CN1257857A - 四氢化荼类化合物、其制备方法和其用途 - Google Patents
四氢化荼类化合物、其制备方法和其用途 Download PDFInfo
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- CN1257857A CN1257857A CN99125832A CN99125832A CN1257857A CN 1257857 A CN1257857 A CN 1257857A CN 99125832 A CN99125832 A CN 99125832A CN 99125832 A CN99125832 A CN 99125832A CN 1257857 A CN1257857 A CN 1257857A
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- alkyl
- ethanoyl
- tetralin
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- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical class C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 title claims description 19
- 238000000034 method Methods 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000003205 fragrance Substances 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- JIKUXBYRTXDNIY-UHFFFAOYSA-N n-methyl-n-phenylformamide Chemical compound O=CN(C)C1=CC=CC=C1 JIKUXBYRTXDNIY-UHFFFAOYSA-N 0.000 claims 1
- 239000000834 fixative Substances 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- -1 acyl group phenyl aldehyde Chemical group 0.000 description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 230000009967 tasteless effect Effects 0.000 description 5
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 4
- 125000002252 acyl group Chemical group 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- GLZPCOQZEFWAFX-YFHOEESVSA-N (Z)-Geraniol Chemical compound CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- KVWWIYGFBYDJQC-UHFFFAOYSA-N methyl dihydrojasmonate Chemical compound CCCCCC1C(CC(=O)OC)CCC1=O KVWWIYGFBYDJQC-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 2
- 239000005792 Geraniol Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- JOZKFWLRHCDGJA-UHFFFAOYSA-N citronellol acetate Chemical compound CC(=O)OCCC(C)CCC=C(C)C JOZKFWLRHCDGJA-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229940113087 geraniol Drugs 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- YHVZVLYNHHTMSL-UHFFFAOYSA-N nona-3,5,7-trien-2-one Chemical compound CC=CC=CC=CC(C)=O YHVZVLYNHHTMSL-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 208000003265 stomatitis Diseases 0.000 description 2
- FQTLCLSUCSAZDY-UHFFFAOYSA-N (+) E(S) nerolidol Natural products CC(C)=CCCC(C)=CCCC(C)(O)C=C FQTLCLSUCSAZDY-UHFFFAOYSA-N 0.000 description 1
- CRDAMVZIKSXKFV-FBXUGWQNSA-N (2-cis,6-cis)-farnesol Chemical compound CC(C)=CCC\C(C)=C/CC\C(C)=C/CO CRDAMVZIKSXKFV-FBXUGWQNSA-N 0.000 description 1
- 239000000260 (2E,6E)-3,7,11-trimethyldodeca-2,6,10-trien-1-ol Substances 0.000 description 1
- NQBWNECTZUOWID-UHFFFAOYSA-N (E)-cinnamyl (E)-cinnamate Natural products C=1C=CC=CC=1C=CC(=O)OCC=CC1=CC=CC=C1 NQBWNECTZUOWID-UHFFFAOYSA-N 0.000 description 1
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 1
- UFLHIIWVXFIJGU-ARJAWSKDSA-N (Z)-hex-3-en-1-ol Chemical compound CC\C=C/CCO UFLHIIWVXFIJGU-ARJAWSKDSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- JOZKFWLRHCDGJA-LLVKDONJSA-N Citronellyl acetate Natural products CC(=O)OCC[C@H](C)CCC=C(C)C JOZKFWLRHCDGJA-LLVKDONJSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- FQTLCLSUCSAZDY-ATGUSINASA-N Nerolidol Chemical compound CC(C)=CCC\C(C)=C\CC[C@](C)(O)C=C FQTLCLSUCSAZDY-ATGUSINASA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000004768 bromobenzenes Chemical class 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical class CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 125000003917 carbamoyl group Chemical class [H]N([H])C(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- NQBWNECTZUOWID-QSYVVUFSSA-N cinnamyl cinnamate Chemical compound C=1C=CC=CC=1\C=C/C(=O)OC\C=C\C1=CC=CC=C1 NQBWNECTZUOWID-QSYVVUFSSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229930002886 farnesol Natural products 0.000 description 1
- 229940043259 farnesol Drugs 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- HIGQPQRQIQDZMP-UHFFFAOYSA-N geranil acetate Natural products CC(C)=CCCC(C)=CCOC(C)=O HIGQPQRQIQDZMP-UHFFFAOYSA-N 0.000 description 1
- HIGQPQRQIQDZMP-DHZHZOJOSA-N geranyl acetate Chemical compound CC(C)=CCC\C(C)=C\COC(C)=O HIGQPQRQIQDZMP-DHZHZOJOSA-N 0.000 description 1
- UFLHIIWVXFIJGU-UHFFFAOYSA-N hex-3-en-1-ol Natural products CCC=CCCO UFLHIIWVXFIJGU-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WPFVBOQKRVRMJB-UHFFFAOYSA-N hydroxycitronellal Chemical compound O=CCC(C)CCCC(C)(C)O WPFVBOQKRVRMJB-UHFFFAOYSA-N 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WASNIKZYIWZQIP-AWEZNQCLSA-N nerolidol Natural products CC(=CCCC(=CCC[C@@H](O)C=C)C)C WASNIKZYIWZQIP-AWEZNQCLSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229930007790 rose oxide Natural products 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- CRDAMVZIKSXKFV-UHFFFAOYSA-N trans-Farnesol Natural products CC(C)=CCCC(C)=CCCC(C)=CCO CRDAMVZIKSXKFV-UHFFFAOYSA-N 0.000 description 1
- CZCBTSFUTPZVKJ-UHFFFAOYSA-N trans-Rosenoxid Natural products CC1CCOC(C=C(C)C)C1 CZCBTSFUTPZVKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- JGQFVRIQXUFPAH-UHFFFAOYSA-N α-citronellol Chemical compound OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q13/00—Formulations or additives for perfume preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/35—Ketones, e.g. benzophenone
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/269—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of only halogenated hydrocarbons
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- 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
- C07C45/004—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with organometalhalides
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- 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
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
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- 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
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/515—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an acetalised, ketalised hemi-acetalised, or hemi-ketalised hydroxyl group
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- 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
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
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- C07C45/86—Use of additives, e.g. for stabilisation
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- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
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- 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
- C07D317/10—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 not condensed with other rings
- C07D317/14—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 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract
式Ⅰ化合物在芳香组合物中用作介体。式Ⅰ中,R1为氢或甲基,R2为烷基。
Description
本发明涉及新型四氢化萘类化合物(hydronaphthalenes)及其制备方法和用途。
芳香组合物由具有不同挥发性的多种组分组成。在贮存和使用中，挥发性强的化合物蒸发较快，从而改变了组合物的性质。为了在更长时间内保持这些组合物的芳香性质，必须采取措施以防止挥发性强的组分较早蒸发。一般将所谓的“介体”加入组合物中。介体化合物和芳香组合物中挥发性强的组分形成疏松的络合物，从而减少了其挥发。介体化合物可以是无味的，也可具有气味，该气味会影响芳香组合物的香味。对于香料商来说，易使用无味的介体，因为它们不产生额外的气味，从而所用剂量在较宽范围都不会改变芳香的性质。另外，无味的介体可用于多种不同的芳香组合物。
现在已经发现式I的化合物为可用作介体的无味化合物：
其中R1为氢或甲基，R2为烷基，特别是C1-12-烷基，并优选C1-4-烷基。
如熟练技术人员所知，由于最初引入的酰基的强钝化作用，邻二酰基芳烃不能够通过母芳烃的二次Friedel-Crafts-酰化反应制备。
原则上，邻酰基苯甲醛可从邻酰基肉桂酸制备，但是，所需的氧化步骤会产生废过渡金属(E.Berner，Acta Chemica Scand.Ser.B，729(1982))。另一种可能是从乙酰基庚三烯制备，但乙酰基庚三烯不易得到，且在最终步骤中要求低产率的空气氧化反应，而该步骤具有潜在危险(M.Senguel，J.Chem.Soc.Perkin Trans.I，2071(1997))。
因此，需要一种避免已知方法的缺点，用于制备式I新化合物的新方法。
已经发现，下述采用易得原料的5步法可得到所需的式I化合物，并且具有良好收率。式中，R1为氢或甲基，Hal代表卤素，特别是Br或Cl，R1为烷基，优选低级烷基，特别是甲基，或者R1-R1也可代表二价烷基残基，从而生成二氧茂烷环，R2为烷基，特别是C1-12-烷基，并优选C1-4-烷基。
在步骤1中，卤代苯，优选溴苯或氯苯，和2，5-二卤-2，5-二甲基己烷稠和。稠和反应在少量路易斯酸催化剂-如氯化铝、氯化铁、氯化铋-存在下进行，这里仅列出许多可进行芳烃的烷基化反应的催化剂的一些。以这种方式获得的取代四氢化萘衍生物IV可以被分离及纯化。引入酰基(步骤2)是通过在Friedel-Crafts-酰化催化剂存在下，四氢化萘IV和活化的酸衍生物的反应来进行的。例如酰基氯或酸酐可用作活化的酸衍生物。催化剂也可为上述的路易斯酸催化剂。为了使步骤更经济，步骤1和2也可不需分离IV就进行。为了避免不希望的副反应，步骤1中催化剂的量必须保持较少并恰好在酰化步骤2前加入另外的催化剂。由于V的酰基不能与Grignard反应(步骤4)相容，因此它要以缩酮形式被保护。这可通过V和醇或邻位酯反应，或通过缩酮交换作用(transketalisation)进行，通过用酸-如路易斯酸或质子酸来催化。酸催化剂的例子有：磺酸、硫酸、粘土等。除了一元醇，二元醇-例如乙二醇-也可使用。通过用镁、锂或烷基锂-例如丁基锂-处理VI，可将化合物VII转变为有机金属化合物，例如锂或镁的衍生物。考虑到经济原因，优选使用镁。甲酰基优选通过有机金属中间体和甲酸或其衍生物反应引入，最容易且经济的是通过甲酰胺类化合物，如二甲基甲酰胺、N-烷基-甲酰苯胺或甲酰基吗啉。尽管分离甲酰基-缩酮VII是可能的，但通过在酸性pH值下用水处理反应混合物使之水解是更实际和经济的，而无需任何其它处理。
式I的化合物是无味的，并在不同的芳香组合物中显示了优异的介体性质，从而达到改进的线性性质，即，芳香性质的高稳定性。这些化合物可用于多种芳香组合物。
下列实施例将阐述本发明，但不局限于此。
实施例1
1，1，4，4-四甲基-6-乙酰基-7-甲酰基-1，2，3，4-四氢化萘
在10℃，经1小时，将溶于480ml二氯乙烷中的219.6克2，5-二氯-2，2，5，5-四甲基-己烷加入到悬浮在217克溴苯的8.4克氯化铝中。搅拌20分钟后，加入204克氯化铝，再加入127克乙酰氯。随后搅料在0℃下搅拌4小时，并在室温下搅拌12小时后，将深色物质倒入2升冰水中。有机相用水洗涤两次，干燥并蒸干。蒸馏残余物可得到240.6克1，1，4，4-四甲基-6-乙酰基-7-溴-1，2，3，4-四氢化萘。
沸点0.08Torr：148-152℃
NMR(CDCl3)：7.5(s，1H)，7.45(s，1H)，2.63(s，3H)，1.67(s，4H)，1.27(s，12H)。
240.6克1，1，4，4-四甲基-6-乙酰基-7-溴-1，2，3，4-四氢化萘、96.7克乙二醇、11克Amberlyst 15和120ml己烷在装有Dean-Stark脱水器的烧瓶中回流过夜。再加入50克乙二醇继续回流12小时。反应混合物用乙醚稀释并滤掉催化剂。溶液用1升含有2克碳酸钠的水洗涤，再用水洗涤两次，干燥并蒸干。从己烷中结晶残余物得到137克1，1，4，4-四甲基-6-乙酰基-7-溴-1，2，3，4-四氢化萘-乙二醇缩酮。
NMR(CDCl3)：7.55(s，1H)，7.47(s，1H)，3.97-4.15(m，2H)，3.69-3.85(m，2H)，1.82(s，3H)，1.65(s，4H)，1.25(s，12H)。
向1.02克悬浮在6ml四氢呋喃的镁屑中缓慢加入310克溴乙烷。当Grignard反应开始时，在回流温度下几分钟内加入溶解于四氢呋喃的10.59克1，1，4，4-四甲基-6-乙酰基-7-溴-1，2，3，4-四氢化萘-乙二醇缩酮。再回流2小时后，在0℃下加入4.5克N，N-二甲基甲酰胺，然后混合物在该温度下搅拌3小时。随后反应混合物回流3小时。然后反应混合物倒入到2NHCl中并用乙醚萃取。有机相用水洗涤，蒸干并用60ml 2NHCl/ml水回流2小时。在常规处理后，可得到8.38克1，1，4，4-四甲基-6-乙酰基-7-甲酰基-1，2，3，4-四氢化萘。
熔点116℃：(己烷)
NMR(CDCl3)：7.84(s，1H)，7.63(s，+H)，2.63(s，1H)，1.71(s，4H)，1.33(s，12H)。
实施例2
1，1，2，4，4-五甲基-6-乙酰基-7-甲酰基-1，2，3，4-四氢化萘
根据实施例1，通过1，1，2，4，4-五甲基-7-溴-1，2，3，4-四氢化萘的酰化反应、乙二醇的缩酮化反应和N-甲酰基吗啉的Grignard反应，制备该化合物。
NMR(CDCl3)：10.2(s，1H)，7.9(s，1H)，7.62(s，1H)，2.64(s，3H)，1.8-2.0(m，1H)，1.68(t，2H)，1.45(dxd，1H)，1.38(s，3H)，1.36(s，3H)，1.10(s，3H)，1.02(d，3H)。
实施例3
1，1，4，4-四甲基-6-乙酰基-7-甲酰基-1，2，3，4-四氢化萘用作介体
可制备一种霉菌性口炎型芳香组合物，该组合物由下列物质组成：
| 组分 | 份 |
| 吲哚 | 5 |
| 乙酸苄酯 | 7 |
| 顺乙酸3-己烯酯(10％) | 7 |
| Rose氧化物(1％) | 5 |
| 二氢茉莉酮酸甲酯(Hedione) | 10 |
| 铃兰醛 | 20 |
| 顺苯甲酸3-己烯酯 | 15 |
| 橙花醇 | 15 |
| 顺3-己烯醇 | 10 |
| 肉桂醇 | 30 |
| 醋酸香茅酯 | 30 |
| 玫瑰醇 | 30 |
| 苯基乙醇 | 20 |
| 香茅醇 | 75 |
| 苯甲酸苄酯 | 70 |
| 香叶醇 | 70 |
| 醋酸香叶酯 | 80 |
| 橙花叔醇 | 80 |
| 法呢醇 | 120 |
| 苯甲醇 | 150 |
| 羟基香茅醛 | 50 |
| 缩二丙二醇 | 101 |
加入标题化合物达到了芳香组合物线性性质的改进，例如芳香组合物的香味可保持更长的时间。
实施例4
1，1，2，4，4-五甲基-6-乙酰基-7-甲酰基-1，2，3，4-四氢化萘用作介体
标题化合物加入到根据实施例3的霉菌性口炎型芳香组合物达到了芳香化组合物线性性质的改进，例如芳香组合物的香味可保持更长的时间。
Claims (13)
1.式I的化合物：
其中R1为氢或甲基，R2为烷基。
2.如权利要求1所述的式I化合物，其中R2为C1-12-烷基，优选C1-4-烷基。
3. 1，1，4，4-四甲基-6-乙酰基-7-甲酰基-1，2，3，4-四氢化萘。
4. 1，1，2，4，4-五甲基-6-乙酰基-7-甲酰基-1，2，3，4-四氢化萘。
5.制备式I化合物的方法，其中R1为氢或甲基，R2为烷基，
该方法包括式II化合物
和式III化合物进行反应，
III式中Hal为卤素，酰化所得的式IV的四氢化萘
以得到式V化合物，
式V化合物和醇或乙二醇反应得到式VI缩酮，其中R1为烷基残基或R1-R1代表二价烷基残基，从而形成二氧茂烷环，然后化合物VI和镁、式VIII的甲酰胺反应得到式I化合物，
其中R3和R4为两个有机残基或成环。
6.如权利要求5所述的方法，其中Hal选自氯或溴。
7.如权利要求5或6的方法，其中化合物IV和或VII在反应期间不需回收。
8.如权利要求5-7任一所述的方法，其中式VIII化合物选自二甲基甲酰胺、N-甲酰基吗啉和N-甲基-甲酰苯胺。
9.式I化合物在芳香组合物中作为介体的用途。
10.含有一种或多种作为介体的式I化合物的芳香组合物。
11.如权利要求10所述的芳香组合物，含有作为介体的1，1，4，4-四甲基-6-乙酰基-7-甲酰基-1，2，3，4-四氢化萘。
12.如权利要求10所述的芳香组合物含有作为介体的1，1，2，4，4-五甲基-6-乙酰基-7-甲酰基-1，2，3，4-四氢化萘。
13.如权利要求10-12任一所述的芳香组合物，含有高挥发性醇。
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|---|---|---|---|
| EP98811229.8 | 1998-12-15 | ||
| EP98811229A EP1010685A1 (en) | 1998-12-15 | 1998-12-15 | New tetrahydronaphthalenes |
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| EP (1) | EP1010685A1 (zh) |
| JP (1) | JP2000219651A (zh) |
| CN (1) | CN1257857A (zh) |
| AU (1) | AU734160C (zh) |
| BR (1) | BR9907426A (zh) |
| CA (1) | CA2292193A1 (zh) |
| PL (1) | PL337106A1 (zh) |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7257300B2 (en) * | 2004-06-03 | 2007-08-14 | Samsung Electronics Co., Ltd. | Method for reducing hydrogen sensitivity of optical fiber |
| CN101200419B (zh) * | 2007-11-22 | 2010-12-22 | 上海力智生化科技有限公司 | 一种合成吐纳麝香的方法 |
| CN102050715A (zh) * | 2011-01-07 | 2011-05-11 | 河南科技大学 | 一种工业吐纳麝香的制备方法 |
| CN105007885A (zh) * | 2013-03-13 | 2015-10-28 | 荷兰联合利华有限公司 | 个人护理组合物中某些芳香组分的延长递送 |
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| JP4744708B2 (ja) * | 2001-03-15 | 2011-08-10 | 大日本住友製薬株式会社 | テトラヒドロナフタレン誘導体の製造方法 |
| DE10228629A1 (de) * | 2002-06-26 | 2004-05-27 | Beiersdorf Ag | Neue antimikrobielle Wirkstoffe |
| MX352873B (es) | 2013-03-13 | 2017-12-13 | Unilever Nv | Composiciones fotoprotectoras con triciclodecano amidas. |
| JP6364032B2 (ja) | 2013-03-13 | 2018-07-25 | ユニリーバー・ナームローゼ・ベンノートシヤープ | トリシクロデカンアミドを含む化粧品組成物 |
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| FR359195A (fr) * | 1905-11-07 | 1906-03-17 | Adolf Vahlaud | Porte-bouquets |
| US2800511A (en) * | 1955-01-28 | 1957-07-23 | Givaudan Corp | Substituted tetrahydronaphthalene aldehydes |
| FR1359195A (fr) * | 1963-02-23 | 1964-04-24 | Procédé de fabrication des aldéhydes |
-
1998
- 1998-12-15 EP EP98811229A patent/EP1010685A1/en not_active Withdrawn
-
1999
- 1999-11-03 ZA ZA9906913A patent/ZA996913B/xx unknown
- 1999-11-16 SG SG9905674A patent/SG84554A1/en unknown
- 1999-11-29 CN CN99125832A patent/CN1257857A/zh active Pending
- 1999-12-10 PL PL99337106A patent/PL337106A1/xx unknown
- 1999-12-14 BR BR9907426-5A patent/BR9907426A/pt not_active IP Right Cessation
- 1999-12-14 AU AU64505/99A patent/AU734160C/en not_active Ceased
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7257300B2 (en) * | 2004-06-03 | 2007-08-14 | Samsung Electronics Co., Ltd. | Method for reducing hydrogen sensitivity of optical fiber |
| CN101200419B (zh) * | 2007-11-22 | 2010-12-22 | 上海力智生化科技有限公司 | 一种合成吐纳麝香的方法 |
| CN102050715A (zh) * | 2011-01-07 | 2011-05-11 | 河南科技大学 | 一种工业吐纳麝香的制备方法 |
| CN102050715B (zh) * | 2011-01-07 | 2013-10-30 | 河南科技大学 | 一种工业吐纳麝香的制备方法 |
| CN105007885A (zh) * | 2013-03-13 | 2015-10-28 | 荷兰联合利华有限公司 | 个人护理组合物中某些芳香组分的延长递送 |
| CN105007885B (zh) * | 2013-03-13 | 2018-06-26 | 荷兰联合利华有限公司 | 个人护理组合物中某些芳香组分的延长递送 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000219651A (ja) | 2000-08-08 |
| PL337106A1 (en) | 2000-06-19 |
| CA2292193A1 (en) | 2000-06-15 |
| EP1010685A1 (en) | 2000-06-21 |
| BR9907426A (pt) | 2000-09-19 |
| SG84554A1 (en) | 2001-11-20 |
| AU6450599A (en) | 2000-06-22 |
| ZA996913B (en) | 2000-06-01 |
| AU734160B2 (en) | 2001-06-07 |
| AU734160C (en) | 2002-02-21 |
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