NL8104495A - NEW CYCLOPROPANIC CARBONIC ACID COMPOUNDS, PROCESS FOR THEIR PREPARATION AND USE IN THE PREPARATION OF PERFUME COMPOSITIONS. - Google Patents
NEW CYCLOPROPANIC CARBONIC ACID COMPOUNDS, PROCESS FOR THEIR PREPARATION AND USE IN THE PREPARATION OF PERFUME COMPOSITIONS. Download PDFInfo
- Publication number
- NL8104495A NL8104495A NL8104495A NL8104495A NL8104495A NL 8104495 A NL8104495 A NL 8104495A NL 8104495 A NL8104495 A NL 8104495A NL 8104495 A NL8104495 A NL 8104495A NL 8104495 A NL8104495 A NL 8104495A
- Authority
- NL
- Netherlands
- Prior art keywords
- formula
- compounds
- methyl
- dimethyl
- propenyl
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims description 28
- 238000002360 preparation method Methods 0.000 title claims description 17
- 238000000034 method Methods 0.000 title claims description 10
- 150000004649 carbonic acid derivatives Chemical class 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 61
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- -1 2,2-dichlorovinyl Chemical group 0.000 claims description 15
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical compound OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 239000002304 perfume Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 125000006020 2-methyl-1-propenyl group Chemical group 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- KPMWGGRSOPMANK-UHFFFAOYSA-N (6-chloro-1,3-benzodioxol-5-yl)methyl 2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical compound CC1(C)C(C=C(C)C)C1C(=O)OCC(C(=C1)Cl)=CC2=C1OCO2 KPMWGGRSOPMANK-UHFFFAOYSA-N 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- PZQSQRCNMZGWFT-QXMHVHEDSA-N propan-2-yl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC(C)C PZQSQRCNMZGWFT-QXMHVHEDSA-N 0.000 claims description 4
- XLOPRKKSAJMMEW-JGVFFNPUSA-N (-)-trans-chrysanthemic acid Chemical compound CC(C)=C[C@H]1[C@H](C(O)=O)C1(C)C XLOPRKKSAJMMEW-JGVFFNPUSA-N 0.000 claims description 3
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 3
- XLOPRKKSAJMMEW-HTQZYQBOSA-N (-)-cis-chrysanthemic acid Chemical compound CC(C)=C[C@@H]1[C@H](C(O)=O)C1(C)C XLOPRKKSAJMMEW-HTQZYQBOSA-N 0.000 claims description 2
- DPZZOBZIZRBXFQ-UHFFFAOYSA-N 3-(2,2-difluoroethenyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C=C(F)F)C1C(O)=O DPZZOBZIZRBXFQ-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 125000000468 ketone group Chemical group 0.000 claims 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 39
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 235000019645 odor Nutrition 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000003480 eluent Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- VNTCVNLNEOVBEE-UHFFFAOYSA-N 2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carbonyl chloride Chemical compound CC(C)=CC1C(C(Cl)=O)C1(C)C VNTCVNLNEOVBEE-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 241000220317 Rosa Species 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- 125000006017 1-propenyl group Chemical group 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 3
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 3
- 235000010254 Jasminum officinale Nutrition 0.000 description 3
- 240000005385 Jasminum sambac Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229940022663 acetate Drugs 0.000 description 3
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VNHCVSAJTOUUBK-UHFFFAOYSA-N 1-(2,2-dichloroethenyl)cyclopropane-1-carboxylic acid Chemical compound ClC(Cl)=CC1(C(=O)O)CC1 VNHCVSAJTOUUBK-UHFFFAOYSA-N 0.000 description 2
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 244000179970 Monarda didyma Species 0.000 description 2
- 235000010672 Monarda didyma Nutrition 0.000 description 2
- MKUWVMRNQOOSAT-UHFFFAOYSA-N but-3-en-2-ol Chemical compound CC(O)C=C MKUWVMRNQOOSAT-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- XLOPRKKSAJMMEW-UHFFFAOYSA-N chrysanthemic acid Chemical compound CC(C)=CC1C(C(O)=O)C1(C)C XLOPRKKSAJMMEW-UHFFFAOYSA-N 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 229960000956 coumarin Drugs 0.000 description 2
- 235000001671 coumarin Nutrition 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 229940067137 musk ketone Drugs 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229940067107 phenylethyl alcohol Drugs 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 1
- XLOPRKKSAJMMEW-SFYZADRCSA-N (+)-trans-chrysanthemic acid Chemical compound CC(C)=C[C@@H]1[C@@H](C(O)=O)C1(C)C XLOPRKKSAJMMEW-SFYZADRCSA-N 0.000 description 1
- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (R)-(+)-citronellol Natural products OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- ZSMBQVAAOHKHDJ-UHFFFAOYSA-N 1-(2-methylprop-1-enyl)cyclopropane-1-carboxylic acid Chemical compound CC(C)=CC1(C(O)=O)CC1 ZSMBQVAAOHKHDJ-UHFFFAOYSA-N 0.000 description 1
- 125000003562 2,2-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000004336 3,3-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910002703 Al K Inorganic materials 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
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N Citronellol Natural products OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 241001672694 Citrus reticulata Species 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- 240000006497 Dianthus caryophyllus Species 0.000 description 1
- 235000009355 Dianthus caryophyllus Nutrition 0.000 description 1
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 1
- 239000005770 Eugenol Substances 0.000 description 1
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
- 241000208152 Geranium Species 0.000 description 1
- UWKAYLJWKGQEPM-LBPRGKRZSA-N Linaloyl acetate Natural products CC(C)=CCC[C@](C)(C=C)OC(C)=O UWKAYLJWKGQEPM-LBPRGKRZSA-N 0.000 description 1
- 235000015511 Liquidambar orientalis 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
- UYOUUGIWAUBXAU-UHFFFAOYSA-N N-diaminophosphorylmethanamine hexane Chemical compound CCCCCC.CNP(N)(N)=O UYOUUGIWAUBXAU-UHFFFAOYSA-N 0.000 description 1
- GLZPCOQZEFWAFX-JXMROGBWSA-N Nerol Natural products CC(C)=CCC\C(C)=C\CO GLZPCOQZEFWAFX-JXMROGBWSA-N 0.000 description 1
- RSPISYXLHRIGJD-UHFFFAOYSA-N OOOO Chemical compound OOOO RSPISYXLHRIGJD-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 240000002505 Pogostemon cablin Species 0.000 description 1
- 235000011751 Pogostemon cablin Nutrition 0.000 description 1
- 244000018633 Prunus armeniaca Species 0.000 description 1
- 235000009827 Prunus armeniaca Nutrition 0.000 description 1
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 1
- OEYQBKYISMRWQB-UHFFFAOYSA-N Santal Natural products C=1C(OC)=CC(O)=C(C2=O)C=1OC=C2C1=CC=C(O)C(O)=C1 OEYQBKYISMRWQB-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000004870 Styrax Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- UZFLPKAIBPNNCA-UHFFFAOYSA-N alpha-ionone Natural products CC(=O)C=CC1C(C)=CCCC1(C)C UZFLPKAIBPNNCA-UHFFFAOYSA-N 0.000 description 1
- GUUHFMWKWLOQMM-UHFFFAOYSA-N alpha-n-hexylcinnamic aldehyde Natural products CCCCCCC(C=O)=CC1=CC=CC=C1 GUUHFMWKWLOQMM-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyloxyacetoaldehyde Natural products CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 1
- JGQFVRIQXUFPAH-UHFFFAOYSA-N beta-citronellol Natural products OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 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
- 239000001551 castor spp. extract Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 235000000484 citronellol Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- LJJVZJSGXHJIPP-UHFFFAOYSA-N ethylpentyl Chemical group [CH2+]CCC[CH]C[CH2-] LJJVZJSGXHJIPP-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229960002217 eugenol Drugs 0.000 description 1
- 238000002618 extracorporeal membrane oxygenation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WPFVBOQKRVRMJB-UHFFFAOYSA-N hydroxycitronellal Chemical compound O=CCC(C)CCCC(C)(C)O WPFVBOQKRVRMJB-UHFFFAOYSA-N 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- UWKAYLJWKGQEPM-UHFFFAOYSA-N linalool acetate Natural products CC(C)=CCCC(C)(C=C)OC(C)=O UWKAYLJWKGQEPM-UHFFFAOYSA-N 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229940041616 menthol Drugs 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- PKAHQJNJPDVTDP-UHFFFAOYSA-N methyl cyclopropanecarboxylate Chemical compound COC(=O)C1CC1 PKAHQJNJPDVTDP-UHFFFAOYSA-N 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 244000045947 parasite Species 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- MDHYEMXUFSJLGV-UHFFFAOYSA-N phenethyl acetate Chemical compound CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- QEYGAMYURHNUMI-UHFFFAOYSA-N propan-2-yl cyclopropanecarboxylate Chemical compound CC(C)OC(=O)C1CC1 QEYGAMYURHNUMI-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- ZCTQGTTXIYCGGC-UHFFFAOYSA-N salicylic acid benzyl ester Natural products OC1=CC=CC=C1C(=O)OCC1=CC=CC=C1 ZCTQGTTXIYCGGC-UHFFFAOYSA-N 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- ZULTYUIALNTCSA-UHFFFAOYSA-N zinc hydride Chemical compound [ZnH2] ZULTYUIALNTCSA-UHFFFAOYSA-N 0.000 description 1
- 229910000051 zinc hydride Inorganic materials 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Cosmetics (AREA)
- Fats And Perfumes (AREA)
Description
% i 813222/vdV/mk ^% i 813222 / vdV / mk ^
Korte aanduiding: Nieuwe cyclopropaancarbonzuurverbindingen, werkwijze voor hun bereiding en hun toepassing bij de bereiding van parfumerende samenstellingen.Short designation: Novel cyclopropanecarboxylic acid compounds, method of their preparation and their use in the preparation of perfuming compositions.
5 De uitvinding heeft betrekking op nieuwe cyclopropaan- carbonzuurverbindingen, een werkwijze voor hun bereiding en hun toepassing bij de bereiding van parfumerende samenstellingen/The invention relates to new cyclopropanecarboxylic acid compounds, a method for their preparation and their use in the preparation of perfuming compositions /
De uitvinding heeft betrekking, in al hun mogelijke / vormen, op verbindingen met de formule 1 van het formuleblad waarin R ofwel 10 een verzadigde, rechte of vertakte, alkylgroep met 1 tot 12 koolstcfatomen voorstelt, die eventueel een cycloalkylgroep draagt welke 3 tot 6 kool-stofatomen bevat of een koolwaterstofgroep met 2 tot 8 koolstofatomen eventueel onderbroken door een zuurstofatoom of een ketonfunktie, ofwel een rechte of vertakte alkenyl of alkynylgroep met 2 tot 8 koolstofatomen 15 ofwel een cycloalkylgroep met 3 tot 12 koolstofatomen die eventueel één of meerdere dubbele bindingen draagt en gesubstitueerd kan zijn door één of meer alkylgroepen, ofwel een eventueel gesubstitueerde aralkylgroep met 7 tot 12 koolstofatomen, R2 en . een alkylgroep met 1 tot 4 koolstofatomen of een halogeenatoom voorstellen alsmede de mengsels van 20 isomeren.The invention relates, in all their possible forms, to compounds of the formula I of the formula sheet wherein R either represents a saturated, straight or branched chain alkyl group having 1 to 12 carbon atoms, optionally bearing a cycloalkyl group carrying 3 to 6 carbon contains atoms or a hydrocarbon group of 2 to 8 carbon atoms optionally interrupted by an oxygen atom or a ketone function, either a straight or branched alkenyl or alkynyl group of 2 to 8 carbon atoms or a cycloalkyl group of 3 to 12 carbon atoms optionally bearing one or more double bonds and may be substituted by one or more alkyl groups, or an optionally substituted aralkyl group having 7 to 12 carbon atoms, R2 and. an alkyl group of 1 to 4 carbon atoms or a halogen atom and the mixtures of 20 isomers.
De verbindingen met formule 1 kunnen voorkomen in talrijke mogelijke isomere vormen; zij bezitten namelijk allen, twee asymetri-sche koolstofatomen op de plaatsen 1 en 3 van de cyclopropaanring en kunnen eveneens één of meerdere asymetrefcentra of asymetrie-assen in het gedeelte 25 R bezitten.The compounds of formula 1 can exist in numerous possible isomeric forms; namely, they all have two asymmetric carbon atoms in positions 1 and 3 of the cyclopropane ring and may also have one or more asymmetry centers or asymmetry axes in the R portion.
Als R een verzadigde alkylgroep voorstelt betreft het bij voorkeur een methyl-, ethyl-, propyl-, isopropyl-, butyl-, isobutyl-, of tert.butyl-, n-pentyl-, n-hexyl-, 2-methylpentyl-, 2,3-dimethylbutyl, n-heptyl-, 2-methylhexyl-, 2,2-dimethylpentyl-, 3,3-dimethylpentyl-, 3-30 ethylpentyl-, n-octyl-, 2,2-dimethylhexyl-, 3,3-dimethylhexyl-> 3-®ethyl 3-ethylpentyl-, nonyl-, 2,4-dimethylheptyl- of n-decylgroep.When R represents a saturated alkyl group, it is preferably a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, or tert-butyl, n-pentyl, n-hexyl, 2-methylpentyl, 2,3-dimethylbutyl, n-heptyl, 2-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 3-30 ethylpentyl, n-octyl, 2,2-dimethylhexyl, 3, 3-dimethylhexyl-> 3-ethyl 3-ethylpentyl, nonyl, 2,4-dimethylheptyl or n-decyl group.
Als R een alkylgroep voorstelt, gesubstitueerd door een cycloalkylgroep of door een koolwaterstofgroep, betreft het bij voorkeur een alkylgroep gesubstitueerd door een eyclopropyl-, cyclopentyl- of cyclo-35 hexylgroep of door een cyclopentenyl- of cyclohexenylgroep.When R represents an alkyl group substituted by a cycloalkyl group or a hydrocarbon group, it is preferably an alkyl group substituted by an eyclopropyl, cyclopentyl or cyclo-hexyl group or by a cyclopentenyl or cyclohexenyl group.
Als R een alkenylgroep voorstelt, betreft het bij voorkeur een butenyl-, isobutenyl- of crotonylgroep.When R represents an alkenyl group, it is preferably a butenyl, isobutenyl or crotonyl group.
Als R een alkynylgroep voorstelt, betreft het bij voorkeur een ethynyl- of propynylgroep.When R represents an alkynyl group, it is preferably an ethynyl or propynyl group.
kO Als R een cycloalkylgroep voorstelt, betreft het bij 8104495 ‘ -2- ι ........ ...... ....... .... ......kO When R represents a cycloalkyl group, 8104495 refers to "-2- ι ........ ...... ....... .... ......
« - . . .«-. . .
voorkeur een cyclopropyl-, cyclopentyl-, cyclohexyl-, eycloheptyl- of cyclo-octylgroep.preferably a cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl group.
Als B een cycloalkylgroep voorstelt die meerdere dubbele bindingen draagt, betreft het bij voorkeur twee dubbele bindingen.When B represents a cycloalkyl group bearing multiple double bonds, it is preferably two double bonds.
5 Als B een cycloalkylgroep voorstelt gesubstitueerd door één of meerdere alkylgroepen, betreft het bij voorkeur een cycloalkylgroep gesubstitueerd door één of meerdere methyl-, ethyl- of n-propylgroepen.When B represents a cycloalkyl group substituted by one or more alkyl groups, it is preferably a cycloalkyl group substituted by one or more methyl, ethyl or n-propyl groups.
Als B een aralkylgroep voorstélt, betreft het bij voorkeur een benzylgroep, of fenylethylgroep, eventueel gesubstitueerd op de 10 ortho, meta of paraplaats door één of meerdere alkylgroepen met 1 tot k koolstofatomen door één of meerdere alkoxygroepen met 1 tot k koolstof-atomen zoals bijvoorbeeld een methoxygroep, door één of meerdere halogeen-atomen zoals bijvoorbeeld een chloor- of fluoratoom, door een trifluor-methylgroep of door een combinatie van deze verschillende substituenten.When B represents an aralkyl group, it is preferably a benzyl group, or phenylethyl group, optionally substituted on the ortho, meta or para site by one or more alkyl groups with 1 to k carbon atoms by one or more alkoxy groups with 1 to k carbon atoms, such as for example a methoxy group, by one or more halogen atoms, such as, for example, a chlorine or fluorine atom, by a trifluoromethyl group or by a combination of these different substituents.
15 Als Rg en B^ een alkylgroep voorstellen, betreft het bij voorkeur een methyl-, ethyl- of n-propylgroep.When R 9 and B 8 represent an alkyl group, it is preferably a methyl, ethyl or n-propyl group.
Als Β^ en E^ een halogeenatoom voorstellen, betreft het bij voorkeur een fluor- of chlooratoom.When en ^ and E ^ represent a halogen atom, it is preferably a fluorine or chlorine atom.
De uitvinding heeft in het bijzonder betrekking op de 20 verbindingen met formule 1 waarin B een rechte of vertakte alkylgroep met 1 tot k koolstofatomen voorstelt, of die verbindingen waarin B een rechte of vertakte alkenyl- of alkynylgroep voorstelt met 2 tot 6 koolstofatomen alsmede op die verbindingen waarin B een benzyl- of fenylethylgroep voorstelt· 25 De uitvinding heeft in het bijzonder betrekking op de verbindingen met formule 1 waarin Rg en B^ identiek zijn.The invention particularly relates to the compounds of formula 1 wherein B represents a straight or branched chain alkyl group having 1 to k carbon atoms, or those compounds in which B represents a straight or branched chain alkenyl or alkynyl group having 2 to 6 carbon atoms as well as to those compounds in which B represents a benzyl or phenylethyl group. The invention relates in particular to the compounds of formula 1 in which Rg and B1 are identical.
De uitvinding heeft meer in het bijzonder betrekking op de verbindingen met formule 1 waarin Rg en B^ elk een methylgroep voorstellen, alsmede op die verbindingen waarin Rg en B^ elk een fluor- of 30 chlooratoom voorstellen.More particularly, the invention relates to the compounds of formula I wherein Rg and B1 each represent a methyl group, and those compounds wherein Rg and B1 each represent a fluorine or chlorine atom.
De uitvinding heeft meer in het bijzonder betrekking op de verbindingen waarvan de bereiding verderop beschreven is in het experimentele gedeelte en in het bijzonder de: - 1-methylethylester van (IR,trans) 2,2-dimethyl 3(2-methyl 1-propenyl) 35 cyclopropaancarbonzuur - crotoi^ster van (1B,trans) 2,2-dimethyl 3(2-methyl 1-propenyl)cyclopropaancarbonzuur, - 1 (3-butenylJester van (1R,trans) 2,2-dimethyl 3(2-methyl 1-propenyl) cyclopropaancarbonzuur, kO - 2-fenylethylester van (1B,trans) 2,2-dimethyl j(2-methyl 1-propenyl)cyclo- 8104495 A- i * -3- propaancarbonzuur, 1-methylethylester van (1S trans) 2,2-dimethyl 3(2-raethyl 1-propenyl)cyclo-propaancarbonzuur, - RS 3(l-butyleen)ester van (IS trans) 2,2-dimethyl 3(2-methyl 1-propenyl) 5 cyclopropaancarbonzuur, - isopropylester van (15 cis) 2,2-dioethyl 3(2-methyl 1-propenyl)cyclopropaancarbonzuur , - l(3-butenyl)ester van (1S cis) 2,2-dimethyl 3(2-methyl 1-propenyl)cyclo-propaancarbonzuur, 10 - methylester van (1R cis) 2,2-dioethyl 3(2,2-difluor 1-ethenyl)cyclopro paancarbonzuur , - methylester van (1H cis) 2,2-dioethyl 3(2,2-dichloorvinyl)cyclopropaan-earbonzuur.The invention more particularly relates to the compounds the preparation of which is described below in the experimental part and in particular the: - 1-methyl ethyl ester of (IR, trans) 2,2-dimethyl 3 (2-methyl 1-propenyl) ) 35 cyclopropanecarboxylic acid - crotester of (1B, trans) 2,2-dimethyl 3 (2-methyl 1-propenyl) cyclopropanecarboxylic acid, - 1 (3-butenylester of (1R, trans) 2,2-dimethyl 3 (2- methyl 1-propenyl) cyclopropanecarboxylic acid, kO - 2-phenylethyl ester of (1B, trans) 2,2-dimethyl j (2-methyl 1-propenyl) cyclo-8104495 A-1 * -3-propanecarboxylic acid, 1-methyl ethyl ester of (1S trans) 2,2-dimethyl 3 (2-raethyl 1-propenyl) cyclopropanecarboxylic acid, - RS 3 (1-butylene) ester of (IS trans) 2,2-dimethyl 3 (2-methyl 1-propenyl) 5 cyclopropanecarboxylic acid - isopropyl ester of (15 cis) 2,2-dioethyl 3 (2-methyl 1-propenyl) cyclopropanecarboxylic acid, - 1 (3-butenyl) ester of (1S cis) 2,2-dimethyl 3 (2-methyl 1-propenyl) ) cyclopropanecarboxylic acid, 10 - methyl ester of (1R cis) 2,2-dioethyl 3 (2,2-di fluorine 1-ethenyl) cyclopropanecarboxylic acid, methyl ester of (1H cis) 2,2-dioethyl 3 (2,2-dichlorovinyl) cyclopropanecarboxylic acid.
De uitvinding heeft eveneens betrekking op een werkwijze 15 voor de bereiding van verbindingen met formule 1 die gekenmerkt is doordat men een zuur met formule 2, waarin en ^ dezelfde betekenis behouden als hierboven, of een funktioneel derivaat van dit zuur, laat reageren met een alcohol met de formule 3 van het formuleblad, waarin B dezelfde betekenis behoudt als hierboven, of een funktioneel derivaat van deze al-20 cohol, ter verkrijging van de gewenste verbinding met formule 1.The invention also relates to a process for the preparation of compounds of the formula 1 which is characterized in that an acid of the formula 2, in which a has the same meaning as above, or a functional derivative of this acid is reacted with an alcohol of formula 3 of the formula sheet, wherein B retains the same meaning as above, or a functional derivative of this alcohol, to give the desired compound of formula 1.
Onder funktioneel derivaat van een zuur verstaat men bij voorkeur een zuur^chloride of een zutuvanhydride.A functional derivative of an acid is preferably understood to mean an acid chloride or a zinc hydride.
De uitvinding heeft meer in het bijzonder betrekking op een werkwijze voor de bereiding van verbindingen met formule 1 die geken-25 merkt is doordat men een chloride van een zuur met formule 2 onderwerpt aan de inwerking van een alcohol met formule 3 onder vorming van de gewenste verbinding met formule 1·The invention more particularly relates to a process for the preparation of compounds of formula 1 which is characterized by subjecting a chloride of an acid of formula 2 to the action of an alcohol of formula 3 to form the desired compound of formula 1
Het spreekt vanzelf dat de andere bekende werkwijzen voor de bereiding van de cyclopropaancarbonzuuresters eveneens gebruikt kunnen 30 worden.It goes without saying that the other known processes for the preparation of the cyclopropanecarboxylic acid esters can also be used.
De verbindingen met formule 1 bezitten belangwekkende organoleptische eigenschappen waardoor men ze in het bijzonder kan gebruiken als parfumerende stoffen.The compounds of the formula I have interesting organoleptic properties, so that they can be used in particular as perfuming agents.
De verbindingen met formule 1 bezitten een aangename geur groene geur 35 bijvoorbeeld een bloemengeur, /bloesemgeur,houtgeur of gekruide geur. In het later volgende experimentele gedeelte zullen de door bepaalde produk-ten met formule 1 ontwikkelde geuren nauwkeuriger worden aangegeven (zie Voorbeeld LVI).The compounds of formula 1 have a pleasant green fragrance, for example a floral, blossom, woody or spicy fragrance. In the later experimental section, the odors developed by certain products of formula 1 will be more accurately indicated (see Example LVI).
De uitvinding heeft derhalve eveneens betrekking op als kO parfumerende stoffen, de verbindingen met formule 1 en in het bijzonder 8104495 ί *Ε ' -4- daarvan de hierboven genoemde voorkeursverbindingen.The invention therefore also relates to the compounds of the formula I, and in particular 8104495, the above-mentioned preferred compounds, as perfuming agents.
Vanwege hun belangwekkende reukeigenschappen, kunnen de verbindingen met formule 1 gebruikt worden als reukstoffen in de parfumindustrie, voor het bereiden van reuksamenstellingen die zelf kunnen dienen 5 als basis voor parfums·Due to their interesting odor properties, the compounds of formula 1 can be used as perfumes in the perfume industry, for the preparation of fragrance compositions which can themselves serve as a basis for perfumes ·
De uitvinding heeft dus betrekking op parfumoende samenstellingen die gekenmerkt zijn doordat zij tenminste een parfumerende stof zoals hierboven omschreven bevatten.Thus, the invention relates to perfumed compositions characterized in that they contain at least one perfuming agent as defined above.
De verbindingen met formule 1 kunnen eveneens gebruikt 10 worden voor de bereiding van hygiënische waren zoals bijvoorbeel deepen, talkprodukten, shampoo's, tandpasta's, badzouten, schuimbadensamenstelling-en of badoliën, deodoranten, voor de bereiding van cosmetische produkten zoals bijvoorbeeld zalven, opmaakverwijderende melkprodukten, lotions, schminken, lippenstiften, en nagellakken· 15 De verbindingen met formule 1 kunnen eveneens gebruikt worden voor de bereiding van oppervlakte-aktieve produkten zoals bijvoorbeeld de wasmiddelen of voor de bereiding van onderhoudsprodukten zoals wassen, of tenslotte voor de bereiding van insecticiden·The compounds of the formula I can also be used for the preparation of hygienic goods such as, for example, deepening, talc products, shampoos, toothpastes, bath salts, bubble bath compositions and / or bath oils, deodorants, for the preparation of cosmetic products such as, for example, ointments, make-up removing milk products, lotions , face paints, lipsticks, and nail polishes · The compounds of the formula I can also be used for the preparation of surface-active products such as for example the detergents or for the preparation of maintenance products such as washing, or finally for the preparation of insecticides ·
De verbindingen met formule 1 kunnen een geur toevoegen 20 aan produkten welke geen geur bezitten; zij kunnen eveneens de geur van samenstellingen die zelf een bepaalde geur bezitten verhogen, prikkelen of wijzigen. Bovendien kunnen zij zoals elk produkt dat een aangename geur bezit, gebruikt worden voor het maskeren van de onaangename geur van een produkt. Natuurlijk worden de parfums, hygiënische produkten, cosmetica, 25 oppervlakte-aktieve produkten en onderhoudsprodukten bereid volgens de in de desbetreffende industriën gebruikelijke technieken. Deze technieken zijn algemeen beschreven in de gespecialiseerde literatuur en hebben hier geen aanleiding gegeven tot bijzondere ontwikkelingen.The compounds of formula 1 can add an odor to products which have no odor; they can also enhance, excite or modify the odor of compositions which themselves have a particular odor. Moreover, like any product that has a pleasant odor, they can be used to mask the unpleasant odor of a product. Naturally, the perfumes, hygiene products, cosmetics, surfactants and maintenance products are prepared according to the techniques customary in the relevant industries. These techniques are generally described in the specialized literature and have not given rise to any special developments here.
‘ Het spreekt vanzelf dat de uitvinding zich ook uitstrekt 30 tot samenstellingen die naast de verbindingen met formule 1, dragerstoffen, modificeermiddelen, fixeermiddelen, conserveermiddelen, stabilisatoren en andere bestanddelen bevatten zoals de dragers, oplosmiddelen, dispergeer-middelen en emulgeermiddelen die gewoonlijk in de desbetreffende industrie gebruikt worden· 35 Als het gaat om in de parfumerie gebruikte produkten, kan men aan de verbindingen met formule 1 andere algemeen aan de parfumeur be- wortel- kende verbindingen toevoegen, hetzij natuurlijke produkten zoals Vetyver·* essence, cederessence, bergamotessence, dennennaaldenessence, citroenessen-ce, jasmijn- of mandarijnessence, of synthetische produkten zoals de ge-^0 woonlijk in de parfumerie gebruikte aldehyden zoals hydroxycitronellal, 8104495 t * -5- ketonen zoals c/-ionon, fenolverbindingen zoals eugenol, alcoholen zoals geraniolt en lactonen zoals cumarine·It goes without saying that the invention also extends to compositions comprising, in addition to the compounds of formula 1, carriers, modifiers, fixatives, preservatives, stabilizers and other ingredients such as the carriers, solvents, dispersants and emulsifiers commonly used in the respective 35. When it comes to products used in perfumery, one can add to the compounds of formula 1 other compounds generally rooting to the perfumer, either natural products such as Vetyver * essence, cedar essence, bergamot essence, pine needle essence , lemon essence, jasmine or mandarin essence, or synthetic products such as the aldehydes commonly used in perfumery such as hydroxycitronellal, 8104495 * 5-ketones such as c-ionone, phenol compounds such as eugenol, alcohols such as geraniol and lactones like coumarin
De te gebruiken hoeveelheden van verbindingen met formule 1 variëren sterk als funktie van de aard van de gekozen verbinding, 5 van het gebruik dat oen er van wil maken, van de intensiteit van de geur die men wenst, alsmede natuurlijk van de aard en van de samenstelling van de andere bestanddelen die men aan de verbinding met formule 1 toevoegt·The amounts of the compounds of the formula I to be used vary widely depending on the nature of the compound selected, on the use to be made of it, on the intensity of the odor desired, and of course on the nature and the composition of the other ingredients added to the compound of formula 1
Hen kan bijvoorbeeld 0,1 tot 2/100 gew·delen van de verbindingen met formule 1 in het geval van oppervlakte-aktieve stoffen 10 bevattende samenstellingen toevoegen·For example, they can add 0.1 to 2/100 parts by weight of the compounds of the formula I in the case of surfactants containing 10 compositions ·
In het geval van parfums kan men bijvoorbeeld 0,1 tot 10/100 gew «delen van verbindingen met formule 1 toevoegen. Als het gaat om het gebruik van verbindingen met formule 1 als basis voor parfums, kan men tot 20 gew.# van de verbindingen met formule 1 gebruiken· 15 De volgende voorbeelden lichten de uitvinding toe zonder haar echter te beperken.In the case of perfumes, for example, 0.1 to 10/100 parts by weight of compounds of formula 1 can be added. When it comes to the use of compounds of formula 1 as the basis for perfumes, up to 20% by weight of the compounds of formula 1 can be used. The following examples illustrate the invention without, however, limiting it.
VOORBEELD I : 1-methylethylester van (1R trans) 2.2-dimcthyl 3-(2-methyl 1-nrouenyl)cyclopropaancarbonzuur·EXAMPLE I: 1-Methyl ethyl ester of (1R trans) 2,2-dimethyl 3- (2-methyl 1-nrouenyl) cyclopropanecarboxylic acid ·
Men koelt een mengsel van 100 ml isopropanol en 15 ml 20 pyridine tot+G,5°C. Hen voegt vervolgens 15 g (1B trans) 2,2-dimethyl 3-(2-methyl 1-propenyl)cyclopropaancarbonzuurchloride toe. Men roert het reactiemengsel 1 uur· Hen voegt water toe en extraheert met methyleenchlo-ride· De organische fasen worden gewassen met zoutzuur, met water, en met een waterige 5^'s natriumbicarbonaat-oplossing· Men droogt en concentreert. 25 Men verkrijgt 12,42 g van de gewenste verbinding na rectificeren. Kookpunt 90°C (4,5 ma kwikdruk).A mixture of 100 ml of isopropanol and 15 ml of pyridine is cooled to + G, 5 ° C. Then 15 g of (1B trans) 2,2-dimethyl 3- (2-methyl 1-propenyl) cyclopropanecarboxylic acid chloride are added to them. The reaction mixture is stirred for 1 hour. Hen is added with water and extracted with methylene chloride. The organic phases are washed with hydrochloric acid, with water, and with an aqueous 5% sodium bicarbonate solution. The mixture is dried and concentrated. 12.42 g of the desired compound are obtained after rectification. Boiling point 90 ° C (4.5 ma mercury pressure).
/•*/^° : 30° + 1,5 (c » 1jf tolueen) VOORBEELD II : 3-buteen-1-ylester van (1R trans) 2.2-dimethyl 3-(2-methyl 1-pronenyl)cyclopropaancarbonzuur.EXAMPLE 2: 3-Buten-1-yl ester of (1R trans) 2,2-dimethyl 3- (2-methyl 1-pronenyl) cyclopropanecarboxylic acid.
30 Men voegt bij 0°C 1,5 g 1-buten 4-ol toe aan 3»7 g 1R1.5 g of 1-buten-4-ol are added to 3 7 g of 1R at 0 ° C
trans 2-dimethyl 3-(2-methyl 1-propenyl)cyclopropaancarbonzuurchloride in hexaanmethylfosfortriamide. Men roert een uur bij 0°C en vervolgens 18 uren bij kamertemperatuur. Men giet uit in water en extraheert met hexaan. Men droogt de organische fasen, . filtreert en concentreert. Men 35 chromatografeert op siliciumoxyde (elutiemiddel benzine 6 - ether 9-1)·trans 2-dimethyl 3- (2-methyl 1-propenyl) cyclopropanecarboxylic acid chloride in hexane-methylphosphoric triamide. It is stirred at 0 ° C for one hour and then at room temperature for 18 hours. It is poured into water and extracted with hexane. The organic phases are dried. filters and concentrates. Chromatographed on silica (eluent gasoline 6 - ether 9-1) ·
Men voegt de fraktiesmet rf = 0,45 bij elkaar en concentreert deze. Men verkrijgt 2,1 g van de gewenste verbinding.The fractions with rf = 0.45 are combined and concentrated. 2.1 g of the desired compound are obtained.
/4/ D : -23,5° + 1i5° ( c = 1# benzeen)./ 4 / D: -23.5 ° + 1i5 ° (c = 1 # benzene).
VOORBEELD III : 2-fenylethylester van (1R trans) 2,2-dimethyl 3(2-methyl 40 1-propenyl)cyclopropaancarbonzuur, 8104495 ♦ t _ -6- . Men voegt 12 g (1R trans) 2-dimethyl 3-(2-methyl 1-pro-penyl)cyclopropaancarbonzuurchloride toe aan een oplossing die 8,5 ml fenylethylalcohol en 50 ml dichloorethaan bevat. Men kookt het reactie-fflengsel *f0 minuten onder terugvloeikoeling en verdampt de oplosmiddelen.EXAMPLE III: 2-phenylethyl ester of (1R trans) 2,2-dimethyl 3 (2-methyl 40 1-propenyl) cyclopropanecarboxylic acid, 8104495 95 t -6-. 12 g of (1R trans) 2-dimethyl 3- (2-methyl 1-propenyl) cyclopropanecarboxylic acid chloride are added to a solution containing 8.5 ml of phenylethyl alcohol and 50 ml of dichloroethane. The reaction mixture is refluxed for 50 minutes and the solvents are evaporated.
5 Men verkrijgt 19,16 g van een verbinding die men rectificeert onder verminderde druk. Men verkrijgt 7,42 g van de gewenste verbinding. Kookpunt : 148°C (1,5 mm kvikdruk).19.16 g of a compound which is rectified under reduced pressure are obtained. 7.42 g of the desired compound are obtained. Boiling point: 148 ° C (1.5 mm kvik pressure).
/^° : -12,5° + 1° (c = 1,4# tolueen)./ ^ °: -12.5 ° + 1 ° (c = 1.4 # toluene).
VOORBEELD IV s Crotonylester van (1R trans) 2.2-dimethyl 3-(2-methyl 1- 10 propenyl) cyclopropaancarbonzuur .EXAMPLE IV Crotonyl ester of (1R trans) 2,2-dimethyl 3- (2-methyl-1-propenyl) cyclopropanecarboxylic acid.
Men voegt bij 0°G 1,6 g crotonylalcohol in 3» 75 g (1R trans) 2,2-dimethyl 3-(2-methyl-1-propenyl)cyclopropaancarbonzuurchloride aan 25 cm3 HMPT toe. Men roert 48 uren bij kamertemperatuur. Men giet uit in water en extraheert met hexaan. Men droogt, zuigt af en concentreert.1.6 g of crotonyl alcohol in 3, 75 g of (1R trans) 2,2-dimethyl 3- (2-methyl-1-propenyl) cyclopropanecarboxylic acid chloride are added at 25C HMPT. It is stirred at room temperature for 48 hours. It is poured into water and extracted with hexane. It is dried, vacuumed and concentrated.
15 Men verkrijgt een olie die men chromatograféert op siliciumoxyde (elutie-middel petroleumether,(Kookpunt 40-70°C) - ethylether 9-1)· Men voegt de frakties met rf = 0,6 bij elkaar en concentreert. Men verkrijgt 2,8 g van de gewenste verbinding.An oil is obtained which is chromatographed on silica (eluent petroleum ether, (Boiling point 40-70 ° C) - ethyl ether 9-1). The fractions are combined with rf = 0.6 and concentrated. 2.8 g of the desired compound are obtained.
/#/_ : -27 + 1° (c = 1,5# benzeen)./ # / _: -27 + 1 ° (c = 1.5 # benzene).
U ψ 20 VOORBEELD V : Ethylester van (1R cis) 2,2-dimethyl 3-(2-metfayl 1-propenyl) cyclopropaancarbonzuur.EXAMPLE V: Ethyl ester of (1R cis) 2,2-dimethyl 3- (2-metfayl-1-propenyl) cyclopropanecarboxylic acid.
Men voegt 4,95 g ethanol en 17 g pyridine toe aan 25 ml benzeen· Men voegt vervolgens bij4l5 tot+20°C 20 g (1R cis) 2,2-dimethyl 3-(2-methyl 1-propenyl)cyclopropaancarbonzuurchloride in 20 ml benzeen toe.4.95 g of ethanol and 17 g of pyridine are added to 25 ml of benzene. 20 g of (1R cis) 2,2-dimethyl 3- (2-methyl 1-propenyl) cyclopropanecarboxylic chloride in 20 ml are then added at 415 to + 20 ° C. ml of benzene.
25 Men roert een nacht bij kamertemperatuur. Men voegt 50 ml water toe. Men decanteert, wast met water droogt. Men destilleert tot droog en verkrijgt een bruine olie die men chroaatografeert op siliciumoxyde (elutie-middel : heptaan). Men verkrijgt 12,8 g van de gewenste verbinding· M/ D : + 47,5° + 1,5 (c = 1,2# ethanol).It is stirred overnight at room temperature. 50 ml of water are added. It is decanted, washed with water and dried. The mixture is distilled to dryness and a brown oil is obtained which is chromatographed on silica (eluent: heptane). 12.8 g of the desired compound M / D: + 47.5 ° + 1.5 (c = 1.2 # ethanol) are obtained.
30 VOORBEELD VI : 1-methylethylester van (1R cis) 2,2-dimethyl 3(2-aethyl 1-propenyl)cyclopropaancarbonzuur.EXAMPLE VI: 1-Methyl ethyl ester of (1R cis) 2,2-dimethyl 3 (2-aethyl 1-propenyl) cyclopropanecarboxylic acid.
Men voegt bij +10 tot +15°C aan een oplossing die 6 g isopropanol, 17 g pyridine en 40 cm3 benzeen bevat, 20^(IR cis) 2,2-dimethyl 3-(2-methyl 1-propenyl)cyclopropaancarbonzuurin 20 cm3 benzeen toe.20 + (IR cis) 2,2-dimethyl 3- (2-methyl 1-propenyl) cyclopropanecarboxylic acid is added to a solution containing 6 g of isopropanol, 17 g of pyridine and 40 cm 3 of benzene at +10 to + 15 ° C. cm3 of benzene.
35 Men roert 72 uren en voegt 50 cm3 heptaan en 50 cm3 water toe. Men roert, decanteert en wast met zoutzuur, met water en met natriumbicarbonaat.The mixture is stirred for 72 hours and 50 ml of heptane and 50 ml of water are added. It is stirred, decanted and washed with hydrochloric acid, with water and with sodium bicarbonate.
Men droogt de organische fasen en leidt deze over siliciumoxyde onder elueren met heptaan. Men destilleert de oplossing tot droog. Men verkrijgt 9,3 g van de gewenste verbinding.The organic phases are dried and passed over silica, eluting with heptane. The solution is distilled to dryness. 9.3 g of the desired compound are obtained.
40 /'Λ/ρ° : +42° + 1,5° ( c = 1# ethanol).40 / 'Λ / ρ °: + 42 ° + 1.5 ° (c = 1 # ethanol).
8104495 « * ,* -7- VOORBEELD VII : 1-aethylethylester van (1S trans) 2,2-dimethyl 3-(2-methvl 1 --propenyl) cyclouropaancarbonzuur .8104495 *, * -7- EXAMPLE VII: 1-Ethyl ethyl ester of (1S trans) 2,2-dimethyl 3- (2-methyl-1-propenyl) cyclouropanecarboxylic acid.
Men voegt bij 0°C, 1 cm2 pyridine toe aan een oplossing die 3,7 g (1S trans) 2,2-dimethyl 3-(2-methyl 1-propenyl)cyclopropaancar-5 bonzuur, 20 cm3 benzeen en 1,5 g isopropanol bevat· Men roert 24 uren bij kamertemperatuur. Men giet het reactiemengsel uit in 20 cm3 2N zoutzuur·At 0 ° C, 1 cm 2 of pyridine is added to a solution containing 3.7 g (1S trans) 2,2-dimethyl 3- (2-methyl 1-propenyl) cyclopropanecarboxylic acid, 20 cm 3 benzene and 1.5 g of isopropanol contains · The mixture is stirred at room temperature for 24 hours. The reaction mixture is poured into 20 ml of 2N hydrochloric acid.
Men decanteer^ wast met een oplossing van 2N natronloog. Men droogt en concentreert tot droog· Men chromatografeert over siliciumoxyde,(elutie-middel : benzeen) en verenigt de frakties met rf = 0,33 en concentreert· 10 Men verkrijgt 2,4 g van de gewenste verbinding· RNM Spectrum CDCl^ - H van de gepaarde methylgroepen van het cyclopropaan, pieken bij 1,13 en 1,27 ppm.Decantation is washed with a solution of 2N sodium hydroxide solution. It is dried and concentrated to dryness. It is chromatographed on silica (eluent: benzene) and the fractions are combined with rf = 0.33 and concentrated. 10 g of the desired compound are obtained. RNM Spectrum CDCl-H of the paired methyl groups of the cyclopropane, peaks at 1.13 and 1.27 ppm.
- H op pLaats 1 van het cyclopropaan, piek bij 1,3 - 1,¼ p.p.m.- H at position 1 of the cyclopropane, peak at 1.3 - 1, ¼ ppm.
15 - H op plaats 3 van het cyclopropaan, piek bij 1,92 - 2,08 p.p.m.15 - H at position 3 of the cyclopropane, peak at 1.92 - 2.08 ppm.
- H op plaats 1 van de propenyl, piek bij 4,83 “ 4,97 p.p.m.- H at position 1 of the propenyl, peak at 4.83 "4.97 ppm.
- H gedragen door de koolstof op de plaats van de carboxylgroep, multi-plet bij 5,03 p.p.m.- H carried by the carbon in place of the carboxyl group, multi-flattened at 5.03 ppm.
- H gedragen door de koolstofatomen op de i plaats van de carboxylgroep, 20 pieken bij 1,18 - 1,3 p.p.m.- H carried by the carbon atoms in the i position of the carboxyl group, 20 peaks at 1.18 - 1.3 ppm.
VOORBEELD VIII : ES 5-buten-2-ylester van (1S trans) 2,2-dimethyl 5(2-methyl 1-propenyl)cyclopronaancarbonzuur.EXAMPLE VIII: ES 5-buten-2-yl ester of (1S trans) 2,2-dimethyl 5 (2-methyl 1-propenyl) cyclopronanecarboxylic acid.
Men voegt 3,75 g (1S trans) 2,2-dimethyl 3-(2-methyl 1-propenyl)cyclopropaancarbonzuurchloride en 1,45 g 1-buten 3-ol in 50 cm3 25 watervrij benzeen toe· Men koelt af tot 0°C en voegt druppelsgewijs 2 cm3 pyridine toe. Men roert 18 uren bij kamertemperatuur en giet uit in een oplossing van 2N zoutzuur. Men droogt boven natriumsulfaat en concentreert tot droog. -Verkregen wordt 4,6 g van een verbinding die men chromatogra-feert over siliciumoxyde (elutiemiddel : benzine G - ethylether 9-1)· 30 Men voegt de frakties met rf = 0,32 bij elkaar en concentreert. Men verkrijgt 2,3 g van de gewenste verbinding.3.75 g of (1S trans) 2,2-dimethyl 3- (2-methyl-1-propenyl) cyclopropanecarboxylic acid chloride and 1.45 g of 1-buten-3-ol in 50 ml of anhydrous benzene are added. ° C and adds 2 cm 3 of pyridine dropwise. It is stirred at room temperature for 18 hours and poured into a solution of 2N hydrochloric acid. It is dried over sodium sulfate and concentrated to dryness. 4.6 g of a compound which is chromatographed on silica are obtained (eluent: gasoline G - ethyl ether 9-1). The fractions are combined with rf = 0.32 and concentrated. 2.3 g of the desired compound are obtained.
/n/f : 1,1*662 VOORBEELD IX : 3-buten-1-ylester van (1S cis) 2,2-dimethyl 3-(2-methyl 1-vrouenyl)cyclopropaancarbonzuur./ n / f: 1.1 * 662 EXAMPLE IX: 3-Buten-1-yl ester of (1S cis) 2,2-dimethyl 3- (2-methyl-1-phenyl) cyclopropanecarboxylic acid.
35 Men voegt bij 0°C 2 g 3-buten-1-ol toe aan een mengsel van 3,79 g (1S cis) 2,2-dimethyl 3-(2-methyl 1-propenyl)cyclopropaancar-bonzuurchloride en 7,8 g HMPT. Men roert 1 uur bij 0°C en 18 uren bij kamertemperatuur. Men giet uit in water en extraheert met hexaan. Men droogt de organische fasen, filtreert en concentreert. Men chromatografeert 40 over siliciumoxyde (elutiemiddel ' petroleumether (kookpunt 40-70°C) - 8104495 ·/ X.2 g of 3-buten-1-ol are added at 0 ° C to a mixture of 3.79 g of (1S cis) 2,2-dimethyl 3- (2-methyl 1-propenyl) cyclopropanecarboxylic acid chloride and 7, 8 g HMPT. The mixture is stirred at 0 ° C for 1 hour and at room temperature for 18 hours. It is poured into water and extracted with hexane. The organic phases are dried, filtered and concentrated. 40 is chromatographed on silica (eluent, petroleum ether (bp 40-70 ° C) - 8104495 / X).
-8- ethylether 9-1)· Men voegt de frakties met rf = 0,5 bij elkaar en concentreert. Verkregen wordt 2,7 g van de gewenste verbinding.Ethyl ether 9-1) The fractions are combined with rf = 0.5 and concentrated. 2.7 g of the desired compound are obtained.
/A7D : -bö° + 2° (c = 0,7# benzeen)./ A7D: -b ° + 2 ° (c = 0.7 # benzene).
VOORBEELD x :methylester van (1R cis) 2,2-dimethyl 3-(2.2-difluorvinyl) 5 cyclonropaancarbonzuur.EXAMPLE x: methyl ester of (1R cis) 2,2-dimethyl 3- (2,2-difluorovinyl) 5 cyclonropanecarboxylic acid.
Men voegt ongeveer 50 cm3 van een oplossing van diazo-methaan in methyleenchloride toe aan een oplossing die 3,2 g (1R cis) 2,2-dimethyl 3-(2,2-difluorvinyl)cyclopropaancarbonzuur en 20 cm3 methyleenchloride bevat. Men concentreert de verkregen oplossing, en chromatogra-10 feert de verkregen olie over siliciumoxyde (elutiemiddel : petroleumether (kookpunt *f0-70°C) - ethylether 9-1)· Men voegt de frakties met rf » 0,5 bij elkaar en concentreert. Men verkrijgt op deze wijze 3,b g van de gewenste verbinding· /oi/^ : +6,5° + 1° (c » 1,7#, benzeen).About 50 cm3 of a solution of diazo-methane in methylene chloride is added to a solution containing 3.2 g (1R cis) 2,2-dimethyl 3- (2,2-difluorovinyl) cyclopropanecarboxylic acid and 20 cm3 methylene chloride. The resulting solution is concentrated, and the resulting oil is chromatographed on silica (eluent: petroleum ether (boiling point * 70-70 ° C) - ethyl ether 9-1). The fractions are combined with rf »0.5 and concentrated. . In this way, 3 g of the desired compound is obtained at 6.5 DEG + 1 DEG (c 1.7 DEG, benzene).
15 VOORBEELDEN XI tot XLI :15 EXAMPLES XI to XLI:
Tewerkgaande op dezelfde wijze als in de voorgaande voorbeelden worden de volgende verbindingen met formule 1 bereid uitgaande van verbindingen met formule 2 en van verbindingen met formule 3· 20 8104495 -9- ' _____—-—-- —I ΖI w s? si5 g s ^ «Proceeding in the same manner as in the previous examples, the following compounds of formula 1 are prepared starting from compounds of formula 2 and of compounds of formula 3 · 20 8104495 -9- '_____—-—-- —I ΖI w s? si5 g s ^ «
It'0- s I ·“ I §It'0- s I “I §
S ° B B · · A S.-HO'SS ° B B · A S.-HO'S
<3 JJ fj · · 8 B >3 ·Η Sj o I ® *H ft ft · · H ° ft -<3 JJ fj · 8 B> 3 · Η Sj o I ® * H ft ft · · H ° ft -
ΛΙ JS ,D · · Pi ft ,, Λ BS JS, D · · Pi ft ,, Λ B
_ Cl Pi · · Λ +> Ö Jo or c ^ & ft ? tj « SZ?5^ 3 © CO ® 3 Λ ί ‘ri m_ Cl Pi · · Λ +> Ö Jo or c ^ & ft? tj «SZ? 5 ^ 3 © CO ® 3 Λ ί‘ ri m
Pi ^ ^ CM *ri 5 Ö p u ij _ . fti j- - - ό ö 3 Ph M g ^ cl 1X1 .. T- j- to > ft « g 11 s & Rtps " ! ? ί ί S .3 r-i o ·- - T- O' ^ C ® ° 2s S »0 Q| L **·» CÖ 3 Ο · ö § I s « l· ^s & & || I s .Pi ^ ^ CM * ri 5 Ö p u ij _. fti j- - - ό ö 3 Ph M g ^ cl 1X1 .. T- j- to> ft «g 11 s & Rtps"!? ί ί S .3 ri o · - - T- O '^ C ® ° 2s S »0 Q | L ** ·» CÖ 3 Ο · ö § I s «l · ^ s & & || I s.
B “r ! “ I S 3 «8 i ïa S »BB “r! “I S 3« 8 i ïa S »B
I ë Ö cvj ^ ·° 5 ” ft Λ ft Ö ft o.I ë Ö cvj ^ · ° 5 ”ft Λ ft Ö ft o.
I ς ! 1¾ o 3 ^ ~ 3 15 ^ S Φ o * £ § t * § § * 0¾ | g * * s -* ~ & I g ί I s I I I « ; * ; 5^ I | s*: J * 4 I *-'141 1¾ II ‘ I * 5 7 i ƒ? II. ΓΙ, I £ ll§i|^i I !&§? j *;***: ! 11 “ I “ 5 - ? tit *, its*. r,i ΙΛI ς! 1¾ o 3 ^ ~ 3 15 ^ S Φ o * £ § t * § § * 0¾ | g * * s - * ~ & I g ί I s I I I «; *; 5 ^ I | s *: J * 4 I * - '141 1¾ II "I * 5 7 i ƒ? II. £, I £ ll§i | ^ i I! & §? j *; ***:! 11 "I" 5 -? tit *, its *. r, i ΙΛ
>2 _| H> 2 _ | H
§ o 9 5 *5 4 z o - Q H Ö§ o 9 5 * 5 4 z o - Q H Ö
6 3 I6 3 I
& £ I& £ I.
ES « AES «A
•Η I Ό PJ• Η I Ό PJ
I © II © I
°t € I ό "8 - ft Λ g ^ H · £ I * £ s° t € I ό "8 - ft Λ g ^ H · £ I * £ s
I g $ X SI g $ X S
©ft £ d d SO S ζ> Λ© ft £ d d SO S ζ> Λ
mJ ,,j ·· Ή β UmJ ,, j ·· Ή β U
W „ T* & H 7 ft £ g Ö w. £ § Ö 8 g CJ OJ r-1 *H _ (VI ft Ö fi 9 ~ s? o 3 ς f {W „T * & H 7 ft £ g Ö w. £ § Ö 8 g CJ OJ r-1 * H _ (VI ft Ö fi 9 ~ s? O 3 ς f {
I g JiS UhII g JiS UhI
I 1 * § ! i'|| 1 I e s s l“ll 8104495 - 1.I 1 * §! i '|| 1 I e s s l “ll 8104495 - 1.
_-10-_ η"' 1 Ε +> |t V >> CM & I Oft •ο Λ —' Pt © 4* - ο +» 1 ti 60 4* «Ν d Χ> Φ ΝΛ Φ *rj 0} 00 Ο CO τ” a U S3 Μ ·Η Ό Ο 1-1 -Ρ ο · > ti Η Φ ,Ο *·Λ — <Μ_-10-_ η "'1 Ε +> | t V >> CM & I Oft • ο Λ -' Pt © 4 * - ο +» 1 ti 60 4 * «Ν d Χ> Φ ΝΛ Φ * rj 0 } 00 Ο CO τ ”a U S3 Μ · Η Ό Ο 1-1 -Ρ ο ·> ti Η Φ, Ο * · Λ - <Μ
OÖ >, Ή ö VO d CO ΙΓ\ IOÖ>, Ή ö VO d CO ΙΓ \ I
ftl S Ε Pt ,Μ 3 I © Ο <Μ © £ +3 ® > οο X - ·η σ» (Q · Ό Φ 0·Η Ο ® ΙΓ\ Ή * +J Ε ti Β 3 Pt CM · XI rO Ο φ · C φ *Η ti ΙΓ\ Ο Ό rtPtSB Μ PtöW Η *Η .Μ *rs Η · r* Ο I Ρ Ο 3 ·Ρ © ·Ηftl S Ε Pt, Μ 3 I © Ο <Μ © £ +3 ®> οο X - · η σ »(Q · Ό Φ 0 · Η Ο ® ΙΓ \ Ή * + J Ε ti Β 3 Pt CM · XI rO Ο φC φ * Η ti ΙΓ \ Ο Ό rtPtSB Μ PtöW Η * Η .Μ * rs Η · r * Ο I Ρ Ο 3 · Ρ © · Η
Οι Ρι +> Ki 3 (4 Π) d «Η >» *Η JOΟι Ρι +> Ki 3 (4 Π) d «Η>» * Η JO
t— to aS «* d Pt Pt d ,Π O JW Pt CU ITS +> Vt CJ N o O H © -\ ti 2 O IN © O· CS Η P Pt Ε Λί © H ©t— to aS «* d Pt Pt d, Π O JW Pt CU ITS +> Vt CJ N o O H © - \ ti 2 O IN © O · CS Η P Pt Ε Λί © H ©
0 - © -PB ^ O O Pt p, © M Pt X0 - © -PB ^ O O Pt p, © M Pt X
Ö Η T- H © · Oil O ft ft 'ri t ti © g >, Pt H Pt H P O H - O Λ fl Η © ·ΗÖ Η T- H © · Oil O ft ft 'ri t ti © g>, Pt H Pt H P O H - O Λ fl Η © · Η
Hijcsi o· ©3 o ιλ ^ 3 w Λ g φ "— m Pt p « © w - !? *, 2 d HEIN tfllN t-S Λ , O C *W XI O >* m « © E © r- rt +> ©OP H ti S3 © v* m · © «· Pt d © © d Pt *p 3 © gHijcsi o © 3 o ιλ ^ 3 w Λ g φ "- m Pt p« © w -!? *, 2 d HEIN tfllN tS Λ, OC * W XI O> * m «© E © r- rt +> © OP H ti S3 © v * m · © «· Pt d © © d Pt * p 3 © g
pro ftHVO dp 3 XS Μ Φ O CQ O £» Xpro ftHVO dp 3 XS Μ Φ O CQ O £ »X
> <rj Pt t h ti P P r—ï O© d ·Η o Pt xs +> > Pt d g » ft o ® Λ 3 x> ^ -p o o ιλ © 5 «3 „ o « © o > o γλ© +> p h S3 ► > - iB ^ ^ d d ir\ © o o r- >ü d o S3 © © - © ΙΛ -PS 8 IA S3 „ ,© ti ti rj> <rj Pt th ti PP r — ï O © d · Ηo Pt xs +>> Pt dg »ft o ® Λ 3 x> ^ -poo ιλ © 5« 3 „o« © o> o γλ © +> ph S3 ►> - iB ^ ^ dd ir \ © oo r-> ü do S3 © © - © ΙΛ -PS 8 IA S3 „, © ti ti rj
WrocvlOCO OO ©Pt -OdO^ W o ö © ·» © ό Pt d d *h 3 ^ © -H p -P P Η Η P ^ © ®.P>PO ©WrocvlOCO OO © Pt -OdO ^ W o ö © · »© ό Pt d d * h 3 ^ © -H p -P P Η Η P ^ © ®.P> PO ©
Pt o O O >9Ï>9 ti tf\ _ O 4* S3 Ό ΙΛ - O -P O -rs dd g CM r- ΕΚ\ς)τ·0 © H M ΜΗ © © Pt* Pt « Md © ti ffl >> IN X» X Pt ©r- CQ Pt Β ü CQ H XS 3 +> d d d ©o to +» +» © £ d P* © > ti © © · © ü xs P p ti c^- d h d ©· w <0 Pt 60 (M 60 © O Pt ©®d*“dPtd60>< ·Η S3 H o d d ·Η Hl ΙΛ Ό _ Η " Η λ d ? « « S « dt P P *f-5 Ct Pt O t- H „ °0 PtfM ptHPtS g»g® f ®Pt o OO> 9Ï> 9 ti tf \ _ O 4 * S3 Ό ΙΛ - O -PO -rs dd g CM r- ΕΚ \ ς) τ · 0 © HM ΜΗ © © Pt * Pt «Md © ti ffl >> IN X »X Pt © r- CQ Pt Β ü CQ H XS 3 +> ddd © o to +» + »© £ d P * ©> ti © © © ü xs P p ti c ^ - dhd © · w <0 Pt 60 (M 60 © O Pt © ®d * “dPtd60> <· Η S3 H odd · Η Hl ΙΛ Ό _ Η" Η λ d? «« S «dt PP * f-5 Ct Pt O t- H „° 0 PtfM ptHPtS g» g® f ®
Pt 'u ·η ό % >siod'"„,-bi«r0S,dS,fe p, Η Φ X» © d OHQd · Pt I Pt dPt 'u · η ό%> siod' "", - bi «r0S, dS, fe p, Η Φ X» © d OHQd · Pt I Pt d
Ot»s60 60© ISO>'«”0 O « O M Ö „ X _ d jd ü ©tMx! CM Pt © 00 +> CO ti trj +3 w © a +> 4agSS‘r?S3C'SSOSSSS600©Od dl uJ H CO d) S *rl © SU fl) ^ ®Ot »s60 60 © ISO> '«' 0 O «O M Ö„ X _ d jd ü © tMx! CM Pt © 00 +> CO ti trj +3 w © a +> 4agSS‘r? S3C'SSOSSSS600 © Od dl uJ H CO d) S * rl © SU fl) ^ ®
I Β I Pt I X K 8 PS I I O I Pt I IHVOIVOII Β I Pt I X K 8 PS I I O I Pt I IHVOIVOI
KA HKA H
1 ë1 ë
Θ XΘ X
1 I1 I
Β HΒ H
H OHO
cq >> S oor >> S o
P CMP CM
I o CM JtI o CM Jt
w Pt KN Ow Pt KN O
Η ©Η ©
HOM >s *HHOM> s * H
.SCO.SCO
h d o CM Η Μ © p h i Pt d 2 H CM O d w w - p « C3 (M Pt tih d o CM Η Μ © p h i Pt d 2 H CM O d w w - p «C3 (M Pt ti
S Q I OS Q I O
h a o r fh a o r f
gH O PgH O P
0 H H W0 H H W
s e ° s § I 8 e ï 1 >|_>1 w g &_ 8104495 __-11-_____ J, ' ^ Ε Η4 Ηλ § Φ Η Ε I rfs e ° s § I 8 e ï 1> | _> 1 w g & _ 8104495 __- 11 -_____ J, '^ Ε Η4 Ηλ § Φ Η Ε I rf
% *- & fc* & 10 £ ft S% * - & fc * & 10 £ ft S
I ^ | g § 15 ® $ II ^ | g § 15 ® $ I
I 3^-¾¾ E > f -7. g A -ë^gg 4Ü « ? e Ύ 4< ft ® ® & « " 3^3 ^ * ui * * ° 3 H v^ci d fl e +> es «2> Λ {3 S I 3 I 1 λΈ £ *· -rl ® *" ® o * m -a Eti g. _ B ö'jd® ZB & -¾¾ £ ftS °E 5 § « d I 3 o ® m § JA * h ^ » . EUh | I s 3 * Έ Ά W-S ^ fti w-£ o 5¾ § S I £ ]L - ^ S ï ^ ™ 3 E ft'iI 3 ^ -¾¾ E> f -7. g A -ë ^ gg 4Ü «? e Ύ 4 <ft ® ® & «" 3 ^ 3 ^ * ui * * ° 3 H v ^ ci d fl e +> es «2> Λ {3 SI 3 I 1 λΈ £ * · -rl ® *" ® o * m -a Eti g. _ B ö'jd® ZB & -¾¾ £ ftS ° E 5 § «d I 3 o ® m § YES * h ^». EUh | I s 3 * Έ Ά W-S ^ fti w- £ o 5¾ § S I £] L - ^ S ï ^ ™ 3 E ft'i
g w 2 0 £ ó ^ -o o 1,- » « O g Jg w 2 0 £ ó ^ -o o 1, - »« O g J
g .3 J 3 1-8 -§ 2&b®ö o| 3 g. ·β I * i 5 |a & ip:; «1 & 1 &g .3 J 3 1-8 -§ 2 & b®ö o | 3 g. Β I * i 5 | a & ip :; «1 & 1 &
S P « o I o ε ft®r- > - § S ^ ° SS P «o I o ε ft®r-> - § S ^ ° S
ö«S *Ö Pt Pt jv 8 ·· ^ Sö Λ I I ^ i & d s*Srt 5! : ; maai;;; if * *Jf !! 5 5: *: -115 ·§ 1 & 1 1, & S3 3·3&.»'&«Γ··-γ>3£ f? S If* ï g Ta I ï I j I - : : ^ ^ J Ö^^l" ^ ll &s &121:111 & I 111 & * & a: 5&SH<M"«K^a|MB2«S ·= ?* S » ° MBS® (iJl-glIll’ElftlIPtlft fA Γ- « I OJ I I Ptö «S * Ö Pt Pt jv 8 ·· ^ Sö Λ I I ^ i & d s * Srt 5! :; mow ;;; if * * Jf !! 5 5: *: -115 · § 1 & 1 1, & S3 3 · 3 &. »'&« Γ ·· -γ> 3 £ f? S If * ï g Ta I ï I j I -:: ^ ^ J Ö ^^ l "^ ll & s & 121: 111 & I 111 & * & a: 5 & SH <M" «K ^ a | MB2« S · = ? * S »° MBS® (iJl-glIll'ElftlIPtlft fA Γ-« I OJ II Pt
JAYES
§ O 7§ O 7
§ I H§ I H
i » j? II I .i »j? II I.
4. è t é4. è t é
f I I If I I I
« g <i S«G <i S
~ E ^ g~ E ^ g
£ g, I£ g, I.
ίπί 11 Η £> -H .2 ,2 n - 5 I q "Tg, fc H <i O 3 > ™ ®ίπί 11 Η £> -H .2, 2 n - 5 I q "Tg, fc H <i O 3> ™ ®
I x «i MI x «i M
g 9 Λ r 3 S^nÖOg 9 Λ r 3 S ^ nÖO
fl I I “ ^ Sfl I I “^ S
Z Η *ri H Ö S « n o a s ” ί j § : & s s s k ξ I g « ^ g III g ris___S[5 4 g -- 8104495 . u _____ - - - ........ ' "*·................"*......Z Η * ri H Ö S «n o a s” ί j §: & s s s k ξ I g «^ g III g ris ___ S [5 4 g - 8104495. u _____ - - - ........ '"* · ................" * ......
I η I ** "VI η I ** "V
1 H* §00 Ö iR ft «-P H £> i1 H * §00 Ö iR ft «-P H £> i
5? H & I & ^ ft S? % d I5? H & I & ^ ft S? % d I
o S o *- CM B ΙΛΟΟΦΟ oöfn w d η -tf- ,fl ,Ο ft d d φ ft I I *8 H · d d ft 3 « ο γλ © ,ο ars 8 3 © o ο ο h in , to ι ο ο ό h d Ο σ» H ,Μ (Μ Ο φ Qi bs f> ^ C φ ΚΛ Ο Φ Ü 5 « & 5 s «ς · ·“ I °o S o * - CM B ΙΛΟΟΦΟ oöfn wd η -tf-, fl, Ο ft dd φ ft II * 8 Hdd ft 3 «ο γλ ©, ο ars 8 3 © o ο ο h in, to ι ο ο ό hd Ο σ »H, Μ (Μ Ο φ Qi bs f> ^ C φ ΚΛ Ο Φ Ü 5« & 5 s «ς · ·“ I °
§ 10 Ϊ 3.. g «. Sh'-oS § H I§ 10 Ϊ 3 .. g «. Sh'-oS § H I
r-> g . Λ ·° 3 g & £ s*" > £ * μ > d d is oo to b -μ d a +J 3 © oj d d xi Α5+» 4» © g W B O >Js! » O 21¾ © ί S s ^r-> g. Λ · ° 3 g & £ s * "> £ * μ> d d is oo to b -μ d a + J 3 © oj d d xi Α5 +» 4 »© g W B O> Js!» O 21¾ © ί S s ^
ö B © cMfOOB-riBBö B © cMfOOB-riBB
g H © d ·Η dHOftHHOd H ft to © ft '"n B O . ft ft tO © §1 -H ft η BO S © Pi' I. J -rj ft CG_ >β © H *rl B 0-0 S Ή ®g H © d · Η dHOftHHOd H ft to © ft '"n BO. ft ft tO © §1 -H ft η BO S © Pi' I. J -rj ft CG_> β © H * rl B 0-0 S Ή ®
S© § S c? : ° b +» c φφ © s § KMS © § S c? : ° b + »c φφ © s § KM
efl -μ Μ R, «ft © 3 ft 'ö _ ό S’ m _§> & IQ H E -P *" O Λ > P Λ Eft B H ft ft Ό >j ft ö n-/ d dft&ft O S _.efl -μ Μ R, «ft © 3 ft 'ö _ ό S’ m _§> & IQ H E -P * "O Λ> P Λ Eft B H ft ft Ό> j ft ö n- / d dft & ft O S _.
o d s J? ft £ ft d b ft o ft o cm d -5¾ ft μ do 3 -μ vo -η -μ (vi O E © ft © ΚΛ © ©H > B © O Ά O f © © ft ECMO >0 B Ό t~ CM B'f" © ft Φ OJ «· >5 |C\ Η Φ ·> φ © S -S o · r- d u o ft d ό ό -μ ό © -μ ρ ίο μ f\j μ d > -μ h « ,λ >ρ-μρμρ85·μ 0-0 cö O S3 O O O O ft ra o cm o i B J- φ d *- © r£*’5ïï5 Ό Ό ft OJ Η Φ Ό Ό -8 J· ft το. If\ φ ·· (0 ^ ft IQ O ll\ ·> K\ © ~ dN>doitO<r-+> -μο +> ft +> t) σ\ Ö N d *“ M r © ·. 3 » B d d B O B © ·* © © * bO (Μ M t- © η B ©ft B 8 B bp (Λ tO d MN® d B B Ό *H H ft I t^dOftHg#- gg«.f_,'eg s^a^fsg·0· V u dj ^ W ^r-J L © ^ jy 4m d®w ®w ®do ο-μ«5« o <m w w ©w ©« © « © «Η «Η ·Η —ΙΦ«Ε« O ·Η ·Η ·Η ·Ηo d s J? ft £ ft db ft o ft o cm d -5¾ ft μ do 3 -μ vo -η -μ (vi OE © ft © ΚΛ © © H> B © O Ά O f © © ft ECMO> 0 B Ό t ~ CM B'f "© ft Φ OJ« ·> 5 | C \ Η Φ ·> φ © S -S o · r- duo ft d ό ό -μ ό © -μ ρ ίο μ f \ j μ d> - μ h «, λ> ρ-μρμρ85 · μ 0-0 cö O S3 OOOO ft ra o cm oi B J- φ d * - © r £ * '5ïï5 Ό Ό ft OJ Η Φ Ό Ό -8 J · ft το If \ φ ·· (0 ^ ft IQ O ll \ ·> K \ © ~ dN> doitO <r - +> -μο +> ft +> t) σ \ Ö N d * “M r © ·. 3 »B dd BOB © · * © © * bO (Μ M t- © η B © ft B 8 B bp (Λ tO d MN® d BB Ό * HH ft I t ^ dOftHg # - gg« .f _, 'eg s ^ a ^ fsg · 0 · V u dj ^ W ^ rJ L © ^ jy 4m d®w ®w ®do ο-μ «5« o <mww © w © «©« © «Η« Η · Η - ΙΦ «Ε« O · Η · Η · Η · Η
IftlftlftlOJ -3* S « I *Ö I I I ft I ft I ft I ft i s +4 d " l § s &IftlftlftlOJ -3 * S «I * Ö I I I ft I ft I ft I ft i s +4 d" l § s &
S OS O
a d Η Ό S >? d a a oa d Η Ό S>? d a a o
Ξ I II I I
> r- J- % , 4» d © o 8 A t d> r- J-%, 4 »d © o 8 A t d
C\1 B w OC \ 1 B w O
Λ s t IT s t I
Λ OO.
+5 h+5 h
© ft E 0 ·· tJ H© ft E 0 ·· tJ H
ΟΙ Ό OΟΙ Ό O
HISHIS
g p· cm o © Η X ·« y-s «ög p · cm o © Η X · «y-s« ö
Ö ftl Η -HÖ ftl Η -H
:H 9 - &* S: H 9 - & * S
g I 4? a d S g ° £ g a ο « λ s P O r- I d > t ^ T- N — 1..... 8 1 0 4 4 9 5 -13- '<***y--. . ... * · ' —g I 4? a d S g ° £ g a ο «λ s P O r- I d> t ^ T- N - 1 ..... 8 1 0 4 4 9 5 -13- '<*** y--. . ... * · '-
φ w I Ht | « Lφ w I Ht | «L
<β I CVJ b 05 Ό ft Al<β I CVJ b 05 Ό ft Al
g ^ 5 O ft *> Og ^ 5 O ft *> O
S Η ® O -sf "jiS Η ® O -sf "ji
1 S * ? ? η V J1 S *? ? η V J
N -s £ ü 3 S? <4 ΆN -s £ ü 3 S? <4 Ά
ï 3 -5 " ® t «Λ Oï 3 -5 "® t« Λ O
§1 *β Η +* Η _ 5 ni l l U >» © O -o ft 'pi, ai £ ft Λ _ h ®§1 * β Η + * Η _ 5 ni l l U> »© O -o ft 'pi, ai £ ft Λ _ h ®
t~ <M3 ► il +* U S J5 Ot ~ <M3 ► il + * U S J5 O
ft N Al W « S _ 8* w £, §° '«ï O 'b o H > 'ö ® H s | g & §1 § *£ Tf ft ö ^ I ^ g 5 ft i 8 £ g °ii & L'rf Sw Z®K\ ü fi Al K ® , >j»BC~ ssct « 3 £ 1 ~ § 2 O 5 § « r |©r. - I .2 | ti,SÏ2dT? > ö go e Pi O © h ft Η Λ fn ti ·Η ^öS S ft 3 ft O ft ft o © ft 3 ft a j> o >0 ft g V o -H > §c^ ^ h H ir 3 © -d; ft ft © ^ sft N Al W «S _ 8 * w £, § ° '« ï O' b o H> 'ö ® H s | g & §1 § * £ Tf ft ö ^ I ^ g 5 ft i 8 £ g ° ii & L'rf Sw Z®K \ ü fi Al K ®,> j »BC ~ ssct« 3 £ 1 ~ § 2 O 5 § «r | © r. - I .2 | ti, Si2dT? > ö go e Pi O © h ft Η Λ fn ti · Η ^ öS S ft 3 ft O ft ft o © ft 3 ft aj> o> 0 ft g V o -H> §c ^ ^ h H ir 3 © -d; ft ft © ^ s
νβ Pi O U O wS B<VI«rti^®Mνβ Pi O U O wS B <VI «rti ^ ®M
W-, m 4>^a ft *» Φ »MW-, m 4> ^ a ft * »Φ» M
r· JS o ® o ö O t> r- »Ö O SS® ö M ^ Ai B Sfc 'Ö ri . O ? ® ΐ Φ *π φ Η K\ Φ H _ ► 2* Ö S λ « ^ ^r · JS o ® o ö O t> r- »Ö O SS® ö M ^ Ai B Sfc 'Ö ri. O? ® ΐ Φ * π φ Η K \ Φ H _ ► 2 * Ö S λ «^ ^
•rl H h CO «Tib'S , ° S ® n .§ r λ J• rl H h CO «Tib'S, ° S ® n .§ r λ J
£ ë F g £ δ *0 & N *8 ^ ^ $£ ë F g £ δ * 0 & N * 8 ^ ^ $
aft +3 ft t“ r- p, -ί- -p >3 & *“ _ S 3 K Saft +3 ft t “r- p, -ί- -p> 3 & *“ _ S 3 K S
+> © ©o i o » o 60 ^ S g Irt ”ë o,+> © © o i o »o 60 ^ S g Irt” ë o,
5*ft B & ** © & *" ® h © η δ HBO5 * ft B & ** © & * "® h © η δ HBO
_l_ bs | X K .· S ΙΛ *Ö Ή <Ö W Η H ij ft t JS rf*« *? HO Π8 fi 1 ft Λ « O I S Λ 5%ö |oë>jgto^oo«o wo o 5 ^ o £ ^ o&gweKiwag , & oi'v, ’oB'V. o^ftlftlislli- (Λ % +3_l_ bs | X K. · S ΙΛ * Ö Ή <Ö W Η H ij ft t JS rf * «*? HO Π8 fi 1 ft Λ «O I S Λ 5% ö | oë> jgto ^ oo« o wo o 5 ^ o £ ^ o & gweKiwag, & oi'v, 'oB'V. o ^ ftlftlislli- (Λ% +3
55 © Η H55 © Η H
« S O OS O O
Ö H ï SÖ H ï S
n & t 8 § .a $ § a I O £ g on & t 8 § .a $ § a I O £ g o
CP HO® HCP HO® H
ft ooft Oft ooft O
H >s Η I ïj» > OW_K\ _ O-----------“H> s Η I ïj »> OW_K \ _ O -----------“
% £ H% £ H
+3 H 5j « ® ft ,+3 H 5j «® ft,
BI BI +> IBI BI +> I
Tc i ö ® öTc i ö ® ö
Ai O Al O B OAi O Al O B O
vy vy ,Ο I ft ift S Λ δ 'τ' 1 o o I o SI SI " 1vy vy, Ο I ft ift S Λ δ 'τ' 1 o o I o SI SI "1
§ & || SI§ & || SI
b 2 s fa © k •H ft ·· H ft S S*b 2 s fa © k • H ft ·· H ft S S *
•«•WO «O O B O• «• WO« O O B O
I Η Η I Η ·· Η HI Η Η I Η ·· Η H
AI ΗΛΙΟ ΗΛΙΟ ,. *Ö OAI ΗΛΙΟ ΗΛΙΟ,. * Ö O
JES >AiO«>AJO®HA10® ca X Ό X λ«οΧ·"^ΌJES> AiO «> AJO®HA10® ca X Ό X λ« οΧ · "^ Ό
S 91&SSS&ë9-&SS 91 & SSS & ë9- & S
g Ils,di®£.ag"£ö B i-ggs^sss^gg g 8?ν·§8^?§8Ρ?1 g_;>| w r* t3 ^1 n»/ r N >1 w v ________ f 8104495 - i.g Ils, di® £ .ag "£ ö B i-ggs ^ sss ^ gg g 8? ν · §8 ^? §8Ρ? 1 g _;> | wr * t3 ^ 1 n» / r N> 1 wv ________ f 8104495 - i.
- ------ ------- ------ -- --- - ------- · -...... ..-- ------ ------- ------ - --- - ------- · -...... ..-
1 % H ’ sf , £ I1% Hsf, £ I.
ï s “i 1 I i ,-· % | B +> r- Pt Pi Η P»ï s “i 1 I i, -% | B +> r- Pt Pi Η P »
I © O OOP II © O OOP I
(M e Ρ A -Η | T-(M e Ρ A -Η | T-
— | <ri a -p- Ρ .P >· H- | <ri a -p- Ρ .P> · H
t<\ cvj ja o - o λ W H IA O ü Cv) Λ Η ΙΛ X O I © +> >» © >, Κλ © ·Η ra © Λ Η ·Η O - t) Pt ·£ εt <\ cvj ja o - o λ W H IA O ü Cv) Λ Η ΙΛ X O I © +>> »©>, Κλ © · Η ra © Λ Η · Η O - t) Pt · £ ε
S £ άι ιλ . ai IS £ άι ιλ. ai I
15 A -, -P Ρ Η* P PJ15 A -, -P Ρ Η * P PJ
B +> p © Ό rf >, HB +> p © Ό rf>, H
•H © 3 .0 *rl r> Pi Pi K\H• H © 3 .0 * rl r> Pi Pi K \ H
r* *0 S P >P O Or * * 0 S P> P O O
I *H .Pip Μ P Pi Η 0 g <\J Ό 0 3 .M +} P* 0 fc>2 m *» I ρ > © ai Ο Λ Λ ra f\] CVJ Pt ·Η ttf W H -P4* g U - P o P ft Η -H £, © ©I * H .Pip Μ P Pi Η 0 g <\ J Ό 0 3 .M +} P * 0 fc> 2 m * »I ρ> © ai Ο Λ Λ ra f \] CVJ Pt · Η ttf WH -P4 * g U - P o P ft Η -H £, © ©
Η p (\J p H © i Pt Λ SBΗ p (\ J p H © i Pt Λ SB
S ω 5 ^ ρ υ Pi h .t ©+i -π g p 5 ta δ >»© b>K'e £ 'ö ^ H 3 Ρ H 0 O O P° _ s I , r- CQ p O O O p © © 0 W h ,S ω 5 ^ ρ υ Pi h .t © + i -π gp 5 ta δ> »© b> K'e £ 'ö ^ H 3 Ρ H 0 OOP ° _ s I, r- CQ p OOO p © © 0 W h,
Sj 4>» _Q _Q +> 60 Pi Ό 3 © — ρ ii I h w- Έ 2 tfePe, ► * ™ 3 „ > co ra r- ra -P S S P Pi _ ^ “Sj 4> »_Q _Q +> 60 Pi Ό 3 © - ρ ii I h w- Έ 2 tfePe, ► * ™ 3„> co ra r- ra -P S S P Pi _ ^ “
r- o ^ O _j JpgiPiO 0 0 QSr- o ^ O _j JpgiPiO 0 0 QS
—»ö p B -p ρ, © a> wo 3 p 3 > © © o s Pi £ ή a o- »ö p B -p ρ, © a> Wed 3 p 3> © © o s Pi £ ή a o
paf 3 0 S K\ Ό Pi © OPIApaf 3 0 S K \ Ό Pi © OPIA
3 Pi > a ιά - _ © Pi o W ,Λ 3 _r >o o © r* ρ Φ P co © r* , L Ρ P K\ 0 <0 3j±b0 P T“ p p3, © & h © pp>p^h © w3+i ©or- -POO © ® o · . © _ +> H » η Ö r- © Γ O 4· Λ ίΑ 0 ft3 Pi> a ιά - _ © Pi o W, Λ 3 _r> oo © r * ρ Φ P co © r *, L Ρ PK \ 0 <0 3j ± b0 PT “p p3, © & h © pp> p ^ h © w3 + i © or- -POO © ® o ·. © _ +> H »η Ö r- © Γ O 4 · Λ ίΑ 0 ft
WOtN © o O «(Μ Ό +> © O IAWOtN © o O «(Μ Ό +> © O IA
©S-4· H>> U © - W ·<~> « W > P - HO - % O B 4> M r « -rl S -P gi^r >» /-N xr Λ pp Ρ Φ -Ρ Ρ Ρ Ο νΟ© S-4 · H >> U © - W · <~> «W> P - HO -% OB 4> M r« -rl S -P gi ^ r> »/ -N xr Λ pp Ρ Φ -Ρ Ρ Ρ Ο νΟ
I Η +> Η Ρ © ©r-sp bO ©BP ©HII Η +> Η Ρ © © r-sp bO © BP © HI
Τ- >ϊ ·· © b +* Η TP *H iH CÖ *Ö g» ra;I +> OΤ-> ϊ ·· © b + * Η TP * H iH CÖ * Ö g »ra; I +> O
Ip Η Ρ O ^ ,PPiP© PiftH M >» ··Ip Η Ρ O ^, PPiP © PiftH M> »··
p© V, © © p -SHp >> ©Op © V, © © p -SHp >> © O
£> ftCA Λ Pi Pi Pi 3 P Pi ¢) ft 5 N ft £1 H ^£> ftCA Λ Pi Pi Pi 3 P Pi ¢) ft 5 N ft £ 1 H ^
+> OrQ 4JOtQOB>©OtiO*H>(MO© b H .P+> OrQ 4JOtQOB> © OtiO * H> (MO © b H .P
0 ρ \ ©P Pi Jd +* - Pi JÖ Ps \ ,Ρ Pi B Pi S W Piifl ©iPWHWT-tP p +> g *k IIP IIS ·Η P p © © © ΙΛ r \ t-r-pjlfUIPillfilllPi B P \0 ρ \ © P Pi Jd + * - Pi JÖ Ps \, Ρ Pi B Pi S W Piifl © iPWHWT-tP p +> g * k IIP IIS · Η P p © © © ΙΛ r \ t-r-pjlfUIPillfilllPi B P \
fAfa
S HS H
HO HHO H
ö I o H ^ i e! S R. & i H 4*· P 2 oQ p a >p a ,s o +> pi w ©ö I o H ^ i e! S R. & i H 4 * · P 2 oQ p a> p a, so +> pi w ©
> IA H S> IA H S
Η I I , * P H p d h Λ P £> P b 3 4) a F a -Ρ ρ © δ +» s ii 2Η I I, * P H p d h Λ P £> P b 3 4) a F a -Ρ ρ © δ + »s ii 2
bp © p ® Sbp © p ® S
1 o 8 o s o (M ja I fit * <?1 o 8 o s o (M yes I fit * <?
P OJ P Al PP OJ P Al P
ia 3 ^ <t '-t 2 Ü I O I oia 3 ^ <t '-t 2 I I O I o
ή s " s " I"s" s "I
s a ft a g as a ft a g a
is q f Iis q f I
•H Pi © Pi ® gi Ό O BO ·· § Ο I H *· Η Η i_i Tl• H Pi © Pi ® gi Ό O BO ·· § Ο I H * · Η Η i_i Tl
~ h 7 S, S I I~ h 7 S, S I I
Ö^H OJHÖ ^ H OJH
gQW^,i=lb Ö & .gQW ^, i = lb Ö &.
ΗΗΡΡΦΗ^>Ρ® J ^ Ρ Φ aPSo-ppmoO SH P ft Ή S Ή a*rlΗΗΡΡΦΗ ^> Ρ® J ^ Ρ Φ aPSo-ppmoO SH P ft Ή S Ή a * rl
Hcg+»opmoop 0^8¾ cqSpokpo s - ρ oHcg + »boost 0 ^ 8¾ cqSpokpo s - ρ o
pÜÖWPiHOtQftHpÜÖWPiHOtQftH
Por*l2 pr-l3 Ö X- l APor * l2 pr-l3 Ö X- l A
>>wr- o>wr- O_________>| w r- O>> wr- o> wr- O _________> | w r- O
“ 8104495 J8104495 J
> _ri5-_ £ ΛΙ Λ ^ , * * £ Η S « Η Λ Η Λ £> 5 ε 'Si> _ri5-_ £ ΛΙ Λ ^, * * £ Η S «Η Λ Η Λ £> 5 ε 'Si
I £ 1 5 1 i II £ 1 5 1 i I
f β ·Η i f « Λ - β 7s 5 ^ ο· ff β · Η i f «Λ - β 7s 5 ^ οf
^ $ (Μ 5 I KNO W^ $ (Μ 5 I ENT W.
^ ι u · δ Wh -£ '-Ϊ^ ι u · δ Wh - £ '- Ϊ
£ ~ § w§ « § Q § " A£ ~ § w§ «§ Q §" A
- § w 2 "a ΐ 15 ö S £ £ η pq © ^ o Q jj § S S £ & & ^ 3 s^ os & 3 o F'Sëü'^iS o- § w 2 "a ΐ 15 ö S £ £ η pq © ^ o Q yy § S S £ & & ^ 3 s ^ os & 3 o F'Sëü '^ iS o
I s g ï ss I S i s„s | h II s g ï ss I S i s „s | Hi
g a S >T o SS m| « § g' “'i I °ιλ S I 5 g «f! S’ . - I * ~ I - I o- ~ I § Λ I · I 11*· s I f * l s 1: 11 - iy« isg" èoo fe-s » s § * » j » »|s i&r 11 ι**, 91“ p |v i!*« tt.- ff* fh «!o:· «Ie ! 1¾2 !|v I:: |f? j|> ||:g a S> T o SS m | «§ g '“' i I ° ιλ S I 5 g «f! S ". - I * ~ I - I o- ~ I § Λ I · I 11 * · s I f * ls 1: 11 - iy «isg" èoo fe-s »s § *» j »» | s i & r 11 ι * *, 91 “p | vi! *« Tt.- ff * fh «! O: ·« Ie! 1¾2! | V I :: | f? J |> ||:
It’*” | η ’* | |“ï | Η H ö " H CIt "*" | η ’* | | “Ï | Η H ö "H C
3|>e ι 1¾. 3|>° |&>° 11^ I 6¾^ &K a< * &<3 |> e ι 1¾. 3 |> ° | &> ° 11 ^ I 6¾ ^ & K a <* & <
*> . H*>. H
g *o I I « 2 W Λ H d 'i o Ö5 O fe ?? 2? o go ft ft ft , . Jj S *3 2¾ 1¾ |o 3 3 II £ ι £ § sa * « ~£h h £ έ g Λ2 d g . ^ 3 $ *51, II la . a a a § έ |gg * o I I «2 W Λ H d 'i o Ö5 O fe ?? 2? o go ft ft ft,. Yy S * 3 2¾ 1¾ | o 3 3 II £ ι £ § sa * «~ £ h h £ έ g Λ2 d g. ^ 3 $ * 51, II la. a a a § έ | g
« ί ί·2 'iS' ÏÏ ΐ -3 I II«Ί ί · 2 'iS' ÏÏ ΐ -3 I II
«I ΰ g ^ & Λ § A 8 ΰ §«I ΰ g ^ & Λ § A 8 ΰ §
11 £ & S S ί I £ & ϊ S11 £ & S S ί I £ & ϊ S
12 I g gi , ΐ 2 « I - 6 I12 I g gi, ΐ 2 «I - 6 I
..5 a ma ·ηη*ο ε & ·· ε ft +* ft ΌΟ —HO Ti >ι Ή ·· τ] ο ïj ο y 2 j U I J ·ΗΗ ·. I ö h 'Ö Η Η 'Ö Η Η S Η λι Η (Μ U ^ Ό Ο Λ1ΦΟΗΙΟ W I ® ΰίίίδ...5 a ma · ηη * ο ε & ·· ε ft + * ft ΌΟ —HO Ti> ι Ή ·· τ] ο ïj ο y 2 j U I J · ΗΗ ·. I ö h 'Ö Η Η' Ö Η Η S Η λι Η (Μ U ^ Ό Ο Λ1ΦΟΗΙΟ W I ® ΰίίίδδ.
η a «I Η ?ι 5 " IIΒλ a « * ς η α λ j 13¾¾. 9”§Φ|3ΑΙ9|&«||&||9|| β1! 13 111111 tt 11! 111111ι3 π 11 ; η 1 ρ Η 1 ρ S 1! ρ Η I s * I ρ ƒ > > W^o >| W τ1 Ο >1 ^ ε Ο > Ν-ρ τ- o>wr- tJ>wT- Μ L 8104495 ^ * V. .η a «I Η? ι 5" IIΒλ a «* ς η α λ j 13¾¾. 9" §Φ | 3ΑΙ9 | & «|| & || 9 || β1! 13 111111 tt 11! 111111ι3 π 11; η 1 ρ Η 1 ρ S 1! ρ Η I s * I ρ ƒ>> W ^ o> | W τ1 Ο> 1 ^ ε Ο> Ν-ρ τ- o> wr- tJ> wT- Μ L 8104495 ^ * V .
-16- rf——' Η i -d 4? S f j? I +> § * i i - f <&-&* f r N il <vl 'J k l-16- rf—— 'Η i -d 4? S f j? I +> § * i i - f <& - & * f r N il <vl 'J k l
ftl m J* K-/ t*\ Pi Pftl m J * K- / t * \ Pi P
w HO? . Ow HO? . O
K\ >j © Η H «VK \> j © Η H «V
ft t $ & I I & Ift t $ & I I & I
JS g (N ^ *P © . SJS g (N ^ * P ©. S
5 ΙίΛΙ ® s +> Ö I 5 .. ^ 5 3 £ 5 a ^ ^ .p. £ ~ ti § g ft5 ΙίΛΙ ® s +> Ö I 5 .. ^ 5 3 £ 5 a ^ ^ .p. £ ~ ti § g ft
m C\J 4) t*, ,Μ +> O ·* OJ O Pm C \ J 4) t *,, Μ +> O · * OJ O P
Ο ►©Λ © 3 CV! , Q £> . HΟ ► © Λ © 3 CV! , Q £>. H
2 (M ft N +) ,-. g 3 r"' ft O ft 3 N2 (M ft N +), -. g 3 r "'ft O ft 3 N
H ,-. 33 © W -H Xi w 3 3 3 2 «f* g w§© g ft o ·« ft 4-> 3 3 vo 3 o ft ·£ 2 ÖC3.Q <H 3 K\ 13© 3 N W ft 3 © © I is* 7 g g ^ s 8 ί s 0« * I I 8 s ? Sr ;«> 5«Γ· ϊ lr ~ k i S « ! § a ^ ° s -2 “So s a ~s > a a w- « ^ ®go ? L ? r ago s s ^ Pi r .-, O r· Ο O ©At" +* H ft O ® ‘T5H, -. 33 © W -H Xi w 3 3 3 2 «f * gw§ © g ft o ·« ft 4-> 3 3 vo 3 o ft · £ 2 ÖC3.Q <H 3 K \ 13 © 3 NW ft 3 © © I is * 7 gg ^ s 8 ί s 0 «* II 8 s? Sr; «> 5« Γ · ϊ lr ~ k i S «! § a ^ ° s -2 “So s a ~ s> a a w-« ^ ®go? L? r ago s s ^ Pi r .-, O r · Ο O © At "+ * H ft O ®" T5
©O ft ft r- +»0 B . ο © H© O ft ft r- + »0 B. ο © H
4j H +1 ö ft +1 3 ft B H +1 © 3 j Al Ift ^4j H +1 ö ft +1 3 ft B H +1 © 3 j Al Ift ^
BO 30 3 O +1 ©p H 5 H CMBO 30 3 O +1 © p H 5 H CM
μ a, n ^ __] n s h rH Ο λ ft © ^ B *ic! Η Ο Ο Ο ΙΛ OO h ö N Λ O 60 "S 2 ft vo ft >j σ\ 3 r- 4-> ft ro ·Η I Η I © O + ©ΟΙ g Η I £. ?* .λ «8 *!? iS ^ +>/~» <P ,-. X >o ij I ΓΛ *0 ·Η H * 13·· BH·· BH·· ©3·· g t- H X> ft H' 3© © >s © S? Λ © 2 _ £ r-l o. f? C. ο, H 3 H 3 ^ ft ,3 H Ö to 3 ft 3 $ 8 |? ft n® t? ft n® .2 |>* ΙδκωΊωομ a, n ^ __] n s h rH Ο λ ft © ^ B * ic! Η Ο Ο Ο ΙΛ OO h ö N Λ O 60 "S 2 ft vo ft> j σ \ 3 r- 4-> ft ro · Η I Η I © O + © ΟΙ g Η I £.? * .Λ« 8 * !? iS ^ +> / ~ »<P, -. X> o ij I ΓΛ * 0 · Η H * 13 ·· BH ·· BH ·· © 3 ·· g t- HX> ft H '3 © ©> s © S? Λ © 2 _ £ rl o. F? C. ο, H 3 H 3 ^ ft, 3 H Ö to 3 ft 3 $ 8 |? Ft n® t? Ft n® .2 | > * ΙδκωΊωο
n pi O' +> Q vr 3 o Ü ft n/ g +> S3 W © W On pi O '+> Q fr 3 o Ü ft n / g +> S3 W © W O
a l "S ©ftQ © ft £ K\I0 I © 2 . ·Η fta l "S © ftQ © ft £ K \ I0 I © 2. · Η ft
fiv r \ g ft \ M ft wT-N^ IM S W I ftl Afiv r \ g ft \ M ft wT-N ^ IM S W I ftl A
HH
OO
|θ| 3 H| θ | 3 H
« H 3 8 3 II «al « — O ,"»· H3 HI Η Η B © êö O ffl *H &«H 3 8 3 II« al «- O," »· H3 HI Η Η B © êö O ffl * H &
>L 3 Η O X> L 3 Η O X
H ff 3 % « OH ff 3% «O
rp p A N f*S »3 2 M S 3 '-i +> S I © © I © > (Λ S CP ^ 55 - --------—-——1. .........rp p AN f * S »3 2 MS 3 '-i +> SI © © I ©> (Λ S CP ^ 55 - --------—-—— 1. ....... ..
Η· · rH · . Ö , s s *· . ï I S I ΐ ®g ft S · 8 S 3 f> f g a g f § g I f § WJ3 ©3 CM Xi 8¾ J. ·? s_x ft go T ft CVI <6 CM ft 13 IXJ 13 w V —' 3 ΙΛ O CM ft ΙΛ ο ΓΛ o ^2 H S 'tA Ο H «j Η Λ 'hli sa ft s sa sa sa f g sa s s ï g .. || gft ©o aft ♦· ε ft § ft «••HO S ft ·» *rl O *H O H 2j 2 <ÖH .. Hft ΌΗ H H M1?1?1RH. Ö, s s * ·. ï I S I ΐ ®g ft S8 S 3 f> f g a g f § g I f § WJ3 © 3 CM Xi 8¾ J. ·? s_x ft go T ft CVI <6 CM ft 13 IXJ 13 w V - '3 ΙΛ O CM ft ΙΛ ο ΓΛ o ^ 2 HS' tA Ο H «j Η Λ 'hli sa ft s sa sa sa fg sa ss ï g .. || gft © o aft ♦ · ε ft § ft «•• HO S ft ·» * rl O * H O H 2j 2 <ÖH .. Hft ΌΗ H H M1? 1? 1
CM X I O Ό O Η I O HIP Η I OCM X I O Ό O Η I O HIP Η I O
η «Μ >> «in b w. b rr sd c n bcCÏIO t<"0 i>c ·* O O © W 3 (M 3 - >s 3 W Λ S ftl ^ W N Q ^η «Μ >>« in b w. b rr sd c n bcCÏIO t <"0 i> c · * O O © W 3 (M 3 -> s 3 W Λ S ftl ^ W N Q ^
C3 r-»H (MO r-sH Λ Η Λ Q Η HC3 r- »H (MO r-sH Λ Η Λ Q Η H
52; q m bK Q Q 3 >o OBr^ QBpjft hH S- ff © 3 '-n η © 3 3 3ΦΗ 3 C ©H 3 30 g i ! isa 5 & sl ! na s na na > > v r O >| ^ ft O >1 w v o>l'w»r- q>|n-x T- tP--52; q m bK Q Q 3> o OBr ^ QBpjft hH S- ff © 3 '-n η © 3 3 3ΦΗ 3 C © H 3 30 g i! isa 5 & sl! na s na na>> v r O> | ^ ft O> 1 w v o> l'w »r- q> | n-x T- tP--
JJ
— 3104495 _-17-__ ΓΒΓ^ ~Z — ~ . ^ ^ i * ^ ft ™ 5 4 Ό w ^ S ® , * 1 h 7 ‘ 1 u ^ ril H f b J- CU £\ β C 'p' b ^ £ ► σ» 00 o I ^ £ fo. © r- -3- « Hl £ . f π 'Ö O b B V rfi •Η Ί~) *·"? H f £ b Ν-ϋ -O *d £ 9 S © I x-n £ ΓΛ vj ·° -° j> « SP <U P tf ® _,- 3104495 _-17 -__ ΓΒΓ ^ ~ Z - ~. ^ ^ i * ^ ft ™ 5 4 Ό w ^ S ®, * 1 h 7 "1 u ^ ril H f b J- CU £ \ β C 'p' b ^ £ ► σ» 00 o I ^ £ fo. © r- -3- «Hl £. f π 'Ö O b BV rfi • Η Ί ~) * · "? H f £ b Ν-ϋ -O * d £ 9 S © I xn £ ΓΛ vj · ° - ° j>« SP <UP tf ® _ ,
^ VI IJ R Q. t-lS ^ p ® 6 H^ VI IJ R Q. t-lS ^ p ® 6 H
r | « ® ® » g ? g £! § 8 3 - If ~r | «® ®» g? g £! § 8 3 - If ~
g 5ï * 1 ï I «IS- § § § <4 § 1 Ig 5ï * 1 ï I «IS- § § § <4 § 1 I
lil £ ' g* I, ^ 43 I S 41 h 'ί § § di p i lil | ^ «h ^ ^ °§s r s r «gi iii 1^° & §· a I ^ £ g I * i & .s c s n I f 7 ü s oeii;l M: «.iv ip :f: il i ::-:::& i*v ip, n« - - <- i.! s | £ | + I ïv ! H J |o+1lil £ 'g * I, ^ 43 I S 41 h' ί § § di p i lil | ^ «H ^ ^ ° §srsr« gi iii 1 ^ ° & § · a I ^ £ g I * i & .scsn I f 7 ü s oeii; l M: «.iv ip: f: il i :: - ::: & i * v ip, n «- - <- i.! s | £ | + I ïv! H J | o + 1
® £ jS ö P c -¾ ε S ΟΙΛ Spo Λ O £\ ® O® £ jS ö P c -¾ ε S ΟΙΛ Spo Λ O £ \ ® O
flSCÖ Ctf φ ** © ·Η -P X fe *S o "T ^ O 4· SS § ^ j* p< * 2?*1 θ ? 1 & £ 1 © ~ + Ά j « h J X ” & *" ” o ® ” £ £ ft ft ft « /3 « x I “ H V^.Q +loö 0§ö OO O «> 60 j> > oj?V? (i Λ \fl ® ° V -p ft «» p sw « ï ^ ? ?* * § g* iip!iSiftio« k\ S V, K B N cvi*-\ o ft \flSCÖ Ctf φ ** © · Η -PX fe * S o "T ^ O 4 · SS § ^ j * p <* 2? * 1 θ? 1 & £ 1 © ~ + Ά j« h JX ”& *" ”O ®” £ £ ft ft ft «/ 3« x I “HV ^ .Q + loö 0§ö OO O«> 60 j>> oj? V? (i Λ \ fl ® ° V -p ft «» p sw «ï ^?? * * § g * iip! iSiftio« k \ S V, K B N cvi * - \ o ft \
*0 |—I , H* 0 | —I, H
^ -«II^ - «II
i «lil I g js £ *i «lil I g js £ *
Μ ® O ® HΜ ® O ® H
§ « f s | Λ « a ü ---- ~~" ~ Η P H~ S « t 1 § . | · 5 ö ® S Λ ö ®ö «o so +>o s o§ «f s | Λ «a ü ---- ~~" ~ Η P H ~ S «t 1 §. | · 5 ö ® S Λ ö ®ö« o so +> o s o
S -O I & S ·? ΛΙ *SS-O I & S? ΛΙ * S
• P (MP ë p WÖ• P (MP ë p WÖ
(\| S --- iö I CÖ V-/ CS(\ | S --- iö I CÖ V- / CS
v2o ΓΛ O (MO (Λ o ^ g H S « j H |v2o ΓΛ O (MO (Λ o ^ g H S «j H |
SI ? I si IISI? I si II
-II -II -II : I I-II -II -II: I I
>-HH ΌΗ HgH H 'O H> -HH ΌΗ HgH H 'O H
g aA°iS«°ig aA ° iS «° i
H (\] Η ·Η ^ Η »·ΗιΗ_ — H*HH (\] Η · Η ^ Η »· ΗιΗ_ - H * H
S o ^ p o «a ►> ocu^poo^p 5 3^Ρθ3ρΡ®&3^0°3δ09S o ^ p o «a ►> ocu ^ poo ^ p 5 3 ^ Ρθ3ρΡ® & 3 ^ 0 ° 3δ09
S S.Hft2Spft*HW‘HftrCHpftrCS S.Hft2Spft * HW "HftrCHpftrC
S W ooom-popg o poffl-popS W ooom popg o poffl doll
ΰ SpPKPOftPP^pPΰ SpPKPOftPP ^ pP
S® oxaUt^opiPiHOai^^Q^^SS® oxaUt ^ opiPiHOai ^^ Q ^^ S
Ot- 1 POr- I Λ P r- I g O τ- I p _>| w r- U >| w r O >|-_s<c_TL__N - >l V.—CL_ N— j { 8104495 -18- VOORBEELD XXXVIII : ft -fenylethvlester van (1R trans) 2.2-dimethyl 3-(2-me thyl 1 -vr onenyl) cyclopropaancarbonzuurOt- 1 POr- I Λ P r- I g O τ- I p _> | w r- U> | w r O> | -_s <c_TL__N -> 1 V. — CL_ N— j {8104495 -18- EXAMPLE XXXVIII: ft-phenylethyl ester of (1R trans) 2,2-dimethyl 3- (2-methyl-1-onenyl) cyclopropanecarboxylic acid
Men roert 1 uur bij 0°C 3,7 g (1B trans) 2,2-dimethyl 3-(2-methyl 1-propenyl) cyclopropaancarbonzuurchloride, 7*6 g HMPT en 2,5 5 g 2?fenylethanol. Men roert vervolgens het reactiemengsel Ï8 uren bij kamertemperatmuj giet uit in water en extraheert met ether. Men droogt de organische fasen en concentreert tot droog en chromatografeert over siliciumoxyde (elutiemiddels benzine G, ether (9-1))· Men verkrijgt op deze wijze 3,3 g van de gewenste verbinding.3.7 g (1B trans) 2,2-dimethyl 3- (2-methyl 1-propenyl) cyclopropanecarboxylic acid chloride, 7 * 6 g HMPT and 2.5 g of 2? Phenylethanol are stirred for 1 hour at 0 ° C. The reaction mixture is then stirred for eight hours at room temperature, poured into water and extracted with ether. The organic phases are dried and concentrated to dryness and chromatographed on silica (eluents gasoline G, ether (9-1)). 3.3 g of the desired compound are obtained in this way.
10 /^/p : ί %5° (c ss 0,85^ benzeen) 15 8104495 _=32=._ '£ a a · ι f £ % * $ - ci £ f !? § £ * f f I oil ^10 / ^ / p: ί% 5 ° (c ss 0.85 ^ benzene) 15 8104495 _ = 32 = ._ '£ a a · ι f £% * $ - ci £ f!? § £ * f f I oil ^
^ <\l cvi i, '-f I^ <\ l cvi i, -f I
£ Ύ 'ΐ - Λ S£ Ύ 'ΐ - Λ S
I Λ " A Η 3 B *£? & Q 't' 5 ^ Σ ^ ? — - *S S 5 - JqJ? 1^858383 I 8 8 8 °i 8 8 "i 8 * Λ | ~ f 8 ? § g 1 £ £ * I 8* ° -5 ! 11¾ «I « e sa I „ S ΐ r S S " 3 f i « Ί I ΐ -'go 41 8 . - !J « S « I ^ g i * s 8“ P S o SSo ί I ^ | * 1 " >OC WS,^ w ^ cl C 2 r- Μ & o r, « COO CO+I «o g & J. I r P ^ « Ο ° ί & S ^ O * &0°I Λ "A Η 3 B * £? & Q 't' 5 ^ Σ ^? - - * S S 5 - JqJ? 1 ^ 858383 I 8 8 8 ° i 8 8" i 8 * Λ | ~ f 8? § g 1 £ £ * I 8 * ° -5! 11¾ «I« e sa I „S ΐ r SS" 3 fi «Ί I ΐ -'go 41 8. -! J« S «I ^ gi * s 8" PS o SSo ί I ^ | * 1 "> OC WS, ^ w ^ cl C 2 r- Μ & or, «COO CO + I« og & J. I r P ^ «Ο ° ί & S ^ O * & 0 °
® “ +1 .° +l OHJ1 « 2,ΙΛ § Η O® “+1. ° + 1 OHJ1« 2, ΙΛ § Η O
s & ^ ! tv £ & 7¼ i ? t5 h ^ β O £ OOI ffl Ü ^ © Η I £ ,© · w ^ ®^-ni « ^ »H ·*“; -g d b , S _» ..s & ^! tv £ & 7¼ i? t5 h ^ β O £ OOI ffl Ü ^ © Η I £, © w ^ ® ^ -ni «^» H * *; -g d b, S _ »..
IS?·· Η H -7« H ” & ί S J? g 0¾ c © _=£> >? ” jc^ >? £ £? g, 5¾ ® cIS? ·· Η H -7 «H” & ί S J? g 0¾ c © _ = £>>? Jc ^>? £ £? g, 5¾ ® c
JS o Q C ® +2 Φ Q fi®+> Ö p Q ijH $ ,QJS o Q C ® +2 Φ Q fi® +> Ö p Q ijH $, Q
ΐ £ >s” ®ftQ 6 Pi \ © P« H © b \ I a) % a sr fg·/ f g g f ?· x' 32* A A \ K ^ \ « k ·< « & w w^S.ΐ £> s ”®ftQ 6 Pi \ © P« H © b \ I a)% a sr fg / f g g f? x '32 * A A \ K ^ \ «k · <« & w w ^ S.
K>K>
^ , H^, H
B ? JB? J
I if ΐ ï i I II if ΐ ï i I I
e g 5 5 £ 5 3e g 5 5 £ 5 3
S S ö Ö C Ö HS S ö Ö C Ö H
Sc « I © g j?Sc «I © g j?
If f ? ? ! 3 _ls S s S s h s Si !i ®§ ®§ © § j? | §1 §2 II f 8 f g *8 8 f 8 Ϊ 8If f? ? ! 3 _ls S s S s h s Si! I ®§ ®§ © § j? | §1 §2 II f 8 f g * 8 8 f 8 Ϊ 8
s t s t st ff q t q Is t s t st ff q t q I
AS AS A I s I AS AAS AS A I s I AS A
£ g, £ & £ & h & & | i? |£ g, £ & £ & h & & | i? |
., 8 S IS, IS S 8 "II II., 8 S IS, S S 8 "II II
«S5 si ·· s h " 8 η h s i ;si Z% A l· : l· r-l ?l S A. I S & 5¾¾ 3^'i 9¾¾ sfl list 1 s s 3§i i's s ill ill §lsl § i ? I $ f l»o § i · 1-6¾ 1 I p I I p I I p f 8 e f gif' g^? > > > W v1 >wr- > -^ v- >1 w__y >1 t- ƒ 8 1 0 4 4 9 5 -20- Υτ“ η 1 η & a ¢1-- • j? $ £ Ρ I to 5 ε Μ ι 3 Ο +> 4) I +» ν* > Η ® a cm ο) ο nj t E pH CM h pj CM I I ►> «VI o -ft«S5 si ·· sh" 8 η hsi; si Z% A l ·: l · rl? L S A. IS & 5¾¾ 3 ^ 'i 9¾¾ sfl list 1 ss 3§ii'ss ill ill §lsl § i? I $ fl »o § i · 1-6¾ 1 I p II p II pf 8 ef gif 'g ^?>>> W v1> wr-> - ^ v-> 1 w__y> 1 t- ƒ 8 1 0 4 4 9 5 -20- Υτ “η 1 η & a ¢ 1-- • j? $ £ Ρ I to 5 ε Μ ι 3 Ο +> 4) I +» ν *> Η ® a cm ο) ο nj t E pH CM h pj CM II ►> «VI o -ft
w CA CM 43 Ο O ^ Iw CA CM 43 Ο O ^ I
I w -P +> Ο H CMI w -P +> Ο H CM
ΓΑ Η SA © P b b B (0 ® Ρ ® H ’ 43 Η I H ^ Ü "Ö b +> b ^ CM Pi P _ 4? Φ P 43 P '-f’ -PP S'© Η SA © P b b B (0 ® Ρ ® H ’43 Η I H ^ Ü“ Ö b +> b ^ CM Pi P _ 4? Φ P 43 P '-f ’-PP S'
P - S φ -ρ Φ I ft ® O OP - S φ -ρ Φ I ft ® O O
Τ-Φ Η © © Φ CA Op*Ö .Τ-Φ Η © © Φ CA Op * Ö.
a <e « a « hp JS H I Ρ Η Ρ Η ΡΟΉ © 63«0'-^CM®,0©b Φ 4* ·Η Pi S I Ρ « 43 I ,Ρ 43 Ρ,φ-Ö 8) g CM Ρ © CM P CM P 4* © ® I ? η « p ® /-^9¾¾. -3¾ 2. P d cm k êCMÖN ® S ΙΛ MSN HP k ft — “>a <e «a« hp JS HI Ρ Η Ρ Η ΡΟΉ © 63 «0 '- ^ CM®, 0 © b Φ 4 * · Η Pi SI Ρ« 43 I, Ρ 43 Ρ, φ-Ö 8) g CM CM © CM P CM P 4 * © ® I? η «p ® / - ^ 9¾¾. -3¾ 2. P d cm k êCMÖN ® S ΙΛ MSN HP k ft - “>
β N - s N «- HP eO I CM Hβ N - s N «- HP eO I CM H
h rap© ® Ρ o rapt- ‘Pg η τ5 Ύ b cq HO·® p O HO I N >J ° I Λh rap © ® Ρ o rapt- "Pg η τ5 Ύ b cq HO · ® p O HO I N> J ° I Λ
a O 43 -P 43 il 043 11 CMP 43 © fA -Pa O 43 -P 43 il 043 11 CMP 43 © fA -P
E3 L SA L· - Ο Η Ό ΦE3 L SA L · - Ο Η Ό Φ
> CO © <M M 3 O P3 © O CM 43 Φ B> CO © <M M 3 O P3 © O CM 43 Φ B
t- O r O v r* o sp ^ ti B w ® wpiivpö N-xp rap op ® 3 3 o 3 o. ho ® β Ό gg,s2 s&“i s i"i · * t i st- O r O v r * o sp ^ ti B w ® wpiivpö N-xp rap op ® 3 3 o 3 o. ho ® β Ό gg, s2 s & “i s i" i · * t i s
►8o >2~ ”2^ ? S § $ « I►8o> 2 ~ ”2 ^? S § $ «I
P ft r- p Pi +1 P ft +1 w p > g ^ P „ ΦΟ ΦΟ ΦΟ P a P 43 Ρ H +1 -Ρ Η Ο +>ΗΟλ P ft B S3 „ _ P _ - ra o raouv to ο iA 3 ο Pi ® P « S ^-P ft r- p Pi +1 P ft +1 wp> g ^ P „ΦΟ ΦΟ ΦΟ P a P 43 Ρ H +1 -Ρ Η Ο +> ΗΟλ P ft B S3„ _ P _ - ra o raouv to ο iA 3 ο Pi ® P «S ^ -
Φ r*ï Ο © }>S - Φ >5 - > H ft CA 'Ö © P ft <MΦ r * ï Ο ©}> S - Φ> 5 -> H ft CA 'Ö © P ft <M
H O IA H ü CA H O CA O CM P > O ft · % X N w’ *·> <~· fA P ^ - 3 P ,43 r-H O IA H ü CA H O CA O CM P> O ft ·% X N w ’* ·> <~ · fA P ^ - 3 P, 43 r-
4lHl I Η + I Η + ® O r- © © PP4lHl I Η + I Η + ® O r- © © PP
® p ·· lp·· lp·· WHHPO -P Ö H ©® p ·· lp ·· lp ·· WHHPO -P Ö H ©
Η © Ρ® P® ® >3 O Φ P W ra P QΗ © Ρ® P® ®> 3 O Φ P W ra P Q
>> ft ® Pi dSÖ^.P» φ § ö ia POQ +» O Q -P O O >j © ü CM Of H © O f e 2 \H PP \ ppvT Sf ft - H - >J Pi H ft > ,Q ft ->> ^ρ,χ ppgt-oiA 43 O g t- IIO i i 2> iic ©PS >> +» Ρ 2 .>> ft ® Pi dSÖ ^ .P »φ § ö ia POQ +» OQ -POO> j © ü CM Of H © O fe 2 \ H PP \ ppvT Sf ft - H -> J Pi H ft>, Q ft - >> ^ ρ, χ ppgt-oiA 43 O g t- IIO ii 2> iic © PS >> + »Ρ 2.
(M r \ ΙΛ r \ lA r \ 43 Λ P3 I O I © ft P3 I(M r \ ΙΛ r \ lA r \ 43 Λ P3 I O I © ft P3 I
HH
OO
4343
fA OfA O
O HO H
b n i -ö | g fc 4 d- 8b n i -ö | g fc 4 d- 8
H 43 I t HH 43 I t H
Q +» Ρ Ρ d HQ + »Ρ Ρ d H
£ O © Φ H O£ O © Φ HO
a * 1 I | | I g ·? ? s sa * 1 I | | I g ·? ? s s
> (x, fA KN 43 BH> (x, fA KN 43 BH
Ρ ^ Ρ Ρ Η PΡ ^ Ρ Ρ Η P
H S 43 Ρ Η P b2 _ >i 3 -Pp bg Λ g ^H S 43 Ρ Η P b2 _> i 3 -Pp bg Λ g ^
43 N © N 43 N -Ρ N H43 N © N 43 N -Ρ N H
•PP B g . +» P ©P b ®o i o ©o ao p• PP B g. + »P © P b ®o i o © o ao p
a 43 CM 43 B 43 1 43 Ha 43 CM 43 B 43 1 43 H
IP '-'P IP CMP >IP '-'P IP CMP>
CM® I® CM® ro PCM® I® CM® ro P
s_/0 CAO S-^O IO Os_ / 0 CAO S- ^ O IO O
ΙΛ § H § A <3 ^ § Η p H Si Ji S ’rel >sO -PO b° 43 p J3P © p 4}P**-PP lp lp a g ft ..Pa o a cm o ΦΟ ·· H O ΦΟ HBO ·· r 43 «BH Ό Η ΗΒΗ Η Η H _ CM p w>a& s <4 sl a j- §ΙΛ § H § A <3 ^ § Η p H Si Ji S 'rel> sO -PO b ° 43 p J3P © p 4} P ** - PP lp lp ag ft ..Pa oa cm o ΦΟ ·· HO ΦΟ HBO ·· r 43 «BH Ό Η ΗΒΗ Η Η H _ CM pw> a & s <4 sl a j- §
S S3 <4 4 Ö « 4 Ö i4 4 S3 «.4 S3 ^ IS S3 <4 4 Ö «4 Ö i4 4 S3« .4 S3 ^ I
I B N ïi p'ra'b Q w" ^1 S b Seo HJ^-sp HpP 3^P H ^-sp HPp §S a © §3®® Bra® w ra © wrap η h ft 0 p ft θ h ft ShS4IBN ïi p'ra'b Q w "^ 1 S b Seo HJ ^ -sp HpP 3 ^ PH ^ -sp HPp §S a © §3®® Bra® w ra © wrap η h ft 0 p ft θ h ft ShS4
s§°g S-^S g°g §°Ss§ ° g S- ^ S g ° g § ° S
abwa Stoft S«a öwa o«o , Ξ o t- I Ofl o t- i ρ ί- i o V ^ f>>v-/r- >wt- > w t- > w t~_ _j> _v->____O"_ L_ 8104495 -21- _______ -.. mini <abwa Stoft S «a öwa o« o, Ξ o t- I Ofl o t- i ρ ί- io V ^ f >> v- / r-> wt-> w t-> wt ~ _ _j> _v-> ____ O "_ L_ 8104495 -21- _______ - .. mini <
π—" I Γ . Iπ— "I Γ. I
i ® e -£j r a ft -H g 73 JJ ο Ό r _ £ g § k Λ «Μ ·3i ® e - £ j r a ft -H g 73 JJ ο Ό r _ £ g § k Λ «Μ · 3
£ ·*& S & «y » S£ · * & S & «y» S
® i § o ft H w -P 3 5 OJ ft ® H £> · Sr»W> fi I O ft o >js jjKN ® 9 _ 1 ™ *§ ft H & -g Ci c 'S, ft Φ ia® i § o ft H w -P 3 5 OJ ft ® H £> · Sr »W> fi I O ft o> js jjKN ® 9 _ 1 ™ * § ft H & -g Ci c 'S, ft Φ ia
I Λ g* ** "SI Λ g * ** "S
t- Ε o o ü Ö « Λ 'ö -p ° ^2t- Ε o o ü Ö «Λ 'ö -p ° ^ 2
,_ e ^ S N "ëS B ö § H, _ ^ S N "ëS B ö § H
ΗΗΛ g0«0«IP| I ► * | t I * ~ Ί s· «ft η o I o *=*2*2 >£, ® ™ 3 2 % °0 g0 «0« IP | I ► * | t I * ~ Ί s · «ft η o I o * = * 2 * 2> £, ® ™ 3 2% °
g +> fl h & fi Ê* 'Ö > 5 © ii i H HWg +> fl h & fi Ê * 'Ö> 5 © ii i H HW
1 J5 4 f & >^§ g ® * 9 g £ w fi cu fi £ t- a > ft « fi ?*? "ë y ·* e S o » +» © ό s s ® q-E s £ g ^ g e ^ " S s 5 ? W ö nS ® ΐ π B M 3 W « fi <S O,43 8 8 ·« öft-PH >ΛΙ <-3 u ft «a +>g ö ή ft tf .fi w ~ ft S , ^ s 3 « o h +» _ -a· SE 2 >1 *' S el* ► ft ^ ft S <& , £ K . » %1 J5 4 f &> ^ § g ® * 9 g £ w fi cu fi £ t- a> ft «fi? *? "ë y · * e S o» + »© ό s s ® q-E s £ g ^ g e ^" S s 5? W ö nS ® ΐ π BM 3 W «fi <SO, 43 8 8 ·« öft-PH> ΛΙ <-3 u ft «a +> g ö ή ft tf .fi w ~ ft S, ^ s 3« oh + »_ -A · SE 2> 1 * 'S el * ► ft ^ ft S <&, £ K. »%
öl 3g.WöOWftS ^ f O B « g | Iöl 3g.WöOWftS ^ f O B «g | I
1« a o B· ^ S K r ° " ©o ft in I Λ cr\ © |° f 3 ί «. I 3 « " g ' * SfrA~- I-SknI, t* ai bs ft r l< ® f3 if\ I φ/^ f w . «o1 «ao B · ^ SK r °" © o ft in I Λ cr \ © | ° f 3 ί «. I 3« "g '* SfrA ~ - I-SknI, t * ai bs ft rl <® f3 if \ I φ / ^ fw. "O
S A. v- jj ^ ^ C\J Η rl Pjö-PiHS A. v- yy ^ ^ C \ J Η rl Pjö-PiH
f S ^^83 Π ï ° N hKN A 1 CO § I * Ji>8in&W|Q>f S ^^ 83 Π ï ° N hKN A 1 CO § I * Ji> 8in & W | Q>
_p r- rj o2c-4J^-r--d-T"r-IT"r<A OSSf-PC^^S_p r- rj o2c-4J ^ -r - d-T "r-IT" r <A OSSf-PC ^^ S
Jj | e&Mljsi t l I S? I © «η « I .fi -sT I «h ΚΛ 55 *q ta 8 S 3Yy | e & Mljsi t l I S? I © «η« I .fi -sT I «h ΚΛ 55 * q ta 8 S 3
2 X2 X
R _i © go ·«R _i © go · «
Hg f3 S 3 % E> H _ü________Hg f3 S 3% E> H _ü ________
Ss ag © 3 5 «Ss ag © 3 5 «
g ft w Sg ft w S
I o - o ΛΙ .§ N ·£I o - o ΛΙ .§ N · £
γ i t Sγ i t S
Λ S Λ 2 Η § H § 6 & & | 5 o -g gΛ S Λ 2 Η § H § 6 & & | 5 o -g g
Ik ik 5 o £ oI I 5 o £ o
Ό Η 'OHOH Η 'OH
W I O ** · PW I O ** · P
·« (M >a N n· «(M> a N n
K - O H - OK - O H - O
M *A w ^ ^ QM * A w ^ ^ Q
lil! 311 i μι lil ^ ^ r_______________Kl-Ü 3±_-—- -8 1 0 4 4 9 5 -22-lil! 311 i μι lil ^ ^ r _______________ Kl-Ü 3 ± _-—- -8 1 0 4 4 9 5 -22-
p-j “ ' Ip-j "" I
0 Η0 Η
Ά j3 I3 j3 I
CM -P r- •H ΦCM -P r- • H Φ
t) d S Ht) d S H
1 3 I >> W © W 431 3 I >> W © W 43
·· ft ' -P·· ft '-P
W 0.1 ©W 0.1 ©
'—' ft H- H
I Λ J.I Λ J.
ΙΟ 0 H WH 0 H W
H 2>H 2>
H p 43 tOH p 43 tO
>3 >3 -P> 3> 3 -P
f 43 Ο © Hf 43 H © H
-P fi ^ a © © ·η d 43 d pq e ό ό © ·*> © CD ·Η I © © ©-P fi ^ a © © · η d 43 d pq e ό ό © · *> © CD · Η I © © ©
SO d W d N B NSO d W d N B N
H I 3 - fl d -H d §W t> W W 3 Φ Ό Jh © - o ^ 5 ί I d fi H W ÖO W (3 ^ W d fq ^ d © H O * s S}iQdftdo43wwdC'i Η ·η d ©re d - o - >ONO>coror-ei43^·HI 3 - fl d -H d §W t> WW 3 Φ Ό Jh © - o ^ 5 ί I d fi HW ÖO W (3 ^ W d fq ^ d © HO * s S} iQdftdo43wwdC'i Η · η d © re d - o -> ONO> coror-ei43 ^ ·
SO U ID 3 d II Ö (8 IISO U ID 3 d II Ö (8 II
r- 43 H +> 3 Pr- 43 H +> 3 P
>s© d <§ o «do re 43(0 eft'-' r-fflw dO -PH > o v_*re red ©ft u o ft o > © B I d ft dor- re · »> © o 3 d d ft E © *-> -PH +1 > ft +1> s © d <§ o «do re 43 (0 eft'- 'r-fflw dO -PH> o v_ * re red © ft uo ft o> © BI d ft dorre ·»> © o 3 dd ft E © * -> -PH +1> ft +1
© Ο · Ό © IQ Ο O© Ο · Ό © IQ Ο O
+» d ft Ό Φ t>3 Q $4 H c> CO ft · d „ HOW ©OC>+ »D ft Ό Φ t> 3 Q $ 4 H c> CO ft · d„ HOW © OC>
© 0 ft re ft f>s z-' ΓΛ +> >» IO© 0 ft re ft f> s z- 'ΓΛ +>> »IO
HH ί> Ο I Η I (QO + 1¾ O KV (VI >» © ^ K l*s H W Ö3 Id·· Η H ·· ©op _ d © >? >y Λ Λ fl IM N ©ft ddHH ί> Ο I Η I (QO + 1¾ O KV (VI> »© ^ K l * s H W Ö3 Id ·· Η H ·· © op _ d ©>?> Y Λ Λ fl IM N © ft dd
Ο H O W \0 -P p Q O © QΟ H O W \ 0 -P p Q O © Q
H >5 · · d S \ +>ftH> 5d S \ +> ft
OdSr--3-fnftO’pO'x' Ο* Τ» « I I ΙΛ r O & \ m * an η o wo o 43 cD d I o s a woOdSr - 3-fnftO’pO'x 'Ο * Τ »« I I ΙΛ r O & \ m * an η o wo o 43 cD d I o s a wo
H W I HH W I H
o © d reo © d re
a 43 © Ha 43 © H
HO +> >5 g h d -pHO +>> 5 g h d -p
g >3 l Ug> 3 l U
> Ο ΙΟ o _____ --S- ' “ : 0 d u u H H d H d <w d £> d •H 43 N 43 « •ö -p d -p d I ft © o © o W d S 4> B 43 *· d I d Id w n w re w re s_/ d w o * o I o id to 3 to 43 to re re H S H & $ &> Ο ΙΟ o _____ --S- '“: 0 duu HH d H d <wd £> d • H 43 N 43« • ö -pd -pd I ft © o © o W d S 4> B 43 * · d I d Id wnw re w re s_ / dwo * o I o id to 3 to 43 to re re HSH & $ &
J? i S I IIJ? i S I II
43 re +> ft © ft © re ·· © o so43 re +> ft © ft © re ·· © o so
·· & ft S Η ·· -Η H·· & ft S Η ·· -Η H
WHO Η ·Η Ο Ό OWHO Η · Η Ο Ό O
Η *β Jj Η >β h > I !>aΗ * β Jj Η> β h> I!> A
S Η I ft HIO HWOS Η I ft HIO HWO
KIhIWO t-3 W ^ t-3 ^KIhIWO t-3 W ^ t-3 ^
3 ·* Η - H W H3 · * Η - H W H
SQWO QW>sQ >» HH'-'?» h ^ d g ^ d ö Ξ to o m o © g a © s W ·Η λ @ ·η ft W ·Η ft S§°^ §°E g- ° 8 S S « d Owft O « ftSQWO QW> sQ> »HH'- '?» h ^ d g ^ d ö Ξ to o m o © g a © s W · Η λ @ · η ft W · Η ft S§ ° ^ § ° E g- ° 8 S S «d Owft O« ft
W p r- -H p I O r- IW p r- -H p I O r- I
> > w >_> s-/ r >| w r-_;_____________ L 8 1 0 4 4 9 5 -23- VOORBEELD LY : Methylester van (1R cis) 2,2-dimethyl 5(2.2-dichloorvinyl) cyclopropaancarbonzuur.>> w> _> s- / r> | w r -_; _____________ L 8 1 0 4 4 9 5 -23- EXAMPLE LY: Methyl ester of (1R cis) 2,2-dimethyl 5 (2,2-dichlorovinyl) cyclopropanecarboxylic acid.
Men voegt 21 cm3 thionylchloride toe aan een oplossing die 50 cm3 hexamethylfosfortriamide en 60 g (1R cis) 2,2-dimethyl 3-(2,2-5 dichloorvinyl)cyclopropaancarbonzuur bevat· Men roert de verkregen oplossing 2 uren, waarna men het reactiemengsel op 0°C brengt en voegt 12 cm3 methanol en 50 cm3 hexamethylfosfortriamide toe. Men roert opnieuw 3 uren bij kamertemperatuur waarna men uitgiet in water· Men decanteert en extraheert met ethylether, behandelt} de etherfasen met aktieve kool en droogt 10 deze· Men filtreert en concentreert tot droog onder verminderde druk bij 30°C. Men verkrijgt een olie die men rectificeert onder een druk van 0,1 mm kwikdruk. Op deze wijze wordt verkregen 60,84 g van de gewenste verbinding. Kookpunt : 66°C.21 ml of thionyl chloride are added to a solution containing 50 ml of hexamethylphosphoric triamide and 60 g (1R cis) 2,2-dimethyl 3- (2,2-5 dichlorovinyl) cyclopropanecarboxylic acid. The resulting solution is stirred for 2 hours and the reaction mixture is stirred. to 0 ° C and adds 12 cm3 of methanol and 50 cm3 of hexamethylphosphoric triamide. It is stirred again for 3 hours at room temperature, after which it is poured into water. Decantation and extraction with ethyl ether are carried out, the ether phases are treated with activated charcoal and dried. The mixture is filtered and concentrated to dryness under reduced pressure at 30 ° C. An oil is obtained which is rectified under a pressure of 0.1 mm of mercury. In this way, 60.84 g of the desired compound are obtained. Boiling point: 66 ° C.
/θ(/^ ι +20° + 1° (c = 1,2# benzeen) 15 /n /21 : 1,4945 VOORBEET.n LVI :/ θ (/ ^ ι + 20 ° + 1 ° (c = 1.2 # benzene) 15 / n / 21: 1.4945 PREVIOUS.n LVI:
Hierna zullen de door enkele verbindingen met de algemene formule 1 ontwikkelde geuren worden beschreven: - Verbinding van Voorbeeld I : rozengeur 20 - Verbinding van Voorbeeld IV : iets groene geur - Verbinding van Voorbeeld II : groene, mentholgeur - Verbinding van Voorbeeld III : geur van anjelier en van rozenbloesem parfum - Verbinding van Voorbeeld VII ï sinaasappelgeur 25 - Verbinding van Voorbeeld VIII : kruidengeur - Verbinding van Voorbeeld XX : koffiegeur, iets groen - Verbinding van Voorbeeld IX : jasmijn - abrikozenpunten - Verbinding van Voorbeeld X : groene geur VOORBEELD LVII: 30 Men bereidt formuleringen met rozensamenstelling uit gaande van de hierna genoemde bestanddelen (in gew.delen) : - Van terpenen ontdane geranium 180 - Citronellol 300 - Gernaylacetaat 45 35 - Nerol 15 - Methylionon 15 - Fenylethylalcohol 1?0 t Bourbonrhodinol 60 - Citronellylacetaat 40 40 - Benjoinresinoide 30 8104495 .τ -sr -2b- - Muskusketon 15 - Aldehyde C 9 1/10 PDG 15 - Alphaionon 15 - Verbinding van Voorbeeld III 300 5 1000 VOORBEELD LVIII :The scents developed by some of the compounds of the general formula I will be described below: - Compound of Example I: rose scent 20 - Compound of Example IV: slightly green scent - Compound of Example II: green, menthol scent - Compound of Example III: scent of carnation and rose blossom perfume - Compound of Example VII - orange scent 25 - Compound of Example VIII: herbal scent - Compound of Example XX: coffee aroma, slightly green - Compound of Example IX: jasmine - apricot points - Compound of Example X: green fragrance EXAMPLE LVII: 30 Rose composition formulations are prepared starting from the components listed below (in parts by weight): - Terpene-depleted geranium 180 - Citronellol 300 - Gernayl acetate 45 35 - Nerol 15 - Methylionone 15 - Phenylethyl alcohol 1 0 t Bourbonrhodinol 60 - Citronelyl acetate 40 40 - Benjoinresinoide 30 8104495 .τ -sr -2b- - Musk ketone 15 - Aldehyde C 9 1/10 PDG 15 - Alphaionon 15 - Verb entry of Example III 300 5 1000 EXAMPLE LVIII:
Men bereidt formuleringen met "Opopona· '* samenstelling uitgaande van de hiernagenoemde bestanddelen (in gew.delen) : - Bergamot 310 10 - Neroli 131 Fch 20 - Patchouli (ontijzerd) 10 - Rozenessence 10 - Vetyverol 60 - Santanol 125Formulations with "Opopona ·" * composition are prepared from the following components (in parts by weight): - Bergamot 310 10 - Neroli 131 Fch 20 - Patchouli (iron) 10 - Rose essence 10 - Vetyverol 60 - Santanol 125
15 - Castoreum resinoide bO15 - Castoreum resinoid bO
- Cumarine 80 - Gammamethylionon 75- Coumarin 80 - Gamma methyl ionone 75
- Vaniline bO- Vaniline bo
- Benjoin resinoide 25- Benjoin resinoide 25
20 - Muskusketon bO20 - Musk ketone BO
- Ambrettemuskus 65 - Verbinding van Voorbeeld IX 100 1000 VOORBEELD LIX; 25 Ken bereidt formuleringen met jasmijnsamenstelling uit gaande van de hiernagenoemde bestanddelen (in gew.delen): - Benzylacetaat 2é0 - Linalylacetaat 60 - Eenylethylalcohol 60 30 - Hexylkaneelzuuraldehyde 90 - Hydroxycitronellal 60 - Benzylsalicylaat 50 - Methylanthranylaat 30 - Linalol b3 35 - Paracresylfenylacetaat 15 - Extra Hang 50 - Santal 30 - Dimethylbenzylcarbinol 15 - Hyperessence styrax 50 bO - Hedion 85 8 1 0 4 4 9 5 -25- - Verbinding van Voorbeeld IX 100 1000 VOORBEELD LX ï Voorbeeld van zepen.Ambrette Musk 65 - Compound of Example IX 100 1000 EXAMPLE LIX; 25 Ken prepares formulations with jasmine composition starting from the following components (in parts by weight): - Benzyl acetate 2O0 - Linalyl acetate 60 - Enylethyl alcohol 60 30 - Hexyl cinnamic aldehyde 90 - Hydroxycitronellal 60 - Benzyl salicylate 50 - Methyl anthhrylphenyl 30 - Linalacrylylphenyl 30 - Linalacyl acetate Hang 50 - Santal 30 - Dimethylbenzylcarbinol 15 - Hyperessence styrax 50 bO - Hedion 85 8 1 0 4 4 9 5 -25- - Compound of Example IX 100 1000 EXAMPLE LX - Example of soaps.
Men bereidt toiletzepen uitgaande van de hiernagenoemde 5 bestanddelen (in gew. delen) : - Handelszeeppasta 1000 - Verbinding van Voorbeeld IX 5.Toilet soaps are prepared from the following 5 components (in parts by weight): - Commercial soap paste 1000 - Compound of Example IX 5.
VOORBEELD LXI : Voorbeeld van waspoeders.EXAMPLE LXI: Example of washing powders.
- Handelswaspoeders 1000 10 - Verbinding van Voorbeeld IX 1 i 8104495Commercial Washing Powders 1000 10 - Compound of Example IX 1 8104495
Claims (11)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8021216 | 1980-10-03 | ||
| FR8021216A FR2491461B1 (en) | 1980-10-03 | 1980-10-03 | NOVEL DERIVATIVES OF CYCLOPROPANE CARBOXYLIC ACID, PROCESS FOR THEIR PREPARATION AND THEIR APPLICATION TO THE PREPARATION OF PERFUMING COMPOSITIONS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NL8104495A true NL8104495A (en) | 1982-05-03 |
Family
ID=9246531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NL8104495A NL8104495A (en) | 1980-10-03 | 1981-10-02 | NEW CYCLOPROPANIC CARBONIC ACID COMPOUNDS, PROCESS FOR THEIR PREPARATION AND USE IN THE PREPARATION OF PERFUME COMPOSITIONS. |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS57131743A (en) |
| CH (1) | CH651010A5 (en) |
| DE (1) | DE3139300A1 (en) |
| FR (1) | FR2491461B1 (en) |
| GB (1) | GB2087384B (en) |
| IT (1) | IT1171563B (en) |
| NL (1) | NL8104495A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4402230A1 (en) * | 2021-09-13 | 2024-07-24 | Symrise AG | Cyclopropanated fragrance compounds |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH610868A5 (en) * | 1975-09-12 | 1979-05-15 | Inventio Ag | Pipe-burst safety device arranged directly at the outlet of the cylinder of a hydraulic lift |
-
1980
- 1980-10-03 FR FR8021216A patent/FR2491461B1/en not_active Expired
-
1981
- 1981-10-01 IT IT49410/81A patent/IT1171563B/en active
- 1981-10-02 DE DE19813139300 patent/DE3139300A1/en not_active Withdrawn
- 1981-10-02 GB GB8129795A patent/GB2087384B/en not_active Expired
- 1981-10-02 CH CH6356/81A patent/CH651010A5/en not_active IP Right Cessation
- 1981-10-02 JP JP56156337A patent/JPS57131743A/en active Pending
- 1981-10-02 NL NL8104495A patent/NL8104495A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| CH651010A5 (en) | 1985-08-30 |
| IT1171563B (en) | 1987-06-10 |
| GB2087384A (en) | 1982-05-26 |
| FR2491461A1 (en) | 1982-04-09 |
| GB2087384B (en) | 1985-07-17 |
| IT8149410A0 (en) | 1981-10-01 |
| DE3139300A1 (en) | 1982-06-16 |
| JPS57131743A (en) | 1982-08-14 |
| FR2491461B1 (en) | 1985-08-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20100034766A1 (en) | Malodor Counteracting Compositions | |
| JPS6133005B2 (en) | ||
| Wege et al. | Synthesis of sesquiterpene antitumor lactones. 6. cis-8a-Vinyloctahydro-3H-2-benzopyran-3, 7-dione, a precursor to vernolepin | |
| WO2008055372A1 (en) | Malodor counteracting compositions | |
| JP5248114B2 (en) | Organic compounds | |
| EP2200701B1 (en) | Dimethylcyclohexyl derivatives as malodor neutralizers | |
| DE60001433T2 (en) | Alpha, beta unsaturated ketones | |
| CN103597063B (en) | Ring 12 carbon dienone derivant as perfuming component | |
| NL8104495A (en) | NEW CYCLOPROPANIC CARBONIC ACID COMPOUNDS, PROCESS FOR THEIR PREPARATION AND USE IN THE PREPARATION OF PERFUME COMPOSITIONS. | |
| JP3022521B2 (en) | New spirocyclic compounds | |
| BRPI0612299A2 (en) | cycloalkylidene - ortho-substituted phenyl acetonitriles and their use as odorants | |
| US9181514B2 (en) | Octahydro-benzofurans and their uses in perfume compositions | |
| EP1280763B1 (en) | Trimethyldecenyl compounds | |
| King et al. | The conundrum of odourless Kahweofuran, a roasting “flavour” of coffee | |
| EP2060567B1 (en) | Regiospecific furan compounds and their use in fragrances | |
| Nussbaumer et al. | Identification of m‐Mentha‐3 (8), 6‐diene (Isosylveterpinolene) in Black Pepper Oil | |
| DE3203977A1 (en) | NEW CYCLOPROPANCARBONIC ACID DERIVATIVES SUBSTITUTED IN 3-POSITION BY A VINYL CHAIN, THEIR PRODUCTION, THE USE THEREOF AS A FRAGRANT, AND THE COMPOSITIONS CONTAINING THEM | |
| US7582600B2 (en) | Use of unsaturated ketones as a perfume | |
| US7476647B2 (en) | Ether lactone | |
| JP4263104B2 (en) | Use of hexenal derivatives as perfumes | |
| Sohilait et al. | Synthesis of 1-(3, 4-methylenedioxyphenyl)-1-butene-3-one from safrole | |
| EP1063229B1 (en) | Alpha, beta-unsaturated ketones | |
| Stappen et al. | Structure–activity relationships of sandalwood odorants: Total synthesis and fragrance properties of cyclopropano-β-santalol | |
| JP4077726B2 (en) | 2-Methyl-4-ethyl-2-octene-1-aldehyde | |
| FR2543134A2 (en) | New cyclopropane derivatives, process for their preparation and their application to the preparation of perfuming compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A85 | Still pending on 85-01-01 | ||
| BV | The patent application has lapsed |