CN1095067A - 噁(噻)-二唑-氧-苯基丙烯酸酯类 - Google Patents
噁(噻)-二唑-氧-苯基丙烯酸酯类 Download PDFInfo
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- CN1095067A CN1095067A CN94104995A CN94104995A CN1095067A CN 1095067 A CN1095067 A CN 1095067A CN 94104995 A CN94104995 A CN 94104995A CN 94104995 A CN94104995 A CN 94104995A CN 1095067 A CN1095067 A CN 1095067A
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229930192474 thiophene Natural products 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 64
- 150000001875 compounds Chemical class 0.000 claims description 50
- -1 thiocarbamoyl Chemical group 0.000 claims description 48
- 229910052799 carbon Inorganic materials 0.000 claims description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 31
- 239000001301 oxygen Substances 0.000 claims description 31
- 229910052760 oxygen Inorganic materials 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 25
- 239000005864 Sulphur Chemical group 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 125000005843 halogen group Chemical group 0.000 claims description 23
- 125000001188 haloalkyl group Chemical group 0.000 claims description 18
- 229910052736 halogen Inorganic materials 0.000 claims description 17
- 150000002367 halogens Chemical group 0.000 claims description 17
- 125000003545 alkoxy group Chemical group 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 239000000460 chlorine Chemical group 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 15
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 11
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052794 bromium Inorganic materials 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
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- 229910052731 fluorine Inorganic materials 0.000 claims description 8
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- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 7
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- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 5
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- 125000004644 alkyl sulfinyl group Chemical group 0.000 claims description 4
- 125000001118 alkylidene group Chemical group 0.000 claims description 4
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000005291 haloalkenyloxy group Chemical group 0.000 claims description 4
- 125000004440 haloalkylsulfinyl group Chemical group 0.000 claims description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 4
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000004866 oxadiazoles Chemical class 0.000 claims description 4
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 claims description 4
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 150000004867 thiadiazoles Chemical class 0.000 claims description 4
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 claims description 2
- 125000005336 allyloxy group Chemical group 0.000 claims description 2
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 2
- 125000001786 isothiazolyl group Chemical group 0.000 claims description 2
- 125000000842 isoxazolyl group Chemical group 0.000 claims description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims description 2
- 125000006216 methylsulfinyl group Chemical group [H]C([H])([H])S(*)=O 0.000 claims description 2
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000002971 oxazolyl group Chemical group 0.000 claims description 2
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 2
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 2
- 125000002098 pyridazinyl group Chemical group 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 2
- 125000001113 thiadiazolyl group Chemical group 0.000 claims description 2
- 125000000335 thiazolyl group Chemical group 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 125000004306 triazinyl group Chemical group 0.000 claims description 2
- 125000001425 triazolyl group Chemical group 0.000 claims description 2
- 125000005034 trifluormethylthio group Chemical group FC(S*)(F)F 0.000 claims description 2
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 2
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- 230000002508 compound effect Effects 0.000 claims 1
- DEDGUGJNLNLJSR-UHFFFAOYSA-N enol-phenylpyruvic acid Chemical compound OC(=O)C(O)=CC1=CC=CC=C1 DEDGUGJNLNLJSR-UHFFFAOYSA-N 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 23
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/06—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles
- C07D271/07—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
- C07D285/08—1,2,4-Thiadiazoles; Hydrogenated 1,2,4-thiadiazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
Abstract
式(I)的新型噁(噻)-二唑-氧-苯基丙烯酸酯
类,它们的制备方法和作为杀虫剂的用途。其中各代
号意义详见说明书。
Description
本发明涉及新的噁(噻)-二唑-氧-苯基丙烯酸酯类及其制备方法和作为杀虫剂的应用。
已知某些取代的3-甲氧基-丙烯酸酯类具有杀菌的性能(参见例如EP178826和EP383117)。
但是,这些先前已知的化合物在其所有的应用场合中,特别是低量、低浓度使用时,活性是不完全令人满意的。
已发现具有通式(Ⅰ)的新的噁(噻)-二唑-氧-苯基丙烯酸酯类:
其中:
R代表卤素,烷基,卤代烷基或 式Ar-A的基团,其中
Ar代表任选取代的芳基或杂芳基,和
A 代表氧、硫,或下式的基团:-OCO,-COO-,-CO-,-CH2-,-CH2CH2,-C≡C-,-CH=CH-,-CHR′-,-CHR′-CH2-,-CH2-CHR′-,-S(O)-,-SO2,-NH-CH2-,-CH2-NH-,-NH-,-N(CH3)-,-CH2O-,-CH2S,-CH2SO-,-CH2SO2-,-OCH2-,-SCH2,-SO-CH2,-SO2CH2-,或直接键合,其中R′代表氢,或与R含义相同,和
Y 代表OCH3或NHCH3,
Z 代表=CH或=N-,和
X 代表氧或硫。
适宜时,分子式(Ⅰ)的化合物根据其取代基性质的不同可以几何和/或光学异构体或不同组成的异构体混合物的形式存在。纯异构体和异构体混合物都在本发明的权利要求之内。
此外,还已发现任选在稀释剂和任选地在反应助剂存在下,分子式(Ⅱ)的2-羟基苯基丙烯酸酯与分子式(Ⅲ)的噁二唑或噻二唑衍生物反应,可得到通式为(Ⅰ)的新的噁(噻)-二唑-氧-苯基丙烯酸酯。
式(Ⅰ)中:
Y 代表OCH3或NHCH3,
Z 代表=CH或=N-,
R 代表卤素、烷基或卤代烷基,或式Ar-A的基团,其中
Ar 代表任选取代的芳基或杂芳基,和
A 代表氧、硫,或下式的基团:-OCO,-COO-,-CO-,-CH2-,-CH2CH2,-C≡C-,-CH=CH-,-CHR′-,-CHR′-CH2-,-CH2-CHR′-,-S(O)-,-SO2,-NH-CH2-,-CH2-NH-,-NH-,-N(CH3)-,-CH2O-,-CH2S,-CH2SO-,-CH2SO2-,-OCH2-,-SCH2,-SO-CH2,-SO2CH2-,或直接键合,其中R′代表氢,或与R含义相同,和
X 代表氧或硫。
式(Ⅱ)中各代号意义与式(Ⅰ)相同。
式(Ⅲ)中,R和X和上述含义相同,
E 代表吸电子离去基团。
最后,还发现通式(Ⅰ)的新的噁(噻)-二唑-氧-苯基丙烯酸酯类具有优良的杀虫活性。
令人惊异的是,本发明的通式(Ⅰ)的噁(噻)-二唑-氧-苯基丙烯酸酯类所呈现的抗危害植物微生物的活性要比现有技术中已知的取代3-甲氧基-丙烯酸酯类好得多。
本发明的噁(噻)-二唑-氧-苯基丙烯酸酯类通常如分子式(Ⅰ)所定义。优选下述分子式(Ⅰ)的化合物,其中
Y 代表OCH3或NHCH3,
Z 代表=CH或=N-,
R 代表氟、氯、溴、碘、C1-C4烷基或C1-C2具有1至5个相同或不同卤原子的卤代烷基或代表式Ar-A-的基团,其中
Ar代表用适当的取代基任选地同取代或异取代一次或多次的6至10个碳原子的芳基,或代表用适当取代基任选地同取代或异取代一次或多次,和/或苯并稠合的具有2至9个碳原子和1至5个相同或不同的杂原子的杂芳基,在各种情况下合适的取代基为:
卤素、氰基、硝基、羟基、氨基、甲酰基、氨基甲酰基、硫代氨基甲酰基,在所有情况下均具有1至6个碳原子的直链或支链的烷基、烷氧基、烷硫基、烷基亚磺酰基或烷基磺酰基,在所有情况下均具有2至6个碳原子的直链或支链的链烯基或链烯氧基,在所有情况下均具有1至6个碳原子和1至13个相同或不同的卤原子的直链或支链的卤代烷基,卤代烷氧基,卤代烷硫基,卤代烷基亚磺酰基或卤代烷基磺酰基,在所有情况下均具有2至6个碳原子和1至13个相同或不同卤原子的直链或支链的卤代链烯基或卤代链烯氧基,在所有情况下在各个烷基部分上均具有1至6个碳原子的直链或支链的N-烷基氨基,二烷基氨基,烷羰基,烷羰氧基,烷氧羰基,烷基磺酰氧基,肟基烷基或烷肟基烷基,在所有情况下均具有1至6个碳原子双键的亚烷基或二氧亚烷基(并任选地被下列基团同取代或异取代一次或多次:卤素和/或1至4个碳原子的直链或支链烷基和/或1至4个碳原子和1至9个相同或不同卤原子的直链或支链卤代烷基),3至7个碳原子的环烷基,2至6个碳原子和1至3个相同或不同的杂原子-特别是氮,氧和/或硫-的3至7元的杂环基,以及苯基,苯氧基,苄基,苄氧基,苯乙基或苯乙氧基,它们在苯基部分上均任选地被下列基团同取代或异取代一次或多次:卤素和/或1至4个碳原子的直链或支链烷基和/或1至4个碳原子和1至9个相同或不同卤原子的直链或支链卤代烷基和/或1至4个碳原子的直链或支链烷氧基和/或1至4个碳原子和1至9个相同或不同卤原子的直链或支链卤代烷氧基,和
A 代表氧、硫或下式的基团:-OCO,-COO-,-CO-,-CH2-,-CH2CH2,-C≡C-,-CH=CH-,-CHR′-,-CHR′-CH2-,-CH2-CHR′-,-S(O)-,-SO2,-NH-CH2-,-CH2-NH-,-NH-,-N(CH3)-,-CH2O-,-CH2S,-CH2SO-,-CH2SO2-,OCH2-,-SCH2,-SO-CH2,-SO2CH2-,或直接键合,其中R′代表氢,或与
R含义相同,和
X 代表氧或硫。
特别优选下述分子式(Ⅰ)的化合物,其中
Y 代表OCH3或NHCH3,
Z 代表=CH或=N-,
R 代表氟、氯、溴、甲基、乙基、正或异丙基、正、异、仲或叔丁基,或代表含1至5个相同或不同F-和Cl原子的C1-C2卤代烷基,或代表式Ar-A-的基团,其中
Ar 代表用合适的取代基任选地同取代或异取代一次至五次的6或10个碳原子的芳基,或代表用合适的取代基任选地同取代或异取代一次至四次,和/或苯并稠合的具有2至9个碳原子和1至3个相同或不同的杂原子(特别是氮,氧和/或硫)的杂芳基,在各种情况下合适的取代基为:
卤素、氰基、硝基、羟基、氨基、甲酰基、氨基甲酰基、硫代氨基甲酰基,在所有情况下均具有1至4个碳原子的直链或支链的烷基、烷氧基、烷硫基、烷基亚磺酰基或烷基磺酰基,在所有情况下均具有2至4个碳原子的直链或支链的链烯基或链烯氧基,在所有情况下均具有1至4个碳原子和1至9个相同或不同的卤原子的直链或支链的卤代烷基,卤代烷氧基,卤代烷硫基,卤代烷基亚磺酰基或卤代烷基磺酰基,在所有情况下均具有2至4个碳原子和1至9个相同或不同卤原子的直链或支链的卤代链烯基或卤代链烯氧基,在所有情况下在各个烷基部分上均具有1至4个碳原子的直链或支链的N-烷基氨基,二烷基氨基,烷基羰基,烷基羰氧基,烷基羰基,烷基磺酰氧基,肟基烷基或烷肟基烷基,在所有情况下均具有1至4个碳原子双键的亚烷基或二氧亚烷基(并任选地被下列基团同取代或异取代一次或多次:卤素和/或1至3个碳原子的直链或支链烷基和/或1至3个碳原子和1至7个相同或不同卤原子的直链或支链卤代烷基),3至6个碳原子的环烷基,4至6个碳原子和1至2个相同或不同的杂原子-特别是氮,氧和/或硫-的5至7元的饱和杂环基,以及苯基,苯氧基,苄基,苄氧基,苯乙基或苯乙氧基,它们在苯基部分上均任选地被下列基团同取代或异取代一次至三次:卤素和/或1至3个碳原子的直链或支链烷基和/或1至3个碳原子和1至7个相同或不同卤原子的直链或支链卤代烷基和/或1至3个碳原子的直链或支链烷氧基和/或1至3个碳原子和1至7个相同或不同卤原子的直链或支链卤代烷氧基,和
A 代表氧,硫,或下式的基团:-S(O)-,-SO2-,-NH-,-N(CH3)-,-CH2O-,-CH2S-,-OCH2-,-SCH2,或直接键合,和
X 代表氧或硫。
极优选下述分子式(Ⅰ)的化合物,其中
R 代表氯、溴、甲基、乙基、CF3、CH2F、CHF2、CCl3、CH2Cl、CHCl2、CFCl2、CF2Cl,或代表式Ar-A-的基团,其中
Ar 代表在各种情况下用合适的取代基任选同取代或异取代一次至三次的苯基或萘基,或代表在所有情况下用合适的取代基任选同取代或异取代一次至三次,和/或苯并稠合的呋喃基,噻吩基,吡咯基,噁唑基,噻唑基,异噁唑基,异噻唑基,吡唑基,咪唑基,噁二唑基,噻二唑基,三唑基,吡啶基,哒嗪基,嘧啶基,吡嗪基或三嗪基。在所有的情况下合适的取代基为:
氟,氯,溴,羟基,氰基,硝基,氨基,甲酰基,氨基甲酰基,硫代氨基甲酰基,甲基,乙基,正或异丙基,正,异,仲或叔丁基,甲氧基,乙氧基,正-或异丙氧基,正-,异-,仲-或叔-丁氧基,甲硫基,乙硫基,甲基亚磺酰基,甲基磺酰基,烯丙基,丁烯基,烯丙氧基,丁烯氧基,三氟甲基,三氟甲氧基,三氟甲硫基,三氟甲基 亚磺酰基,三氟甲基磺酰基,二甲基氨基,二乙基氨基,乙酰基,乙酰氧基,甲基磺酰氧基,乙基磺酰氧基,甲氧基羰基,乙氧基羰基,肟基甲基,肟基乙基,甲肟基甲基,甲肟基乙基,乙肟基甲基,乙肟基乙基,丙-1,3-二基,丁-1,4-二基,二氧亚甲基,二氧亚乙基,二氧亚丙基,二氟二氧亚甲基,四氟二氧亚乙基,环丙基,环戊基,环己基,1-吡咯烷基,1-哌啶基,1-全氢化吖庚因基,4-吗啉基,或在所有情况下被氟、氯、溴、甲基、乙基、甲氧基、乙氧基、三氟甲基和/或三氟甲氧基任选地同取代或异取代一次至三次的苯基,苯氧基,苄基或苄氧基,和
A 代表氧,硫,或下式的基团:-S(O)-,-SO2-,-NH-,-N(CH3)-,-CH2O-,-CH2S-,-OCH2-,-SCH2,或直接键合,和
X 代表氧或硫。
其中X代表硫的分子式(Ⅰ)的化合物是令人感兴趣的。
其中Z代表≡CH-和Y代表-OCH3或Z代表=N-和Y代表OCH3或NHCH3的化合物也特别令人感兴趣。
除了在制备实例中提及的化合物以外,还可逐一列出下列式(Ⅰa)的3-甲氧基-2-苯基-丙烯酸酯类化合物:
其中X代表硫、R的含义如表1所示,或其中X代表氧、R的含义如表1所示。
表1
表1(续)
表1(续)
表1(续)
表1(续)
表1(续)
表1(续)
表1(续)
表1(续)
表1(续)
表1(续)
表1(续)
表1(续)
此外,还可提及分子式(Ⅰb)和(Ⅰc)的化合物
其中X代表硫、R含义如表1所示或X代表氧、R含义如表1所示。
例如,以2-(2-羟基苯基)-3-甲氧基-丙烯酸甲酯和5-氯-3-苯氧基-1,2,4-噻二唑作原料,本发明的方法的反应过程可用下式表示:
实施本发明方法所需的原料2-羟基苯基丙烯酸酯类按分子式(Ⅱ)定义。分子式(Ⅱ)的2-羟基苯基丙烯酸酯类是已知的(例如可参看EP242081,EP468684和EP477631)。
实施本发明方法还需要的原料二唑衍生物通常按分子式(Ⅲ)定义。在分子式(Ⅲ)中,R优选代表在描述本发明的分子式(Ⅰ)化合物时已经叙及的优选的那些基团。E代表一个吸电子的离去基团,优选代表卤素,特别是氯、溴或碘,或代表均是任选取代的烷基磺酰氧基、烷氧基磺酰氧基或芳基磺酰氧基,例如甲基磺酰氧基,三氟甲基磺酰氧基,甲氧基磺酰氧基,乙氧基磺酰氧基或对甲苯磺酰氧基。
分子式(Ⅲ)的噻二唑衍生物是众所周知的,也可用与现有方法(例如参见DE2242187;DE1132379)相似的方法得到,例如,使分子式(Ⅳ)的脒衍生物
其中
R 的含义同前,或其酸加成盐,任选在稀释剂如二氯甲烷的存在下,并任选在反应助剂,例如氢氧化钠存在下,于温度-20℃和+60℃之间与三氯甲基亚磺酰氯反应。
分子式(Ⅳ)的脒衍生物是一种众所周知的有机化合物,也可用相似于现有方法的方式得到(例如参见EP325336)。
分子式(Ⅲ)的噁二唑衍生物则是新的。它们可以使分子式(Ⅴ)的噁二唑酮类
与氯化剂,例如,POCl3,任选在合适的溶剂和任选在合适的碱存在下进行反应得到。
分子式(Ⅴ)的化合物与POCl3在吡啶中进行反应极为有利。
分子式(Ⅴ)的噁二唑酮类衍生物是熟知的,也可用类似于现有方法的方式得到(例如参见Chem Ber.98,152和153页;Chem.Ber.22,24页)。
惰性有机溶剂是实施本发明方法的合适的稀释剂。这类溶剂特别包括脂肪、脂环或芳香(任选被卤代)烃类,例如汽油,苯,甲苯,二甲苯,氯苯,二氯苯,石油醚,己烷,环己烷、二氯甲烷,氯仿或四氯化碳;醚类,如乙醚,二异丙醚,二噁烷,四氢呋喃或乙二醇二甲醚或乙二醇二乙醚;腈类,如乙腈,丙腈,或苄腈;酰胺类,如N,N-二甲基甲酰胺,N,N-二甲基乙酰胺,N-甲基甲酰苯胺,N-甲基吡咯烷酮或六甲基磷酰胺;或亚砜类,如二甲基亚砜。
本发明的方法也可任选在两相体系(例如,水/甲苯或水/二氯甲烷)并任选在合适的相转移催化剂存在下进行。可以提及的这类催化剂的实例有:四丁基碘化铵,四丁基溴化铵,四丁基氯化铵,三丁基甲基溴化鏻,三甲基-C13/C15-烷基氯化铵,三甲基-C13/C15-烷基溴化铵,二苄基二甲基硫酸铵甲酯,二甲基-C12/C14-烷基苄基氯化铵,二甲基C12/C14烷基苄基溴化铵,四丁基氢氧化铵三乙基苄基氯化铵,甲基三辛基氯化铵,三甲基苄基氯化铵,15-冠(醚)-5,18-冠(醚)-6或三[2-(2-甲氧基-乙氧基)-乙基]-胺。
本发明的方法优选在合适的反应助剂存在下进行。所有通常的无机或有机碱都适用作助剂。包括例如碱土金属或碱金属的氢化物,氢氧化物,氨化物,醇化物,乙酸盐类,碳酸盐类或碳酸氢盐类,例如氢化钠,氨基化钠,甲醇钠,乙醇钠,叔丁醇钾,氢氧化钠,氢氧化钾,氢氧化铵,乙酸钠,乙酸钾,乙酸钙,乙酸铵,碳酸钠,碳酸钾,碳酸氢钾,碳酸氢钠或碳酸铵,以及叔胺类,如三甲胺,三乙胺,三丁胺,N,N-二甲基苯胺,吡啶,N-甲基哌啶,N,N-二甲基氨基吡啶,二氮杂双环辛烷(DABCO),二氮杂双环壬烯(DBN)或二氮杂双环十一碳烯(DBU)。
实施本发明的方法时,反应温度可在较宽的范围内变化。通常,反应温度在-30℃和+120℃之间,优选在-20℃和+60℃之间。
本发明的方法一般在常压下进行。但也可能加压或减压进行。
为了实施本发明的方法,每摩尔分子式(Ⅱ)的2-羟基苯基丙烯酸酯通常要用1.0至10.0摩尔,优选1.0至5.0摩尔的分子式(Ⅲ)的二唑衍生物,并任选采用1.0至5.0摩尔,优选1.0至2.5摩尔的反应助剂。反应的实施以及反应产物的处理及分离可按常规方法进行(这一点也可参看制备实施例)。
分子式(Ⅰ)的最终产物可用通常的方法,如柱色谱或重结晶的方法提纯。
产物的表征可以用熔点法,如果化合物不结晶则可用折光指数法或氢核磁共振谱(1H-NMR)法。
本发明的活性化合物呈现很强的杀微生物性质,实际上可用来控制有害的微生物。该活性化合物适合作植物保护剂,特别是作杀菌剂。
在植物保护中,杀菌剂用来控制下列纲或亚纲菌类,如根肿菌纲,卵菌亚纲,壶菌纲,接合菌亚纲,子囊菌纲,担子菌纲和半短菌纲。
一此引起上述属名的真菌性疾病的细菌可作为例子提出,但不局限于此:
腐霉属类,例如,Pythium ultimum;
疫霉属类,例如,马铃薯疫霉;
假霜霉属类,例如humili或-cubense假霜霉;
单轴霉属类,例如,葡萄霜霉菌;
霜霉属类,例如,白菜霜霉菌;
白粉菌属类,例如,麦类白粉菌;
单丝壳属类,例如,黄瓜白粉病球壳霉;
叉丝单囊壳属类,例如,苹果白粉病霉;
黑星菌属类,例如,苹果黑星病菌;
核球壳菌属类,例如,圆筒形的核球壳菌或禾本类核球壳菌(分生孢子形:德斯霉,异名:长蠕孢属);
旋胞腔菌属类,例如,小麦根腐病旋孢霉;
(分生孢子形:德斯霉,异名:长蠕孢属);
单孢锈菌属类,例如,菜豆单孢锈菌;
柄锈属类,例如,隐藏的柄锈属;
腥黑粉菌属类,例如,腥黑粉菌骨疽;
黑粉菌属类,例如,裸黑粉菌或燕麦属黑粉菌;
薄膜革菌属类,例如,笄木薄膜革菌;
pyricularia类,例如pyricularia oryzae;
镰刀霉属类,例如,黄色镰刀霉;
葡萄孢属类,例如,灰绿葡萄孢属;
壳针孢属类,例如,麦类颖斑枯病壳针孢霉;
细球壳菌属类,例如,Leptosphaeria nodorum;
尾孢菌属类,例如,具灰白毛的尾孢菌;
交链孢霉属类,例如,甘蓝黑斑病交链孢,
由于在抗植物病害所需要的浓度下,植物对活性化合物有很好的耐药性,使得可对植物地面上部分,植物增长的茎和种子以及土壤进行处理。
在这方面,本发明的活性化合物用来控制谷类的病害特别有效,例如,在小麦和大麦上的真谷类白粉菌(禾白粉菌)的抗致病因剂,或在小麦叶斑病(麦类颖斑枯病壳针孢
的抗致病因剂,或作为水果和蔬菜栽培时病害的控制剂,例如,真葡萄白粉菌(葡萄霜霉菌)的抗致病因剂或苹果疤痕(苹果黑星菌)的抗致病因剂,或抗马铃薯疫霉属病害。除此之外,本发明的活性化合物还具有良好的玻璃试管内活性。
活性化合物根据其特定的物理和/或化学性质,可被加工成常用的制剂,如溶液,乳液,悬浮液,粉末,泡沫状物,糊状物,颗粒,气雾剂,聚合物微囊和涂料种子微囊,以及超低剂量的冷雾制剂和热雾制剂。
这些制剂可按通常的方法制备,例如将活性化合物与稀释剂,即液体溶剂,加压液化气,和/或固体载体,并任选用表面活性剂,即乳化剂和/或分散剂,和/或发泡剂一起混合。当用水作稀释剂时,例如有机溶剂,也可用作助溶剂,合适的液体溶剂主要有:芳烃,如二甲苯,甲苯或烷基萘,氯代芳烃或氯代脂肪烃,如氯苯,氯代乙烯或二氯甲烷,脂肪烃,如环己烷或烷属烃,例如矿物油馏份,醇类,如丁醇或乙二醇及其醚和酯类,酮类,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,以及水;液化气稀释剂或载体是指在室温和大气压下为气体的液体,例如气雾剂抛射剂,如卤代烃类以及丁烷,丙烷,氮和二氧化碳;适合的固体载体有:例如磨细的天然矿土,如高岭土,粘土,云母,白垩,石英,缘坡缕石,蒙脱石或硅藻土,和磨细的合成矿物,如高度分散的硅石,氧化铝和硅酸盐类;适用作丸剂的固体载体:例如碾碎并分级的天然岩石如方解石,大理石,浮石,海泡石和白云石,以及合成的无机和有机石粉的颗粒,和有机物质颗粒如锯末,椰子壳,玉米芯和烟草杆;合适的乳化剂和/或发泡剂有:例如非离子和阴离子乳化剂,如聚氧乙烯脂肪酸酯类,聚氧乙烯脂肪醇醚类,例如烷基芳基聚乙二醇醚类,烷基磺酸酯类,烷基硫酸酯类,芳基磺酸酯类以及蛋白水解产物;合适的分散剂:例如木质素-亚硫酸盐废液和甲基纤维素。
胶粘剂如羧甲基纤维素和粉末、颗粒或胶乳形式的天然或合成的聚合物,如阿拉伯胶,聚乙烯醇和聚乙酸乙烯酯,以及天然的磷脂,如脑磷脂和卵磷脂,和合成磷脂都可在制剂中应用。其它的添加剂可以是矿物油和植物油。
也可能应用着色剂和无机颜料(例如氧化铁,二氧化钛和普鲁士兰)和有机染料(如茜素染料,偶氮染料和金属酞菁染料)和痕量的营养素(如铁,镁,硼,铜,钴,钼和锌的盐类)。
制剂通常含有0.1%和95(重量)的活性化合物,优选为0.5%至90%。
本发明的活性化合物在制剂中可与其它已知的活性化合物,如杀菌剂,杀虫剂,杀螨剂和除草剂混合,也可与肥料和生长调节剂混合。
活性化合物既可直接使用也可以制剂的形式使用,也可以制备后即用的形式使用,如随时可用的溶液,悬浮液,可湿性粉末,糊剂,可溶性粉末,可喷撒粉末和颗粒。它们可以通常的方式施用,例如用水浇灌,喷洒,喷雾,散播,撒粉,喷泡沫,涂刷等等。还可以超低剂量的方法施用活性化合物,或将活性化合物制剂或活性化合物本身注入土壤中。植物的种子也可以进行处理。
在处理植物部分时,活性化合物在使用形式中的浓度可在相当大的范围内变动。通常为1%至0.0001%(重量),优选为0.5%至0.01%(重量)。
在处理种子时,活性化合物的量一般要求是每千克种子0.001至50克,优选0.01至10克。
处理土壤时,要求在施用处活性化合物的浓度为0.00001%至0.1%(重量),优选为0.0001%至0.02%(重量)。
制备实施例:
实施例1:
0.25克(0.009摩尔)氢化钠(80%石蜡油溶液)在-20℃下加至1.6克(0.008摩尔)3-苯氧基-5-氯-1,2,4-噻二唑和1.6克(0.008摩尔)2-羟基苯基-3-甲氧基丙烯酸甲酯(例如参见EP242081)在50毫升无水二甲基甲酰胺中的混合物中,并使反应混合物缓慢升至室温,后处理时,在用冰冷却的同时加入15毫升饱和碳酸氢钠水溶液,该混合物然后各用20毫升乙醚萃取三次,此后水相用稀盐酸酸化,再各用20毫升乙酸乙酯萃取三次。合并有机相,在真空下干燥和浓缩,残余物用硅胶柱色谱提纯(洗脱液:二氯甲烷/乙酸乙酯100∶1)。
得到油状的1.8克(理论值的62%)2-[2-(3-苯氧基-1,2,4-噻二唑-5-基氧)-苯基]-3-甲氧基丙烯酸甲酯。
1H-NMR(CDCl3/四甲基硅烷):
δ=3.67(s,
3H);3.80(s,
3H);7.25(m,
4H);7.4(m,
5H)7.6(s,1H)
ppm.
实施例2:
1.5克(0.05摩尔)氢化钠(80%石蜡油溶液)在-20℃下加至10.5克(0.05摩尔)的3-(4′-甲基苯氧基)-5-氯-1,2,4-噁二唑和10.4克(0.05摩尔)2-羟基苯基-3-甲氧基丙烯酸甲酯(参见例如EP242081)在50毫升无水二甲基甲酰胺中的混合物中,并使反应混合物缓慢升到室温。为进行后处理,将混合物倾入水中,并各用20毫升乙醚萃取三次,合并有机相,在真空下干燥和浓缩,残余物用硅胶色谱提纯(洗脱液:二氯甲烷)。
得到油状的10.5克(理论值的55%)2-[2-(3-{4′-甲基苯氧基}-1,2,4-噁二唑-5-基氧)-苯基]-3-甲氧基丙烯酸甲酯。
1H-NMR(CDCl3/四甲基硅烷):
δ=2.34(3H);
3.68(3H);3.79
(3H);7.1-7.5
(8H)7.59(1H)
ppm.
起始化合物的制备:
实施例Ⅲ-1
首先,在室温和搅拌下,将1.6毫升(0.0151摩尔)三氯甲烷亚磺酰氯加到2.9克(0.017摩尔)苯氧基-甲脒盐酸化物(参见例如EP325336)在30毫升的二氯甲烷中的溶液中,然后,在-8℃、搅拌并同时用冰冷却下,加入7.5克(0.084摩尔)45%浓度的氢氧化钠水溶液。反应混合物然后升至室温,并在此温度下再搅拌2小时。在进行后处理时,加入16克干燥硫酸钠,然后将反应混合物搅拌10分钟,用硅藻土过滤,再用二氯甲烷洗涤,滤液在真空下浓缩。
得到2.1克(理论值的62%)熔点为171℃的3-苯氧基-5-氯-1,2,4-噻二唑。
实施例3-2
28.8克(0.15摩尔)的
(参见Chem.Ber.98,第152和153页)被加到28毫升POCl3中,然后,将11.9克(0.15摩尔)吡啶加到此混合物中。此混合物在回流下沸腾4小时,过量的POCl3被汽提出来;然后,将混合物倾入冰水中,用二氯甲烷萃取。此混合物浓缩后加入乙醚;将不溶物过滤出来,滤液被浓缩。得到22克(理论值的69.7%)产品。
质谱:214,210,175,147,107,91,77,39
实施例Ⅲ-3,A:
292.8克(1.502摩尔)3-(4-吡啶基)-1,2,4-噻二唑啉-(4H)-5-硫酮和315克(2.282摩尔)碳酸钾,以及作为催化剂的在900毫升碳酸二甲酯中的冠醚18-冠(醚)-6一起加热至沸腾回流2天,冷却到室温以后,混合物在真空下浓缩,溶解在二氯甲烷中,然后用水摇荡萃取数次,有机相用硫酸钠干燥,在真空下浓缩。
产量:230.7克(74%),熔点92℃
实施例Ⅲ-3
69克(1.5mol)甲酸和3克作为催化剂的钼酸铵加入在900毫升二氯甲烷中的156.8克(0.75摩尔)3-(4-吡啶基)-5-甲基-硫代-1,2,4噻二唑(见上面的例3-3,A)中,然后在强烈搅拌下,滴加218.6克(2.25摩尔)35%浓度的过氧化氢溶液,继续在室温下搅拌此混合物过液,而后分离出有机相,用水摇荡萃取,用硫酸钠干燥后,在真空下浓缩。
产量:119.5克(66%),熔点135℃
下列通式(Ⅰ)的各种3-甲氧基-苯基丙烯酸酯类可按相应的方法并根据一般的制备程序得到:
*)1H-NMR谱图是在氘氯仿(CDCl3)或六氘二甲基亚砜(DMSO-d6)中用四甲基硅烷(TMS)作内标测得。化学位移δ的值以ppm表示。
通式(Ⅰ)下列的各种3-甲氧基-2-苯基-丙烯酸酯类可按相应的方法并根据一般的制备程序得到。
*)1H-NMR谱图是在氘氯仿(CDCl3)或六氘二甲基亚砜(DMSO-d6)中用四甲基硅烷(TMS)作内标测得。化学位移δ的值以ppm表示。
应用实施例
用下列化合物作后述的应用实施例中的对比物质:
3-甲氧基-2-(2-苯甲酸基苯基)-丙烯酸酯
(见于EP178826)
实施例A
黑星菌试验(苹果)/保护
溶剂:4.7份(重量)丙酮
乳化剂:0.3份(重量)烷基-芳基-聚乙二醇醚
合适的活性化合物的制剂制法如下:将1份(重量)活性化合物与所述量的溶剂和乳化剂混合,该浓缩物再用水稀释至所需要的浓度。
为测定保护活性,将幼小的植物用活性化合物制剂喷洒至透湿。在喷洒层干燥后,该植物用苹果疤致病菌(苹果黑星菌族)分生孢子水悬浮液接种,然后在20℃和100%相对湿度的培养箱内保持一天。
然后将植物置于20℃和相对湿度70%的温室内。
接种后12天进行评价。
这个试验清楚地表明,制备实施例2,6,7,8,15,16,18,19和20的化合物与先前技术情况相比有着优越的活性,活性化合物在10ppm浓度下的有效率最高达100%。
实施例B
单轴霉菌试验(葡萄藤)/保护
溶剂:4.7份(重量)丙酮
乳化剂:0.3份(重量)烷基-芳基-聚乙二醇醚
配制合适的活性化合物的制剂的方法如下:将1份(重量)活性化合物与所述量的溶剂和乳化剂混合,浓缩物再用水稀释到所需要的浓度。
为测定保护活性,将幼小植物用活性化合物制剂喷洒至湿透,在喷洒层干燥后,该植物用葡萄霜霉菌孢子水悬浮液接种,然后在20℃至22℃,相对湿度100%的湿度试验箱内保持一天,该植物然后在21℃和相对湿度90%的温室内放置5天。再将植物加湿在湿度试验箱内放置一天。
在接种后6天进行评价。
这个试验清楚表明,制备实施例2,6,7,8,14,15,16,17,18,19和20的化合物与先前技术的情况相比显示优越的活性,这些活性化合物在10ppm浓度时呈现70%至100%的有效率。
实施例C:
疫霉菌试验(马铃薯)/保护
溶剂:4.7份(重量)丙酮
乳化剂:0.3份(重量)烷基-芳基聚乙二醇醚
配制合适的活性化合物的制剂的方法如下:将1份(重量)活性化合物与所述量的溶剂和乳化剂混合,浓缩液再用水稀释至所需要的浓度。
为测定保护活性,将幼小植物用活性化合物制剂喷洒至透湿,在喷洒层干燥后,该植物用疫霉菌感染原的孢子水悬浮液接种。
将该植物置于20℃,相对湿度100%的培养箱内。
在接种后3天进行评价。
这个试验清楚表明,制备实施例2,16和19的化合物与先前技术的情况相比显示出优越的活性,这些活性化合物在10ppm的浓度下的有效率最高达100%。
实施例D:
溶剂:10份(重量)N-甲基吡咯烷酮
乳化剂:0.6份(重量)烷基-芳基-聚乙二醇醚
配制合适的活性化合物制剂的方法如下:将1份(重量)活性化合物与所述量的溶剂和乳化剂混合,该浓缩液再用水稀释至所需要的浓度。
该植物再放置于约20℃和相对湿度约80%的温室内。
在接种后7天进行评价。
这个试验清楚表明,制备实施例2的化合物与先有技术的情况相比显示很高的活性,该活性化合物在100ppm浓度下有效率达100%。
Claims (10)
1、通式(Ⅰ)的噁(噻)-二唑-氧-苯基丙烯酸酯类
其中
Y代表OCH3或NHCH3,
Z代表=CH或=N-,
R代表卤素,烷基或卤代烷基,或式Ar-A的基团,其中
Ar代表任选取代的芳基或杂芳基,和
A代表氧、硫,或下式的基团:-OCO,-COO-,-CO-,-CH2-,-CH2CH2,-C≡C-,-CH=CH-,-CHR′-,-CHR′-CH2-,-CH2-CHR′-,-S(O)-,-SO2,-NH-CH2-,-CH2-NH-,-NH-,-N(CH3)-,-CH2O-,-CH2S,-CH2SO-,-CH2SO2-,OCH2-,-SCH2,-SO-CH2,-SO-CH2,-SO2CH2-,或直接键合,其中R′代表氢,或与R含义相同,和
X代表氧或硫。
2、根据权利要求1的式(Ⅰ)的化合物,其中R代表氟、氯、溴、碘、C1-C4烷基或C1-C2具有1至5个相同或不同卤原子的卤代烷基或代表式Ar-A-的基团,其中Ar代表用适当的取代基任选地同取代或异取代一次或多次的6至10个碳原子的芳基,或代表适当取代基任选地同取代或异取代一次或多次,和/或苯并稠合的具有2至9个碳原子和1至5个相同或不同的杂原子的杂芳基,在各种情况下合适的取代基为:
卤素、氰基、硝基、羟基、氨基、甲酰基、氨基甲酰基、硫代氨基甲酰基,在所有情况下均具有1至6个碳原子的直链或支链的烷基、烷氧基、烷硫基、烷基亚磺酰基或烷基磺酰基,在所有情况下均具有2至6个碳原子的直链或支链的链烯基或链烯氧基,在所有情况下均具有1至6个碳原子和1至13个相同或不同的卤原子的直链或支链的卤代烷基,卤代烷氧基,卤代烷硫基,卤代烷基亚磺酰基或卤代烷基磺酰基,在所有情况下均具有2至6个碳原子和1至13个相同或不同的卤原子的直链或支链的卤代链烯基或卤代链烯氧基,在所有情况下在各个烷基部分上均具有1至6个碳原子的直链或支链的N-烷基氨基,二烷基氨基,烷羰基,烷羰氧基,烷氧羰基,烷基磺酰氧基,肟基烷基或烷肟基烷基,在所有情况下均具有1至6个碳原子双键的亚烷基或二氧亚烷基(并任选地被下列基团同取代或异取代一次或多次:卤素和1或1至4个碳原子的直链或支链烷基和/或1至4个碳原子和1至9个相同或不同卤原子的直链或支链卤代烷基),3至7个碳原子的环烷基,2至6个碳原子和1至3个相同或不同的杂原子-特别是氮,氧和/或硫-的3至7元的杂环基,以及苯基,苯氧基,苄基,苄氧基,苯乙基或苯乙氧基,它们在苯基部分上均任选地被下列基团同取代或异取代一次或多次:卤素和/或1至4个碳原子的直链或支链烷基和/或1至4个碳原子和1至9个相同或不同卤原子的直链或支链卤代烷基和/或1至4个碳原子的直链或支链烷氧基和/或1至4个碳原子和1至9个相同或不同卤原子的直链或支链卤代烷氧基,和
A 代表氧、硫或下式的基团:-OCO,-COO-,-CO-,-CH2-,-CH2CH2,-C≡C-,-CH=CH-,-CHR′-,-CHR′-CH2-,-CH2-CHR′-,-S(O)-,-SO2,-NH-CH2-,-CH2-NH-,-NH-,-N(CH3)-,-CH2O-,-CH2S,-CH2SO-,-CH2SO2-,OCH2-,-SCH2,-SO-CH2,-SO2CH2-,或直接键合,其中R′代表氢,或与R含义相同,和
X代表氧或硫。
3、根据权利要求1的分子式(Ⅰ)的化合物,其中R代表氟、氯、溴、甲基、乙基、正或异丙基、正、异、仲或叔丁基,或代表含1至5个相同或不同F-和Cl原子的C1-C2卤代烷基,或代表式Ar-A-的基团,其中
Ar 代表用合适的取代基任选地同取代或异取代一次至五次的6或10个碳原子的芳基,或代表用合适的取代基任选地同取代或异取代一次至四次,和/或苯并稠合的具有2至9个碳原子和1至3个相同或不同的杂原子(特别是氮,氧和/或硫)的杂芳基,在各种情况下合适的取代基为:
卤素、氰基、硝基、羟基、氨基、甲酰基、氨基甲酰基、硫代氨基甲酰基,在所有情况下均具有1至4个碳原子的直链或支链的烷基、烷氧基、烷硫基、烷基亚磺酰基或烷基磺酰基,在所有情况下均具有2至4个碳原子的直链或支链的链烯基或链烯氧基,在所有情况下均具有1至4个碳原子和1至9个相同或不同的卤原子的直链或支链的卤代烷基,卤代烷氧基,卤代烷硫基,卤代烷基亚磺酰基或卤代烷基磺酰基,在所有情况下均具有2至4个碳原子和1至9个相同或不同卤原子的直链或支链的卤代链烯基或卤代链烯氧基,在所有情况下在各个烷基部分上均具有1至4个碳原子的直链或支链的N-烷基氨基,二烷基氨基,烷基羰基,烷基羰氧基,烷氧羰基,烷基磺酰氧基,肟基烷基或烷肟基烷基,在所有情况下均具有1至4个碳原子双键的亚烷基或二氧亚烷基(并任选地被下列基团同取代或异取代一次或多次:卤素和/或1至3个碳原子的直链或支链烷基和/或1至3个碳原子和1至7个相同或不同卤原子的直链或支链卤代烷基),3至6个碳原子的环烷基,4至6个碳原子和1至2个相同或不同的杂原子-特别是氮,氧和/或硫-的5至7元的饱和杂环基,以及苯基,苯氧基,苄基,苄氧基,苯乙基或苯乙氧基,它们在苯基部分上均任选地被下列基团同取代或异取代一次或三次:卤素和/或1至3个碳原子的直链或支链烷基和/或1至3个碳原子和1至7个相同或不同卤原子的直链或支链卤代烷基和/或1至3个碳原子的直链或支链烷氧基和/或1至3个碳原子和1至7个相同或不同卤原子的直链或支链卤代烷氧基,和
A 代表氧,硫,或下式的基团:-S(O)-,-SO2-,-NH-,-N(CH3)-,-CH2O-,-CH2S-,-OCH2-,-SCH2,或直接键合,和
X 代表氧或硫。
4、根据权利要求1的分子式(Ⅰ)的化合物,其中
R 代表氯、溴、甲基、乙基、CF3、CH2F、CHF2、CCl3、CH2Cl、CHCl2、CFCl2、CF2Cl,或代表式Ar-A-的基团,其中
Ar 代表在各种情况下用合适的取代基任选同取代或异取代一次至三次的苯基或萘基,或代表在所有情况下用合适的取代基任选同取代或异取代一次至三次,和/或苯并稠合的呋喃基,噻吩基,吡咯基,噁唑基,噻唑基,异噁唑基,异噻唑基,吡唑基,咪唑基,噁二唑基,噻二唑基,三唑基,吡啶基,哒嗪基,嘧啶基,吡嗪基或三嗪基,在所有的情况下合适的取代基为:
氟,氯,溴,羟基,氰基,硝基,氨基,甲酰基,氨基甲酰基,硫代氨基甲酰基,甲基,乙基,正或异丙基,正,异,仲或叔丁基,甲氧基,乙氧基,正-或异丙氧基,正-,异-,仲-或叔-丁氧基,甲硫基,乙硫基,甲基亚磺酰基,甲基磺酰基,烯丙基,丁烯基,烯丙氧基,丁烯氧基,三氟甲基,三氟甲氧基,三氟甲硫基,三氟甲基 亚磺酰基,三氟甲基磺酰基,二甲基氨基,二乙基氨基,乙酰基,乙酰氧基,甲基磺酰氧基,乙基磺酰氧基,甲氧基羰基,乙氧基羰基,肟基甲基,肟基乙基,甲肟基甲基,甲肟基乙基,乙肟基甲基,乙肟基乙基,丙-1,3-二基,丁-1,4-二基,二氧亚甲基,二氧亚乙基,二氧亚丙基,二氟二氧亚甲基,四氟二氧亚乙基,环丙基,环戊基,环己基,1-吡咯烷基,1-哌啶基,1-全氢化吖庚因基,4-吗啉基,或在所有情况下被氟、氯、溴、甲基、乙基、甲氧基、乙氧基、三氟甲基和/或三氟甲氧基任选地同取代或异取代一次至三次的苯基,苯氧基,苄基或苄氧基,和
A 代表氧,硫,或下式的基团:-S(O)-,-SO2-,-NH-,-N(CH3)-,CH2O-,-CH2S-,OCH2-,-SCH2-,或直接键合,和
X 代表氧或硫。
5、虫害控制剂,其特征在于含有至少一种按权利要求1至4中任一项的分子式(Ⅰ)的化合物。
6、控制虫害的方法,其特征在于按权利要求1至4任一项的分子式(Ⅰ)的化合物作用于虫害和/或其栖息处。
7、按权利要求1至4中任一项的分子式(Ⅰ)的化合物用于控制虫害的用途。
8、制备通式(Ⅰ)的噁(噻)-二唑-氧-苯基丙烯酸酯类的方法,
其中
Y代表OCH3或NHCH3,
Z代表=CH或=N-,
R代表卤素、烷基或卤代烷基,或式Ar-A的基团,其中
Ar代表任选取代的芳基或杂芳基,和
A 代表氧、硫,或下式的基团:-OCO,-COO-,-CO-,-CH2-,-CH2CH2-,-C≡C-,-CH=CH-,-CHR′-,-CHR′-CH2-,-CH2-CHR′-,-S(O)-,-SO- 2,-NH-CH2-,-CH2-NH-,-NH-,-N(CH3)-,-CH2O-,-CH2S,-CH2SO-,-CH2SO2-,OCH2-,-SCH2,-SO-CH2,-SO2CH2-,或直接键合,其中R′代表氢,或与R含义相同,和
X 代表氧或硫。
其特征在于分子式(Ⅱ)的α-羟基苯基丙烯酸酯类任选在稀释剂并任选在反应助剂存在下
与分子式(Ⅲ)的噁二唑或噻二唑衍生物反应。
其中R和X的含义同上,和
E 代表吸电子的离去基团。
9、制备虫害控制剂的方法,其特征在于根据权利要求1至4中任一项的分子式(Ⅰ)的化合物与稀释剂和/或表面活性剂混合。
10、分子式(Ⅲa)的噁二唑衍生物
其中
R 含义同权利要求1中所述,和
E 代表离去基团。
Applications Claiming Priority (4)
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DE4314501 | 1993-05-03 | ||
DEP4314501.9 | 1993-05-03 | ||
DEP4341066.9 | 1993-12-02 | ||
DE4341066A DE4341066A1 (de) | 1993-05-03 | 1993-12-02 | Oxa(Thia)-diazol-oxy-phenylacrylate |
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CN1095067A true CN1095067A (zh) | 1994-11-16 |
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CN94104995A Pending CN1095067A (zh) | 1993-05-03 | 1994-05-03 | 噁(噻)-二唑-氧-苯基丙烯酸酯类 |
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EP (1) | EP0623604B1 (zh) |
JP (1) | JPH06329649A (zh) |
CN (1) | CN1095067A (zh) |
AU (1) | AU5937994A (zh) |
BR (1) | BR9401670A (zh) |
DE (2) | DE4341066A1 (zh) |
HU (1) | HUT71699A (zh) |
IL (1) | IL109500A0 (zh) |
TW (1) | TW254843B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1298710C (zh) * | 2002-01-17 | 2007-02-07 | 住友化学工业株式会社 | 噻二唑化合物及其应用 |
CN1321117C (zh) * | 2002-10-11 | 2007-06-13 | 住友化学株式会社 | 噻二唑化合物及其用途 |
CN100391950C (zh) * | 2002-11-08 | 2008-06-04 | 住友化学株式会社 | 1,2,4-噻二唑化合物及其用途 |
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ES2140543T3 (es) * | 1993-08-13 | 2000-03-01 | Zeneca Ltd | Derivados de tia- y oxadiazol y su uso como fungicidas o insecticidas. |
DE19723195A1 (de) | 1997-06-03 | 1998-12-10 | Bayer Ag | Fluormethoximinoverbindungen |
WO2000015637A1 (en) * | 1998-09-16 | 2000-03-23 | Dow Agrosciences Llc | 2-methoxyimino -2-(pyridinyloxymethyl) phenyl acetamides with 5 membered heterocyclic rings on the pyridine ring as fungicides |
KR100311846B1 (ko) | 1999-07-05 | 2001-10-18 | 우종일 | 신규 아크릴레이트계 살균제 |
ZA200601274B (en) * | 2003-10-15 | 2007-05-30 | Sumitomo Chemical Co | 1,2,4-thiadiazole compounds and pests controlling composition containing the same |
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GB8619236D0 (en) * | 1986-08-06 | 1986-09-17 | Ici Plc | Fungicides |
IL87020A (en) * | 1987-07-11 | 1996-09-12 | Schering Agrochemicals Ltd | History of acrylic acid and their use as pesticides |
GB8908875D0 (en) * | 1989-04-19 | 1989-06-07 | Ici Plc | Fungicides |
GB8914797D0 (en) * | 1989-06-28 | 1989-08-16 | Ici Plc | Fungicides |
MY107955A (en) * | 1990-07-27 | 1996-07-15 | Ici Plc | Fungicides. |
FR2697252B1 (fr) * | 1992-10-28 | 1994-12-09 | Fournier Ind & Sante | Dérivés de 1,2,3,5,6,7,8,8a-octahydro-5,5,8a-triméthyl-(8abeta)-6-isoquinolineamine, leur procédé de préparation et leur utilisation en thérapeutique. |
GB9320744D0 (en) * | 1992-11-04 | 1993-12-01 | Zeneca Ltd | Oxa and thiadiazole derivatives |
-
1993
- 1993-12-02 DE DE4341066A patent/DE4341066A1/de not_active Withdrawn
-
1994
- 1994-03-31 TW TW083102806A patent/TW254843B/zh active
- 1994-04-11 AU AU59379/94A patent/AU5937994A/en not_active Abandoned
- 1994-04-20 DE DE59409817T patent/DE59409817D1/de not_active Expired - Fee Related
- 1994-04-20 EP EP94106122A patent/EP0623604B1/de not_active Expired - Lifetime
- 1994-04-26 JP JP6110408A patent/JPH06329649A/ja active Pending
- 1994-05-02 IL IL10950094A patent/IL109500A0/xx unknown
- 1994-05-02 HU HU9401273A patent/HUT71699A/hu unknown
- 1994-05-02 BR BR9401670A patent/BR9401670A/pt not_active Application Discontinuation
- 1994-05-03 CN CN94104995A patent/CN1095067A/zh active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1298710C (zh) * | 2002-01-17 | 2007-02-07 | 住友化学工业株式会社 | 噻二唑化合物及其应用 |
CN1321117C (zh) * | 2002-10-11 | 2007-06-13 | 住友化学株式会社 | 噻二唑化合物及其用途 |
CN100391950C (zh) * | 2002-11-08 | 2008-06-04 | 住友化学株式会社 | 1,2,4-噻二唑化合物及其用途 |
Also Published As
Publication number | Publication date |
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EP0623604A3 (de) | 1995-03-01 |
DE4341066A1 (de) | 1994-11-10 |
JPH06329649A (ja) | 1994-11-29 |
HUT71699A (en) | 1996-01-29 |
AU5937994A (en) | 1994-11-10 |
DE59409817D1 (de) | 2001-09-13 |
HU9401273D0 (en) | 1994-08-29 |
BR9401670A (pt) | 1994-12-06 |
EP0623604B1 (de) | 2001-08-08 |
IL109500A0 (en) | 1994-08-26 |
EP0623604A2 (de) | 1994-11-09 |
TW254843B (zh) | 1995-08-21 |
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