NO127968B - - Google Patents
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- NO127968B NO127968B NO00793/71*[A NO79371A NO127968B NO 127968 B NO127968 B NO 127968B NO 79371 A NO79371 A NO 79371A NO 127968 B NO127968 B NO 127968B
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- Norway
- Prior art keywords
- formula
- acid
- chrysanthemum
- methyl
- acid ester
- Prior art date
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- 150000002148 esters Chemical class 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 22
- -1 4-(2-methyl-phenoxy)-2-butynyl Chemical group 0.000 claims description 19
- 241000723353 Chrysanthemum Species 0.000 claims description 11
- 235000007516 Chrysanthemum Nutrition 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 230000000749 insecticidal effect Effects 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 23
- 239000000203 mixture Substances 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 229910052783 alkali metal Inorganic materials 0.000 description 13
- 239000007858 starting material Substances 0.000 description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- XLOPRKKSAJMMEW-UHFFFAOYSA-N chrysanthemic acid Chemical compound CC(C)=CC1C(C(O)=O)C1(C)C XLOPRKKSAJMMEW-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 241000238631 Hexapoda Species 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000002917 insecticide Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000012453 solvate Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- RPUJAOFSZSEVPC-UHFFFAOYSA-N 4-chlorobut-2-yn-1-ol Chemical compound OCC#CCCl RPUJAOFSZSEVPC-UHFFFAOYSA-N 0.000 description 2
- ZEVUHRJDTWDODR-UHFFFAOYSA-N 4-chlorobut-2-ynoxybenzene Chemical compound ClCC#CCOC1=CC=CC=C1 ZEVUHRJDTWDODR-UHFFFAOYSA-N 0.000 description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- VQXSOUPNOZTNAI-UHFFFAOYSA-N Pyrethrin I Natural products CC(=CC1CC1C(=O)OC2CC(=O)C(=C2C)CC=C/C=C)C VQXSOUPNOZTNAI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000004495 emulsifiable concentrate Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- LNJXZKBHJZAIKQ-UHFFFAOYSA-N 1,1,1,2-tetrachloro-3-(2,3,3,3-tetrachloropropoxy)propane Chemical compound ClC(Cl)(Cl)C(Cl)COCC(Cl)C(Cl)(Cl)Cl LNJXZKBHJZAIKQ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RCHDLEVSZBOHOS-UHFFFAOYSA-N 1,4-dichlorobut-2-yne Chemical group ClCC#CCCl RCHDLEVSZBOHOS-UHFFFAOYSA-N 0.000 description 1
- 241001124076 Aphididae Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 239000005909 Kieselgur Substances 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 241000699670 Mus sp. Species 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 241001280974 Synanthedon myopaeformis Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000012447 hatching Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
Landscapes
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Nærværende oppfinnelse vedrorer krysantemumsyreestere av den generelle formel The present invention relates to chrysanthemum acid esters of the general formula
hvor R betyr hydrogen eller en lavere alkylgruppe. where R means hydrogen or a lower alkyl group.
Disse forbindelser har insekticid virkning og er anvendbare som insekticider. These compounds have insecticidal action and are useful as insecticides.
Betegnelsen "lavere alkyl" betyr rettkjedete og forgrenete alkylgrupper med et forholdsvis lavt antall karbonat.omer, f. eks. metyl, etyl, propyl, isopropyl, butyl og tert.butyl. The term "lower alkyl" means straight-chain and branched alkyl groups with a relatively low number of carbon atoms, e.g. methyl, ethyl, propyl, isopropyl, butyl and tert.butyl.
En foretrukken klasse av krysantemumsyreestere ifolge oppfinnelsen er de forbindelser hvor R betegner hydrogen, og dette på grunn av deres særlig hoye insekticide virkning, og da særlig 4-fenoksy-2-butynyl (-)-cis/trans-2,2-dimetyl-3-(2-metyl-propenyl)-cyklopropankarboksylsyreester, En ytterligere foretrukken forbindelse er 4-(2-metyl-fenoksy-2-butynyl(-) A preferred class of chrysanthemum acid esters according to the invention are those compounds where R denotes hydrogen, and this because of their particularly high insecticidal effect, and especially 4-phenoxy-2-butynyl (-)-cis/trans-2,2-dimethyl- 3-(2-methyl-propenyl)-cyclopropanecarboxylic acid ester, A further preferred compound is 4-(2-methyl-phenoxy-2-butynyl(-)
-cis/trans-2,2-dimetyl-3-(2-metyl-propenyl)-cyklopropankar-boksylsyreester, fordi den likeledes har særlig hoy aktivitet overfor insekter. - Fra norsk patentsoknad nr. 4849/69 er fenyl-butynyl-krysante^ mumsyreestere kjente, hvilke - slik som det fremgår av neden-stående tabell - er esterene ifolge oppfinnelsen underlegne. -cis/trans-2,2-dimethyl-3-(2-methyl-propenyl)-cyclopropanecarboxylic acid ester, because it likewise has particularly high activity against insects. - From Norwegian patent application No. 4849/69, phenyl-butynyl-chrysanthemum acid esters are known, which - as can be seen from the table below - are inferior to the esters according to the invention.
De ovennevnte krysantemumsyre-estere kan fremstilles ved at man omsetter et syreklorid eller syrebromid med den generelle formel The above-mentioned chrysanthemum acid esters can be prepared by reacting an acid chloride or acid bromide with the general formula
med en alkohol med den generelle formel, hvor R har ovenfor angitte betydning, eller ved at man omsetter et alkalimetallsalt, et solvsalt eller et tri(lavere alkyl)-aminsalt av en krysantemum-monokarboksylsyre med et halogenid med den generelle formel with an alcohol of the general formula, where R has the meaning given above, or by reacting an alkali metal salt, a solvate or a tri(lower alkyl)amine salt of a chrysanthemum monocarboxylic acid with a halide of the general formula
hvor R ovenfor angitte betydning, og where R above indicated meaning, and
Hal betyr et halogen, Hal means a halogen,
eller ved at man omsetter en forbindelse med den generelle formel or by reacting a compound with the general formula
med et alkalimetallsalt av en fenol med den generelle formel with an alkali metal salt of a phenol of the general formula
hvor R har de ovenfor angitte betydninger. where R has the meanings given above.
Ifolge en utforelsesform av fremgangsmåten omsettes et syreklorid eller et syrebromid med formel II med en alkohol med formel III. According to one embodiment of the method, an acid chloride or an acid bromide of formula II is reacted with an alcohol of formula III.
De som utgangsmaterialer med formel II anvendte syreklorider -fvS:tS5 syrebromider er kjente—forbindelser, og kan fremstilles ved klorering eller broméring fra de tilsvarende monokarboksyl-syrene (f.eks. ved hjelp av tionylklorid, fosfortribromid o.1.) . The acid chlorides -fvS:tS5 acid bromides used as starting materials with formula II are known compounds, and can be prepared by chlorination or bromination from the corresponding monocarboxylic acids (e.g. using thionyl chloride, phosphorus tribromide, etc.).
De foretrukne utgangsmaterialene med formel II er syreklori-dene. The preferred starting materials of formula II are the acid chlorides.
De som utgangsmaterialer anvendte alkoholer med formel III kan f.eks. fremstilles ved omsetning av en halogenbutynol med den generelle formel The alcohols of formula III used as starting materials can e.g. is produced by reacting a halobutynol with the general formula
hvor Hal har den ovenfor angitte betydning, where Hal has the above meaning,
med et alkalimetallsalt av en fenol med ovenstående formel VI. Fortrinnsvis omsettes et klorid med formel VII med et na-triumsalt av en fenol VI. Fortrinnsvis finner omsetningen sted ved hoyere temperatur, f.eks. ved 50 - 70°C, i et inert organisk løsningsmiddel, f.eks. en lavere alkanol (f.eks. metanol eller etanol). with an alkali metal salt of a phenol of the above formula VI. Preferably, a chloride of formula VII is reacted with a sodium salt of a phenol VI. Preferably, the reaction takes place at a higher temperature, e.g. at 50 - 70°C, in an inert organic solvent, e.g. a lower alkanol (eg methanol or ethanol).
Omsetningen av et syreklorid eller syrebromid med formel II med en alkohol med formel III kan hensiktsmessig foretas i nærvær av et syrebindende middéi. Egnede syrebindéndé midler er alkalimetallkarbonater, f.eks. natriumkarbonat, aikalime-tallbikarbonater, som f.eks. natriumbikarbonat, og tertiære The reaction of an acid chloride or acid bromide of formula II with an alcohol of formula III can conveniently be carried out in the presence of an acid binding agent. Suitable acid binders are alkali metal carbonates, e.g. sodium carbonate, aikalime tall bicarbonates, such as sodium bicarbonate, and tertiary
organiske aminer, som f.eks. trietylamin, pyridin, etc. organic amines, such as triethylamine, pyridine, etc.
Det foretrukne syrebindende midlet er pyridin. Det er hensiktsmessig å gjennomfore reaksjonen i nærvær av et inert organisk losningsmiddel, f.eks. et hydrokarbon, som f.eks. benzen, toluen eller xylen, en eter, som f.eks. dietyleter eller dioksan, eller et halogenert hydrokarbon, som f.eks. metylenklorid eller kloroform eller lignende. Det er også hensiktsmessig å gjennomfore reaksjonen i et temperaturområde fra ca. 0° til ca. 30°C, fortrinnsvis ved ca. 20°C, og under en inert atmosfære, som f.eks. nitrogen eller argon. The preferred acid scavenger is pyridine. It is convenient to carry out the reaction in the presence of an inert organic solvent, e.g. a hydrocarbon, such as benzene, toluene or xylene, an ether, such as diethyl ether or dioxane, or a halogenated hydrocarbon, such as methylene chloride or chloroform or the like. It is also appropriate to carry out the reaction in a temperature range from approx. 0° to approx. 30°C, preferably at approx. 20°C, and under an inert atmosphere, such as nitrogen or argon.
En ytterligere fremgangsmåte består i om- A further method consists in re-
setning av et alkalimetallsalt, et solvsalt eller et tri(lavere alkyD-aminsalt av en krysantemum-monokarboksylsyre med et halogenid med ovenstående formel IV. addition of an alkali metal salt, a solvate or a tri(lower alkylD-amine salt) of a chrysanthemum monocarboxylic acid with a halide of the above formula IV.
Alkalimetallsaltene og tri(lavere alkyl)-aminsaltene kan f.eks. fremstilles ved at man behandler en krysantemum-mono-karbok-sylsyre, som forekommer i et inert organisk losningsmiddel, The alkali metal salts and tri(lower alkyl)amine salts can e.g. is produced by treating a chrysanthemum mono-carboxylic acid, which occurs in an inert organic solvent,
som f.eks. en lavere alkanol, f.eks. etanol, med den beregne-de mengden av en alkalimetallhydroksydlosning eller et tri(lavere alkyl)amin. Foretrukne alkalimetallsalter er natrium- og kaliumsalter og foretrukne tri(lavere alkyl)-aminsalter er trietylaminsalter. Solvsalter kan erholdes ved å behandle et alkalimetallsalt, f.eks. natriumsaltet, i en vandig losning med solvnitrat. like for example. a lower alkanol, e.g. ethanol, with the calculated amount of an alkali metal hydroxide solution or a tri(lower alkyl)amine. Preferred alkali metal salts are sodium and potassium salts and preferred tri(lower alkyl)amine salts are triethylamine salts. Sulfur salts can be obtained by treating an alkali metal salt, e.g. the sodium salt, in an aqueous solution with solvnitrate.
De som utgangsmaterialer med formel IV anvendte halogenid-forbindelser kan f.eks. erholdes ved at dihalogenbutyn med den generelle formel The halide compounds used as starting materials with formula IV can e.g. is obtained by dihalobutyne with the general formula
hvor Hal har den ovenfor angitte betydning, omsettes med et alkalimetallsalt av en fenol med formel VI. Det foretrukne dihalogenbutyn med formel IX er 1,4-diklor-2-butyn, og dette blir fortrinnsvis omsatt med en natrium-forbindelse av en fenol med formel VI. Det er hensiktsmessig å gjennomfore reaksjonen i et inert, organisk losningsmiddel, where Hal has the above meaning, is reacted with an alkali metal salt of a phenol of formula VI. The preferred dihalobutyne of formula IX is 1,4-dichloro-2-butyne, and this is preferably reacted with a sodium compound of a phenol of formula VI. It is appropriate to carry out the reaction in an inert, organic solvent,
som f.eks. en lavere alkanol, såsom metanol eller etanol, ved hoyere temperatur, f.eks. ved en temperatur mellom, ca. 50 og 70°C. like for example. a lower alkanol, such as methanol or ethanol, at a higher temperature, e.g. at a temperature between, approx. 50 and 70°C.
Omsetningen av et alkalimetallsalt, et soivsalt eller et tri-(lavere alkyl)-aminsalt av en krysantemum-monokarboksylsyre med et halogenid med formel IV foretas helst i et inert organisk losningsmiddel. Fortrinnsvis anvendes ketoner, som f.eks. aceton, metyletylketon eller diglym. Omsetningen foretas fortrinnsvis ved hoyere temperatur, hvorved det er hensiktsmessig å anvende reaksjonsblandingéns tilbakelbpstemperatur. Det er fordelaktig å foreta omsetningen i inert atmosfære, som f.eks. nitrogen eller argon. The reaction of an alkali metal salt, a sodium salt or a tri-(lower alkyl)amine salt of a chrysanthemum monocarboxylic acid with a halide of formula IV is preferably carried out in an inert organic solvent. Ketones are preferably used, such as e.g. acetone, methyl ethyl ketone or diglyme. The reaction is preferably carried out at a higher temperature, whereby it is appropriate to use the reflux temperature of the reaction mixture. It is advantageous to carry out the turnover in an inert atmosphere, such as e.g. nitrogen or argon.
En annen fremgangsmåte består i at man omsetter en forbindelse med formel V méd et alkalimetallsalt av en fenol med formel VI, hvorved man erholder en ester med formel I. Another method consists in reacting a compound of formula V with an alkali metal salt of a phenol of formula VI, whereby an ester of formula I is obtained.
Utgangsmaterialene med formel V kan f.eks. fremstilles ved omsetning av et klorid eller bromid med ovenstående formel II med 4-klor-2-butyn-l-ol. Denne reaksjon kan gjennomfores på samme måte som den tidligere beskrevne omsetningen av et syreklorid- eller syrebromid-utgangsmateriale med formel II med et alkoholutgangsmateriale med formel III. The starting materials with formula V can e.g. is prepared by reacting a chloride or bromide of the above formula II with 4-chloro-2-butyn-1-ol. This reaction can be carried out in the same way as the previously described reaction of an acid chloride or acid bromide starting material of formula II with an alcohol starting material of formula III.
Alkalimetallsalter av fenoler med formel VI er kjente og kan fremstilles ved hjelp av vanlige fremgangsmåter. Alkali metal salts of phenols of formula VI are known and can be prepared using usual methods.
Det er hensiktsmessig å foreta omsetningen av et utgangsmateriale med formel V méd et alkalimetallsalt av en fenol med formel VI i nærvær av et inert, organisk losningsmiddel, som f.eks. et hydrokarbon, som benzen, toluen eller xylen, et halogenert hydrokarbon, såsom kloroform eller metylenklorid eller lignende. Reaksjonen kan' fortrinnsvis skje ved hoyere temperatur, hvorved det ér hensiktsmessig'å anvende reaksjonsblandingéns tilbakelopstemperaturl Videre er det hensiktsmés-ig å foreta omsetningen i'inert åtmbsfæré védnjéip av hitro- It is appropriate to carry out the reaction of a starting material of formula V with an alkali metal salt of a phenol of formula VI in the presence of an inert, organic solvent, such as e.g. a hydrocarbon such as benzene, toluene or xylene, a halogenated hydrocarbon such as chloroform or methylene chloride or the like. The reaction can preferably take place at a higher temperature, whereby it is expedient to use the reflux temperature of the reaction mixture. Furthermore, it is expedient to carry out the reaction in an inert atmosphere against high-
gen eller argon. gen or argon.
Det er bemerkelsesverdig at krysantemumsyredelen i formel I kan oppvise såvel geometrisk som optisk isomeri. Estrene ifolge oppfinnelsen omfatter således selvsagt alle mulige geometri-ske og optiske isomerer, såvel, som blandinger av disse. En slik blanding erholder man når man som utgangsmateriale anven-der en syre-kloridblanding eller en syrebromidblanding, en alkalimetallsalt-utgangsmaterial-blanding, en solvsalt-utgangsmaterial-blanding, en tri(lavere alkyl)-aminsalt-utgangsmaterial-blanding eller en utgangsmaterial-blanding med formel V, hvilken kan erholdes ved å utgå fra den i handelen tilgjengelige krysantemum-monokarboksylsyre, som består av en racemisk cis/trans-blanding med et cis/trans-forhold på ca. 30:70%. It is noteworthy that the chrysanthemum acid moiety in formula I can exhibit both geometric and optical isomerism. The esters according to the invention therefore naturally include all possible geometric and optical isomers, as well as mixtures thereof. Such a mixture is obtained when an acid chloride mixture or an acid bromide mixture, an alkali metal salt starting material mixture, a solvate starting material mixture, a tri(lower alkyl)amine salt starting material mixture or a starting material mixture of formula V, which can be obtained by starting from the commercially available chrysanthemum monocarboxylic acid, which consists of a racemic cis/trans mixture with a cis/trans ratio of approx. 30:70%.
Som allerede nevnt er estrene ifolge oppfinnelsen anvendbare som insekticider. De oppviser aktivitet overfor et flertall insekter, særlig overfor Musea domestica, og de er spesielt virksomme når de anvendes sammen med kjente pyretrinsynergi-ster, som f.eks. piperonylbutoksyd, 1,2-metylendioksy)-4-[2-(ok-tylsulf inyl )-propyl]-benzen, bis(2,3,3,3-tetraklor-propyl)-eter eller lignende. Dessuten oppviser estrene en meget liten toksisitet overfor pattedyr og mennesker. F.eks. har 4-fenoksy-2-butynyl{-)-cis/trans-2,2-dimetyl-3-(2-metylpropenyl)-cyklo-propankarboksylsyre-esteren en LD^-verdi på 1600 mg/kg p.o. overfor mus og oppviser en aktivitet overfor Musea domestica av samme storrelsesorden som pyretrinekstrakt .og DDT. Denne forbindelse har også virkning på de svarte bonneblad-lusene og epleviklere. As already mentioned, the esters according to the invention can be used as insecticides. They show activity against a majority of insects, particularly against Musea domestica, and they are particularly effective when used together with known pyrethrin synergists, such as e.g. piperonyl butoxide, 1,2-methylenedioxy)-4-[2-(octylsulfinyl)-propyl]-benzene, bis(2,3,3,3-tetrachloro-propyl)-ether or the like. Furthermore, the esters show very little toxicity to mammals and humans. E.g. the 4-phenoxy-2-butynyl{-)-cis/trans-2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylic acid ester has an LD^ value of 1600 mg/kg p.o. against mice and exhibits an activity against Musea domestica of the same order of magnitude as pyrethrin extract and DDT. This compound also has an effect on the black bonne leaf aphids and apple borers.
Estrene ifolge oppfinnelsen kan anvendes i form av vanlige insekticide preparater, og da sammen med et aksepterbart bæremateriale. Disse preparatene kan foreligge i flytende form, som f.eks. sprayløsning eller spraysuspensjon, eller i fast form, som.f.eks. stov eller granulat, hvorved begge former inneholder et aksepterbart bæremiddel. Uttrykket "aksepterbart bæremiddel":, anvendes i foreliggende beskri-velse for å betegne et middel som er inert i forhold til esteren med formel I, hvorved midlet opploser eller dispergerer esteren uten å innvirke på dennes aktivitet, og videre at omgi-velsene, hvor preparatet brukes, som f.eks. avling, jordbunn, redskap osv. ikke blir skadet. F.eks.kan yæskeblandingen for-tynnes med vann og pulverstov eller granulater utspes med inerte, faste bæremidler. Når ved fremstillingen av de insekticide preparatene faste bærestoffer anvendes, så kan disse være talkum, fin leire, siliciumdioksyd eller lignende, hvilke ikke forårsaker spaltning av esteren. Hvis ester med formel I anvendes i væskeblanding, så kan denne blandingen være emulgeringsmiddel og/eller formålstjenelige løsningsmidler. De insekticide preparatene kan, hvis onsket, inneholde vanlige tilset-ninger, som f.eks. fuktemiddel eller lignende, og preparatene kan også inneholde andre insekticider og/eller synergiske stoffer. The esters according to the invention can be used in the form of ordinary insecticidal preparations, and then together with an acceptable carrier material. These preparations can be in liquid form, such as e.g. spray solution or spray suspension, or in solid form, such as dust or granules, whereby both forms contain an acceptable carrier. The term "acceptable carrier": is used in the present description to denote an agent which is inert in relation to the ester of formula I, whereby the agent dissolves or disperses the ester without affecting its activity, and furthermore that the surroundings, where the preparation is used, such as crop, soil, implements etc. are not damaged. For example, the ice mixture can be diluted with water and powdered dust or granules are spread out with inert, solid carriers. When solid carriers are used in the manufacture of the insecticidal preparations, these can be talc, fine clay, silicon dioxide or the like, which do not cause cleavage of the ester. If the ester of formula I is used in a liquid mixture, then this mixture can be an emulsifier and/or expedient solvents. The insecticidal preparations can, if desired, contain common additives, such as e.g. wetting agent or similar, and the preparations may also contain other insecticides and/or synergistic substances.
En virksom mengde av en insekticid blanding kan på vanlig måte anvendes for bekjempelse av insekter ved f.eks. sproytning, forstovning osv.. Fortrinnsvis inneholder faste blandinger og flytende blandinger ca. 0,5 til 25 vekt-%, fortrinnsvis ca. An effective amount of an insecticidal mixture can be used in the usual way for combating insects by e.g. spraying, atomizing, etc. Preferably, solid mixtures and liquid mixtures contain approx. 0.5 to 25% by weight, preferably approx.
1 - 10% av esteren med formel I. Valget av konsentrasjonen av 1 - 10% of the ester of formula I. The choice of the concentration of
esteren med formel I og hyppigheten med hvilken man behandler et insektbefengt område avhenger selvsagt av flere faktorer, som f.eks. insekt-arten og dennes utyiklings-stadium, det anvendte insekticide preparatet og den anvendte metoden. the ester of formula I and the frequency with which one treats an insect-infested area obviously depends on several factors, such as e.g. the insect species and its hatching stage, the insecticidal preparation used and the method used.
Det er bemerkelsesverdig at de insekticide blandingene kan fremstilles fra holdbare konsentrater, som f.eks. fra fuktig stov eller fra et emulsjonskonsentrat, hvilke inneholder ca. 10 - 80 vekt-% av en ester med formel I. Konsentratene kan utspes med et bærestoff eller med flere forskjellige bærestoffer til en konsentrasjon som er egnet for behandling av et aktuelt insekt-område. Emulgerte konsentrater kan f.eks. erholdes ved at man opploser en ester med formel I i et egnet losningsmiddel, og ved at man tilsetter et i losningsmidlet It is noteworthy that the insecticidal mixtures can be prepared from stable concentrates, such as e.g. from moist dust or from an emulsion concentrate, which contain approx. 10 - 80% by weight of an ester of formula I. The concentrates can be diluted with a carrier or with several different carriers to a concentration that is suitable for treating a relevant insect area. Emulsified concentrates can e.g. is obtained by dissolving an ester of formula I in a suitable solvent, and by adding a
<opplosbart emulgeringsmiddel. Egnede organiske, og vanligvis med vann ikke-blandbare løsningsmidler, er hydrokarboner som f.eks. tbluen eller xylen, klorerte hydrokarboner, som f.eks. <soluble emulsifier. Suitable organic, and usually water immiscible, solvents are hydrocarbons such as e.g. tbluen or xylene, chlorinated hydrocarbons, such as e.g.
perkloretylen, ketoner, estere, osv., eller blandinger derav. Aromatiske hydrokarboner og ketoner foretrekkes som løsnings-midler. Som emulgeringsmiddel kan man anvende overflateaktive stoffer, hvilke utgjor fra ca. 5-15 vekt-% av emulsjons-konsentratet. Det anvendes fortrinnsvis ikke-ioniske overflateaktive stoffer. perchlorethylene, ketones, esters, etc., or mixtures thereof. Aromatic hydrocarbons and ketones are preferred as solvents. Surfactants can be used as emulsifiers, which make up from approx. 5-15% by weight of the emulsion concentrate. Non-ionic surfactants are preferably used.
De i de folgende eksempler nevnte krysantemum-monokarboksyl-syrer er de i handelen tilgjengelige (i)-karboksylsyrene, hvilke består'<a>v' en cis/trans-bland<i>r<i>g i et forhold på ca. 30:70. Det i eksemplene nevnte krysantemum-monokarboksylsyreklorid ble fremstilt av den samme syren. The chrysanthemum monocarboxylic acids mentioned in the following examples are the commercially available (i)-carboxylic acids, which consist of a cis/trans mixture in a ratio of approx. 30:70. The chrysanthemum monocarboxylic acid chloride mentioned in the examples was prepared from the same acid.
EKSEMPEL 1 EXAMPLE 1
En opplesning av 75,6 g krysantemumsyre i 250 ml etanol ble titrert til noytralpunktet med en 2 N vandig natriumhydroksydlosning. Den erholdte lbsningen ble inndampet til torrhet, hvoretter restén ble tilsatt etanol og igjen inndampet. Den erholdte réstén ble destillert flere ganger med benzen, inn-til restens vekt tilsvarte det teoretiske utbyttet av natriumsaltet til krysantemum-monokarboksylsyren. Destillasjonsresten ble deretter tilsatt 2 liter diglym, blandingen ble omrort ved 100°C under nitrogenatmosfære og samtidig ble 81 g l-klor-4-fenoksy-2-butyn tilsatt i lopet av 1/2 time. Den erholdte blandingen ble omrort 5 dager ved 150°C (oljebad-temperatur). Utfelt natriumklorid ble filtrert, og filtratet ble inndampet under redusert trykk. Den sirupaktige resten ble opplost i dietyleter og losningen deretter vasket to ganger med 2 N vandig natriumhydroksydlosning. Vaskevannet ble ekstrahert med dietyleter, og dé forenede eterholdige losningene ble i nevnte rekkefolge vasket med vann, mettet vandig natriumbi-karbonatibsning og kbksaltlbsning, tbrket over vannfri natriumsulfat, filtrert og inndampet. Resten ble inndampet ved hjelp av en oljepumpe under nitrogenåtmosfære og i nærvær av spor av hydrokinon. Man erholdt på denne måte 4-fenoksy-2-butynyl(-)-cis/trans-2,2-dimetyl-3-(2-metylpropenyl)-cyklo-propankarboksylsyreester méd et kokepunkt på i60 180°C/ 0,25 mm (badtemperatur 200 - 205°C). Utbyttet var ca. 50 %. Uomsatt l-klor-4-fenoksy-2-butyn ble gjenvunnet. A reading of 75.6 g of chrysanthemum acid in 250 ml of ethanol was titrated to the neutral point with a 2 N aqueous sodium hydroxide solution. The solution obtained was evaporated to dryness, after which ethanol was added to the residue and evaporated again. The residue obtained was distilled several times with benzene, until the weight of the residue corresponded to the theoretical yield of the sodium salt of the chrysanthemum monocarboxylic acid. The distillation residue was then added to 2 liters of diglyme, the mixture was stirred at 100°C under a nitrogen atmosphere and at the same time 81 g of 1-chloro-4-phenoxy-2-butyne was added over the course of 1/2 hour. The resulting mixture was stirred for 5 days at 150°C (oil bath temperature). Precipitated sodium chloride was filtered, and the filtrate was evaporated under reduced pressure. The syrupy residue was dissolved in diethyl ether and the solution was then washed twice with 2 N aqueous sodium hydroxide solution. The wash water was extracted with diethyl ether, and the combined ether solutions were washed in the aforementioned order with water, saturated aqueous sodium bicarbonate solution and sodium bicarbonate solution, washed over anhydrous sodium sulfate, filtered and evaporated. The residue was evaporated by means of an oil pump under a nitrogen atmosphere and in the presence of traces of hydroquinone. 4-phenoxy-2-butynyl(-)-cis/trans-2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylic acid ester with a boiling point of i60 180°C/ 0.25 mm was obtained in this way (bath temperature 200 - 205°C). The yield was approx. 50%. Unreacted 1-chloro-4-phenoxy-2-butyne was recovered.
EKSEMPEL 2 EXAMPLE 2
En opplosning av 14,5 g 4-(2-metyl-fenoksy)-butyn-l-ol og 12 ml torr pyridin i 100 ml torr benzen ble i lopet av 15 minutter behandlet med en opplosning av krysantemum-monokarboksylsyreklorid i benzen. Den erholdte blandingen ble omrort 16 timer ved 20°C under nitrogenatmosfære, hvoretter det utfelte pyridinhydrokloridet ble filtrert og vasket med benzen. De forenede vaskevannene og filtratet ble i nevnte rekkefolge vasket to ganger med 5 N saltsyre, to ganger med 2 N vandig natriumhydroksydlosning, én gang med 2 N saltsyre, to ganger med mettet vandig natriumbikarbonatlosning og to ganger med koksaltlosning, torket over vannfri natriumsulfat, filtrert og inndampet. Den sirupaktige resten (25 g) ble kromatografert ved hjelp av lOO g noytral aluminiumoksyd med petroleter (koke-område 40 - 60°C) som elueringsmiddel. Ved inndampning av elua-tet erholdt man 15 g analytisk ren 4-(2-metyl-fenoksy)-2-buty-nyl (+)cis/trans-2,2-dimetyl-3-(2-metyl-propenyl)-cyklo-propan-20 A solution of 14.5 g of 4-(2-methyl-phenoxy)-butyn-1-ol and 12 ml of dry pyridine in 100 ml of dry benzene was treated in the course of 15 minutes with a solution of chrysanthemum monocarboxylic acid chloride in benzene. The resulting mixture was stirred for 16 hours at 20°C under a nitrogen atmosphere, after which the precipitated pyridine hydrochloride was filtered and washed with benzene. The combined washing waters and the filtrate were washed in the aforementioned order twice with 5 N hydrochloric acid, twice with 2 N aqueous sodium hydroxide solution, once with 2 N hydrochloric acid, twice with saturated aqueous sodium bicarbonate solution and twice with sodium bicarbonate solution, dried over anhydrous sodium sulfate, filtered and evaporated. The syrupy residue (25 g) was chromatographed using 100 g of neutral alumina with petroleum ether (boiling range 40 - 60°C) as eluent. By evaporation of the eluate, 15 g of analytically pure 4-(2-methyl-phenoxy)-2-butynyl (+)cis/trans-2,2-dimethyl-3-(2-methyl-propenyl)- cyclo-propane-20
karboksylsyreesterj nD = 1,5 290. carboxylic acid esterj nD = 1.5 290.
EKSEMPEL 3 EXAMPLE 3
Fremstilling av utgangsmaterialet: Preparation of the starting material:
En opplosning av 8,6 g 4-klor-2-butyn-l-ol bg 11,85 g torr pyridin i 120 ml torr benzen ble i lopet av 15 minutter under nitrogenatmosfære og ved romtemperatur behandlet med en opplosning av 14 g krysantemumsyreklorid i 50 ml benzen. Den erholdte blandingen ble omrort 19 timer ved 25°C, hvoretter det utfelte pyridinhydrokloridet ble filtrert og vasket med benzen. De forenede vaskevann og filtratet ble i nevnte rekkefolge vasket to ganger med 2 N saltsyre, én gang med 2 N vandig natriumhydroksydlosning, én gang med 2 N saltsyre, to ganger med mettet vandig natriumbikarbonatlosning og to ganger med koksaltlosning, torket over vannfri natriumsulfat, filtrert og inndampet. Ved destillasjon av resten erholdt man 15,3 g 4-klor-2-butynyl(-)-cis/trans-2,2-dimetyl-3-(2-metyl-propenyl)-cyklopropankarboksylsyreester med et kokepunkt på 120 - 122°C/0,45 mm; n^° = 1,5010. A solution of 8.6 g of 4-chloro-2-butyn-1-ol bg 11.85 g of dry pyridine in 120 ml of dry benzene was over the course of 15 minutes under a nitrogen atmosphere and at room temperature treated with a solution of 14 g of chrysanthemum acid chloride in 50 ml of benzene. The resulting mixture was stirred for 19 hours at 25°C, after which the precipitated pyridine hydrochloride was filtered and washed with benzene. The combined washings and the filtrate were washed in the aforementioned order twice with 2 N hydrochloric acid, once with 2 N aqueous sodium hydroxide solution, once with 2 N hydrochloric acid, twice with saturated aqueous sodium bicarbonate solution and twice with sodium bicarbonate solution, dried over anhydrous sodium sulfate, filtered and evaporated. Distillation of the residue yielded 15.3 g of 4-chloro-2-butynyl(-)-cis/trans-2,2-dimethyl-3-(2-methyl-propenyl)-cyclopropanecarboxylic acid ester with a boiling point of 120 - 122° C/0.45mm; n^° = 1.5010.
Folgende eksempler skal nærmere anskueliggjøre fremstillingen av preparater inneholdende de insekticide forbindelser ifolge The following examples shall provide a clearer picture of the preparation of preparations containing the following insecticidal compounds
. oppfinnelsen. . the invention.
EKSEMPEL 4 EXAMPLE 4
2,5 g 4-fenoksy-2-butynyl(+)-cis/trans-2,2-dimetyl-3-(2-metyl-propenyl)-cyklopropankarboksylsyreester ble opplost i så mye kerosin at man fikk et sluttvolum på 100 ml. Den erholdte losningen egnet seg for anvendelse som spraylosning. 2.5 g of 4-phenoxy-2-butynyl(+)-cis/trans-2,2-dimethyl-3-(2-methyl-propenyl)-cyclopropanecarboxylic acid ester were dissolved in enough kerosene to give a final volume of 100 ml . The solution obtained was suitable for use as a spray solution.
EKSEMPEL 5 EXAMPLE 5
20 g 4-fenoksy-2-butynyl(i)-cis/trans-2,2-dimetyl-3-(2-metyl-propenyl)-cyklopropankarboksylsyreester, IO g honoksylan-15 (et ikke-ionisk fuktemiddel) og 70 g xylen ga etter grundig blanding en losning som kunne anvendes som emulgerbart konsen-trat. Forst ble det emulgerbare konsentratet emulgert med tilstrekkelig mye vann, slik at det tilsvarte 10 gangers for-tynning. 20 g of 4-phenoxy-2-butynyl(i)-cis/trans-2,2-dimethyl-3-(2-methyl-propenyl)-cyclopropanecarboxylic acid ester, 10 g of honoxylan-15 (a nonionic wetting agent) and 70 g After thorough mixing, the xylene gave a solution that could be used as an emulsifiable concentrate. First, the emulsifiable concentrate was emulsified with a sufficient amount of water, so that it corresponded to a 10-fold dilution.
EKSEMPEL 6 EXAMPLE 6
2,5 g 4-fenoksy-2-butynyl(-)-cis/trans-2,2-dimetyl-3-(2-metyl-propenyl)-cyklopropankarboksylsyreester ble opplost i 20 ml aceton, hvoretter 97,5 g diatoméjord, 300 mesh, ble tilsatt losningen.Den erholdte blandingen ble grundig omrort i en morter. Acetonen ble deretter fordampet, og man fikk et 2,5 %'ig pulverstov. 2.5 g of 4-phenoxy-2-butynyl(-)-cis/trans-2,2-dimethyl-3-(2-methyl-propenyl)-cyclopropanecarboxylic acid ester were dissolved in 20 ml of acetone, after which 97.5 g of diatomaceous earth, 300 mesh, was added to the solution. The resulting mixture was thoroughly stirred in a mortar. The acetone was then evaporated, and a 2.5% powder dust was obtained.
Claims (4)
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CH (1) | CH566710A5 (en) |
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DE (1) | DE2108779A1 (en) |
DK (1) | DK131458B (en) |
ES (1) | ES388773A1 (en) |
FR (1) | FR2084122A5 (en) |
GB (1) | GB1290226A (en) |
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IL (1) | IL36151A (en) |
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US4118505A (en) * | 1973-04-20 | 1978-10-03 | Sumitomo Chemical Company, Limited | Novel cyclopropanecarboxylates |
FR2426673A1 (en) * | 1978-05-25 | 1979-12-21 | Nat Res Dev | PYRETHRINE TYPE PESTICIDES |
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1970
- 1970-03-03 GB GB1003470A patent/GB1290226A/en not_active Expired
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1971
- 1971-02-03 CH CH162771A patent/CH566710A5/xx not_active IP Right Cessation
- 1971-02-05 ZA ZA710743A patent/ZA71743B/en unknown
- 1971-02-08 IL IL36151A patent/IL36151A/en unknown
- 1971-02-17 IE IE186/71A patent/IE35157B1/en unknown
- 1971-02-17 NL NL7102103A patent/NL7102103A/xx unknown
- 1971-02-19 CS CS1281A patent/CS171695B2/cs unknown
- 1971-02-24 DE DE19712108779 patent/DE2108779A1/en active Pending
- 1971-03-02 SE SE7102657A patent/SE371813B/xx unknown
- 1971-03-02 AT AT175671A patent/AT309891B/en not_active IP Right Cessation
- 1971-03-02 ES ES388773A patent/ES388773A1/en not_active Expired
- 1971-03-02 BE BE763665A patent/BE763665A/en unknown
- 1971-03-02 NO NO00793/71*[A patent/NO127968B/no unknown
- 1971-03-03 FR FR7107262A patent/FR2084122A5/fr not_active Expired
- 1971-03-03 DK DK97471AA patent/DK131458B/en unknown
Also Published As
Publication number | Publication date |
---|---|
DE2108779A1 (en) | 1971-09-16 |
IL36151A (en) | 1974-10-22 |
DK131458B (en) | 1975-07-21 |
ES388773A1 (en) | 1974-02-16 |
IE35157L (en) | 1971-09-03 |
AT309891B (en) | 1973-09-10 |
FR2084122A5 (en) | 1971-12-17 |
NL7102103A (en) | 1971-09-07 |
BE763665A (en) | 1971-09-02 |
SE371813B (en) | 1974-12-02 |
IE35157B1 (en) | 1975-11-26 |
CS171695B2 (en) | 1976-10-29 |
DK131458C (en) | 1975-12-08 |
CH566710A5 (en) | 1975-09-30 |
ZA71743B (en) | 1971-10-27 |
IL36151A0 (en) | 1971-04-28 |
GB1290226A (en) | 1972-09-20 |
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