NO149385B - 1-PHENYL-CYCLOBUTANE CARBOXYLATE COMPOUNDS WITH EFFECTS ON INSECTS (INSECTA) AND SPIDER ANIMALS (ARACHNIDA) - Google Patents
1-PHENYL-CYCLOBUTANE CARBOXYLATE COMPOUNDS WITH EFFECTS ON INSECTS (INSECTA) AND SPIDER ANIMALS (ARACHNIDA) Download PDFInfo
- Publication number
- NO149385B NO149385B NO784246A NO784246A NO149385B NO 149385 B NO149385 B NO 149385B NO 784246 A NO784246 A NO 784246A NO 784246 A NO784246 A NO 784246A NO 149385 B NO149385 B NO 149385B
- Authority
- NO
- Norway
- Prior art keywords
- compounds
- stated
- phenyl
- phenoxybenzyl
- carboxylate
- Prior art date
Links
- 241000238631 Hexapoda Species 0.000 title claims description 8
- 241000239223 Arachnida Species 0.000 title claims description 6
- 241000500891 Insecta Species 0.000 title claims description 4
- 230000000694 effects Effects 0.000 title claims description 4
- JHZRNLRTNIDFKG-UHFFFAOYSA-N 1-phenylcyclobutane-1-carboxylic acid Chemical class C=1C=CC=CC=1C1(C(=O)O)CCC1 JHZRNLRTNIDFKG-UHFFFAOYSA-N 0.000 title claims description 3
- 241000239290 Araneae Species 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 45
- 229910052739 hydrogen Inorganic materials 0.000 claims description 33
- 229910052731 fluorine Inorganic materials 0.000 claims description 18
- 239000000460 chlorine Substances 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- -1 methylenedioxy group Chemical group 0.000 claims description 13
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims 4
- XEHVFKKSDRMODV-UHFFFAOYSA-N ethynyl Chemical compound C#[C] XEHVFKKSDRMODV-UHFFFAOYSA-N 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 83
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 27
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- 241000255925 Diptera Species 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 20
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
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- WABPPBHOPMUJHV-UHFFFAOYSA-N Sesamex Chemical compound CCOCCOCCOC(C)OC1=CC=C2OCOC2=C1 WABPPBHOPMUJHV-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
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- 238000002474 experimental method Methods 0.000 description 3
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- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 2
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- XYSRHOKREWGGFE-UHFFFAOYSA-N 1-(4-chlorophenyl)cyclobutane-1-carboxylic acid Chemical compound C=1C=C(Cl)C=CC=1C1(C(=O)O)CCC1 XYSRHOKREWGGFE-UHFFFAOYSA-N 0.000 description 2
- GIODGGUATRIZGS-UHFFFAOYSA-N 1-(4-ethoxyphenyl)-2,2,3,3-tetrafluorocyclobutane-1-carboxylic acid Chemical compound C1=CC(OCC)=CC=C1C1(C(O)=O)C(F)(F)C(F)(F)C1 GIODGGUATRIZGS-UHFFFAOYSA-N 0.000 description 2
- NRADNMCTIXLUCF-UHFFFAOYSA-N 1-(4-ethoxyphenyl)cyclobutane-1-carboxylic acid Chemical compound C1=CC(OCC)=CC=C1C1(C(O)=O)CCC1 NRADNMCTIXLUCF-UHFFFAOYSA-N 0.000 description 2
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- TXWOGHSRPAYOML-UHFFFAOYSA-M cyclobutanecarboxylate Chemical compound [O-]C(=O)C1CCC1 TXWOGHSRPAYOML-UHFFFAOYSA-M 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
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- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical class OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
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- ZKLVHUGMBFBAFN-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2,2,3,3-tetrafluorocyclobutane-1-carboxylic acid Chemical compound C=1C=C2OCOC2=CC=1C1(C(=O)O)CC(F)(F)C1(F)F ZKLVHUGMBFBAFN-UHFFFAOYSA-N 0.000 description 1
- BHKKSKOHRFHHIN-MRVPVSSYSA-N 1-[[2-[(1R)-1-aminoethyl]-4-chlorophenyl]methyl]-2-sulfanylidene-5H-pyrrolo[3,2-d]pyrimidin-4-one Chemical compound N[C@H](C)C1=C(CN2C(NC(C3=C2C=CN3)=O)=S)C=CC(=C1)Cl BHKKSKOHRFHHIN-MRVPVSSYSA-N 0.000 description 1
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- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
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- 239000000077 insect repellent Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 231100000225 lethality Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003228 microsomal effect Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- XVDBWWRIXBMVJV-UHFFFAOYSA-N n-[bis(dimethylamino)phosphanyl]-n-methylmethanamine Chemical compound CN(C)P(N(C)C)N(C)C XVDBWWRIXBMVJV-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 description 1
- VJFUPGQZSXIULQ-XIGJTORUSA-N pyrethrin II Chemical compound CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VJFUPGQZSXIULQ-XIGJTORUSA-N 0.000 description 1
- 229940015367 pyrethrum Drugs 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 238000000611 regression analysis Methods 0.000 description 1
- 229940080817 rotenone Drugs 0.000 description 1
- JUVIOZPCNVVQFO-UHFFFAOYSA-N rotenone Natural products O1C2=C3CC(C(C)=C)OC3=CC=C2C(=O)C2C1COC1=C2C=C(OC)C(OC)=C1 JUVIOZPCNVVQFO-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
Foreliggende oppfinnelse vedrører 1-fenyl-cyklobutan-karboksylatforbindelser med virkning mot insekter (Insecta) The present invention relates to 1-phenyl-cyclobutane-carboxylate compounds with action against insects (Insecta)
og edderkoppdyr (Arachnida), og det særegne ved forbindels- and arachnids (Arachnida), and the peculiarity of connecting
ene i henhold til oppfinnelsen er at de har den generelle formel (1) one according to the invention is that they have the general formula (1)
hvori R<1> er lavere alkoksy, tetrafluoretoksy, fluor, klor wherein R<1> is lower alkoxy, tetrafluoroethoxy, fluorine, chlorine
2 12 2 12
eller brom, R er hydrogen eller R og R danner sammen en metylendioksy-gruppe, R er en av følgende grupper (a) til or bromine, R is hydrogen or R and R together form a methylenedioxy group, R is one of the following groups (a) to
(f) (f)
hvori <y>\ Y^, Y^, Y^, Y^ og Y^ er like eller forskjellige og hver står for hydrogen eller fluor, brom eller klor, med den betingelse at når R er fluor, klor eller brom har minst en av Y 1 - Y 6 en annen betydning enn hydrogen. wherein <y>\ Y^, Y^, Y^, Y^ and Y^ are the same or different and each represents hydrogen or fluorine, bromine or chlorine, with the proviso that when R is fluorine, chlorine or bromine has at least one of Y 1 - Y 6 a meaning other than hydrogen.
Betegnelsene "Insecta" og "Arachnida" referer seg til de systematiske klassebetegnelser for ledd-dyr. Den i det følgende anvendte betegnelse "insekticid" og "insecticid virkning" refererer til virking overfor disse klasser av ledd-dyr. Det er ved forsøk konstatert at forbindelsene av formel (I) er aktive overfor midd. The terms "Insecta" and "Arachnida" refer to the systematic class designations for arthropods. The terms "insecticide" and "insecticide action" used in the following refer to action against these classes of arthropods. It has been established by experiment that the compounds of formula (I) are active against mites.
Kjente forbindelser som kan betraktes som beslektet med forbindelsene med formel I er dem hvori gruppene (a) til (f) er tilstede som forestrende grupper med chrysantemsyre i kommersielle eller eksperimentelle pyrethroider. DE-A-2.653.189 beskriver en lignende klasse av estere. Known compounds which may be considered related to the compounds of formula I are those in which the groups (a) to (f) are present as esterifying groups with chrysanthemic acid in commercial or experimental pyrethroids. DE-A-2,653,189 describes a similar class of esters.
DE-0-2.733.746 beskriver forbindelser med formel I hvori DE-0-2,733,746 describes compounds of formula I in which
16 12 16 12
alle grupper Y til Y er hydrogen, R og R er hver hydrogen, eller fluor, klor, brom eller metyl og R<3> er en av gruppene (a), (c) og (e) ovenfor. Disse forbindelser omfattes ikke av den foreliggende oppfinnelse. 1 2 Foretrukket er R etoksy eller propoksy og R er hydrogen. Forbindelser hvori R 1 og R 2 danner metylendioksygruppen er også foretrukket. all groups Y to Y are hydrogen, R and R are each hydrogen, or fluoro, chloro, bromo or methyl and R<3> is one of groups (a), (c) and (e) above. These compounds are not covered by the present invention. 1 2 Preferably, R is ethoxy or propoxy and R is hydrogen. Compounds in which R 1 and R 2 form the methylenedioxy group are also preferred.
Foretrukket er også R 3en av gruppene (a), (c) og (e) som definert ovenfor-. Also preferred is R 3 of the groups (a), (c) and (e) as defined above-.
Det foretrekkes også at fra en til alle seks av gruppene It is also preferred that from one to all six of the groups
Y 1 til Y 6 er en fluorgruppe idet eventuell resterende gruppe er hydrogen. Tetrafluor-substituering (Y 1 , Y 2, Y 1 to Y 6 is a fluorine group, with any remaining group being hydrogen. Tetrafluoro substitution (Y 1 , Y 2 ,
Y<3>, Y<4> = F; Y<5>, Y<6> = H) foretrekkes spesielt. Y<3>, Y<4> = F; Y<5>, Y<6> = H) is particularly preferred.
Spesielt foretrukne forbindelser i samsvar med oppfinnelsen er'følgende: 3<1->fenpksybenzyl-1-(3,4-metylendioksyfenyl)-2,2,3,3-tetra-f luorcyklobutankarboksylat og dets Ok-cyan og o(-etynyl-derivater: 3<1->fenoksybenzyl-1-(4-etoksyfenyl)-2,2,3,3-tetrafluor-cyklobutankarboksylat og dets ct -cyan og 0^ -etynyl-derivater. Particularly preferred compounds in accordance with the invention are the following: 3<1->phenoxybenzyl-1-(3,4-methylenedioxyphenyl)-2,2,3,3-tetrafluorocyclobutanecarboxylate and its O-cyan and o(-ethynyl -derivatives: 3<1->phenoxybenzyl-1-(4-ethoxyphenyl)-2,2,3,3-tetrafluorocyclobutanecarboxylate and its ct -cyan and 0^ -ethynyl derivatives.
3 3
Forbindelsene med formel I hvori R er en av gruppene The compounds of formula I in which R is one of the groups
(a) til (f) er ytterst aktive som insekticider, med en insekticid aktivitet av størrelsesorden større enn de fleste kjente insekticider. Visse forbindelser har også egenskapen med kontakt-avstøtning overfor insekter. Forbindelsene i henhold til oppfinnelsen er generelt mer aktive overfor fluer enn forbindelsene i henhold til ovennevnte DE-A-2.653.189. (a) to (f) are extremely active as insecticides, with an insecticidal activity of an order of magnitude greater than most known insecticides. Certain compounds also have the property of contact repellency towards insects. The compounds according to the invention are generally more active against flies than the compounds according to the above-mentioned DE-A-2,653,189.
Forbindelsene med formel I er optisk aktive og kan oppdeles i deres optiske isomerer ved konvensjonelle metoder. Oppfinnelsen omfatter således de individuelle (+) og (-) optiske isomerer av forbindelsene såvel som deres racemiske The compounds of formula I are optically active and can be resolved into their optical isomers by conventional methods. The invention thus encompasses the individual (+) and (-) optical isomers of the compounds as well as their racemics
(-) former^(-) forms^
Det bemerkes også at de insekticide virkninger av optiske isomerer av forbindelsen I med R = (a) til (f) kan være forskjellige med en størrelsesorden eller mer. It is also noted that the insecticidal activities of optical isomers of compound I with R = (a) to (f) may differ by an order of magnitude or more.
De forbindelser I hvori R er en av gruppene (a) til (f) kan fremstilles ved forestring av den fri syre (formel I, The compounds I in which R is one of the groups (a) to (f) can be prepared by esterification of the free acid (formula I,
3 - 3 3 3 - 3 3
R ' = H) med den passende alkohol R OH, hvori R er en av gruppene (a) til (f). Denne forestring kan gjennomførés ved hvilken som helst passende kjent metode f.eks. ved direkte reaksjon eller ved foregående omdannelse av.syren og/eller alkoholen til et passende reaktivt derivat, eller ved en omestrinsreaksjon mellom alkoholen R 3 OH (R 3 = (a) til (f) ) og en lavere alkylester av syren. R' = H) with the appropriate alcohol R OH, wherein R is one of the groups (a) to (f). This esterification can be carried out by any suitable known method, e.g. by direct reaction or by previous conversion of the acid and/or alcohol into a suitable reactive derivative, or by an omestrin reaction between the alcohol R 3 OH (R 3 = (a) to (f) ) and a lower alkyl ester of the acid.
Syren (formel I, R 3 = H) fremstilles ved reaksjon mellom en passende substituert benzylforbindelse og et passende substituert 1,3-dihalogenpropan til å danne en 1-fenyl-cyklobutanforbindelse som kan hydrolyseres til syren. Dette reaksjonsskjerna er som følger: The acid (formula I, R 3 = H) is prepared by reaction between an appropriately substituted benzyl compound and an appropriately substituted 1,3-dihalopropane to form a 1-phenyl-cyclobutane compound which can be hydrolyzed to the acid. This reaction core is as follows:
Z representerer en gruppe som aktiverer benzylmetylenet og selv senere kan hydrolyseres til en karboksylgruppe, f.eks. -C=N 12 12 eller -COOEt; X står for klor, brom eller jod; R , R , Y , Y , Y<3>, Y^, Y~* og Y^ er som ovenfor definert. En alternativ fremstillingsmåte for syren (formel I, R 3=H) som 12 3 4 sin lavere alkylester er ved addering av olefinet Y Y C=CY Y til den substituerte fenylakrylester med formel II Z represents a group that activates the benzyl methylene and itself can later be hydrolyzed to a carboxyl group, e.g. -C=N 12 12 or -COOEt; X stands for chlorine, bromine or iodine; R , R , Y , Y , Y<3>, Y^, Y~* and Y^ are defined as above. An alternative preparation method for the acid (formula I, R 3=H) as 12 3 4's lower alkyl ester is by adding the olefin Y Y C=CY Y to the substituted phenyl acrylic ester of formula II
hvori R er' en lavere alkylgruppe og R1, R2, Y<1>, Y<2>, Y<3>, Y4, Y<5 >og Y^ har den ovennevnte betydning. wherein R is a lower alkyl group and R1, R2, Y<1>, Y<2>, Y<3>, Y4, Y<5> and Y^ have the above meaning.
Estere med formel I (R<3>= lavere alkyl) hvori Y<3>=Y<4>=F og Esters of formula I (R<3>= lower alkyl) in which Y<3>=Y<4>=F and
12 5 6 12 5 6
Y =Y =Y =Y =H kan fremstilles ved forst og fremstille Y =Y =Y =Y =H can be produced by first and produce
3 4 12 3 4 12
forbindelsene hvori Y =Y =F, Y =Y =C1 i samsvar med den foregående metode (under anvendelse av diklordifluoretylen) og etterfølgende hydrogenering av produktet til å erstatte klor-gruppene med hydrogen. the compounds in which Y =Y =F, Y =Y =C1 in accordance with the preceding method (using dichlorodifluoroethylene) and subsequent hydrogenation of the product to replace the chlorine groups with hydrogen.
De estere II hvori Y^=Y^=H kan fremstilles ved hjelp av folgende generelle metoder: (1) En lavere alkylester av den passende substituerte fenyl-eddiksyre (V) kondenseres med et dilavere alkyloksalat i nærvær av et basisk katalysator til å fremstille enolatsaltet (IV). (2) Opplosningen av enolatsaltet surgjores til å gi det tilsvarende fenyloksaloacetat (III). (3) Forbindelsen III omsettes med formaldehyd under alkaliske betingelser til å gi fenyl-hydroksymetylacetatet som ved dehydratisering (ekelte ganger spontant) gir fenylakrylesteren (II). The esters II in which Y^=Y^=H can be prepared by the following general methods: (1) A lower alkyl ester of the appropriately substituted phenylacetic acid (V) is condensed with a dilower alkyl oxalate in the presence of a basic catalyst to prepare the enolate salt (IV). (2) The solution of the enolate salt is acidified to give the corresponding phenyl oxaloacetate (III). (3) The compound III is reacted with formaldehyde under alkaline conditions to give the phenyl-hydroxymethyl acetate which on dehydration (sometimes spontaneously) gives the phenyl acrylic ester (II).
Dette reaksjonsforlop illustreres i det etterfolgende totale reaksjonsskjema. Det er klart at de spesifikke syrer og baser som angitt kan erstattes med andre passende forbindelser. Også lavere alkylestere andre enn etylesteréne som vist.kan.anvendes. This reaction sequence is illustrated in the following overall reaction scheme. It will be understood that the specific acids and bases indicated may be replaced by other suitable compounds. Lower alkyl esters other than the ethyl esters as shown can also be used.
Når Y 5 =Y 6=F kan esterne II fremstilles ved hjelp av metoden beskrevet av D.G. Naae og D.J. Burton, Synthetic Communications, 3, 197-200 (1973). I denne metode omsettes den passende f enyl-ke j:o-ester med formel VI med dibromdifluormetan (CBr2F2 ) i nærvær av 2 mol tris (dimetylamino)fosfin og et passende løsningsmiddel som f.eks. diglym eller triglym When Y 5 =Y 6 =F, the esters II can be prepared using the method described by D.G. Naae and D.J. Burton, Synthetic Communications, 3, 197-200 (1973). In this method, the appropriate phenyl j:o ester of formula VI is reacted with dibromodifluoromethane (CBr 2 F 2 ) in the presence of 2 mol of tris (dimethylamino)phosphine and a suitable solvent such as e.g. diglyme or triglyme
hvori Ph har den ovennevnte betydning og R er en lavere alkylgruppe. wherein Ph has the above meaning and R is a lower alkyl group.
Den generelle metode til dannelse av esterne i henhold til oppfinnelsen er som folger: "hvori A er The general method of forming the esters according to the invention is as follows: "where A is
Hvori R1, R<2>, Y<1>, Y<2>, Y<3>, Y<4>, Y5 og Y6 har den ovennevnte betydning og R 3er en av gruppene (a) til (f) angitt ovenfor. Wherein R1, R<2>, Y<1>, Y<2>, Y<3>, Y<4>, Y5 and Y6 have the above meaning and R 3 is one of the groups (a) to (f) set forth above .
Alternativt kan etylesteren omdannes direkte som folger: Alternatively, the ethyl ester can be converted directly as follows:
De nye forbindelser beskrevet heri kan opploses i passende organisk løsningsmiddel, eller en blanding av løsningsmidler, til å danne oppløsninger eller bringes i vandig suspensjon ved å dispergere organiske losningsmiddellosninger av forbindelsene i vann, til å gi nyttige flytende blandinger, som f.eks. kan innlemmes i dispersjoner av aerosoltypen med de vanlige aerosol-drivmidler. The novel compounds described herein can be dissolved in a suitable organic solvent, or a mixture of solvents, to form solutions or brought into aqueous suspension by dispersing organic solvent solutions of the compounds in water, to give useful liquid compositions, such as can be incorporated into dispersions of the aerosol type with the usual aerosol propellants.
Forbindelsene kan også innblandes i faste preparater som kan omfatte inerte faste fortynningsmidler eller bærere, til å danne nyttige faste preparater. Slike blandinger kan også omfatte andre substanser som f.eks. fuktemidler, dispergeringsmidler eller klebemidler, og kan framstilles i granulerte eller andre former til å tilveiebringe sakte., frigivelse av forbindelsene over et forlenget tidsroiru Forbindelsene kan anvendes i slike preparater enten som det eneste giftige middel eller i kombinasjon med andre insekticider, som f.eks. pyretrum, rotenon, eller med fungicide eller baktericide midler, til å gi preparater nyttige for husholdnings- og landbruks-forstovnings-preparater og sprøytemidler, tekstilbeleggings- og impregnerings-midler,.og lignende.. The compounds may also be incorporated into solid preparations which may include inert solid diluents or carriers, to form useful solid preparations. Such mixtures can also include other substances such as e.g. wetting agents, dispersing agents or adhesives, and may be prepared in granular or other forms to provide slow release of the compounds over an extended period of time. The compounds may be used in such preparations either as the sole toxic agent or in combination with other insecticides, such as . pyrethrum, rotenone, or with fungicidal or bactericidal agents, to provide preparations useful for household and agricultural dusting preparations and pesticides, textile coating and impregnation agents, and the like..
Spesielt .kan Ae nye forbindelser fordelaktig kombineres med andre substanser som har en synergistisk eller potensierende virkning.. Generelt er slike.substanser av-klassen av mikro-somale oks/daseinhibitorer, dvs. de hindrer avgiftningen av insekticidene i insekter frembragt ved innvirkningen av oksyda-tive enzymer.. Typiske substanser av denne type er pyretrin-synergistene hvorav de følgende er. eksempler: In particular, Ae new compounds can advantageously be combined with other substances that have a synergistic or potentiating effect. In general, such substances are of the class of microsomal ox/dase inhibitors, i.e. they prevent the detoxification of the insecticides in insects produced by the action of oxida -tive enzymes.. Typical substances of this type are the pyrethrin synergists of which the following are. examples:
("Sesoxane", "Sesamex" og "Sulphoxide" er yaremerkebetegnelser)... ("Sesoxane", "Sesamex" and "Sulphoxide" are brand names)...
Det er funnet at "Sesoxane" (fremstilt av Shulton Inc., Clifton, N.J., USA) er spesielt brukbar som potensiator. Mengden av "Sesoxane" som anvendes kan variere fra 1/1000 til den femdobbelte vekt av forbindelsen I idet det foretrukne område, er fra 1/100 til like vektdeler. Piperpnyl-butoksyd er også en nyttig potensiator i lignende mengder.. "Sesoxane" (manufactured by Shulton Inc., Clifton, N.J., USA) has been found to be particularly useful as a potentiator. The amount of "Sesoxane" used can vary from 1/1000 to five times the weight of compound I, the preferred range being from 1/100 to equal parts by weight. Piperpnyl butoxide is also a useful potentiator in similar amounts.
Fremstillingen og egenskapene .av forbindelsene i henhold til oppfinnelsen illustreres ved hjelp av de folgende spesifikke eksempler.. The production and properties of the compounds according to the invention are illustrated by means of the following specific examples.
EKSEMPEL 1 (Sammenligningseksempel) EXAMPLE 1 (Comparison example)
(a) 1-( 4- klorfenyl) cyklobutan- nitril (a) 1-(4-Chlorophenyl)cyclobutanenitrile
4-klorbenzyl-cyanid (10 g).i torr DMSO (20 ml) ble tilsatt .i lopet av 5 min. til en omrort suspensjon av natriumhydrid (4,4 g) i DMSO ved 25°C under argon. Blandingen ble omrort i-.. 4-chlorobenzyl cyanide (10 g) in dry DMSO (20 ml) was added over 5 min. to a stirred suspension of sodium hydride (4.4 g) in DMSO at 25°C under argon. The mixture was stirred in-..
30 min. og deretter ble en lpsning av .1,3-dibrompropan (27 g) i torr DMSO (50 ml) tilsatt i lopet av 30 min. mens temperaturen i reaksjonsblandingen ble holdt ved 25 - 30°C. Etter omroring 30 min. and then a solution of .1,3-dibromopropane (27 g) in dry DMSO (50 ml) was added over the course of 30 min. while the temperature of the reaction mixture was maintained at 25 - 30°C. After stirring
ytterligere 40 min. ved denne temperatur ble reaksjonsblandingen tilsatt til isblandet vann (500 ml) og ekstrahert med diklormetan (3 x 75 ml). Ekstraktene ble inndampet og resten ekstrahert med dietyleter (4 x 50 ml). De andre ekstrakter ble vasket med vann, torket over vannfritt natriumsulfat og inndampet til å gi en olje (10,8 g) som ved destillasjon ga nitrilet (kokepunkt 90°C/ 10~<6> Torr ) Utbytte 5,4 g (43%). another 40 min. at this temperature the reaction mixture was added to ice-water (500 ml) and extracted with dichloromethane (3 x 75 ml). The extracts were evaporated and the residue extracted with diethyl ether (4 x 50 ml). The other extracts were washed with water, dried over anhydrous sodium sulfate and evaporated to give an oil (10.8 g) which on distillation gave the nitrile (boiling point 90°C/ 10~<6> Torr ) Yield 5.4 g (43 %).
Analyse: C 68,48%, H 5,49%, Cl 18,3%, C^H^Cl N Analysis: C 68.48%, H 5.49%, Cl 18.3%, C^H^Cl N
krever teoretisk: C 68,93%, H 5,25%, Cl 18,5%. theoretically requires: C 68.93%, H 5.25%, Cl 18.5%.
(b) 1-( 4- klorfenyl) cyklobutan- karboksylsyre (b) 1-(4-Chlorophenyl)cyclobutanecarboxylic acid
1-(4-klorfenyl)cyklobutan-nitril (5 g) ble blandet med etylen-glykol (60 ml) og 40% vekt/vekt vandig kaliumhydroksydlosning (80 ml) og kokt under argon i 18 timer. Blandingen ble avkjolt, tilsatt til isblandet vann og ekstrahert med dietyl-eter. Det vandige lag ble surgjort og bunnfallet ble frafiltrert, vasket med vann, torket og omkrystallisert fra petroleter (kokepunkt 40 - 60°C) til å gi syren som hvite nåler med smp. 88 - 89°C, utbytte 4,5 g (82%). 1-(4-Chlorophenyl)cyclobutanenitrile (5 g) was mixed with ethylene glycol (60 mL) and 40% w/w aqueous potassium hydroxide solution (80 mL) and boiled under argon for 18 h. The mixture was cooled, added to ice water and extracted with diethyl ether. The aqueous layer was acidified and the precipitate was filtered off, washed with water, dried and recrystallized from petroleum ether (boiling point 40 - 60°C) to give the acid as white needles of m.p. 88 - 89°C, yield 4.5 g (82%).
Analyse: C 62,70%, H 5,14%, Cl 16,5%. 0 15-, 2% Cj^H^CLC^ Analysis: C 62.70%, H 5.14%, Cl 16.5%. 0 15-, 2% Cj^H^CLC^
krever teoretisk C 62,72%, H 5,26%, Cl 16,83%, 0 15,2%. theoretically requires C 62.72%, H 5.26%, Cl 16.83%, O 15.2%.
(c) 3'- fenoksybenzyl- 1-( 4- klorfenyl) cyklobutan- karboksylat (c) 3'-phenoxybenzyl-1-(4-chlorophenyl)cyclobutanecarboxylate
1-(4-klorfenyl)cyklobutan-karboksylsyre (1 g) ble opplost i tionylklorid (1 ml) og oppvarmet under tilbakelbp i 40 min. Overskudd av tionylklorid ble fjernet under vakuum og resten ble opptatt i petroleter 40 - 60°C (40 ml) og tilsatt i lopet av 15 min. til en omrort blanding av 3-fenoksybenzyl-alkohol (1,1 g), pyridin (1 ml), benzen (50 ml) og petroleter 40 - 60°C 1-(4-Chlorophenyl)cyclobutanecarboxylic acid (1 g) was dissolved in thionyl chloride (1 ml) and heated under reflux for 40 min. Excess thionyl chloride was removed under vacuum and the residue was taken up in petroleum ether 40 - 60°C (40 ml) and added over the course of 15 min. to a stirred mixture of 3-phenoxybenzyl alcohol (1.1 g), pyridine (1 ml), benzene (50 ml) and petroleum ether 40 - 60°C
(50 ml) opprettholdt ved 10°C. Blandingen ble omrort ved (50 ml) maintained at 10°C. The mixture was stirred by
20 - 25°C i 3 timer og deretter tilsatt til isblandet vann, 20 - 25°C for 3 hours and then added to ice-mixed water,
vasket med 0,5M saltsyre, vann, fortynnet natriumbikarbonat-losnrng og torket over vannfritt. natriumsulfat. Losningsmidlet ble avdampet til å gi en olje (2,3 g) som etter kromatografering på silikagel, eluering med benzen/petroleter, ga esteren 1,52 g (82%). washed with 0.5M hydrochloric acid, water, dilute sodium bicarbonate solution and dried over anhydrous. sodium sulfate. The solvent was evaporated to give an oil (2.3 g) which after chromatography on silica gel, eluting with benzene/petroleum ether, gave the ester 1.52 g (82%).
Analyse: C 72,87%, H 5,30%, Cl 9,2%, 0 12,1%. Analysis: C 72.87%, H 5.30%, Cl 9.2%, O 12.1%.
C24H21C103 krever teoretisk: C 73,37%, H 5,39%, Cl 9,0%, 0 12,2%. C24H21C103 theoretically requires: C 73.37%, H 5.39%, Cl 9.0%, O 12.2%.
EKSEMPEL 2 EXAMPLE 2
(a) 1-( 4- etoksyfenyl) cyklobutan- karboksyl- syre (a) 1-(4- ethoxyphenyl) cyclobutane carboxylic acid
Etyl-4-etoksyfenylacetat (14 g) i vannfri dietyl-eter (20 ml) Ethyl 4-ethoxyphenyl acetate (14 g) in anhydrous diethyl ether (20 ml)
ble tilsatt til en omrort suspensjon av natri-umamid (5,3 g) i flytende ammoniakk (400 ml) i lopet av 3 min. og blandingen omrort i ytterligere 20 min. 1,3-dibrompropan (14 g) i dietyl-eter (10 ml) ble tilsatt i lopet av 20 min. og blandingen omrort i 17 timer. 50 ml mettet ammoniumklorid-losning ble tilsatt og reaksjonsblandingen ekstrahert med dietyleter. Avdamping av losningsmidlet ga en rest (17,4 g) som etter kromatografering på silikagel ved éluering med benzen/kloroform ga en olje (7,2 g). Oljen ble opplost i etanol (50 ml) og 10% natriumhydroksydlosning (50 ml) ble tilsatt. Blandingen ble kokt under tilbakelop i 3 timer, avkjolt, tilsatt til isblandet vann og ekstrahert med dietyleter'. Detvadige lag ble surgjort og bunnfallet ble frafiltrert, vasket med vann, torket og omkrystallisert fra petroleter 40 - 60°C til å gi syren 5,2 g (35%) smp. 90 - 91°C. was added to a stirred suspension of sodium amide (5.3 g) in liquid ammonia (400 ml) over 3 min. and the mixture stirred for a further 20 min. 1,3-dibromopropane (14 g) in diethyl ether (10 ml) was added over 20 min. and the mixture stirred for 17 hours. 50 ml of saturated ammonium chloride solution was added and the reaction mixture was extracted with diethyl ether. Evaporation of the solvent gave a residue (17.4 g) which after chromatography on silica gel by elution with benzene/chloroform gave an oil (7.2 g). The oil was dissolved in ethanol (50 mL) and 10% sodium hydroxide solution (50 mL) was added. The mixture was refluxed for 3 hours, cooled, added to ice-water and extracted with diethyl ether. The aqueous layer was acidified and the precipitate was filtered off, washed with water, dried and recrystallized from petroleum ether 40 - 60°C to give the acid 5.2 g (35%) m.p. 90 - 91°C.
Analyse: c'"71',04%, H 7,23%, 0 22,0% Analysis: c'"71'.04%, H 7.23%, 0 22.0%
C13H16°3 krevet teoretisk C 70,89%, H 7 ,' 32%, O 21,8%." C13H16°3 theoretically required C 70.89%, H 7 ,' 32%, O 21.8%."
(b) 3'- fenoksybenzyl- 1-( 4- etoksyfenyl) cyklobutan- karboksylat (b) 3'-phenoxybenzyl-1-(4-ethoxyphenyl)cyclobutanecarboxylate
1-(4-etoksyfenyl)cyklobutan-karboksylsyre (1 g) ble kokt under tilbakelop i tionylklorid (1 ml) i 30 min. og overskudd tionylklorid fjernet under vakuum. Resten ble opptatt i petroleter 40 - 60°C (25 ml) og tilsatt i lopet av 5 min. til en omrort blanding av 3-fenoksybenzyl-alkohol (1,1 g) pyridin ( 1 ml) 1-(4-Ethoxyphenyl)cyclobutanecarboxylic acid (1 g) was refluxed in thionyl chloride (1 ml) for 30 min. and excess thionyl chloride removed under vacuum. The residue was taken up in petroleum ether 40 - 60°C (25 ml) and added over the course of 5 min. to a stirred mixture of 3-phenoxybenzyl alcohol (1.1 g) pyridine (1 ml)
benzen (25 ml) og petroleter 40 - 60°C (25 ml) ved 15°C. benzene (25 ml) and petroleum ether 40 - 60°C (25 ml) at 15°C.
Blandingen ble omrort ved 15°C i 3 timer og deretter tilsatt The mixture was stirred at 15°C for 3 hours and then added
til isblandet vann og ekstrahert med dietyleter. Ekstrakten ble 'vasket med vann, 0,5M saltsyre, og natriumbikarbonatlosning og deretter torket over vannfritt natriumsulfat og losningsmidlet fjernet til å gi en olje (2,1 g). Kromatografering på to ice-water and extracted with diethyl ether. The extract was washed with water, 0.5M hydrochloric acid, and sodium bicarbonate solution and then dried over anhydrous sodium sulfate and the solvent removed to give an oil (2.1 g). Chromatography on
silikagel, eluering med benzen ga esteren (1,5 g) (82%). silica gel, elution with benzene gave the ester (1.5 g) (82%).
Analyse: C 77,55%, H 6,65%, 0 16,0% Analysis: C 77.55%, H 6.65%, O 16.0%
C26H26°4 krever teoretisk C 77,59%, H 6,51%, 0 15,9%. C26H26°4 theoretically requires C 77.59%, H 6.51%, O 15.9%.
EKSEMPEL 3 EXAMPLE 3
(a ) 2- ( 4- etoksyf enyl ) propensyre.- etyl- ester (a) 2- (4-ethoxy enyl) propenic acid.- ethyl ester
Denne del av eksemplet viser den. generelle metode for å This part of the example shows it. general method to
fremstille 2-aryl-akryl-syre-esterene. (Formel II). prepare the 2-aryl acrylic acid esters. (Formula II).
Alkohol-fritt natrium-etoksyd nyfremstilt fra natrium (13,9 g) Alcohol-free sodium ethoxide freshly prepared from sodium (13.9 g)
og overskudd av etanol ble oppslemmet i torr benzen (200 ml). and excess ethanol was slurried in dry benzene (200 mL).
Til denne suspensjon ble dietyloksalat (88,5 g) tilsatt i lopet To this suspension, diethyl oxalate (88.5 g) was added in the batch
av 15 min.- Etyl-p-etoksyfenylacetat (V) (114,2 g) ble tilsatt til den resulterende klare gule losning i lopet av 30 min. ved romtemperatur. Etter ytterligere 1 time storknet reaksjonsblandingen. Det faste natriumdietyl-2-p"-etoksyfenyl-3-etoksy-3-oksydo-oksaloacetat (IV) ble utgnidd og vasket godt med eter. of 15 min.- Ethyl p-ethoxyphenyl acetate (V) (114.2 g) was added to the resulting clear yellow solution over the course of 30 min. at room temperature. After a further 1 hour, the reaction mixture solidified. The solid sodium diethyl 2-p"-ethoxyphenyl-3-ethoxy-3-oxido-oxaloacetate (IV) was triturated and washed well with ether.
De kombinerte eterekstrakter ble inndampet til et lite volum til The combined ether extracts were evaporated to a further small volume
å gi en ytterligere saltmengde. to give an additional amount of salt.
Det totale utbytte var 227,4 g. The total yield was 227.4 g.
Natriumsaltet ble surgjort ved å tilsette det i porsjoner til The sodium salt was acidified by adding it in portions to
en godt omrort emulsjon av like deler av dietyleter og fortynnet eddiksyre (omtrent 10%). Etter separering ble eter-, laget vasket med vann og fortynnet natriumbikarbonatlosning og torket med vannfritt natriumsulfat. Etter avdamping av eter ble den resterende olje krystallisert fra petroleter (kokepunkt 60 - 80°C) til å gi dietyl-2-p-etoksyfenyloksaloacetat (III) a well-stirred emulsion of equal parts diethyl ether and dilute acetic acid (about 10%). After separation, the ether layer was washed with water and dilute sodium bicarbonate solution and dried with anhydrous sodium sulfate. After evaporation of the ether, the remaining oil was crystallized from petroleum ether (boiling point 60 - 80°C) to give diethyl 2-p-ethoxyphenyl oxaloacetate (III)
(143,8 g) (85%), smp. 59 - 60°C. (143.8 g) (85%), m.p. 59 - 60°C.
Keto-esteren III (143,8 g) ble omrort i fortynnet formaldehyd-lbsning (62 ml 37% formaldehyd + vann 220 ml) og til suspensjonen ble kaliumkarbonatlosning (54,5g i vann 280 ml) tilsatt dråpevis. Ved avsluttet tilsetning ble eter tilsatt til den . omrorte suspensjon for å opplose det gummiaktige'bunnfall som hadde dannet seg og etter ytterligere 15 min. begynte gassutvikling. Når denne gassutvikling opphorte (etter omtrent 2 timer) ble reaksjonsblandingen ekstrahert med ytterligere eter og de kombinerte eterekstrakter ble vasket med vann og inndampet etter torking over Na^SO^. Utbyttet av etyl-2-(4-etoksyfenyl)propenoat (ii) (isolert som en gul olje) var 97,8 g (79,8%). (b) et/ 1- 1-( 4- etoksyfenyl)- 2, 2, 3, 3- tetrafluorcyklo- butan-kar boksylat • The keto ester III (143.8 g) was stirred in dilute formaldehyde solution (62 ml 37% formaldehyde + water 220 ml) and to the suspension potassium carbonate solution (54.5 g in water 280 ml) was added dropwise. At the end of the addition, ether was added to it. stirred the suspension to dissolve the gummy precipitate that had formed and after a further 15 min. gas development began. When this gas evolution ceased (after about 2 hours), the reaction mixture was extracted with additional ether and the combined ether extracts were washed with water and evaporated after drying over Na 2 SO 4 . The yield of ethyl 2-(4-ethoxyphenyl)propenoate (ii) (isolated as a yellow oil) was 97.8 g (79.8%). (b) et/ 1- 1-( 4- ethoxyphenyl)- 2, 2, 3, 3- tetrafluorocyclobutanecarboxylate •
2-(4-etoksyfenyl)propensyre-etyl-ester (13,2 g), ble blandet med benzen (7,5 ml), a-pinen (2 dråper;) N-etyldiisopropyl-amin (2 dråper) og tetrafluoretylen (15,5 ml) og oppvarmet til 150 - 15 5°C ,i 24 timer og deretter ved 155 - 160°C i 17- timer. Etter avdamping av flyktige materialer ble resten (16,6.g). opplost i diklormetan og kromatografert på en kolonne av ...... silikagel til å gi esteren som en farvelos' olje 14,5 g (75%). Analyse: C 56,47%, H 5,24%, F 23,4%. 2-(4-Ethoxyphenyl)propenoic acid ethyl ester (13.2 g) was mixed with benzene (7.5 ml), α-pinene (2 drops;) N-ethyldiisopropylamine (2 drops) and tetrafluoroethylene ( 15.5 ml) and heated to 150 - 155°C for 24 hours and then at 155 - 160°C for 17 hours. After evaporation of volatile materials, the residue (16.6.g) was dissolved in dichloromethane and chromatographed on a column of ... silica gel to give the ester as a colorless oil 14.5 g (75%). Analysis: C 56.47%, H 5.24%, F 23.4%.
<C>15H16<F>4°3 krever teoretisk C 56,2 5%, H.5,04%, F 2-3,7%..• <C>15H16<F>4°3 theoretically requires C 56.2 5%, H.5.04%, F 2-3.7%..•
(c) i-( 4- etoks/ fenyl)- 2, 2, 3, 3- tetrafluorcyklobutan-kar boks yl syre (c) i-(4-ethoxy/phenyl)-2,2,3,3-tetrafluorocyclobutane-carboxylic acid
Etyl-1-(4-etoksyfenyl)-2,2,3,3-tetrafluorcyklobutan-karboksylat (14,5 g) ble opplost i etanol (100 ml) og 10% vekt/vekt losning av natriumhydroksyd i vann (100 ml) ble tilsatt og blandingen kokt under tilbakelop i 2,5 timer. Blandingen ble avkjolt, tilsatt til isblandet vann og ekstrahert med dietyleter. Det vandige lag ble surgjort .og bunnfallet ble frafiltrert, vasket med vann, torket og krystallisert fra 50 - 80°C petroleter til å gi syren med smp. 112 - 113°C. Utbytte 11,2 g.(85%). Ethyl 1-(4-ethoxyphenyl)-2,2,3,3-tetrafluorocyclobutane carboxylate (14.5 g) was dissolved in ethanol (100 mL) and a 10% w/w solution of sodium hydroxide in water (100 mL) was added and the mixture refluxed for 2.5 hours. The mixture was cooled, added to ice water and extracted with diethyl ether. The aqueous layer was acidified and the precipitate was filtered off, washed with water, dried and crystallized from 50-80°C petroleum ether to give the acid with m.p. 112 - 113°C. Yield 11.2 g. (85%).
Analyse: C 53,20%, H 4,22%, F 25,9%. Analysis: C 53.20%, H 4.22%, F 25.9%.
C13H12F4°3 krever teoretisk C 53,43%, H 4,14%, F 26,0%. C13H12F4°3 theoretically requires C 53.43%, H 4.14%, F 26.0%.
(d) 3'- fenoksybenzyl- 1-( 4- etoksyfen/ l)- 2, 2, 3, 3- tetrafluor-c yklobutan- karboksylat (d) 3'-phenoxybenzyl-1-(4-ethoxyphen/l)-2,2,3,3- tetrafluorocyclobutanecarboxylate
1-(4-etoksyfenyl)-2,2,3,3-tetrafluorcyklobutan-karboksylsyre (0,9 g) ble kokt under tilbakelop med tionylklorid (1 ml) i 45 min. og overskudd av tionylklorid ble fjernet under vakuum. Resten ble opplost i petroleter 40 - 60°C (40 ml) og tilsatt i lopet av 5 min. til en blanding av 3-fenoksybenzyl-alkohol 1-(4-Ethoxyphenyl)-2,2,3,3-tetrafluorocyclobutanecarboxylic acid (0.9 g) was refluxed with thionyl chloride (1 ml) for 45 min. and excess thionyl chloride was removed under vacuum. The residue was dissolved in petroleum ether 40 - 60°C (40 ml) and added over the course of 5 min. to a mixture of 3-phenoxybenzyl alcohol
(1 g) pyridin (1 ml), benzen (2 5 ml), og petroleter 40 - 60°C (1 g) pyridine (1 ml), benzene (2 5 ml), and petroleum ether 40 - 60°C
(25 ml) holdt ved 20°C. Blandingen ble omrort i 3 timer og deretter tilsatt til isblandet vann og ekstrahert med dietyleter. Ekstrakten ble vasket med vann, 0,5M saltsyre og natriumbikarbonatlosning, torket over vannfritt natriumsulfat og losningsmidlet avdampet til å gi en olje (2 g). Kromatografering på silikagel ved eluering med benzen ga esteren 1,2 g (82%). (25 ml) kept at 20°C. The mixture was stirred for 3 hours and then added to ice-water and extracted with diethyl ether. The extract was washed with water, 0.5M hydrochloric acid and sodium bicarbonate solution, dried over anhydrous sodium sulfate and the solvent evaporated to give an oil (2 g). Chromatography on silica gel eluting with benzene gave the ester 1.2 g (82%).
Analyse: C 65,45%, H 4,84%, F 16,0%.. Analysis: C 65.45%, H 4.84%, F 16.0%..
<C>26<H>22<F>4°4 krever teoretisk C 65,82%, H 4,67%, F 16,0%.. <C>26<H>22<F>4°4 theoretically requires C 65.82%, H 4.67%, F 16.0%..
EKSEMPEL 4 EXAMPLE 4
(a) (-) enantiomer av 1-( 4- etoksyfenyl)- 2, 2, 3, 3- tetrafluor-cyklobutan- karboksylsyre (a) (-) enantiomer of 1-(4- ethoxyphenyl)- 2, 2, 3, 3- tetrafluoro-cyclobutane- carboxylic acid
a(+)-(1-naftyl)etylamin ble tilsatt til en losning av den racemiske syre (2g) (fremstilt som i eksempel 3(c)) i etylacetat (75 ml) og n-heksan. Det salt som dannet seg ble krystallisert fire ganger fra etylacetat ved romtemperatur. (+) (-) saltet ble spaltet med saltsyre (IM) og resten omkrystallisert to ganger fra etanol. (-) syren hadde cx^q = -118,2 og smp. 194°C og ble oppnådd i 15% utbytte. α(+)-(1-Naphthyl)ethylamine was added to a solution of the racemic acid (2g) (prepared as in Example 3(c)) in ethyl acetate (75ml) and n-hexane. The salt formed was crystallized four times from ethyl acetate at room temperature. The (+) (-) salt was cleaved with hydrochloric acid (1M) and the residue recrystallized twice from ethanol. The (-) acid had cx^q = -118.2 and m.p. 194°C and was obtained in 15% yield.
(b) (-) 3'- fenoksybenzyl- 1-( 4- etoksyfenyl)- 2, 2, 3, 3- tetra-fluorcyklobutan- karboksylat (b) (-) 3'-phenoxybenzyl- 1-(4- ethoxyphenyl)- 2, 2, 3, 3- tetrafluorocyclobutane- carboxylate
Den isolerte (-) syre, 0,2 g, ble kokt under tilbakelop i tionylklorid (1 ml) i en time. Etter avdamping av overskudd av tionylklorid ble resten opplost i petroleter (kokepunkt 60 - 80°C) og tilsatt til 3-fenoksybenzyl-alkohol (0,139 g) og pyridin (0,238 g) i benzen (3 ml) og petroleter (3 ml). Reaksjonsblandingen ble omrort over natten, bråkjolt med isblandet vann, vasket med vann og losningsmiddellaget fraskilt og torket over en molekylsikt. Etter avdamping av losningsmidlet ble den rene ester oppnådd som en viskos væske ved kromatografering i silikagel' under anvendelse av metylenklorid'som elueringsmiddel. Utbytte 99,1%, a<®>Q = -58v2. The isolated (-) acid, 0.2 g, was refluxed in thionyl chloride (1 mL) for one hour. After evaporation of excess thionyl chloride, the residue was dissolved in petroleum ether (boiling point 60 - 80°C) and added to 3-phenoxybenzyl alcohol (0.139 g) and pyridine (0.238 g) in benzene (3 ml) and petroleum ether (3 ml). The reaction mixture was stirred overnight, quenched with ice water, washed with water and the solvent layer separated and dried over a molecular sieve. After evaporation of the solvent, the pure ester was obtained as a viscous liquid by chromatography on silica gel using methylene chloride as eluent. Yield 99.1%, a<®>Q = -58v2.
EKS EMPEL" 5 EKS EMPEL" 5
(a) 1-( 3, 4- metylendioksyfenyl)- 2, 2, 3, 3- tetrafluorcyklobutan-karboksylsyre (a) 1-(3,4-methylenedioxyphenyl)-2,2,3,3-tetrafluorocyclobutanecarboxylic acid
En blanding av etyl-2-(3,4-metylendioksyfenyl)propenoat (2,2 g), tetrafluoretylen (5 ml), -t-pinen (1 dråpe), N-etyldiisopropyl-amin (1 dråpe) og benzen (10 ml) ble oppvarmet ved 150 - 155°C A mixture of ethyl 2-(3,4-methylenedioxyphenyl)propenoate (2.2 g), tetrafluoroethylene (5 ml), -t-pinene (1 drop), N-ethyldiisopropylamine (1 drop) and benzene (10 ml) was heated at 150 - 155°C
i 24 timer og deretter ved 160 - 165°C i 16 timer og deretter avkjolt. Losningsmidlet ble avdampet og etterlot en olje (3,0 g). for 24 hours and then at 160 - 165°C for 16 hours and then cooled. The solvent was evaporated leaving an oil (3.0 g).
Denne olje ble renset ved kromatografering på silikagel under anvendelse av benzen zom elueringsmiddel og ga 1,4 g (44%) etyl-1-(3,4-met/len-dioksofenyl)-2,2,3,3-tetrafluorcyklobutan-karboksylat. This oil was purified by chromatography on silica gel using benzene as an eluent to give 1.4 g (44%) of ethyl 1-(3,4-methylene-dioxophenyl)-2,2,3,3-tetrafluorocyclobutane- carboxylate.
Etylesteren ble h/drolysert ved koking under tilbakelop i The ethyl ester was hydrolyzed by refluxing
2 timer med en blanding av kaliumhydroksyd (5 g), vann (50 ml) og etanol (50 ml). Etanol ble fjernet ved avdamping og den vandige rest ekstrahert med dietyleter. Det vandige lag ble surgjort og bunnfallet frafiltrert, torket og omkrystallisert fra petroleter' (kokepunkt 60 - 80°)/dietyleter til å gi 0,9 g av syren som hvite krystaller med smp. 168 - 169°C. 2 hours with a mixture of potassium hydroxide (5 g), water (50 ml) and ethanol (50 ml). Ethanol was removed by evaporation and the aqueous residue extracted with diethyl ether. The aqueous layer was acidified and the precipitate filtered off, dried and recrystallized from petroleum ether' (boiling point 60 - 80°)/diethyl ether to give 0.9 g of the acid as white crystals of m.p. 168 - 169°C.
Analyse: C 49,62%, H 2,72%, F 25,8%. Analysis: C 49.62%, H 2.72%, F 25.8%.
C12H8F4°4 krever teoretisk C 49,33%, H 2,76%, F 26,0%. C12H8F4°4 theoretically requires C 49.33%, H 2.76%, F 26.0%.
(b) 3' fenoksybenzyl- 1-( 3, 4- metylendioksyfen/ l)- 2, 2, 3, 3-tetrafluorc/ klobutan- karboksylat (b) 3' phenoxybenzyl-1-(3,4-methylenedioxyphene/1)-2,2,3,3-tetrafluoroc/clobutane-carboxylate
Syren fremstilt under eksempel 5(a) (0,5 g) ble blandet med tionylklorid (1 ml) og kokt under tilbakelop i 45 min. Overskudd av tionylklorid ble fjernet under vakuum. Resten ble opplost i petroleter (kokepunkt 40 - 60°) (5 ml) og tilsatt i lopet av 5 min. til en omrort blanding av 3-fenoksybenzyl-alkohol (0,4 g), pyridin (0,5 ml), benzen (15 ml) og petroleter (kokepunkt 40 - 60°) (15 ml). Etter omroring over natten ved romtemperatur ble blandingen tilsatt til isblandet vann og ekstrahert med dietyleter. Eterekstrakten ble vasket med fortynnet saltsyre, vann, natriumbikarbonatlosning og torket over vannfritt natriumsulfat. Avdamping av eter etterlot en oljeaktig rest (0,78 g) som ble renset ved kromatografering på silikagel med benzen som elueringsmiddel til å gi 0,7 g 3-fenoksy-benzyl-esteren som en klar gul olje. The acid prepared in Example 5(a) (0.5 g) was mixed with thionyl chloride (1 ml) and refluxed for 45 min. Excess thionyl chloride was removed under vacuum. The residue was dissolved in petroleum ether (boiling point 40 - 60°) (5 ml) and added over the course of 5 min. to a stirred mixture of 3-phenoxybenzyl alcohol (0.4 g), pyridine (0.5 ml), benzene (15 ml) and petroleum ether (boiling point 40 - 60°) (15 ml). After stirring overnight at room temperature, the mixture was added to ice-water and extracted with diethyl ether. The ether extract was washed with dilute hydrochloric acid, water, sodium bicarbonate solution and dried over anhydrous sodium sulfate. Evaporation of ether left an oily residue (0.78 g) which was purified by chromatography on silica gel eluting with benzene to give 0.7 g of the 3-phenoxy-benzyl ester as a clear yellow oil.
Analyse: C 63,54%, H 4,01%, F 15,9%. Analysis: C 63.54%, H 4.01%, F 15.9%.
C25<H>18<F>4°5 krever teoretisk C 63,30%, H 3,82%, F 16,0%. C25<H>18<F>4°5 theoretically requires C 63.30%, H 3.82%, F 16.0%.
EKSEMPLER 6 til 2 0 EXAMPLES 6 to 2 0
Ved å anvende den generelle metode angitt i eksempel 3 ble de , folgehde forbindelser gjengitt i tabell 1 oppnådd fra de tilsvarende utgangsmaterialer. By applying the general method indicated in Example 3, the following compounds reproduced in Table 1 were obtained from the corresponding starting materials.
Elementæranalyse, spektra og andre karakteriserende data var i samsvar med de angitte strukturer. Elemental analysis, spectra and other characterizing data were consistent with the stated structures.
Tabell 1 omfatter forbindelsene fra eksemplene 1, 2, 3, 4 og 5 for lettere oversikt. Table 1 includes the compounds from examples 1, 2, 3, 4 and 5 for an easier overview.
EKSEMPEL 21 EXAMPLE 21
Den biologiske -aktivitet av de nye cyklobutan-estere ble undersokt ved en testrekke med resultater samlet i den etter-følgende tabell 2. The biological activity of the new cyclobutane esters was investigated in a series of tests with results collected in the following table 2.
Insekticid aktivitet ble undersokt mot vanlig husflue, Musea domestica, og saueflue, Lucilia cuprina. De metoder som ble anvendt var som folger: Insecticidal activity was investigated against the common housefly, Musea domestica, and the sheep fly, Lucilia cuprina. The methods used were as follows:
(i ) Husfluer (i ) Houseflies
(a) Forbindelsen alene (a) The compound alone
Forsok ble gjennomført under anvendelse av en standard DDT-omfindtlig stamme (WHO/IN/1) av M. domestica. Forbindelsen ble tilfort i acetonlosning ved "hjelp av en mikro-nål til dorsum av thorax på 2 dogn gamle hunfluer formert fra puppestadiet med gjennomsnittlig vekt 2,2 - 2,5 g/100 pupper. De voksne fluer ble tilfort vann og en diett av sukker alene og holdt ved 26°C og 70% relativ fuktighet. Dødeligheten ble bestemt 48 timer etter behandling og sammenlignet med acetonbehandlede kontrolldyr. Fluer som ikke var i stand til å bevege seg eller stå normalt ble ansett.som dode. LD^Q-verdi ble oppnådd fra et regnemaskin-program basert på tre grupper på 10 fluer i hvert doseringsnivå. LD^Q-verdien for DDT bestemt under de samme betingelser var 0,26 pg/flue. Experiments were carried out using a standard DDT-susceptible strain (WHO/IN/1) of M. domestica. The compound was administered in acetone solution by means of a micro-needle to the dorsum of the thorax of 2 day-old female flies bred from the pupal stage with an average weight of 2.2 - 2.5 g/100 pupae. The adult flies were administered water and a diet of sugar alone and maintained at 26°C and 70% relative humidity. Mortality was determined 48 hours after treatment and compared to acetone-treated control animals. Flies unable to move or stand normally were considered dead. LD^Q- value was obtained from a calculator program based on three groups of 10 flies at each dosage level.The LD^Q value for DDT determined under the same conditions was 0.26 pg/fly.
(b) Potensiering (b) Potentiation
Forbindelsen ble også testet på insekter beskrevet ovenfor i forbindelse med potentiatoren "Sesoxane" ved forbehandling av insektet med 1 pg av potentiatoren i aceton. The compound was also tested on insects described above in connection with the potentiator "Sesoxane" by pre-treating the insect with 1 µg of the potentiator in acetone.
Dødeligheten ble bestemt 48 timer etter behandling og sammenlignet med aceton tog aceton/potentiatorkontroller. Mortality was determined 48 hours after treatment and compared with acetone and acetone/potentiator controls.
LD^Q-verdi ble bestemt som beskrevet ovenfor. LD^Q value was determined as described above.
For DDT, med den samme potentiator, var LD5Q-verdien 0,24 pg/ flue. For DDT, with the same potentiator, the LD5Q value was 0.24 pg/fly.
Omtrent de samme nivåer av potentiering ble oppnådd når "Sesoxane" ble erstattet med en like stor mengde piperonyl-bu toks yd. Approximately the same levels of potentiation were obtained when "Sesoxane" was replaced with an equal amount of piperonyl butox yd.
(c) Insekt- avstotning (c) Insect repellent
Avstotningstester ble gjennomfort med samme stamme av husfluer som i dodelighetstestene. Hunfluer som var minst 2 dager gamle, som ikke tidligere var tilfort protein, ble dagen for testen bedovet med CO2 og telt opp i beholdere som hver rommet 20 fluer. Disse ble tilfort vann og fast sukrose. På testdagen ble f6de og vann fjernet om morgenen (kl. 9.00). Da testene ble gjennomfort bare mellom kl. 12.00 og kl. 17.30 ble fluene derfor holdt fastende i minst 3 timer for testingen. Repellency tests were carried out with the same strain of houseflies as in the lethality tests. Female flies that were at least 2 days old, which had not previously been fed protein, were anesthetized with CO2 on the day of the test and counted in containers each containing 20 flies. These were supplemented with water and solid sucrose. On the test day, food and water were removed in the morning (09:00). When the tests were carried out only between 12.00 and At 17.30 the flies were therefore kept fasting for at least 3 hours for the testing.
Testen innbefatter bruk av tiltreknings-lokkemidler som testforbindelsen ble påfort. Disse ble utsatt for fluene og antallet fluer som landet på hvert lokkemiddel ble notert. Lokkemidlene besto av aluminiumskaler med areal 5,94 cm 2 fylt med vanlige brodgjær blandet med vann og blitt oppvarmet til å gi en fast overflatefilm. The test involves the use of attractants to which the test compound was applied. These were exposed to the flies and the number of flies that landed on each lure was noted. The baits consisted of aluminum shells with an area of 5.94 cm 2 filled with common bridging yeast mixed with water and heated to produce a solid surface film.
Hver gruppe på 20 fluer ble anvendt ved et forsok hvor 7 skåler ble behandlet med en gradert fortynnet rekke av testforbindelsen under anvendelse av aceton som løsningsmiddel, sammen med en-skål behandlet med aceton som en kontroll. Konsentrasjonen av forbindelsen utgjorde fra 0,031 pg/pl som ble doblet ved hvert nivå opp til 2,0 jig/ul. Etthundrmikroliter av hver oppløsning ble pipettert jevnt over overflaten av hver skål og etterlatt inntil acetonet var avdampet. Each group of 20 flies was used in an experiment where 7 dishes were treated with a graded dilution series of the test compound using acetone as solvent, along with one dish treated with acetone as a control. The concentration of the compound ranged from 0.031 pg/µl which doubled at each level up to 2.0 µg/µl. One hundred microliters of each solution was pipetted evenly over the surface of each dish and left until the acetone had evaporated.
De fluene som ble anvendt ble sluppet inn i dandard The flies used were released into dandard
205 mm x 205 "mm x 255 mm bur av' trådnetting og fikk aklimatisere seg i proverommet som ble holdt'ved en 'temperatur på 2 6°C + l°C og fuktighet omtrent 60%, i 10 min. for de 205 mm x 205 "mm x 255 mm wire mesh cages and allowed to acclimatize in the test room maintained at a temperature of 2 6°C + 1°C and humidity approximately 60%, for 10 min. for the
behandlede skåler ble fort inn i hvert bur. For bruken ble skålene merket på baksiden og deretter tilfeldig blandet for å unngå bestemte tendenser ved bedommelsen. Ved den 30 min. test "ble antallet fluer på overflaten av hver skål notert i det forste og annet minutt etter innforing av lokkemidlene og deretter annet hvert minutt. På denne måte ble det foretatt seksten opptellinger for hver konsentrasjon, idet summen av disse ble anvendt for en regressjonsanalyse av konsentrasjons-virkningen. En totalt opptelling av landingene for hver konsentrasjon ble også oppnådd og anvendt for beregning av avstotningsindeks (IR). Alle relevante tester ble gjennomfort med friske fluer og lokkemidler, og forbindelsene ble behandlet i tre gjentatte grupper. treated bowls were quickly inserted into each cage. For use, the bowls were marked on the back and then randomly mixed to avoid certain tendencies in the judgement. At the 30 min. test "the number of flies on the surface of each dish was noted in the first and second minutes after the introduction of the baits and then every other minute. In this way sixteen counts were made for each concentration, the sum of these being used for a regression analysis of concentration effect. A total count of the landings for each concentration was also obtained and used for the calculation of repellency index (IR). All relevant tests were carried out with fresh flies and lures, and the compounds were treated in three replicate groups.
Det totale antall fluer som ble notert for hver skål for de The total number of flies recorded for each dish for those
syv konsentrasjonsnivåer ble oppsummert og gjennomsnittsberegnet. I den folgende formel er denne betegnelse angitt ved (N), hvor seven concentration levels were summarized and averaged. In the following formula, this designation is indicated by (N), where
(C) angir antall fluer notert på kontrollen: (C) indicates the number of flies noted on the control:
(ii) Sauefluer (ii) Sheep flies
(a) Insekticid virkning (a) Insecticidal action
Forbindelsene ble testet for aktivitet mot en dieldrin-omtålelig stamme (LBB) som var blitt samlet for dieldrin-bruk på området. The compounds were tested for activity against a dieldrin-tolerant strain (LBB) that had been collected for dieldrin use in the field.
Testforbindelsen ble påfort i acetonlosning, 0,5 ul fordelt med en Drummond.mikropipette til dorsum av thorax på 2-3 dager gamle hunfluer. Voksne fluer ble tilfort vann og sukker-alene holdt ved 2 5°C og 60 - 70% RH. Dødeligheten ble bestemt etter 24 timer. Urorlige fluer ble betraktet som dode. LD^-verdiene, på basis av konsentrasjon, ble interpolert fra en grafisk fremstilling under anvendelse av et computer-program. Sammenlignings-LD^-tall for DDT og dieldrin er 0,17 henhv. 0,025 ug/insekt. The test compound was applied in acetone solution, 0.5 µl distributed with a Drummond micropipette to the dorsum of the thorax of 2-3 day old female flies. Adult flies were supplied with water and sugar alone kept at 25°C and 60 - 70% RH. Mortality was determined after 24 hours. Restless flies were considered dead. The LD^ values, on a concentration basis, were interpolated from a graphical representation using a computer program. Comparative LD^ figures for DDT and dieldrin are 0.17 respectively. 0.025 ug/insect.
(b) EoteQtiering (b) EoteQtiering
Potentiering med "Sesoxane" ble undersokt som beskrevet ovenfor ved husfluetestene. Potentiation with "Sesoxane" was examined as described above in the housefly tests.
(c) A vstotning (c) Assistance
Avstotning ble bestemt som beskrevet ovenfor ved husfluetestene, med unntagelse av at lokkemidlene besto av en agar-gel inneholdende frisk kvegblod. Repulsion was determined as described above in the housefly tests, with the exception that the baits consisted of an agar gel containing fresh bovine blood.
Testmetodene er beskrevet i BRD Offenlegungsschrift nr. 2.653.189 publisert 8. juni 1977, se eks. 38 i (c) The test methods are described in BRD Offenlegungsschrift No. 2,653,189 published on 8 June 1977, see e.g. 38 in (c)
(husfluer) og 38 iii(c) (sauefluer). (house flies) and 38 iii(c) (sheep flies).
Claims (11)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU281877 | 1977-12-19 |
Publications (3)
Publication Number | Publication Date |
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NO784246L NO784246L (en) | 1979-06-20 |
NO149385B true NO149385B (en) | 1984-01-02 |
NO149385C NO149385C (en) | 1984-04-11 |
Family
ID=3693310
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO784246A NO149385C (en) | 1977-12-19 | 1978-12-18 | 1-PHENYL-CYCLOBUTANE CARBOXYLATE COMPOUNDS WITH EFFECTS ON INSECTS (INSECTA) AND SPIDER ANIMALS (ARACHNIDA) |
NO794117A NO149946C (en) | 1977-12-19 | 1979-12-17 | PREPARATIONS FOR THE FIGHT AGAINST INSECTS (INSECTA) AND SPIDER ANIMALS (ARACHNIDA) CONTAINING CYCLOBUTANCHARAN BOXYLATES |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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NO794117A NO149946C (en) | 1977-12-19 | 1979-12-17 | PREPARATIONS FOR THE FIGHT AGAINST INSECTS (INSECTA) AND SPIDER ANIMALS (ARACHNIDA) CONTAINING CYCLOBUTANCHARAN BOXYLATES |
Country Status (2)
Country | Link |
---|---|
MX (1) | MX6273E (en) |
NO (2) | NO149385C (en) |
-
1978
- 1978-12-15 MX MX759978U patent/MX6273E/en unknown
- 1978-12-18 NO NO784246A patent/NO149385C/en unknown
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1979
- 1979-12-17 NO NO794117A patent/NO149946C/en unknown
Also Published As
Publication number | Publication date |
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NO794117L (en) | 1979-06-20 |
NO784246L (en) | 1979-06-20 |
NO149946C (en) | 1984-07-25 |
NO149385C (en) | 1984-04-11 |
MX6273E (en) | 1985-03-05 |
NO149946B (en) | 1984-04-16 |
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