DE2929725A1 - METHOD FOR PRODUCING 3- (2,2-DICHLOR-VINYL) -2,2-DIMETHYLCYCLOPROPAN-1-CARBONIC ACID ESTERS - Google Patents
METHOD FOR PRODUCING 3- (2,2-DICHLOR-VINYL) -2,2-DIMETHYLCYCLOPROPAN-1-CARBONIC ACID ESTERSInfo
- Publication number
- DE2929725A1 DE2929725A1 DE19792929725 DE2929725A DE2929725A1 DE 2929725 A1 DE2929725 A1 DE 2929725A1 DE 19792929725 DE19792929725 DE 19792929725 DE 2929725 A DE2929725 A DE 2929725A DE 2929725 A1 DE2929725 A1 DE 2929725A1
- Authority
- DE
- Germany
- Prior art keywords
- dimethyl
- cyclopropane
- acid esters
- formula
- vinyl
- 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.)
- Withdrawn
Links
- -1 2,2-DICHLOR-VINYL Chemical class 0.000 title description 5
- 238000004519 manufacturing process Methods 0.000 title description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical class ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- LLMLSUSAKZVFOA-UHFFFAOYSA-N 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid Chemical class CC1(C)C(C=C(Cl)Cl)C1C(O)=O LLMLSUSAKZVFOA-UHFFFAOYSA-N 0.000 claims description 7
- 239000003085 diluting agent Substances 0.000 claims description 6
- 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 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 claims description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 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 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 239000007858 starting material Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000012230 colorless oil Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- BKNIHVRMZADYLF-UHFFFAOYSA-N dichloro(dichlorophosphoryl)methane Chemical compound ClC(Cl)P(Cl)(Cl)=O BKNIHVRMZADYLF-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- XDOKVFJJVSLHDJ-UHFFFAOYSA-N 1-[dichloromethyl(ethoxy)phosphoryl]oxyethane Chemical compound CCOP(=O)(C(Cl)Cl)OCC XDOKVFJJVSLHDJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XJMFIMBSWLGRQW-UHFFFAOYSA-N P(O)(O)=O.ClCCl Chemical class P(O)(O)=O.ClCCl XJMFIMBSWLGRQW-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- JGBNZSAEXMBBJN-UHFFFAOYSA-N dichloro(dimethoxyphosphoryl)methane Chemical compound COP(=O)(OC)C(Cl)Cl JGBNZSAEXMBBJN-UHFFFAOYSA-N 0.000 description 2
- IXTGXVWLIBNABC-UHFFFAOYSA-N dichloromethylphosphonic acid Chemical class OP(O)(=O)C(Cl)Cl IXTGXVWLIBNABC-UHFFFAOYSA-N 0.000 description 2
- QPTWKDNRYCGMJM-UHFFFAOYSA-N ethyl 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CCOC(=O)C1C(C=C(Cl)Cl)C1(C)C QPTWKDNRYCGMJM-UHFFFAOYSA-N 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 2
- LMHHRCOWPQNFTF-UHFFFAOYSA-N s-propan-2-yl azepane-1-carbothioate Chemical compound CC(C)SC(=O)N1CCCCCC1 LMHHRCOWPQNFTF-UHFFFAOYSA-N 0.000 description 2
- 230000000707 stereoselective effect Effects 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PPNCOQHHSGMKGI-UHFFFAOYSA-N 1-cyclononyldiazonane Chemical compound C1CCCCCCCC1N1NCCCCCCC1 PPNCOQHHSGMKGI-UHFFFAOYSA-N 0.000 description 1
- VEQMUQZKBLIXLT-UHFFFAOYSA-N 2,3-dimethylcyclopropane-1-carboxylic acid Chemical class CC1C(C)C1C(O)=O VEQMUQZKBLIXLT-UHFFFAOYSA-N 0.000 description 1
- ZFFBIQMNKOJDJE-UHFFFAOYSA-N 2-bromo-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Br)C(=O)C1=CC=CC=C1 ZFFBIQMNKOJDJE-UHFFFAOYSA-N 0.000 description 1
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- COFSKYDAGRALHJ-UHFFFAOYSA-N P(O)(O)=O.ClC Chemical class P(O)(O)=O.ClC COFSKYDAGRALHJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 description 1
- BWRORBTYAAVGTK-UHFFFAOYSA-N [Na+].[K+].CC[O-].CC(C)(C)[O-] Chemical compound [Na+].[K+].CC[O-].CC(C)(C)[O-] BWRORBTYAAVGTK-UHFFFAOYSA-N 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000005530 alkylenedioxy group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- ZFZXRNVTYVRULM-UHFFFAOYSA-N ethyl 3-formyl-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CCOC(=O)C1C(C=O)C1(C)C ZFZXRNVTYVRULM-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- KVSRWNPBUMDYOQ-UHFFFAOYSA-N methyl 3-formyl-2,2-dimethylcyclopropane-1-carboxylate Chemical compound COC(=O)C1C(C=O)C1(C)C KVSRWNPBUMDYOQ-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000003012 phosphoric acid amides Chemical class 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 description 1
- DAXNHRYAZCESNW-UHFFFAOYSA-N propan-2-yl 3-formyl-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CC(C)OC(=O)C1C(C=O)C1(C)C DAXNHRYAZCESNW-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von 3-(2,2-Dichlor-vinyl)-2,2-Process for the preparation of 3- (2,2-dichloro-vinyl) -2,2-
dimethyl-cyclopropan-1 -carbonsäureestern Die Erfindung betrifft ein neues Verfahren zur Herstellung von bekannten 3- (2, 2-Dichlor-vinyl) -2, 2-dimethyl-cyclopropan- 1 -carbonsäureestern.dimethyl-cyclopropane-1-carboxylic acid esters The invention relates to a new process for the preparation of known 3- (2, 2-dichloro-vinyl) -2, 2-dimethyl-cyclopropane- 1 -carboxylic acid esters.
Es ist bekannt, daß man 3-(2,2-Dichlor-vinyl)-2,2-dimethyl-cyclopropan-1 -carbonsäureester erhält, wenn man 3-Formyl-2 , 2-dimethyl-cyclopropan- 1 -carbonsäureester mit Triphenyl-phosphin in Tetrachlorkohlenstoff umsetzt (vergleiche DE-OS 2 326 077).It is known that 3- (2,2-dichloro-vinyl) -2,2-dimethyl-cyclopropane-1 -carboxylic acid ester is obtained when 3-formyl-2,2-dimethyl-cyclopropane-1-carboxylic acid ester with triphenylphosphine to form carbon tetrachloride (compare DE-OS 2 326 077).
Nach dieser Synthesemethode erhält man die gewünschten Produkte jedoch nur in mäßigen Ausbeuten.However, this synthesis method gives the desired products only in moderate yields.
Es ist weiter bekannt, daß man 1,1-Dichlor-alkene erhält, wenn man Lithiumsalze von Dichlormethan-phosphonsäureestern mit Aldehyden oder Ketonen umsetzt (vergleiche Synthesis 1975, 535-536).It is also known that 1,1-dichloro-alkenes are obtained if Lithium salts of dichloromethane phosphonic acid esters with aldehydes or ketones (see Synthesis 1975, 535-536).
Die Herstellung der Lithiumsalze von Dichlormethanphosphonsäureestern ist jedoch relativ aufwendig: man erhält sie aus Chlormethan-phosphonsäureestern durch Umsetzung mit Butyllithium und Tetrachlorkohlenstoff bei -750C, wobei sorgfältig getrocknete Lösungsmittel zu verwenden sind und eine Inertgasatmosphäre erforderlich ist.The production of the lithium salts of dichloromethane phosphonic acid esters however, it is relatively complex: they are obtained from chloromethane phosphonic acid esters by reaction with butyllithium and carbon tetrachloride at -750C, being careful Dried solvents are to be used and an inert gas atmosphere is required is.
Es wurde nun gefunden, daß man 3-(2,2-Dichlor-vinyl)-2, 2-dimethyl-cyclopropan-1 -carbonsäureester der Formel I in welcher R für Alkyl oder für einen im Alkoholteil von Pyrethroiden üblichen Rest steht, erhält, wenn man 3-Formyl-2 ,2-dimethyl-cyclopropan-1 -carbonsäureester der Formel II in welcher R die oben angegebene Bedeutung hat, mit Dichlormethan-derivaten der Formel III in welcher R1 und R2 einzeln für Alkyl, Phenyl, Alkoxy, Phenoxy oder zusammen für Alkandiyl (Alkylen) oder Alkandioxy (Alkeylendioxy) stehen, in Gegenwart einer Base und gegebenenfalls unter Verwendung eines Verdünnungsmittels bei Temperaturen zwischen -50 und +50°C umsetzt.It has now been found that 3- (2,2-dichloro-vinyl) -2, 2-dimethyl-cyclopropane-1-carboxylic acid esters of the formula I. in which R represents alkyl or a radical customary in the alcohol part of pyrethroids is obtained when 3-formyl-2,2-dimethyl-cyclopropane-1-carboxylic acid ester of the formula II in which R has the meaning given above, with dichloromethane derivatives of the formula III in which R1 and R2 individually represent alkyl, phenyl, alkoxy, phenoxy or together represent alkanediyl (alkylene) or alkanedioxy (alkeylenedioxy), in the presence of a base and optionally using a diluent at temperatures between -50 and + 50 ° C.
Es ist als überraschend anzusehen, daß man nach dem erfindungsgemäßen Verfahren 3-(2,2-Dichlor-vinyl)-2,2-dimethyl-cyclopropan-1 -carbonsäureester wesentlich einfacher und kostengünstiger in guten Ausbeuten erhält als man in Anbetracht des Standes der Technik erwarten konnte. Das Verfahren eignet sich außerdem zur stereoselektiven Synthese der cis- bzw. trans-Verbindungen der Formel I, da bei der Einführung der Doppelbindung weitgehend keine Isomerisierung der entsprechenden Ausgangsverbindungen auftritt.It is to be regarded as surprising that after the invention Process 3- (2,2-dichloro-vinyl) -2,2-dimethyl-cyclopropane-1-carboxylic acid ester is essential Easier and cheaper in good yields than is obtained in view of the State of the art could be expected. The method is also suitable for stereoselective Synthesis of the cis or trans compounds of the formula I, since the introduction of the Double bond largely no isomerization of the corresponding starting compounds occurs.
Verwendet man als Ausgangstoffe beispielsweise Dichlormethan-phosphonsäure-dimethylester und 3-Formyl-2,2-dimethyl-cyclopropan-1 -carbonsäure-iso-propylester sowie als Base Ralium-iso-propylat, so kann die Reaktion dieser Verbindungen durch folgendes Formelschema skizziert werden: Die als Ausgangsstoffe zu verwendenden 3-Formyl-2,2-dimethyl-cyclopropan-1-carbonsäureester sind durch Formel (II) definiert. Vorzugsweise steht darin R für geradkettiges oder verzweigtes Alkyl mit 1 bis 4 Kohlenstoffatomen.If, for example, dichloromethane-phosphonic acid dimethyl ester and 3-formyl-2,2-dimethyl-cyclopropane-1-carboxylic acid isopropyl ester and ralium isopropylate as base are used, the reaction of these compounds can be outlined by the following equation : The 3-formyl-2,2-dimethyl-cyclopropane-1-carboxylic acid esters to be used as starting materials are defined by formula (II). R therein preferably stands for straight-chain or branched alkyl having 1 to 4 carbon atoms.
Als Beispiele seien 3-Formyl-2,2-dimethyl-cyclopropan-1-carbonsäure-methylester, -ethylester, -n-propylester, iso-propylester, -n-butylester, -iso-butylester, -sek.-butylester und tert.-butylester genannt.Examples are 3-formyl-2,2-dimethyl-cyclopropane-1-carboxylic acid methyl ester, -ethyl ester, -n-propyl ester, iso-propyl ester, -n-butyl ester, -iso-butyl ester, -sec.-butyl ester and tert-butyl ester.
Ausgangsverbindungen der Formel (II) sind bekannt (vergleiche DE-OS 2 615 160; Tetrahedron Lett. 1978, 1847-1870; US-P 3 679 667).Starting compounds of the formula (II) are known (see DE-OS 2,615 160; Tetrahedron Lett. 1978, 1847-1870; US-P 3,679,667).
Die weiter als Ausgangsverbindungen zu verwendenden Dichlormethan-derivate sind durch Formel (III) definiert. Vorzugsweise stehen darin R1 und R2 einzeln für Alkoxy mit 1 bis 4 Kohlenstoffatomen oder für Phenoxy oder beide Reste R1 und R2 stehen zusammen für geradkettiges oder verzweigtes Alkandioxy (Alkylendioxy) mit 2 bis. 5 Kohlenstoffatomen.The dichloromethane derivatives to be used further as starting compounds are defined by formula (III). Preferably are in it R1 and R2 individually for alkoxy with 1 to 4 carbon atoms or for phenoxy or both Rests R1 and R2 together stand for straight-chain or branched alkanedioxy (alkylenedioxy) with 2 to. 5 carbon atoms.
Als Beispiele seien Dichlormethan-phosphonsäure-dimethylester, -diethylester und -diphenylester genannt.Examples are dichloromethane-phosphonic acid dimethyl ester and diethyl ester and called diphenyl esters.
Die Verbindungen der Formel (III) sind bekannt oder können nach an sich bekannten Verfahren hergestellt werden (vgl. Synthesis 1975, 535-536; Tetrahedron Letters 1975, 609-610; ibid. 1975, 4409-4410).The compounds of the formula (III) are known or can be used according to known processes (cf. Synthesis 1975, 535-536; Tetrahedron Letters 1975, 609-610; ibid. 1975, 4409-4410).
Man erhält Dichlormethan-phosphonsäureester der Formel (III) beispielsweise durch Umsetzung von Dichlormethanphosphonsäuredichlorid (vergleiche GB-PS 707 961) mit Natrium- oder Kalium-salzen von Hydroxyverbindungen, wie z.B. mit Natrium- oder Kalium-methylat, -ethylat, -n- und -iso-propylat, -n-, iso-, sek.- und tert.-butylat, gegebenenfalls in Gegenwart eines Verdünnungsmittels, wie z.B. Toluol, bei Temperaturen zwischen O und 500C. Zur Reinigung der Produkte wird gegebenenfalls nach Filtration destilliert.Dichloromethane-phosphonic acid esters of the formula (III) are obtained, for example by converting dichloromethanephosphonic acid dichloride (compare GB-PS 707 961) with sodium or potassium salts of hydroxy compounds, such as with sodium or Potassium methylate, ethylate, n- and iso-propylate, -n-, iso-, sec- and tert-butylate, optionally in the presence of a diluent such as toluene at temperatures between 0 and 500C. To clean the products, if necessary, after filtration distilled.
Das erfindungsgemäße Verfahren wird vorzugsweise unter Verwendung von Verdünnungsmitteln durchgeführt. Als solche kommen praktisch alle inerten organischen Lösungsmittel, insbesondere aprotisch polare Solventien in Frage. Hierzu gehören Ether, wie z.B. Gylcol-dimethylether, Diglycol-dimethylether, Tetrahydrofuran und Dioxan, Carbonsäureamide, wie z.B. Dimethylformamid, Dimethylacetamid und N-Methyl-pyrrolidon, Sulfoxide und Sulfone, wie z.B. Dimethylsulfoxid und Tetramethylensulfon, Phosphorsäureamide, wie z.B. Hexamethylphosphorsäuretriamid, sowie Nitrile, wie z.B. Acetonitril und Propionitril.The method of the invention is preferably used carried out by diluents. As such, virtually all inert organic come Solvents, in particular aprotic polar solvents in question. These include Ethers such as glycol dimethyl ether, diglycol dimethyl ether, tetrahydrofuran and Dioxane, carboxamides, such as dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone, Sulfoxides and sulfones, such as dimethyl sulfoxide and tetramethylene sulfone, Phosphoric acid amides, such as hexamethylphosphoric acid triamide, and nitriles, such as e.g. acetonitrile and propionitrile.
Beim erfindungsgemäßen. Verfahren können die in der organisch-chemischen Synthese üblichen Basen verwendet werden. Hierzu gehören insbesondere Alkalihydroxide, wie z.B. Natrium- und Kalium-hydroxid, Alkalialkoholate, wie z.B. Natrium- und Kalium-methylat, Natrium- und Kalium-ethylat, Natrium- und Kalium-iso-propylat, Natrium-und Kalium-tert.-butylat, Alkalihydride, wie z.B. Natrium-und Kalium-hydrid, Alkaliamide, wie z.B. Natrium- und Kalium-amid, Alkyllithiumverbindungen, wie z.B. Butyllithium, sowie Amine, wie z.B. Diazabicyclononan und Diazabicycloundecen.When the invention. Process can be used in the organic chemical Synthesis usual bases can be used. These include in particular alkali hydroxides, such as sodium and potassium hydroxide, alkali alcoholates such as sodium and potassium methylate, Sodium and potassium ethylate, sodium and potassium isopropylate, sodium and potassium tert-butylate, Alkali hydrides such as sodium and potassium hydride, alkali amides such as sodium and potassium amide, alkyl lithium compounds such as butyl lithium, and amines such as e.g., diazabicyclononane and diazabicycloundecene.
Alkoholate werden als Basen besonders bevorzugt.Alcoholates are particularly preferred as bases.
Die Reaktionstemperatur wird zwischen -50 und +50°C, vorzugsweise zwischen -30 und +300C gehalten. Das erfindungsgemäße Verfahren wird im allgemeinen bei Normaldruck durchgeführt.The reaction temperature is between -50 and + 50 ° C, preferably kept between -30 and + 300C. The inventive method is generally carried out at normal pressure.
Je Mol 3-Formyl-2 , 2-dimethyl-cyclopropan-1 -carbonsäureester der Formel (II) werden 1 bis 1,5 Mol, vorzugsweise 1 bis 1.2 Mol Dichlormethan-derivat der Formel (III) und 1 bis 1,5 Mol, vorzugsweise 1 bis 1,2 Mol Base eingesetzt.Per mole of 3-formyl-2,2-dimethyl-cyclopropane-1-carboxylic acid ester of Formula (II) are 1 to 1.5 moles, preferably 1 to 1.2 moles of dichloromethane derivative of formula (III) and 1 to 1.5 mol, preferably 1 to 1.2 mol of base are used.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens werden die Ausgangs stoffe der Formeln (II) und (III) in einem der oben angegebenen Verdünnungsmittel bei Temperaturen zwischen -30 und +100C vorgelegt und mit der Lösung einer Base in einem der oben angegebenen Verdünnungsmittel tropfenweise versetzt. Dann läßt man das Reaktionsgemisch auf Raumtemperatur kommen und rührt einige Stunden nach.In a preferred embodiment of the method according to the invention the starting materials of the formulas (II) and (III) are in one of the above Submitted diluents at temperatures between -30 and + 100C and with the Solution of a base in one of the diluents given above are added dropwise. The reaction mixture is then allowed to come to room temperature and is stirred for a few hours after.
Die Aufarbeitung erfolgt auf übliche Weise: man gießt das Reaktionsgemisch in Wasser und extrahiert mit einem mit Wasser nicht mischbaren Lösungsmittel, wie z.B. Methylenchlorid. Die Extrakte werden mit verdünnter Natronlauge und dann mit Wasser gewaschen, getrocknet und filtriert. Vom Filtrat wird das Lösungsmittel abgezogen und das als Rückstand verbleibende Produkt durch Vakuumdestillation gereinigt. Zur Charakterisierung dient der Siedepunkt.Working up is carried out in the usual way: the reaction mixture is poured in water and extracted with a water-immiscible solvent such as e.g. methylene chloride. The extracts are diluted with sodium hydroxide and then with Washed water, dried and filtered. The solvent is drawn off from the filtrate and the product remaining as residue is purified by vacuum distillation. To the The boiling point is used for characterization.
Da die als Ausgangsverbindungen eingesetzten 3-Formyl-2, 2-dimethyl-cyclopropan-1 -carbonsäureester der Formel (II) wie auch die erfindungsgemäß herzustellenden 3-(2,2-Dichlor-vinyl)-2,2-dimethyl-cyclopropan-1-carbonsäureester der Formel (I) jeweils asymmetrische Kohlenstoffatome aufweisen, können die Verbindungen der Formeln (I) und (II) in einer entsprechenden Anzahl von stereoisomeren Formeln auftreten.Since the 3-formyl-2,2-dimethyl-cyclopropane-1 used as starting compounds carboxylic acid esters of the formula (II) as well as the 3- (2,2-dichloro-vinyl) -2,2-dimethyl-cyclopropane-1-carboxylic acid esters to be prepared according to the invention of the formula (I) each have asymmetric carbon atoms, the compounds of formulas (I) and (II) in a corresponding number of stereoisomeric formulas appear.
Das erfindungsgemäße Verfahren bezieht sich auf die stereoselektive Herstellung von Verbindungen der Formel (I), die entweder in Form der einzelnen Stereoisomeren oder als Gemische von Stereoisomeren erhalten werden.The inventive method relates to the stereoselective Preparation of compounds of formula (I), either in the form of the individual Stereoisomers or as mixtures of stereoisomers are obtained.
Die nach dem erfindungsgemäßen Verfahren herzustellenden 2,2-Dimethyl-3-(2,2-dichlor-vinyl)-cyclopropan-1-carbonsäureester können als Zwischenprodukte zur Herstellung von insektizid und akarizid wirksamen Pyrethroiden verwendet werden (vergleiche DE-OS 2 326 077).The 2,2-dimethyl-3- (2,2-dichloro-vinyl) -cyclopropane-1-carboxylic acid esters to be prepared by the process according to the invention Can be used as intermediates for the production of insecticidal and acaricidal agents Pyrethroids are used (see DE-OS 2 326 077).
Beispiel 1 Zu einer Mischung von 48 g (0,22 Mol) Dichlormethanphosphonsäure-diethylester und 34 g (0,2 Mol) 3-Formyl-2, 2-dimethyl-cyclopropan-1 -carbonsäure-ethylester in 200 ml Tetrahydrofuran wird bei -150C eine Suspension von 24,6 g (0,22 Mol) Kalium-tert.-butylat in 20 ml Dimethylformamid tropfenweise gegeben. Nach beendeter Zugabe wird das Reaktionsgemisch auf 200C erwärmt und zwei Stunden bei dieser Temperatur gerührt.example 1 To a mixture of 48 g (0.22 mol) of dichloromethanephosphonic acid diethyl ester and 34 g (0.2 mol) of 3-formyl-2,2-dimethyl-cyclopropane-1-carboxylic acid ethyl ester in 200 ml of tetrahydrofuran is added at -150C Suspension of 24.6 g (0.22 mol) of potassium tert-butoxide in 20 ml of dimethylformamide was added dropwise. When the addition is complete, the reaction mixture is heated to 200 ° C. and stirred for two hours at this temperature.
Dann wird das Reaktionsgemisch in 400 ml Wasser gegossen.The reaction mixture is then poured into 400 ml of water.
Die wäßrige Lösung wird zweimal mit je 200 ml Methylenchlorid extrahiert. Die vereinigten organischen Extrakte werden einmal mit 100 ml 5 %iger Natronlauge und zweimal mit Wasser gewaschen, über Natriumsulfat getrocknet und dann eingedampft. Der Rückstand wird fraktioniert destilliert. Man erhält 42 g (88,6 % der Theorie) 3-(2,2-Dichlor-vinyl)-2,2-dimethyl-cyclopropan-1 -carbonsäure-ethylester in Form eines farblosen Öls vom Siedepunkt 80-950C/2 mbar.The aqueous solution is extracted twice with 200 ml of methylene chloride each time. The combined organic extracts are once with 100 ml of 5% sodium hydroxide solution and washed twice with water, dried over sodium sulfate and then evaporated. The residue is fractionally distilled. 42 g (88.6% of theory) are obtained 3- (2,2-dichloro-vinyl) -2,2-dimethyl-cyclopropane-1-carboxylic acid ethyl ester in the form of a colorless oil with a boiling point of 80-950C / 2 mbar.
Beispiel 2 Die Umsetzung wird analog Beispiel 1 mit den gleichen Ausgangsverbindungen durchgeführt, wobei jedoch an Stelle von Kalium-tert.-butylat als Base Natriumethylat (15 g) verwendet wird und die Reaktionstemperatur am Anfang bei +100C gehalten wird. Man erhält 24,5 g (51,6 % der Theorie) 3-(2.,2-Dichlor-vinyl)-2,2-dimethyl-cyclopropan-1 -carbonsäure-ethylester in Form eines farbloses Öls vom Siedepunkt 80-95 OC/2 mbar.Example 2 The reaction is carried out analogously to Example 1 with the same starting compounds, but instead of potassium tert-butoxide sodium ethoxide (15 g) is used as the base and the reaction temperature is kept at + 100 ° C. at the beginning. 24.5 g (51.6% of theory) of ethyl 3- (2nd, 2-dichloro-vinyl) -2,2-dimethyl-cyclopropane-1-carboxylate are obtained in the form of a colorless oil with a boiling point of 80-95 OC / 2 mbar.
Beispiel 3 Die Umsetzung wird analog Beispiel 1 mit den gleichen Ausgangsverbindungen durchgeführt, wobei jedoch an Stelle einer Lösung von Kalium-tert.-butylat in Dimethylformamid eine Lösung der gleichen Base in 100 ml Tetrahydrofuran verwendet wird. Man erhält 38 g (80 % der Theorie) 3-(2,2-Dichlor-vinyl)-2,2-dimethyl-cyclopropan- 1 -carbonsäure-ethylester in Form eines farblosen Öls vom Siedepunkt 80-950C/2 mbar.Example 3 The reaction is carried out as in Example 1 with the same starting compounds, but instead of a solution of potassium tert-butoxide in dimethylformamide, a solution of the same base in 100 ml of tetrahydrofuran is used. 38 g (80% of theory) of ethyl 3- (2,2-dichloro-vinyl) -2,2-dimethyl-cyclopropane-1-carboxylate are obtained in the form of a colorless oil with a boiling point of 80 ° -950 ° C./2 mbar.
Als Ausgangsstoffe zu verwendende Dichlormethan-phosphonsäureester der Formel (III) können beispielsweise wie folgt hergestellt werden: In eine Mischung aus 720 g (6 Mol) Chloroform und 274 g (2 Mol) Phosphortrichlorid werden portionsweise 266 g (2 Mol) Aluminiumchlorid gegeben.Dichloromethane-phosphonic acid esters of the formula (III) to be used as starting materials can be prepared, for example, as follows: 266 g (2 mol) of aluminum chloride are added in portions to a mixture of 720 g (6 mol) of chloroform and 274 g (2 mol) of phosphorus trichloride.
Das Reaktionsgemisch wird dann 12 Stunden unter Rückfluß zum Sieden erhitzt. Anschließend wird das Lösungsmittel im Vakuum abgezogen und der Rückstand wird in 2 1 Methylenchlorid aufgenommen. Dazu werden bei OOC 440 ml konz. Salzsäure getropft und es wird etwa zwei Stunden bei dieser Temperatur nachgerührt. Die organische Phase wird abgetrennt, über Natrium getrocknet und eingeengt. Der Rückstand wird fraktioniert destilliert.The reaction mixture is then refluxed for 12 hours heated. The solvent is then stripped off in vacuo and the residue is taken up in 2 l of methylene chloride. For this purpose, 440 ml of conc. hydrochloric acid added dropwise and it is stirred for about two hours at this temperature. The organic Phase is separated off, dried over sodium and concentrated. The residue will fractionally distilled.
Man erhält 258 g (64,5 % der Theorie) Dichlormethanphosphonsäuredichlorid in Form eines farblosen Öls vom Siedepunkt 48-500C/1 mbar. 258 g (64.5% of theory) of dichloromethanephosphonic acid dichloride are obtained in the form of a colorless oil with a boiling point of 48 ° -500 ° C./1 mbar.
Zu einer Lösung von 227,5 g (1,13 Mol) Dichlormethanphosphonsäuredichlorid in 800 ml Toluol werden bei 5-100C 153,5 g (2,26 Mol) Natriumethylat in 800 ml Ethanol getropft. Das Reaktionsgemisch wird fünf Stunden bei 200C nachgerührt. Dann wird abgesaugt, das Filtrat eingeengt und der Rückstand fraktioniert destilliert.To a solution of 227.5 g (1.13 mol) of dichloromethanephosphonic acid dichloride in 800 ml of toluene, 153.5 g (2.26 mol) of sodium ethoxide in 800 ml of ethanol are added at 5-100 ° C. dripped. The reaction mixture is stirred at 200 ° C. for five hours. Then it will be Sucked off, the filtrate was concentrated and the residue was fractionally distilled.
Man erhält 195 g (78 % der Theorie) Dichlormethan-phosphonsäure-diethylester in Form eines farblosen Öls vom Siedepunkt 840C/1 mbar.195 g (78% of theory) of diethyl dichloromethane-phosphonic acid are obtained in the form of a colorless oil with a boiling point of 840C / 1 mbar.
Claims (1)
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19792929725 DE2929725A1 (en) | 1979-07-21 | 1979-07-21 | METHOD FOR PRODUCING 3- (2,2-DICHLOR-VINYL) -2,2-DIMETHYLCYCLOPROPAN-1-CARBONIC ACID ESTERS |
| US06/165,871 US4296241A (en) | 1979-07-21 | 1980-07-02 | Preparation of 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropane-1-carboxylic acid derivatives |
| EP80103847A EP0022971B1 (en) | 1979-07-21 | 1980-07-07 | Process for the preparation of 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropane-1-carboxylic acid derivatives |
| DE8080103847T DE3062343D1 (en) | 1979-07-21 | 1980-07-07 | Process for the preparation of 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropane-1-carboxylic acid derivatives |
| HU801788A HU182691B (en) | 1979-07-21 | 1980-07-17 | Process for preparing 3-/2,2-dichloro-vinyl/-2,2-dimethyl-cyclopropane-carboxylic acid and esters thereof |
| DK309080A DK309080A (en) | 1979-07-21 | 1980-07-17 | METHOD FOR PREPARING 3- (2,2-DICHLORVINYL) -2,2-DIMETHYL-CYCLOPROPAN-1-CARBOXYLIC ACID DERIVATIVES |
| DD80222735A DD152125A5 (en) | 1979-07-21 | 1980-07-18 | PROCESS FOR PREPARING 3- (2,2-DICHLOR-VINYL) -2,2-DIMETHYLCYCLOPROPAN-1-CARBOXYLIC ACID DERIVATIVES |
| IL60630A IL60630A0 (en) | 1979-07-21 | 1980-07-18 | Preparation of 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropane-1-carboxylic acid derivatives |
| BR8004486A BR8004486A (en) | 1979-07-21 | 1980-07-18 | PROCESS FOR PREPARING ACID DERIVATIVES 3- (2,2-DICLORO-VINYL) -2,2-DIMETHYL-CYCLOPROPANE-1-CARBOXYLIC |
| JP9820080A JPS5616440A (en) | 1979-07-21 | 1980-07-19 | Manufacture of 33*2*22dichloroovinyl**2*22 dimethyllcyclopropanee11carboxylic acid derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19792929725 DE2929725A1 (en) | 1979-07-21 | 1979-07-21 | METHOD FOR PRODUCING 3- (2,2-DICHLOR-VINYL) -2,2-DIMETHYLCYCLOPROPAN-1-CARBONIC ACID ESTERS |
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| Publication Number | Publication Date |
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| DE2929725A1 true DE2929725A1 (en) | 1981-02-12 |
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| DE19792929725 Withdrawn DE2929725A1 (en) | 1979-07-21 | 1979-07-21 | METHOD FOR PRODUCING 3- (2,2-DICHLOR-VINYL) -2,2-DIMETHYLCYCLOPROPAN-1-CARBONIC ACID ESTERS |
Country Status (2)
| Country | Link |
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| JP (1) | JPS5616440A (en) |
| DE (1) | DE2929725A1 (en) |
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| EP1625861A4 (en) | 2003-05-21 | 2012-04-11 | Jms Co Ltd | Container for serum production and method of regenerative medicine using the same |
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- 1979-07-21 DE DE19792929725 patent/DE2929725A1/en not_active Withdrawn
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- 1980-07-19 JP JP9820080A patent/JPS5616440A/en active Pending
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