CN1332736A - 合成5-(α-羟基烷基)苯并[1,3]二氧杂环戊烯的方法 - Google Patents
合成5-(α-羟基烷基)苯并[1,3]二氧杂环戊烯的方法 Download PDFInfo
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- CN1332736A CN1332736A CN99815117A CN99815117A CN1332736A CN 1332736 A CN1332736 A CN 1332736A CN 99815117 A CN99815117 A CN 99815117A CN 99815117 A CN99815117 A CN 99815117A CN 1332736 A CN1332736 A CN 1332736A
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- dioxole
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- FTNJQNQLEGKTGD-UHFFFAOYSA-N 1,3-benzodioxole Chemical class C1=CC=C2OCOC2=C1 FTNJQNQLEGKTGD-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000015572 biosynthetic process Effects 0.000 title abstract 4
- 238000003786 synthesis reaction Methods 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000005917 acylation reaction Methods 0.000 claims abstract description 6
- 230000010933 acylation Effects 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 150000008065 acid anhydrides Chemical class 0.000 claims description 11
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 230000002829 reductive effect Effects 0.000 claims description 8
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical compound C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 claims description 7
- -1 aliphatic anhydrides Chemical class 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- MYEIDJPOUKASEC-UHFFFAOYSA-N Dihydrosafrole Chemical compound CCCC1=CC=C2OCOC2=C1 MYEIDJPOUKASEC-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- VHVOLFRBFDOUSH-UHFFFAOYSA-N Isosafrole Natural products CC=CC1=CC=C2OCOC2=C1 VHVOLFRBFDOUSH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 239000011630 iodine Chemical group 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- VHVOLFRBFDOUSH-NSCUHMNNSA-N Isosafrole Chemical compound C\C=C\C1=CC=C2OCOC2=C1 VHVOLFRBFDOUSH-NSCUHMNNSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- TUCIXUDAQRPDCG-UHFFFAOYSA-N benzene-1,2-diol Chemical compound OC1=CC=CC=C1O.OC1=CC=CC=C1O TUCIXUDAQRPDCG-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Chemical group 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 abstract description 17
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000002917 insecticide Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000000376 reactant Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical group OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- XILIYVSXLSWUAI-UHFFFAOYSA-N 2-(diethylamino)ethyl n'-phenylcarbamimidothioate;dihydrobromide Chemical compound Br.Br.CCN(CC)CCSC(N)=NC1=CC=CC=C1 XILIYVSXLSWUAI-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 125000005605 benzo group Chemical group 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- ABADUMLIAZCWJD-UHFFFAOYSA-N 1,3-dioxole Chemical group C1OC=CO1 ABADUMLIAZCWJD-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- BHUIUXNAPJIDOG-UHFFFAOYSA-N Piperonol Chemical compound OCC1=CC=C2OCOC2=C1 BHUIUXNAPJIDOG-UHFFFAOYSA-N 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- 235000013599 spices Nutrition 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- RVBJGSPBFIUTTR-UHFFFAOYSA-N 3,4-Methylenedioxypropiophenone Chemical compound CCC(=O)C1=CC=C2OCOC2=C1 RVBJGSPBFIUTTR-UHFFFAOYSA-N 0.000 description 2
- RMNWUXPEDRCTHB-UHFFFAOYSA-N 5-prop-1-enyl-1,3-benzodioxole Chemical compound CC=CC1=CC=C2OCOC2=C1.CC=CC1=CC=C2OCOC2=C1 RMNWUXPEDRCTHB-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 239000000341 volatile oil Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- ZHKALZZEGVFZQA-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)ethanol Chemical compound CC(O)C1=CC=C2OCOC2=C1 ZHKALZZEGVFZQA-UHFFFAOYSA-N 0.000 description 1
- PXFYAFDHWSXVLU-UHFFFAOYSA-N 1-(3,4-Methylenedioxyphenyl)-propane-1-ol Chemical compound CCC(O)C1=CC=C2OCOC2=C1 PXFYAFDHWSXVLU-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- HBQUIIALDZGRDX-UHFFFAOYSA-N 5-prop-2-enyl-1,3-benzodioxole Chemical compound C=CCC1=CC=C2OCOC2=C1.C=CCC1=CC=C2OCOC2=C1 HBQUIIALDZGRDX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000004263 Ocotea pretiosa Nutrition 0.000 description 1
- 244000227633 Ocotea pretiosa Species 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 150000005528 benzodioxoles Chemical class 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930003944 flavone Natural products 0.000 description 1
- 150000002213 flavones Chemical class 0.000 description 1
- 235000011949 flavones Nutrition 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229940081310 piperonal Drugs 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
- C07D317/54—Radicals substituted by oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Fats And Perfumes (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
本发明涉及合成5-(α-羟烷基)苯并[1,3]二氧杂环戊烯的三步法。所述方法包括:(ⅰ)用焦儿茶酚(1,2-二羟基苯)与二卤代或二烷氧基烷烃反应,以生成苯并[1,3]二氧杂环戊烯衍生物;(ⅱ)将该苯并[1,3]二氧杂环戊烯衍生物5-位进行选择性催化酰化,以形成5-链烷酰基苯并[1,3]二氧杂环戊烯,和接下来的(ⅲ)将其还原成5-(α-羟烷基)苯并[1,3]二氧杂环戊烯。本发明还描述了可使用上述方法获得的新的苯并二氧杂环戊烯。本发明方法在工业实施上是简单的,并且对环境的影响很小;使用该方法能以高产率获得有重要应用价值的衍生物,特别是用于香料工业和杀虫剂产业的衍生物。
Description
发明领域
本发明属于合成苯并二氧杂环戊烯的领域,特别涉及在香料工业和杀虫剂产业中合成苯并二氧杂环戊烯。
现有技术
多种具有生物活性的天然物例如黄酮和生物碱含有亚甲二氧基-1,2-苯(也称为苯并[1,3]二氧杂环戊烯)基团。
例如,苯并[1,3]二氧杂环戊烯可用于治疗肝脏病症(Chem.Abstracts,1990,452534)。
然而,这些衍生物应用最广泛的领域是香料、调味剂、和杀虫剂领域。包含苯并[1,3]二氧杂环戊烯基团的具有杀虫活性的化合物在很多出版物中有记载(例如Bull.Soc.Chim.France,1964,1892-1895)。
5-(2-丙烯基)-苯并[1,3]二氧杂环戊烯(黄樟脑)是许多精油的组分,在这些精油中,黄樟油其占大约75%(Oswald等人,Biochim.Biophys.Acta 230,237(1971))。
5-(1-丙烯基)-苯并[1,3]二氧杂环戊烯(异黄樟脑)是用于香料中的香精,并且用作肥皂的除臭剂;异黄樟脑可用于合成胡椒醛(洋茉莉醛,苯并[1,3]二氧杂环戊烯-5-甲醛)—工业上用于生产香料和香味物质的另一香精。
同样,5-羟甲基苯并[1,3]二氧杂环戊烯(胡椒基醇)及其衍生物在上述应用领域中有很大的工业应用价值。本发明满足了确定出合成胡椒基醇及其衍生物的有效方法的需要。
现有技术中描述了多种具有该目的的方法。最广泛使用的方法是用下式所示醛与格氏试剂(溴化烷基镁)反应,以获得在5-位被α-羟烷基取代的苯并二氧杂环戊烯衍生物(参见例如US-A-3946040)。由苯并[1,3]二氧杂环戊烯的5-酮基取代的衍生物可制得同样化合物(DE-A-2210374)。
尽管从分析角度来看上述合成方法是可以使用的,但是在工业应用方面其仍然存在着显著的局限性。这些反应事实上需要使用已经包含苯并二氧杂环戊烯环的产品:这样的产品远非能方便获得的产品,并且非常昂贵。此外,格氏反应是用非常不稳定并且难以处理的反应物和无水溶剂(例如镁、乙醚、四氢呋喃)进行的,因此必须在生产车间内采用昂贵的安全预防措施。
作为在苯并二氧杂环戊烯环上引入取代基的方法,选择性地酰化迄今为止据证明难以在工业上应用,这是因为该方法的产率很低,并且酰化产物难以纯化;例如在WOA-9639133中,酰化的苯并二氧杂环戊烯难以纯化,并包括反复进行的脱色处理。其它作者报道,使用昂贵的解决方案实现了苯并二氧杂环戊烯的选择性酰化,例如使产物通过沸石催化剂床(J.Chem.Soc.Chem.Commun.,1994,717)。
由于存在所指出的局限性,因此需要制备5-羟烷基苯并二氧杂环戊烯的有效方法。特别是要寻求能以大规模在工业上实施、并且可以用易于进行且对环境影响很小的反应来进行的方法。最后,还需要使用便于获得且成本很低的产品作为反应物的合成方法。
发明简述
本发明涉及合成5-(α-羟烷基)苯并[1,3]二氧杂环戊烯的三步法。所述方法包括:(i)用焦儿茶酚(1,2-二羟基苯)与二卤代或二烷氧基烷烃反应,以生成苯并[1,3]二氧杂环戊烯衍生物;(ii)将该苯并[1,3]二氧杂环戊烯衍生物5-位进行选择性催化酰化,以形成5-链烷酰基苯并[1,3]二氧杂环戊烯,和接下来的(iii)将其还原成5-(α-羟烷基)苯并[1,3]二氧杂环戊烯。本发明还描述了可使用上述方法获得的新的苯并二氧杂环戊烯。本发明方法在工业实施上是简单的,并且对环境的影响很小;使用该方法能以高产率获得有重要应用价值的衍生物,特别是用于香料工业和杀虫剂产业的衍生物。发明详述
本发明的主题是合成5-(α-羟烷基)苯并[1,3]二氧杂环戊烯的新方法。所述方法包括下述步骤:a)在70℃-190℃,将1,2-二羟基苯(焦儿茶酚)(I)在偶极非质子传递溶剂中与式(II)化合物反应,其中R1选自H、和C1-C3直链或支链烷基,以及X选自氯、氟、溴、碘、和C1-C5直链或支链烷氧基,以获得式(III)产物,其中R1定义同上;b)在酰化催化剂存在下,将化合物(III)与式(IV)脂族酸酐或式(V)脂族酸反应,其中R2是C1-C19直链或支链烷基,以获得式(VI)化合物,其中R1和R2定义同上;c)将化合物(VI)还原,以获得式(VII)5-(α-羟基烷基)苯并[1,3]二氧杂环戊烯。
反应a)在偶极非质子传递溶剂中进行。优选的这类溶剂是N,N-二甲基甲酰胺、N,N-二甲基乙酰胺和二甲亚砜。该反应温度为反应混合物的回流温度,并且一般为70℃-190℃。当使用N,N-二甲基甲酰胺作为反应溶剂时,反应温度一般为110℃-150℃、更优选为110℃-130℃。
反应a)可在碘盐存在下进行。在这种情况下,该盐优选选自LiI、NaI、KI、CaI2。
用于反应a)的式(II)反应物的选择取决于所要合成的终产物(VII)的性质:如果目的是获得在2-位没有取代基的苯并[1,3]二氧杂环戊烯,则可以选取其中R1=H的式(II)反应物。这样的产品的实例有二氯甲烷和二甲氧基甲烷。如果目的是获得在2-位被烷基取代的苯并二氧杂环戊烯,则可以选取其中R1是欲引入到苯并二氧杂环戊烯环上的烷基的式(II)反应物。合适的R1基团是甲基、乙基、正丙基、和异丙基。
如上所述,式(II)反应物含有两个X=卤素或两个X=C1-C5直链或支链烷氧基。
如果使用其中X=卤素的式(II)衍生物,则反应a)在无机碱存在下进行,该无机碱优选选自NaOH、KOH、Na2CO3、和K2CO3。优选将固态的无机碱(例如碳酸盐)以细粉的形式加到反应混合物中。
当使用其中X=C1-C5直链或支链烷氧基的式(II)衍生物时,反应a)在酯交换催化剂存在下进行,该催化剂优选选自CH3ONa、C2H5ONa、(C4H9)2SnO、和Ti(OC4H9)4。
可使用各种方法将上述反应物混合。
在优选的实施方案中,如下所述进行反应a):将化合物(II)与偶极非质子传递溶剂和无机碱(或酯交换催化剂)混合。然后向加热至回流温度的所得混合物中加入焦儿茶酚。该加入优选这样进行,即,滴加通过将焦儿茶酚、衍生物(II)和偶极非质子传递溶剂混合所获得的液体混合物。
将由此获得的混合物加热回流1-3小时,然后终止该反应。通过分馏或者在蒸汽流中蒸馏使终产物(III)同反应溶剂和未反应的衍生物(II)分离。
反应物优选以下述摩尔比使用:焦儿茶酚∶无机碱∶化合物(II)=1∶1∶2,所述比例的化合物(II)优选分配在最初的混合物和含有焦儿茶酚的滴加混合物中。
上述反应以90%以上、一般大约95%的产率制得了式(III)产物。
酰化反应b)生成了式(VI)5-链烷酰基苯并[1,3]二氧杂环戊烯。该反应采用适当的酸或酸酐作为酰化剂,并优选通过选自ZnO、ZnCl2、FeCl2、FeCl3、FeSO4、Fe2(SO4)3、FeO、Fe2O3、H3PO4、HClO4、和多磷酸的化合物进行催化。对于该反应,特别优选的催化剂是高氯酸(HClO4)。该反应任选在惰性溶剂存在下进行;这样的溶剂的实例有环己烷、甲基环己烷、十氢萘、二氯乙烷、和四氯乙烷。
当使用酸(V)作为酰化剂时,所用的苯并二氧杂环戊烯/酸(V)的摩尔比为5∶1-0.5∶1,优选为1∶1。当使用酸酐(IV)作为酰化剂时,苯并二氧杂环戊烯/酸酐(IV)的摩尔比为3∶1-1∶1,并且优选为2∶1。
反应温度介于0℃-反应混合物沸点最低的组分的沸点之间。
可使用各种方法将上述反应物混合。在优选的实施方案中,将苯并[1,3]二氧杂环戊烯(III)与酰化催化剂混合,然后向该混合物中缓慢地加入所选的酸或酸酐。
该反应在1-7小时内完成。通过用有机溶剂、优选二氯甲烷萃取,然后将有机相分馏来从反应混合物中分离出5-链烷酰基苯并[1,3]二氧杂环戊烯(VI)。
在优选的实施方案中,将在步骤b)结束时获得的反应混合物再循环:通过向该用过的混合物中再加入一定量前面使用的酰化催化剂和一定量的式(IV)或(V)酰化剂来进行该过程;可以、但不是必须再加入一定量的式(III)苯并[1,3]二氧杂环戊烯;这些加入优选使苯并二氧杂环戊烯与酰化剂的摩尔比保持在上述范围内。
然后将该富含反应物的混合物在与第一个循环相同的反应条件下(时间和温度)反应。所述再循环操作可进行一次或多次。
在步骤c)中,将5-链烷酰基苯并[1,3]二氧杂环戊烯(VI)还原成5-(α-羟烷基)苯并[1,3]二氧杂环戊烯(VII)。一般而言,在该步骤中可使用任何还原反应。例如,可在催化剂例如钯、铂或钌存在下使用氢还原。该催化剂可以负载在惰性基质上:这类体系的实例有Pd/碳、Pt/碳、Ru/碳、Pd/氧化铝、和Pd/硫酸钡。可提及的其它还原剂有PtO2、PtO、阮内镍、NaBH4、和LiAIH4。
反应条件(时间、温度、压力)和反应物的比例是本领域这些类型反应中常用的条件和比例。例如,当在催化剂存在下使用氢气时,操作温度优选为20℃-100℃,压力为1巴-60巴,并且可在适当溶剂例如甲醇、乙醇、丙醇、异丙醇、和丁醇存在下进行反应。
在本发明中描述的方法代表着使用便于获得且成本很低的非杂环反应物(焦儿茶酚)作为原料合成5-(α-羟烷基)苯并[1,3]二氧杂环戊烯的第一个实例。可在上述三步反应中获得的高产率使得能获得大量终产物。
反应步骤a)还能够在无需进行单独的烷基化步骤(在2-位)的条件下即可获得2-烷基取代的苯并[1,3]二氧杂环戊烯。
可通过上述方法获得的2-烷基取代的产物是新的,并且构成了本发明的另一方面。
优选的一组式VIII产物是其中R1为甲基、乙基、正丙基、和异丙基的产物。
式(VII)衍生物,无论它们在苯并[1,3]二氧杂环戊烯环的2-位是否被取代,除了本身作为香精和香味物质的应用价值以外,还可用作反应物来制备类似衍生物,并且在香料工业和杀虫剂生产中有特别重要的价值。这些化合物的优选实例由5-烷基苯并[1,3]二氧杂环戊烯代表,特别是5-丙基苯并[1,3]二氧杂环戊烯(二氢黄樟脑)。因此本发明还包括这些产物的制备,它们可通过将在上述步骤c)中获得的式(VII)衍生物进一步还原而制得。5-烷基苯并[1,3]二氧杂环戊烯也可以用一个还原反应由式(VI)化合物直接制得。当通过这种方式制备时,式(VII)衍生物是作为中间体形成的,但是不进行分离:对于这种情况,优选使用负载在惰性基质上的金属例如Pd/C、Pt/C、和Pd/BaSO4作为还原催化剂。
5-(1-丙烯基)苯并[1,3]二氧杂环戊烯(异黄樟脑)是可通过本发明方法制得的衍生物的另一实例。对于该衍生物的制备,是将在步骤c)中制得的式(VII)5-羟烷基苯并[1,3]二氧杂环戊烯进行脱水反应。这样的脱水反应在文献中是已知的,并且可在合适的溶剂例如苯、甲苯、二甲苯、三甲基苯、二氯乙烷、和四氯乙烷存在下,在有机酸或无机酸例如硝酸、硫酸、盐酸、高氯酸、乙酸、三氟乙酸、苯磺酸、和对甲苯磺酸存在下,在所用溶剂的沸点温度下,通过共沸除去反应生产的水来进行。
5-(1-丙烯基)-苯并[1,3]二氧杂环戊烯又可转化成胡椒醛,或者通过进一步的还原反应转化成5-丙基苯并[1,3]二氧杂环戊烯(二氢黄樟脑)。
通过下述非限制性实施例来举例说明本发明。实验部分1.制备苯并[1,3]二氧杂环戊烯
向104g(0.75mol)细磨碎的碳酸钾在440ml N,N-二甲基甲酰胺中的混合物内加入45ml(0.7mol)二氯甲烷,将所得混合物加热至回流温度(128-130℃)。
然后滴加溶于110ml N,N-二甲基甲酰胺和45ml(0.7mol)二氯甲烷中的75g(0.68mol)焦儿茶酚溶液。
滴加完毕后,将该混合物再加热回流2小时,冷却,然后过滤。
将由此获得的溶液在常压下蒸馏,收集(40-41℃)到42ml二氯甲烷。然后向其中加入400ml水(每次50ml),在98-100℃蒸馏,获得了由苯并[1,3]二氧杂环戊烯和水组成的共沸物,最后在152-153℃蒸馏出N,N-二甲基甲酰胺。
从苯并[1,3]二氧杂环戊烯与水的混合物中分离出产物,水相加入饱和氯化钠溶液,然后用60ml二氯甲烷萃取两次。
将产物与有机溶液合并,在25℃/20mbar蒸发,获得了78g苯并[1,3]二氧杂环戊烯。2.制备5-丙酰基苯并[1,3]二氧杂环戊烯
向冷却至0-5℃的73.2g(0.6mol)苯并[1,3]二氧杂环戊烯与1ml 70%高氯酸的混合物中缓慢地加入38.1ml(0.3mol)丙酸酐,在加入期间将温度保持在0-5℃。
一旦加入完毕,即将该混合物再搅拌3小时,让温度升至室温。用50ml二氯甲烷与50ml水稀释该混合物,搅拌半小时,然后分离出有机相。将有机相依次用30ml 2M氢氧化钠水溶液和水洗涤,最后用硫酸钠干燥。
将有机相在常压下蒸馏,在40-41℃收集二氯甲烷,在55℃/1.3mbar蒸馏未反应的苯并[1,3]二氧杂环戊烯(44g),最后在125-130℃/1.3mbar蒸馏产物(34.5g)。
向含有44g未反应的苯并[1,3]二氧杂环戊烯的反应混合物中加入29.2g(0.24mol)苯并[1,3]二氧杂环戊烯和1ml 70%高氯酸。向冷却至0-5℃的所得混合物中加入38.1ml(0.3mol)丙酸酐。使用上述方法,分离出44g未反应的苯并[1,3]二氧杂环戊烯和34.5g所需产物。3.制备5-(α-羟丙基)苯并[1,3]二氧杂环戊烯
在氮气流下,向250-ml多颈烧瓶内加入溶于100ml甲醇中的30g 5-丙酰基苯并[1,3]二氧杂环戊烯(0.268mol)。在25℃,用20分钟滴加溶于50ml甲醇中的7g NaBH4(0.185mol);然后将该反应混合物加热回流。2小时后,将该混合物冷却,在减压下除去甲醇,将该混合物用100ml HCl 2M稀释,并用CH2Cl2萃取两次。将合并的有机相用100ml H2O洗涤,减压浓缩,获得了30.07g浓厚的澄清油状物,GC、MS、NMR(1H、13C、DEPT)分析证实了其与所需产物一致。
或者,如下所述制备5-(α-羟丙基)苯并[1,3]二氧杂环戊烯:将溶于150ml异丙醇中的30g 5-丙酰基苯并[1,3]二氧杂环戊烯(0.168mol)和1g Ru/C 5%倒入1-升高压反应釜中。密封该反应釜,用氮气使其呈惰性,在搅拌下用H2产生1巴的压力。在1巴的恒定氢气压力下将该混合物搅拌1小时;然后用氮气冲洗并过滤。通过将溶剂减压蒸发,获得了30g浓厚的油状物,GC、MS、NMR(1H、13C、DEPT)分析证实了其与所需产物一致。制备5-丙基苯并[1,3]二氧杂环戊烯(二氢黄樟脑)
将34.5g 5-丙酰基苯并[1,3]二氧杂环戊烯(0.19mol)溶于100ml异丙醇中,并加入2g 50%湿Pd/C 5%。
将该混合物置于反应釜中,并在4巴的压力下于40℃氢化。
将该混合物过滤,并在40℃/20mbar蒸发,在108-109℃/18mbar蒸馏,获得了油状物(31g),GC、MS、NMR(1H、13C、DEPT)分析证实了其与所需产物一致。5.制备5-[(E)1-丙烯基]-1,3-苯并二氧杂环戊烯
向100-ml多颈烧瓶中加入溶于50ml甲苯中的5g 5-(α-羟乙基)苯并[1,3]二氧杂环戊烯(27mmol)和对-甲苯磺酸晶体。将该反应混合物加热回流,通过共沸收集反应所形成的水。2小时后,将10mlNaOH 2M加到该冷却的混合物中,将该混合物搅拌15分钟。一旦两相分开,即把有机相减压浓缩,获得了黄色油状物,通过蒸馏(90℃,1mmHg)纯化。
获得了4.1g澄清的淡黄色油状物,GC、MS、NMR(1H、13C、DEPT)分析证实了其与所需产物一致。
Claims (14)
2.权利要求1的方法,其中在反应a)中使用的所述偶极非质子传递溶剂选自N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、和二甲亚砜。
3.根据权利要求1-2任一项的方法,其中反应a)在碘盐存在下进行。
4.根据权利要求1-3任一项的方法,其中反应b)通过选自HClO4、ZnO、ZnCl2、FeCl2、FeCl3、FeSO4、Fe2(SO4)3、FeO、Fe2O3、H3PO4、和多磷酸的化合物进行催化。
5.根据权利要求1-4任一项的方法,其中反应b)是在惰性溶剂存在下进行。
6.根据权利要求1-5任一项的方法,其中在反应b)中,苯并二氧杂环戊烯/酸(V)的摩尔比为5∶1-0.5∶1。
7.根据权利要求1-5任一项的方法,其中在反应b)中,苯并二氧杂环戊烯/酸酐(IV)的摩尔比为3∶1-1∶1。
8.根据权利要求1-7任一项的方法,其中将从反应b)获得的反应混合物进行再循环使用。
9.根据权利要求1-8任一项的方法,其中将式(VII)衍生物进一步还原,形成5-烷基苯并[1,3]二氧杂环戊烯。
10.根据权利要求9的方法,其中所述式(VII)衍生物为5-(α-羟丙基)苯并[1,3]二氧杂环戊烯,并且所述5-烷基苯并[1,3]二氧杂环戊烯是5-丙基苯并[1,3]二氧杂环戊烯(二氢黄樟脑)。
11.根据权利要求1-8任一项的方法,其中将所述式(VII)衍生物进一步脱水,形成5-(1-链烯基)苯并[1,3]二氧杂环戊烯。
12.根据权利要求11的方法,其中所述(VII)衍生物是5-(α-羟丙基)苯并[1,3]二氧杂环戊烯,并且所述5-(1-链烯基)苯并[1,3]二氧杂环戊烯是5-(1-丙烯基)苯并[1,3]二氧杂环戊烯(异黄樟脑)。
14.权利要求13的化合物,其中R1代表甲基、乙基、正丙基、或异丙基。
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ITMI98A002857 | 1998-12-30 | ||
IT1998MI002857A IT1304513B1 (it) | 1998-12-30 | 1998-12-30 | Processo per la sintesi di 5-(alfa-idrossialchil)benzo(1,3)diossoli. |
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EP2289889A1 (en) | 2009-08-18 | 2011-03-02 | Endura S.p.a. | Substituted alkynyl phenoxy compounds and their uses |
CN102070596B (zh) * | 2011-01-22 | 2013-02-27 | 浙江大学 | 二氢黄樟素的制备方法 |
GB201104156D0 (en) | 2011-03-11 | 2011-04-27 | Rothamstead Res Ltd | Compositions and methods for controlling pesticide resistant pests |
EP3141115A1 (en) | 2015-09-09 | 2017-03-15 | Endura S.p.a. | Substituted methylenedioxybenzyl compounds and their uses as synergists |
EP3141116B1 (en) | 2015-09-09 | 2018-06-13 | Endura S.p.a. | 5,7-disubstituted 2,3-dihydrobenzofurans and their use as synergists |
WO2018150230A1 (en) | 2017-02-14 | 2018-08-23 | Anthea Aromatics Private Limited | A process for preparation of alkenyl and alkyl derivatives of alkylenedioxybenzene |
WO2022161628A1 (en) | 2021-01-29 | 2022-08-04 | Endura S.P.A. | Process for the preparation of 3,4-methylenedioxypropiophenone |
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GB1097270A (en) * | 1965-10-13 | 1968-01-03 | Shell Int Research | Process for the preparation of methylene dioxybenzene, 1,3-benzoxathiole and derivatives thereof |
US3908000A (en) * | 1971-03-19 | 1975-09-23 | Hoffmann La Roche | Propynyl benzyl ethers as insecticidal agents |
CH583677A5 (zh) * | 1972-02-03 | 1977-01-14 | Basf Ag | |
JPS56164178A (en) * | 1980-05-23 | 1981-12-17 | Mitsubishi Chem Ind Ltd | Preparation of 4-hydroxy-1,3-benzodioxole |
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US5420301A (en) * | 1988-03-18 | 1995-05-30 | Ciba-Geigy Corporation | Process for the preparation of substituted difluorobenzo-1,3-dioxoles |
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DE4133155A1 (de) * | 1991-10-07 | 1993-04-08 | Bayer Ag | Verfahren zur herstellung von 2,2-difluorbenzo (1,3)-dioxol-carbaldehyden und neuen zwischenprodukten |
US5696301A (en) * | 1996-01-23 | 1997-12-09 | Ube Industries, Ltd. | Process for preparing protocatechualdehyde |
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CN106632228B (zh) * | 2016-08-05 | 2019-07-02 | 成都建中香料香精有限公司 | 一种二氢黄樟素的制备方法 |
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RU2243224C2 (ru) | 2004-12-27 |
CA2352249A1 (en) | 2000-07-13 |
KR20010083955A (ko) | 2001-09-03 |
IT1304513B1 (it) | 2001-03-19 |
ITMI982857A1 (it) | 2000-06-30 |
ATE256676T1 (de) | 2004-01-15 |
JP4845266B2 (ja) | 2011-12-28 |
US6342613B1 (en) | 2002-01-29 |
DE69913735D1 (de) | 2004-01-29 |
WO2000040575A1 (en) | 2000-07-13 |
AU1037700A (en) | 2000-07-24 |
JP2002534423A (ja) | 2002-10-15 |
BR9916471A (pt) | 2001-09-18 |
CA2352249C (en) | 2007-09-11 |
AU756172B2 (en) | 2003-01-09 |
ITMI982857A0 (it) | 1998-12-30 |
KR100682160B1 (ko) | 2007-02-12 |
DE69913735T2 (de) | 2004-07-29 |
BR9916471B1 (pt) | 2010-12-14 |
EP1140894B1 (en) | 2003-12-17 |
CN1138769C (zh) | 2004-02-18 |
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