DE2365939A1 - CYCLOPENTENE AND METHOD FOR PRODUCING IT - Google Patents
CYCLOPENTENE AND METHOD FOR PRODUCING ITInfo
- Publication number
- DE2365939A1 DE2365939A1 DE19732365939 DE2365939A DE2365939A1 DE 2365939 A1 DE2365939 A1 DE 2365939A1 DE 19732365939 DE19732365939 DE 19732365939 DE 2365939 A DE2365939 A DE 2365939A DE 2365939 A1 DE2365939 A1 DE 2365939A1
- Authority
- DE
- Germany
- Prior art keywords
- formula
- compound
- hydrogen
- optional bond
- alkylidene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 title claims description 10
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 37
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- -1 alkyl radical Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- 239000003205 fragrance Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000001118 alkylidene group Chemical group 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 150000002084 enol ethers Chemical class 0.000 claims description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 4
- 239000003377 acid catalyst Substances 0.000 claims 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 229930014626 natural product Natural products 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N citronellol Chemical compound OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (R)-(+)-citronellol Natural products OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-N 0.000 description 2
- YMDBBTFDBCRGLP-UHFFFAOYSA-N 1-methyl-2-methylidene-3-prop-1-en-2-ylcyclopentan-1-ol Chemical compound CC(=C)C1CCC(C)(O)C1=C YMDBBTFDBCRGLP-UHFFFAOYSA-N 0.000 description 2
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- 239000003810 Jones reagent Substances 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 150000001241 acetals Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- JGQFVRIQXUFPAH-UHFFFAOYSA-N beta-citronellol Natural products OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000000484 citronellol Nutrition 0.000 description 2
- 239000001926 citrus aurantium l. subsp. bergamia wright et arn. oil Substances 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- HFJRKMMYBMWEAD-UHFFFAOYSA-N dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 0.000 description 2
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- MDHYEMXUFSJLGV-UHFFFAOYSA-N phenethyl acetate Chemical compound CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 description 2
- 229940067107 phenylethyl alcohol Drugs 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229940072033 potash Drugs 0.000 description 2
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 1
- XCEXBRKEGXBUJE-ATFAPYMMSA-N (5r,6r)-6,10-dimethyl-3-propan-2-ylidenespiro[4.5]dec-9-en-8-ol Chemical compound C[C@@H]1CC(O)C=C(C)[C@]11CC(=C(C)C)CC1 XCEXBRKEGXBUJE-ATFAPYMMSA-N 0.000 description 1
- WEFHSZAZNMEWKJ-KEDVMYETSA-N (6Z,8E)-undeca-6,8,10-trien-2-one (6E,8E)-undeca-6,8,10-trien-2-one (6Z,8E)-undeca-6,8,10-trien-3-one (6E,8E)-undeca-6,8,10-trien-3-one (6Z,8E)-undeca-6,8,10-trien-4-one (6E,8E)-undeca-6,8,10-trien-4-one Chemical compound CCCC(=O)C\C=C\C=C\C=C.CCCC(=O)C\C=C/C=C/C=C.CCC(=O)CC\C=C\C=C\C=C.CCC(=O)CC\C=C/C=C/C=C.CC(=O)CCC\C=C\C=C\C=C.CC(=O)CCC\C=C/C=C/C=C WEFHSZAZNMEWKJ-KEDVMYETSA-N 0.000 description 1
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QYYQTLLGVAPKPN-UHFFFAOYSA-N 1-ethylcyclopentene Chemical compound CCC1=CCCC1 QYYQTLLGVAPKPN-UHFFFAOYSA-N 0.000 description 1
- NDACTLNPNAMFLK-UHFFFAOYSA-N 1-methoxy-3-methylbut-1-ene Chemical compound COC=CC(C)C NDACTLNPNAMFLK-UHFFFAOYSA-N 0.000 description 1
- YOWQWFMSQCOSBA-UHFFFAOYSA-N 2-methoxypropene Chemical compound COC(C)=C YOWQWFMSQCOSBA-UHFFFAOYSA-N 0.000 description 1
- DQZVSZVABWENGU-UHFFFAOYSA-N 2-methyl-3-(2-methyl-5-prop-1-en-2-ylcyclopenten-1-yl)propanal Chemical compound O=CC(C)CC1=C(C)CCC1C(C)=C DQZVSZVABWENGU-UHFFFAOYSA-N 0.000 description 1
- VDSHBKQGQVFNIH-UHFFFAOYSA-N 2-methyl-3-(2-methyl-5-prop-1-en-2-ylcyclopenten-1-yl)propanoic acid Chemical compound OC(=O)C(C)CC1=C(C)CCC1C(C)=C VDSHBKQGQVFNIH-UHFFFAOYSA-N 0.000 description 1
- MCOLWCWFSIVJRV-UHFFFAOYSA-N 3-(2-methyl-5-prop-1-en-2-ylcyclopenten-1-yl)propanoic acid Chemical compound CC(=C)C1CCC(C)=C1CCC(O)=O MCOLWCWFSIVJRV-UHFFFAOYSA-N 0.000 description 1
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 1
- PCFHYANYPQEMPU-UHFFFAOYSA-N 4-(2,2,3-trimethyl-5-bicyclo[2.2.1]heptanyl)cyclohexan-1-ol Chemical compound CC1(C)C(C)C2CC1CC2C1CCC(O)CC1 PCFHYANYPQEMPU-UHFFFAOYSA-N 0.000 description 1
- DMGPXLFAXQJGKK-UHFFFAOYSA-N 4-(2-methyl-5-prop-1-en-2-ylcyclopenten-1-yl)butan-2-one Chemical compound CC(=O)CCC1=C(C)CCC1C(C)=C DMGPXLFAXQJGKK-UHFFFAOYSA-N 0.000 description 1
- ZOZSJYCYIPAERC-UHFFFAOYSA-N 4-(2-methyl-5-propan-2-ylcyclopenten-1-yl)butan-2-one Chemical compound CC(C)C1CCC(C)=C1CCC(C)=O ZOZSJYCYIPAERC-UHFFFAOYSA-N 0.000 description 1
- 240000007185 Albizia julibrissin Species 0.000 description 1
- 235000011468 Albizia julibrissin Nutrition 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 238000006418 Brown reaction Methods 0.000 description 1
- 241000195940 Bryophyta Species 0.000 description 1
- 240000007436 Cananga odorata Species 0.000 description 1
- 241000218645 Cedrus Species 0.000 description 1
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 240000008772 Cistus ladanifer Species 0.000 description 1
- 235000005241 Cistus ladanifer Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005770 Eugenol Substances 0.000 description 1
- 241000116713 Ferula gummosa Species 0.000 description 1
- 235000010254 Jasminum officinale Nutrition 0.000 description 1
- 240000005385 Jasminum sambac Species 0.000 description 1
- 239000004869 Labdanum Substances 0.000 description 1
- 235000019501 Lemon oil Nutrition 0.000 description 1
- SUAUILGSCPYJCS-UHFFFAOYSA-N Musk ambrette Chemical compound COC1=C([N+]([O-])=O)C(C)=C([N+]([O-])=O)C=C1C(C)(C)C SUAUILGSCPYJCS-UHFFFAOYSA-N 0.000 description 1
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 1
- 241000219492 Quercus Species 0.000 description 1
- 244000303379 Styrax officinalis Species 0.000 description 1
- 235000001361 Styrax officinalis Nutrition 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- QUMXDOLUJCHOAY-UHFFFAOYSA-N alpha-methylbenzyl acetate Natural products CC(=O)OC(C)C1=CC=CC=C1 QUMXDOLUJCHOAY-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 229940062909 amyl salicylate Drugs 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010619 basil oil Substances 0.000 description 1
- 229940018006 basil oil Drugs 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001444 canarium indicum l. oil Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000010634 clove oil Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 150000001941 cyclopentenes Chemical class 0.000 description 1
- CWRKZMLUDFBPAO-UHFFFAOYSA-N dec-4-enal Chemical compound CCCCCC=CCCC=O CWRKZMLUDFBPAO-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- VWWMOACCGFHMEV-UHFFFAOYSA-N dicarbide(2-) Chemical compound [C-]#[C-] VWWMOACCGFHMEV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- NYNCZOLNVTXTTP-UHFFFAOYSA-N ethyl 2-(1,3-dioxoisoindol-2-yl)acetate Chemical compound C1=CC=C2C(=O)N(CC(=O)OCC)C(=O)C2=C1 NYNCZOLNVTXTTP-UHFFFAOYSA-N 0.000 description 1
- 229960002217 eugenol Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000004864 galbanum Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RBBOWEDMXHTEPA-UHFFFAOYSA-N hexane;toluene Chemical compound CCCCCC.CC1=CC=CC=C1 RBBOWEDMXHTEPA-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000171 lavandula angustifolia l. flower oil Substances 0.000 description 1
- 239000010501 lemon oil Substances 0.000 description 1
- 229930007744 linalool Natural products 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- BRMYZIKAHFEUFJ-UHFFFAOYSA-L mercury diacetate Chemical compound CC(=O)O[Hg]OC(C)=O BRMYZIKAHFEUFJ-UHFFFAOYSA-L 0.000 description 1
- KEAMHLARELVHDQ-UHFFFAOYSA-N methyl 3-(2-methyl-5-prop-1-en-2-ylcyclopenten-1-yl)propanoate Chemical compound COC(=O)CCC1=C(C)CCC1C(C)=C KEAMHLARELVHDQ-UHFFFAOYSA-N 0.000 description 1
- 235000011929 mousse Nutrition 0.000 description 1
- JROJIDFJTHBZBD-UHFFFAOYSA-N n,n-dimethoxypropan-2-amine Chemical compound CON(OC)C(C)C JROJIDFJTHBZBD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000001738 pogostemon cablin oil Substances 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 238000000526 short-path distillation Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000010679 vetiver oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/21—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing rings other than six-membered aromatic rings
-
- 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
- C07C45/51—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
- C07C45/513—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 etherified hydroxyl group
-
- 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
- C07C45/51—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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
- C11B9/003—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing less than six carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
- Cosmetics (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
19, Juli 1976July 19, 1976
PatentanwältePatent attorneys
Dr Fr.«Lederer 2365939 Dr Fr. «Lederer 2365939
6510/83-001 6510/8 3-001
L. Givaudan & Cie Societe Anonyme, Vernier-Geneve (Schweiz)L. Givaudan & Cie Societe Anonyme, Vernier-Geneve (Switzerland)
Die Erfindung betrifft Cyclopentene und ein Verfahren zu deren Herstellung. Die erfindungsgemässen Cyclopentene haben die FormelThe invention relates to cyclopentene and a process for their preparation. The cyclopentene according to the invention have the formula
worin R Hydroxy oder Niederalkoxy undwherein R is hydroxy or lower alkoxy and
2
R Wasserstoff, Niederalkyl oder Nieder-2
R is hydrogen, lower alkyl or lower
' alkyliden'alkylidene
darstellen und die gestrichelt gezeichnete Linie eine fakultative Bindung bedeutet.represent and the dashed line means an optional bond.
609850/108S609850 / 108S
In der Torliegenden Anmeldung definiert der Ausdruck "Nieder-" in Zusammenhang mit Alkyl-, Alkoxy- oder Alkylidenresten Gruppen mit bis zu 6 Kohlenstoff atomen«The expression defines in the registration at the door "Lower" in connection with alkyl, alkoxy or alkylidene radicals Groups with up to 6 carbon atoms «
Die Erfindung betrifft ferner die Verwendung der Verbindungen der Formel I als Riechstoffe sowie Riechst of fkomposi· tionen, gekennzeichnet durch einen Gehalt an einer Verbindung der Formel I. -The invention also relates to the use of the compounds of the formula I as fragrances and fragrances of fkomposi · functions, characterized by a content of a compound of the formula I. -
Untergruppen von erfindungsgemässen Verbindungen der Formel I werden durch die folgenden Formeln Ia und Ib beschrieben Subgroups of compounds of the formula I according to the invention are described by the following formulas Ia and Ib
IaYes
IbIb
in denen R und die gestrichelt gezeichnete Linie die oben angegebenen Bedeutungen haben und R einen Uiederalkylrest darstelltein which R and the dashed line have the meanings given above and R is a lower alkyl radical
Das" erfindungsgemässe Verfahren ist dadurch gekennzeichnet , dass man eine Verbindung der FormelThe "inventive method is characterized in that a compound of the formula
■6Q9850/108S■ 6Q9850 / 108S
IIII
in Gegenwart eines sauren Katalysators mit einem Enoläther der Formelin the presence of an acidic catalyst with an enol ether the formula
oder einem entsprechenden Acetal der Formelor a corresponding acetal of the formula
worin R einen Niederalkylrest darstellt undwherein R represents a lower alkyl radical and
R Wasserstoff, Niederalkyl oder Nieder-R is hydrogen, lower alkyl or lower
alkenyl bedeutet,alkenyl means
'umsetzt, gegebenenfalls eine erhaltene 3-Isopropeny!verbindung katalytisch zu der entsprechenden 3-Isopropy!verbindung hydriert, einen erhaltenen Aldehyd der Formel'converts, possibly a 3-isopropeny! compound obtained catalytically hydrogenated to the corresponding 3-isopropyl compound, an obtained aldehyde of the formula
IIIIII
zur entsprechenden Säure der Formelto the corresponding acid of the formula
R2 R 2
609850/1089609850/1089
IaYes
oxydiert und gewünschtenfalls diese in einen entsprechenden Ester der Formel 'oxidized and, if desired, this into a corresponding one Ester of the formula '
•worin Ir eine Niederalkylgruppe darstellt, überführt.• where Ir represents a lower alkyl group, convicted.
Bei der erfindungsgemässen Umsetzung ist es vorteilhaft, den Enoläther in Ueberschuss einzusetzen, wobei etwa 3 Aequivalente ausreichen. Verwendet man anstelle des Enoläthers das entsprechende Acetal, so werden-etwas geringere Ausbeuten an Verbindungen in erhalten. ' . ...In the implementation according to the invention, it is advantageous to use the enol ether in excess, with about 3 equivalents sufficient. If the corresponding acetal is used instead of the enol ether, the yields are somewhat lower to get connections in. '. ...
Die Umsetzung findet in Gegenwart eines sauren Katalysators statt. Als katalytisch wirksames saures Mittel verwendet manzweckmässigerweise starke Mineralsaüren wie Schwefel- oder Phosphorsäure, saure Salze wie z„B«, Kaliumbisulfat, Pyridinhydrochlorid oder Quecksilberacetat, starke organische Säuren .wie z.B. p-Toluolsulfonsäure 8 Oxalsäure und Trichloressigsäure oder Lewis-Säuren wie z.B» Zinkchlorid oder Bort-rifluoridätherat. Die Konzentration des Katalysators in Reaktionsgemisch beträgt zweckmässig etwa Ο,ΟΙ-Ι,Ο?^ vorzugs'rfeise etwa 0sl-0,3^.The reaction takes place in the presence of an acidic catalyst. As catalytically active acidic agent used manzweckmässigerweise strong Mineralsaüren such as sulfuric or phosphoric acid, acid salts, such as "B", potassium bisulfate, pyridine hydrochloride or mercuric acetate, strong organic acids .as for example, p-toluenesulfonic acid 8 oxalic acid and trichloroacetic acid, or Lewis acids such as "zinc chloride or boron rifluoride etherate. The concentration of the catalyst in the reaction mixture is expediently about Ο, ΟΙ-Ι, Ο? ^ Preferably about 0 s l-0.3 ^.
• Die Umsetzung kann sowohl mit als auch ohne LösungsndLttel durchgeführt werden« Als Lösungsmittel können zäB. Kohlenwasserstoffe wie Benzol, 'Toluol^ Hexan? Heptan,, Isooctan oder Petroläther verwendet werden» ITach einer speziellen Ausführungsfors wird während der Reaktion das Lösungsmittel und/oder der• The reaction can be both performed without LösungsndLttel as "The solvents can, like, hydrocarbons such as benzene, '^ toluene hexane? Heptane, isooctane or petroleum ether can be used. According to a special execution, the solvent and / or the
609S5"0/108S " " ' ' ■ . ■609S5 "0 / 108S" "'' ■. ■
während der Reaktion entstehende Alkohol abdestilliert.alcohol formed during the reaction is distilled off.
. ' ' ; Die Reaktion wird vorzugsweise "bei erhöhter Temperatur, beispielsweise oberhalb 500C, insbesondere bei der Rückfluss-•fceraperatur des Reaktionsgemisches, durchgeführt. Es kann unter Normaldruck wie auch unter Ueberdruck gearbeitet werden. Die Vervrendung eines Inertgases, wie z.B. Stickstoff oder Argon, ist bevorzugt. In einer speziellen Ausführungsforni wird die umsetzung in einem Autoklaven durch Erhitzen unter Inertgas auf eine Innentemperatur von etwa 150° durchgeführt. Das Ende der Reaktion macht sich durch einen deutlichen Druckabfall bemerkbar.. ''; The reaction is preferably "at elevated temperature, for example above 50 0 C, especially in the backflow • fceraperatur of the reaction mixture, carried out. It can be carried out under normal pressure as well as under positive pressure. The Vervrendung of an inert gas such as nitrogen or argon, is In a special embodiment, the reaction is carried out in an autoclave by heating under an inert gas to an internal temperature of about 150 ° C. The end of the reaction is indicated by a marked drop in pressure.
Die katalytische Hydrierung einer 3-Isopropenylverbindung der Formel III zur entsprechenden 3-Isopropylverbindung kann in an sich bekannter V/eise in Gegenwart von beispielsweise einem Edelmetall, vorzugsweise Palladium oder Platin,ggf. auf einem geeigneten Träger, vorzugsweise auf Calciumcarbonat oder Bariumsulfat, erfolgen. ■The catalytic hydrogenation of a 3-isopropenyl compound of formula III to the corresponding 3-isopropyl compound can in a known manner in the presence of, for example, a noble metal, preferably palladium or platinum, if necessary. on a suitable carrier, preferably on calcium carbonate or barium sulfate. ■
Die Oxydation von Aldehyden der Formel in zu den entsprechenden Säuren der Formel la kann in an sich bekannter Weise erfolgen, z.B. mit Jones-Reagens (CrO^/HpSO.). Ebenso . The oxidation of aldehydes of the formula in to the corresponding acids of the formula la can be carried out in a manner known per se, for example with Jones reagent (CrO ^ / HpSO.). As well .
können, die Säuren Ia in an sich bekannter Weise in die Hiederalky!ester der Formel Ib übergeführt werden.can, the acids Ia in a known manner in the Lower alkyl esters of the formula Ib are converted.
. Die Verbindungen der Formel I zeichnen sich durch besondere Riechstoffeigenschaften, insbesondere durch frische, holzige, camphrige, würzige, teilweise auch blumige ,"""esterartige oder schwach süssliche Geruchsnoten aus. Sie können ' demgemäss als Riechstoffe zur Herstellung von Riechstoffkompositionen, wie Parfüms und Parfümbasen, bzw. zur Parfümierung von technischen und kosmetischen Produkten aller Art, z.B. von festen und flüssigen Detergentien, synthetischen. The compounds of the formula I are distinguished by particular fragrance properties, in particular by fresh, woody, camphor-like, spicy, sometimes also flowery, """ester-like or slightly sweet odor notes , or for perfuming technical and cosmetic products of all kinds, such as solid and liquid detergents, synthetic
609850/1089 '609850/1089 '
Waschmitteln, Aerosolen, Seifen, Cremes oder Lotionen Verwendung finden. . .Use detergents, aerosols, soaps, creams or lotions Find. . .
Geeignete Konzentrationen der erfindungsgenäss erhältlichen Verbindungen sind bei Verwendung als Riechstoff in Parfümkoapositionen 1-30$, in Fertigprodukten wie Shampoos, Seifen, Lotionen etc. etwa 0,001-1^.Suitable concentrations of the compounds obtainable according to the invention are when used as a fragrance in perfume co-positions $ 1-30, in finished products such as Shampoos, soaps, lotions, etc. about 0.001-1 ^.
Die Verbindungen der Formel I sind ferner Ausgangsverbindungen für die Herstellung von Produkten, die ebenfalls Riechstoff- bzw. Aromastoffeigenschaften besitzen und entsprechend verwendet werden können.The compounds of the formula I are also starting compounds for the production of products that also Have fragrance or flavor properties and can be used accordingly.
S088S0/1089S088S0 / 1089
■ Reaktionsscherna■ reaction scheme
III'-lIII'-l
1111
IV'-lIV'-l
1111
R- R -
R IV"-1R IV "-1
609850/1089609850/1089
Verbindungen der Formel I, in denen R Wasserstoff oder Niederalkyl'darstellt (i'-l bzw» 1"-I)1, können beispielsweise durch die im vorstehenden Schema dargestellte Reaktionsfolge in Verbindungen vom Spiran- bzw* Azulentyρ übergeführt werden.Compounds of the formula I in which R represents hydrogen or lower alkyl (i'-1 or »1" -I) 1 can be converted, for example, into compounds of spirane or azulentyρ by the reaction sequence shown in the above scheme.
Die Cyclopentene der Formeln III8-l bzw. III"-1 können in an sich bekannter V/eise aus den Verbindungen I!-l bzw. I"-l durch Umsetzung mit einer metallorganischen Verbindungf insbesondere nit einem Alkalimetallacetylid oder mit einer Grignardverbindung der FormelThe cyclopentene of the formulas III 8 -1 or III "-1 can be prepared in a known manner from the compounds I ! -1 or I" -1 by reaction with an organometallic compound f, in particular with an alkali metal acetylide or with a Grignard compound the formula
MgHaIMgHaI
worin B7 Wasserstoff oder Methyl und Hai Chlorwhere B7 is hydrogen or methyl and Hal is chlorine
oder Brom darstellt,
erhalten werden.or represents bromine,
can be obtained.
Falle der Umsetzung mit einem Acetylid ist es erforderlich,· die zunächst erhaltene Verbindung der FornelIt is the case of the reaction with an acetylide required · the connection of the formula initially obtained
OH VI-IOH VI-I
worin R Wassserstoff oder Niederalkyl darstelltwherein R is hydrogen or lower alkyl
2 ·2 ·
R die oben angegebene Bedeutung hat,R has the meaning given above,
in an sich "bekannter Weise,, doh» in Gegenwart eines Lindlar- · Katalysators (Pd/CaCO~ mit PbO vergiftet), katalytisch partiell &tt hydrieren. ·in a manner known per se "doh" in the presence of a Lindlar · Catalyst (Pd / CaCO ~ poisoned with PbO), catalytic partial & tt hydrogenate. ·
■ S098B0/10II "■ S098B0 / 10II "
Die Verbindungen der Formeln III'-l bzw. III"-1 können dann unter Dehydratisierung zu den Verbindungen IV'-1 bzw. rV"-l cyclisiert werden. Die dehydratisierende Cyclisierung kann in an sich bekannter Weise durchgeführt werden. Als Cyclisationsmittel verwendet man zweckmässig starke anorganische oder organische Protonensäuren, wie z.B. Schwefelsäure, Phosphorsäure, p-Toluolsulfonsäure oder Trichloressigsäure, saure Salze wie Kaliumbisulfat oder Lewis-Säuren, wie z.B. Zinntetrachlorid, Aluminiumtrichlorid oder Bortrifluoridätherat. Als Lösungsmittel kommen beispielsweise aliphatisch^ und aromatische Kohlenwasserstoffes die ggf. chloriert oder nitriert sein können, oder Aether in Frage, wie Benzol, Toluol, Hexan, Heptan, Isooctan, Diäthyläther, Dioxan und Tetrahydrofuran. Die Reaktionstemperatur kann bei etwa -30° bis etwa 12O0C liegen; sie liegt vorzugsweise etwa zwischen 0° und Raumtemperatur.The compounds of the formulas III'-1 or III "-1 can then be cyclized with dehydration to give the compounds IV'-1 or rV" -l. The dehydrating cyclization can be carried out in a manner known per se. Strong inorganic or organic protic acids such as sulfuric acid, phosphoric acid, p-toluenesulfonic acid or trichloroacetic acid, acid salts such as potassium bisulfate or Lewis acids such as tin tetrachloride, aluminum trichloride or boron trifluoride etherate are expediently used as cyclizing agents. Suitable solvents are, for example, aliphatic and aromatic hydrocarbons, which may optionally be chlorinated or nitrated, or ethers, such as benzene, toluene, hexane, heptane, isooctane, diethyl ether, dioxane and tetrahydrofuran. The reaction temperature may be about -30 ° to about 12O 0 C; it is preferably approximately between 0 ° and room temperature.
' Als Nebenprodukte können bei der Cyclisierung einer Verbindung der Formel III'-1 Verbindungen der Formeln VII-I ■und VIII-I entstehen'As by-products in the cyclization of a compound of the formula III'-1 compounds of the formulas VII-I ■ and VIII-I arise
VII-IVII-I
VIII-IVIII-I
worin R , R und R die oben genannten Bedeutungen ' .haben und .. . .- ......in which R, R and R have the meanings given above '.have and ... .- ......
R11' C1-6-AUCyllden darstellt.R 11 'represents C 1-6 AU clusters.
Bei der Cyclisierung von Verbindungen der Formel III"-1In the cyclization of compounds of the formula III "-1
609850/1089 ' ■609850/1089 '■
kann man neben den Verbindungen der Formel IV-I Verbindungen vom Azulentyp der Formel V"-l in Ausbeuten bis zu etwa 70^ erhalten.can be used in addition to the compounds of the formula IV-I compounds of the azul type of the formula V "-l in yields of up to about 70 ^ obtain.
Beispiel 1 ■ m .Example 1 ■ m .
Zu einem in einem Laborautoklaven gekühlten Gemisch von 76 g 3-Isopropenyl-l-methyl~2-methylen-cyclopentan-l-ol und 120 g Isopropenylmethylather -wurden 15 Tropfen 85/Sige Phosphorsäure gegeben. Hach Begasung mit Stickstoff 'wurde der Autoklav in einem Oelbad von ISO0 auf eine Innenteaiperatur von 150° gebracht und bis zu einem deutlichen Druckabfall auf dieser Temperatur gehalten (etwa 50-75 Minuten). Das Keaktionsgemisch wurde durch Intensivkühlung abgeschreckt, mit fester Pottasche versetzt und unter vermindertem Druck am Rotationsverdampfer eingeengt. Durch fraktionierte Destillation über fester Pottasche wurden 58 g (βΟ/ί) 3-Iso- ·15 drops of 85% phosphoric acid were added to a mixture, cooled in a laboratory autoclave, of 76 g of 3-isopropenyl-1-methyl-2-methylenecyclopentan-1-ol and 120 g of isopropenyl methyl ether. After gassing with nitrogen, the autoclave was brought to an internal temperature of 150 ° in an ISO 0 oil bath and kept at this temperature until there was a significant drop in pressure (about 50-75 minutes). The reaction mixture was quenched by intensive cooling, solid potash was added and the mixture was concentrated under reduced pressure on a rotary evaporator. By fractional distillation over solid potash, 58 g (βΟ / ί) 3-iso-
propenyl-l-methyl--2-(3-oxobutyl)-cyclopent-l-en, Kp.Λ m = pn usuxpropenyl-l-methyl - 2- (3-oxobutyl) -cyclopent-l-ene, bp. Λ m = pn u s ux
69772°, nz = 1,4836, erhalten. Die Verbindung hat einen holzigen, camphrigen, jononartigen Geruch.69772 °, nz = 1.4836, is obtained. The compound has a woody, camphor-like, ionic odor.
' Beispiel 2 ' Example 2
4 g 3-Isopropenyl-l-methyl-2-(3-oxobutyl)-cyclopent-l-en wurden in 50 ml Aethylacetat in Gegenwart von 400 mg Palladium auf Calciumcarbonat (5/^ig) hydriert. Nach Aufnahme von einem Aequivalent Wasserstoff wurde die Lösung über Gelite filtriert s eingeengt und unter Hochvakuum destilliert. Es ^mrden 4 g 3-Isopropyl-l-methyl-2-(3-oxobutyl)-cyclopent-l-en erhalten^4 g of 3-isopropenyl-l-methyl-2- (3-oxobutyl) -cyclopent-l-ene were hydrogenated in 50 ml of ethyl acetate in the presence of 400 mg of palladium on calcium carbonate (5%). After uptake of one equivalent of hydrogen, the solution was filtered Gelite s concentrated and distilled under high vacuum. 4 g of 3-isopropyl-1-methyl-2- (3-oxobutyl) -cyclopent-1-ene were obtained
^-0,0O5 et5 70°· 4 =.1.4709, τΒη3Λ^Μα = 1725, 1390/70 und 1170 cm . Die Verbindung hat einen holzigen s "blumigen Geruch. ^ -0.0O 5 et 5 70 ° 4 = .1.4709, τΒ η3Λ ^ Μα = 1725, 1390/70 and 1170 cm . The compound has a woody s "flowery odor.
609B50/108609B50 / 108
Zu einem in einem Laborautoklaven auf -15° abgekühlten Gemisch von 76 g 3-Isopropenyl-l-nethyl-2-methylen~cyclopentan-1-ol und 72 g Aethylvinyläther wurden 12 Tropfen 85^ige Phosphorsäure gegeben. Nach Begasung mit Argon wurde der Autoklav in einem Oelbad von 180° auf eine Innentemperatur von 150° gebracht, was etwa 15 Minuten dauerte, und bis zu einem deutlichen Druckabfall auf dieser Temperatur gehalten (etwa 100 Hinuten). Das Reaktionsgeaisch wurde dann abgeschreckt, in Aether aufgenommen, mit wässriger Bicarbonatlösung und V/asser gewaschen, die Lösung über wasserfreiem Magnesiumsulfat getrocknet und unter vermindertem Druck eingeengt. Das als gelbes OeI erhaltene Rohprodukt (110 g) wurde fraktioniert und lieferte 61 g (68fo) reines 2-(2-Fonnyläthyl)-3-isopropenyl-l-inethyl-cyclopent-l-en mit holzigem,12 drops of 85% phosphoric acid were added to a mixture, cooled to -15 ° in a laboratory autoclave, of 76 g of 3-isopropenyl-1-methyl-2-methylenecyclopentan-1-ol and 72 g of ethyl vinyl ether. After gassing with argon, the autoclave was brought to an internal temperature of 150 ° in an oil bath at 180 °, which took about 15 minutes, and was kept at this temperature until a significant drop in pressure (about 100 minutes). The reaction mixture was then quenched, taken up in ether, washed with aqueous bicarbonate solution and water, the solution was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The crude product obtained as a yellow oil (110 g) was fractionated and yielded 61 g (68fo) of pure 2- (2-formylethyl) -3-isopropenyl-1-ynethyl-cyclopent-1-ene with woody,
onon
erdigem Geruch; Kp.0j2 = 64-65°; n£u = 1,4888: 1^^^ = 3080, 2725, 1725, 1642, 1440, 1370, 1060 und 895 cm-1.earthy smell; Bp 0j2 = 64-65 °; n £ u = 1.4888: 1 ^^^ = 3080, 2725, 1725, 1642, 1440, 1370, 1060 and 895 cm- 1 .
3,6 g 2-(2-Formyläthyl)-3-isopropenyl-l-methyl-cyclopen-i 1-en wurden in 80 ml Aethylacetat in Gegenwart von 500 mg Palladium auf Calciumcarbonat (5S^ig) hydriert. Nach Aufnahme von einem Aequivalent Viasserstoff wurde die Lösung über Celite filtriert, eingeengt und unter Hochvakuum der Kurzwegdestillation unterworfen..Es wurde 2-(2-Forinyläthyl)-3-isopropyl-1-methyl-cyclopent-l-en von frischem, holzigem Geruch in quantitativer Ausbeute erhalten, Kp. n nn, etwa = 1,4703, ^Pilm^max = 2740, 1728, 1470, 1335,3.6 g of 2- (2-formylethyl) -3-isopropenyl-1-methyl-cyclopen-i 1-en were hydrogenated in 80 ml of ethyl acetate in the presence of 500 mg of palladium on calcium carbonate (5S ^ ig). After taking up one equivalent of hydrogen, the solution was filtered through Celite, concentrated and subjected to short-path distillation under high vacuum. 2- (2-Forinylethyl) -3-isopropyl-1-methyl-cyclopent-1-ene had a fresh, woody odor obtained in quantitative yield, bp n nn , about = 1.4703, ^ Pilm ^ max = 2740, 1728, 1470, 1335,
1368 und 1100 cm"1 1368 and 1100 cm " 1
609850/1089609850/1089
Eine Lösung von 25 g 2-(2-Forinyläthyl)-3--isopropenyl-1-methyl-cyclopent-l-en in 1200 ml Aceton wurde bei -10° mit 55 ml Jones-Reagens versetzt. Das braune Reaktionsgemisch wurde auf Sis/lvatriunibicarbonatlQsung gegossen, Aetherextraktion, Neutralwaschen mit JTatriumbicarbonat-, gesättigter Natriunchloridlösung und Wasser, Trocknung des Extraktes mit Magnesiumsulfat und Entfernung des Lösungsmittels unter vermindertem Druck lieferte 20 g (80;$) eines schwach gelben, öligen Rohproduktes, aus dem durch Destillation 15 g reines 2-(2~Carboxyäthyl)-3-isopropenyl-l-meth.yl-cyclopent-1-en erhalten wurden, Kp.Q Q = 102°, 1^p11111 1 v aax= 3600-A solution of 25 g of 2- (2-forinylethyl) -3 - isopropenyl-1-methyl-cyclopent-1-ene in 1200 ml of acetone was treated with 55 ml of Jones reagent at -10 °. The brown reaction mixture was poured onto sodium bicarbonate solution, ether extraction, washing neutral with sodium bicarbonate, saturated sodium chloride solution and water, drying of the extract with magnesium sulfate and removal of the solvent under reduced pressure yielded 20 g (80%) of a pale yellow, oily crude product 15 g of pure 2- (2 ~ carboxyethyl) -3-isopropenyl-1-meth.yl-cyclopent-1-ene were obtained by distillation, b.p. QQ = 102 °, 1 ^ p 11111 1 v aax = 3600-
2400, 1720, 1645, 1450, 1420, 1380, 1330, 1290, 1220, 1085, 945 und 900 cm" . Die Verbindung hat einen holzigen, würzigen, schwach süsslichen und etwas muffigen Geruch.2400, 1720, 1645, 1450, 1420, 1380, 1330, 1290, 1220, 1085, 945 and 900 cm ". The compound has a woody, spicy, slightly sweet and somewhat musty odor.
Ein Gemisch aus 2 g 2-(2-Carboxyäthyl)-3-isopropenyll-methyl~cyclopent~l-en, 150 ml absolutem Benzol und 4 ml Dimethoxy-dimethylamino-methan wurde 5 Stunden zum Rückfluss erhitzt. Die Lösung wurde eingeengt und der als rotes OeI erhaltene Rückstand an 50 g Kieselgel mit Hexan/Aether (19:1) chromatographiert. Es wurden 1,95 g (91$) 2-(2-Carbomethoxyäthyl)-3-isopropenyl-l-methyl-cyclopent-l-en erhalten,A mixture of 2 g of 2- (2-carboxyethyl) -3-isopropenyl-methyl-cyclopent-1-ene, 150 ml of absolute benzene and 4 ml of dimethoxy-dimethylamino-methane was used for 5 hours Heated to reflux. The solution was concentrated and the residue obtained as red oil on 50 g of silica gel with hexane / ether (19: 1) chromatographed. 1.95 g ($ 91) of 2- (2-carbomethoxyethyl) -3-isopropenyl-1-methyl-cyclopent-1-ene were obtained obtain,
onon
Kp.OfO1 etwa 700, n™ = ls476l> ir^.^ β 5100, 1742, 1645,Kp. OfO1 about 700, n ™ = ls476l> ir ^. ^ Β 5 100, 1742, 1645,
1440, 1375, 1330, 1255, 1195, 1170, 1085, 1025, 990, 895 "und 840 cm"* . Die Verbindung hat einen blumigen, holzigen, esterartigen Geruch.1440, 1375, 1330, 1255, 1195, 1170, 1085, 1025, 990, 895 "and 840 cm" *. The compound has a flowery, woody, ester-like odor.
6098 50/10896098 50/1089
Zu einem in einem Laborautoklaven auf -30° gekühlten Gemisch von 76 g 3-Isopropenyl-l-methyl-2-methylencyclopentaii-1-ol und 130 g Aethyl-1-propenyl-äther wurden 15 Tropfen 85&Lge Phosphorsäure gegeben. Nach Begasung mit Stickstoff -wurde der Autoklav in einem Oelbad von ISO0 auf eine Innentemperatur von 150° gebracht, was etwa 15 Minuten .dauerte, und bis zu einem deutlichen Druckabfall (etwa 75 Minuten) auf dieser Temperatur gehalten. Das Reaktionsgemisch wurde dann abgeschreckt, in Aether aufgenormen, mit wässriger Bicarbonatlösung und Wasser gewaschen, die Lösung über wasserfreiem MagneSi1ImSuIfat getrocknet und unter vermindertem Druck eingeengt. Das als gelbes OeI erhaltene Rohprodukt (135 g) wurde fraktioniert und lieferte 64 g (67$) reines 2-(2-?orayipropyl)-3-isopropenyl-l-methyl-cyclopent-l-en mit holzigem,15 drops of 85% phosphoric acid were added to a mixture, cooled to -30 ° in a laboratory autoclave, of 76 g of 3-isopropenyl-1-methyl-2-methylenecyclopentai-1-ol and 130 g of ethyl 1-propenyl ether. After gassing with nitrogen, the autoclave was brought to an internal temperature of 150 ° in an ISO 0 oil bath, which took about 15 minutes, and was kept at this temperature until there was a significant drop in pressure (about 75 minutes). The reaction mixture was then quenched standards up in ether, washed with aqueous bicarbonate and water, the solution over anhydrous Magnesi 1 ImSuIfat dried and concentrated under reduced pressure. The crude product obtained as a yellow oil (135 g) was fractionated and gave 64 g (67 $) of pure 2- (2-? Orayipropyl) -3-isopropenyl-l-methyl-cyclopent-l-ene with woody,
2020th
•erdigem, muffigem Geruch, Kp. Q 0Qr. - 51°,. nß = 1,4825,• earthy, musty smell, Kp. Q 0Qr . - 51 ° ,. n ß = 1.4825,
XßFilm:v)max = 3°90' 2730' 173^ lß45, 1460, 1380 und 893 cm""1. Xβ film : v) max = 3 ° 90 ' 2730 ' 173 ^ l3 45, 1460, 1380 and 893 cm "" 1 .
Iu Analogie su der in Beispiel 5 beschriebenen Weise wurden 18 g 2-(2-Formylpropyl)-3-isopropenyl-l-methylcyclopent-1-en zu 2-(2-Carboxypropyl)-3-isopropenyl-lmethyl-cyclopent-1-en (Ausbeute 13,2 g = 68$) oxydiert,Iu analogy to the manner described in Example 5 18 g of 2- (2-formylpropyl) -3-isopropenyl-1-methylcyclopent-1-ene were obtained to 2- (2-carboxypropyl) -3-isopropenyl-1-methyl-cyclopent-1-ene (Yield 13.2 g = 68 $) oxidized,
max
1460, 1440, 1418, 1375, 1290, 1245, 940 und 895 cm""1. ·
Die Verbindung hat einen schwach holzig säuerlichen Geruch.Max
1460, 1440, 1418, 1375, 1290, 1245, 940 and 895 cm "" 1 . · The compound has a slightly woody, sour odor.
In Analogie zu der in Beispiel 6 beschriebenen V/eise wurden 3,12 g 2-(2-Cärbo::ypropyl)-3-isopropenyl-l-methylcyclopent-1-en verestert. Das ölige Rohprodukt wurde anIn analogy to the procedure described in Example 6, 3.12 g of 2- (2-Carbo :: ypropyl) -3-isopropenyl-1-methylcyclopent-1-ene were obtained esterified. The oily crude product was on
60 98.5 0 / 1 08960 98.5 0/1 089
100 g Kieselgel rait Hexan/Aether (95°1) chromatographiert. Nach Destillation im Hochvakuum wurden 2,96 g (37?°) reines 2-(2-Carbomethozypropyl)-3-isopropenyl-l--:nethyl-cyclopent--l-en erhalten; Ep.OfO2 = 70°, ΐξ° = 1,4728, IRpill3: >> .aax = 3090, 1740, 1642, 1460, 1435, 1370, 1325, 1285, 1250, 1195, 1170, 1120, 1085, 1060, 1035, 990, 890, 835 und 765 cm"1. Die Verbindung hat einen carapherartigen Geruch.100 g of silica gel with hexane / ether (95 ° 1) are chromatographed. After distillation in a high vacuum, 2.96 g (37 °) of pure 2- (2-carbomethozypropyl) -3-isopropenyl-1 -: ethyl-cyclopent-1-ene were obtained; Ep. OfO2 = 70 °, ΐξ ° = 1.4728, IR pill3 : >>. aax = 3090, 1740, 1642, 1460, 1435, 1370, 1325, 1285, 1250, 1195, 1170, 1120, 1085, 1060, 1035, 990, 890, 835 and 765 cm " 1. The compound has a caraphor-like odor.
- Beispiel 10 - Example 10
Nach der in Beispiel 7 beschriebenen Methode wurde durch Umsetzung von 30,-4 g 3-Isopropenyl-l-methyl-2-methylen-cyelopentan-1-ol mit 50 g I<Iethyl-(3-methyl-l-butenyl)-äther in Gegenwart von 7 Tropfen 85$iger Phosphorsäure 2-(2-Fomyl-3-methyl~butyl)-3-isopropenyl-l-methyl-cyclopent-l-en According to the method described in Example 7, by reacting 30.4 g of 3-isopropenyl-1-methyl-2-methylenecyelopentan-1-ol with 50 g of methyl (3-methyl-1-butenyl) ether in Presence of 7 drops of 85% phosphoric acid 2- (2-formyl-3-methyl-butyl) -3-isopropenyl-1-methyl-cyclopent-1-ene
20 in 455&iger Ausbeute dargestellt, Kp. Q 0QC- = 55-56°, n^ = 1,4808, IRpilm:^max =3080, 2725, 1725, 1642, 1460/40s 1390/70 und 890 cm*"-1·. Die Verbindung hat einen cedrigen, holzigen, entfernt blumigen Geruch. " .20 shown in 455% yield, bp. Q 0QC - = 55-56 °, n ^ = 1.4808, IRp ilm : ^ max = 3080, 2725, 1725, 1642, 1460/40 s 1390/70 and 890 cm * " - 1 ·. The compound has a cedar, woody, vaguely floral odor. ".
Ein Gemisch aus 7,6 g 3-Isopropenyl-l-methyl-2-inethylencyclopentan-1-ol und 8,1 g l,l-Dimethoxy-3-niethyl-3-l3uten wurde in Gegenwart von 100 mg frisch hergestelltes, trockenes Pyridinhydrochlorid unter Stickstoff in einem Oelbad von 100° 15 Stunden erhitzt unter kontinuierlicher Entfernung dss entstehenden Methanols. Bs wurde dann 7 Stunden auf 150° erhitzt und schliesslich auf ein Gemisch aus Bis und. Aether gegossene Die ätherische Phase wurde mit Bicarbonatlösung und Wasser gewaschen, mit wasserfreies Magnesiumsulfat getrocknet und unter vermindertem Druck eingeengt „ !lach Destillation des öligen Rohproduktes wurden 6,5 g 2-(2-Forinjl= 5-methyl-2-butenyl)-3-isopropenyl~l-methjl-cjclopent-l-eaA mixture of 7.6 g of 3-isopropenyl-1-methyl-2-ynethylene cyclopentan-1-ol and 8.1 g of 1,1-dimethoxy-3-diethyl-3-13utene was in the presence of 100 mg of freshly prepared, dry pyridine hydrochloride under nitrogen in an oil bath of 100 ° heated for 15 hours with continuous removal of the resulting methanol. Bs was then at 150 ° for 7 hours heated and finally to a mixture of bis and. Ether The ethereal phase was poured with bicarbonate solution and water, dried with anhydrous magnesium sulfate and concentrated under reduced pressure after distillation of the oily crude product were 6.5 g of 2- (2-Forinjl = 5-methyl-2-butenyl) -3-isopropenyl ~ l-methjl-cjclopent-l-ea
20
erhalten, ^■ 0,^ξ%^'>fa20th
received, ^ ■ 0 , ^ ξ% ^ ' > fa
3100, 2760, 1675, 1635, 1440, 1375, 1155, 1060 und 895 ca"1. Die Verbindung hat einen holzigen, blumigen, fruchtig ßüsslichen Geruch. ·3100, 2760, 1675, 1635, 1440, 1375, 1155, 1060 and 895 approx " 1. The compound has a woody, flowery, fruity-sweet odor. ·
Beispiel 12 Komposition mit phantasiebluaiger Note: Example 12 Composition with a fancy blue note:
« - — - .Ambrette musk ...
«- - -.
* in Phthalsäurediäthy!ester 609850/1089* in phthalic acid diethyester 609850/1089
* in Phthalsäurediäthy!ester 609850/1089 "* in phthalic acid diethyester 609850/1089 "
Claims (1)
R Wasserstof f, 2Tiederal±yl oder ITiederalkylidenρ
R hydrogen, 2-lower al ± yl or IT-lower alkylidene
R Wasserstoff, ITiederalkyl oder Nieder-ρ
R hydrogen, IT lower alkyl or lower
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH404072A CH565728A5 (en) | 1972-03-17 | 1972-03-17 |
Publications (3)
Publication Number | Publication Date |
---|---|
DE2365939A1 true DE2365939A1 (en) | 1976-12-09 |
DE2365939B2 DE2365939B2 (en) | 1980-05-08 |
DE2365939C3 DE2365939C3 (en) | 1981-01-15 |
Family
ID=4268690
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19732365939 Expired DE2365939C3 (en) | 1972-03-17 | 1973-03-15 | Cyclopentenes, processes for their production and fragrance compositions |
DE19732313017 Expired DE2313017C3 (en) | 1972-03-17 | 1973-03-15 | Cyclopentenes and processes for their preparation |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19732313017 Expired DE2313017C3 (en) | 1972-03-17 | 1973-03-15 | Cyclopentenes and processes for their preparation |
Country Status (6)
Country | Link |
---|---|
JP (2) | JPS5422968B2 (en) |
CH (1) | CH565728A5 (en) |
DE (2) | DE2365939C3 (en) |
FR (1) | FR2176786B1 (en) |
GB (1) | GB1379874A (en) |
NL (2) | NL160800C (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2513995C2 (en) * | 1975-03-29 | 1984-04-12 | Basf Ag, 6700 Ludwigshafen | Cyclopentene derivatives |
GB8813557D0 (en) * | 1988-06-08 | 1988-07-13 | James River Graphics Ltd | Coating composition & coated paper |
FR2735399B1 (en) * | 1995-06-16 | 1997-07-25 | Inst Francais Du Petrole | NOVEL CATALYTIC COMPOSITION BASED ON TRANSITIONAL METAL COMPLEXES AND METHOD FOR THE HYDROGENATION OF UNSATURATED COMPOUNDS |
US6187386B1 (en) * | 1996-05-30 | 2001-02-13 | Joseph W. Hundley | Liquid sealant composition and method of using same |
-
1972
- 1972-03-17 CH CH404072A patent/CH565728A5/xx not_active IP Right Cessation
-
1973
- 1973-02-23 NL NL7302559A patent/NL160800C/en not_active IP Right Cessation
- 1973-03-15 DE DE19732365939 patent/DE2365939C3/en not_active Expired
- 1973-03-15 DE DE19732313017 patent/DE2313017C3/en not_active Expired
- 1973-03-15 JP JP3047573A patent/JPS5422968B2/ja not_active Expired
- 1973-03-16 FR FR7309483A patent/FR2176786B1/fr not_active Expired
- 1973-03-16 GB GB1266573A patent/GB1379874A/en not_active Expired
-
1978
- 1978-02-03 JP JP1137978A patent/JPS53109957A/en active Granted
-
1979
- 1979-05-28 NL NL7904191A patent/NL7904191A/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
CH565728A5 (en) | 1975-08-29 |
JPS4911850A (en) | 1974-02-01 |
DE2313017B2 (en) | 1979-07-12 |
NL7302559A (en) | 1973-09-19 |
DE2313017C3 (en) | 1980-03-20 |
NL160800C (en) | 1979-12-17 |
JPS5422968B2 (en) | 1979-08-10 |
NL7904191A (en) | 1979-09-28 |
FR2176786A1 (en) | 1973-11-02 |
FR2176786B1 (en) | 1979-01-12 |
JPS53109957A (en) | 1978-09-26 |
DE2365939B2 (en) | 1980-05-08 |
DE2313017A1 (en) | 1973-09-27 |
NL160800B (en) | 1979-07-16 |
GB1379874A (en) | 1975-01-08 |
DE2365939C3 (en) | 1981-01-15 |
JPS5440616B2 (en) | 1979-12-04 |
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