FR2740133A1 - NOVEL N-NAPHTYL CARBAMATES, THEIR PREPARATION PROCESS AND THEIR APPLICATION AS PESTICIDES - Google Patents
NOVEL N-NAPHTYL CARBAMATES, THEIR PREPARATION PROCESS AND THEIR APPLICATION AS PESTICIDES Download PDFInfo
- Publication number
- FR2740133A1 FR2740133A1 FR9512331A FR9512331A FR2740133A1 FR 2740133 A1 FR2740133 A1 FR 2740133A1 FR 9512331 A FR9512331 A FR 9512331A FR 9512331 A FR9512331 A FR 9512331A FR 2740133 A1 FR2740133 A1 FR 2740133A1
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- FR
- France
- Prior art keywords
- radical
- formula
- alkyl
- compound
- compounds
- 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.)
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- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title description 6
- 239000000575 pesticide Substances 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 102
- 125000005843 halogen group Chemical group 0.000 claims abstract description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 17
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 14
- 230000000895 acaricidal effect Effects 0.000 claims abstract description 12
- 230000000855 fungicidal effect Effects 0.000 claims abstract description 9
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 7
- -1 alkyl radical Chemical class 0.000 claims description 77
- 239000000203 mixture Substances 0.000 claims description 53
- 125000004432 carbon atom Chemical group C* 0.000 claims description 39
- 150000003254 radicals Chemical group 0.000 claims description 32
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical compound COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000001624 naphthyl group Chemical group 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000000642 acaricide Substances 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 239000002917 insecticide Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000002524 organometallic group Chemical group 0.000 claims description 6
- 230000000361 pesticidal effect Effects 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- RMRFFCXPLWYOOY-UHFFFAOYSA-N allyl radical Chemical compound [CH2]C=C RMRFFCXPLWYOOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 240000002390 Pandanus odoratissimus Species 0.000 claims description 2
- 235000005311 Pandanus odoratissimus Nutrition 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 101150058891 alc1 gene Proteins 0.000 claims description 2
- 101150117093 alc2 gene Proteins 0.000 claims description 2
- 150000005840 aryl radicals Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000002619 bicyclic group Chemical group 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical group C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002950 monocyclic group Chemical group 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- QVCOXWYMPCBIMH-UHFFFAOYSA-N prop-2-ynyl carbamate Chemical compound NC(=O)OCC#C QVCOXWYMPCBIMH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 239000000417 fungicide Substances 0.000 claims 1
- 230000000749 insecticidal effect Effects 0.000 abstract description 4
- 125000003302 alkenyloxy group Chemical group 0.000 abstract 2
- 125000003545 alkoxy group Chemical group 0.000 abstract 2
- 125000005133 alkynyloxy group Chemical group 0.000 abstract 2
- 125000005108 alkenylthio group Chemical group 0.000 abstract 1
- 125000004414 alkyl thio group Chemical group 0.000 abstract 1
- 125000005109 alkynylthio group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 23
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 239000000843 powder Substances 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 241000196324 Embryophyta Species 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- DEQYTNZJHKPYEZ-UHFFFAOYSA-N ethyl acetate;heptane Chemical compound CCOC(C)=O.CCCCCCC DEQYTNZJHKPYEZ-UHFFFAOYSA-N 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 244000045947 parasite Species 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000008187 granular material Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 241000228452 Venturia inaequalis Species 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000012312 sodium hydride Substances 0.000 description 5
- 229910000104 sodium hydride Inorganic materials 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 206010063409 Acarodermatitis Diseases 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 241000447727 Scabies Species 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 4
- 208000005687 scabies Diseases 0.000 description 4
- 125000004505 1,2,4-oxadiazol-5-yl group Chemical group O1N=CN=C1* 0.000 description 3
- 241000238876 Acari Species 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 241000123650 Botrytis cinerea Species 0.000 description 3
- 241000233866 Fungi Species 0.000 description 3
- 241001330975 Magnaporthe oryzae Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 239000005645 nematicide Substances 0.000 description 3
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- UOBYKYZJUGYBDK-UHFFFAOYSA-M 2-naphthoate Chemical compound C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-M 0.000 description 2
- PPWNCLVNXGCGAF-UHFFFAOYSA-N 3,3-dimethylbut-1-yne Chemical compound CC(C)(C)C#C PPWNCLVNXGCGAF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241001480061 Blumeria graminis Species 0.000 description 2
- 0 CC1(C=C(C[N+](N)[O-])C(C=C*(*)C=C2)=C2C=C1)N Chemical compound CC1(C=C(C[N+](N)[O-])C(C=C*(*)C=C2)=C2C=C1)N 0.000 description 2
- 101150041968 CDC13 gene Proteins 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 241000255925 Diptera Species 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 241001481703 Rhipicephalus <genus> Species 0.000 description 2
- 240000004460 Tanacetum coccineum Species 0.000 description 2
- 241001454293 Tetranychus urticae Species 0.000 description 2
- 241001617088 Thanatephorus sasakii Species 0.000 description 2
- ROVGZAWFACYCSP-MQBLHHJJSA-N [2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OC1C(C)=C(C\C=C/C=C)C(=O)C1 ROVGZAWFACYCSP-MQBLHHJJSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000002316 fumigant Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 229940015367 pyrethrum Drugs 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 2
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical compound C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- ORHBGEQYIZTYHV-UHFFFAOYSA-N 1,1-di(propan-2-yl)urea Chemical compound CC(C)N(C(C)C)C(N)=O ORHBGEQYIZTYHV-UHFFFAOYSA-N 0.000 description 1
- GTJQQQLNBIADOX-UHFFFAOYSA-N 1,1-diphenylpropylphosphane Chemical compound C=1C=CC=CC=1C(P)(CC)C1=CC=CC=C1 GTJQQQLNBIADOX-UHFFFAOYSA-N 0.000 description 1
- KVTHPKXDLVYNCH-UHFFFAOYSA-N 2-iodoethylbenzene Chemical compound ICCC1=CC=CC=C1 KVTHPKXDLVYNCH-UHFFFAOYSA-N 0.000 description 1
- IIVWHGMLFGNMOW-UHFFFAOYSA-N 2-methylpropane Chemical compound C[C](C)C IIVWHGMLFGNMOW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- ICPOKTZORRQGLK-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound C[C](C)C=C ICPOKTZORRQGLK-UHFFFAOYSA-N 0.000 description 1
- QBGONPQFBDUVPG-UHFFFAOYSA-N 4-chloro-n'-hydroxybenzenecarboximidamide Chemical compound ON=C(N)C1=CC=C(Cl)C=C1 QBGONPQFBDUVPG-UHFFFAOYSA-N 0.000 description 1
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 description 1
- BGPCNRRMNRNIFR-UHFFFAOYSA-N 7-bromo-1-nitronaphthalene Chemical compound C1=C(Br)C=C2C([N+](=O)[O-])=CC=CC2=C1 BGPCNRRMNRNIFR-UHFFFAOYSA-N 0.000 description 1
- 241001136249 Agriotes lineatus Species 0.000 description 1
- 241001674044 Blattodea Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000218645 Cedrus Species 0.000 description 1
- 241000530549 Cercospora beticola Species 0.000 description 1
- 241000256135 Chironomus thummi Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 241000489975 Diabrotica Species 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 241000221785 Erysiphales Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010061217 Infestation Diseases 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- 241001337998 Machilus Species 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 241000883290 Myriapoda Species 0.000 description 1
- 241000736122 Parastagonospora nodorum Species 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 241001281803 Plasmopara viticola Species 0.000 description 1
- 241001281805 Pseudoperonospora cubensis Species 0.000 description 1
- 241000221535 Pucciniales Species 0.000 description 1
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- 241000813090 Rhizoctonia solani Species 0.000 description 1
- 241000221662 Sclerotinia Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001351 alkyl iodides Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000005393 dicarboximide group Chemical group 0.000 description 1
- IIJREXIVDSIOFR-UHFFFAOYSA-N dichloromethane;heptane Chemical compound ClCCl.CCCCCCC IIJREXIVDSIOFR-UHFFFAOYSA-N 0.000 description 1
- MWPIIMNHWGOFBL-UHFFFAOYSA-N dichloromethane;toluene Chemical compound ClCCl.CC1=CC=CC=C1 MWPIIMNHWGOFBL-UHFFFAOYSA-N 0.000 description 1
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 239000004495 emulsifiable concentrate Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 1
- NYXHSRNBKJIQQG-UHFFFAOYSA-N methyl n-methylcarbamate Chemical compound CNC(=O)OC NYXHSRNBKJIQQG-UHFFFAOYSA-N 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- QCVFLUSIBKAKPC-UHFFFAOYSA-N n'-hydroxy-4-(trifluoromethyl)benzenecarboximidamide Chemical compound ON=C(N)C1=CC=C(C(F)(F)F)C=C1 QCVFLUSIBKAKPC-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000003032 phytopathogenic effect Effects 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- SFXOHDOEOSCUCT-UHFFFAOYSA-N styrene;hydrochloride Chemical compound Cl.C=CC1=CC=CC=C1 SFXOHDOEOSCUCT-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- XXKNPBDPZLPLFF-UHFFFAOYSA-N tert-butyl naphthalene-1-carboxylate Chemical compound C1=CC=C2C(C(=O)OC(C)(C)C)=CC=CC2=C1 XXKNPBDPZLPLFF-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- AVCVDUDESCZFHJ-UHFFFAOYSA-N triphenylphosphane;hydrochloride Chemical compound [Cl-].C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 AVCVDUDESCZFHJ-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
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
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/20—N-Aryl derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
-
- 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
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
- C07C271/30—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a six-membered aromatic ring being part of a condensed ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
La présente invention concerne de nouveaux N-naphtyl carbamates, leur procédé de préparation et leur application comme pesticides. The present invention relates to new N-naphthyl carbamates, their preparation process and their application as pesticides.
L'invention a pour objet les composés de formule (I) :
dans lesquels - X représente un atome d'hydrogène, un atome d'halogène, un radical alkyle, alkényle ou alkynyle, O-alkyle, O-alkényle ou
O-alkynyle, S-alkyle, S-alkényle ou S-alkynyle, renfermant jusqu'à 12 atomes de carbone éventuellement substitué par un ou plusieurs atomes d'halogène, ou X représente un radical
NO2, CN ou
dans lequel R a et Rb identiques ou différents l'un de l'autre représentent un atome d'hydrogène ou un radical alkyle renfermant jusqu'à 4 atomes de carbone, ou Ra et Rb forment ensemble avec l'atome d'azote auquel ils sont liés un radical hétérocyclique, renfermant éventuellement un autre hétéroatome choisi parmi l'oxygène, le soufre et l'azote, saturé ou insaturé, mono ou bicyclique, aromatique ou non aromatique.The subject of the invention is the compounds of formula (I):
in which - X represents a hydrogen atom, a halogen atom, an alkyl, alkenyl or alkynyl, O-alkyl, O-alkenyl or
O-alkynyl, S-alkyl, S-alkenyl or S-alkynyl, containing up to 12 carbon atoms optionally substituted by one or more halogen atoms, or X represents a radical
NO2, CN or
in which R a and Rb identical or different from each other represent a hydrogen atom or an alkyl radical containing up to 4 carbon atoms, or Ra and Rb form together with the nitrogen atom to which they are linked a heterocyclic radical, optionally containing another heteroatom chosen from oxygen, sulfur and nitrogen, saturated or unsaturated, mono or bicyclic, aromatic or non-aromatic.
- Y en position 6 ou 7 représente soit un radical alkyle, alkényle ou alkynyle renfermant jusqu'à 12 atomes de carbone éventuellement substitué par un ou plusieurs atomes d'halogène, par un radical O-alkyle,
O-alkényle ou O-alkynyle linéaire, ramifié ou cyclique ren fermant jusqu'à 12 atomes de carbone, par un radical
S-alkyle, S-alkényle ou S-alkynyle, linéaire, ramifié ou cyclique renfermant jusqu'à 12 atomes de carbone, par un radical NO2, par un radical C-N, par un radical
dans lequel R c et Rd, identiques ou différents représentent un atome d'hydrogène, un radical alkyle, linéaire ou ramifié, renfermant jusqu'à 4 atomes de carbone, par un radical
dans lequel Re, Rf et Rg, identiques ou différents, représentent un radical allyle, linéaire, ramifié ou cylique, renfermant jusqu'à 4 atomes de carbone, éventuellement substitué par un ou plusieurs atomes d'halogène, soit un radical aryle éventuellement substitué par un ou plusieurs atomes d'halogène, un ou plusieurs radicaux hydroxyle, un ou plusieurs radicaux alkyle, alkényle, alkynyle, linéaires ou ramifiés, aryle ou hétéroaryle éventuellement substitués par un ou plusieurs atomes d'halogène, un ou plusieurs radicaux O-alkyle ou S-alkyle éventuellement substitués par un ou plusieurs atomes d'halogène, un ou plusieurs radicaux CN, NO2, CO2R', R' représentant un radical alkyle renfermant jusqu'à 8 atomes de carbone, soit un radical O-alkyle, O-alkényle ou O-alkynyle, linéaire, ramifié ou cyclique renfermant jusqu'à 12 atomes de carbone, éventuellement substitué par un ou plusieurs des substituents mentionnés ci-dessus pour Y, lorsque Y représente un radical alkyle, soit un radical
dans lesquels Rh et Ri représentent un atome d'hydrogène ou un radical alkyle éventuellement substitué, renfermant jus qu'à 12 atomes de carbone, soit un radical
dans lequel Rk et R1 identiques ou différents l'un de l'autre, représentent un atome d'hydrogène, un radical alkyle, alkényle ou alkynyle, renfermant jusqu'à 12 atomes de carbone éventuellement substitué, un radical aryle ou hétéroaryle, - Z représente un radical alkyle, alkényle ou alkynyle,
O-alkyle, O-alkényle ou O-alkynyle, renfermant jusqu'à 4 atomes de carbone, éventuellement substitué par un ou plusieurs atomes d'halogène, ou Z représente un radical NH2, NHalcl ou
dans lequel alc1 et alc2 identiques ou différents l'un de l'autre représentent un radical alkyle renfermant jusqu'à 8 atomes de carbone, - R représente un atome d'hydrogène, un radical alkyle, alkényle ou alkynyle, O-alkyle, O-alkényle ou O-alkynyle,
S-alkyle, S-alkényle ou S-alkynyle, renfermant jusqu'à 12 atomes de carbone, éventuellement substitué par un ou plusieurs atomes d'halogène, par un radical CN, par un radical alkoxy renfermant jusqu'à 8 atomes de carbone, sous toutes leurs formes isomères possibles ainsi que leur mélange.Y in position 6 or 7 represents either an alkyl, alkenyl or alkynyl radical containing up to 12 carbon atoms optionally substituted by one or more halogen atoms, by an O-alkyl radical,
Linear, branched or cyclic O-alkenyl or O-alkynyl with up to 12 carbon atoms enclosed by a radical
S-alkyl, S-alkenyl or S-alkynyl, linear, branched or cyclic containing up to 12 carbon atoms, by a NO2 radical, by a CN radical, by a radical
in which R c and Rd, identical or different, represent a hydrogen atom, an alkyl radical, linear or branched, containing up to 4 carbon atoms, by a radical
in which Re, Rf and Rg, identical or different, represent an allyl radical, linear, branched or cylindrical, containing up to 4 carbon atoms, optionally substituted by one or more halogen atoms, or an aryl radical optionally substituted by one or more halogen atoms, one or more hydroxyl radicals, one or more alkyl, alkenyl, alkynyl, linear or branched, aryl or heteroaryl radicals optionally substituted by one or more halogen atoms, one or more O-alkyl radicals or S-alkyl optionally substituted by one or more halogen atoms, one or more radicals CN, NO2, CO2R ', R' representing an alkyl radical containing up to 8 carbon atoms, ie an O-alkyl, O-alkenyl radical or O-alkynyl, linear, branched or cyclic containing up to 12 carbon atoms, optionally substituted by one or more of the substituents mentioned above for Y, when Y represents a ra dical alkyl, or a radical
in which Rh and Ri represent a hydrogen atom or an optionally substituted alkyl radical, containing up to 12 carbon atoms, ie a radical
in which Rk and R1, which are identical or different from each other, represent a hydrogen atom, an alkyl, alkenyl or alkynyl radical, containing up to 12 optionally substituted carbon atoms, an aryl or heteroaryl radical, - Z represents an alkyl, alkenyl or alkynyl radical,
O-alkyl, O-alkenyl or O-alkynyl, containing up to 4 carbon atoms, optionally substituted by one or more halogen atoms, or Z represents an NH2, NHalcl or
in which alc1 and alc2 which are identical or different from each other represent an alkyl radical containing up to 8 carbon atoms, - R represents a hydrogen atom, an alkyl, alkenyl or alkynyl, O-alkyl, O radical -alkenyl or O-alkynyl,
S-alkyl, S-alkenyl or S-alkynyl, containing up to 12 carbon atoms, optionally substituted by one or more halogen atoms, by a CN radical, by an alkoxy radical containing up to 8 carbon atoms, in all their possible isomeric forms as well as their mixture.
Dans la définition des substituants - alkyle représente de préférence un radical méthyle, éthyle, propyle, isopropyle, butyle, isobutyle, sec-butyle ou tertbutyle, - alkényle représente de préférence un radical vinyle, allyle ou 1, 1-diméthylallyle, - alkynyle représente de préférence un radical éthynyle ou propynyle, - aryle représente de préférence un radical phényle ou naphtyle, - le radical hétérocyclique est de préférence un radical thiazolyle, oxazolyle, isothiazolyle, isoxazolyle, thiadiazolyle ou oxadiazolyle (1,2,4 ou 1,3,4), triazolyle, imidazolyle, pyrazolyle, morpholinyle ou pyrrolidinyle, - halogène représente de préférence un atome de brome, de fluor ou de chlore. In the definition of the substituents - alkyl preferably represents a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl radical, - alkenyl preferably represents a vinyl, allyl or 1, 1-dimethylallyl radical, - alkynyl represents preferably an ethynyl or propynyl radical, - aryl preferably represents a phenyl or naphthyl radical, - the heterocyclic radical is preferably a thiazolyl, oxazolyl, isothiazolyl, isoxazolyl, thiadiazolyl or oxadiazolyl radical (1,2,4 or 1,3, 4), triazolyl, imidazolyl, pyrazolyl, morpholinyl or pyrrolidinyl, - halogen preferably represents a bromine, fluorine or chlorine atom.
Parmi les composés de l'invention, on peut citer les composés de formule (I) tels que définis ci-dessus, dans lesquels X représente un atome d'hydrogène, ceux dans lesquels Y est en position 7 sur le noyau naphtyle et notamment ceux dans lesquels Y représente un radical alkynyle renfermant jusqu'à 8 atomes de carbone éventuellement substitué, comme par exemple ceux dans lesquels Y représente un radical
ou encore ceux dans lesquels Y représente un radical
Among the compounds of the invention, mention may be made of the compounds of formula (I) as defined above, in which X represents a hydrogen atom, those in which Y is in position 7 on the naphthyl nucleus and in particular those in which Y represents an alkynyl radical containing up to 8 optionally substituted carbon atoms, such as for example those in which Y represents a radical
or those in which Y represents a radical
Parmi les composés de l'invention, on peut citer les composés de formule (I), tels que définis ci-dessus, dans lesquels R représente un atome d'hydrogène, ceux dans lesquels R représente un radical alkyle renfermant jusqu'à 4 atomes de carbone comme par exemple un radical méthyle ou éthyle, ceux dans lesquels R représente un radical alkynyle renfermant jusqu'à 6 atomes de carbone, comme par exemple un radical -CH2-C--CH les composés de formule (I) dans lesquels R représente un radical alkényle, renfermant jusqu'à 4 atomes de carbone, comme par exemple un radical allyle. Among the compounds of the invention, mention may be made of the compounds of formula (I), as defined above, in which R represents a hydrogen atom, those in which R represents an alkyl radical containing up to 4 atoms of carbon such as for example a methyl or ethyl radical, those in which R represents an alkynyl radical containing up to 6 carbon atoms, such as for example a radical -CH2-C - CH the compounds of formula (I) in which R represents an alkenyl radical containing up to 4 carbon atoms, for example an allyl radical.
Parmi les composés préférés de l'invention, on peut également citer les composés de formule (I) dans lesquels Z représente un radical alcoxy renfermant jusqu'à 2 atomes de carbone, par exemple un radical méthoxy. Among the preferred compounds of the invention, mention may also be made of the compounds of formula (I) in which Z represents an alkoxy radical containing up to 2 carbon atoms, for example a methoxy radical.
L'invention a plus particulièrement pour objet les composés de formule (I) dont la préparation est donnée ciaprès dans la partie expérimentale et tout spécialement le composé de l'exemple 3 ou encore les composés des exemples 1, 2 et 4. A more particular subject of the invention is the compounds of formula (I) the preparation of which is given below in the experimental part and very especially the compound of Example 3 or also the compounds of Examples 1, 2 and 4.
L'invention a également pour objet un procédé de préparation des composés de formule (I), caractérisé en ce que l'on soumet un composé de formule (II)
dans lequel le groupement OH est en position 6 ou 7 sur le noyau naphtyle et Z conserve la signification précédente, à l'action d'un composé susceptible de substituer à OH un groupement facilement clivable L pour obtenir le composé de formule (III)
que l'on soumet si désiré, à l'action d'un composé susceptible d'introduire le radical X1 sur le noyau naphtyle pour obtenir le composé de formule (IV) :
dans lequel X1 a la même signification que X à l'exception de l'hydrogène et L et Z conservent leur signification précédente, puis soumet le composé de formule (III) ou (IV) à l'action d'un agent de couplage organométallique susceptible d'intro- duire le radical Y pour obtenir le composé de formule (IA) :
dans laquelle X, Y et Z conservent leur signification précédente et si désiré soumet le composé (IA) à l'action d'un composé de formule (V)
R1Hal (v) dans lequel Hal représente un atome d'halogène et R1 a la même signification que R à l'exception de l'hydrogène, pour obtenir le composé de formule (1B > correspondant
dans lequel X, Y, R1 et Z conservent leur signification précédente.The subject of the invention is also a process for preparing the compounds of formula (I), characterized in that a compound of formula (II) is subjected
in which the OH group is in position 6 or 7 on the naphthyl ring and Z retains the above meaning, to the action of a compound capable of substituting for OH an easily cleavable group L to obtain the compound of formula (III)
which is subjected if desired, to the action of a compound capable of introducing the radical X1 on the naphthyl nucleus to obtain the compound of formula (IV):
in which X1 has the same meaning as X with the exception of hydrogen and L and Z retain their previous meaning, then subjects the compound of formula (III) or (IV) to the action of an organometallic coupling agent capable of introducing the radical Y to obtain the compound of formula (IA):
in which X, Y and Z retain their previous meaning and if desired subjects the compound (IA) to the action of a compound of formula (V)
R1Hal (v) in which Hal represents a halogen atom and R1 has the same meaning as R with the exception of hydrogen, to obtain the compound of formula (1B> corresponding
in which X, Y, R1 and Z retain their previous meaning.
Dans un mode de réalisation préférée - le groupement facilement clivable est de préférence un triflate, un mésylate ou un tosylate, - l'agent susceptible d'introduire le groupe clivable est un anhydride par exemple l'anhydride trifluorométhylsulfonique et l'on opère en présence d'une base comme par exemple une amine telle que la triéthylamine ou la pyridine, - le radical X1 peut être introduit au moyen de N-chlorosuccinimide, ou du N-bromosuccinimide lorsque X1 représente un atome de chlore ou de brome, et la réaction a lieu de préférence au sein d'un acide organique comme l'acide acétique, - la réaction avec le composé de formule (III) ou (IV) et l'agent de couplage organometallique est réalisée au sein d'un solvant dipolaire aprotique comme l'acétonitrile ou le diméthylformamide en présence d'une amine tertiaire comme la triéthylamine, d'un catalyseur au palladium comme (Ph3P)PdCl2 et d'un catalyseur à base de cuivre comme l'iodure cuivreux selon la réaction de Heck, - la réaction du composé de formule (IA) avec le composé de formule (IV) a lieu de préférence en présence d'une base comme l'hydrure de sodium en opérant dans le DMF, ou en présence de LDA en opérant dans le THF. In a preferred embodiment - the easily cleavable group is preferably a triflate, a mesylate or a tosylate, - the agent capable of introducing the cleavable group is an anhydride for example trifluoromethylsulfonic anhydride and the operation is carried out in the presence a base such as for example an amine such as triethylamine or pyridine, the radical X1 can be introduced by means of N-chlorosuccinimide, or N-bromosuccinimide when X1 represents a chlorine or bromine atom, and the reaction preferably takes place within an organic acid such as acetic acid, - the reaction with the compound of formula (III) or (IV) and the organometallic coupling agent is carried out within an aprotic dipolar solvent such as acetonitrile or dimethylformamide in the presence of a tertiary amine such as triethylamine, a palladium catalyst such as (Ph3P) PdCl2 and a copper-based catalyst such as cuprous iodide depending on the reaction Heck n, - the reaction of the compound of formula (IA) with the compound of formula (IV) takes place preferably in the presence of a base such as sodium hydride by operating in DMF, or in the presence of LDA in operating in THF.
L'invention a également pour objet un procédé de préparation, caractérisé en ce que l'on soumet un composé de formule (VI)
dans laquelle HalA représente un atome d'halogène à l'action d'un agent de réduction pour obtenir le composé de formule (VII)
que l'on soumet à l'action d'un composé de formule (VIII) ZCOHalB (VIII) dans lequel Z conserve sa signification précédente et HalB représente un atome d'halogène pour obtenir le composé de formule (IX)
puis soumet le composé de formule (IX) à l'action d'un composé de formule (X) HalcR' (X) dans lequel R' représente un radical alkyle et Halc représente un atome d'halogène, pour obtenir le composé de formule (1c) correspondant
puis, si désiré soumet le composé (Ic) à l'action d'un agent de couplage organométallique, susceptible d'introduire le radical Y1, Y1 représentant toutes les valeurs de Y à l'ex- ception d'halogène pour obtenir le composé de formule (ID)
dans lequel Y1, Z et R' conservent leur signification précédente.The subject of the invention is also a preparation process, characterized in that a compound of formula (VI) is subjected
in which HalA represents a halogen atom with the action of a reducing agent to obtain the compound of formula (VII)
which is subjected to the action of a compound of formula (VIII) ZCOHalB (VIII) in which Z retains its previous meaning and HalB represents a halogen atom to obtain the compound of formula (IX)
then subjects the compound of formula (IX) to the action of a compound of formula (X) HalcR '(X) in which R' represents an alkyl radical and Halc represents a halogen atom, to obtain the compound of formula (1c) corresponding
then, if desired, subjects the compound (Ic) to the action of an organometallic coupling agent, capable of introducing the radical Y1, Y1 representing all the values of Y with the exception of halogen to obtain the compound of formula (ID)
in which Y1, Z and R 'retain their previous meaning.
Dans un mode de réalisation préféré - la réaction de réduction du composé de formule (VI) a lieu en utilisant l'hydrazine en présence de rhodium sur charbon, - la réaction entre les composés (VII) et (VIII) a lieu au sein d'un mélange de dichlorométhane et d'eau en présence de bicarbonate de sodium ou d'une base équivalente, - l'alkylation du composé (IX) a lieu à l'aide d'un iodure d'alkyle en présence d'une base forte comme l'hydrure de sodium en opérant dans le tétrahydrofuranne, - la réaction réalisée sur le composé (Ic) avec l'agent de couplage organométallique a lieu dans les mêmes conditions préférentielles que celles utilisées pour le composé (III) ou (IV). In a preferred embodiment - the reduction reaction of the compound of formula (VI) takes place using hydrazine in the presence of rhodium on carbon, - the reaction between the compounds (VII) and (VIII) takes place within '' a mixture of dichloromethane and water in the presence of sodium bicarbonate or an equivalent base, - the alkylation of compound (IX) takes place using an alkyl iodide in the presence of a base strong like sodium hydride by operating in tetrahydrofuran, - the reaction carried out on the compound (Ic) with the organometallic coupling agent takes place under the same preferential conditions as those used for the compound (III) or (IV) .
Les composés utilisés comme produits de départ pour la préparation des produits de l'invention sont des produits commerciaux. The compounds used as starting materials for the preparation of the products of the invention are commercial products.
Les produits obtenus lors de la mise en oeuvre du procédé de l'invention sont des produits nouveaux. The products obtained during the implementation of the process of the invention are new products.
L'invention a donc pour objet à titre de produits chimiques nouveaux, les composés de formules (III), (IV), (VII) et (IX). The subject of the invention is therefore, as new chemicals, the compounds of formulas (III), (IV), (VII) and (IX).
Les composés de formule (I) présentent d'intéressantes propriétés qui permettent leur utilisation dans la lutte contre les parasites. Il peut s'agir de la lutte contre les parasites des végétaux, qu'il s'agisse des parasites du sol ou des parties aériennes, des parasites des locaux et des parasites des animaux à sang chaud. The compounds of formula (I) have interesting properties which allow their use in the fight against parasites. It can be the fight against plant parasites, whether soil or aerial parasites, parasites from premises and parasites from warm-blooded animals.
Les composés de formule (I) présentent des propriétés insecticides, acaricides ainsi que des propriétés fongicides. The compounds of formula (I) have insecticidal, acaricidal and fungicidal properties.
Les produits de formule (I) peuvent également être utilisés pour lutter contre les insectes dans les locaux, pour lutter notamment contre les mouches, les moustiques et les blattes. The products of formula (I) can also be used to fight against insects in premises, to fight in particular against flies, mosquitoes and cockroaches.
Les produits de formule (I) peuvent aussi être utilisés pour lutter contre les insectes et autres parasites du sol, par exemple les coléoptères, comme Diabrotica, les taupins et les vers blancs, les myriapodes comme les scutigérelles et les blaniules, et les diptères comme les cécydomies et les lépidoptères comme les noctuelles terricoles. The products of formula (I) can also be used to fight against insects and other soil parasites, for example beetles, such as Diabrotica, wireworms and white worms, myriapods such as scutigeria and blaniules, and dipterans as midge moths and lepidoptera such as ground moths.
Les produits de formule (I) possèdent également d'excellentes activités acaricides comme le montrent les résultats des tests biologiques figurant ci-après. The products of formula (I) also have excellent acaricidal activities as shown by the results of the biological tests given below.
Les composés de formule (I) peuvent être utilisés pour lutter contre les acariens parasites des animaux, pour lutter par exemple contre les tiques et notamment les tiques du genre de Boophilus, ceux du genre Hyalomnia, ceux du genre
Amblyomnia et ceux du genre Rhipicephalus ou pour lutter contre toutes sortes de gales et notamment la gale sarcoptique, la gale psoroptique et la gale chorioptique. The compounds of formula (I) can be used to fight against parasitic mites of animals, to fight for example against ticks and in particular ticks of the genus Boophilus, those of the genus Hyalomnia, those of the genus
Amblyomnia and those of the genus Rhipicephalus or to fight against all kinds of scabies and in particular sarcoptic scabies, psoroptic scabies and chorioptic scabies.
L'invention a donc également pour objet les compositions pesticides destinées à la lutte contre les parasites des animaux à sang chaud, les parasites des locaux et des végétaux, caractérisées en ce qu'elles renferment au moins l'un des produits de formule (I) définis ci-dessus. The invention therefore also relates to pesticide compositions intended for the fight against parasites of warm-blooded animals, parasites of premises and plants, characterized in that they contain at least one of the products of formula (I ) defined above.
L'invention a notamment pour objet les compositions insecticides renfermant comme principe actif au moins l'un des produits définis ci-dessus, ainsi que les compositions acaricides renfermant comme principe actif au moins l'un des produits définis ci-dessus. The invention particularly relates to insecticide compositions containing as active principle at least one of the products defined above, as well as acaricide compositions containing as active principle at least one of the products defined above.
Dans ces compositions destinées à l'usage agricole et à l'usage dans les locaux, la ou les matières actives peuvent être additionnées éventuellement d'un ou plusieurs autres agents pesticides. Ces compositions peuvent se présenter sous forme de poudres, granulés, suspensions, émulsions, solutions, solutions pour aérosols, bandes combustibles, appâts ou autres préparations employées classiquement pour l'utilisation de ce genre de composés. In these compositions intended for agricultural use and for use in premises, the active ingredient (s) can optionally be added with one or more other pesticidal agents. These compositions can be in the form of powders, granules, suspensions, emulsions, solutions, solutions for aerosols, combustible strips, baits or other preparations conventionally used for the use of this type of compound.
Outre le principe actif, ces compositions contiennent, en général, un véhicule et/ou un agent tensio-actif, non ionique, assurant, en outre, une dispersion uniforme des substances constitutives du mélange. Le véhicule utilisé peut être un liquide, tel que l'eau, l'alcool, les hydrocarbures ou autres solvants organiques, une huile minérale, animale ou végétale, une poudre telle que le talc, les argiles, les silicates, le kieselguhr ou un solide combustible. In addition to the active principle, these compositions generally contain a vehicle and / or a non-ionic surfactant, ensuring, moreover, a uniform dispersion of the constituent substances of the mixture. The vehicle used can be a liquid, such as water, alcohol, hydrocarbons or other organic solvents, a mineral, animal or vegetable oil, a powder such as talc, clays, silicates, kieselguhr or a solid fuel.
Les compositions insecticides selon l'invention contiennent de préférence de 0,005 % à 10 % en poids de matière active. The insecticidal compositions according to the invention preferably contain from 0.005% to 10% by weight of active material.
Selon un mode opératoire avantageux, pour un usage dans les locaux, les compositions selon l'invention sont utilisées sous forme de compositions fumigantes. According to an advantageous procedure, for use in premises, the compositions according to the invention are used in the form of fumigant compositions.
Les compositions selon l'invention peuvent alors être avantageusement constituées, pour la partie non active, d'un serpentin insecticide (ou coil) combustible, ou encore d'un substrat fibreux incombustible. Dans ce dernier cas, le fumigant obtenu après incorporation de la matière active est placé sur un appareil chauffant tel qu'un émanateur électri que. The compositions according to the invention can then advantageously consist, for the non-active part, of a combustible insecticide coil (or coil), or also of an incombustible fibrous substrate. In the latter case, the fumigant obtained after incorporation of the active material is placed on a heating device such as an electric emanator.
Dans le cas où l'on utilise un serpentin insecticide, le support inerte peut être, par exemple, composé de marc de pyrèthre, poudre de Tabu (ou poudre de feuilles Machilus
Thumbergii), poudre de tige de pyrèthre, poudre de feuille de cèdre, poudre de bois (telle que de la sciure de pin) amidon et poudre de coque de noix de coco.In the case where an insecticide coil is used, the inert support can be, for example, composed of pyrethrum marc, Tabu powder (or Machilus leaf powder
Thumbergii), pyrethrum stem powder, cedar leaf powder, wood powder (such as pine sawdust) starch and coconut shell powder.
La dose de matière active peut alors être, par exemple, de 0,03 à 1 % en poids. The dose of active ingredient can then be, for example, from 0.03 to 1% by weight.
Dans le cas où l'on utilise un support fibreux incombustible, la dose de matière active peut alors être, par exemple, de 0,03 à 95 % en poids. In the case where an incombustible fibrous support is used, the dose of active material can then be, for example, from 0.03 to 95% by weight.
Les compositions selon l'invention pour un usage dans les locaux peuvent aussi être obtenues en préparant une huile pulvérisable à base de principe actif, cette huile imbibant la mèche d'une lampe et étant alors soumise à la combustion. The compositions according to the invention for use in premises can also be obtained by preparing a sprayable oil based on active principle, this oil soaking the wick of a lamp and then being subjected to combustion.
La concentration du principe actif incorporé à l'huile est, de préférence, de 0,03 à 95 % en poids. The concentration of the active ingredient incorporated in the oil is preferably from 0.03 to 95% by weight.
Les compositions insecticides selon l'invention, comme les compositions acaricides et nématicides, peuvent être additionnées éventuellement d'un ou plusieurs autres agents pesticides. Les compositions acaricides et nématicides peuvent se présenter notamment sous forme de poudre, granulés, suspensions, émulsions, solutions. The insecticide compositions according to the invention, like the acaricide and nematicide compositions, can optionally be added with one or more other pesticidal agents. The acaricide and nematicide compositions can be in particular in the form of powder, granules, suspensions, emulsions, solutions.
Pour l'usage acaricide, on utilise de préférence des poudres mouillables, pour pulvérisation foliaire, contenant de 1 à 80 % en poids de matière active ou des liquides pour pulvérisation foliaire contenant de 1 à 500 g/l de principe actif. On peut également employer des poudres pour poudrages foliaires contenant de 0,05 à 3 % de matière active. For acaricide use, wettable powders are preferably used for foliar spraying containing from 1 to 80% by weight of active ingredient or liquids for foliar spraying containing from 1 to 500 g / l of active principle. It is also possible to use powders for leaf dusting containing from 0.05 to 3% of active material.
Pour l'usage nématicide, on utilise de préférence des liquides pour traitement des sols contenant de 300 à 500 g/l de principe actif. For nematicide use, liquids are preferably used for treating soils containing 300 to 500 g / l of active ingredient.
Les composés de formule (I) présentent une excellente activité fongicide. Ils permettent de lutter contre les champignons qui ont déjà pénétré à l'intérieur des tissus des végétaux. Ce qui est particulièrement intéressant dans le cas où il n'est plus possible de lutter contre les maladies causées par les champignons une fois que la contamination a déjà eu lieu. Le spectre d'activité des composés de formule (I) couvre un grand nombre de champignons phytopathogènes d'importance économique variée, par exemple Pyricularia oryzae, Venturia inaequalis, Cercospora beticola, Erysiphicaceae (Sp. poudre d'oïdium), Fusarium-, Drechslera- et
Leptosphaeria-, Plasmopara viticola, Phytophtora infestans,
Pseudoperonospora cubensis, rhizoctonia solani, rouilles diverses, souches de Botrytis cinerea sensibles et résistantes au BCM- et/ou au Dicarboximide-, Sclerotinia solerotiorum, souches de Pseudocercosporella herpotrichoïdesrésistantes au BMC et Pellicularia sasakii.The compounds of formula (I) exhibit excellent fungicidal activity. They make it possible to fight against the fungi which have already penetrated inside the tissues of plants. This is particularly interesting in the case where it is no longer possible to control the diseases caused by the fungi once the contamination has already taken place. The activity spectrum of the compounds of formula (I) covers a large number of phytopathogenic fungi of various economic importance, for example Pyricularia oryzae, Venturia inaequalis, Cercospora beticola, Erysiphicaceae (Sp. Powdery mildew), Fusarium-, Drechslera - and
Leptosphaeria-, Plasmopara viticola, Phytophtora infestans,
Pseudoperonospora cubensis, rhizoctonia solani, various rusts, strains of Botrytis cinerea sensitive and resistant to BCM- and / or Dicarboximide-, Sclerotinia solerotiorum, strains of Pseudocercosposporella herpotrichoides resistant to BMC and Pellicularia sasakii.
L'invention a particulièrement pour objet les compositions fongicides renfermant comme principe actif un composé tel que défini ci-dessus. The invention particularly relates to fungicidal compositions containing as active ingredient a compound as defined above.
Les compositions fongicides selon l'invention renferment de préférence de 0,001 à 1 % en poids de composés de formule (I). The fungicidal compositions according to the invention preferably contain from 0.001 to 1% by weight of compounds of formula (I).
De plus, les composés de l'invention peuvent être aussi utilisés dans différents secteurs industriels par exemple pour protéger le bois ou comme agent de conservation des peintures. In addition, the compounds of the invention can also be used in different industrial sectors, for example to protect wood or as a preservative for paints.
L'invention s'étend également aux compositions fongicides qui renferment outre les composés de formule (I) des agents de formulation appropriés. The invention also extends to fungicidal compositions which contain, in addition to the compounds of formula (I), suitable formulating agents.
L'invention a tout spécialement pour objet les compositions pesticides et notamment les compositions insecticides, acaricides et fongicides renfermant comme principe actif au moins un composé des exemples 1, 2, 3 ou 4. A very particular subject of the invention is the pesticidal compositions and in particular the insecticidal, acaricidal and fungicidal compositions containing as active principle at least one compound of examples 1, 2, 3 or 4.
Les formulations possibles varient en fonction de paramètres biologiques et physicochimiques. Il peut s'agir par exemple de poudres mouillables, de concentrés émulsifiables, de solutions aqueuses, d'émulsions, de solutions à vaporiser, de dispersions dans l'huile ou dans l'eau, de suspoémulsions, de poudres, d'agents de traitement des semences, de granulés par exemple de microgranulés, de granulés à pulvériser, de granulés enduits, de granulés d'absorption, de granulés dispersibles dans l'eau, de formulation ULV, de microcap sules, de cires ou d'appâts. The possible formulations vary according to biological and physicochemical parameters. They can be, for example, wettable powders, emulsifiable concentrates, aqueous solutions, emulsions, spray solutions, dispersions in oil or in water, suspoemulsions, powders, treatment of seeds, of granules for example of microgranules, of granules to be sprayed, of granules coated, of absorption granules, of granules dispersible in water, of ULV formulation, of microcapsules, of waxes or of baits.
EXEMPL : (7-(3,3-diméthyl 1-butynyl) 1-nAphthalényl) carbamate de méthyle
Stade A : (((7-(trifluorométhyl) sulfonyl) oxy) 1-naphthalényl) carbamate de méthyle
On agite à une température inférieure à 100C sous azote, un mélange de 2,2 g de 7-hydroxy l-naphthalényl carbamate de méthyle et 60 ml de chlorure de méthylène. On ajoute de la triéthylamine et goutte à goutte 1,65 ml d'anhydride trifluorométhyl sulfonique. On maintient le milieu réactionnel sous agitation pendant 1 heure. On le verse sur l'eau et extrait trois fois à l'éther éthylique. On lave les phases organiques réunies à l'eau. On sèche sur sulfate de sodium et évapore le solvant sous pression réduite. On chromatographie le résidu sur silice en éluant avec le mélange heptane acétate d'éthyle (8-2). On isole 2,6 g du produit recherché.EXAMPLE: (7- (3,3-dimethyl 1-butynyl) 1-nAphthalenyl) methyl carbamate
Stage A: (((7- (trifluoromethyl) sulfonyl) oxy) 1-naphthalenyl) methyl carbamate
Stirred at a temperature below 100C under nitrogen, a mixture of 2.2 g of methyl 7-hydroxy l-naphthalenyl carbamate and 60 ml of methylene chloride. Triethylamine is added and 1.65 ml of trifluoromethyl sulfonic anhydride is added dropwise. The reaction medium is kept under stirring for 1 hour. It is poured over water and extracted three times with ethyl ether. The combined organic phases are washed with water. It is dried over sodium sulfate and the solvent is evaporated off under reduced pressure. The residue is chromatographed on silica, eluting with a heptane ethyl acetate mixture (8-2). 2.6 g of the desired product are isolated.
F = 103,1. F = 103.1.
rf = 0,55 (heptane-acétate d'éthyle 8-2).rf = 0.55 (heptane-ethyl acetate 8-2).
RMN (CDCl3) 3,84 (S, 3H, OMe) - 6,84 (large 1H NHCO)
IR (CDCl3) 3427 cm 1 NH 1740 cm'l CO
Stade B : (7-(3,3-diméthyl 1-butynyl) l-naphthalényl) carbamate de méthyle
On agite à OOC sous azote un mélange de 30 g du produit obtenu au stade précédent, 60 ml de diméthylformamide et 40 ml de triéthylamine. On ajoute 25 ml de 3,3-diméthyl 1-butyne, 1,2 g de chlorure de triphényl phosphine palladium et 0,4 g d'iodure de cuivre. On maintient le milieu réactionnel sous agitation à 200C pendant 18 heures. On verse dans l'eau et extrait à l'éther éthylique. On lave les phases organiques réunies avec de l'eau, sèche et évapore le solvant. On chromatographie sur silice, éluant heptane-acétate d'éthyle (8-2). On isole 22 g du produit recherché Rf = 0,45 (heptane-acétate d'éthyle 8-2). F = 1270C.NMR (CDCl3) 3.84 (S, 3H, OMe) - 6.84 (broad 1H NHCO)
IR (CDCl3) 3427 cm 1 NH 1740 cm'l CO
Stage B: (7- (3,3-dimethyl 1-butynyl) 1-naphthalenyl) methyl carbamate
A mixture of 30 g of the product obtained in the preceding stage, 60 ml of dimethylformamide and 40 ml of triethylamine is stirred at OOC under nitrogen. 25 ml of 3,3-dimethyl 1-butyne, 1.2 g of triphenyl phosphine palladium chloride and 0.4 g of copper iodide are added. The reaction medium is kept under stirring at 200C for 18 hours. It is poured into water and extracted with ethyl ether. The combined organic phases are washed with water, dried and the solvent is evaporated. Chromatography on silica, eluting heptane-ethyl acetate (8-2). 22 g of the desired product are isolated Rf = 0.45 (heptane-ethyl acetate 8-2). F = 1270C.
RMN (CDCl3) 1,36 (s) H du terbutyle ; 3,83 (s) H du CO2Me. 1 H NMR (CDCl3) 1.36 (s) of terbutyl; 3.83 (s) H of CO2Me.
EXEMPLE 2 : (7-(3,3-diméthyl 1-butynyl) 1-naphthalényl) méthyl carbamate de méthyle
On agite à OOC sous atmosphère d'azote une solution renfermant 1,124 g de produit préparé au stade précédent et 10 ml de diméthylformamide. On ajoute 0,19 g d'hydrure de sodium à 50 % dans l'huile, maintient l'agitation 30 minutes avant d'ajouter 0,3 ml d'iodure de méthyle et maintient l'agitation à nouveau pendant 3 heures. On verse le milieu réactionnel dans l'eau et extrait à l'éther éthylique. On lave à l'eau les phases organiques réunies, sèche sur sulfate de magnésium et évapore le solvant sous pression réduite. On chromatographie le résidu sur silice en éluant avec un mélange heptane-acétate d'éthyle (80-20). On isole 0,8 g de produit attendu, Rf = 0,5 (acétate d'éthyle-heptane 1-1) F = 123,80C. EXAMPLE 2: (7- (3,3-dimethyl 1-butynyl) 1-naphthalenyl) methyl methyl carbamate
A solution containing 1.124 g of product prepared in the preceding stage and 10 ml of dimethylformamide is stirred at OOC under a nitrogen atmosphere. 0.19 g of 50% sodium hydride in the oil is added, the stirring is continued for 30 minutes before adding 0.3 ml of methyl iodide and the stirring is continued for 3 hours. The reaction medium is poured into water and extracted with ethyl ether. The combined organic phases are washed with water, dried over magnesium sulfate and the solvent is evaporated off under reduced pressure. The residue is chromatographed on silica eluting with a heptane-ethyl acetate mixture (80-20). 0.8 g of expected product is isolated, Rf = 0.5 (ethyl acetate-heptane 1-1) F = 123.80C.
RMN (CDC13) 1,37 (9H,s) tBu ; 3,37 (3H,s) Me-N ; 3,59 (s) et 3,89 (m large) OMe.NMR (CDCl3) 1.37 (9H, s) tBu; 3.37 (3H, s) Me-N; 3.59 (s) and 3.89 (m wide) OMe.
EXEMPLE 3 : (7-(3,3-diméthyl 1-butynyl) l-naphthalényl) (2 propynyl) carbamate de méthyle
On introduit sous agitation à 00/+50C, 0,4 g d'hydrure de sodium à 50 % dans l'huile dans une solution renfermant 2 g du produit obtenu au stade B de l'exemple 1 et 20 ml de diméthylformamide. On laisse la température revenir à la température ambiante en maintenant l'agitation pendant 30 minutes. On introduit ensuite à une température inférieure à 300C, 1,6 ml de bromure de propargyle en solution toluénique à 80 %. On agite 18 heures à la température ambiante, traite à l'eau et extrait à l'éther isopropylique. On lave avec une solution saturée de chlorure de sodium, sèche sur sulfate de sodium et amène à sec. On obtient 2,31 g de produit recherché brut que l'on chromatographie sur silice en éluant avec le mélange chlorure de méthylène-heptane 70/30, on obtient 2,0 g de produit recherché. F = 1390C. Rf - 0,55 (CH2Cl2).EXAMPLE 3: (7- (3,3-dimethyl 1-butynyl) 1-naphthalenyl) (2 propynyl) methyl carbamate
0.4 g of 50% sodium hydride in oil in a solution containing 2 g of the product obtained in Stage B of Example 1 and 20 ml of dimethylformamide is introduced with stirring at 00 / + 50C. The temperature is allowed to return to room temperature while maintaining stirring for 30 minutes. 1.6 ml of propargyl bromide in 80% toluene solution is then introduced at a temperature below 300C. The mixture is stirred for 18 hours at room temperature, treated with water and extracted with isopropyl ether. Washed with saturated sodium chloride solution, dried over sodium sulfate and brought to dryness. 2.31 g of crude desired product are obtained which is chromatographed on silica eluting with a methylene chloride-heptane 70/30 mixture, 2.0 g of the desired product is obtained. F = 1390C. Rf - 0.55 (CH2Cl2).
RMN (CDCl3) 1,36 (9H,s) tBu ; 3,63 (sl) ; 3,92 CO2Me ; 4,11 (dd), 4,88 (dl) NCH2 ; 2,27 (t) -C=-CH. NMR (CDCl3) 1.36 (9H, s) tBu; 3.63 (sl); 3.92 CO2Me; 4.11 (dd), 4.88 (dl) NCH2; 2.27 (t) -C = -CH.
IR (CDCl3) 1701 cm 1 =CO ; 3308 cm'l =-CH ; 2248-2218 cm 1 C=C
EXEMPLE 4 : éthyl (7-(3,3-diméthyl 1-butynyl) 1-naphthalényl) carbamate de méthyle
En opérant comme à l'exemple 2 ou 3, à partir de 5 g du produit obtenu au stade B de l'exemple 1, et de 2,7 ml de bromure d'éthyle on obtient 4,75 g le produit recherché.IR (CDCl3) 1701 cm 1 = CO; 3308 cm'l = -CH; 2248-2218 cm 1 C = C
EXAMPLE 4 methyl (7- (3,3-dimethyl 1-butynyl) 1-naphthalenyl) methyl carbamate
By operating as in Example 2 or 3, starting from 5 g of the product obtained in Stage B of Example 1, and from 2.7 ml of ethyl bromide, 4.75 g of the desired product is obtained.
F=1470C.F = 1470C.
RMN (CDCl3) 1,36 (s) tBu ; 3,58 (sl) et 3,85 (large) CO2Me ; 1,18 (t), NCH2CH3 ; 3,47 (m) et 4,10 (m) NCH2CH3. NMR (CDCl3) 1.36 (s) tBu; 3.58 (sl) and 3.85 (broad) CO2Me; 1.18 (t), NCH2CH3; 3.47 (m) and 4.10 (m) NCH2CH3.
IR 1691 cm 1 CO ; 2223 cm'l C--C. IR 1691 cm 1 CO; 2223 cm'l C - C.
EXEMPLE 5 : (7-bromo 1-naphthalényl) méthoxy carbamate de méthyle
Stade A : 7-bromo N-hydroxy l-naphthalénamine
On agite sous atmosphère d'azote à une température inférieure à 100C, une solution renfermant 2,0 g de 7-bromo 1-nitro naphthalène dans 40 ml de tétrahydrofuranne. On ajoute 0,16 g de rhodium sur charbon. On ajoute goutte à goutte 0,96 ml d'hydrate d'hydrazine. On agite le mélange pendant 30 minutes à une température inférieure à 100C et laisse remonter la température à la température ambiante. Au bout d'une heure à la température ambiante, on filtre le mélange. On extrait à l'éther éthylique et lave les phases organiques réunies avec de l'eau. On sèche sur sulfate de sodium. On évapore le solvant. On obtient 1,9 g de produit recherché que l'on utilise tel quel dans le stade suivant.EXAMPLE 5 Methyl (7-bromo 1-naphthalenyl) methoxy carbamate
Stage A: 7-bromo N-hydroxy l-naphthalenamine
Stirred under a nitrogen atmosphere at a temperature below 100C, a solution containing 2.0 g of 7-bromo 1-nitro naphthalene in 40 ml of tetrahydrofuran. 0.16 g of rhodium is added on charcoal. 0.96 ml of hydrazine hydrate is added dropwise. The mixture is stirred for 30 minutes at a temperature below 100C and the temperature is allowed to rise to room temperature. After one hour at room temperature, the mixture is filtered. Extraction is carried out with ethyl ether and the combined organic phases are washed with water. Dried over sodium sulfate. The solvent is evaporated. 1.9 g of sought product is obtained which is used as it is in the following stage.
Stade B : (7-bromo l-naphthalényl) hydroxy carbamate de méthyle
On agite à une température inférieure à lO0C, un mélange de 1,9 g de produit obtenu au stade A, 80 ml de chlorure de méthylène, 10 ml d'eau et 1,6 g de carbonate acide de sodium.Stage B: methyl (7-bromo 1-naphthalenyl) hydroxy carbamate
A mixture of 1.9 g of product obtained in Stage A, 80 ml of methylene chloride, 10 ml of water and 1.6 g of sodium acid carbonate is stirred at a temperature below 10 ° C.
On ajoute 2,1 ml de méthyl chloroformate pendant 5 minutes.2.1 ml of methyl chloroformate are added over 5 minutes.
On agite le mélange réactionnel pendant 1 heure et demie à la température ambiante. On verse le mélange réactionnel dans l'eau et ajoute 20 ml d'acide chlorhydrique N. On extrait à l'éther éthylique et lave les phases organiques à l'eau. On sèche sur sulfate de sodium et évapore le solvant sous pression réduite. On obtient 2,2 g de produit recherché que l'on utilise tel quel dans le stade suivant.The reaction mixture is stirred for 1.5 hours at room temperature. The reaction mixture is poured into water and 20 ml of N hydrochloric acid are added. The mixture is extracted with ethyl ether and the organic phases are washed with water. It is dried over sodium sulfate and the solvent is evaporated off under reduced pressure. 2.2 g of sought product is obtained which is used as it is in the following stage.
Stade C : (7-bromo l-naphthalényl) méthoxy carbamate de méthyle
On agite sous atmosphère d'azote, à une température inférieure à 100C un mélange de 2,2 g de produit préparé au stade précédent et 40 ml de tétrahydrofuranne. On ajoute 0,37 g d'hydrure de sodium à 50 % dans l'huile, agite pendant 15 minutes, ajoute 0,8 ml d'iodure de méthyle et agite le mélange réactionnel pendant 30 minutes. On verse dans l'eau et extrait à l'éther éthylique. On lave les phases organiques à l'eau, sèche sur sulfate de magnésium et évapore le solvant sous pression réduite. On chromatographie sur silice en éluant avec le mélange heptane-acétate d'éthyle (9-1). On obient 1,2 g du produit recherché. rf = 0,5 (acétate d'éthyle-heptane 1-1) F = 129,10C. Stage C: methyl (7-bromo 1-naphthalenyl) methoxy carbamate
A mixture of 2.2 g of product prepared in the preceding stage and 40 ml of tetrahydrofuran is stirred under a nitrogen atmosphere, at a temperature below 100 ° C. 0.37 g of 50% sodium hydride in oil is added, the mixture is stirred for 15 minutes, 0.8 ml of methyl iodide is added and the reaction mixture is stirred for 30 minutes. It is poured into water and extracted with ethyl ether. The organic phases are washed with water, dried over magnesium sulfate and the solvent is evaporated off under reduced pressure. Chromatography on silica eluting with the heptane-ethyl acetate mixture (9-1). 1.2 g of the desired product are obtained. rf = 0.5 (ethyl acetate-heptane 1-1) F = 129.10C.
RMN (CDC13) 3,80 (6H,s) 2 x OMe
IR (CDC13) 1730 cm'l CO
EXEMPLE 6 : (7-(3,3-diméthyl 1-butynyl) 1-naphthalényl) méthoxy carbamate de méthyle
On agite une solution renfermant 1,2 g du produit préparé à l'exemple précédent, 5 ml de triéthylamine et 10 ml de diméthylformamide. On maintient la solution sous agitation à OOC, ajoute 0,8 ml de 3,3-diméthyl l-butyne, 0,12 g de chlorure de triphénylphosphine palladium et 0,04 g d'iodure de cuivre. On agite pendant 18 heures à 200C. On verse le mélange réactionnel dans l'eau et extrait à l'éther éthylique. On lave les phases organiques réunies à l'eau, sèche sur sulfate de magnésium et évapore le solvant. On chromatographie le résidu sur silice en éluant avec le mélange heptaneacétate d'éthyle (9-1). On isole 0,81 g de produit recherché
F = 98,40C. Rf = 0,5 (heptane-acétate d'éthyle 1-1)
RMN (CDCl3) 1,35 (9H,s) tBu ; 3,78 (3H,s) OMe ; 3,80 (3H,s) OMe.NMR (CDC13) 3.80 (6H, s) 2 x OMe
IR (CDC13) 1730 cm'l CO
EXAMPLE 6: (7- (3,3-dimethyl 1-butynyl) 1-naphthalenyl) methyl methoxy carbamate
A solution containing 1.2 g of the product prepared in the previous example, 5 ml of triethylamine and 10 ml of dimethylformamide is stirred. The solution is kept under stirring at OOC, 0.8 ml of 3,3-dimethyl 1-butyne, 0.12 g of triphenylphosphine chloride palladium and 0.04 g of copper iodide are added. The mixture is stirred for 18 hours at 200C. The reaction mixture is poured into water and extracted with ethyl ether. The combined organic phases are washed with water, dried over magnesium sulfate and the solvent is evaporated. The residue is chromatographed on silica, eluting with an ethyl heptaneacetate mixture (9-1). 0.81 g of sought product is isolated
F = 98.40C. Rf = 0.5 (heptane-ethyl acetate 1-1)
NMR (CDCl3) 1.35 (9H, s) tBu; 3.78 (3H, s) OMe; 3.80 (3H, s) OMe.
EXEMPLE 7 : méthoxy (7-(2-(triméthylsilyl) éthynyl) 1-naph thalényl) carbamate de méthyle
En opérant comme à l'exemple précédent, en utilisant le triméthylsilyle éthyne, on a obtenu le produit recherché.EXAMPLE 7 methyl methoxy (7- (2- (trimethylsilyl) ethynyl) 1-naphthalenyl) carbamate
By operating as in the previous example, using trimethylsilyl ethyne, the desired product was obtained.
F = 128,90C. F = 128.90C.
EXEMPLE 8 : (7-(2-(triméthylsilyl) éthynyl) 1-naphthalinyl) carbamate de méthyle
En opérant comme à l'exemple 1 stade B, en utilisant le triméthylsilyle éthyne, on a obtenu le produit recherché.EXAMPLE 8: (7- (2- (trimethylsilyl) ethynyl) 1-naphthalinyl) methyl carbamate
By operating as in Example 1 stage B, using trimethylsilyl ethyne, the desired product was obtained.
F = 140,70C. F = 140.70C.
EXEMPLE 9 : (2-propynyl) (7-(2-(triméthylsilyl éthynyl > 1 naphthslényl) carbamate de méthyle
On agite à -600C sous atmosphère d'azote une solution de 0,61 ml de di-isopropylamine dans 15 Ml de tétrahydrofuranne.EXAMPLE 9: methyl (2-propynyl) (7- (2- (trimethylsilyl ethynyl> 1 naphthslényl) carbamate)
A solution of 0.61 ml of di-isopropylamine in 15 ml of tetrahydrofuran is stirred at -600 ° C. under a nitrogen atmosphere.
On ajoute 3 ml de n-butyl lithium (1,6 M). On laisse remonter la température à -200C puis refroidit de nouveau le mélange à -600C et ajoute une solution comprenant 1,32 g du produit de l'exemple 8, dans 10 ml de tétrahydrofuranne. On laisse remonter la température à -300C et maintient à cette température pendant 30 minutes. On refroidit le mélange à -600C, introduit ensuite 0,50 ml de bromure de propargyle en solution toluénique à 80 %. On agite le mélange 18 heures à la température ambiante, ajoute de l'eau et extrait à l'éther éthylique. On lave les phases organiques réunies avec de l'eau. On sèche sur sulfate de sodium et on évapore le solvant. On obtient 2,0 g de solide que l'on chromatographie sur silice en éluant avec le mélange chlorure de méthylène toluène 50-50, on obtient 0,35 g de produit attendu.3 ml of n-butyl lithium (1.6 M) are added. The temperature is allowed to rise to -200C and then the mixture is again cooled to -600C and a solution comprising 1.32 g of the product of Example 8 is added in 10 ml of tetrahydrofuran. The temperature is allowed to rise to -300C and maintained at this temperature for 30 minutes. The mixture is cooled to -600C, then 0.50 ml of propargyl bromide in 80% toluene solution is introduced. The mixture is stirred for 18 hours at room temperature, water is added and the mixture is extracted with ethyl ether. The combined organic phases are washed with water. It is dried over sodium sulfate and the solvent is evaporated. 2.0 g of solid are obtained which is chromatographed on silica eluting with a methylene toluene chloride mixture 50-50, 0.35 g of expected product is obtained.
F = 138,10C. F = 138.10C.
Rf : 0,25, CH2Cl2-toluène (50-50).Rf: 0.25, CH2Cl2-toluene (50-50).
RMN (CDCl3) 0,29 (9H,s), Me3Si ; 2,27 (lH,t) H-C-C- ; 4,13 (lH,dl), 4,86 (1H,dl) -CH2-N-CO ; 3,63 (sl) - 3,70 (large) CO2Me
IR (CHCl3) 3308 cm 1 H-C--C 2153 cm'l C-C 1701 cm'l obtenu au stade B de l'exemple 1 et de l'iodure de phényl éthyle, on a obtenu le produit recherché. F = 124,90C. NMR (CDCl3) 0.29 (9H, s), Me3Si; 2.27 (1H, t) HCC-; 4.13 (1H, dl), 4.86 (1H, dl) -CH2-N-CO; 3.63 (sl) - 3.70 (wide) CO2Me
IR (CHCl3) 3308 cm 1 HC - C 2153 cm'l CC 1701 cm'l obtained in Stage B of Example 1 and phenyl ethyl iodide, the desired product was obtained. F = 124.90C.
EXEMPLE 11 : Acide 8-((méthoxycarbonyl) amino) 2-naphtha lênecarboxyl ique
On met dans un autoclave sous pression de 10 bars d'oxyde de carbone, un mélange de 40 g du produit obtenu au stade A de l'exemple 1, 1,2 g de diacétate de palladium, 3,5 g de 1,3 bis(diphényl) phosphinopropane, 55 g d'acétate de potassium et 400 ml de diméthylsulfoxyde. On agite pendant 24 heures à 20-250C. On verse le mélange réactionnel dans un litre d'eau, ajoute 20 ml d'une solution de soude à 400 g/l et un litre de chlorure de méthylène. On extrait les phases organiques à l'aide d'une solution aqueuse sodée. On acidifie les phases aqueuses à pH = 1 à l'aide d'acide chlorhydrique.EXAMPLE 11 Acid 8 - ((methoxycarbonyl) amino) 2-naphthha lenecarboxylic acid
A mixture of 40 g of the product obtained in Stage A of Example 1, 1.2 g of palladium diacetate, 3.5 g of 1.3 is placed in an autoclave under pressure of 10 bars of carbon monoxide. bis (diphenyl) phosphinopropane, 55 g of potassium acetate and 400 ml of dimethyl sulfoxide. Stir for 24 hours at 20-250C. The reaction mixture is poured into a liter of water, 20 ml of a 400 g / l sodium hydroxide solution and a liter of methylene chloride are added. The organic phases are extracted using an aqueous sodium solution. The aqueous phases are acidified to pH = 1 using hydrochloric acid.
On obtient un précipité que l'on essore et lave à l'eau. On sèche à 500C et obtient 24,5 g de produit recherché.A precipitate is obtained which is drained and washed with water. Dry at 500C and obtain 24.5 g of the desired product.
F = 2300C.F = 2300C.
EXEMPLE 12 : 8-((méthoxycarbonyl) amino) 2-naphthaléne- carboxylate de (l,1-diméthyléthyle)
On introduit à 200C, 2 g d'acide préparé à l'exemple précédent dans 30 ml d'acétate d'éthyle. On agite et introduit goutte à goutte en une heure environ 19,5 ml de O-terbutyl N,N-diisopropylurée. On agite pendant 17 heures à 20-250C, on filtre et lave à l'acétate d'éthyle. On amène le filtrat à sec, on chromatographie sur silice, en éluant avec du chlorure de méthylène. On obtient 2,49 g de produit recherché (résine).EXAMPLE 12: 8 - ((methoxycarbonyl) amino) 2-naphthalene-carboxylate of (1,1-dimethylethyl)
Is introduced at 200C, 2 g of acid prepared in the previous example in 30 ml of ethyl acetate. About 19.5 ml of O-terbutyl N, N-diisopropylurea are stirred and added dropwise over one hour. Stirred for 17 hours at 20-250C, filtered and washed with ethyl acetate. The filtrate is brought to dryness and chromatographed on silica, eluting with methylene chloride. 2.49 g of sought product (resin) is obtained.
RMN (CDCl3) 1,65 (9H,s) ; 3,84 (3H,s).NMR (CDCl3) 1.65 (9H, s); 3.84 (3H, s).
Microanalyse H % N 8 o %
Calculé 6,35 4,65 21,24
Trouvé 6,3 4,25
EXEMPLE 13 : 8-((méthoxycarbonyl) méthylamino) 2-naphthaléne- carboxylate de (1,1-diméthyléthyle)
En opérant comme à l'exemple 2, à partir du produit obtenu à l'exemple 12 et de l'iodure de méthyle, on a obtenu le produit recherché. F = 108"C. Microanalysis H% N 8 o%
Calculated 6.35 4.65 21.24
Found 6.3 4.25
EXAMPLE 13: 8 - ((methoxycarbonyl) methylamino) 2-naphthalene-carboxylate of (1,1-dimethylethyl)
By operating as in Example 2, starting from the product obtained in Example 12 and methyl iodide, the desired product was obtained. F = 108 "C.
EXEMPLE 14 : 8-((méthoxycarbonyl) (2-propynyl) amino) 2 naphthalénecarboxylate de (1,1-diméthyléthyle)
En opérant comme à l'exemple 2, à partir du produit obtenu à l'exemple 12 et du bromure de propargyle, on a obtenu le produit recherché.EXAMPLE 14: 8 - ((methoxycarbonyl) (2-propynyl) amino) 2 (1,1-dimethylethyl) naphthalenecarboxylate
By operating as in Example 2, starting from the product obtained in Example 12 and propargyl bromide, the desired product was obtained.
EXEMPLE 15 : 7-t3-(4-trifluorométhylphényl) 1,2, 4-oxadiazol- syl) naphtalène carbamate de méthyle
On introduit à 200C, 5 g du produit de l'exemple 11, dans 100 ml de chlorure de méthylène. On ajoute 1 goutte de diméthyl formamide et ensuite goutte à goutte une suspension renfermant 2 ml de chlorure d'oxalyle et 10 ml de chlorure de méthylène. On agite pendant 2 heures et amène à sec. On reprend avec du toluène et ajoute 4,3 g de 4-trifluorométhylbenzamidoxime et 3,5 ml de triéthylamine. On agite pendant 2 heures à 200C et porte au reflux pendant 17 heures. On amène à sec, reprend le résidu avec du méthanol, essore et lave les cristaux obtenus. On sèche et obtient 5,85 g du produit recherché, fondant à 2400C.EXAMPLE 15: 7-t3- (4-trifluoromethylphenyl) 1,2,4-oxadiazol-syl) methyl naphthalene carbamate
5 g of the product of Example 11 are introduced at 200 ° C. into 100 ml of methylene chloride. 1 drop of dimethyl formamide is added and then dropwise a suspension containing 2 ml of oxalyl chloride and 10 ml of methylene chloride. The mixture is stirred for 2 hours and brought to dryness. The residue is taken up in toluene and 4.3 g of 4-trifluoromethylbenzamidoxime and 3.5 ml of triethylamine are added. Stirred for 2 hours at 200C and brought to reflux for 17 hours. It is brought to dryness, the residue is taken up with methanol, drained and washed the crystals obtained. Dried and obtained 5.85 g of the desired product, melting at 2400C.
En opérant comme précédemment, en utilisant au départ le composé de l'exemple 15, on a obtenu les produits suivants
EXEMPLE 16 : [7-[3-(4-trifluorométhylphényl) 1,2, 4-oxadiazol- 5yl] 1-naphtalényl] méthyl carbamate de méthyle F = 1590C. By operating as above, initially using the compound of Example 15, the following products were obtained
EXAMPLE 16: [7- [3- (4-trifluoromethylphenyl) 1,2,4-oxadiazol-5yl] 1-naphthalenyl] methyl methyl carbamate F = 1590C.
EXEMPLE 17 : [7-[3-(4-trifluorométhylphényl) 1,2,4-oxadiazol 5yl] 1-naphtalényl] éthyl carbamate de méthyle F = 1520C. EXAMPLE 17: [7- [3- (4-trifluoromethylphenyl) 1,2,4-oxadiazol 5yl] 1-naphthalenyl] ethyl methyl carbamate F = 1520C.
EXEMPLE 18 : [7-[3-(4-trifluorométhylphenyl) 1,2,4-oxadiazol Syl] 1-naphtalényl] propargyl carbamate de méthyle F = 1280C. EXAMPLE 18 Methyl [7- [3- (4-trifluoromethylphenyl) 1,2,4-oxadiazol Syl] 1-naphthalenyl] propargyl carbamate F = 1280C.
En opérant comme à l'exemple 15, en utilisant au départ le composé de l'exemple 11 et le 4-chlorobenzamidoxime, on a préparé le produit suivant
EXEMPLE 19 : t7-t(3-(4-chlorophényl) 1,2,4-oxadiazol-5yl] 1naphtalène] carbamate de méthyle
F = 2410C.By operating as in Example 15, initially using the compound of Example 11 and 4-chlorobenzamidoxime, the following product was prepared
EXAMPLE 19: t7-t (3- (4-chlorophenyl) 1,2,4-oxadiazol-5yl] 1naphthalene] methyl carbamate
F = 2410C.
En opérant comme précédemment, en utilisant au départ le composé de l'exemple 19, on a obtenu les produits suivants
EXEMPLE 20 : [7-[3-(4-chlorophényl) 1,2,4-oxadiazol-5yll 1 naphtalényl] méthyl carbamate de méthyle F = 1820C. By operating as above, initially using the compound of Example 19, the following products were obtained
EXAMPLE 20: [7- [3- (4-chlorophenyl) 1,2,4-oxadiazol-5yll 1 naphthalenyl] methyl methyl carbamate F = 1820C.
EXEMPLE 21 : t7-t3-(4-chlorophényl) 1,2,4-oxadiazol-5yl 1 naphtAlenyl] propargyl] carbamate de méthyle F = 1430C. EXAMPLE 21: t7-t3- (4-chlorophenyl) 1,2,4-oxadiazol-5yl 1 methyl naphtAlenyl] propargyl] carbamate F = 1430C.
EXEMPLE 22 : t7-t3-(4-chlorophényl) 1,2,4-oxadiazol-5yl 1 naphtalenyl] éthyl) carbamate de méthyle F = 1650C. EXAMPLE 22: t7-t3- (4-chlorophenyl) 1,2,4-oxadiazol-5yl 1 naphthalenyl] ethyl) methyl carbamate F = 1650C.
Etude de l'activité des composés de l'invention - Etude de l'activité acaricide sur Tetranychus Urticae
On utilise des plants de haricot comportant 2 feuilles infestées de 30 femelles de Tetranychus Urticae par feuille et mis sous bonette aérée sous plafond lumineux en lumière constante. Les plants sont traités au pistolet Fisher : 4 ml de solution toxique par plant d'un mélange à volume égal d'eau et d'acétone. On laisse sécher pendant une 1/2 heure puis on procède à l'infestation. Les contrôles de mortalité sont effectués au bout de 3 jours.Study of the activity of the compounds of the invention - Study of the acaricidal activity on Tetranychus Urticae
Bean plants are used comprising 2 leaves infested with 30 females of Tetranychus Urticae per leaf and placed under an airy candy box under a bright ceiling in constant light. The plants are treated with a Fisher spray gun: 4 ml of toxic solution per plant of a mixture with equal volume of water and acetone. Leave to dry for 1/2 hour and then proceed with the infestation. Mortality checks are carried out after 3 days.
Résultats : Dès la dose de 100 ppm, les produits de l'invention présentent une activité acaricide intéressante.Results: From the dose of 100 ppm, the products of the invention exhibit an advantageous acaricidal activity.
- Etude de l'activité fongicide sur Phytophtora infestans (PI), Plasmora viticola (PV), Erysiphe graminis (EG), Pyricularia oryzae (PO), Pellicularia sasakii, Botrytis cinerea (BC), Venturia inaequalis (VI) et Leptosphaeria nodorum (LN). - Study of the fungicidal activity on Phytophtora infestans (PI), Plasmora viticola (PV), Erysiphe graminis (EG), Pyricularia oryzae (PO), Pellicularia sasakii, Botrytis cinerea (BC), Venturia inaequalis (VI) and Leptosphaeria nodorum ( LN).
On applique sur des plantes tests, par pulvérisation ou par trempage de la base de la tige, des solutions ou des suspensions aqueuses des composés de l'invention, à des concentrations appropriées, comprenant en outre un agent mouillant. Les plantes ou parties de plantes sont ensuite traitées avec l'agent pathogène désiré et conservées ensuite dans un environnement contrôlé, dans des conditions permettant de maintenir la croissance de la plante et le développement de la maladie. Aqueous solutions or suspensions of the compounds of the invention are applied to test plants, by spraying or by soaking the base of the stem, at appropriate concentrations, further comprising a wetting agent. The plants or parts of plants are then treated with the desired pathogen and then stored in a controlled environment, under conditions which allow the growth of the plant and the development of the disease to be maintained.
Le degré d'efficacité des produits est évalué par rapport à un témoin non traité infesté. A une concentration inférieure ou égale à 500 ppm, les composés de l'invention présentent une très bonne activité. The degree of efficacy of the products is evaluated compared to an infested untreated control. At a concentration less than or equal to 500 ppm, the compounds of the invention exhibit very good activity.
Claims (24)
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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FR9512331A FR2740133A1 (en) | 1995-10-20 | 1995-10-20 | NOVEL N-NAPHTYL CARBAMATES, THEIR PREPARATION PROCESS AND THEIR APPLICATION AS PESTICIDES |
AU73115/96A AU7311596A (en) | 1995-10-20 | 1996-10-18 | N-naphthylcarbamates and their use as pesticides |
PCT/GB1996/002534 WO1997014675A1 (en) | 1995-10-20 | 1996-10-18 | N-naphthylcarbamates and their use as pesticides |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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FR9512331A FR2740133A1 (en) | 1995-10-20 | 1995-10-20 | NOVEL N-NAPHTYL CARBAMATES, THEIR PREPARATION PROCESS AND THEIR APPLICATION AS PESTICIDES |
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FR2740133A1 true FR2740133A1 (en) | 1997-04-25 |
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FR9512331A Pending FR2740133A1 (en) | 1995-10-20 | 1995-10-20 | NOVEL N-NAPHTYL CARBAMATES, THEIR PREPARATION PROCESS AND THEIR APPLICATION AS PESTICIDES |
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AU (1) | AU7311596A (en) |
FR (1) | FR2740133A1 (en) |
WO (1) | WO1997014675A1 (en) |
Citations (6)
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DE963427C (en) * | 1952-12-17 | 1957-05-09 | Cassella Farbwerke Mainkur Ag | Process for the production of new anesthetically acting aminocarboxamides |
US4568684A (en) * | 1981-07-02 | 1986-02-04 | Basf Aktiengesellschaft | N-Substituted 2-methylnaphthylamides, their preparation, and fungicides containing these compounds |
JPH0262853A (en) * | 1988-08-27 | 1990-03-02 | Nippon Oil & Fats Co Ltd | Fluorine-containing acid amide derivative and production thereof |
DE3837500A1 (en) * | 1988-11-04 | 1990-05-23 | Hoechst Ag | NEW RADIATION-SENSITIVE COMPOUNDS, MADE BY THIS RADIATION-SENSITIVE MIXTURE AND RECORDING MATERIAL |
DE4026544A1 (en) * | 1989-08-22 | 1991-02-28 | Fuji Photo Film Co Ltd | Light sensitive compsn. contg. -imino-diazo-quinone n-sulphonyl cpd. - and alkali-soluble polymer of positive type useful as resist |
EP0661261A1 (en) * | 1994-01-03 | 1995-07-05 | Bristol-Myers Squibb Company | Phenyl or phenylalkyl substituted naphtalene derivatives having retinoid-like activity as well as anti-tumor activities |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
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MY110439A (en) * | 1991-02-07 | 1998-05-30 | Ishihara Sangyo Kaisha | N-phenylcarbamate compound, process for preparing the same and biocidal composition for control of harmful organisms |
FR2689886B1 (en) * | 1992-04-14 | 1995-08-18 | Roussel Uclaf | NOVEL DERIVATIVES OF A-7-ETHYNYL ALPHA- (METHOXYMETHYLENE) 1-NAPHTHALENE ACID, THEIR PREPARATION PROCESS AND THEIR APPLICATION AS PESTICIDES. |
-
1995
- 1995-10-20 FR FR9512331A patent/FR2740133A1/en active Pending
-
1996
- 1996-10-18 AU AU73115/96A patent/AU7311596A/en not_active Abandoned
- 1996-10-18 WO PCT/GB1996/002534 patent/WO1997014675A1/en active Application Filing
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DE963427C (en) * | 1952-12-17 | 1957-05-09 | Cassella Farbwerke Mainkur Ag | Process for the production of new anesthetically acting aminocarboxamides |
US4568684A (en) * | 1981-07-02 | 1986-02-04 | Basf Aktiengesellschaft | N-Substituted 2-methylnaphthylamides, their preparation, and fungicides containing these compounds |
JPH0262853A (en) * | 1988-08-27 | 1990-03-02 | Nippon Oil & Fats Co Ltd | Fluorine-containing acid amide derivative and production thereof |
DE3837500A1 (en) * | 1988-11-04 | 1990-05-23 | Hoechst Ag | NEW RADIATION-SENSITIVE COMPOUNDS, MADE BY THIS RADIATION-SENSITIVE MIXTURE AND RECORDING MATERIAL |
DE4026544A1 (en) * | 1989-08-22 | 1991-02-28 | Fuji Photo Film Co Ltd | Light sensitive compsn. contg. -imino-diazo-quinone n-sulphonyl cpd. - and alkali-soluble polymer of positive type useful as resist |
EP0661261A1 (en) * | 1994-01-03 | 1995-07-05 | Bristol-Myers Squibb Company | Phenyl or phenylalkyl substituted naphtalene derivatives having retinoid-like activity as well as anti-tumor activities |
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CHEMICAL ABSTRACTS, vol. 87, no. 13, 26 September 1977, Columbus, Ohio, US; abstract no. 102512, GOMEZ PARRA, VICENTE: "Synthesis of azasteroids" XP002006722 * |
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WO1997014675A1 (en) | 1997-04-24 |
AU7311596A (en) | 1997-05-07 |
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