CN1348434A - Method for producing upsilon, delta unsaturated ketones by carroll reaction - Google Patents
Method for producing upsilon, delta unsaturated ketones by carroll reaction Download PDFInfo
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- CN1348434A CN1348434A CN99812906A CN99812906A CN1348434A CN 1348434 A CN1348434 A CN 1348434A CN 99812906 A CN99812906 A CN 99812906A CN 99812906 A CN99812906 A CN 99812906A CN 1348434 A CN1348434 A CN 1348434A
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- methyl
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- alcohol
- karol
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- 150000002576 ketones Chemical class 0.000 title claims abstract description 15
- 238000006563 Carroll rearrangement reaction Methods 0.000 title abstract 2
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 34
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract 7
- -1 methoxyl group Chemical group 0.000 claims description 43
- 229910052799 carbon Inorganic materials 0.000 claims description 28
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 21
- 150000002148 esters Chemical class 0.000 claims description 21
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 claims description 19
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 claims description 19
- 229930007744 linalool Natural products 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- FQTLCLSUCSAZDY-UHFFFAOYSA-N (+) E(S) nerolidol Natural products CC(C)=CCCC(C)=CCCC(C)(O)C=C FQTLCLSUCSAZDY-UHFFFAOYSA-N 0.000 claims description 12
- FQTLCLSUCSAZDY-ATGUSINASA-N Nerolidol Chemical compound CC(C)=CCC\C(C)=C\CC[C@](C)(O)C=C FQTLCLSUCSAZDY-ATGUSINASA-N 0.000 claims description 12
- WASNIKZYIWZQIP-AWEZNQCLSA-N nerolidol Natural products CC(=CCCC(=CCC[C@@H](O)C=C)C)C WASNIKZYIWZQIP-AWEZNQCLSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000000457 gamma-lactone group Chemical group 0.000 claims description 3
- 230000006872 improvement Effects 0.000 claims description 3
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 claims description 3
- IUDWWFNDSJRYRV-UHFFFAOYSA-N 3,7-dimethyloct-1-en-3-ol Chemical compound CC(C)CCCC(C)(O)C=C IUDWWFNDSJRYRV-UHFFFAOYSA-N 0.000 claims 1
- CCCXGQLQJHWTLZ-UHFFFAOYSA-N geranyl linalool Natural products CC(=CCCC(=CCCCC(C)(O)CCC=C(C)C)C)C CCCXGQLQJHWTLZ-UHFFFAOYSA-N 0.000 claims 1
- IQDXAJNQKSIPGB-HQSZAHFGSA-N geranyllinalool Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CCC(C)(O)C=C IQDXAJNQKSIPGB-HQSZAHFGSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 abstract description 36
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 25
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract 1
- 239000004411 aluminium Substances 0.000 description 29
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- JKUYRAMKJLMYLO-UHFFFAOYSA-N tert-butyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OC(C)(C)C JKUYRAMKJLMYLO-UHFFFAOYSA-N 0.000 description 9
- 150000001721 carbon Chemical group 0.000 description 8
- DJAHKBBSJCDSOZ-AJLBTXRUSA-N (5z,9e,13e)-6,10,14,18-tetramethylnonadeca-5,9,13,17-tetraen-2-one;(5e,9e,13e)-6,10,14,18-tetramethylnonadeca-5,9,13,17-tetraen-2-one Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CC\C(C)=C/CCC(C)=O.CC(C)=CCC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CCC(C)=O DJAHKBBSJCDSOZ-AJLBTXRUSA-N 0.000 description 7
- 229940009827 aluminum acetate Drugs 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 229950006156 teprenone Drugs 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 5
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 5
- LTUMRKDLVGQMJU-IUBLYSDUSA-N farnesyl acetone Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CCC(C)=O LTUMRKDLVGQMJU-IUBLYSDUSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 4
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- LTUMRKDLVGQMJU-UHFFFAOYSA-N famesylacetone Natural products CC(C)=CCCC(C)=CCCC(C)=CCCC(C)=O LTUMRKDLVGQMJU-UHFFFAOYSA-N 0.000 description 4
- HNZUNIKWNYHEJJ-FMIVXFBMSA-N geranyl acetone Chemical compound CC(C)=CCC\C(C)=C\CCC(C)=O HNZUNIKWNYHEJJ-FMIVXFBMSA-N 0.000 description 4
- HNZUNIKWNYHEJJ-UHFFFAOYSA-N geranyl acetone Natural products CC(C)=CCCC(C)=CCCC(C)=O HNZUNIKWNYHEJJ-UHFFFAOYSA-N 0.000 description 4
- 150000002596 lactones Chemical class 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- UHEPJGULSIKKTP-UHFFFAOYSA-N sulcatone Chemical compound CC(C)=CCCC(C)=O UHEPJGULSIKKTP-UHFFFAOYSA-N 0.000 description 4
- XHYJMHUBEDCSPT-UHFFFAOYSA-N C(C)(=O)O.C(C)(=O)[Al](C(C)=O)C(C)=O Chemical compound C(C)(=O)O.C(C)(=O)[Al](C(C)=O)C(C)=O XHYJMHUBEDCSPT-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012038 nucleophile Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003509 tertiary alcohols Chemical class 0.000 description 3
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical group CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- AKGGYBADQZYZPD-UHFFFAOYSA-N benzylacetone Chemical compound CC(=O)CCC1=CC=CC=C1 AKGGYBADQZYZPD-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical class CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 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
- PVGHQBCTMALNFO-UHFFFAOYSA-N 2-acetyl-3-oxobutanoic acid Chemical compound CC(=O)C(C(C)=O)C(O)=O PVGHQBCTMALNFO-UHFFFAOYSA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JRTBBCBDKSRRCY-UHFFFAOYSA-N 3,7-dimethyloct-6-en-3-ol Chemical compound CCC(C)(O)CCC=C(C)C JRTBBCBDKSRRCY-UHFFFAOYSA-N 0.000 description 1
- XHRGPLDMNNGHCX-UHFFFAOYSA-N 3-Methylbutyl 3-oxobutanoate Chemical compound CC(C)CCOC(=O)CC(C)=O XHRGPLDMNNGHCX-UHFFFAOYSA-N 0.000 description 1
- ALZLTHLQMAFAPA-UHFFFAOYSA-N 3-Methylbutyrolactone Chemical compound CC1COC(=O)C1 ALZLTHLQMAFAPA-UHFFFAOYSA-N 0.000 description 1
- BDCLDNALSPBWPQ-UHFFFAOYSA-N 3-oxohexanoic acid Chemical compound CCCC(=O)CC(O)=O BDCLDNALSPBWPQ-UHFFFAOYSA-N 0.000 description 1
- 240000007185 Albizia julibrissin Species 0.000 description 1
- 235000011468 Albizia julibrissin Nutrition 0.000 description 1
- 101150114104 CROT gene Proteins 0.000 description 1
- 238000005821 Claisen rearrangement reaction Methods 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 241000921313 Phyllopodium Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 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
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 1
- UNRQTHVKJQUDDF-UHFFFAOYSA-N acetylpyruvic acid Chemical compound CC(=O)CC(=O)C(O)=O UNRQTHVKJQUDDF-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 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
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000004718 beta keto acids Chemical class 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-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
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000002350 geranyl group Chemical group [H]C([*])([H])/C([H])=C(C([H])([H])[H])/C([H])([H])C([H])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BAWIJQDONYVQRF-UHFFFAOYSA-N geranylfarnesylacetone Natural products CC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=O BAWIJQDONYVQRF-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JPTOCTSNXXKSSN-UHFFFAOYSA-N methylheptenone Chemical compound CCCC=CC(=O)CC JPTOCTSNXXKSSN-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- LMHHRCOWPQNFTF-UHFFFAOYSA-N s-propan-2-yl azepane-1-carbothioate Chemical compound CC(C)SC(=O)N1CCCCCC1 LMHHRCOWPQNFTF-UHFFFAOYSA-N 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical group CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011949 solid catalyst Substances 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
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Classifications
-
- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
-
- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
- C07C45/676—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton by elimination of carboxyl groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for producing gamma , delta -unsaturated ketones of general formula (I) by reacting an acetoacetic alkyl ester with an allyl alcohol or a propargyl alcohol of general formula (II) in which R<1> can represent H or a saturated or unsaturated, branched hydrocarbon radical which is optionally substituted by methoxy groups and which has 1 to 33 C-atoms, and the dashed line can represent another bond between the C-atoms carrying the same. The reaction is carried out at temperatures ranging from 150 to 220 DEG C in an optionally modified Carroll reaction, in the presence of an aluminum catalyst, and by distilling off the alkanol formed during the reaction. The inventive method is characterized in that an acetoacetic ester of general formula (III) is used as an acetoacetic alkyl ester in which R<2> represents an alkyl group with 1 to 4 C-atoms.
Description
The present invention relates to be reflected at Al catalysts and have preparation γ down, the modification method of delta unsaturated ketone, especially methyl heptenone, geranyl acetone and farnesyl acetone or their dihydro derivative or geranyl geranyl acetone with Karol.
The chain lengthening that means vinyl carbinol or propargyl alcohol and acetylacetic ester or diketene of Karol reaction, and generate γ, delta unsaturated ketone.For example, this reaction is undertaken by following reaction scheme:
Thereby in committed step, the acetylacetic ester of new unsaturated alcohol, this ester at first are ketogenetic by vinyl carbinol or propargyl alcohol and acetylacetic ester or diene, are rearranged into beta-keto acid by Claisen rearrangement, then its automatic decarboxylation.Preliminary research about the Karol reaction is described among J.Am.Chem.Soc.65 (1943) 1992-1998.
From nineteen fifty for beginning, this reaction is used for the preparation of terpene in every way.For example as the required terpenes 2-methyl of the main precursor of vitamin A and vitamin-E-2-heptene-6-ketone, 6,10-dimethyl-5,9-11 carbon diene-ketone (geranyl acetone) and 6,10,14-trimethylammonium-5,9,13-15 carbon triolefin-2 ketone (farnesyl acetone) prepare with technical scale with the Karol reaction.
For example, GB 695 313 has just disclosed in gas phase in 300-600 ℃ and has used the Karol reaction that allyl group or crot(on)yl acetylacetic ester carry out.
US 2628250 has disclosed by 2-methyl-3-butene-2-pure and mild diketene and has prepared 2-methyl-2-heptene-6-ketone.
US 2660608 has pointed out by tetrahydrochysene nerolidol and diketene and has prepared the tetrahydrochysene farnesyl acetone.
As the Karol catalyst for reaction, be to utilize aluminium alkoxide by the method for US 2795617, especially molecular formula is Al (O-CH (CH
3)
2)
3Aluminum isopropylate, its consumption is 0.8-2.5mol% based on the alcohol that uses as raw material.
According to the method for GB 886 353, for Karol reaction, be to use aluminium complex with methyl ethyl diketone or acetylacetic ester, as three (acetopyruvic acid) aluminium, three (methyl-acetoacetic acid) aluminium or three (ethyl acetoacetic acid) aluminium as catalyzer.
Under the situation of the Karol reaction of formerly known acetylacetic ester and uncle's vinyl carbinol or propargyl alcohol, generally be to use methyl or ethyl ester as Acetacetic acid alkyl ester.The carbonic acid gas one that the lower boiling alcohol that discharges in the acetoacetylization of unsaturated alcohol (methyl alcohol or ethanol) forms with decarboxylation the time is distilled out when reacting.
It is satisfied fully that the productive rate that is reached in the Karol reaction of using methyl acetoacetate or methyl aceto acetate still can not make us for plant-scale application.This is because the at first used reaction times is longer and second because the following fact, promptly under this reaction conditions, the beta-unsaturated ketone that is generated is measured slightly and is hydrogenated to the alcohol that is difficult to remove, and has so just reduced productive rate.
Thereby an object of the present invention is to shorten in the catalytic Karol reaction of aluminium, thereby reaction times of delta unsaturated ketone and improve the possibility that continuous processing is operated by vinyl carbinol or propargyl alcohol and acetylacetic ester prepared in reaction γ.A further object of the invention is further to improve productive rate.
Now, make us finding uncannily, when acetylacetic ester with the tertiary alcohol, when substituting methyl acetoacetate (AME) or methyl aceto acetate as the trimethyl carbinol, tertiary amyl alcohol (2-methyl fourth-2-alcohol) or dimethyl propyl methyl alcohol (2-methylpent-2-alcohol), the Karol reaction more promptly proceeds to γ, delta unsaturated ketone, and have higher productive rate, promptly generate less by product.If the application high-grade, thereby more valuable unsaturated alcohol is when making initial compounds, these improvement are particularly importants.This is particularly useful for 3,7-dimethyl-1,6-octadiene-3-alcohol (linalool), 3,7,11-trimethylammonium-1,6,10-12 carbon triolefin-3-alcohol (nerolidol), 3,7,10-trimethylammonium-1,6-12 carbon diene-3-alcohol (dihydro linalool) and be particularly suitable for E, E-3,7,11,15-tetramethyl--1,6,10, the application of 14-six tetraenes-3-alcohol (E, E-geranyl linalool).
Although EP 376859 B1 disclose; if use the tertiary alcohol; as the ester of the trimethyl carbinol or tertiary amyl alcohol as acetylacetic ester; at nucleophile; in the acetoacetylization as alkanol, alkylamine or alkyl sulfhydryl and acetylacetic ester or derivatives thereof, also can obtain good productive rate, but the reaction of this and Karol is irrelevant; and relate to turn into the functionallization of usefulness by the acetoacetyl of lower molecular weight or polymeric nucleophile, lower molecular weight or polymeric nucleophile finally as coating to improve dyeing.
The present invention relates to the γ of general formula I, the preparation method of delta unsaturated ketone,
This method be by the vinyl carbinol of general formula I I or propargyl alcohol and Acetacetic acid alkyl ester in the Karol reaction of randomly improvement in the presence of Al catalysts in temperature 150-220 ℃ reaction, and distill simultaneously and remove the alkanol of generation,
R in the formula
1Be the saturated or unsaturated branching of H, randomly alkyl with 1-33 carbon atom that replaces by methoxyl group and dotted line can be the other keys that has between its carbon atom, and this method comprises that the acetylacetic ester that uses general formula III is as Acetacetic acid alkyl ester
R in the formula
2It is alkyl with 1-4 carbon atom.
Make us uncannily, utilize method of the present invention, just can obtain senior γ by simple method and continuous processing operation, delta unsaturated ketone, for plant-scale method, this is desirable especially, and its productive rate is the 92-96% of theoretical value, even one of used reactive component is inexcessive or only slightly excessive.In addition, a very big advantage is the space-time yield that method of the present invention can increase the previously known method.
For the reaction of formula (II) alcohol, method of the present invention is a particularly important, the R in the formula (II)
1It is the group of general formula I V
N is that the integer of 1-5 and X and Y or two are H or X is that methoxyl group and Y are H in the formula, or X and Y be the other key that carries between the carbon atom of X and Y together, as 3,7-dimethyl-1,6-octadiene-3-alcohol (linalool), 3,7-dimethyl-1-octene-3-alcohol, 3,7,11-trimethylammonium-1,6,10-12 carbon triolefin-3-alcohol (nerolidol), 3,7,11-trimethylammonium-1-dodecylene-3-alcohol, 3,7,11-trimethylammonium-1,6-12 carbon diene-3-alcohol (dihydro nerolidol) and 3,7,11,15-tetramethyl--1,6,10,14-(E, E) 16 carbon tetraene-3-alcohol (E, E-geranyl linalool).
The application of etheric acid tertiary butyl ester or etheric acid tert-pentyl ester has the advantage of the by product that reacts more rapidly and avoid following.The amount of used reactant is preferably so carried out, so that the mol ratio of the Acetacetic acid alkyl ester of the alcohol of general formula I I and general formula III is 0.8-1.2, and preferred 0.95-1.10.
The organo-aluminium compound that is suitable for the inventive method mainly is the compound of formula V
R in the formula
4Be branching or straight chained alkyl or alkoxyl group with 1-4 carbon atom, preferable methyl or ethyl, R
5And R
6Be branching or straight chained alkyl or alkoxyl group with 1-5 carbon atom, preferable methyl or 2-butyl, R
7Be branching or the straight chained alkyl with 1-4 carbon atom, m and n can be the integers of 0-3, wherein n+m≤3 and three aryloxy aluminium.Particularly preferably be the liquid aluminium compound, especially wherein R
5Be methyl, R
6It is the aluminum compound of butyl and n+m=3 and ratio n/m＞0.3.
Therefore the catalyzer of mentioning at first is rudimentary three aluminium alkoxides, as three aluminum methylates, three aluminum ethylates, aluminum isopropylate, three aluminium secondary butylates, with the methyl ethyl diketone acidifying thing of this three alkane aluminium and stoichiometric quantity, the compound that generates in the reaction of Acetacetic acid alkyl ester or propanedioic acid alkyl ester reaction dealcoholysis simultaneously and transesterify.Example is the triacetyl aluminum acetate, praseodynium acid aluminium, single acetyl acetate diethyl aluminium alcoholates, single acetyl acetate aluminum-diisopropoxide, diacetyl acetic acid list aluminum isopropylate.
Preferred three aluminium alkoxides, particularly aluminum isopropylate and three aluminium secondary butylates of using.Extremely preferred the utilization mixed the triacetyl aluminum acetate, it is produced by aluminium secondary butylate or aluminum isopropylate and methyl acetoacetate reaction cancellation 2-butanols or Virahol and methoxyl group and the 2-butanols that disengages or the transesterify of Virahol simultaneously, and wherein the transesterify degree should be higher than 30%.
We think, three aryloxy aluminium are the aluminium salt of aromatic hydroxy compound, also can promptly be had the alkyl and the alkoxyl group of 1-4 carbon atom by low alkyl group or alkoxyl group as triphenol aluminium, three cresols aluminium, three xylenol aluminium, three naphthols aluminium, their aryl, hydroxyl or phenyl replace.Particularly advantageous in the middle of them is to use more wield triphenol aluminium.
It is favourable using the solution of liquid catalyst or solid catalyst and these catalyzer are added in the reaction vessel with liquid form.For example, can use like this three aluminium alkoxides that are dissolved in Acetacetic acid alkyl ester or be dissolved in Acetacetic acid alkyl ester and the mixture of the alcohol of a kind of general formula I I in three aluminium alkoxides.
The consumption of aluminum compound generally is that its concentration is not less than the aluminium of 0.05% weight and is reacting the aluminium that is no more than 6% weight when beginning in reaction mixture.Based on the Acetacetic acid alkyl ester of desire reaction, need the aluminum compound of 0.5-5mol% usually.For the aluminum isopropylate and the above-mentioned mixing triacetyl aluminum acetate that is made by aluminium secondary butylate and methyl acetoacetate of preferred use, based on desire reaction Acetacetic acid alkyl ester, for example consumption is about 1-3mol%.
When using boiling point to be lower than the vinyl carbinol of 120 ℃ formula II, during as 2-methyl-3-butene-2-alcohol, be particularly advantageous if Karol is reflected in the gamma lactone as the cyclic carbonate of the general formula VI of solvent or formula VII,
Basic R in the formula
1, R
2And R
3Be H, methyl or ethyl, preferred H or methyl, and R
4Be H, methyl, ethyl, sec.-propyl, phenyl or methoxymethyl, preferred H or methyl.
5 yuan of cyclic carbonates as formula VI are, except that common alkylene carbonates, and as ethylene carbonate, carbonic acid 1, the inferior propyl ester of 2-, the inferior isobutyl ester of carbonic acid and carbonic acid 1,2-Aden ester, i.e. R in the carbonic ether of general formula VI
1-R
4Be H or methyl, or R
1-R
3Be H or methyl and R
4Be ethyl, also have those wherein R
1-R
3Also ethyl and R
4Be H, methyl, ethyl, sec.-propyl, the carbonic ether of phenyl or methoxymethyl.
Used cyclic carbonate also can be very inexpensively at industrial corresponding alkylene oxide and the CO of passing through
2Prepared in reaction.Usually boiling of they is so high, and the temperature that consequently under atmospheric pressure reaches 170 ℃ is also no problem.
5 membered ring lactones of suitable especially general formula VII are gamma-butyrolactone and 3-methyl-gamma-butyrolactone, particularly gamma-butyrolactone.
Gamma-butyrolactone according to the used general formula VII of the present invention also can be by corresponding butanediol dehydrogenation in industrial advantageously preparation.
The alkanol that generates in reaction attack to cyclic carbonate or lactone under reaction conditions is so to make us insignificant uncannily, so that for example when using Texacar PC, solvent can be reused until 10 reaction cycle need not purify (referring to case of comparative examples 1b) in per step.At γ, cyclic carbonate that is separated after delta unsaturated ketone separates or lactone can drop into new reaction cycle and without make-up catalyst.The residual of unreacted acetylacetic ester loses in solvent and not.
Generally based on the γ that generates, delta unsaturated ketone is 50-1000% weight to the consumption of 5 yuan of cyclic carbonate esters and 5 membered ring lactones, preferred 100-500% weight.
When using boiling point to be higher than 140 ℃ formula II pure, the solvent that need not add obvious amount also can advantageously carry out the Karol reaction.This is good in the processing of reaction mixture.
Method of the present invention can be carried out in batches and continuously.When this law was carried out continuously, advantageously, initial compounds and catalyzer were driven into the reaction vessel and the reaction product that are equipped with heating bath and additional coacervation device (carbonic acid gas that the pure and mild discharge that is used for being eliminated generates) and obtain with a upflow tube.
When using method of the present invention, the γ of the general formula I of being pursued, delta unsaturated ketone can be used simple method, obtains with wonderful high yield.The tertiary alcohol by the acetylacetic ester cancellation can almost completely reclaim.
Embodiment
Embodiment 1a
2-methyl-3-butene-2-alcohol reacts with tert-butyl acetoacetate Karol in 180 ℃ in Texacar PC
Be that the mixture of 2-methyl-3-butene-2-pure and mild 39.8g tert-butyl acetoacetate of 92% is added drop-wise to 50ml (45g) carbonic acid 1 in 170 ℃ with 25.7g purity in 2 hours process, inferior propyl ester of 2-and 2.8g are separately in (pressing GB 886 353) pivalyl aluminum acetate mixture of catalysts of preparation.During dripping, CO
2Emit strongly with the low-boiling-point substance that is gone out by continuous still battery (boiling point 80-85 ℃).After being added dropwise to complete, mixture is stirred 10 minutes again, no longer emits until gas, then cooling.Under approximate 100mbar, singlings 2.5g and 30.9g are distilled out by the 96-98% main distillate fraction that pure 2-methyl-the 2-heptene-6-ketone constitutes then.Productive rate (with the quantity of distillation residue in mutually together) be 92% of theoretical value
Embodiment 1b (comparative examples)
2-methyl-3-butene-2-alcohol and methyl acetoacetate be at carbonic acid 1, the reaction in the inferior propyl ester of 2-
A) with 29.03g (0.25mol) methyl acetoacetate (AME; Purity 98%) and 23.68g (0.275mol) 2-methyl-3-butene-2-alcohol (MBE; Purity 94%) at 180 ℃, stir down, squeezed into 45g carbonic acid 1 in the process at 2 hours, in (pressing GB 886353) pivalyl aluminum acetate mixture of catalysts that inferior propyl ester of 2-and 2.8g prepare separately.During this period, CO
2Overflow and the 8g low-boiling-point substance is distilled out, this low-boiling-point substance is made of about 2/3 methyl alcohol and unreacted 2-methyl-3-butene-2-alcohol of about 1/3.Continued to stir the mixture 30 minutes under 180 ℃ then, cooling then under decompression 100mbar, distills in desirable 2-methyl-2-heptene-6-ketone reaction mixture.
B) distillation residue that generate under this situation were mixed in the process at 2 hours at 180 ℃ with the AME and the MBE of above-mentioned consumption once more, mixture was stirred 30 minutes at 180 ℃, then cooling and from wherein distilling out resultant 2-methyl-2-heptene-6-ketone.
C) repetitive operation b again) 8 times, the average yield of 10 crowdes 2-methyl-2-heptene-6-ketone is 88% of a theoretical value altogether, based on the MBE (target gas chromatography determination in using) of reaction.
Embodiment 2a
3,7-dimethyl-1,6-octadiene-3-alcohol (linalool) generates 6 with tert-butyl acetoacetate, 10-dimethyl-5, the Karol reaction of 9-ten-carbon diene-2-ketone
The 5.6g pivalyl aluminum acetate (be similar to GB 866 353 by aluminum isopropylate preparation) of packing into is heated to 180 ℃ and in the process uniform mixture of 115.7g linalool and 128g tert-butyl acetoacetate was being squeezed into reaction vessel at 2 hours under this temperature.In this process, generate CO automatically
2And the trimethyl carbinol, its cohesion.Isolate the 51g trimethyl carbinol.After charging is finished, stirred the mixture cooling then 20 minutes in interior temperature 180-190 ℃ again.Reaction effluent distills being decompressed under the 0.1mbar.At this moment in two kinds of cuts, obtain 139.7g 6 altogether, 10-dimethyl-5,9-11 carbon diene-2-ketone (geranyl acetone), it is equivalent to 96% of theoretical yield.
Embodiment 2b (comparative examples)
The Karol reaction of linalool and methyl acetoacetate
As embodiment 2a) in, the described Al catalysts of the 5.6g that packs into and 115.4g linalool and 94g methyl acetoacetate pumped in the reaction vessel of 180 ℃ of temperature.CO in this process
2Automatically generate the methyl alcohol cohesion with methyl alcohol.As embodiment 2a) in, restir reaction soln 20 minutes is until CO
2Emit and stop, cooling then.Under reduced pressure heat up in a steamer, obtain the 133g geranyl acetone.Productive rate is 91.5% of a theoretical value.As by product, 1.6g 6 is arranged, 10-dimethyl-5,9-11 carbon diene-2-alcohol generates, it is at embodiment 2a) in be not detected.
Embodiment 3a
3,7,11,15-tetramethyl--1,6,10,14 (E, E) 16 carbon tetraene-3-alcohol (E, E-geranyl linalool) generates 6,10 with tert-butyl acetoacetate, 14,18-tetramethyl--5,9,13, the Karol reaction of 17-19 carbon tetraene-2-ketone (geranyl geranyl acetone)
2.5g tri-tert etheric acid aluminium is dissolved in the 42.1g tert-butyl acetoacetate at 40 ℃, and with 72.5g E, E-geranyl linalool in 20 ℃ of addings wherein.The gained mixture squeezed into equably upflow tube is housed and is connected the horizontal reacting by heating container that distills bridge.Input speed fixes on and makes mean residence time is 10 minutes.Interior temperature is 190-200 ℃.During reaction, there is the 15g trimethyl carbinol to be distilled out.
After charging is finished, the distillation reaction effluent.Obtain 75.9g geranyl geranyl acetone, purity 98.8%.This is equivalent to 92% of theoretical yield.
Embodiment 3b (comparative examples)
E, E-geranyl linalool and methyl acetoacetate generate the Karol reaction of geranyl geranyl acetone
2.2g pivalyl aluminum acetate is dissolved in the 37.6g methyl acetoacetate also with this solution and 87g E, the mixing of E-geranyl linalool in 60 ℃.Gained solution is squeezed into example 3a equably) in the described horizontal reacting container, the speed of pumping into will with effective reaction volume coupling so that mean residence time is 10 ± 0.5 minutes.At interior temperature 190-200 ℃, the mixture successive reaction generates the geranyl geranyl acetone.After the charging fully, reheat reactor content 10 minutes is passed to cold reaction effluent then.Distill under 0.3mbar, generation 84.2g purity is 97.1% geranyl geranyl acetone in main distillate fraction.This is equivalent to 85% of theoretical yield.
Embodiment 4a
The Karol reaction of nerolidol and etheric acid 2 '-methyl fourth-2 '-Ji ester
5.6g pivalyl aluminum acetate is packed into and embodiment 4a) described in the identical reaction vessel, be heated to 190 ℃.The mixture of the isoamyl acetoacetate (purity＞98%) that 166g nerolidol and 139g are made from Virahol and diketene with a kind of known method itself evenly drips 2 hours process.Make temperature of reaction in this process, remain on 190-200 ℃ by heating.After finishing charging, restir mixture 15 minutes, cooling then.Obtain the 212g coarse fodder, it is distilled under 0.1mbar.Two kinds of cuts provide the 178.7g farnesyl acetone.This is equivalent to 91% of theoretical yield.
Embodiment 4b (comparative examples)
The reaction of nerolidol and methyl acetoacetate
5.6g pivalyl aluminum acetate packed into be equipped with measuring apparatus, paddle agitator and have the reflux exchanger that is connected and the 500ml reaction vessel of the 10cm post of distillation bridge.Be heated to 180-190 ℃.In 2 hours process, the uniform mixture of 166.5g (0.75mol) nerolidol and 94g (0.81mol) methyl acetoacetate is evenly squeezed into.Make temperature of reaction remain on 180-190 ℃ by indirect heating.The methyl alcohol cohesion that generates.Finish reinforced after, restir mixture 15 minutes, cooling then.Obtain the 208g coarse fodder, it is being distilled under decompression greatly.In two kinds of cuts, isolate farnesyl acetone 167g altogether.This is equivalent to 85% of theoretical yield.
Embodiment 5
The Karol reaction of nerolidol and etheric acid 2 '-methyl-2 '-pentyl ester (etheric acid dissident ester)
With the 2.8g pivalyl aluminum acetate embodiment 4a that packs into) described in reaction vessel.In temperature of reaction is 190-220 ℃, and in 1 hour process, the mixture of the etheric acid dissident ester that 83g nerolidol and 75g are made by isohexyl alcohol and diketene is squeezed into.After finishing charging, reaction mixture 200 ℃ of restir 10 minutes, is emitted the end postcooling at gas.Obtain the 108g coarse fodder, it is being distilled under decompression greatly.Isolate 88g proof gold silk tree benzylacetone in this way.This is equivalent to 90% of theoretical yield.
Embodiment 6
A) E of the present invention, the reaction of E-geranyl linalool and tert-butyl acetoacetate
With 263ml by 145g (0.5mol) E, E-geranyl linalool, the reaction soln that 5g etheric acid tri-tert aluminium and 83g (0.525mol) tert-butyl acetoacetate are formed is with in the reaction vessel of squeezing into magnetic in speed 5.6ml/ minute and stirring, and this reaction vessel is heated to 190-200 ℃ and at central (the effective volume 45ml that is equivalent to flask) upflow tube is arranged by a 100ml three pre-flasks with heating jacket.Obtain 185g crude product and 30.5g low-boiling-point substance like this.Crude product contains 13% unreacted E, E-geranyl linalool and 79% required geranyl geranyl acetone.
B) E, the reaction of E-geranyl linalool and methyl acetoacetate (comparative examples)
By 145g (0.5mol) E, E-geranyl linalool, 5g etheric acid tri-tert aluminium and 61g (0.525mol) methyl acetoacetate are squeezed into above-mentioned being heated in 190-200 ℃ the above-mentioned reaction vessel under 5.0ml/ minute speed with 234ml.Obtain 199.9g crude product and 5.7g low-boiling-point substance like this.Crude product contains 53% unreacted E, E-geranyl linalool and 34% required geranyl phyllopodium acetone only.
Embodiment 6a and comparative examples 6b show more clearlyly, react than with the previous methyl acetoacetate obviously rapider (fast 3-10 doubly) that is generally used for Karol reaction with tert-butyl acetoacetate.
Claims (7)
1. γ who prepares general formula I, the method for delta unsaturated ketone
This method be by the vinyl carbinol of general formula I I or propargyl alcohol and Acetacetic acid alkyl ester at temperature 150-220 ℃, in the presence of Al catalysts, react and distills out simultaneously the alkanol of generation own by the Karol of randomly improvement
R in the formula
1Be that the saturated or unsaturated ramose of H, the alkyl with 1-33 carbon atom that randomly replaces by methoxyl group and dotted line can be the other keys that carries between its carbon atom, the acetylacetic ester of usefulness general formula III is as Acetacetic acid alkyl ester
R in the formula
2It is alkyl with 1-4 carbon atom.
2. method as claimed in claim 1, it is characterized in that used is Karol reaction with the acetylacetic ester of general formula III,
R in the formula
2It is methyl.
3. method as claimed in claim 1 is characterized in that using R
1Be a kind of alcohol of the group of general formula I V vinyl carbinol as general formula I I
In the formula n be the integer of 1-5 and X and Y the two be that H or X are that methoxyl group and Y are H, or X and Y are the other key that carries between the carbon atom of X and Y together.
4. method as claimed in claim 1 is characterized in that using 2-methyl-3-butene-2-alcohol, linalool, 6,7-dihydro linalool, nerolidol, 10, and 11-dihydro nerolidol or geranyl linalool are as the vinyl carbinol of general formula I I.
5. method as claimed in claim 3 is characterized in that, when using 2-methyl-3-butene-2-alcohol as the vinyl carbinol of general formula I I, it is to carry out in the gamma lactone as the cyclic carbonate of the general formula VI of solvent or general formula VII that Karol reacts
Wherein basic R
3, R
4And R
5Be H, methyl or ethyl and R
6Be H, methyl, ethyl, sec.-propyl, phenyl or methoxymethyl.
6. method as claimed in claim 4 is characterized in that, when using 2-methyl-3-butene-2-alcohol as the vinyl carbinol of general formula I I, it is to carry out in the gamma lactone of the cyclic carbonate of general formula VI or general formula VII that Karol reacts
Basic R in the formula
3, R
4, R
5And R
6Be H or methyl.
7. method as claimed in claim 1 is characterized in that, when using boiling point to be higher than 140 ℃ general formula I I pure, the carrying out of Karol reaction need not be added the solvent of significant quantity.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19840746.7 | 1998-09-07 | ||
| DE19840746A DE19840746A1 (en) | 1998-09-07 | 1998-09-07 | Process for the production of gamma, delta-unsaturated ketones by Carroll reaction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1348434A true CN1348434A (en) | 2002-05-08 |
Family
ID=7880056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99812906A Pending CN1348434A (en) | 1998-09-07 | 1999-09-02 | Method for producing upsilon, delta unsaturated ketones by carroll reaction |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP1112245A1 (en) |
| JP (1) | JP2002524435A (en) |
| KR (1) | KR20010074970A (en) |
| CN (1) | CN1348434A (en) |
| AU (1) | AU5858399A (en) |
| CA (1) | CA2343521A1 (en) |
| DE (1) | DE19840746A1 (en) |
| ID (1) | ID27392A (en) |
| IL (1) | IL141689A0 (en) |
| WO (1) | WO2000014046A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050714A (en) * | 2010-12-08 | 2011-05-11 | 成都自豪药业有限公司 | Method for synthesizing Teprenone |
| CN103058839A (en) * | 2013-01-25 | 2013-04-24 | 四川源基制药有限公司 | Process for synthesizing and purifying teprenone |
| CN104326890A (en) * | 2014-11-21 | 2015-02-04 | 山东新和成药业有限公司 | Continuous process method for Carroll reaction |
| CN104513117A (en) * | 2013-10-08 | 2015-04-15 | 中国科学院大连化学物理研究所 | Catalytically asymmetric synthesis method of chiral [beta]-acetenyl ketone compound |
| CN116212943A (en) * | 2022-12-05 | 2023-06-06 | 江苏宏邦化工科技有限公司 | Preparation method of novel alkaline catalyst and application of novel alkaline catalyst in preparation of methyl heptenone |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002121165A (en) * | 2000-10-16 | 2002-04-23 | Kuraray Co Ltd | Method for producing unsaturated ketone |
| JP2002121166A (en) * | 2000-10-16 | 2002-04-23 | Kuraray Co Ltd | Method for producing unsaturated ketone |
| WO2008047690A1 (en) * | 2006-10-11 | 2008-04-24 | Eisai R & D Management Co., Ltd. | Process for preparing geranylgeranylacetone |
| CN106946672A (en) | 2015-12-11 | 2017-07-14 | 帝斯曼知识产权资产管理有限公司 | The method for manufacturing the ketone of 6,10,14 trimethylpentadecane 2 |
| WO2018108606A1 (en) | 2016-12-12 | 2018-06-21 | Dsm Ip Assets B.V. | Process for the manufacture of 6,10-dimethylundecan-2-one, isophytol, alpha-tocopherol (acetate) and further intermediates thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH493453A (en) * | 1968-07-23 | 1970-07-15 | Basf Ag | Process for the preparation of 6,10-dimethyl-undecatrien- (3,5,10) -one- (2) |
| DE2928944A1 (en) * | 1979-07-18 | 1981-02-12 | Basf Ag | IMPROVED METHOD FOR PRODUCING HIGHER UNSATURATED KETONES |
| DE19647117A1 (en) * | 1996-11-14 | 1998-05-28 | Basf Ag | Process for the production of gamma, delta-unsaturated ketones by Caroll reaction in cyclic carbonates or gamma-lactones as solvents |
| US6051741A (en) * | 1997-10-17 | 2000-04-18 | Basf Aktiengesellschaft | Preparation of γ,δ-unsaturated ketones by the Carroll reaction, novel catalysts therefor and the preparation thereof |
-
1998
- 1998-09-07 DE DE19840746A patent/DE19840746A1/en not_active Withdrawn
-
1999
- 1999-09-02 AU AU58583/99A patent/AU5858399A/en not_active Abandoned
- 1999-09-02 CN CN99812906A patent/CN1348434A/en active Pending
- 1999-09-02 WO PCT/EP1999/006447 patent/WO2000014046A1/en not_active Application Discontinuation
- 1999-09-02 IL IL14168999A patent/IL141689A0/en unknown
- 1999-09-02 ID IDW20010546A patent/ID27392A/en unknown
- 1999-09-02 KR KR1020017002894A patent/KR20010074970A/en not_active Application Discontinuation
- 1999-09-02 EP EP99946093A patent/EP1112245A1/en not_active Withdrawn
- 1999-09-02 CA CA002343521A patent/CA2343521A1/en not_active Abandoned
- 1999-09-02 JP JP2000568806A patent/JP2002524435A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102050714A (en) * | 2010-12-08 | 2011-05-11 | 成都自豪药业有限公司 | Method for synthesizing Teprenone |
| CN102050714B (en) * | 2010-12-08 | 2014-02-05 | 重庆恒韵医药有限公司 | Method for synthesizing Teprenone |
| CN103058839A (en) * | 2013-01-25 | 2013-04-24 | 四川源基制药有限公司 | Process for synthesizing and purifying teprenone |
| CN103058839B (en) * | 2013-01-25 | 2014-12-17 | 四川源基制药有限公司 | Process for synthesizing and purifying teprenone |
| CN104513117A (en) * | 2013-10-08 | 2015-04-15 | 中国科学院大连化学物理研究所 | Catalytically asymmetric synthesis method of chiral [beta]-acetenyl ketone compound |
| CN104513117B (en) * | 2013-10-08 | 2016-08-10 | 中国科学院大连化学物理研究所 | A kind of catalysis method of asymmetric synthesis of chiral beta-acetenyl ketonic compound |
| CN104326890A (en) * | 2014-11-21 | 2015-02-04 | 山东新和成药业有限公司 | Continuous process method for Carroll reaction |
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| CN116212943A (en) * | 2022-12-05 | 2023-06-06 | 江苏宏邦化工科技有限公司 | Preparation method of novel alkaline catalyst and application of novel alkaline catalyst in preparation of methyl heptenone |
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| Publication number | Publication date |
|---|---|
| JP2002524435A (en) | 2002-08-06 |
| AU5858399A (en) | 2000-03-27 |
| IL141689A0 (en) | 2002-03-10 |
| DE19840746A1 (en) | 2000-03-09 |
| KR20010074970A (en) | 2001-08-09 |
| ID27392A (en) | 2001-04-05 |
| WO2000014046A1 (en) | 2000-03-16 |
| EP1112245A1 (en) | 2001-07-04 |
| CA2343521A1 (en) | 2000-03-16 |
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