JPH028032B2 - - Google Patents
Info
- Publication number
- JPH028032B2 JPH028032B2 JP58030491A JP3049183A JPH028032B2 JP H028032 B2 JPH028032 B2 JP H028032B2 JP 58030491 A JP58030491 A JP 58030491A JP 3049183 A JP3049183 A JP 3049183A JP H028032 B2 JPH028032 B2 JP H028032B2
- Authority
- JP
- Japan
- Prior art keywords
- alcohol
- aliphatic carboxylic
- lower aliphatic
- carboxylic acid
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical compound C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 claims description 14
- RRBYUSWBLVXTQN-UHFFFAOYSA-N tricyclene Chemical compound C12CC3CC2C1(C)C3(C)C RRBYUSWBLVXTQN-UHFFFAOYSA-N 0.000 claims description 8
- RRBYUSWBLVXTQN-VZCHMASFSA-N tricyclene Natural products C([C@@H]12)C3C[C@H]1C2(C)C3(C)C RRBYUSWBLVXTQN-VZCHMASFSA-N 0.000 claims description 8
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 claims description 7
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 claims description 7
- 229930006739 camphene Natural products 0.000 claims description 7
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 4
- RZKSECIXORKHQS-UHFFFAOYSA-N Heptan-3-ol Chemical compound CCCCC(O)CC RZKSECIXORKHQS-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- CFXJOMGPUADAJE-UHFFFAOYSA-N 2,2-dimethyl-3-methylidenebicyclo[2.2.1]heptan-5-ol Chemical compound C1C(O)C2C(=C)C(C)(C)C1C2 CFXJOMGPUADAJE-UHFFFAOYSA-N 0.000 description 16
- CFXJOMGPUADAJE-XHNCKOQMSA-N (1s,4s,5r)-2,2-dimethyl-3-methylidenebicyclo[2.2.1]heptan-5-ol Chemical compound C1[C@@H](O)[C@@H]2C(=C)C(C)(C)[C@H]1C2 CFXJOMGPUADAJE-XHNCKOQMSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003115 supporting electrolyte Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QKFFSWPNFCXGIQ-UHFFFAOYSA-M 4-methylbenzenesulfonate;tetraethylazanium Chemical compound CC[N+](CC)(CC)CC.CC1=CC=C(S([O-])(=O)=O)C=C1 QKFFSWPNFCXGIQ-UHFFFAOYSA-M 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- -1 sesquiterpene hydrocarbons Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002168 ethanoic acid esters Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229930003658 monoterpene Natural products 0.000 description 2
- 150000002773 monoterpene derivatives Chemical class 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000341 volatile oil Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical compound CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 1
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 241000723353 Chrysanthemum Species 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 241000721346 Chrysanthemum japonense Species 0.000 description 1
- 235000008641 Chrysanthemum japonense Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- MQFIKAWTCOXAAY-UHFFFAOYSA-N acetic acid;n-butylbutan-1-amine Chemical compound CC([O-])=O.CCCC[NH2+]CCCC MQFIKAWTCOXAAY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- GDCXBZMWKSBSJG-UHFFFAOYSA-N azane;4-methylbenzenesulfonic acid Chemical compound [NH4+].CC1=CC=C(S([O-])(=O)=O)C=C1 GDCXBZMWKSBSJG-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 description 1
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 1
- 229940116229 borneol Drugs 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- LUZAPQMJJZFVKB-UHFFFAOYSA-N butan-1-amine;phosphoric acid Chemical compound CCCCN.CCCCN.CCCCN.OP(O)(O)=O LUZAPQMJJZFVKB-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000002577 monoterpenes Nutrition 0.000 description 1
- NKNFUMKGJYKPCT-UHFFFAOYSA-N n,n-diethylethanamine;sulfuric acid Chemical compound [O-]S([O-])(=O)=O.CC[NH+](CC)CC.CC[NH+](CC)CC NKNFUMKGJYKPCT-UHFFFAOYSA-N 0.000 description 1
- PNLVIPVKIAPZTP-UHFFFAOYSA-N n,n-dimethylmethanamine;perchloric acid Chemical compound C[NH+](C)C.[O-]Cl(=O)(=O)=O PNLVIPVKIAPZTP-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 150000003151 propanoic acid esters Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229930004725 sesquiterpene Natural products 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
【発明の詳細な説明】
本発明は２，２−ジメチル−３−メチレンビシ
クロ〔２、２、１〕ヘプタン−５−オール又はそ
の低級脂肪族カルボン酸エステルの製造方法に関
し、詳しくはトリシクレン及び／又はカンフエン
を低級脂肪族カルボン酸中で電解酸化し、必要に
応じ酸化生成物を加水分解し、ついで生成した
２，２−ジメチル−３−メチレンビシクロ〔２、
２、１〕ヘプタン−５−オール又はその低級脂肪
族カルボン酸エステルを分離することを特徴とす
る２，２−ジメチル−３−メチレンビシクロ
〔２、２、１〕ヘプタン−５−オール又はその低
級脂肪族カルボン酸エステルの製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 2,2-dimethyl-3-methylenebicyclo[2,2,1]heptan-5-ol or its lower aliphatic carboxylic acid ester. Alternatively, camphene is electrolytically oxidized in a lower aliphatic carboxylic acid, the oxidation product is hydrolyzed as necessary, and the resulting 2,2-dimethyl-3-methylenebicyclo[2,
2,2-dimethyl-3-methylenebicyclo[2,2,1]heptan-5-ol or a lower aliphatic carboxylic acid ester thereof, characterized in that 2,1] heptan-5-ol or a lower aliphatic carboxylic acid ester thereof is separated The present invention relates to a method for producing an aliphatic carboxylic acid ester.
２，２−ジメチル−３−メチレンビシクロ
〔２、２、１〕ヘプタン−５−オールは松原らに
よつて野路菊（Chrysanthemum japonense）の
精油中から単離されたモノテルペンアルコールで
あり〔このアルコールはノジギクアルコールと称
される；Tetrahedron LettersNo.48、4219〜4222
（1974）〕、野路菊の芳香を有し、香料の香気成分
として有用である。またこのノジギクアルコール
の低級脂肪族カルボン酸エステルも優雅な花香様
の芳香を有し、香料の香気成分として有用であ
る。 2,2-dimethyl-3-methylenebicyclo[2,2,1]heptan-5-ol is a monoterpene alcohol isolated from the essential oil of Chrysanthemum japonense by Matsubara et al. is called Nojigiku alcohol; Tetrahedron Letters No. 48, 4219-4222
(1974)], it has the aroma of Noji chrysanthemum and is useful as an aroma component in perfumes. This lower aliphatic carboxylic acid ester of Nojigiku alcohol also has an elegant flower-like aroma and is useful as an aroma component of fragrances.
従来、ノジギクアルコールはカンフエンを塩素
ガスにより塩素化し、ついでこれを酢酸カリウム
でアセトキシ化し、さらに加水分解することによ
り合成されることが報告されているが〔D.L.Dull
et al.、J.Org.Chem.、29、3095（1964）〕、この方
法は収率、選択性などの面で必ずしも満足のいく
ものではない。また、カンフエン又はトリシクレ
ンを支持電解質として酢酸リチウムを用いかつス
テンレススチール電極を使用して電解酸化し、つ
いで生成物をケン化することによりカンフエニラ
ンアルデヒド、ボルネオール、2β−カンフエニ
リルアルコールなどが得られることが報告されて
いるが〔松原ら、第16回香料・テルペンおよび精
油化学に関する討論会講演要旨集、第111〜112頁
（1972年）〕、該電解酸化反応又はケン化反応によ
つてノジギクアルコール又はそのエステルが生成
したとの報告はない。 Conventionally, it has been reported that Nojigiku alcohol is synthesized by chlorinating camphene with chlorine gas, then acetoxylating it with potassium acetate, and further hydrolyzing it [DLDull
et al., J.Org.Chem., 29, 3095 (1964)], this method is not necessarily satisfactory in terms of yield, selectivity, etc. In addition, camphenyl aldehyde, borneol, 2β-camphenyl alcohol, etc. can be obtained by electrolytically oxidizing camphene or tricyclene using lithium acetate as a supporting electrolyte and a stainless steel electrode, and then saponifying the product. It has been reported that [Matsubara et al., Abstracts of the 16th Symposium on Flavor, Terpene and Essential Oil Chemistry, pp. 111-112 (1972)], the electrolytic oxidation reaction or saponification reaction There is no report that Nojigiku alcohol or its ester was produced.
本発明者らはモノ及びセスキテルペン炭化水素
類の電解酸化について鋭意研究を重ねた結果、ト
リシクレン及び／又はカンフエン低級脂肪族カル
ボン酸中で電解酸化するとノジギクアルコールの
低級脂肪族カルボン酸エステルが高選択率で得ら
れること、またこのノジギクアルコールの低級脂
肪族カルボン酸エステルは加水分解により容易に
ノジギクアルコールに誘導されることを見出し、
本発明に至つた。 As a result of extensive research into the electrolytic oxidation of mono- and sesquiterpene hydrocarbons, the present inventors found that when electrolytically oxidized in tricyclene and/or camphene lower aliphatic carboxylic acid, the lower aliphatic carboxylic acid ester of Nojigik alcohol is highly selective. We found that this lower aliphatic carboxylic acid ester of Nojigiku alcohol can be easily derived into Nojikiku alcohol by hydrolysis,
This led to the present invention.
本発明の方法では基質として、トリシクレン、
カンフエン又はこれらの混合物を使用することが
できるが、トリシクレンを基質として用いた場合
に最も選択性よく目的化合物を得ることができ
る。電解酸化反応は低級脂肪族カルボン酸中で行
なわれる。低級脂肪族カルボン酸としては酢酸、
プロピオン酸、酪酸、吉草酸、カプロン酸、ヘプ
タン酸、カプリル酸などが挙げられるが、特に酢
酸の使用が好ましい。これら低級脂肪族カルボン
酸は溶媒として使用される他にそれ自体反応試剤
として作用するため、本発明の電解酸化反応によ
れば、使用する低級脂肪族カルボン酸に対応する
ノジギクアルコールのエステルが得られる。低級
脂肪族カルボン酸の使用量は基質１モルに対して
20〜100モル、好ましくは40〜80モルである。な
お、反応系内に電解酸化反応を阻害しない酢酸メ
チル、酢酸エチルなどの溶媒が存在していてもよ
い。また水が存在する系で本発明の電解酸化反応
が行なわれる場合には、上記エステルの他にノジ
ギクアルコールが生成し、これら両者の混合物が
得られる。 In the method of the present invention, tricyclene,
Although camphene or a mixture thereof can be used, the target compound can be obtained with the highest selectivity when tricyclene is used as a substrate. The electrolytic oxidation reaction is carried out in lower aliphatic carboxylic acids. Examples of lower aliphatic carboxylic acids include acetic acid,
Examples include propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, and the use of acetic acid is particularly preferred. These lower aliphatic carboxylic acids are used as solvents and also act as reaction reagents, so according to the electrolytic oxidation reaction of the present invention, esters of Nojigik alcohol corresponding to the lower aliphatic carboxylic acids used can be obtained. . The amount of lower aliphatic carboxylic acid used is per mole of substrate.
The amount is 20 to 100 mol, preferably 40 to 80 mol. Note that a solvent such as methyl acetate or ethyl acetate that does not inhibit the electrolytic oxidation reaction may be present in the reaction system. Further, when the electrolytic oxidation reaction of the present invention is carried out in a system where water is present, nojigikku alcohol is produced in addition to the above-mentioned ester, and a mixture of the two is obtained.
本発明の電解酸化反応においては適当な支持電
解質を使用することが好ましい。支持電解質とし
ては基質又は反応生成物と非反応性でかつ電解酸
化反応を阻害しないものが好ましく、例えば塩化
カリ、硫酸マグネシウム、燐酸バリウム、過塩素
酸リチウム、過塩素酸ナトリウム、酢酸カリウ
ム、酢酸ストロンチウム、ｐ−トルエンスルホン
酸ナトリウムなどのナトリウム、カリウム、バリ
ウム、カルシウム、ストロンチウム、マグネシウ
ムの如きアルカリ金属又はアルカリ土類金属のハ
ロゲン化物、硫酸塩、燐酸塩、過塩素酸塩、酢酸
塩又はトルエンスルホン酸塩；硫酸アンモニウ
ム、過塩素酸アンモニウム、酢酸アンモニウム、
ｐ−トルエンスルホン酸アンモニウムなどのアン
モニウム塩；燐酸ｎ−ブチルアンモニウム、酢酸
ジｎ−ブチルアンモニウム、塩化トリエチルアン
モニウム、硫酸トリエチルアンモニウム、過塩素
酸トリメチルアンモニウム、ｐ−トルエンスルホ
ン酸テトラエチルアンモニウムの如き炭素数１〜
６のアルキル基を有する第１級〜第４級アンモニ
ウムカチオンのハロゲン化物、硫酸塩、燐酸塩、
過塩素酸塩、酢酸塩又はトルエンスルホン酸塩；
トリメチルアミン、トリエチルアミン、ジイソプ
ロピルアミン、ブチルアミン、ピロリジン、ピペ
ラジン、ピリジン、ピコリンなどの鎖状又は環状
のアミン類；フツ素化ホウ素ナトリウム、塩素化
ホウ素ナトリウムなどのハロゲン化ホウ素金属塩
などを単独で、又は２種以上の混合物で使用する
ことができる。特に好ましい支持電解質としてア
ミン類及びアンモニウム塩が挙げられる。支持電
解質の使用量は、使用する支持電解質及び溶媒の
種類と必要とする電流密度とにより変化するもの
であり、例えばｐ−トルエンスルホン酸テトラエ
チルアンモニウムを支持電解質として使用する場
合、基質１モル、酢酸70モルに対し0.1〜1.0モル
が好ましい。 In the electrolytic oxidation reaction of the present invention, it is preferable to use a suitable supporting electrolyte. The supporting electrolyte is preferably one that is non-reactive with the substrate or reaction product and does not inhibit the electrolytic oxidation reaction, such as potassium chloride, magnesium sulfate, barium phosphate, lithium perchlorate, sodium perchlorate, potassium acetate, and strontium acetate. , halides, sulfates, phosphates, perchlorates, acetates of alkali metals or alkaline earth metals such as sodium, potassium, barium, calcium, strontium, magnesium, such as sodium p-toluenesulfonate, or toluenesulfonic acid. Salt; ammonium sulfate, ammonium perchlorate, ammonium acetate,
Ammonium salts such as ammonium p-toluenesulfonate; carbon atoms such as n-butylammonium phosphate, di-n-butylammonium acetate, triethylammonium chloride, triethylammonium sulfate, trimethylammonium perchlorate, and tetraethylammonium p-toluenesulfonate; ~
Halides, sulfates, phosphates of primary to quaternary ammonium cations having 6 alkyl groups,
perchlorate, acetate or toluenesulfonate;
Chain or cyclic amines such as trimethylamine, triethylamine, diisopropylamine, butylamine, pyrrolidine, piperazine, pyridine, picoline; boron metal salts such as sodium borofluoride and sodium borochloride alone or in combination Can be used in mixtures of more than one species. Particularly preferred supporting electrolytes include amines and ammonium salts. The amount of supporting electrolyte used varies depending on the type of supporting electrolyte and solvent used and the required current density. For example, when tetraethylammonium p-toluenesulfonate is used as the supporting electrolyte, 1 mol of substrate, acetic acid It is preferably 0.1 to 1.0 mol per 70 mol.
本発明の電解酸化反応は低級脂肪族カルボン酸
中で行なわれるため、電極は例えば金、白金、金
若しくは白金でメツキしたチタン、炭素、過酸化
鉛などの耐酸性のものが好ましく使用される。反
応収率及び選択率の面で特に好結果を与える材質
は炭素、白金又は白金でメツキしたチタンであ
る。電流密度としては５〜50ｍＡ／cm2、好ましく
は10〜20ｍＡ／cm2の範囲であり、この値は端子電
圧によつて調整することができる。理論電気量は
2F／molであるが、実際には3.0〜4.5F／molを用
いてノジギクアルコールの低級脂肪族カルボン酸
エステルへの転化率を高めるのが好ましい。反応
は10〜45℃のような比較的広範囲の温度で可能で
あるが、特に15〜25℃の温度範囲で行なうのが実
際的である。なお、一定温度での反応が望まれる
ならば、通常の手段により反応系を冷却又は加熱
すればよい。 Since the electrolytic oxidation reaction of the present invention is carried out in a lower aliphatic carboxylic acid, acid-resistant electrodes such as gold, platinum, titanium plated with gold or platinum, carbon, or lead peroxide are preferably used. Materials which give particularly good results in terms of reaction yield and selectivity are carbon, platinum or titanium plated with platinum. The current density is in the range of 5 to 50 mA/cm 2 , preferably 10 to 20 mA/cm 2 , and this value can be adjusted by adjusting the terminal voltage. The theoretical amount of electricity is
Although it is 2F/mol, it is actually preferable to use 3.0 to 4.5F/mol to increase the conversion rate of Nojigikku alcohol to lower aliphatic carboxylic acid ester. Although the reaction is possible over a relatively wide range of temperatures, such as from 10 to 45°C, it is particularly practical to carry out the reaction in the temperature range from 15 to 25°C. Incidentally, if a reaction at a constant temperature is desired, the reaction system may be cooled or heated by conventional means.
本発明における電解酸化反応は連続式又は回分
式で行なうことができる。電解酸化反応後、例え
ば、反応混合液又はそれから減圧下に溶媒を留去
して得られる残留物を水又は希アルカリ水溶液中
に注ぎ、これをヘキサンなどの適当な溶媒で抽出
することにより、目的とするノジギクアルコール
の低級脂肪族カルボン酸エステル又はこれとノジ
ギクアルコールとを含む油分を分離することがで
きる。この油分の中には目的生成物の他に、副生
する３，５−ジアセトキシカンフアン、３，５−
ジプロピオニルオキシカンフアンなどの３，５−
ジアシルオキシカンフアンを少量含むことがあ
る。この油分から蒸留などの通常一般に用いられ
る分離方法によりノジギクアルコールの低級脂肪
族カルボン酸エステル又はこれとノジギクアルコ
ールとを分離取得することができる。 The electrolytic oxidation reaction in the present invention can be carried out continuously or batchwise. After the electrolytic oxidation reaction, for example, the reaction mixture or the residue obtained by distilling off the solvent from it under reduced pressure is poured into water or a dilute alkaline aqueous solution, and this is extracted with a suitable solvent such as hexane to achieve the desired purpose. It is possible to separate the lower aliphatic carboxylic acid ester of Nojichoku alcohol or the oil containing this and Nojichoku alcohol. In addition to the target product, this oil contains by-produced 3,5-diacetoxycamphane, 3,5-
3,5- such as dipropionyloxycamphane
May contain small amounts of diacyloxycamphane. A lower aliphatic carboxylic acid ester of Nojichoku alcohol or this and Nojichoku alcohol can be separated and obtained from this oil by a commonly used separation method such as distillation.
電解酸化反応により得られたノジギクアルコー
ルの低級脂肪族カルボン酸エステルはこれを単離
精製し又はすることなく常法に従つて加水分解す
ることによりノジギクアルコールとすることがで
きる。 The lower aliphatic carboxylic acid ester of Nojichoku alcohol obtained by the electrolytic oxidation reaction can be made into Nojichoku alcohol by hydrolyzing it according to a conventional method with or without isolation and purification.
以下に、本発明を実施例により具体的に説明す
る。 The present invention will be specifically explained below using examples.
実施例 １
トリシクレン（GLC純度100％）1.36ｇと支持
電解質としてのｐ−トルエンスルホン酸テトラエ
チルアンモニウム2.50ｇを酢酸40mlに溶かし、こ
の溶液をビーカー型無隔膜セルに入れ、炭素電極
を用い、電流密度10ｍＡ／cm2、通電量4F／mol、
温度20〜29℃の条件下で定電流電解を行なつた。
反応終了後、反応混合液から減圧下、約40℃で酢
酸を留去し、残存する僅少量の酢酸を炭酸カリウ
ム水溶液で中和したのち、反応混合物をｎ−ヘキ
サンの50mlずつ３回、合計150mlを用いて抽出し
た。抽出液を水洗し、無水硫酸マグネシウムで乾
燥したのち、ヘキサンを留去することにより油状
物1.25ｇを得た。ついで、この油状物をエタノー
ル50mlに溶かし、これに２規定カセイソーダ10ml
を加え、得られた混合物を1.5時間加熱還流した。
反応混合液からエタノールを減圧下に留去し、残
渣の油分を水中に注ぎ、これをｎ−ヘキサンで抽
出した。抽出液を水洗し、無水硫酸マグネシウム
で乾燥したのち、追い出し蒸留を行ない、FID−
GLC分布比57％を有する粗製ノジギクアルコー
ル1.02ｇを得た。さらに、この粗製ノジギクアル
コールをエタノールから再結晶することにより、
mp.55〜57.5℃の白色結晶としてノジギクアルコ
ール0.30ｇを得た。この生成物の物性値を次に示
す。Example 1 1.36 g of tricyclene (GLC purity 100%) and 2.50 g of tetraethylammonium p-toluenesulfonate as a supporting electrolyte were dissolved in 40 ml of acetic acid, this solution was placed in a beaker-type membraneless cell, and a current density was adjusted using a carbon electrode. 10mA/cm 2 , current flow 4F/mol,
Constant current electrolysis was performed at a temperature of 20-29°C.
After the reaction was completed, acetic acid was distilled off from the reaction mixture at about 40°C under reduced pressure, and the remaining small amount of acetic acid was neutralized with an aqueous potassium carbonate solution. Extraction was performed using 150 ml. The extract was washed with water, dried over anhydrous magnesium sulfate, and then the hexane was distilled off to obtain 1.25 g of an oily substance. Next, dissolve this oil in 50ml of ethanol, and add 10ml of 2N caustic soda to this.
was added, and the resulting mixture was heated under reflux for 1.5 hours.
Ethanol was distilled off from the reaction mixture under reduced pressure, and the residual oil was poured into water, which was extracted with n-hexane. After washing the extract with water and drying with anhydrous magnesium sulfate, expulsion distillation was performed and FID-
1.02 g of crude Nojigiku alcohol with a GLC distribution ratio of 57% was obtained. Furthermore, by recrystallizing this crude Nojigiku alcohol from ethanol,
0.30 g of Nojigiku alcohol was obtained as white crystals with a temperature of 55 to 57.5°C. The physical properties of this product are shown below.
IRスペクトル（cm-1）：3320、2960、1660、
1050、1030、880
NMRスペクトル（90MHz）δCDCl3 ppn：
0.95、1.02（each ｓ、6H）；
2.61（bs、1H）；3.7〜3.9（ｍ、1H）；
4.64、4.85（each ｓ、2H）
実施例 ２
トリシクレン（GLC純度100％）1.32ｇと支持
電解質としてのトリエチルアミン1.56ｇを酢酸40
mlに溶かし、この溶液をビーカー型無隔膜セルに
入れ、炭素電極を用い、電流密度10ｍＡ／cm2、通
電量4F／mol、温度20〜29℃の条件下で定電流電
解を行なつた。反応終了後、実施例１と同様に処
理することにより油状物1.25ｇを得た。ついで、
この油状物を実施例１と同様に加水分解したの
ち、蒸留することにより、FID−GLC分布比57％
を有する粗製ノジギクアルコール0.98ｇを得た。
この粗製ノジギクアルコールをエタノールから再
結晶することにより、ノジギクアルコールの白色
結晶0.51ｇを得た。IR spectrum (cm -1 ): 3320, 2960, 1660,
1050, 1030, 880 NMR spectrum (90MHz) δ CDCl3 ppn : 0.95, 1.02 (each s, 6H); 2.61 (BS, 1H); 3.7-3.9 (m, 1H); 4.64, 4.85 (each s, 2H) Implemented Example 2 Add 1.32 g of tricyclene (GLC purity 100%) and 1.56 g of triethylamine as a supporting electrolyte to 40 g of acetic acid.
This solution was placed in a beaker-type non-diaphragm cell, and constant current electrolysis was performed using a carbon electrode at a current density of 10 mA/cm 2 , a current flow rate of 4 F/mol, and a temperature of 20 to 29°C. After the reaction was completed, the same procedure as in Example 1 was carried out to obtain 1.25 g of an oily substance. Then,
This oily substance was hydrolyzed in the same manner as in Example 1, and then distilled to obtain a FID-GLC distribution ratio of 57%.
0.98 g of crude Nojigiku alcohol having the following properties was obtained.
This crude Nojigiku alcohol was recrystallized from ethanol to obtain 0.51 g of white crystals of Nojikiku alcohol.
実施例 ３
カンフエン（GLC純度100％）2.72ｇと支持電
解質としてのｐ−トルエンスルホン酸テトラエチ
ルアンモニウム5.02ｇを酢酸80mlに溶かし、これ
をビーカー型無隔膜セルに入れ、炭素電極を用
い、電流密度10ｍＡ／cm2、通電量4F／mol、温度
29℃の条件下で定電流電解を行なつた。反応終了
後、実施例１と同様に処理することにより油状物
2.62ｇを得た。ついで、この油状物を実施例１と
同様に加水分解したのち、蒸留することにより
FID−GLC分布比19％を有する粗製ノジギクアル
コール2.65ｇを得た。この粗製ノジギクアルコー
ルをエタノールから再結晶することにより、ノジ
ギクアルコールの白色結晶0.43ｇを得た。Example 3 2.72 g of camphene (GLC purity 100%) and 5.02 g of tetraethylammonium p-toluenesulfonate as a supporting electrolyte were dissolved in 80 ml of acetic acid, placed in a beaker-type membraneless cell, and using a carbon electrode at a current density of 10 mA. /cm 2 , current flow 4F/mol, temperature
Constant current electrolysis was performed at 29°C. After the reaction is completed, the oily substance is removed by the same treatment as in Example 1.
2.62g was obtained. Next, this oily substance was hydrolyzed in the same manner as in Example 1, and then distilled to obtain
2.65 g of crude Nojigiku alcohol with a FID-GLC distribution ratio of 19% was obtained. This crude Nojigiku alcohol was recrystallized from ethanol to obtain 0.43 g of white crystals of Nojikiku alcohol.
実施例 ４
トリシクレン（GLC純度100％）1.36ｇを実施
例１と同様に電解酸化し、得られた反応混合液か
ら同様の抽出操作により、ノジギクアルコールの
酢酸エステルを含む油状物1.30ｇを得た。この油
状物を減圧下に蒸留することにより、bp.98℃／
７mmHgの留分としてノジギクアルコールの酢酸
エステル0.73ｇを得た。この生成分の物性値を次
に示す。Example 4 1.36 g of tricyclene (GLC purity 100%) was electrolytically oxidized in the same manner as in Example 1, and 1.30 g of an oil containing acetic acid ester of Nojigik alcohol was obtained by the same extraction operation from the resulting reaction mixture. . By distilling this oil under reduced pressure, bp.98℃/
0.73 g of acetic acid ester of Nojigiku alcohol was obtained as a 7 mmHg fraction. The physical properties of this product are shown below.
IRスペクトル（cm-1）：2980、1740、1660、
1380、1250、1230、1030、890
NMRスペクトル（90MHz）δCDCl3 ppn：
0.98、1.02（each ｓ、6H）；
2.00（ｓ、3H）；2.75（bs、1H）；
4.5〜4.7（ｍ、1H）；4.70、4.95（each ｓ、2H）
実施例 ５
実施例１において酢酸40mlの代りにプロピオン
酸40mlを用いて同様の電解酸化反応を行ない、得
られた反応混合液から同様の抽出操作により、ノ
ジギクアルコールのプロピオン酸エステルを含む
油状物1.32ｇを得た。この油状物を減圧下に蒸留
することにより、bp.101℃／７mmHgの留分とし
てノジギクアルコールのプロピオン酸エステル
0.81ｇを得た。この生成物の物性値を次に示す。IR spectrum (cm -1 ): 2980, 1740, 1660,
1380, 1250, 1230, 1030, 890 NMR spectrum (90MHz) δ CDCl3 ppn : 0.98, 1.02 (each s, 6H); 2.00 (s, 3H); 2.75 (BS, 1H); 4.5-4.7 (m, 1H) ; 4.70, 4.95 (each s, 2H) Example 5 A similar electrolytic oxidation reaction was carried out in Example 1 using 40 ml of propionic acid instead of 40 ml of acetic acid, and from the resulting reaction mixture, Nojigi 1.32 g of an oil containing propionic ester of alcohol was obtained. By distilling this oil under reduced pressure, the propionic acid ester of Nojigik alcohol was obtained as a fraction of bp.101℃/7mmHg.
0.81g was obtained. The physical properties of this product are shown below.
IRスペクトル（cm-1）：2980、1740、1660、
1180、1020、890
NMRスペクトル（90MHz）δCDCl3 ppn：
1.00、1.04（each ｓ、6H）；
1.10（ｔ、3H）；2.27（ｑ、2H）；
2.75（bs、1H）；4.5〜4.7（ｍ、1H）；
4.70、4.96（each ｓ、2H）IR spectrum (cm -1 ): 2980, 1740, 1660,
1180, 1020, 890 NMR spectrum (90MHz) δ CDCl3 ppn : 1.00, 1.04 (each s, 6H); 1.10 (t, 3H); 2.27 (q, 2H); 2.75 (bs, 1H); 4.5-4.7 (m , 1H); 4.70, 4.96 (each s, 2H)
Claims (1)
肪族カルボン酸中で電解酸化し、必要に応じ酸化
生成物を加水分解し、ついで生成した２，２−ジ
メチル−３−メチレンビシクロ〔２、２、１〕ヘ
プタン−５−オール又はその低級脂肪族カルボン
酸エステルを分離することを特徴とする２，２−
ジメチル−３−メチレンビシクロ〔２、２、１〕
ヘプタン−５−オール又はその低級脂肪族カルボ
ン酸エステルの製造方法。[Scope of Claims] 1. Electrolytic oxidation of tricyclene and/or camphene in a lower aliphatic carboxylic acid, hydrolysis of the oxidation product as necessary, and then the produced 2,2-dimethyl-3-methylenebicyclo[2 , 2,1] 2,2- characterized by separating heptan-5-ol or its lower aliphatic carboxylic acid ester
Dimethyl-3-methylenebicyclo[2,2,1]
A method for producing heptane-5-ol or a lower aliphatic carboxylic acid ester thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58030491A JPS59157290A (en) | 1983-02-24 | 1983-02-24 | Manufacture of 2,2-dimethyl-3-methylenebicyclo (2,2,1)heptane-5-ol or its ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58030491A JPS59157290A (en) | 1983-02-24 | 1983-02-24 | Manufacture of 2,2-dimethyl-3-methylenebicyclo (2,2,1)heptane-5-ol or its ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59157290A JPS59157290A (en) | 1984-09-06 |
| JPH028032B2 true JPH028032B2 (en) | 1990-02-22 |
Family
ID=12305303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58030491A Granted JPS59157290A (en) | 1983-02-24 | 1983-02-24 | Manufacture of 2,2-dimethyl-3-methylenebicyclo (2,2,1)heptane-5-ol or its ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59157290A (en) |
-
1983
- 1983-02-24 JP JP58030491A patent/JPS59157290A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59157290A (en) | 1984-09-06 |
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