HU189554B - Process for the epimerization of trans-chrysanthemum acid esters - Google Patents
Process for the epimerization of trans-chrysanthemum acid esters Download PDFInfo
- Publication number
- HU189554B HU189554B HU8221A HU2182A HU189554B HU 189554 B HU189554 B HU 189554B HU 8221 A HU8221 A HU 8221A HU 2182 A HU2182 A HU 2182A HU 189554 B HU189554 B HU 189554B
- Authority
- HU
- Hungary
- Prior art keywords
- trans
- cis
- mixture
- formula
- methyl
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000006345 epimerization reaction Methods 0.000 title claims abstract description 9
- 239000002253 acid Substances 0.000 title abstract description 5
- 150000002148 esters Chemical class 0.000 title description 8
- 239000000203 mixture Substances 0.000 claims abstract description 116
- XLOPRKKSAJMMEW-HTQZYQBOSA-N (-)-cis-chrysanthemic acid Chemical compound CC(C)=C[C@@H]1[C@H](C(O)=O)C1(C)C XLOPRKKSAJMMEW-HTQZYQBOSA-N 0.000 claims abstract description 16
- -1 alkyl trans chrysanthemate Chemical compound 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000002585 base Substances 0.000 claims abstract description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 5
- 239000000460 chlorine Substances 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 239000011630 iodine Substances 0.000 claims abstract description 5
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 68
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- XLOPRKKSAJMMEW-SFYZADRCSA-N (+)-trans-chrysanthemic acid Chemical compound CC(C)=C[C@@H]1[C@@H](C(O)=O)C1(C)C XLOPRKKSAJMMEW-SFYZADRCSA-N 0.000 claims description 22
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 15
- LKPFWCPZERQLFI-UHFFFAOYSA-N 2,4,6-trimethylpyridine;hydrochloride Chemical compound Cl.CC1=CC(C)=NC(C)=C1 LKPFWCPZERQLFI-UHFFFAOYSA-N 0.000 claims description 13
- 125000005907 alkyl ester group Chemical group 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- YCBWLMWEQURJHX-UHFFFAOYSA-N 4-(trifluoromethyl)cyclohexan-1-amine Chemical compound NC1CCC(C(F)(F)F)CC1 YCBWLMWEQURJHX-UHFFFAOYSA-N 0.000 claims description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 claims description 4
- VGKZBAMIYUHSMU-UHFFFAOYSA-N 4-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylic acid Chemical compound OC(=O)C1CCC(NC(=O)N(CCCl)N=O)CC1 VGKZBAMIYUHSMU-UHFFFAOYSA-N 0.000 claims description 3
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 claims description 3
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 claims description 3
- URAZVWXGWMBUGJ-UHFFFAOYSA-N di(propan-2-yl)azanium;chloride Chemical compound [Cl-].CC(C)[NH2+]C(C)C URAZVWXGWMBUGJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- NGDSBQHTMKGUQU-UHFFFAOYSA-N methenamine hydrochloride Chemical compound Cl.C([N@@](C1)C2)[N@]3C[N@@]2C[N@@]1C3 NGDSBQHTMKGUQU-UHFFFAOYSA-N 0.000 claims description 3
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 claims description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- ISYORFGKSZLPNW-UHFFFAOYSA-N propan-2-ylazanium;chloride Chemical compound [Cl-].CC(C)[NH3+] ISYORFGKSZLPNW-UHFFFAOYSA-N 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 abstract description 9
- 125000000217 alkyl group Chemical group 0.000 abstract description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract 2
- 150000001450 anions Chemical class 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 72
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 64
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 48
- XLOPRKKSAJMMEW-SFYZADRCSA-M (R,R)-chrysanthemate Chemical compound CC(C)=C[C@@H]1[C@@H](C([O-])=O)C1(C)C XLOPRKKSAJMMEW-SFYZADRCSA-M 0.000 description 45
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 45
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 32
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 28
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 28
- 229940043279 diisopropylamine Drugs 0.000 description 16
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 16
- 238000003756 stirring Methods 0.000 description 15
- XLOPRKKSAJMMEW-UHFFFAOYSA-N chrysanthemic acid Chemical compound CC(C)=CC1C(C(O)=O)C1(C)C XLOPRKKSAJMMEW-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 12
- 235000019799 monosodium phosphate Nutrition 0.000 description 12
- 238000003822 preparative gas chromatography Methods 0.000 description 12
- 239000001488 sodium phosphate Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 6
- 239000010779 crude oil Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000012047 saturated solution Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XUNXRBCZHURUPV-UHFFFAOYSA-N 2,2,4a,7,7-pentamethyl-3,4,5,6-tetrahydro-1h-1,8-naphthyridine;hydrochloride Chemical compound Cl.C1CC(C)(C)N=C2NC(C)(C)CCC21C XUNXRBCZHURUPV-UHFFFAOYSA-N 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- AESUECJLDNUSMZ-UHFFFAOYSA-N [Li]CCCC.C1CCCCC1 Chemical compound [Li]CCCC.C1CCCCC1 AESUECJLDNUSMZ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- OEOPGVPCZRQSMQ-UHFFFAOYSA-N 2,2,4a,7,7-pentamethyl-3,4,5,6-tetrahydro-1h-1,8-naphthyridine Chemical compound C1CC(C)(C)N=C2NC(C)(C)CCC21C OEOPGVPCZRQSMQ-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- HVNYTMRNKOKJDT-UHFFFAOYSA-N 2-chloro-1,3,2-dioxaborolane Chemical compound ClB1OCCO1 HVNYTMRNKOKJDT-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- JVYMKTAPCLSXLC-UHFFFAOYSA-N COClO Chemical compound COClO JVYMKTAPCLSXLC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KLJPJQLKSTTYTK-UHFFFAOYSA-N butyl(chloro)silane Chemical compound CCCC[SiH2]Cl KLJPJQLKSTTYTK-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- OBOQYRKDOSNKFJ-UHFFFAOYSA-N chloro(dimethoxy)borane Chemical compound COB(Cl)OC OBOQYRKDOSNKFJ-UHFFFAOYSA-N 0.000 description 1
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical class OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- LGTLXDJOAJDFLR-UHFFFAOYSA-N diethyl chlorophosphate Chemical compound CCOP(Cl)(=O)OCC LGTLXDJOAJDFLR-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- OZECFIJVSAYAPH-UHFFFAOYSA-N ethyl-di(propan-2-yl)azanium;chloride Chemical compound Cl.CCN(C(C)C)C(C)C OZECFIJVSAYAPH-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- XLZXAQOITBVJSE-UHFFFAOYSA-N n-ethylpropan-2-amine;hydrochloride Chemical compound Cl.CCNC(C)C XLZXAQOITBVJSE-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229910052700 potassium Chemical group 0.000 description 1
- 239000011591 potassium Chemical group 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Chemical group 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C61/16—Unsaturated compounds
- C07C61/35—Unsaturated compounds having unsaturation outside the rings
- C07C61/37—Chrysanthemumic acid
-
- 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
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Catalysts (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8102828A FR2499979A1 (fr) | 1981-02-13 | 1981-02-13 | Procede d'epimerisation d'acides trans chrysanthemiques |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| HU189554B true HU189554B (en) | 1986-07-28 |
Family
ID=9255157
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| HU8221A HU189554B (en) | 1981-02-13 | 1982-01-06 | Process for the epimerization of trans-chrysanthemum acid esters |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4447637A (en, 2012) |
| EP (1) | EP0058591B1 (en, 2012) |
| JP (1) | JPS57150636A (en, 2012) |
| AT (1) | ATE9685T1 (en, 2012) |
| CA (1) | CA1192909A (en, 2012) |
| DE (1) | DE3260852D1 (en, 2012) |
| FR (1) | FR2499979A1 (en, 2012) |
| HU (1) | HU189554B (en, 2012) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5380940A (en) * | 1992-06-26 | 1995-01-10 | Aldrich Chemical Company, Inc. | Bis(bicyclo(2.2.2)octyl)haloboranes |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2036088A5 (en, 2012) * | 1969-03-04 | 1970-12-24 | Roussel Uclaf | |
| US3836568A (en) * | 1970-12-28 | 1974-09-17 | Sumitomo Chemical Co | Process for production of lower alkyl esters of cis-chrysanthemum monocarboxylic acid |
| JPS5612625B2 (en, 2012) * | 1972-09-07 | 1981-03-23 | ||
| US3989654A (en) * | 1973-11-22 | 1976-11-02 | Sumitomo Chemical Company, Limited | Process for preparing cis-chrysanthemic acid |
| US4166064A (en) * | 1978-02-13 | 1979-08-28 | Fmc Corporation | Process for preparing high cis 3-(2,2,2-trichloroethyl)-2,2-dimethylcyclopropane-1-carboxylates |
| FR2432012A1 (fr) * | 1978-07-24 | 1980-02-22 | Roussel Uclaf | Procede de preparation d'esters d'alcoyle de l'acide dl cis chrysanthemique |
| DE2965745D1 (en) * | 1978-10-27 | 1983-07-28 | Ici Plc | Process of separating cis and trans isomers of cyclopropane carboxylic acids |
| FR2464939A1 (fr) * | 1979-09-10 | 1981-03-20 | Roussel Uclaf | Nouveaux derives substitues du cyclopropene, leur procede de preparation et leur application dans la synthese de precurseurs de l'acide dl cis chrysanthemique |
| IT1131883B (it) * | 1980-07-02 | 1986-06-25 | Montedison Spa | Processo per la sintesi stereoselettiva di ciclopropancarbossilati intermaedi per piretroidi |
-
1981
- 1981-02-13 FR FR8102828A patent/FR2499979A1/fr active Granted
-
1982
- 1982-01-06 HU HU8221A patent/HU189554B/hu not_active IP Right Cessation
- 1982-01-28 DE DE8282400158T patent/DE3260852D1/de not_active Expired
- 1982-01-28 EP EP82400158A patent/EP0058591B1/fr not_active Expired
- 1982-01-28 AT AT82400158T patent/ATE9685T1/de active
- 1982-02-09 US US06/347,278 patent/US4447637A/en not_active Expired - Lifetime
- 1982-02-12 JP JP57019851A patent/JPS57150636A/ja active Granted
- 1982-02-12 CA CA000396135A patent/CA1192909A/fr not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2499979A1 (fr) | 1982-08-20 |
| EP0058591B1 (fr) | 1984-10-03 |
| CA1192909A (fr) | 1985-09-03 |
| FR2499979B1 (en, 2012) | 1984-05-04 |
| ATE9685T1 (de) | 1984-10-15 |
| US4447637A (en) | 1984-05-08 |
| JPH0314012B2 (en, 2012) | 1991-02-25 |
| EP0058591A1 (fr) | 1982-08-25 |
| DE3260852D1 (en) | 1984-11-08 |
| JPS57150636A (en) | 1982-09-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| HU90 | Patent valid on 900628 | ||
| HMM4 | Cancellation of final prot. due to non-payment of fee |