | 1982-01-31 | Lilly Co Eli | N-alkylated diphenylamine derivatives,method of preparing them and an insecticidal,arachnicidal and ectoparasiticidal composition containing them |
JPS58113151A (ja) | 1981-12-26 | 1983-07-05 | Ishihara Sangyo Kaisha Ltd | シフエニルアミン系化合物及びそれを含有する有害生物防除剤 |
US4670596A (en) | 1983-08-01 | 1987-06-02 | Eli Lilly And Company | Diphenylamine compounds |
JPH01186849A (ja) | 1988-01-19 | 1989-07-26 | Sumitomo Chem Co Ltd | ジフェニルアミン誘導体、その製造法およびそれを有効成分とする有害生物防除剤 |
PL174903B1 (pl) | 1994-10-05 | 1998-10-30 | Akad Rolniczo Tech | Sposób otrzymywania chloropochodnych amin aromatycznych |
CN1073550C (zh) * | 1997-12-15 | 2001-10-24 | 中国科学院上海有机化学研究所 | N-(二硝基三氟甲基)-取代的-2-甲基苯胺衍生物、制备方法及用途 |
US6939887B2 (en) | 2001-01-30 | 2005-09-06 | Sumitomo Pharmaceuticals Co., Ltd. | Benzimidazolidinone derivatives |
JP4412449B2 (ja) | 2002-04-02 | 2010-02-10 | 日産化学工業株式会社 | ジアミノレゾルシノール化合物の製造法 |
JPWO2005035498A1 (ja) | 2003-10-08 | 2006-12-21 | 住友製薬株式会社 | 含窒素二環性化合物の摂食調節剤としての用途 |
WO2009037707A2 (en) | 2007-09-20 | 2009-03-26 | Ramot At Tel Aviv University Ltd. | N-phenyl anthranilic acid derivatives and uses thereof |
US8183418B2 (en) | 2008-12-18 | 2012-05-22 | E. I. Du Pont De Nemours And Company | Process for the synthesis of dihalodinitrotoluene |
-
2010
- 2010-03-22 CN CN201010129005.6A patent/CN102199095B/zh active Active
-
2011
- 2011-03-21 WO PCT/CN2011/071983 patent/WO2011116671A1/zh active Application Filing
- 2011-03-21 US US13/578,787 patent/US9061967B2/en active Active
- 2011-03-21 CN CN201180009273.7A patent/CN102762530B/zh active Active
- 2011-03-21 EP EP11758781.6A patent/EP2551258B1/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4152460A (en) * | 1978-01-30 | 1979-05-01 | Eli Lilly And Company | 3-Chloro-2,6-dinitro-N-(substituted phenyl)-4-(trifluoromethyl)benzenamines |
US4304791A (en) * | 1980-01-08 | 1981-12-08 | Eli Lilly And Company | Benzenamines, formulations, and fungicidal method |
US4407820A (en) * | 1981-03-19 | 1983-10-04 | Eli Lilly And Company | Diphenylamine compounds |
CN1333205A (zh) * | 2000-07-10 | 2002-01-30 | 浙江省化工研究院 | 含氟取代的二苯胺衍生物 |
Also Published As
Publication number | Publication date |
---|---|
US9061967B2 (en) | 2015-06-23 |
EP2551258A1 (en) | 2013-01-30 |
CN102199095A (zh) | 2011-09-28 |
CN102762530B (zh) | 2014-07-02 |
US20120309844A1 (en) | 2012-12-06 |
CN102762530A (zh) | 2012-10-31 |
EP2551258B1 (en) | 2018-10-31 |
WO2011116671A1 (zh) | 2011-09-29 |
EP2551258A4 (en) | 2013-10-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102199095B (zh) | 一种取代二苯胺类化合物及其制备与应用 | |
CN101668748B (zh) | 取代嘧啶醚类化合物及其应用 | |
CN102395569B (zh) | 含取代苯胺基嘧啶基团的e-型苯基丙烯酸酯类化合物及其应用 | |
JPH04290805A (ja) | 除草性カルボキシアミド誘導体 | |
KR20100020454A (ko) | 살진균제 헤테로사이클릴-피리미디닐-아미노 유도체 | |
CN102336744B (zh) | 取代三唑啉酮醚类化合物及其作为杀菌、杀虫、杀螨剂的用途 | |
US8969332B2 (en) | Aryloxy dihalopropenyl ether compounds and uses thereof | |
CN103539681B (zh) | 一种取代的二苯胺类化合物及其应用 | |
CN102993100B (zh) | 取代吡唑(硫)酮类化合物及其用途 | |
CN101875639A (zh) | 取代嘧啶醚类化合物及其应用 | |
CN102336742A (zh) | 一种取代三唑啉酮醚类化合物及其应用 | |
BRPI0619838A2 (pt) | composições fungicidas, derivado de amida de ácido carboxìlico e métodos para controlar fungos nocivos, doenças de plantas, proteger plantas de cultivo e melhorar o rendimento dos cultivos | |
CN101205187B (zh) | 取代芳基醚类化合物及其制备与应用 | |
CN102827071B (zh) | 取代氰基苯胺类化合物及其应用 | |
CN103288771B (zh) | 异噻唑类化合物及其作为杀菌剂的用途 | |
CN102827032B (zh) | 含氰基二苯胺类化合物及其应用 | |
CN104803929A (zh) | 一种取代肟醚类化合物及其用途 | |
CN102827034B (zh) | 含对二氰基苯胺类化合物及其应用 | |
CN103087041B (zh) | 含二芳醚的吡唑酰胺类化合物作为农用杀菌剂的用途 | |
CN102827033B (zh) | 含邻二氰基苯胺类化合物及其应用 | |
CN110963963A (zh) | 一种吡啶酰胺类化合物及其杀菌用途 | |
CN102464622B (zh) | 取代嘧啶氨类化合物及其应用 | |
CN101205202B (zh) | 取代苯基脲类化合物及其制备与应用 | |
CN103570642B (zh) | 一种异噻唑啉酮类化合物及其作为杀菌剂的用途 | |
CN108976167A (zh) | 一种取代苯肼类化合物及其应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C41 | Transfer of patent application or patent right or utility model | ||
TR01 | Transfer of patent right |
Effective date of registration: 20160122 Address after: 110021 Liaodong Road, Tiexi District, Liaoning, No. 8-1, No. Patentee after: SHENYANG SINOCHEM PESTICIDE CHEMICAL RESEARCH AND DEVELOPMENT CO., LTD. Address before: 100031 Beijing, Xicheng District, the door of the revitalization of the main street, No. 28 Patentee before: Sinochem Corporation Patentee before: Shenyang Research Institute of Chemical Industry |