CN1075477A - 具除草活性的n-氰基哒嗪酮 - Google Patents
具除草活性的n-氰基哒嗪酮 Download PDFInfo
- Publication number
- CN1075477A CN1075477A CN93101027A CN93101027A CN1075477A CN 1075477 A CN1075477 A CN 1075477A CN 93101027 A CN93101027 A CN 93101027A CN 93101027 A CN93101027 A CN 93101027A CN 1075477 A CN1075477 A CN 1075477A
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- CN
- China
- Prior art keywords
- cyano
- halogen
- group
- pyridazinone
- formula
- Prior art date
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- OBKLQOOUWUPYQC-UHFFFAOYSA-N 6-oxo-1,5-dihydropyridazine-2-carbonitrile Chemical class O=C1CC=CN(C#N)N1 OBKLQOOUWUPYQC-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 35
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 34
- 150000002367 halogens Chemical class 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 125000003118 aryl group Chemical group 0.000 claims abstract description 19
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 12
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 241000196324 Embryophyta Species 0.000 claims abstract description 9
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 9
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 7
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000011541 reaction mixture Substances 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 10
- ATDGTVJJHBUTRL-UHFFFAOYSA-N cyanogen bromide Chemical compound BrC#N ATDGTVJJHBUTRL-UHFFFAOYSA-N 0.000 claims description 7
- AAILEWXSEQLMNI-UHFFFAOYSA-N 1h-pyridazin-6-one Chemical compound OC1=CC=CN=N1 AAILEWXSEQLMNI-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- CPZLKSSMZLLSBN-UHFFFAOYSA-N 6-oxo-1h-pyridazine-5-carbonitrile Chemical compound O=C1NN=CC=C1C#N CPZLKSSMZLLSBN-UHFFFAOYSA-N 0.000 claims description 2
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- -1 5-phenylbenzene-4-(1H)-pyridazinone Chemical compound 0.000 description 19
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 19
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- 229910052801 chlorine Inorganic materials 0.000 description 15
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
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- 150000001875 compounds Chemical class 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
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- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZCKJSOZZDMZSAZ-UHFFFAOYSA-N 4,6-dimethoxy-3-phenylpyridazine Chemical compound N1=NC(OC)=CC(OC)=C1C1=CC=CC=C1 ZCKJSOZZDMZSAZ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
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- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
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- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
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- 229910052796 boron Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
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- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
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- 229940125904 compound 1 Drugs 0.000 description 1
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- 239000007859 condensation product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004966 cyanoalkyl group Chemical group 0.000 description 1
- WPBXOELOQKLBDF-UHFFFAOYSA-N cyanogen iodide Chemical compound IC#N WPBXOELOQKLBDF-UHFFFAOYSA-N 0.000 description 1
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- 238000006900 dealkylation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
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- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
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- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 235000019357 lignosulphonate Nutrition 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
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- 239000004579 marble Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000011785 micronutrient Substances 0.000 description 1
- 235000013369 micronutrients Nutrition 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 229940113162 oleylamide Drugs 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- CTYRPMDGLDAWRQ-UHFFFAOYSA-N phenyl hydrogen sulfate Chemical compound OS(=O)(=O)OC1=CC=CC=C1 CTYRPMDGLDAWRQ-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000003531 protein hydrolysate Substances 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000012056 up-stream process Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
- C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members 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
- C07D237/14—Oxygen atoms
- C07D237/16—Two oxygen atoms
-
- 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
- A01N47/40—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 a double or triple bond to nitrogen, e.g. cyanates, cyanamides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
- C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members 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
- C07D237/14—Oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
本发明涉及式I所示的新的具有除草活性的
N-氰基哒嗪酮类化合物,它们的制备方法,含有它们
的除草组合物以及控制杂草的方法,其中,基团R1,
R2和R3相互分别表示氢、卤素、氨基、氰基、烷基、芳
基、芳烷基、烷氧基或芳氧基。
Description
本发明是有关新的具除草活性的N-氰基哒嗪酮,它们的制备方法,含有新的N-氰基哒嗪酮的除草组合物和它们的制备方法,以及防除杂草的方法。
US-PS3967952和US-PS4013658揭示了在1-氮位置被带有1-3个碳原子的烷基取代的具有除草活性的3,5-二苯基-4-(1H)-哒嗪酮和-哒嗪硫酮。但是作为除草所需的施用率过高。
出人意料的是已发现的新的N-氰基哒嗪-4-酮,即使在低施用率下也具有优良的除草活性。
本发明所涉及的N-氰基哒嗪酮其通式为
式中R1,R2和R3相互分别代表氢,卤素,氨基,硝基,氰基,烷基,芳
基,芳烷基,烷氧基或芳基氧基。
在本文中,卤素基团被理解为氟、氯、溴或碘,优选氯或溴,氨基被理解为未取代的氨基,或是被烷基或芳基取代的氨基,或是在杂环中或杂环上的氨基。烷基特别优选1至4个碳原子的烷基,它们可以是未取代的或被卤素,氨基,硝基,氰基,烷氧基或芳基氧基取代,优选未取代的或被卤素取代的烷基,例如甲基,乙基,异丙基,丁基,三氟甲基或三氟乙基。芳基被理解为是未取代的或被卤素,氨基,硝基,氰基,烷基,芳基,芳烷基,烷氧基或芳基氧基单取代或多取代的,优选未取代或被卤素,硝基,氰基或烷基单取代或多取代的苯基。
在烷氧基或芳基氧基中的烷基或芳基具有上述含义。在本文中,优选烷氧基,特别优选的是1至8个碳原子烷氧基,尤其特别优选1至6个碳原子的烷氧基。通式Ⅰ所示的化合物中优选R1,R2和R3相互分别代表氢,卤素,烷氧基或芳基的化合物。
特别优选的是,R1代表卤素或芳基,更优选的是未取代的或被卤素,硝基,氰基,烷基或烷氧基单取代或多取代的苯基,R2代表氢或卤素基团,和R3代表烷氧基,卤素基团或芳基,特别优选未取代的或被卤素取代的苯基。
本发明还涉及通式Ⅰ所示的N-氰基哒嗪酮的制备方法,
式中R1,R2和R3相互分别代表氢,卤素,氨基,硝基,氰基,烷基,芳基,芳烷基,烷氧基或芳基氧基。该方法包括将溶解或悬浮在于反应条件下呈惰性的稀释剂中的式Ⅱ所示的羟基哒嗪用碱和卤化氰处理或与之反应,并从反应混合物中分离出生成的通式Ⅰ所示的氰基哒嗪酮,
在式Ⅱ中,R1,R2和R3含义如上。
为了制备式Ⅰ所示的化合物,可使溶解于或悬浮于在反应条件下呈惰性的溶剂中的式Ⅱ所示的羟基哒嗪与无机碱或有机碱和卤化氰反应,所述溶剂例如有氯代烃类如二氯甲烷、二氯乙烷、三氯乙烷,酮类如丙酮、二丁酮,醚类如二异丙醚,二噁烷,酰胺如二甲基甲酰胺,二烷基亚砜如二甲亚砜,醇类如甲醇,乙醇,二异丙醇,水或上面所述稀释剂的混合物;碱例如有氢氧化钠,氢化钠,碳酸钠,氢氧化钾,氢化钾或碳酸钾,氨,胺类如三乙胺,吡啶,优选胺类,特别优选三乙胺;卤化氰例如有氯化氰,溴化氰或碘化氰,优选氯化氰或溴化氰。不同寻常的是反应可在水中或含有机稀释剂的含水混合物中进行。
通常,卤化氰和碱的用量相对于式Ⅱ所示的羟基哒嗪来说,至少是等摩尔量的或过量的,但是,在某些情况下,使用过量的式Ⅱ所示的羟基哒嗪也可以有利于反应。碱和卤化氰是在大约-70℃至所用稀释剂沸点温度下加入,温度的选择取决于所用反应物的化学结构。添加碱和卤化氰的温度优选-10℃至60℃,特别优选从接近0℃至室温。反应混合物的温度通常随着卤化氰的加入而升高。在加入卤化氰时也可以任选地进行冷却。待投料完毕时,可让反应在给定的温度下进一步进行,或者如果最高至所用稀释剂的沸点是合适的,也可加热反应混合物使反应完全。但是通常不需要加热。优选在室温下加入碱和卤化氰,使反应在产生的温度下进行,而不进行外部冷却或加热。
与酰卤相比较,卤化氰不与哒嗪环4位上的氧原子反应,而出人意料地与哒嗪环1位上的氮原子反应。
反应可以用常规方法如色谱法监测。当反应结束时,以方便的方法如过滤或萃取从反应混合物中将卤化氰中的卤素和碱形成的盐除去,而有机稀释剂被蒸去。留下呈油状或结晶状残渣的所需要的式Ⅰ所示的N-氰基哒嗪酮。如果必要,可将残渣作进一步纯化处理,例如色谱或重结晶。
在式Ⅰ化合物中R1是芳基和R3是卤素的情况下,被R3键合的6位特别具有反应性,所以R3可以被其它官能基取代。例如1-氰基-3-苯基-6-氯代哒嗪-4-酮中的氯原子在有机溶剂中与碘化钠反应,可以转化为1-氰基-3-苯基-6-碘代哒嗪-4-酮。这意味着,用别的官能基取代哒嗪环上6位的官能团可以从式Ⅰ所示的化合物得到另外的式Ⅰ化合物。
式Ⅱ所示的起始化合物的制备是已知的,例如DE4013734中的方法和通过用合适的哒嗪与碱金属氢氧化物反应或通过4-羟基哒嗪的脱烷基反应制备,例如借助于碱金属氢化物和烷基硫醇,反应是在于反应条件下呈惰性的稀释剂中进行的。
例如,3-芳基-4-羟基-6-溴化哒嗪可通过3-芳基-4,6-二溴哒嗪与氢氧化钠在二噁烷/水中反应制备,3-苯基-4-羟基-6-甲氧基哒嗪可以由4,6-二甲氧基-3-苯基哒嗪与氢化钠和丁硫醇在二甲基甲酰胺中反应制备。3-芳基烷氧基哒嗪可以例如用相应的3-芳基卤代哒嗪与碱金属醇化物反应制备。3-芳基卤代哒嗪,如3-(3′-三氟甲基苯基)-4,6-二氯哒嗪可以由3-芳基哒嗪-6-酮在氯氧化磷中用红磷和元素卤素经卤化反应制备。较长时间的卤化反应可以使哒嗪环上全部4、5和6位分步被卤化。
按照本发明的N-氰基哒嗪酮具有优良的除草作用,因此丰富了本领域。它们适合于防除如谷类、玉米、可食用块茎植物,白菜,鹰咀豆,番茄和洋葱这些农作物中的双子叶,还有单子叶种子传播的杂草。
它们特别适合于防除上述农作物中的下述杂草,如
反枝苋(AMARE)-红根
Anthemis arvenisis(ANTAR)-corn chamomile
矢车菊(CENCY)-玉米花
藜(CHEAL)-
稗(ECHCG)
猪殃殃(GALAP)
稻槎菜(LAPCO)
繁缕(STEME)
本发明还涉及除草组合物,它除了含有添加剂和/或载体外,还含有至少一种如上式Ⅰ所示的N-氰基哒嗪酮。
除草组合物可用已知的方法加工成制剂,例如将有效成分与填充剂,如液体溶剂,加压液化的气体和/或固体载体相混合,还可以任选使用表面活性剂如乳化剂和/或分散剂和/或润湿剂和/或发泡剂。如果用水作填充剂,那么有机溶剂也可作为例如助溶剂。适合的液体溶剂主要是:芳香族化合物如二甲苯,甲苯或烷基萘,氯化芳香烃或氯化脂肪烃如二氯甲烷,三氯代苯,脂肪族如环己烷或链烷烃,如矿物油馏分,醇类如丁醇或乙二醇以及它们的醚和酯,酮如丙酮,甲乙酮,甲基异丁基酮或环己酮,强极性溶剂如二甲基甲酰胺和二甲基亚砜,还有水。液化气体填充剂或载体指的是那些在常温和大气压下成气体状态的液体,例如气溶胶推进剂,如卤代烃类以及丁烷,丙烷,氮气和二氧化碳;适合的固体载体如下:例如天然地下岩石如高岭土、粘土、滑石、白垩、石英、活性白土,蒙脱土或硅藻土,和人造产品如高分散性的硅石,矾土和硅酸盐;下面是适合于颗粒剂用的固体载体:粉碎并分级的天然岩石如方解石、大理石、浮石、海泡石、白云石,还有无机和有机碎片的人造颗粒,以及有机物质的颗粒剂如锯木屑、椰子壳、玉米芯和烟草梗;适合于作乳化剂和/或发泡剂的物质有:例如非离子和离子型表面活性剂如聚氧乙撑山梨糖醇酐妥尔油酯,油酰基甲基牛磺酸钠,聚氧乙撑脂肪酸酯,聚氧乙撑脂肪醇醚,例如烷芳基聚乙二醇醚,烷基磺酸盐,烷基硫酸盐,芳基硫酸盐和芳烷基磺酸盐,还有蛋白质水解产物。可以利用的润湿剂例子是聚氧乙基化烷基酚,聚氧乙基化油酰胺或硬脂酰胺,烷基磺酸盐或烷基苯基磺酸盐。下面是适合于作分散剂的物质:例如木质素磺酸盐,或芳基磺酸盐与甲醛的缩合产物。
胶粘着剂和增稠剂如羧甲基纤维素,甲基纤维素,粉状和颗粒状或胶乳状的天然和合成的聚合物如阿拉伯胶,聚乙烯醇或聚醋酸乙烯酯可用于剂型之中。
着色剂如无机色素,例如氧化铁、氧化钛,普鲁士兰和有机染料如茜素,偶氮和金属酞花青染料,和微量营养元素如铁、镁、硼、铜、钴、钼和锌的盐也能用于剂型中。
通常,剂型中含有0.1~95%重量的活性成分,优选为0.5~ 90%之间。
活性成分可以以它们的剂型形式使用,也可以进一步稀释而得的制剂形式使用,例如可供现用的溶液、乳液、悬浮剂、粉剂、膏剂和颗粒剂。可湿性粉剂是在水中能均匀分散的制剂,它除了有效成分外,还含有润湿剂。如果必要,它可加入稀释剂和惰性物质。乳油的制备方法是将有效成分溶在一个有机溶剂中并添加一种或多种乳化剂而成。粉剂是通过将有效成分与细的分散的固体载体一起磨碎加工而成。
它们可用常规方法使用,例如泼浇,浸渍,喷洒,雾化,烟雾,薰蒸,注射,形成浆液,喷粉,撒施,干法种子处理,薰蒸种子处理,湿法种子处理,浆液处理或包衣。
本发明组合物的用量因外部条件而异,特别是温度和湿度。它可以在很大范围内变化,通常用量为0.1和5公斤有效成分/公顷,优选0.1至1.7公斤/公顷。
实施例1
将10.35g 3-苯基-4-羟基-6-氯哒嗪(0.05mol)悬浮于100ml丙酮中,在室温和搅拌下加入6.07g三乙胺(0.06mol)。约半小时后,将溶有6.36g溴化氰(0.06mol)的丙酮溶液滴加到反应混合物中,在此过程中反应混合物温度稍有上升。搅拌过夜,滤去已沉淀的溴化三乙基铵,蒸去有机溶剂。将结晶状残渣溶解于100ml水中,过滤,水洗并干燥。
得到11.3g 1-氰基-3-苯基-6-氯代哒嗪-4-酮,收率为理论值的97%。用二异丙基醚/丙酮(7∶3)重结晶,得到熔点为120至121℃的白色结晶。
如果用5.3g溴化氰(0.05mol),在同样反应条件下得到类似的结果。
实施例2
将12.55g 3-苯基-4-羟基-6-溴哒嗪(0.05mol)悬浮于100ml丙酮中,在室温和搅拌下加入7.6g三乙胺(0.075mol)。搅拌半小时后,将溶有10.6g溴化氰(0.1mol)的100ml丙酮滴加到反应混合物中,在滴加过程中,反应温度稍稍升高。搅拌过夜,滤去沉淀的溴化三乙基铵,蒸去有机溶剂。残渣溶解于100ml水中,滤出得到的固体,用水洗涤并干燥。
得到12.6g 1-氰基-3-苯基-6-溴哒嗪-4-酮,其收率为理论值的91%。
为了进一步纯化产物,粗产物经硅胶柱层析,用氯仿作洗脱剂,继之在丙酮/二异丙基醚混合物中重结晶,得到熔点为152~155℃的白色结晶。
实施例3
将413.3g 3-苯基-4-羟基-6-氯哒嗪(2.0mol)溶于含80g氢氧化钠的1.6升水溶液中,并加入1.6升丙酮。于25℃下向此溶液中加入211.9g溴化氰(2.0mol)。在此过程中,温度升至31℃,而pH值由9降至6。在室温下搅拌2小时后,抽滤出固体沉淀物,用丙酮水溶液洗涤并干燥。
得到425g 1-氰基-3-苯基-6-氯哒嗪-4-酮,其收率为理论值的92%。产物在浓度为5% NaHCO3水溶中经搅拌后,用水洗涤并干燥,测得其熔点为117~120℃。
实施例4
在-3至0℃下,将56.7g氯气通入含有10.8g氯化钠和1.7ml浓盐酸的577ml水溶液中,向此水溶液中加入217.7ml 30%(重量百分比)氰化钠水溶液,得到氯化氰的水溶液。
在-5℃下,向此溶液中加入含有82.6g 3-苯基-4-羟基-6-氯哒嗪(0.4mol)和16g氢氧化钠的417ml水溶液和667ml丙酮。混合物在室温下搅拌4小时,抽滤生成的沉淀物,用水洗并干燥。
得到90g 1-氰基-3-苯基-6-氯哒嗪-4-酮,其收率为理论值的97%,熔点为117~119℃。
实施例5
用实施例4所述的方法,但用二噁烷/水取代丙酮/水。得到理论收率96%的1-氰基-3-苯基-6-氯哒嗪-4-酮,其熔点为120~121℃。
实施例6
按实施例4的方法,但用水而不用丙酮作溶剂。得到理论收率97%的1-氰基-3-苯基-6-氯哒嗪-4-酮,熔点117~119℃。
表1中所列举的化合物是使用合适的起始原料按上面实施例1至6所述的方法制备的。
实施例24
将87.5g 1-氰基-3-苯基-6-氯哒嗪-4-酮(0.378mol)和136g碘化钠溶于700ml丙酮中,溶液回流88小时。然后,蒸去溶剂,残渣用水研磨。滤出在研磨过程中形成的固体并干燥。
得到116g 1-氰基-3-苯基-6-碘化哒嗪-4-酮,其收率为理论值的95%。
经过柱层析(SiO2,CHCl3)纯化后,再用二异丙基醚/丙酮(7∶3)重结晶,测得其熔点为135~137℃。
实施例25
在室温并搅拌下,将含有85.8g溴氧化磷(0.3mol)的150ml甲苯溶液加入到20.6g 3-苯基-4-羟基-6-氯哒嗪(0.1mol)中,回流此混合物3小时。除去在此过程中生成的溴化氢气体。待反应结束,将反应混合物倒入冰中,得到的糊状产物在石油醚中研磨可使其固化。滤出固体物,用水洗涤并干燥。
得到27.1g 3-苯基-4,6-二溴代哒嗪,基收率为理论值的88%,熔点为145~146℃。
实施例26
将47.0g 3-苯基-4,6-二溴代哒嗪(0.15mol)在300ml二噁烷中回流,然后在10分钟内用溶有17g氢氧化钠(0.43mol)的50ml水溶液进行处理。在回流温度下经4.5小时后,蒸去二噁烷,将
固体残渣溶在热水中。借助于活性碳滤出焦油状残渣,加入盐酸直至反应呈明显的酸性,在此过程中形成一固体沉淀。滤出固体物,用水使其成浆状物,边加热边加入氨水使其溶解。用盐酸再次酸化使固体沉淀,滤出,用水洗涤并干燥。
得到24.2g 3-苯基-4-羟基-6-溴代哒嗪,其收率为理论值的64%,熔点210~215℃。
实施例27
将96.1g 3-(3′-三氟甲基苯基)哒嗪-6-酮悬浮于400ml氯氧化磷中,用12.4g红磷处理。氯气慢慢通入到悬浮液中,在此过程中温度上升,然后通过外部加热使混合物温度保持在接近95℃。1.75小时后反应完全。将反应混合物冷却至室温,倒入冰中,在此过程中同时加入氨水中和形成的酸。滤出得到的固体,干燥并用己烷重结晶。
得到84.4g 3-(3′-三氟甲基苯基)-4,6-二氯代哒嗪,其收率为理论值的72%,熔点80-81.5℃。
实施例28-32
按实施例16所述的方法使用合适的起始原料制得下列产物:
28.3-(4′-溴苯基)-4,6-二氯代哒嗪,其熔点170~171℃,
29.3-(3′,4′-二氯苯基)-4,6-二氯代哒嗪,其熔点153-154.5℃,
30.3-(2′-氟代苯基)-4,6-二氯代哒嗪,其熔点96~98℃,
31.3-(4′-氰基苯基)-4,6-二氯代哒嗪,其熔点为210-222℃和
32.3-(4′-乙基苯基)-4,6-二氯代哒嗪,其熔点为35~39℃。
实施例33
将70g 3-苯基哒嗪-6-酮(0.41mol)和10g红磷悬浮于300ml氯氧化磷中。在搅拌下向此悬浮液中通入氯气,在这一过程中反应温度起初升高,开始采用冷却,然后通过加热混合物的方式使反应温度保持在70~75℃。3小时后,让反应混合物冷却至室温,倒入冰中,加入氨水以中和生成的酸。滤出得到的固体,用水洗涤,然后用乙醇重结晶2次。
得到88.9g 3,4,5-三氯-6-苯基哒嗪,其收率是理论值的84%,熔点120~121.5℃。
实施例34-36
按实施例22所述的方法,使用合适的起始原料,得到以下产物:
34.3,4,5-三氯-6-(4′-溴代苯基)哒嗪,其熔点为164-167℃,
35.3,4,5-三氯-6-(4′-氯代苯基)哒嗪,其熔点为155~159℃和
36.3,4,5-三氯-6-(4′-氟代苯基)哒嗪,其熔点为153-155℃
实施例37
将75g 3,4,5-三氯-6-(4′-氯代苯基)哒嗪(0.255mol)溶解在沸点温度下的300ml二噁烷中,加入100ml水。在30分钟内向此溶液中滴加入含20.4g氢氧化钠的150ml水溶液。蒸去溶剂、残渣溶在热水中。通过加入盐酸水溶液,固体被沉淀、滤出沉淀物,为达纯化之目的,将沉淀物先溶在稀氨水中,继之加入盐酸使其再沉淀。滤出固体物,用乙醇/二甲亚砜混合物重结晶,得到36.6g 3,5-二氯-4-羟基-6-(4′-氯苯基)哒嗪,其收率为理论值的52%,熔点272-278℃(分解)。
实施例38-40
按实施例26所述的方法,使用合适的起始原料,得到以下产物:
38.3,5-二氯-4-羟基-6-苯基哒嗪,其熔点190-193℃,
39.3,5-二氯-4-羟基-6-(4′-氟代苯基)哒嗪,其熔点266~270℃和
40.3,5-二氯-4-羟基-6-(4′-溴代苯基)哒嗪,其熔点276-281℃。
实施例41
将45g 3-苯基-4,6-二氯哒嗪(0.2mol)溶在600ml甲醇中,加入含108g浓度为30%甲醇钠的甲醇溶液(0.6mol),此反应混合物回流7小时。反应混合物冷却后滤出生成的氯化钠沉淀,蒸去有机相。残渣置于二氯甲烷/水中,有机相用水震荡萃取,再用硫酸钠干燥,蒸去溶剂。残渣用环己烷重结晶。
得到39.9g 3-苯基-4,6-二甲氧基哒嗪,其收率为理论值的92%,熔点53~54℃。
实施例42
按实施例41中所述的方法但用丁醇钠取代甲醇钠。可以得到呈浅色不含氯的油状4,6-二丁氧基-3-苯基哒嗪。
实施例43
将39.9g 3-苯基-4,6-二甲氧基哒嗪(0.18mol)溶于500ml二甲基甲酰胺中,在室温下加入含4.9g80%氢化钠悬浮液的矿物油。向反应混合物中滴加18.4g丁硫醇(0.2mol),在此过程中温度稍稍上升。混合物在室温下搅拌数小时后,在100℃下加热5小时,于是溶剂被蒸去。残渣置于水/环己烷中,水相用环己烷震荡萃取,再加醋酸酸化,滤出在此过程中形成的固体沉淀,用水洗涤并干燥。得到32.5g 3-苯基-4-羟基-6-甲氧基哒嗪,其收率为理论值的87%,产物用甲醇∶二甲基甲酰胺(1∶1)重结晶后的熔点为204~209℃。
实施例44
用3-苯基-4,6-二丁氧基哒嗪作起始原料,按实施例41所述的方法可得到熔点为217-220℃的3-苯基-4-羟基-6-丁氧基哒嗪。
实施例45
将0.5份化合物1与5份N-油酰基-N-甲基牛磺酸钠,3份二异丁基萘磺酸钠,10份木质素磺酸钙和81.5份高岭土充分混合,继之将混合物在轨道磨中磨1小时。
如此得到的可湿性粉剂适合于制备除草喷雾混合物。
实施例46
将10份化合物1溶于30份二甲苯和40份N-甲基吡咯烷酮中、再加入10份含有十二烷基苯磺酸钙和乙氧基化妥尔油脂肪酸的乳化剂混合物。得到浓乳油,它适于制备除草喷雾混合物。
实施例47
将25份化合物1与5份N-油酰基-N-甲基牛磺酸钠,3份二异丁基萘磺酸钠,10份木质素磺酸钙,25份AttaclayR和32份高岭土充分混合,继之混合物在轨道磨中磨1小时。
得到的可湿性粉剂适合于制备除草喷雾混合物。
实施例48
将60份化合物1与5份N-油酰基-N-甲基牛磺酸钠,3份月桂基硫酸钠,10份木质素磺酸钙和22份AttaclayR充分混合,继之混合物在轨道磨中磨1小时。
得到的可湿性粉剂适合于制备除草喷雾混合物。
实施例49
将90份化合物1与4份N-油酰基-N-甲基牛磺酸钠,2份二异丁基萘磺酸钠和4份沉淀的二氧化硅充分混合,继之混合物在轨道磨中磨1小时。
得到的可湿性粉剂适合于制备除草喷雾混合物。
为了测定新的N-氰基哒嗪酮类的活性,将一定量的活性物质对供试植物进行芽后处理(3至6叶期)。供试植物被评估2-3次。所给出的数值是所有数值的平均值。其结果按表2中EWRC分级1-9进行评价。
用作对照Chemie Linz AG公司制造的已知的除草剂Lentagran(6-氯-3-苯基哒嗪-4-基-B-辛基硫化碳酸酯)。使用量以克有效成分/公顷计。在某些情况下制剂与NOPON11E一起使用。NOPON11E是由Sunoil公司制造的商品制剂,它含有99%的石蜡油和1%的乳化剂。
Claims (10)
2、按照权利要求1的N-氰基哒嗪酮,其中R1,R2和R3相互分别代表氢,卤素,烷氧基或芳基基团。
3、按照权利要求1的N-氰基哒嗪酮,其中R1代表氢或芳基基团。
4、按照权利要求1的N-氰基哒嗪酮,其中R1代表卤素或芳基基团,R2代表氢或卤素基团和R3代表烷氧基,卤素或芳基基团。
5、按照权利要求1的N-氰基哒嗪酮,其中芳基是未取代的或被卤素,氰基,硝基或烷基单取代或多取代的苯基。
7、按照权利要求6的方法,包括用胺作为碱和用氯化氰或溴化氰作为卤化氰。
9、制备除草组合物的方法,包括将按照权利要求1的式Ⅰ所示的至少一种N-氰基哒嗪酮与助剂和/或载体混合。
10、控制杂草的方法,包括使按照权利要求1中式1所示的N-氰基哒嗪酮或按照权利要求8的除草组合物作用于杂草上或其生长环境中。
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CN93101027A Pending CN1075477A (zh) | 1992-02-17 | 1993-02-16 | 具除草活性的n-氰基哒嗪酮 |
Country Status (28)
Country | Link |
---|---|
US (1) | US5462914A (zh) |
EP (1) | EP0556647A1 (zh) |
JP (1) | JPH069574A (zh) |
KR (1) | KR930017878A (zh) |
CN (1) | CN1075477A (zh) |
AT (1) | AT397085B (zh) |
AU (1) | AU647687B2 (zh) |
BG (1) | BG97448A (zh) |
BR (1) | BR9300589A (zh) |
CA (1) | CA2089451A1 (zh) |
CZ (1) | CZ19693A3 (zh) |
EE (1) | EE9400149A (zh) |
HR (1) | HRP930192A2 (zh) |
HU (1) | HUT64042A (zh) |
IL (1) | IL104449A0 (zh) |
JO (1) | JO1744B1 (zh) |
LV (1) | LV10152A (zh) |
MA (1) | MA22803A1 (zh) |
MD (1) | MD940047A (zh) |
MX (1) | MX9300855A (zh) |
NZ (1) | NZ245706A (zh) |
PL (1) | PL297750A1 (zh) |
RO (1) | RO108239B1 (zh) |
SI (1) | SI9300085A (zh) |
SK (1) | SK9593A3 (zh) |
TR (1) | TR26712A (zh) |
TW (1) | TW221369B (zh) |
ZA (1) | ZA93648B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017036266A1 (zh) * | 2015-07-01 | 2017-03-09 | 中国科学院上海有机化学研究所 | 3-芳基哒嗪酮类化合物、制备方法、农药组合物及用途 |
CN106831600A (zh) * | 2017-03-03 | 2017-06-13 | 常州沃腾化工科技有限公司 | 3‑苯基‑4‑6‑二氯哒嗪的制备方法 |
WO2019149260A1 (zh) * | 2018-02-02 | 2019-08-08 | 青岛清原化合物有限公司 | 哒嗪醇类化合物及其衍生物、制备方法、除草组合物和应用 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5506228A (en) * | 1995-02-23 | 1996-04-09 | Merck & Co., Inc. | 2,6-diaryl pyridazinones with immunosuppressant activity |
US5670504A (en) * | 1995-02-23 | 1997-09-23 | Merck & Co. Inc. | 2,6-diaryl pyridazinones with immunosuppressant activity |
KR20010014410A (ko) * | 1997-07-01 | 2001-02-26 | 미우라 아끼라 | 3-치환된 페닐-4-할로피리다진 유도체, 이를 유효성분으로 하는 농약 및 이의 중간체 |
CN101538245B (zh) * | 2008-03-18 | 2011-02-16 | 中国科学院上海药物研究所 | 一类哒嗪酮类化合物及其制备方法和制备药物的用途 |
US9212146B2 (en) | 2008-03-18 | 2015-12-15 | Shanghai Institute Of Materia Medica, Chinese Academy Of Sciences | Substituted pyridazinones for the treatment of tumors |
CN110128352A (zh) * | 2018-02-02 | 2019-08-16 | 青岛清原化合物有限公司 | 哒嗪醇类化合物及其衍生物、制备方法、除草组合物和应用 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2741615A (en) * | 1952-11-22 | 1956-04-10 | Merck & Co Inc | N-substituted dihydrodesoxynorcodeine compounds |
AT237962B (de) * | 1962-11-10 | 1965-01-25 | Chemie Linz Ag | Selektiv wirkendes, herbizides Mittel |
DE2229758A1 (de) * | 1972-06-19 | 1974-01-17 | Lentia Gmbh | Neue pyridazinverbindungen, ihre herstellung und verwendung |
AT334133B (de) * | 1974-12-17 | 1976-12-27 | Chemie Linz Ag | Herbizides mittel |
US3967952A (en) * | 1975-07-03 | 1976-07-06 | Eli Lilly And Company | 3,5-Diphenyl-4(1H)-pyridazinones(thiones) |
US4013658A (en) * | 1975-07-03 | 1977-03-22 | Eli Lilly And Company | Synthesis of 3,5-diphenyl-4(1h)-pyridazinones |
US4732603A (en) * | 1980-10-03 | 1988-03-22 | Rohm And Haas Company | 1-aryl-1,4-dihydro-4-oxo-5-carboxypyridazine derivatives and their use as plant growth regulators and hybridizing agents |
JPS63264575A (ja) * | 1987-04-20 | 1988-11-01 | Daicel Chem Ind Ltd | フエノキシピリダジン誘導体、その製造法ならびに植物生長調整剤および除草剤組成物 |
FR2634199B1 (fr) * | 1988-07-13 | 1990-09-14 | Rhone Poulenc Agrochimie | Composes herbicides et les compositions les contenant |
AT397598B (de) * | 1990-04-05 | 1994-05-25 | Agrolinz Agrarchemikalien | Herbizides mittel |
DE4013734A1 (de) * | 1990-04-28 | 1991-10-31 | Agrolinz Agrarchemikalien Muen | Herbizides mittel |
-
1992
- 1992-02-17 AT AT0025892A patent/AT397085B/de not_active IP Right Cessation
-
1993
- 1993-01-19 NZ NZ245706A patent/NZ245706A/en unknown
- 1993-01-20 IL IL104449A patent/IL104449A0/xx unknown
- 1993-01-29 ZA ZA93648A patent/ZA93648B/xx unknown
- 1993-01-29 TW TW082100534A patent/TW221369B/zh active
- 1993-02-04 EP EP93101695A patent/EP0556647A1/de not_active Withdrawn
- 1993-02-10 TR TR93/0138A patent/TR26712A/xx unknown
- 1993-02-12 CA CA002089451A patent/CA2089451A1/en not_active Abandoned
- 1993-02-12 AU AU33028/93A patent/AU647687B2/en not_active Ceased
- 1993-02-15 KR KR1019930002038A patent/KR930017878A/ko not_active Application Discontinuation
- 1993-02-15 CZ CZ93196A patent/CZ19693A3/cs unknown
- 1993-02-15 RO RO93-00185A patent/RO108239B1/ro unknown
- 1993-02-15 BG BG97448A patent/BG97448A/xx unknown
- 1993-02-16 PL PL29775093A patent/PL297750A1/xx unknown
- 1993-02-16 SK SK9593A patent/SK9593A3/sk unknown
- 1993-02-16 HR HR930192A patent/HRP930192A2/hr not_active Application Discontinuation
- 1993-02-16 LV LV930121A patent/LV10152A/xx unknown
- 1993-02-16 JP JP5027000A patent/JPH069574A/ja not_active Withdrawn
- 1993-02-16 JO JO19931744A patent/JO1744B1/en active
- 1993-02-16 CN CN93101027A patent/CN1075477A/zh active Pending
- 1993-02-16 HU HU9300425A patent/HUT64042A/hu unknown
- 1993-02-16 BR BR9300589A patent/BR9300589A/pt not_active Application Discontinuation
- 1993-02-16 MA MA23096A patent/MA22803A1/fr unknown
- 1993-02-17 MX MX9300855A patent/MX9300855A/es unknown
- 1993-02-17 SI SI19939300085A patent/SI9300085A/sl unknown
-
1994
- 1994-02-15 MD MD94-0047A patent/MD940047A/ro not_active Application Discontinuation
- 1994-04-01 US US08/221,464 patent/US5462914A/en not_active Expired - Fee Related
- 1994-11-22 EE EE9400149A patent/EE9400149A/xx unknown
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017036266A1 (zh) * | 2015-07-01 | 2017-03-09 | 中国科学院上海有机化学研究所 | 3-芳基哒嗪酮类化合物、制备方法、农药组合物及用途 |
CN106831600A (zh) * | 2017-03-03 | 2017-06-13 | 常州沃腾化工科技有限公司 | 3‑苯基‑4‑6‑二氯哒嗪的制备方法 |
CN106831600B (zh) * | 2017-03-03 | 2019-04-12 | 常州沃腾化工科技有限公司 | 3-苯基-4-6-二氯哒嗪的制备方法 |
WO2019149260A1 (zh) * | 2018-02-02 | 2019-08-08 | 青岛清原化合物有限公司 | 哒嗪醇类化合物及其衍生物、制备方法、除草组合物和应用 |
Also Published As
Publication number | Publication date |
---|---|
JO1744B1 (en) | 1993-10-30 |
HU9300425D0 (en) | 1993-05-28 |
IL104449A0 (en) | 1993-05-13 |
SK9593A3 (en) | 1993-09-09 |
JPH069574A (ja) | 1994-01-18 |
EE9400149A (et) | 1995-12-15 |
TR26712A (tr) | 1995-05-15 |
ATA25892A (de) | 1993-06-15 |
PL297750A1 (en) | 1993-11-02 |
AU647687B2 (en) | 1994-03-24 |
EP0556647A1 (de) | 1993-08-25 |
US5462914A (en) | 1995-10-31 |
MX9300855A (es) | 1993-08-01 |
AU3302893A (en) | 1993-08-19 |
TW221369B (zh) | 1994-03-01 |
CA2089451A1 (en) | 1993-08-18 |
ZA93648B (en) | 1993-09-02 |
CZ19693A3 (en) | 1994-01-19 |
SI9300085A (en) | 1993-09-30 |
HUT64042A (en) | 1993-11-29 |
NZ245706A (en) | 1994-11-25 |
BR9300589A (pt) | 1993-08-24 |
LV10152A (lv) | 1994-10-20 |
MA22803A1 (fr) | 1993-10-01 |
HRP930192A2 (en) | 1995-12-31 |
RO108239B1 (ro) | 1994-03-31 |
AT397085B (de) | 1994-01-25 |
MD940047A (ro) | 1995-08-31 |
BG97448A (en) | 1994-03-24 |
KR930017878A (ko) | 1993-09-20 |
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