EP0000925A1 - Procédé de préparation d'acides cyclopropanecarboxyliques insaturés, ainsi que leurs esters - Google Patents
Procédé de préparation d'acides cyclopropanecarboxyliques insaturés, ainsi que leurs esters Download PDFInfo
- Publication number
- EP0000925A1 EP0000925A1 EP78100687A EP78100687A EP0000925A1 EP 0000925 A1 EP0000925 A1 EP 0000925A1 EP 78100687 A EP78100687 A EP 78100687A EP 78100687 A EP78100687 A EP 78100687A EP 0000925 A1 EP0000925 A1 EP 0000925A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- compounds
- reaction
- alkenyl
- dimethylcyclopropene
- esters
- 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- Withdrawn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
- 150000002148 esters Chemical class 0.000 title claims abstract description 14
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical class OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 title description 3
- 238000004519 manufacturing process Methods 0.000 title 1
- ZHYHTHWCDOOOJU-UHFFFAOYSA-N 3,3-dimethylcyclopropene Chemical compound CC1(C)C=C1 ZHYHTHWCDOOOJU-UHFFFAOYSA-N 0.000 claims abstract description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 chloroformic acid ester Chemical class 0.000 claims abstract description 15
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims abstract description 4
- 150000004820 halides Chemical class 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 150000002681 magnesium compounds Chemical class 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- XLOPRKKSAJMMEW-SFYZADRCSA-N Chrysanthemic acid Natural products CC(C)=C[C@@H]1[C@@H](C(O)=O)C1(C)C XLOPRKKSAJMMEW-SFYZADRCSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- XLOPRKKSAJMMEW-UHFFFAOYSA-N chrysanthemic acid Chemical compound CC(C)=CC1C(C(O)=O)C1(C)C XLOPRKKSAJMMEW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000012442 inert solvent Substances 0.000 claims description 3
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 230000000707 stereoselective effect Effects 0.000 claims 1
- 230000017105 transposition Effects 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 33
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- 239000000243 solution Substances 0.000 description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- 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 description 5
- MUPYMRJBEZFVMT-UHFFFAOYSA-N 1-chloro-4-dimethoxyphosphorylsulfanylbenzene Chemical compound COP(=O)(OC)SC1=CC=C(Cl)C=C1 MUPYMRJBEZFVMT-UHFFFAOYSA-N 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 229940091250 magnesium supplement Drugs 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000002901 organomagnesium compounds Chemical class 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 229940077744 antacid containing magnesium compound Drugs 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PBIJFSCPEFQXBB-UHFFFAOYSA-N 1,1-dimethylcyclopropane Chemical compound CC1(C)CC1 PBIJFSCPEFQXBB-UHFFFAOYSA-N 0.000 description 2
- MRLAULBRWNYTDV-UHFFFAOYSA-N 1,3,3-trimethylcyclopropene Chemical compound CC1=CC1(C)C MRLAULBRWNYTDV-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- BJVFGWYBOLMUEM-UHFFFAOYSA-M CC(=C)C[Mg]Cl Chemical compound CC(=C)C[Mg]Cl BJVFGWYBOLMUEM-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- YMWBTMBPEHUMBA-FAKHFBMMSA-N [(3r,3as,4s,8as)-3-hydroxy-6,8a-dimethyl-8-oxo-3-propan-2-yl-2,3a,4,5-tetrahydro-1h-azulen-4-yl] (e)-2-methylbut-2-enoate Chemical compound C\C=C(/C)C(=O)O[C@H]1CC(C)=CC(=O)[C@@]2(C)CC[C@@](O)(C(C)C)[C@H]12 YMWBTMBPEHUMBA-FAKHFBMMSA-N 0.000 description 2
- 150000000475 acetylene derivatives Chemical class 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000004791 alkyl magnesium halides Chemical class 0.000 description 2
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical compound OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- OOXWYYGXTJLWHA-UHFFFAOYSA-N cyclopropene Chemical compound C1C=C1 OOXWYYGXTJLWHA-UHFFFAOYSA-N 0.000 description 2
- 150000001943 cyclopropenes Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- BXIIJPAVISPOGI-UHFFFAOYSA-N 1,1,2-trimethylcyclopropane Chemical compound CC1CC1(C)C BXIIJPAVISPOGI-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- CGHIBGNXEGJPQZ-UHFFFAOYSA-N 1-hexyne Chemical compound CCCCC#C CGHIBGNXEGJPQZ-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- CAMUWNSZYGVVIV-UHFFFAOYSA-N 2-ethenylhept-6-enoic acid Chemical compound OC(=O)C(C=C)CCCC=C CAMUWNSZYGVVIV-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- 241000250966 Tanacetum cinerariifolium Species 0.000 description 1
- VXSIXFKKSNGRRO-MXOVTSAMSA-N [(1s)-2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate;[(1s)-2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-3-[(e)-3-methoxy-2-methyl-3-oxoprop-1-enyl Chemical class CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1.CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VXSIXFKKSNGRRO-MXOVTSAMSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- VIMXTGUGWLAOFZ-ZJUUUORDSA-N ethyl (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical compound CCOC(=O)[C@@H]1[C@@H](C=C(C)C)C1(C)C VIMXTGUGWLAOFZ-ZJUUUORDSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229960000869 magnesium oxide Drugs 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 description 1
- 229940070846 pyrethrins Drugs 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000036633 rest Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
Definitions
- Esters of 2,2-dimethyl-3-alkenyl-cyclopropylcarboxylic acid and derivatives substituted in the alkylene radical are important insecticides.
- the best-known representatives of this class are the "pyrethrins" found in the flower heads of the Pyrethrum Chrysanthemum cinerariae folium, which are esters of chrysanthemic acid, a 2,2-dimethyl-3 ( ⁇ -methylpropenyl) cyclopropanecarboxylic acid. which can occur in the cis and trans forms.
- 2,2-dimethyl-3-alkenylcyclopropanecarboxylic acids or their esters can be obtained in good yields and high purity from the cheap starting materials isobutene, chloroform, alkenyl chloride or butadiene or isoprene, magnesium and carbon dioxide or chloroformic acid ester by the process according to the invention.
- the process according to the invention works with 3,3-dimethylcyclopropene as a starting material.
- 3,3-Dimethylcyclopropene is available in a three-step process from chloroform and isobutene in yields of 50 to 70%. It was surprisingly found that alkenyl magnesium halides and dialkenyl and alkenediyl and alkadienediyl magnesium compounds add very easily and in high conversions of dimethylcyclopropene, see the following reaction scheme 1.
- the magnesium compound obtained can be obtained by the known reaction with carbon dioxide and then convert hydrolysis in high yields to the corresponding 2,2-dimethyl-3 (Z) -alkenylcyclopropyl-carboxylic acids (see regarding the CO 2 reaction of organomagnesium compounds: Houben-Weyl-Müller, Methods of Organic Chemistry, Volume 13 / IIa, p. 247, Thieme-Verlag, Stuttgart 1973).
- the magnesium compounds 2 can also be reacted in a manner known per se with ethyl chloroformate or other analog esters of chloroformic acid to give the corresponding esters of cyclopropanecarboxylic acids (for the reaction of organomagnesium compounds with chloroformic acid esters, see Houben-Weyl-Müller, Methods of Organic Chemistry, Volume 13 / IIa, p. 462, Thieme-Verlag, Stuttgart 1973)).
- the invention accordingly relates to a process for the preparation of 2,2-dimethyl-3-alkenyl-cyclopropanecarboxylic acids or their esters, the process being characterized in that 3,3-dimethylcyclopropene is reacted with alkenyl magnesium halide and / or dialkenyl magnesium compounds, the reaction product is reacted with carbon dioxide or a chloroformic acid ester and the reaction product which has now been obtained is hydrolyzed.
- the cyclopropene derivative behaves very similarly to the 1-alkynes, which also react with evolution of ethane and substitution of the hydrogen with Mg:
- 1-Alkynes are less reactive than the basic body, acetylene (see Houben-Weyl-Müller, Methods of Organic Chemistry, Volume 13 / IIa, p. 136, Thieme-Verlag Stuttgart, 1973).
- Alkenyl magnesium halides show a behavior similar to that of alkyl magnesium halides. It was found that 2-methyl-2-propenylmagnesium chloride only reacts with 1-hexyne with substitution in the sense of the following reaction equation:
- organomagnesium compound to dimethylcyclopropene can be carried out at temperatures between -20 ° and + 100 ° C, preferably between -10 ° and + 40 ° C, in inert solvents, for example aliphatic or aromatic hydrocarbons, for example pentane, hexane, heptane, benzene, toluene or in open-chain or cyclic ethers, for example dimethyl, diethyl, diisopropyl or dibutyl ether, tetrahydrofuran, dimethoxyethane, diglyme or dioxane.
- inert solvents for example aliphatic or aromatic hydrocarbons, for example pentane, hexane, heptane, benzene, toluene or in open-chain or cyclic ethers, for example dimethyl, diethyl, diisopropyl or dibutyl ether, tetrahydrofuran, dime
- the reaction of the primary addition products with CO 2 or the chloroformate is carried out in a manner known per se, see the references cited above in Houben-Weyl-Müller, Volume 13 / IIa.
- the final hydrolysis is also carried out in a manner known per se, for example at from 0 ° C. to room temperature in an aqueous acidic medium, preferably at the same time tiger dissolution of the split off magnesium as a salt in the aqueous solution.
- alkenediylmagnesium and alkadienylmagnesium react predominantly only in a molar ratio of 1: 1 with dimethylcyclopropane, e.g.
- Acid catalysis in the process according to the invention can be used to isomerize compounds initially obtained with a ⁇ -double bond to compounds with an ⁇ -double bond if at least one hydrogen atom is still present in the ⁇ -position in the reaction product obtained, for example
- Mass spectrum (70 eV): m / e no M + , 248 (M + - H 2 0), 222 (M + - CO 2 ), 204, 113.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT5977/77 | 1977-08-18 | ||
| AT597777A AT352098B (de) | 1977-08-18 | 1977-08-18 | Verfahren zur herstellung von 2,2-dimethyl-3- alkenyl-cyclopropancarbonsaeuren bzw. ihren estern |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0000925A1 true EP0000925A1 (fr) | 1979-03-07 |
Family
ID=3581599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100687A Withdrawn EP0000925A1 (fr) | 1977-08-18 | 1978-08-17 | Procédé de préparation d'acides cyclopropanecarboxyliques insaturés, ainsi que leurs esters |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0000925A1 (fr) |
| AT (1) | AT352098B (fr) |
| DK (1) | DK366078A (fr) |
| ES (1) | ES472652A1 (fr) |
| IT (1) | IT1098286B (fr) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1396649A (fr) * | 1963-04-23 | 1965-04-23 | Sumitomo Chemical Co | Procédé de fabrication d'esters de l'acide transchrysanthémique |
| US3810949A (en) * | 1969-12-24 | 1974-05-14 | Ethyl Corp | Intermolecular addition |
| NL7402879A (fr) * | 1973-03-05 | 1974-09-09 |
-
1977
- 1977-08-18 AT AT597777A patent/AT352098B/de not_active IP Right Cessation
-
1978
- 1978-08-17 ES ES472652A patent/ES472652A1/es not_active Expired
- 1978-08-17 EP EP78100687A patent/EP0000925A1/fr not_active Withdrawn
- 1978-08-18 DK DK366078A patent/DK366078A/da unknown
- 1978-08-18 IT IT7826840A patent/IT1098286B/it active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1396649A (fr) * | 1963-04-23 | 1965-04-23 | Sumitomo Chemical Co | Procédé de fabrication d'esters de l'acide transchrysanthémique |
| US3810949A (en) * | 1969-12-24 | 1974-05-14 | Ethyl Corp | Intermolecular addition |
| NL7402879A (fr) * | 1973-03-05 | 1974-09-09 |
Non-Patent Citations (2)
| Title |
|---|
| CHEMISTRY AND INDUSTRY (1976), no. 14, Seite 609 * |
| METHODEN DER ORGANISCHEN CHEMIE, Houben-Weyl-M}ller, Band 13/IIa, Thieme Verlag, Stuttgart 1973, Seiten 247-248-462 * |
Also Published As
| Publication number | Publication date |
|---|---|
| DK366078A (da) | 1979-02-19 |
| ATA597777A (de) | 1979-02-15 |
| IT7826840A0 (it) | 1978-08-18 |
| IT1098286B (it) | 1985-09-07 |
| ES472652A1 (es) | 1979-03-16 |
| AT352098B (de) | 1979-08-27 |
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