DE2066032C2 - Derivatives of cis-3,3-dimethyl-2- (2'-oxo-3'-X-cyclopentylidenemethylidenemethyl) -cyclopropane-1-carboxylic acid and processes for their preparation - Google Patents
Derivatives of cis-3,3-dimethyl-2- (2'-oxo-3'-X-cyclopentylidenemethylidenemethyl) -cyclopropane-1-carboxylic acid and processes for their preparationInfo
- Publication number
- DE2066032C2 DE2066032C2 DE2066032A DE2066032A DE2066032C2 DE 2066032 C2 DE2066032 C2 DE 2066032C2 DE 2066032 A DE2066032 A DE 2066032A DE 2066032 A DE2066032 A DE 2066032A DE 2066032 C2 DE2066032 C2 DE 2066032C2
- Authority
- DE
- Germany
- Prior art keywords
- dimethyl
- cyclopropane
- oxo
- carboxylic acid
- cis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title description 4
- 238000002360 preparation method Methods 0.000 title description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 45
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 238000011282 treatment Methods 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 238000004821 distillation Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 241000238631 Hexapoda Species 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 7
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- -1 Alkali metal amides Chemical class 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 241000257226 Muscidae Species 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 230000000749 insecticidal effect Effects 0.000 description 5
- 150000004714 phosphonium salts Chemical class 0.000 description 5
- 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 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 4
- 150000002596 lactones Chemical class 0.000 description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- AFEOKIGLYCQHAZ-UHFFFAOYSA-N (5-benzylfuran-3-yl)methanol Chemical compound OCC1=COC(CC=2C=CC=CC=2)=C1 AFEOKIGLYCQHAZ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 230000000699 topical effect Effects 0.000 description 3
- PTQGFDXPHNRDCV-CRCLSJGQSA-N (1s,3s)-3-formyl-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)[C@@H](C=O)[C@@H]1C(O)=O PTQGFDXPHNRDCV-CRCLSJGQSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 241000257159 Musca domestica Species 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
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000002147 killing effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052717 sulfur Chemical group 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- SFDXJGBNXVTWEB-UHFFFAOYSA-N 1-formylcyclopropane-1-carboxylic acid Chemical compound OC(=O)C1(C=O)CC1 SFDXJGBNXVTWEB-UHFFFAOYSA-N 0.000 description 1
- YSULOORXQBDPCU-UHFFFAOYSA-N 2-(trimethylazaniumyl)ethanehydrazonate;hydrochloride Chemical compound [Cl-].C[N+](C)(C)CC(=O)NN YSULOORXQBDPCU-UHFFFAOYSA-N 0.000 description 1
- VOVAKSXCTQYGIH-UHFFFAOYSA-N 2-formylcyclopropane-1-carboxylic acid Chemical compound OC(=O)C1CC1C=O VOVAKSXCTQYGIH-UHFFFAOYSA-N 0.000 description 1
- JIBQDZMAERMTKB-UHFFFAOYSA-N 3-(triphenyl-$l^{5}-phosphanylidene)thiolan-2-one Chemical compound O=C1SCCC1=P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 JIBQDZMAERMTKB-UHFFFAOYSA-N 0.000 description 1
- PTQGFDXPHNRDCV-UHFFFAOYSA-N 3-formyl-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C=O)C1C(O)=O PTQGFDXPHNRDCV-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 241000208822 Lactuca Species 0.000 description 1
- 235000003228 Lactuca sativa Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-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
- 241000985245 Spodoptera litura Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 150000005840 aryl radicals Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 210000000038 chest Anatomy 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical compound OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- UTVVREMVDJTZAC-UHFFFAOYSA-N furan-2-amine Chemical compound NC1=CC=CO1 UTVVREMVDJTZAC-UHFFFAOYSA-N 0.000 description 1
- 125000000457 gamma-lactone group Chemical group 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003791 organic solvent mixture Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 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
- 239000002904 solvent Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000001874 trioxidanyl group Chemical group [*]OOO[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/27—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/36—Oxygen or sulfur atoms
- C07D207/38—2-Pyrrolones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/58—One oxygen atom, e.g. butenolide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/30—Hetero atoms other than halogen
- C07D333/32—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
IOIO
2020th
in derin the
bedeuten.mean.
2. Verfahren zur Herstellung der Verbindungen gemäß Anspruch 1, dadurch gekennzeichnet, daß man in an sich bekannter Weise eine racemische oder optisch aktive cis-33-Dimethyl-2-formyl-cyclopropan-1-carbonsäure entweder in Gegenwart einer starken Base mit einem 2-Oxo-3-X-cydopentyItriarylphosphoniumsalz, das in dem basischen Milieu in J5 Form eines Ylids vorliegen kann, oder in neutralem Milieu mit einem 2-Oxo-3-X-cyclopentyliden-triarylphosphoran, wobei X die in Anspruch 1 angegebenen Bedeutungen besitzt, umsetzt, die so erhaltene2. Process for the preparation of the compounds according to claim 1, characterized in that one in a known manner a racemic or optically active cis-33-dimethyl-2-formyl-cyclopropane-1-carboxylic acid either in the presence of a strong base with a 2-oxo-3-X-cydopentyItriarylphosphonium salt, which in the basic medium in J5 May be in the form of a ylid, or in a neutral medium with a 2-oxo-3-X-cyclopentylidene-triarylphosphorane, where X has the meanings given in claim 1, the thus obtained
cis-3^-DimethyI-2-(2'-oxo-3'-X-cycIopentylidenmethyl)-cyclopropan-1 -carbonsäure gegebenenfalls reinigt und in ihr Kaliumsalz oder Chlorid überführt.cis -3 ^ -Dimethyl-2- (2'-oxo-3'-X-cycIopentylidenemethyl) -cyclopropane-1-carboxylic acid optionally cleanses and converts it into its potassium salt or chloride.
4545
5050
c!S-33-Dimethy-2-(2'-oxo-3'-X-cyclopentylidenmethyl)-cyclopropan-1-carbonsäure gemäß dem Patentanspruch 1. Sie stellen wertvolle Zwischenprodukte dar.c! S-33-Dimethy-2- (2'-oxo-3'-X-cyclopentylidenemethyl) -cyclopropane-1-carboxylic acid according to claim 1. They are valuable intermediates.
Besonders hervorzuheben sind das Kaliumsalz der (IR, 2S), (1S-2R> oder racemischen cis-33-Dimethyl-2-(2'-oxo-3'-öxa-cyclopentylidenmethyl)-cyclopropan-1-carbonsäure; das Chlorid der (IR, 2S), (IS, 2R)- oder racemischen cis-3j3-Dimethyl-2-(2'-oxo-3'-oxa-cyQlopentylidenmelhyl)-cyclopropan-1-carbonsäure und das Chlorid der (IR, 2S), (IS, 2R)- oder racemischen cis-3r3-Dimethyl-2-(2'-oxo-3'-thia-cyclopentylidenmethyl)-cyclopropan-1 -carbonsäure.Particularly noteworthy are the potassium salt of (IR, 2S), (1S-2R> or racemic cis-33-dimethyl-2- (2'-oxo-3'-oxa-cyclopentylidenemethyl) -cyclopropane-1-carboxylic acid; the chloride of (IR, 2S), (IS, 2R) - or racemic cis-3j3-dimethyl-2- (2'-oxo-3'-oxa-cyclopentylidenemethyl) -cyclopropane-1-carboxylic acid and the chloride of (IR, 2S) , (IS, 2R) - or racemic cis-3 r 3-dimethyl-2- (2'-oxo-3'-thia-cyclopentylidenemethyl) -cyclopropane-1-carboxylic acid.
Aus den erfindungsgemäßen Verbindungen erhält man insbesondere die racemischen oder optisch aktiven 3,3-Dimethyl-2-(2'-oxo-3'-X-cyclopeniylidenmethyl)-cy-The racemic or optically active compounds are obtained in particular from the compounds according to the invention 3,3-dimethyl-2- (2'-oxo-3'-X-cyclopeniylidenemethyl) -cy- H3CH 3 C
OR'OR '
in der X ein Sauerstoff- oder Schwefelatom und R' einen Rest der allgemeinen Formelin which X is an oxygen or sulfur atom and R 'is a radical of the general formula
-CH2 -CH 2
bedeuten.mean.
Die Verbindungen der Formel Γ können eine cis-Struktur der Konfiguration (IR, 2S) oder (IS, 2R) oder eine racemische Struktur aufweisen.The compounds of the formula Γ can have a cis structure of the configuration (IR, 2S) or (IS, 2R) or have a racemic structure.
Die Verbindungen der Formel Γ besitzen interessante insektizide Eigenschaften, aufgrund deren sie auf dem Gebiet der Landwirtschaft und im Haushalt zur Bekämpfung von schädlichen Insekten verwendet werden können.The compounds of formula Γ have interesting insecticidal properties, due to which they are used in the field of agriculture and household Control of harmful insects can be used.
Die hohe insektizide Aktivität der Verbindungen der Formel Γ mit der cis-Konfiguration (IR, 2S) ist besonders bemerkenswert, denn bei den Verbindungen mit Pyrethrinoid-Struktur haben eher die Derivate der trans-Konfiguration (IR, 2R) eine beachtliche insektizide AktivitätThe high insecticidal activity of the compounds of formula Γ with the cis configuration (IR, 2S) is particularly noteworthy, because in the compounds with a pyrethrinoid structure, the derivatives of trans configuration (IR, 2R) shows considerable insecticidal activity
Das 5- Benzyl-3-furyl-methyl-3,3-dimethyl-2S-(2'-oxo-3'-oxa-cyclopentylidenmethyI)-cyclopropan-lR-carboxylat beispielsweise besitzt gegenüber Hausfliegen eine »Knock-dlown«-Wirkung, die etwa zweimal stärker ist als diejenige des dl-Allethrolonyl-d-trans-chrysanthemats oder als diejenige des dl-Allethrolonyl-d-trans-pyrethrats.5-Benzyl-3-furyl-methyl-3,3-dimethyl-2S- (2'-oxo-3'-oxa-cyclopentylidenemethyl) -cyclopropane-IR-carboxylate, for example, possesses house flies a "knock-dlown" effect that is about twice as strong is as that of dl-allethrolonyl-d-trans-chrysanthemate or as that of dl-allethrolonyl-d-trans-pyrethrate.
Die vorteilhaften Insektiziden Eigenschaften gehen aus den nachstehend aufgeführten Versuchen hervor.The beneficial insecticidal properties go from the experiments listed below.
5-Benzyl-3-furylmethyl-3,3-cis-dimethyl-2S-(2'-oxo-3'-oxacyclopentylidenmethyl)-cyclopropan-5-benzyl-3-furylmethyl-3,3-cis-dimethyl-2S- (2'-oxo-3'-oxacyclopentylidenemethyl) -cyclopropane- 1 R-carboxylat (Verbindung A),1 R-carboxylate (compound A),
5-Benzyl-3-furylmethyl-3>cis-dimethyl-2S-(2'-oxo-3'-thiiacyclopenthylidenmethyl)-cyclopropan-1 R-carbonylat (Verbindung C)5-Benzyl-3-furylmethyl-3> cis-dimethyl-2S- (2'-oxo-3'-thiiacyclopenthylidenemethyl) -cyclopropane-1R-carbonylate (compound C)
6060 und die bekannten Verbindungen:and the known connections:
dl-Alle-US-PSdl-all-US-PS
d-trans-Chrysanthemumsäure-ester von throlon (Verbindung B) bekannt aus 27 68 965, sowied-trans-chrysanthemum acid ester of throlon (compound B) known from 27 68 965, as well as
5-Benz)l-3-furylmethyl-33-dimethyl-2R-(2'-methyl-1 '-propenylj-cyclopropan-1 R-carboxylat (Verbindung Et') bekannt aus BE-PS 6 90 984.5-Benz) l-3-furylmethyl-33-dimethyl-2R- (2'-methyl-1 '-propenylj-cyclopropane-1R-carboxylate (compound Et') known from BE-PS 6 90 984.
In der nachstehenden Tabelle bedeutet % KD die Prozent der getöteten Insekten.In the table below,% KD means the percent of insects killed.
K.T50 oder KT30 bedeutet die Zeit, nach der 50% oder 90% der Tiere getötet waren.K.T50 or KT 30 means the time after which 50% or 90% of the animals have been killed.
A. Test gegenüber Hausfliegen durch
direkte Zerstäubung mit dem »Tour de Potter«A. Test against house flies
direct atomization with the "Tour de Potter"
Untersuchung der SofortwirkungInvestigation of the immediate effect
Man verwendet 4 Tage alte weibliche und männliche Hausfliegen. Die Behandlungen werden durch direkte Zerstäubung mit einem »Tour de Potter« durchgeführt, wobei man für jede Behandlung 2 cm3 einer acetonischen Lösung des zu testenden Produktes einsetzt Je Dosis werden 5 Wiederholungen durchgeführt, und zwar bei (jeder Wiederholung) jeweils mit 20 Exemplaren. 4-day-old female and male house flies are used. The treatments are carried out by direct atomization with a "Tour de Potter", 2 cm 3 of an acetone solution of the product to be tested being used for each treatment. 5 repetitions are carried out per dose, with 20 copies each time.
Man zählt die getöteten Insekten jeweils 2, 4, 8, (12) und 16 Minuten nach der Behandlung. Die Tests werden im Vergleich zu der Verbindung B durchgeführt.The insects killed are counted 2, 4, 8, (12) and 16 minutes after the treatment. The tests will compared to compound B.
Die erhaltenen Versuchsresultate sind in der folgenden Tabelle zusammengefaßt (»AS/1« bedeutet darin Aktivsubstanz/Liter).The experimental results obtained are summarized in the following table ("AS / 1" means in it Active substance / liter).
11,092.2
11.0
94,0100
94.0
100100
100
100100
100
I 50J 500
I 50
2,021.5
2.0
24,285.5
24.2
51,691.1
51.6
60,097.9
60.0
55,896.6
55.8
4,42.6
4.4
7,23.8
7.2
I 50f 500
I 50
12,584.5
12.5
7,7<2
7.7
2)6.8
2 )
Kontrollecontrol
3,53.5
') Wert bestimmt auf logarithmischen Papier. 2) 90%ige Abtötung tier Insekten nicht erreicht.') Value determined on logarithmic paper. 2 ) 90% kill of animal insects not achieved.
2,32.3
4,74.7
5,05.0
FolgerungInference
Tabelle I zeigt, daß Verbindung C eine höhere Sofortwii-kung besitzt als Verbindung B.Table I shows that compound C has a higher immediate effect than compound B.
B. Test gegenüber der Hausfliege durch topische
Anwendung Untersuchung der abtötenden WirkungB. Test against the house fly by topical
Application Investigation of the killing effect
Man verwendet weibliche Hausfliegen. Die Behandlungen werden durch topische Anwendung durchgeführt, wobei man 1 μΙ acetonische Lösung anwendet, die auf den Rückenthorax jedes Insekts aufgebracht wird. Je Dosis werden 3 Wiederholungen durchgeführt, und zwar mit jeweils 50 Exemplaren (pro Wiederholung).Female house flies are used. The treatments are carried out by topical application, using 1 μΙ acetone solution, which is applied to the back thorax of each insect. Ever Dose are performed 3 repetitions, each with 50 copies (per repetition).
Man bestimmt die Abtötung nach 24 Stunden. Die Tests werden im Vergleich zu Verbindung B durchgeführt. The kill is determined after 24 hours. The tests are performed against Compound B.
Die erhaltenen Versuchsresultate sind in der folgenden Tabelle zusammengefaßt.The experimental results obtained are summarized in the following table.
FolgerungInference
Tabelle II zeigt, daß Verbindung A eine Tötungsaktivität derselben Größenordnung besitzt wie Verbindung B. Table II shows that compound A has a killing activity of the same order of magnitude as compound B.
C. Test gegenüber der Hausfliege
durch Zerstäubung in der Kammer
von Kearns und MarchC. House fly test
by atomization in the chamber
by Kearns and March
Untersuchung der SofortwirkungInvestigation of the immediate effect
Man verwendet weibliche Hausfliegen. Die Behandlungen werden durch direkte Zerstäubung in der Kammer von Kearns und March durchgeführt, wobei man 0,2 ml einer Lösung des zu testenden Produkts in einer Mischung aus gleichen Volumenteilen Aceton und Kerosin einsetzt. Je Dosis werden 3 Wiederholungen durchgeführt, mit jeweils 50 Exemplaren (pro Wiederholung). Female house flies are used. The treatments are by direct atomization in the Chamber of Kearns and March, wherein 0.2 ml of a solution of the product to be tested in a mixture of equal parts by volume of acetone and kerosene is used. 3 repetitions are made for each dose performed, with 50 copies each (per repetition).
2, 4, 6, 8, 10 und 15 Minuten nach der Behandlung werden die getöteten Insekten gezählt.The insects killed are counted 2, 4, 6, 8, 10 and 15 minutes after the treatment.
Die Tests werden im Vergleich mit Verbindung B durchgeführt.The tests are carried out in comparison with compound B.
Die erhaltenen Vergleichsresultate sind in den folgenden Tabellen zusammengefaßtThe comparison results obtained are summarized in the following tables
FolgerungInference
Wenn man die KTso-Werte in ein Diagramm mit Abszisse und logarithmischer Ordinate derart einträgt, daß die den KT50-Werten entsprechenden Dosen auf der Abszisse und die KTso-Werte auf der Ordinate liegen, befinden sich die der Verbindung A entsprechenden 4 Punkte auf einer Kurve mit exponentiellemIf you enter the KTso values in a diagram with the abscissa and logarithmic ordinate, that the doses corresponding to the KT50 values are on the abscissa and the KTso values on the ordinate are, the 4 points corresponding to connection A are on a curve with exponential
Verlauf; die einem KTso-Wert von 5,5 entsprechende Dosis beträgt 56 mg/1, d. h. daß bei Verbindung A eine Dosis von 56 mg/1 denselben KTso-Wert erzielt wie 500 mg der Verbindung B.Course; the dose corresponding to a KT 50 value of 5.5 is 56 mg / l, i.e. H. that at connection A a A dose of 56 mg / 1 achieves the same KT 50 value as 500 mg of compound B.
Daraus ergibt sich, daß in bezug auf den KTso-Wert Verbindung A eine 9mal schnellere Wirkung besitzt als Verbindung B.It follows that with regard to the KT 50 value, compound A has an effect 9 times faster than Connection B.
Dosis in mg AS/IDose in mg AS / I
% KD 2 Min.% KD 2 min.
4Mi-.. 6 Min. 4min .. 6 min.
8 Min.8 min.
10 Min.10 min.
in Sek.in sec.
Verbindung C 500 54,0 68,0 76,0 100 100 102Compound C 500 54.0 68.0 76.0 100 100 102
Verbindung B 500 2,0 24,5 44,9 51,0 63,2 442Connection B 500 2.0 24.5 44.9 51.0 63.2 442
') Graphisch bestimmt auf logarithmischem Papier.') Graphically determined on logarithmic paper.
FolgerungInference
Tabelle IV zeigt, d?J3 Verbindung C 4,3rnal aktiver ist als Verbindung B.Table IV shows that J3 Compound C is 4.3 times more active as connection B.
O. Test gegenüber Prodenia litura (Raupen)
durch topische AnwendungO. Test against Prodenia litura (caterpillars)
by topical application
Man führt die Behandlung durch, indem man 4 μΙ der acetonischen Lösung der zu untersuchenden Verbindung auf Salatblätter-Kügelchen mit 10 mm Durchmesser anwendet.The treatment is carried out by adding 4 μΙ the acetone solution of the compound to be investigated on lettuce leaf beads with a diameter of 10 mm applies.
Pro Behandlung setzt man 10 Exemplare ein. 24 und 48 Stunden nach der Behandlung wird die Abtötung
bestimmt.
'. 5 Das Vergleichsprodukt ist Verbindung B'.10 copies are used per treatment. The death rate is determined 24 and 48 hours after the treatment.
'. 5 The comparative product is compound B '.
Die folgende Tabelle faßt die erhaltenen Versuchsresultate zusammen.The following table summarizes the experimental results obtained.
mg Λ S/ldose
mg Λ S / l
24 Stunden% Kill
24 hours
500500
500
20002000
2000
87.5
0100
87.5
0
100
0100
100
0
Verbindung B'
KontrolleCompound C
Connection B '
control
FolgerungInference
Verbindung C besitzt eine höhere Aktivität als Verbindung B'.Compound C has a higher activity than compound B '.
Die Erfindung betrifft ferner ein Verfahren zur Herstellung der racemischen oder optisch aktivenThe invention also relates to a process for the preparation of the racemic or optically active ones
cis-33-Dimethyl-2-(2'-oxo-3'-X-cyclopentyIidenmethyl)-cyclopropan-l -carbonsäurederivate der allgemeinen Formel I, das in dem Reaktionsschema erläutert und dadurch gekennzeichnet ist, daß man eine racemische oder optisch aktive cis-33-Dimethyl-2-formyl-cyclopropan-1-carbonsäure der allgemeinen Formel Il gemäß Reaktionsschema entweder in Gegemwart einer starken Base mit einem eine 2-Oxo-3-X-cyclopentylgruppe tragenden Phosphoniumsalz der allgemeinen Formel III (Reaktionsschema), das in basischem Milieu in Form eines Ylids der allgemeinen Formel IHa vorliegen kann, oder in neutralem Milieu mit einem 2-Oxo-3-X-cyclopentyliden-triarylphosphoran der allgemeinen Formel tels, wie ζ. Β. Tetrahydrofuran, arbeitet.cis-33-Dimethyl-2- (2'-oxo-3'-X-cyclopentyIidenemethyl) -cyclopropane-l -carboxylic acid derivatives of the general formula I, which are illustrated in the reaction scheme and characterized in that a racemic or optically active cis-33-dimethyl-2-formyl-cyclopropane-1-carboxylic acid is used of the general formula II according to the reaction scheme either in the presence of a strong Base with a 2-oxo-3-X-cyclopentyl group-bearing phosphonium salt of the general formula III (Reaction scheme), which can be present in a basic medium in the form of an ylid of the general formula IHa, or in a neutral medium with a 2-oxo-3-X-cyclopentylidene-triarylphosphorane using the general formula, such as ζ. Β. Tetrahydrofuran, works.
Das 2-Oxo-3-X-cyclopentylidentriphenylphosphoran kanr durch Einwirkung einer Base, beispielsweise von Natriumcarbonat, Kaliumcarbonat oder Natronlauge,The 2-oxo-3-X-cyclopentylidene triphenylphosphorane canr by the action of a base, for example sodium carbonate, potassium carbonate or caustic soda,
ϊ auf ein 2-Oxo-3-X-cyclopentyltΓiphenylphosphoniumhalogenid hergestellt werden [vgl. beispielsweise S. Fliszar, R. F. Hudson und G. Salvadori, HeIv. Chem. Acta, 46,1580(1963)].ϊ on a 2-oxo-3-X-cyclopentyltΓiphenylphosphonium halide are produced [cf. for example S. Fliszar, R. F. Hudson and G. Salvadori, HeIv. Chem. Acta, 46, 1580 (1963)].
Nach der Kondensation der 3,3-Dimethyl-2-formylcyclopropan-1 -carbonsäure der Formel II mit dem Phosphoniumsalz der Formel III oder mit dem Phosphoran der Formel IM' kann die dabei erhaltene 3,3-Dimethyl-2-(2'-oxu-3'-X-cyclopentylidenmethyl)-cyclopropan-1-carbonsäure (Formel Γ mit R' = H) gerei-After the condensation of the 3,3-dimethyl-2-formylcyclopropane-1 -carboxylic acid of the formula II with the phosphonium salt of the formula III or with the phosphorane of the formula IM 'can be obtained 3,3-Dimethyl-2- (2'-oxu-3'-X-cyclopentylidenemethyl) -cyclopropane-1-carboxylic acid (Formula Γ with R '= H)
i) nigt werden, indem man beispielsweise die nicht-umge· setzten Aldehydfraktionen durch Behandlung mit dem Reagens T oder durch Umwandlung der Säure in das Salz insbesondere in ein Salz einer optisch aktiven Base entfernt und das diastereoisomere Salz durch Kristalli-i) be changed by, for example, the non-vice set aldehyde fractions by treatment with the reagent T or by converting the acid into the Salt removed in particular in a salt of an optically active base and the diastereoisomeric salt by crystalline
Λλ- -.« cation rAinicFt wnHpi man nar^h rlpm Äncäiiprn mit pinprΛλ- -. «Cation rAinicFt wnHpi man nar ^ h rlpm Äncäiiprn with pinpr
cis-3,3-Dimethyl-2-(2'-oxo-3'-X-cyclopentylidenmethyl)-cyclopropan-1-carbonsäure (Formel Γ mit R' = H). die in den 1- und 2-Stellungen die gleiche Konfiguration aufweist wie die eingesetzte cis-3.3-Dimethyl-2-formylcyclopropan-1-carbonsäure und daß man diese cis-3.3-Dimethyl-2-(2'-oxo-3'-X-cyclopentylidenmethyl)-cyclo- propan-1-carbonsäure in ihr Kaliumsalz oder Chlorid überführt.cis -3,3-Dimethyl-2- (2'-oxo-3'-X-cyclopentylidenemethyl) -cyclopropane-1-carboxylic acid (Formula Γ with R '= H). which in the 1 and 2 positions have the same configuration like the cis-3,3-dimethyl-2-formylcyclopropane-1-carboxylic acid used and that this cis-3,3-dimethyl-2- (2'-oxo-3'-X-cyclopentylidenemethyl) -cyclo-propane-1-carboxylic acid in its potassium salt or chloride convicted.
Als Phosphoniumsalz der Formel III. das 2-Oxo-3-X-cyclopentyltriarylphosphoniumgruppe enthält, verwendet man insbesondere ein (2-Oxo-3-X-cyclopentyl)triarylphosphoniumsalz. beispielsweise ein (2-Oxo-3-Xcyclopentyljtriphenylphosphoniumbromid oder -jodid, das unter der Einwirkung einer Base ein (2-Oxo-3-X-Cyclopentyliden)triarylphosphoran liefert. Man kann auch ein ^-Oxo-S-X-cyclopentylJ-bis-idialkylaminoJarylphosphoniumsalz oder ein (2-Oxo-3-X-cyclopentyIXdialkylaminoj-diarylphosphoniumsalz verwenden.As the phosphonium salt of the formula III. the 2-oxo-3-X-cyclopentyltriarylphosphonium group contains, one uses in particular a (2-oxo-3-X-cyclopentyl) triarylphosphonium salt. for example a (2-Oxo-3-Xcyclopentyljtriphenylphosphonium bromide or iodide which, under the action of a base, forms a (2-oxo-3-X-cyclopentylidene) triarylphosphorane supplies. One can also use a ^ -oxo-S-X-cyclopentylJ-bis-idialkylaminoJarylphosphonium salt or a (2-Oxo-3-X-cyclopentyIXdialkylaminoj-diarylphosphonium salt use.
Beispiele für starke Basen, in deren Gegenwart die Kondensation des Phosphoniumsalzes der Formel III mit der 3.3-Dimethyl-2-formy1-cyclopropan-l -carbonsäure der Formel Il durchgeführt wird, sind die Alkalimetallhydride, beispielsweise Natriumhydrid, die Alkalirnetallamide. beispielsweise Natriumamid. die Alkalimetallalkoholate, beispielsweise Natriummethanolat. Natriumäthanolat. Kaliiim-tert.-butylat. die Alkyllithiumverbindungen. beispielsweise Methyllithium.Examples of strong bases, in the presence of which the condensation of the phosphonium salt of the formula III with the 3,3-dimethyl-2-formy1-cyclopropane-1-carboxylic acid of the formula II is carried out, the alkali metal hydrides, for example sodium hydride, the Alkali metal amides. for example sodium amide. the alkali metal alcoholates, for example sodium methoxide. Sodium ethanolate. Potassium tert-butoxide. the alkyl lithium compounds. for example methyl lithium.
Die Kondensation der 3J-Dimethyl-2-formyl-cyclopropan-1-carbonsäure der Formel Il mit dem Phosphoniumsalz wird zweckmäßigerweise im Milieu eines organischen Lösungsmittels oder eines organischen LösungsmittelgemisrVies. beispielsweise Methanol. Äthanol. Methylenchlorid. Dichloräthan. Chloroform. Diäthylenglykolmonoäthyläther. Diäthylenglykoldiäthyläther, Äthyläther, Dimethylsulfoxyd. Tetrahydrofuran. Dimethoxyäthan und Dimethylformamid, durchgeführt. The condensation of 3J-dimethyl-2-formyl-cyclopropane-1-carboxylic acid of the formula II with the phosphonium salt is expediently in the medium of an organic solvent or an organic Solvent mixture for example methanol. Ethanol. Methylene chloride. Dichloroethane. Chloroform. Diethylene glycol monoethyl ether. Diethylene glycol diethyl ether, ethyl ether, dimethyl sulfoxide. Tetrahydrofuran. Dimethoxyethane and dimethylformamide carried out.
Gemäß einer bevorzugten Ausführungsform der vorliegenden Erfindung verwendet man als Phosphorreagens mit einer 2-Oxo-3-X-cyc!opentyIgruppe ein 2-Oxo-3-X-cyclopentylidentriaΓylphosphoΓan der Formel ΠΓ und insbesondere ein 2-Oxo-3-X-cyclopentyIidentriphenylphosphoran. According to a preferred embodiment of the present invention, the phosphorus reagent used is with a 2-oxo-3-X-cyc! opentyIgruppe a 2-oxo-3-X-cyclopentylidentriaΓylphosphoΓan of the formula ΠΓ and especially a 2-oxo-3-X-cyclopentyIidentriphenylphosphoran.
Die Kondensation des 2-OxO-S-X-CyCIOpCmVUdCntriarylphosphorans der Formel III' mit der 33-Dimethyl-2-formyl-cyclopropan-l-carbonsäure wird in Abwesenheit eines basischen Agens durchgeführt wobei man im Milieu eines aprotischen polaren Lösungsmit-Säure die reine Verbindung erhält.The condensation of the 2-OxO-S-X-CyCIOpCmVUdCntriarylphosphorans of the formula III 'with 33-dimethyl-2-formyl-cyclopropane-1-carboxylic acid is carried out in the absence of a basic agent whereby the pure compound is obtained in the medium of an aprotic polar solvent with acid.
Das Säurechlorid der Formel I (Ri=CI) erhält man leicht durch Einwirkung von Oxalylchlorid auf ein Alkalimetallsalz der entsprechenden Säure, beispielsweise das Kaliumsalz.The acid chloride of the formula I (Ri = CI) is obtained easily by the action of oxalyl chloride on an alkali metal salt of the corresponding acid, for example the potassium salt.
Das Kaliumsalz dieser Säure (Formel Γ mit R = H) selbst erhält man leicht durch Einwirkung eines Alkalimetallmethylats oder eines Alkalimetallhydroxyds in stöchi(* ■»etrischer Menge auf die entsprechende Säure.The potassium salt of this acid (formula Γ with R = H) itself is easily obtained by the action of an alkali metal methylate or an alkali metal hydroxide in stoichi (* ■ »etric amount to the corresponding Acid.
Bezüglich der Herstellung der beim anmeldungsgemäßen Verfahren einzusetzenden Ausgangsstoffe, der Weiterverarbeitung der anmeldungsgemäßen Verbindungen der Formel I zu insektizid wirksamen Endprodukten der Formel Γ sowie der damit erhältlichen Insektiziden Zusammensetzungen, wird auf die allgemeine Beschreibung der DE-PS 20 29 043 (Stammpatent). Spalte 9 und 10, verwiesen.With regard to the production of the starting materials to be used in the process according to the application, the Further processing of the compounds of the formula I according to the application to give insecticidally active end products of the formula Γ as well as the insecticidal compositions obtainable with it, is based on the general Description of DE-PS 20 29 043 (parent patent). Columns 9 and 10, referenced.
Die folgenden Beispiele erläutern die Erfindung.The following examples illustrate the invention.
Herstellung der als Ausgangsmaterial verwendetenManufacture of the used as the starting material
2-formylcyclopropan-1 -carbonsäure (I R. 2S)
in Form des inneren Hemiacylals2-formylcyclopropane-1-carboxylic acid (I R. 2S)
in the form of the inner hemiacylal
Stufe ALevel a
Dimethylketal der trans-3 J-Dimethyl-2-formyl-cyclopropan-1 -carbonsäure (1R. 2R)Dimethyl ketal of trans-3 J-dimethyl-2-formyl-cyclopropane-1 -carboxylic acid (1R. 2R)
In 100 ecm Methanol gibt man unter einer Stickstoffatmosphäre 13.8 g trans-SJ-Dimethyi^-formyl-cyclopropan-1-carbonsäure (IR. 2R). hält die Lösung 22 Stun.'.in lang unter Rückfluß, wobei man das Destillat über eine mit »Siliporit« (einem entwässerten Alkalimetallaluminosilikat) gefüllte Kolonne recyclisiert engt zur Trockne ein. isoliert die Kristalle, die mit einer öligen Verunreinigung getränkt sind, die man durch Absaugen entfernt, nimmt das Kristallisat in Petroläther (Kp. 65 bis 75=C) auf. saugt ab. trocknet und erhält 11.7 g des Dimethylketals der trans-SJ-Dimethyl^-formyl-cyclopropan-1 -carbonsäure (IR. 2R). F. 65C C.13.8 g of trans-SJ-Dimethyi ^ -formyl-cyclopropane-1-carboxylic acid (IR.2R) are added to 100 ecm of methanol under a nitrogen atmosphere. keeps the solution under reflux for 22 hours, the distillate being recycled through a column filled with "Siliporit" (a dehydrated alkali metal aluminosilicate) concentrated to dryness. isolating the crystals, which are impregnated with an oily impurity which is removed by suction, the crystals are taken up in petroleum ether (bp. = 65 to 75 C). sucks. dries and receives 11.7 g of the dimethyl ketal of trans-SJ-Dimethyl ^ -formyl-cyclopropane-1-carboxylic acid (IR.2R). F. 65 C C.
Analyse fürG,H,6O<(188.22)
Ber.: C 57.43. H 8,57%:
gef.: C 57,6. H 8,5%.Analysis for G, H, 6O <(188.22)
Calc .: C 57.43. H 8.57%:
Found: C 57.6. H 8.5%.
Auf analoge Weise erhält man, ausgehend von der trans-33-Dimethyi-2-formyi-cyciopropan- i -carbonsäure (IS, 2S) oder der racemischen trans-33-Dimethyl-2-In an analogous manner, starting from trans-33-dimethyl-2-formyl-cyciopropan-i-carboxylic acid (IS, 2S) or the racemic trans-33-dimethyl-2-
formyl-cyclopropan-1 -carbonsäure (IRS, 2RS), das Dimethylketal der transOJ-Dimethyl^-formyl-cydopropan-1-carbonsäure (!S, 2S), F. 65"C, bzw. das Dimethylketal der racemischen trans-3,3-Dimethyl-2-formylcyclopropan-1 -carbonsäure (I RS, 2RS).formyl-cyclopropane-1-carboxylic acid (IRS, 2RS), the Dimethyl ketal of transOJ-Dimethyl ^ -formyl-cydopropane-1-carboxylic acid (! S, 2S), m.p. 65 "C, or the dimethyl ketal of the racemic trans-3,3-dimethyl-2-formylcyclopropane-1 -carboxylic acid (I RS, 2RS).
Stufe BLevel B.
Lacton des Hemimethylketals derLactone of the hemimethyl ketal
cisO^-Dimethyl^-formyl-cyclopropan-cisO ^ -Dimethyl ^ -formyl-cyclopropane-
1-carbonsäure (I R, 2S)1-carboxylic acid (I R, 2S)
In 175 ecm Benzol gibt man unter üiner Stickstoffatmosphäre 5 g Dimethylketal der trans-3,3-Dimethyl-2-formyl-cyclopropan-!-carbonsäure (IR, 2R) und 0,21 g p-Toluolsulfonsäure. Man bringt die Reaktionsmischung ι > zum Rückfluß und hält sie während der Destillation unter Rückfluß, wobei man das Reaktionsvolumen durch kontinuierliche Zugabe von Benzol konstant hält. Nach 6 Stunden kühlt man ab, entfernt das Benzol durch tirtn aipf^t Hip Rpalf tirvncmicrhunir In 175 cc of benzene is added, with üiner nitrogen atmosphere 5 g dimethyl ketal of trans-3,3-dimethyl-2-formyl-cyclopropane - - carboxylic acid (IR, 2R) and 0.21 g p-toluene sulfonic acid. The reaction mixture is brought to reflux and kept under reflux during the distillation, the reaction volume being kept constant by continuously adding benzene. After 6 hours it is cooled and the benzene is removed by tirtn aipf ^ t Hip Rpalf tirvncmicrhunir
..—, o . σ ..—, o . σ
in pinp >min pinp> m
wäßrige, Eis enthaltende Natriumbicarbonatlösung, extrahiert dann mit Äther und engt zur Trockne ein und erhält 1,9 g Lacton des Hemimethylketals der cis-3.3-Dimethyl-2-formyl-cyclopropan-1-carbonsäure (IR. 2S). Kp.60°C/0,3mm Hg. r,aqueous sodium bicarbonate solution containing ice, then extracted with ether and concentrated to dryness and receives 1.9 g of lactone of the hemimethyl ketal of cis-3,3-dimethyl-2-formyl-cyclopropane-1-carboxylic acid (IR. 2S). Bp 60 ° C / 0.3mm Hg. R,
I R-Spektrum (Chloroform):IR spectrum (chloroform):
Es bestätigt die Abwesenheit von freiem Hydroxyl und weist eine Bande bei 1764 cm-' auf, die der Carbonylgruppe eines y-Lactons entspricht. inIt confirms the absence of free hydroxyl and has a band at 1764 cm- 'that of the Corresponds to the carbonyl group of a γ-lactone. in
Auf analoge Weise erhält man, ausgehend von den Dimethylketalen der trans-33-Dimethyl-2-formyl-cyclopropan-1-carbonsäure (IS, 2S) bzw. der racemischen Säure (IRS, 2RS), die Lactone der Hemimethylketale der cis-33-Dimethyl-2-formyl-cyclopropan-1 -carbon- s? säure (1S, 2R) bzw. der racemischen Säure (1 RS, 2SR).In an analogous manner, starting from the dimethyl ketals of trans-33-dimethyl-2-formyl-cyclopropane-1-carboxylic acid (IS, 2S) or the racemic acid (IRS, 2RS), the lactones of the hemimethyl ketals the cis-33-dimethyl-2-formyl-cyclopropane-1-carbon- s? acid (1S, 2R) or the racemic acid (1 RS, 2SR).
Stufe CLevel C
cis-S.S-Dimethyl^-formyl-cyclopropan-cis-S.S-dimethyl ^ -formyl-cyclopropane-
l-carbonsäure(IR,2S) 4"l-carboxylic acid (IR, 2S) 4 "
in Form des inneren Hemiacylalsin the form of the inner hemiacylal
In ein Gemisch aus 25 ecm Wasser und 12,5 ecm Dioxan gibt man die 1,9 g des Lactons des Hemimethylketals der cisOJ-Dimethyl^-formyl-cyclopropan-l-carbonsäure (IR, 2S), hält 1 Stunde lang bei 60°C, engt unter vermindertem Druck zur Trockne ein und erhält 035 g der cis^-Dimethyl^-formyl-cyclopropan-l -carbonsäure (IR, 2S), F. 1140C, die in Form des inneren Hemicylals vorliegt Eine Probe dieses Produkts wird in Isopropyläther kristallisiert, F. 116° C, [«]?= + 103° (c= 1%, Methanol). The 1.9 g of the lactone of the hemimethyl ketal of cisOJ-dimethyl ^ -formyl-cyclopropane-1-carboxylic acid (IR, 2S) are added to a mixture of 25 ecm of water and 12.5 ecm of dioxane and is kept at 60 ° for 1 hour C, concentrated under reduced pressure to dryness and obtains 035 g of cis ^ -dimethyl ^ -formyl-cyclopropane-l -carboxylic acid (IR, 2S), mp 114 0 C, which is in the form of the inner Hemicylals a sample of this product is crystallized in isopropyl ether, mp 11 6 ° C, [«]? = + 103 ° (c = 1%, methanol).
Auf analoge Weise erhält man, ausgehend von den Lactonen der Hemimethylketale der cis-33-Dimethyl-2-formyl-cyclopropan-1 -carbonsäure (IS, 2R) oder der racemischen Säure, die inneren Hemiacylale der cis-33-D!methyI-2-formyl-cyclopropan-1 -carbonsäure (IS, 2R), F. 1160C, [«]?= -102° (c= 1%, Äthanol) bzw. der racemischen Säure. In an analogous manner , starting from the lactones of the hemimethyl ketals of cis-33-dimethyl-2-formyl-cyclopropane-1-carboxylic acid (IS, 2R) or the racemic acid, the inner hemiacylals of cis-33-D! MethyI- 2-formyl-cyclopropane-1-carboxylic acid (IS, 2R), mp 116 0 C, [ «]? = -102 ° (c = 1%, ethanol) or the racemic acid.
6060
Betspiel 1Bet game 1
cis-33-DimethyI-cis-33-dimethyl
2S-(2'-oxo-3'-oxa-cyclopentylidenmethyI) cyclopropan-1 R-carbonsäure2S- (2'-oxo-3'-oxa-cyclopentylidenemethyl) cyclopropane-1R-carboxylic acid
In eine Lösung von 2,1 g Natrhimmethanolat in 20 ecm Methanol gibt man unter einer Stickstoffatmosphäre eine Lösung von 13,2 g (2-Oxo-3-oxa-cyclopen-In a solution of 2.1 g of sodium methoxide in 20 ecm of methanol are added under a nitrogen atmosphere to a solution of 13.2 g (2-oxo-3-oxa-cyclopene
65 tyljtriphenylphosphoniumbromid (hergestellt nach S. Fliszar et Coll., HeIv. 46, 1580 (1963)), in 50 ecm Methylenchlorid, bringt die Reaktionsmischung zum Rückfluß, hält sie 30 Minuten lang unter Rückfluß, gibt 2,2 g cis-3,3-Dimethyl-2-formyl-cyclopropan-l-carbonsäure (IR, 2S), die in Form des inneren Hemiacylals und gelöst in 30 ecm Methylenchlorid vorliegt, zu, hält I Stunde und 30 Minuten lang unter Rückfluß, kühlt die Reaktionsmischung, gießt sie in eine wäßrige gesättigte Natriumbicarbonatlösung, entfernt die neutralen Fraktionen durch Extraktionen mit Methylenchlorid, säuert die wäßrige Phase durch eine wäßrige Lösung von Konzentrierter Chlorwasserstoffsäure an, sättigt sie mit Natriumchlorid, extrahiert mit Äthyläther, vereinigt die ätherischen Extrakte, trocknet sie, engt sie unter vermindertem Druck zur Trockne ein, gibt zu dem Rückstand 1,9 g Reagens T oder Trimethylaminoacetohydrazidchlorid, 1,9 ecm Äthanol und 1,9 ecm Essigsäure. Man bringt die Reaktionsmischung zum Rückfluß, hält «if> 1 .Stunde lang unter Rückfluß, gießt sie in ein Gemisch ius Wasser, Eis und 3 ecm einer wäßrigen ΊΟ η Natriumhydroxydlösung, extrahiert die Nicht-Aldehydfraktion mit Äthyläther, trocknet die ätherischen Extrakte, engt sie unter vermindertem Druck zur Trockne ein, kristallisiert den Rückstand in einem Gemisch aus Isopropyläther und Methanol (3/1) und erhält 0,40 g cis-3,3-Dimethyl-2S-(2'-oxo-3'-oxa-cyclopentylidenmethyl)cyclopropan-1 R-carbonsäure. F. 65 tyltriphenylphosphonium bromide (prepared according to S. Fliszar et Coll., HeIv. 46, 1580 (1963)), in 50 ecm of methylene chloride, brings the reaction mixture to reflux, keeps it under reflux for 30 minutes, gives 2.2 g of cis-3, 3-Dimethyl-2-formyl-cyclopropane-1-carboxylic acid (IR, 2S), which is present in the form of the internal hemiacylal and dissolved in 30 ecm of methylene chloride, is refluxed for 1 hour and 30 minutes, the reaction mixture is cooled and poured them in an aqueous saturated sodium bicarbonate solution, removed the neutral fractions by extractions with methylene chloride, acidified the aqueous phase with an aqueous solution of concentrated hydrochloric acid, saturates it with sodium chloride, extracted with ethyl ether, combined the ethereal extracts, dried them, concentrated them under reduced pressure Pressurize to dryness, add 1.9 g of reagent T or trimethylaminoacetohydrazide chloride, 1.9 ecm of ethanol and 1.9 ecm of acetic acid to the residue. The reaction mixture is brought to reflux, refluxed for> 1 hour, poured into a mixture of water, ice and 3 cm of an aqueous sodium hydroxide solution, the non-aldehyde fraction is extracted with ethyl ether, the ethereal extracts are dried and concentrated it to dryness under reduced pressure, the residue crystallizes in a mixture of isopropyl ether and methanol (3/1) and receives 0.40 g of cis-3,3-dimethyl-2S- (2'-oxo-3'-oxa- cyclopentylidenemethyl) cyclopropane-1R-carboxylic acid. F.
I77°C, [λ][S"-+22° (c= 0,59%, Äthanol). Aus den Kristallisationsmutterlaugen erhält man eine zweite Fraktion von 0,18 g, F. 176"C.177 ° C, [λ] [S "- + 22 ° (c = 0.59%, ethanol) A second fraction of 0.18 g, melting point 176 ° C., is obtained.
Analyse für Cn H14O1 (210,23)
ber.: C 62,84, H 6.71%:
gef.: C 62,7, H 6,6%.Analysis for C n H 14 O 1 (210.23)
calc .: C 62.84, H 6.71%:
Found: C 62.7, H 6.6%.
UV-Spektrum (Äthanol):UV spectrum (ethanol):
λ max bei 245 bis 246 ηιμ (ε = 15 700).λ max at 245 to 246 ηιμ (ε = 15 700).
Auf analoge Weise erhält man, ausgehend von der cis-3,3-Dimethyl-2-formyl-cyclopropan-l -carbonsäure (IS, 2R) oder der racemischen cis-33-Dimethyl-2-formyl-cyclopropan-1 carbonsäure, die cis-33-Dimethyl-2R-(2'-oxo-3'-oxa-cyclopentylidenmethyl)-cyclopropanlS-carbonsäure, F. 1770C. [λ]?=-21° (c=0,59%, Äthanol), bzw. die racemische cis-3,3-Dimethyl-2-(2'-oxo-S'-oxa-cyclopentylidenmethylJcyclopropan-1 -carbonsäure. In an analogous manner, starting from the cis-3,3-dimethyl-2-formyl-cyclopropane-1-carboxylic acid (IS, 2R) or the racemic cis-33-dimethyl-2-formyl-cyclopropane-1-carboxylic acid, the cis-33-Dimethyl-2R- (2'-oxo-3'-oxa-cyclopentylidenemethyl) -cyclopropane / S-carboxylic acid, m.p. 177 0 C. [λ]? = - 21 ° (c = 0.59%, ethanol) , or the racemic cis-3,3-dimethyl-2- (2'-oxo-S'-oxa-cyclopentylidenemethyl / cyclopropane-1-carboxylic acid.
cis-33-Dimethyl-2S-cis-33-dimethyl-2S-
(2'-oxo-3'-oxa-cyclopentylidenmethyl)-(2'-oxo-3'-oxa-cyclopentylidenemethyl) -
cyclopropan-1 R-carbonsäurecyclopropane-1R-carboxylic acid
In 250 ecm Tetrahydrofuran gibt man unter einer Stickstoffatmosphäre 5,5 g 2-Oxo-3-cyclopentylidentriphenylphosphoran (hergestellt nach S. Fliszar, R. F. Hudson et G. Salvadori, Herlv. Chim. Acta, 46, 1580 (1963)), bringt die Reaktionsmischung zum Rückfluß, gibt 2^6 g cis-33-DimethyI-2-formyl-cvcIopropan-lcarbonsäure (IR, 2S), die in Form des inneren Hemiacylals vorliegt, geiöst in 10 ecm Tetrahydrofuran zu und hält 6 Stunden lang unter Rückfluß. Man entfernt das Tetrahydrofuran durch Destillation unter vermindertem Druck, gibt zu dem Rückstand Methylenchlorid zu, extrahiert die gebildete Säure mit einer wäßrigen gesättigten Natriumbicarbonatlösung, wäscht die vereinigten wäßrigen Phasen mit Methylenchlorid, säuert sie mit einer wäßrigen konzentrierten Lösung von Chlorwasserstoffsäure an, extrahiert die wäßrige saure 5.5 g of 2-oxo-3-cyclopentylidenetriphenylphosphorane (prepared according to S. Fliszar, RF Hudson et G. Salvadori, Herlv. Chim. Acta, 46, 1580 (1963)) are added to 250 ecm of tetrahydrofuran under a nitrogen atmosphere Reaction mixture to reflux, adds 2 ^ 6 g of cis-33-dimethyl-2-formyl-cvcIopropane-lcarboxylic acid (IR, 2S), which is in the form of the inner hemiacylal, dissolved in 10 ecm of tetrahydrofuran and refluxed for 6 hours. The tetrahydrofuran is removed by distillation under reduced pressure, methylene chloride is added to the residue, the acid formed is extracted with an aqueous saturated sodium bicarbonate solution, the combined aqueous phases are washed with methylene chloride, acidified with an aqueous concentrated solution of hydrochloric acid, and the aqueous acid is extracted
Phase mit Methylenchlorid, vereinigt die Methylenchloridextrakte, trocknet sie und engt sie durch Destillation unter vermindertem Druck zur Trockne ein und erhält 3,1 g cis-3,3-Dimethyl-2S-(2'-oxo-3'-oxa-cyclopentylidenmethyl)-cyclopropan-l R-carbonsäure, F. 177°C, [Λ]» = + 22" (c=0,59%, Äthanol), die mit der in Beispiel I erhaltenen Verbindung identisch ist.Phase with methylene chloride, combine the methylene chloride extracts, dry them and concentrate them to dryness by distillation under reduced pressure and obtain 3.1 g of cis-3,3-dimethyl-2S- (2'-oxo-3'-oxa-cyclopentylidenemethyl) -cyclopropane-l R-carboxylic acid, melting point 177 ° C, [ Λ ] »= + 22" (c = 0.59%, ethanol), which is identical to the compound obtained in Example I.
S-Benzyl^-furylmethyl-cis-SJ-dimethyl^S-S-Benzyl ^ -furylmethyl-cis-SJ-dimethyl ^ S-
(2'-oxo-3'-oxa-cyclopentylidenmethyl)-(2'-oxo-3'-oxa-cyclopentylidenemethyl) -
cyclopropan-1 R-carboxylatcyclopropane-1R-carboxylate
a) Kaliumsalz der cis-3,3-Dimethyl-2S-a) Potassium salt of cis-3,3-dimethyl-2S-
(2'-oxo-3'-oxa-cyclopentylidenmethyl)-(2'-oxo-3'-oxa-cyclopentylidenemethyl) -
cyclopropan-l R-carbonsäurecyclopropane-1 R-carboxylic acid
In 2 ecm Methanol gibt man unter einer Stickstoffatmosphäre 0,520 g cis-3,3-Dimethyl-2S-(2'-oxo-3'-oxaryrlnnpntylidpnmelhyl)-ryrlnnrnnnn-l R-rarbnnsäiirr gibt in Gegenwart von Phenolphthalein tropfenweise die zur Erreichung des Umschlagpunktes des Phenolphthaleins in Rosa erforderliche Menge an 5%iger Lösung von Kaliumhydroxyd in Methanol zu, entfernt das Methanol durch Destillation unter vermindertem Druck, dann durch Zugabe von Benzol und Destillation unter vermindertem Druck. Man erhält so das Kaliumsalz der cis-33-Dimethyl-2,S-(2'-oxo-3'-oxa-cyclopentylidenmethylj-cyclopropan-1 R-carbonsäure.In 2 ecm of methanol is added under a nitrogen atmosphere 0.520 g of cis -3,3-dimethyl-2S- (2'-oxo-3'-oxaryrlnnnpntylidpnmelhyl) -ryrlnnrnnnn-1 R-acidic acid gives dropwise in the presence of phenolphthalein the amount of 5% strength required to reach the pink phenolphthalein transition point To a solution of potassium hydroxide in methanol, the methanol is removed by distillation under reduced pressure Pressure, then by addition of benzene and distillation under reduced pressure. That's how you get it Potassium salt of cis-33-dimethyl-2, S- (2'-oxo-3'-oxa-cyclopentylidenemethylj-cyclopropane-1 R-carboxylic acid.
b) Chlorid der cis-3J-Dimethyl-2S-b) chloride of cis-3J-dimethyl-2S-
(2'-oxo-3'-oxa-cyclopentylidenmethyl)-(2'-oxo-3'-oxa-cyclopentylidenemethyl) -
cyclopropan-1 R-carbonsäurecyclopropane-1R-carboxylic acid
Zu dem im Abschnitt a) erhaltenen Kaliumsalz gibt man 10 ecm Benzol, dann setzt man unter einer Stickstoffatmosphäre 0,5 ecm Pyridin und dann tropfenweise 0,630 g Oxalylchlorid, gelöst in 5 ecm Benzol zu, entfernt durch Filtrieren die gebildeten unlöslichen Teile, rührt 1 Stunde lang bei Raumtemperatur, entfernt das Lösungsmittel durch Destillation unter verminder- 4n tem Druck, dann durch Zugabe von Benzol und Destillation unter vermindertem Druck. Man erhält auf diese Weise das Chlori-i der cis-33-Dimethyl-2S-(2'-To the potassium salt obtained in section a) is added 10 ecm of benzene, then placed under a Nitrogen atmosphere 0.5 ecm pyridine and then dropwise 0.630 g of oxalyl chloride, dissolved in 5 ecm of benzene, removed the insoluble ones formed by filtration Parts, stirred for 1 hour at room temperature, removed the solvent by distillation under reduced 4n tem pressure, then by adding benzene and distillation under reduced pressure. One receives on in this way the chlori-i of the cis-33-dimethyl-2S- (2'-
oxo-S'-oxa-cyclopentylidenmethyiJ-cyclopropan-1R-carbonsäure. 4->oxo-S'-oxa-cyclopentylidenemethyl-cyclopropane-1R-carboxylic acid. 4->
c) Kondensation des Säurechlorids mit
5- Benzyl-3-furyl-methylalkoholc) Condensation of the acid chloride with
5-benzyl-3-furyl-methyl alcohol
Bei +50C gibt man zu dem im Abschnitt b) erhaltenen und in 10 ecm Benzol suspendierten Säurechlorid tropfenweise eine Lösung von 0,515 g 5-Benzyl-3-furyl-methylalkohol in 5 ecm Benzol und 0,5 ecm Pyridin zu, rührt 15 Stunden lang bei Umgebungstemperatur, gibt die Reaktionsmischung auf ein Gemisch aus 50 ecm einer wäßrigen 2 η Chlorwasserstoffsäurelösung und Eis, trennt die Benzolphase durch Dekantation ab, wäscht sie nacheinander mit Wasser, mit einer wäßrigen gesättigten Natriumbicarbonatlösung, dann mit Wasser, extrahiert die wäßrigen Phasen mit Äthyläther, vereinigt die organischen Phasen, trocknet sie, engt sie unter vermindertem Druck znr Trockne ein, reinigt den Rückstand durch Chromatographie an SilikageL indem man die Kolonne mit einem Benzol/Äthylacetat/Triäthylamin (68/30/2)-Genrisch sättigt und mit einem Benzol/Äthylacetat es (70/30)-Gemisch mit einem Zusatz von 0,2% Triethylamin eluiert, und erhält 0,690 g S-Benzyl-S-fürylmethylcis-33-dimethyI)-2S-{2'-oxo-3'-oxa-cyclopentyiidenme- thyl)-cyclopropan-1R-carboxylat, [λ]" = 0° ± I' (c= 0,48%, Äthanol).At +5 0 C are added to the b section) obtained and suspended in 10 cc of benzene acid chloride was added dropwise a solution of 0.515 g of 5-benzyl-3-furyl-methyl alcohol in 5 cc of benzene and 0.5 cc of pyridine, stirred for 15 For hours at ambient temperature, the reaction mixture is poured into a mixture of 50 ecm of an aqueous 2 η hydrochloric acid solution and ice, the benzene phase is separated off by decantation, washed successively with water, with an aqueous saturated sodium bicarbonate solution, then with water, the aqueous phases are extracted with Ethyl ether, combine the organic phases, dry them, concentrate them to dryness under reduced pressure, purify the residue by chromatography on silica gel by saturating the column with a benzene / ethyl acetate / triethylamine (68/30/2) mixture and with a Benzene / ethyl acetate (70/30) mixture eluted with an addition of 0.2% triethylamine, and received 0.690 g of S-benzyl-S-fürylmethylcis-33-dimethyI) -2S- {2'-oxo-3'- oxa-cyclopent yiidenemethyl) cyclopropane-1R-carboxylate, [λ] "= 0 ° ± 1 ' (c = 0.48%, ethanol).
Analyse für C2>H24O,(380,42)
ber.: C 72,61, H 6.36%;
gef.: C 72,7, H 6,3%.Analysis for C 2 > H 24 O, (380.42)
calc .: C 72.61, H 6.36%;
Found: C 72.7, H 6.3%.
UV-Spektrum (Äthanol):
λ max bei 224 πιμ. Ε|* =476
Infl. bei etwa 241 mu, E J* = 422.UV spectrum (ethanol):
λ max at 224 πιμ. Ε | * = 476
Infl. at about 241 mu, EJ * = 422.
cis-3,3-Dimethyl-2S-cis-3,3-dimethyl-2S-
(2'-oxo-3'-thia-cyclopentylidenmethyl)-(2'-oxo-3'-thia-cyclopentylidenemethyl) -
cyclopropan-l R-carbonsäurecyclopropane-1 R-carboxylic acid
In 120 ecm Tetrahydrofuran gibt man 4,6 g 2-Oxo-3-thia-cyclopentylidentriphenylphosphoran [beschrieben in H. Zimmer et CoIU Tetrahedron Lett. Nr. 52, 5435 (1968)] und 1,8 g des inneren Hemiacylals der cis-3,3-Dimpthy!-2-lprmyl-ryHnnrr>nan-l-rarhnn<;;iiirp (IR. ?S), bringt die Reaktionsmischung zum Rückfluß, hält sie 4 Stunden lang unter Rückfluß, entfernt das Tetrahydrofuran durch Destillation unter vermindertem Druck, gibt dann Methylenchlorid zu, extrahiert die organische Phase mit einer wäßrigen Lösung von Natriumbicarbonat, säuert die wäßrige alkalische Phase auf pH = 2 an. extrahiert mit Methylenchlorid, trocknet die Methylenchloridphase, engt sie durch Destillation unter vermindertem Dme!: zur Trockne ein, teigt den Rückstand in Isopropyläther an und erhält 2,140 g cis-3,3-Dimethyl-2S-(2'-oxo-3'-thia-cyclopentylidenmethyl)-cyclopropan-l R-carbonsäure, F. 1610C.4.6 g of 2-oxo-3-thia-cyclopentylidene-triphenylphosphorane [described in H. Zimmer et CoIU Tetrahedron Lett. No. 52, 5435 (1968)] and 1.8 g of the inner hemiacylal of the cis-3,3-Dimpthy! -2-lprmyl-ryHnnrr> nan-l-rarhnn <;; iiirp (IR.? S), brings the reaction mixture is refluxed and refluxed for 4 hours, the tetrahydrofuran is removed by distillation under reduced pressure, then methylene chloride is added, the organic phase is extracted with an aqueous solution of sodium bicarbonate, the aqueous alkaline phase is acidified to pH = 2. extracted with methylene chloride, the methylene chloride phase dries, it is concentrated to dryness by distillation under reduced Dme !:, pastes the residue in isopropyl ether and receives 2.140 g of cis-3,3-dimethyl-2S- (2'-oxo-3'- thia-cyclopentylidenemethyl) -cyclopropane-1 R-carboxylic acid, F. 161 0 C.
KMR-Spektrum (Deuterochloroform)KMR spectrum (deuterochloroform)
Das KMR-Spektrum stimmt mit der cis-Konfiguration des Ringes überein. Es setzt sich zusammen ausSignalen
bei 72 — 82 Hz, entsprechend Wasserstoffatomen der Methylgruppen in 3-Stellung:
Signalen bei 109 bis 124 Hz, entsprechend Wasserstoffatomen in 1- und 2-Stellung des Cyclopropanringes;
The KMR spectrum agrees with the cis configuration of the ring. It is composed of signals at 72 - 82 Hz, corresponding to hydrogen atoms of the methyl groups in the 3-position:
Signals at 109 to 124 Hz, corresponding to hydrogen atoms in the 1- and 2-positions of the cyclopropane ring;
Signalen bei 173-209Hz, entsprechend Wasserstoffatomen in 4- und 5-Stellung des 2-Oxo-3'-thiacyclopentylringes; Signals at 173-209Hz, corresponding to hydrogen atoms in the 4- and 5-positions of the 2-oxo-3'-thiacyclopentyl ring;
Signalen zwischen 401 und 413Hz, entsprechend dem Äthylenwasserstoff,Signals between 401 and 413Hz, accordingly the ethylene hydrogen,
ein Signal bei 550 Hz, entsprechend dem Carboxylwasserstoff. a signal at 550 Hz, corresponding to the carboxylic hydrogen.
5-BenzyI-3-furylmethyl-cis-3,3-dimethyl-2S-5-BenzyI-3-furylmethyl-cis-3,3-dimethyl-2S-
(2'-oxo-3'-thiacyclopentylidenmethyI)-(2'-oxo-3'-thiacyclopentylidenemethyl) -
cyclopropan-1 R-carboxylatcyclopropane-1R-carboxylate
Stufe ALevel a
Chlorid der cis-33-Dimethyl-2S-Chloride of cis-33-dimethyl-2S-
(2'-oxo-3'-thiacycIopentylidenmethyl)-(2'-oxo-3'-thiacycIopentylidenemethyl) -
cyclopropan-l R-carbonsäurecyclopropane-1 R-carboxylic acid
In 16 ecm Methylenchlorid gibt man 1,850 g cis-33-Dimethyl-2S-(2'-oxo-3'-thia-cyclopentyIidenmethyl)-cyclopropan-l R-carbonsäure, dann 2 ecm Thionylchlorid, rührt bei Raumtemperatur 1 Stunde und 30 Minuten lang, entfernt die flüchtigen Fraktionen durch Destillation unter vermindertem Druck und erhält das Chlorid dercis-33-Dimethyl-2S-(2'-oxo-3'-thia-cyclopentyliden-1.850 g of cis-33-dimethyl-2S- (2'-oxo-3'-thia-cyclopentyIidenmethyl) -cyclopropane-1 are added to 16 ecm of methylene chloride R-carboxylic acid, then 2 ecm thionyl chloride, stirred at room temperature for 1 hour and 30 minutes long, removes the volatile fractions by distillation under reduced pressure and obtains the chloride dercis-33-dimethyl-2S- (2'-oxo-3'-thia-cyclopentylidene-
mitihylJ-cyclopropan-lR-carbonsäure, das so wie es ist für die folgende Stufe verwendet wird.mitihylJ-cyclopropane-IR-carboxylic acid, as it is is used for the following stage.
Stufe BLevel B.
S-BenzylO-furylmethyi-cis-S^-dimetlvyl-iS-(2'-oxo-3'-thia-cyclopentylidenmcthyl)- S-BenzylO-furylmethyi-cis-S ^ -dimetlvyl-iS- (2'-oxo-3'-thia-cyclopentylidenemethyl) -
cyclopropan-1 R-carboxylatcyclopropane-1R-carboxylate
In eine Mischung aus 10 ecm Benzol und 3 ecm Pyridin gibt man das in der Stufe A erhaltene Säurechlorid, fügt 1,54 g 5-Benzyl-3-furyl-methylalkohol, gelöst in 7 ecm Benzol, zu, rührt 15 Stunden lang bei Raumtemperatur, entfernt den gebildeten Niederschlag durch Filtrieren, wäscht das Filtrat nacheinander mit einer wäßrigen 2 η Chlorwasserstoffsäurelösung, mit Wasser, mit einer wäßrigen Natriumbicarbonatlösung, mit Wasser, trocknet, engt durch Destillation unter vermindertem Druck zur Trockne ein und reinigt den Rückstand durch Chromatographie an Silikage), indem man mit einem Benzol/Äthylacetat (80/20)-Gemisrh eluiert und erhält 2,650 g 5-Benzyl-3-furylmethyl-cis-3.3-dimeth\'-2S(2'-oxo-3'-thia-cyclopentylidenmethyl)-cyclopropan-1 R-carboxylat, [«]?? = + 10,5" (c= 1%, Ätha-In a mixture of 10 ecm benzene and 3 ecm The acid chloride obtained in stage A is added to pyridine, 1.54 g of 5-benzyl-3-furyl-methyl alcohol are added, dissolved in 7 ecm benzene, stirred for 15 hours Room temperature, the precipitate formed is removed by filtration, and the filtrate is washed successively an aqueous 2 η hydrochloric acid solution, with water, with an aqueous sodium bicarbonate solution, with water, dries, evaporates to dryness by distillation under reduced pressure and cleans the Residue by chromatography on silica) by mixing with a benzene / ethyl acetate (80/20) mixture elutes and receives 2.650 g of 5-benzyl-3-furylmethyl-cis-3.3-dimeth \ '- 2S (2'-oxo-3'-thia-cyclopentylidenemethyl) -cyclopropane-1 R-carboxylate, [«] ?? = + 10.5 "(c = 1%, etha-
KMR-Spektrum (Deuterochloroform)KMR spectrum (deuterochloroform)
Das KMR-Spektrum stimmt mit der cis-Konfiguration des Ringes überein. Es setzt sich zusammen aus:The KMR spectrum agrees with the cis configuration of the ring. It is made up of:
Signalen bei 74 - 79 Hz, entsprechend den Wasserstoffen der Methylgruppen in 3-Stellung;
Signalen bei 95- 103,5- 112,5- 122 Hz, entsprechend den Wasserstoffen des Cyclopropyls;
Signalen bei 168-212Hz, entsprechend ±;n Wasserstoffen des Cyclopentane;
einem Signal bei 235 Hz, entsprechend den Wasserstoffatomen von Cl I2 des Benzylrestes:
einem Signal bei 293,8 Hz, entsprechend den Wasserstoffatomen der — CO2 — Cl^-Gruppe;
einem Signal bei 362,1 Hz, entsprechend dem Wasserstoffatom in 4-Stellungdes Furanrinfes;
Signalen bei 405,5-415,5 Hz, entsprechend dem
Äthylen wasserstoff;Signals at 74-79 Hz, corresponding to the hydrogens of the methyl groups in the 3-position;
Signals at 95-103.5-112.5-122 Hz, corresponding to the hydrogens of cyclopropyl;
Signals at 168-212Hz, corresponding to ±; n hydrogen of cyclopentane;
a signal at 235 Hz, corresponding to the hydrogen atoms of Cl I 2 of the benzyl residue:
a signal at 293.8 Hz, corresponding to the hydrogen atoms of the - CO2 - Cl ^ group;
a signal at 362.1 Hz, corresponding to the hydrogen atom in position 4 of the furan amine;
Signals at 405.5-415.5 Hz, corresponding to the ethylene hydrogen;
einem Signal bei 435 H?. pnKprprhrnd rlrn
Wasserstoffatomen des Benzolkerns;
eirem Signal hei 449,5 Hz, entsprechend dem
Wasserstoff in 2-Stellung des Furaminges.a signal at 435 H ?. pnKprprhrnd rlrn hydrogen atoms of the benzene nucleus;
A signal at 449.5 Hz, corresponding to the hydrogen in the 2-position of the furamine.
Reaktionsschema
H1CReaction scheme
H 1 C
H3CH 3 C
OOOHOOOH
H2C H2C CH-P—H 2 CH 2 C CH-P—
Salzsalt
= 0= 0
(ΠΙ)(ΠΙ)
liegt in basischem Milieu in folgender Form voroccurs in the following form in a basic medium
(ma)(ma)
H2C-H2CH 2 CH 2 C
θ φ/ -C-P-θ φ / -C-P-
oderor
C =PC = P
H2C C = <H 2 CC = <
oder auchor
(ΠΓ)(ΠΓ)
H2C-H2C H 2 CH 2 C
ArAr
/ C = P — Ar / C = P - Ar
\ O Ar\ O Ar
(Ar = Arylrest)(Ar = aryl radical)
H3CH 3 C
H,C C-R1 H, C CR 1
(D(D
Claims (1)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR6919693A FR2045177A5 (en) | 1969-06-13 | 1969-06-13 | |
FR7021682A FR2097244A6 (en) | 1969-06-13 | 1970-06-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
DE2066032C2 true DE2066032C2 (en) | 1982-04-22 |
Family
ID=26215107
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE2029043A Expired DE2029043C3 (en) | 1969-06-13 | 1970-06-12 | 5-Benzyl-3-furylmethyl-cis-3,3-dimethyl-2- (2'-oxo-3'-X-cyclopentylidenemethyl) -cyclopropane-1-carboxylates, processes for their preparation and insecticides containing these compounds |
DE2066032A Expired DE2066032C2 (en) | 1969-06-13 | 1970-06-12 | Derivatives of cis-3,3-dimethyl-2- (2'-oxo-3'-X-cyclopentylidenemethylidenemethyl) -cyclopropane-1-carboxylic acid and processes for their preparation |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE2029043A Expired DE2029043C3 (en) | 1969-06-13 | 1970-06-12 | 5-Benzyl-3-furylmethyl-cis-3,3-dimethyl-2- (2'-oxo-3'-X-cyclopentylidenemethyl) -cyclopropane-1-carboxylates, processes for their preparation and insecticides containing these compounds |
Country Status (7)
Country | Link |
---|---|
BE (1) | BE751749A (en) |
CA (1) | CA943555A (en) |
CH (1) | CH527154A (en) |
DE (2) | DE2029043C3 (en) |
FR (2) | FR2045177A5 (en) |
GB (1) | GB1308650A (en) |
NL (1) | NL165737C (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2326077C2 (en) * | 1972-05-25 | 1985-12-12 | National Research Development Corp., London | Unsaturated cyclopropanecarboxylic acids and their derivatives, their preparation and insecticides containing them |
ZA7911B (en) * | 1978-01-31 | 1980-01-30 | Roussel Uclaf | Optically-active substituted benzyl alcohol and process for preparing it |
FR2426673A1 (en) * | 1978-05-25 | 1979-12-21 | Nat Res Dev | PYRETHRINE TYPE PESTICIDES |
FR2499071A1 (en) * | 1981-02-05 | 1982-08-06 | Roussel Uclaf | NOVEL DERIVATIVES OF CYCLOPROPANE CARBOXYLIC ACID SUBSTITUTED INTO 3 BY A VINYL CHAIN, PROCESS FOR THEIR PREPARATION AND THEIR APPLICATION AS SCENTED AGENTS |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1168797A (en) * | 1965-12-09 | 1969-10-29 | Nat Res Dev | Cyclopropane Carboxylic Acid Derivatives and their use as Insecticides |
-
1969
- 1969-06-13 FR FR6919693A patent/FR2045177A5/fr not_active Expired
-
1970
- 1970-06-10 BE BE751749D patent/BE751749A/en not_active IP Right Cessation
- 1970-06-12 CA CA085,436*7A patent/CA943555A/en not_active Expired
- 1970-06-12 DE DE2029043A patent/DE2029043C3/en not_active Expired
- 1970-06-12 CH CH892670A patent/CH527154A/en not_active IP Right Cessation
- 1970-06-12 FR FR7021682A patent/FR2097244A6/fr not_active Expired
- 1970-06-12 DE DE2066032A patent/DE2066032C2/en not_active Expired
- 1970-06-15 GB GB2896070A patent/GB1308650A/en not_active Expired
- 1970-06-15 NL NL7008694.A patent/NL165737C/en not_active IP Right Cessation
Non-Patent Citations (1)
Title |
---|
NICHTS-ERMITTELT * |
Also Published As
Publication number | Publication date |
---|---|
GB1308650A (en) | 1973-02-21 |
CA943555A (en) | 1974-03-12 |
NL165737B (en) | 1980-12-15 |
DE2029043C3 (en) | 1982-04-22 |
DE2029043B2 (en) | 1981-04-23 |
BE751749A (en) | 1970-12-10 |
NL165737C (en) | 1981-05-15 |
FR2045177A5 (en) | 1971-02-26 |
NL7008694A (en) | 1970-12-15 |
CH527154A (en) | 1972-08-31 |
DE2029043A1 (en) | 1970-12-17 |
FR2097244A6 (en) | 1972-03-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE2742546C2 (en) | Esters of cyclopropanecarboxylic acids with a polyhalogenated substituent, process for their preparation and pesticidal, antifungal and veterinary agents | |
DE2439177C2 (en) | (±) -? -Cyan-3-phenoxybenzyl- (1R, trans) - and (1R, cis) -2,2-dimethyl-3- (2,2-dibromovinyl) -cyclopropanecarboxylate and (S) -? -Cyan-3-phenoxybenzyl- (1R, cis) -2,2-dimethyl-3- (2,2-dibromovinyl) -cyclopropanecarboxylate, process for the preparation of the (S) -isomer and insecticides containing these compounds | |
DE1935386B2 (en) | Optically active inner hemiacylals of cis-33-dimethyl-2-formyl-cyclopropane-1-carboxylic acids and processes for their preparation and their racemates | |
DE2827627A1 (en) | NEW COMPOUNDS WITH A CYCLOPROPAN RING, PROCESS FOR THEIR PRODUCTION AND THEIR USE IN THE PRODUCTION OF CYCLOPROPANE DERIVATIVES WITH A DIHALOVINYL CHAIN | |
DE1668603B2 (en) | Substituted cyclopropanecarboxylic acid esters and process for their preparation | |
EP0125506A1 (en) | 5-(2,6-Dichloro-4-trifluoromethyl-phenoxy)-2-nitrobenzaldehyde-diacetacylal | |
DE2066032C2 (en) | Derivatives of cis-3,3-dimethyl-2- (2'-oxo-3'-X-cyclopentylidenemethylidenemethyl) -cyclopropane-1-carboxylic acid and processes for their preparation | |
DE2717414C2 (en) | ||
DE2616756A1 (en) | MEANS AFFECTING PLANT GROWTH AND THEIR USE | |
DE2907609C2 (en) | ||
CH640219A5 (en) | METHOD FOR CONVERTING A STEREOISOMER IN ITS DIASTEREOISOMER. | |
DE1149353B (en) | Process for the preparation of 6- [2 ', 6', 6'-trimethylcyclohexen- (1 ') - yl] -4-methylhexadien- (3, 5) -yne- (1) (íÀC-hydrocarboníÂ) | |
DE2903268A1 (en) | NEW ESTERS OF CYCLOPROPANCARBONIC ACIDS WITH A POLYHALOGENATED SUBSTITUENT, METHOD FOR THEIR PRODUCTION AND PESTICIDE COMPOSITIONS | |
DE1180759B (en) | Process for the preparation of bicyclic ª € lactones | |
DE2822472A1 (en) | METHOD FOR PRODUCING ESTERS OF M-PHENOXY-BENZYL ALCOHOL AND ITS ALPHA-CYANO AND ALPHA-AETHINYL DERIVATIVES WITH CARBONIC ACIDS | |
DE2740701C2 (en) | Process for the preparation of cyclopropanecarboxylic acid esters of optically active allethrolone | |
DE1493297B2 (en) | ORGANIC COMPOUNDS OF THE GENERAL FORMULA CH LOW 3-CH LOW 2-CH = CH- (CH LOW 2) LOW M-CH = CH- (CH LOW 2) LOW N-X AND THE METHOD FOR THEIR PRODUCTION | |
EP0053756B1 (en) | 2,6-diethyl-3,5-dimethyl-2,3-dihydro-4h-pyran, process for its preparation and its use in the early identification and location of and in combating lasioderma serricorne f | |
DE69210639T2 (en) | 3- (3,3,3-trifluoro-2-chloropropenyl) -2,2-dimethylcyclopropanecarboxylic acid ester, process for their preparation and their use as pesticide | |
CH647750A5 (en) | TWO-RING AROMATIC INSECTICIDES. | |
DE2624177A1 (en) | PROCESS FOR THE PREPARATION OF M-BENZOYLHYDRATROPIC ACID | |
DE1543804C (en) | Furylmethyl alcohols and process for their preparation | |
DE2263880A1 (en) | METHOD OF DIVISION OF A CYCLOPENTENOLON INTO OPTICAL ISOMERS | |
AT282578B (en) | Process for the preparation of new cyclopropanecarboxylic acid esters | |
DE2356125A1 (en) | NEW CARBOCYCLIC CYCLOPROPANE COMPOUNDS, METHODS OF MANUFACTURING AND INSECTICIDE COMPOSITIONS |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
OI | Miscellaneous see part 1 | ||
OI | Miscellaneous see part 1 | ||
OD | Request for examination | ||
8126 | Change of the secondary classification |
Ipc: C07D333/32 |
|
AC | Divided out of |
Ref country code: DE Ref document number: 2029043 Format of ref document f/p: P |
|
D2 | Grant after examination | ||
8339 | Ceased/non-payment of the annual fee |