DE3781425T3 - Verfahren zur Herstellung von alpha,beta-ungesättigten Aldehyden. - Google Patents
Verfahren zur Herstellung von alpha,beta-ungesättigten Aldehyden.Info
- Publication number
- DE3781425T3 DE3781425T3 DE3781425T DE3781425T DE3781425T3 DE 3781425 T3 DE3781425 T3 DE 3781425T3 DE 3781425 T DE3781425 T DE 3781425T DE 3781425 T DE3781425 T DE 3781425T DE 3781425 T3 DE3781425 T3 DE 3781425T3
- Authority
- DE
- Germany
- Prior art keywords
- radical
- formula
- chloride
- methyl
- group
- 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 - Fee Related
Links
- 238000000034 method Methods 0.000 title claims description 27
- 150000001299 aldehydes Chemical class 0.000 title description 12
- 238000004519 manufacturing process Methods 0.000 title description 4
- -1 alkenyl radical Chemical class 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 23
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 12
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 12
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910001516 alkali metal iodide Inorganic materials 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 5
- 150000001204 N-oxides Chemical class 0.000 claims description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 5
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 4
- 235000009518 sodium iodide Nutrition 0.000 claims description 4
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 3
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 3
- 229940045803 cuprous chloride Drugs 0.000 claims description 3
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- YODDEHYDMMDDCV-UHFFFAOYSA-N (3,7-dimethyl-8-oxoocta-2,6-dienyl) acetate Chemical compound CC(=O)OCC=C(C)CCC=C(C)C=O YODDEHYDMMDDCV-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 8
- 239000005708 Sodium hypochlorite Substances 0.000 description 8
- WPMFOBQJRQAIKY-JXMROGBWSA-N [(2e)-6-chloro-3,7-dimethylocta-2,7-dienyl] acetate Chemical compound CC(=O)OC\C=C(/C)CCC(Cl)C(C)=C WPMFOBQJRQAIKY-JXMROGBWSA-N 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 7
- LFMTUFVYMCDPGY-UHFFFAOYSA-N n,n-diethylethanamine oxide Chemical compound CC[N+]([O-])(CC)CC LFMTUFVYMCDPGY-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000007844 bleaching agent Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 5
- 125000004423 acyloxy group Chemical group 0.000 description 5
- 235000011089 carbon dioxide Nutrition 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 150000007973 cyanuric acids Chemical class 0.000 description 5
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 235000019341 magnesium sulphate Nutrition 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- WLAUCMCTKPXDIY-JXMROGBWSA-N (2e)-1-chloro-3,7-dimethylocta-2,6-diene Chemical compound CC(C)=CCC\C(C)=C\CCl WLAUCMCTKPXDIY-JXMROGBWSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 229940043350 citral Drugs 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 3
- 229940073608 benzyl chloride Drugs 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- HIGQPQRQIQDZMP-UHFFFAOYSA-N geranil acetate Natural products CC(C)=CCCC(C)=CCOC(C)=O HIGQPQRQIQDZMP-UHFFFAOYSA-N 0.000 description 3
- HIGQPQRQIQDZMP-DHZHZOJOSA-N geranyl acetate Chemical compound CC(C)=CCC\C(C)=C\COC(C)=O HIGQPQRQIQDZMP-DHZHZOJOSA-N 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229950009390 symclosene Drugs 0.000 description 3
- UYPYRKYUKCHHIB-UHFFFAOYSA-N trimethylamine N-oxide Chemical compound C[N+](C)(C)[O-] UYPYRKYUKCHHIB-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- WLAUCMCTKPXDIY-YFHOEESVSA-N (2z)-1-chloro-3,7-dimethylocta-2,6-diene Chemical compound CC(C)=CCC\C(C)=C/CCl WLAUCMCTKPXDIY-YFHOEESVSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- LPDDKAJRWGPGSI-UTCJRWHESA-N [(z)-3-methyl-4-oxobut-2-enyl] acetate Chemical compound CC(=O)OC\C=C(\C)C=O LPDDKAJRWGPGSI-UTCJRWHESA-N 0.000 description 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- PUSKHXMZPOMNTQ-UHFFFAOYSA-N ethyl 2,1,3-benzoselenadiazole-5-carboxylate Chemical compound CCOC(=O)C1=CC=C2N=[Se]=NC2=C1 PUSKHXMZPOMNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000002397 field ionisation mass spectrometry Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- IHPVBFUYOYLWDL-UHFFFAOYSA-N potassium;nitromethane Chemical compound [K+].[O-][N+]([O-])=C IHPVBFUYOYLWDL-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- YHRUHBBTQZKMEX-YFVJMOTDSA-N (2-trans,6-trans)-farnesal Chemical group CC(C)=CCC\C(C)=C\CC\C(C)=C\C=O YHRUHBBTQZKMEX-YFVJMOTDSA-N 0.000 description 1
- YHRUHBBTQZKMEX-UHFFFAOYSA-N (2E,6E)-3,7,11-trimethyl-2,6,10-dodecatrien-1-al Chemical group CC(C)=CCCC(C)=CCCC(C)=CC=O YHRUHBBTQZKMEX-UHFFFAOYSA-N 0.000 description 1
- BASMANVIUSSIIM-UHFFFAOYSA-N 1-chloro-2-(chloromethyl)benzene Chemical compound ClCC1=CC=CC=C1Cl BASMANVIUSSIIM-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 1
- OQJWBWUEDSZTOY-UHFFFAOYSA-N 2,6-dimethylhepta-2,6-dienal Chemical compound CC(=C)CCC=C(C)C=O OQJWBWUEDSZTOY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- SEPQTYODOKLVSB-UHFFFAOYSA-N 3-methylbut-2-enal Chemical group CC(C)=CC=O SEPQTYODOKLVSB-UHFFFAOYSA-N 0.000 description 1
- SSIMHHUMYMHNID-UHFFFAOYSA-N 4-(chloromethyl)phenol Chemical compound OC1=CC=C(CCl)C=C1 SSIMHHUMYMHNID-UHFFFAOYSA-N 0.000 description 1
- GVKAVGPGTZFANE-UHFFFAOYSA-N 4-ethyl-4-oxidomorpholin-4-ium Chemical compound CC[N+]1([O-])CCOCC1 GVKAVGPGTZFANE-UHFFFAOYSA-N 0.000 description 1
- 125000003119 4-methyl-3-pentenyl group Chemical group [H]\C(=C(/C([H])([H])[H])C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- WAZPLXZGZWWXDQ-UHFFFAOYSA-N 4-methyl-4-oxidomorpholin-4-ium;hydrate Chemical compound O.C[N+]1([O-])CCOCC1 WAZPLXZGZWWXDQ-UHFFFAOYSA-N 0.000 description 1
- FYGPOJHISFEZAE-UHFFFAOYSA-N 7-chloro-2,6-dimethylhepta-1,5-diene Chemical compound CC(=C)CCC=C(C)CCl FYGPOJHISFEZAE-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- YHRUHBBTQZKMEX-FBXUGWQNSA-N E,E-Farnesal Chemical group CC(C)=CCC\C(C)=C/CC\C(C)=C/C=O YHRUHBBTQZKMEX-FBXUGWQNSA-N 0.000 description 1
- 238000000023 Kugelrohr distillation Methods 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-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
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 description 1
- URVYVINLDPIJEH-ZZXKWVIFSA-N [(e)-4-chloro-3-methylbut-2-enyl] acetate Chemical compound CC(=O)OC\C=C(/C)CCl URVYVINLDPIJEH-ZZXKWVIFSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- QDTCBEZXBDUOCR-UHFFFAOYSA-N n,n-dibutylbutan-1-amine oxide Chemical compound CCCC[N+]([O-])(CCCC)CCCC QDTCBEZXBDUOCR-UHFFFAOYSA-N 0.000 description 1
- PGFPZGKEDZGJQZ-UHFFFAOYSA-N n,n-dimethylmethanamine oxide;dihydrate Chemical compound O.O.C[N+](C)(C)[O-] PGFPZGKEDZGJQZ-UHFFFAOYSA-N 0.000 description 1
- BRWMGQIDLLHJHL-UHFFFAOYSA-N n,n-dipropylpropan-1-amine oxide Chemical compound CCC[N+]([O-])(CCC)CCC BRWMGQIDLLHJHL-UHFFFAOYSA-N 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/21—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Claims (10)
1. Verfahren zur Herstellung eines α,β-ungesättigten Aldehyds der
allgemeinen Formel (I)
worin R¹, R² und R³ unabhängig voneinander ein Wasserstoffatom, wobei
R¹ und R² nicht beide gleichzeitig Wasserstoff sein dürfen, oder ein
Alkyloder Alkenyl-Rest sind, der unsubstituiert oder mit einem Niederacyloxy
Rest substituiert ist, umfassend den Umsetzungsschritt zwischen einem
Allylchlorid der Formel (II)
worin R¹, R² und R³ entsprechend die vorstehend angegebenen
Bedeutungen haben, und einem aus der Gruppe von Tri(niederalkyl)amin N-Oxiden
der Formel
worin R&sup4; einen Niederalkylrest mit 2 bis 4 Kohlenstoffatomen darstellt, und
N-Niederalkylmorpholin N-Oxiden der Formel
worin R&sup5; einen Niederalkylrest mit 1 bis 4 Kohlenstoffatomen darstellt,
ausgewählten Aminoxid, in Gegenwart eines Alkalimetalljodids oder eines
Kupferhalogenids.
2. Verfahren nach Anspruch 1, worin in dem Allylchlorid der Formel (II) R¹ ein
5-Acetoxy-3-methyl-3-pentenyl-Rest ist, R² ein Wasserstoffatom ist und R³
ein Methyl-Rest ist.
3. Verfahren nach Anspruch 1, worin in dem Allylchlorid der Formel (II) R¹ ein
4-Methyl-3-pentenyl-Rest ist, R² ein Methyl-Rest ist und R³ ein
Wasserstoffatom ist.
4. Verfahren nach Anspruch 1, worin in dem Allylchlorid der Formel (II) R¹ ein
4,8-Dimethyl-3,7-octadienyl-Rest ist, R² ein Methyl-Rest ist und R³ ein
Wasserstoffatom ist.
5. Verfahren nach Anspruch 1, worin in dem Allylchlorid der Formel (II) R¹ ein
Acetoxymethyl-Rest ist, R² ein Wasserstoffatom ist und R³ ein Methyl-Rest
2C) ist.
6. Verfahren nach Anspruch 1, worin in dem Allylchlorid der Formel (II) R¹ ein
Methyl-Rest ist, R² ein Methyl-Rest ist und R³ ein Wasserstoffatom ist.
7. Verfahren nach Anspruch 1, worin das Alkalimetalljodid ein aus der Gruppe
von Lithiumjodid, Natriumjodid und Kaliumjodid ausgewähltes Mitglied ist.
8. Verfahren nach Anspruch 1, worin das Kupferhalogenid ein aus der Gruppe
von Kupfer(I)chlorid, Kupfer(II)chlorid, Kupfer(I)bromid, Kupfer(II)bromid und
Kupfer(I)jodid ausgewähltes Mitglied ist.
9. Verfahren nach Anspruch 1, worin die Umsetzung bei einer Temperatur von
20 bis 80ºC durchgeführt wird.
10. Verfahren nach Anspruch 1, worin die Umsetzung in einem Lösungsmittel
durchgeführt wird.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61045104A JPS62201845A (ja) | 1986-02-28 | 1986-02-28 | 不飽和アルデヒドの製造方法 |
JP14506986A JPS632941A (ja) | 1986-06-20 | 1986-06-20 | α,β−不飽和アルデヒドの製造方法 |
Publications (3)
Publication Number | Publication Date |
---|---|
DE3781425D1 DE3781425D1 (de) | 1992-10-08 |
DE3781425T2 DE3781425T2 (de) | 1993-04-01 |
DE3781425T3 true DE3781425T3 (de) | 1998-03-05 |
Family
ID=26385061
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE3781425T Expired - Fee Related DE3781425T3 (de) | 1986-02-28 | 1987-02-18 | Verfahren zur Herstellung von alpha,beta-ungesättigten Aldehyden. |
Country Status (4)
Country | Link |
---|---|
US (1) | US4745229A (de) |
EP (1) | EP0234496B2 (de) |
DE (1) | DE3781425T3 (de) |
DK (1) | DK99587A (de) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63227530A (ja) * | 1987-03-17 | 1988-09-21 | Kuraray Co Ltd | 塩素化オレフイン性化合物の製造方法 |
DE3722807A1 (de) * | 1987-07-10 | 1989-01-19 | Hoechst Ag | Neue 3,5-dihydroxycarbonsaeuren und deren derivate, verfahren zu ihrer herstellung, ihre verwendung als arzneimittel, pharmazeutische praeparate und zwischenprodukte |
FR2663023B1 (fr) * | 1990-06-11 | 1992-07-31 | Rhone Poulenc Nutrition Animal | Procede de transformation de n-oxydes d'amines tertiaires en aldehydes. |
EP0489454A1 (de) * | 1990-12-05 | 1992-06-10 | Duphar International Research B.V | Verwendung eines Allylchlorids zur Darstellung eines Aldehyds |
DE4206170A1 (de) * | 1992-02-28 | 1993-09-02 | Basf Ag | Verfahren zur herstellung von heterocyclischen aldehyden und ketonen |
CN100410230C (zh) * | 2006-05-17 | 2008-08-13 | 绍兴文理学院 | 1-氯-2-甲基-4-烃酰氧基-2-丁烯制备方法 |
JP6249938B2 (ja) | 2014-12-25 | 2017-12-20 | 信越化学工業株式会社 | 4−アルキル−3−メチレンブチル=カルボキシレートの製造方法 |
JP6254518B2 (ja) | 2014-12-25 | 2017-12-27 | 信越化学工業株式会社 | 7−メチル−3−メチレン−7−オクテニル=ハライド及びその製造方法並びに7−メチル−3−メチレン−7−オクテニル=プロピオネートの製造方法 |
JP6249937B2 (ja) | 2014-12-25 | 2017-12-20 | 信越化学工業株式会社 | 1−(2−アシロキシエチル)シクロプロピル=スルホネート化合物及び4−アルキル−3−メチレンブチル=カルボキシレートの製造方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1317560A (de) * | 1961-04-05 | 1963-05-08 | ||
GB1291246A (en) * | 1969-07-11 | 1972-10-04 | Bush Boake Allen Ltd | IMPROVED PRODUCT OF alpha beta-UNSATURATED ALDEHYDES |
FR2432009A1 (fr) * | 1978-07-27 | 1980-02-22 | Prod Chim Auxil Synthese | Procede de preparation du meta-phenoxy-benzaldehyde |
DE2948058A1 (de) * | 1979-11-29 | 1981-06-04 | Dynamit Nobel Ag, 5210 Troisdorf | Verfahren zur herstellung substituierter benzaldehyde |
US4540826A (en) * | 1983-08-12 | 1985-09-10 | Phillips Petroleum Company | Process for preparing olefinic aldehydes |
-
1987
- 1987-02-13 US US07/015,095 patent/US4745229A/en not_active Expired - Lifetime
- 1987-02-18 DE DE3781425T patent/DE3781425T3/de not_active Expired - Fee Related
- 1987-02-18 EP EP87102298A patent/EP0234496B2/de not_active Expired - Lifetime
- 1987-02-26 DK DK099587A patent/DK99587A/da not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
DK99587A (da) | 1987-08-29 |
US4745229A (en) | 1988-05-17 |
EP0234496A2 (de) | 1987-09-02 |
DE3781425T2 (de) | 1993-04-01 |
DE3781425D1 (de) | 1992-10-08 |
EP0234496B2 (de) | 1997-07-23 |
DK99587D0 (da) | 1987-02-26 |
EP0234496A3 (en) | 1989-11-29 |
EP0234496B1 (de) | 1992-09-02 |
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Legal Events
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8363 | Opposition against the patent | ||
8366 | Restricted maintained after opposition proceedings | ||
8339 | Ceased/non-payment of the annual fee |