JPH0139409B2 - - Google Patents
Info
- Publication number
- JPH0139409B2 JPH0139409B2 JP56088882A JP8888281A JPH0139409B2 JP H0139409 B2 JPH0139409 B2 JP H0139409B2 JP 56088882 A JP56088882 A JP 56088882A JP 8888281 A JP8888281 A JP 8888281A JP H0139409 B2 JPH0139409 B2 JP H0139409B2
- Authority
- JP
- Japan
- Prior art keywords
- terpene
- alcohol
- carboxylic acid
- reaction
- present
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000002585 base Substances 0.000 description 12
- 150000001733 carboxylic acid esters Chemical class 0.000 description 9
- 235000007586 terpenes Nutrition 0.000 description 9
- XXIKYCPRDXIMQM-UHFFFAOYSA-N Isopentenyl acetate Chemical compound CC(C)=CCOC(C)=O XXIKYCPRDXIMQM-UHFFFAOYSA-N 0.000 description 8
- -1 Terpene alcohols Chemical class 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 8
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 8
- 150000003505 terpenes Chemical class 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-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
- 239000006227 byproduct Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000004714 phosphonium salts Chemical group 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- FQTLCLSUCSAZDY-UHFFFAOYSA-N (+) E(S) nerolidol Natural products CC(C)=CCCC(C)=CCCC(C)(O)C=C FQTLCLSUCSAZDY-UHFFFAOYSA-N 0.000 description 1
- CRDAMVZIKSXKFV-FBXUGWQNSA-N (2-cis,6-cis)-farnesol Chemical compound CC(C)=CCC\C(C)=C/CC\C(C)=C/CO CRDAMVZIKSXKFV-FBXUGWQNSA-N 0.000 description 1
- 239000000260 (2E,6E)-3,7,11-trimethyldodeca-2,6,10-trien-1-ol Substances 0.000 description 1
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 1
- 239000001371 (5E)-3,5-dimethylocta-1,5,7-trien-3-ol Substances 0.000 description 1
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 1
- JKXQKGNGJVZKFA-UHFFFAOYSA-N 1-chloro-3-methylbut-2-ene Chemical compound CC(C)=CCCl JKXQKGNGJVZKFA-UHFFFAOYSA-N 0.000 description 1
- DLHQZZUEERVIGQ-UHFFFAOYSA-N 3,7-dimethyl-3-octanol Chemical compound CCC(C)(O)CCCC(C)C DLHQZZUEERVIGQ-UHFFFAOYSA-N 0.000 description 1
- SEPQTYODOKLVSB-UHFFFAOYSA-N 3-methylbut-2-enal Chemical compound CC(C)=CC=O SEPQTYODOKLVSB-UHFFFAOYSA-N 0.000 description 1
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CMNQIVHHHBBVSC-UHFFFAOYSA-N 5-hydroxy-3,4-dihydro-2h-isoquinolin-1-one Chemical compound O=C1NCCC2=C1C=CC=C2O CMNQIVHHHBBVSC-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 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
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- GLZPCOQZEFWAFX-JXMROGBWSA-N Nerol Natural products CC(C)=CCC\C(C)=C\CO GLZPCOQZEFWAFX-JXMROGBWSA-N 0.000 description 1
- FQTLCLSUCSAZDY-ATGUSINASA-N Nerolidol Chemical compound CC(C)=CCC\C(C)=C\CC[C@](C)(O)C=C FQTLCLSUCSAZDY-ATGUSINASA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010478 Prins reaction Methods 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ZJIQIJIQBTVTDY-SREVYHEPSA-N dehydrolinalool Chemical compound CC(=C)\C=C/CC(C)(O)C=C ZJIQIJIQBTVTDY-SREVYHEPSA-N 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229930002886 farnesol Natural products 0.000 description 1
- 229940043259 farnesol Drugs 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 229930007744 linalool Natural products 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WASNIKZYIWZQIP-AWEZNQCLSA-N nerolidol Natural products CC(=CCCC(=CCC[C@@H](O)C=C)C)C WASNIKZYIWZQIP-AWEZNQCLSA-N 0.000 description 1
- VAUKWMSXUKODHR-UHFFFAOYSA-M pentyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCC)C1=CC=CC=C1 VAUKWMSXUKODHR-UHFFFAOYSA-M 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 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 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- CRDAMVZIKSXKFV-UHFFFAOYSA-N trans-Farnesol Natural products CC(C)=CCCC(C)=CCCC(C)=CCO CRDAMVZIKSXKFV-UHFFFAOYSA-N 0.000 description 1
- KKLAORVGAKUOPZ-UHFFFAOYSA-M trimethyl(phenyl)azanium;iodide Chemical compound [I-].C[N+](C)(C)C1=CC=CC=C1 KKLAORVGAKUOPZ-UHFFFAOYSA-M 0.000 description 1
- BFPOZPZYPNVMHU-UHFFFAOYSA-M trimethyl-[3-(trifluoromethyl)phenyl]azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC(C(F)(F)F)=C1 BFPOZPZYPNVMHU-UHFFFAOYSA-M 0.000 description 1
- VKZIUXSJJSEBAK-UHFFFAOYSA-M trimethyl-[3-(trifluoromethyl)phenyl]azanium;iodide Chemical compound [I-].C[N+](C)(C)C1=CC=CC(C(F)(F)F)=C1 VKZIUXSJJSEBAK-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明はテルペン系アルコールの製造法に関
し、更に詳細にはテルペン系アルコールのカルボ
ン酸エステルを窒素塩基あるいはリン塩基触媒及
びそれ以外のアルカリ性物質の存在下、アルコー
ル分解してテルペン系アルコールを製造する方法
に関する。
テルペン系アルコールは香料、医薬あるいは農
薬などの中間体として、工業上極めて重要なる物
質であり、その製造方法も種々の方法が知られて
いる。たとえば、プレノールの合成法としては、
塩化プレニルをカルボン酸の存在下アルカリ
加水分解する方法（特公昭55−3333号）
酢酸プレニルを水の存在下アルカリ加水分解
する方法（特開昭52−10207号）
イソブテンとホルムアルデヒドのプリンス反
応により生成する３―メチル―３―ブテン―１
―オールを異性化する方法（特開昭51−70708
号）。
などである。
しかしながら）の方法では２―メチル―３―
ブテン―２―オールを多く生成し、プレノール収
率は非常に低い。）の方法では、ほぼ選択的に
プレノールが得られるものの、20〜30％と高濃度
のアルカリ水溶液を大量（酢酸プレニルに対し、
１倍モル以上）に使用する為、重合物等を生成
し、収率はさほぼ高くない（80〜90mol％）。又、
酢酸プレニルに対し等量の酢酸ナトリウムを生成
する為、この回収等が必要となり、工業的には不
利となるを免れない。）の方法ではプレノール
と３―メチル―３―ブテン―１―オール、３―メ
チルブタン―１―アール、３―メチル―２―ブテ
ン―１―アールなどの混合物となり、高純度プレ
ノールが得がたいという欠点を有する。
しかるに、本発明者らはこうした従来方法の不
都合に鑑み、高率的な合成法について鋭意研究を
行なつた結果、テルペン系アルコールのカルボン
酸エステルを窒素塩基あるいはリン塩基触媒及び
それ以外のアルカリ性物質の存在下、アルコール
分解することにより、ほとんど副生成物なしにな
しに高収率でテルペン系アルコールを製造する方
法を見出し、本発明を完成させたものである。
すなわち本発明の方法は、窒素塩基あるいはリ
ン塩基触媒及び少量のアルカリ性物質の存在下テ
ルペン系アルコールのカルボン酸エステルを低級
アルコールとエステル交換（アルコール分解）せ
しめ、テルペン系アルコールを生成する方法であ
り、特開昭52−10207号発明などに比して温和な
条件下で反応せしめる為、ほとんど副生成物もな
く、高収率でテルペン系アルコールを製造するこ
とができる工業的に非常に優れた方法である。
又、本発明の方法ではテルペン系アルコールカル
ボン酸エステルのカルボン酸は主として、低級ア
ルコールのカルボン酸エステルとして回収され、
この低級アルコールのカルボン酸エステルは常法
により、容易に無水のカルボン酸アルカリ塩に変
えうるので、そのままテルペンハロゲン化物のエ
ステル化に供する事が出来るという工業上、経済
的に優れた利点を有する。
本発明に於けるテルペン系アルコールとは、
一般式
The present invention relates to a method for producing terpene-based alcohols, and more specifically to a method for producing terpene-based alcohols by alcohol decomposing carboxylic acid esters of terpene-based alcohols in the presence of a nitrogen base or phosphorus base catalyst and other alkaline substances. Regarding. Terpene alcohols are industrially extremely important substances as intermediates for fragrances, medicines, agricultural chemicals, etc., and various methods for producing them are known. For example, methods for synthesizing prenol include a method of alkaline hydrolysis of prenyl chloride in the presence of a carboxylic acid (Japanese Patent Publication No. 55-3333) and a method of alkaline hydrolysis of prenyl acetate in the presence of water (Japanese Patent Publication No. 52-10207). ) 3-Methyl-3-butene-1 produced by the Prins reaction of isobutene and formaldehyde
- Method for isomerizing all (Japanese Patent Application Laid-Open No. 51-70708
issue). etc. However, in the method of 2-methyl-3-
It produces a lot of buten-2-ol and the prenol yield is very low. ), prenol can be obtained almost selectively, but a large amount of a highly concentrated alkaline aqueous solution of 20 to 30% (relative to prenyl acetate,
(more than 1 times the mole), polymers, etc. are produced, and the yield is not very high (80-90 mol%). or,
Since sodium acetate is produced in an equal amount to prenyl acetate, recovery, etc. is necessary, which is inevitably disadvantageous from an industrial perspective. ) method results in a mixture of prenol and 3-methyl-3-buten-1-ol, 3-methylbutan-1-al, 3-methyl-2-buten-1-al, etc., and has the disadvantage that it is difficult to obtain high-purity prenol. have However, in view of these disadvantages of the conventional methods, the present inventors conducted intensive research on high-efficiency synthesis methods and found that carboxylic acid esters of terpene alcohols can be synthesized using nitrogen base or phosphorus base catalysts and other alkaline substances. The present invention was completed by discovering a method for producing terpene-based alcohols in high yields with almost no by-products by alcoholysis in the presence of alcohol. That is, the method of the present invention is a method in which a carboxylic acid ester of a terpene alcohol is transesterified (alcohololyzed) with a lower alcohol in the presence of a nitrogen base or phosphorus base catalyst and a small amount of an alkaline substance to produce a terpene alcohol. Since the reaction is carried out under milder conditions than the invention of JP-A No. 52-10207, there are almost no by-products, and it is an industrially excellent method that can produce terpene-based alcohols in high yields. It is.
In addition, in the method of the present invention, the carboxylic acid of the terpene alcohol carboxylic ester is mainly recovered as a lower alcohol carboxylic ester,
This lower alcohol carboxylic acid ester can be easily converted into anhydrous alkali carboxylic acid salt by a conventional method, so it has an excellent industrial and economical advantage that it can be directly used for esterification of terpene halides. The terpene alcohol in the present invention has the general formula
【式】R1―OH、[Formula] R 1 -OH,
【式】 〔式中R1は[Formula] [In the formula, R 1 is
【式】
（ｎ＝１〜10）で示されるイソプレノイド基、２
重結合転移イソプレノイド基、環化イソプレノイ
ド基、またはこれらの部分的あるいは完全水素化
物であり、R2は水素原子、ビニル基、エチニル
基、または炭素数10以下の直鎖または分枝アルキ
ル基であり、R3は水素原子または炭素数10以下
の直鎖または分枝アルキル基であり、R4はエチ
ル基、ビニル基、またはエチニル基を表わす。〕
であり、具体的にはプレノール、リナロール、デ
ヒドロリナロール、テトラヒドロリナロール、ゲ
ラニオール、ネロール、ネロリドール、フアルネ
ソールなどを挙げることができる。
またテルペン系アルコールのカルボン酸エステ
ルとしては、前記テルペン系アルコールのぎ酸、
酢酸、プロピオン酸、酪酸など低級カルボン酸エ
ステルを挙げることができる。
窒素塩基あるいはリン塩基としては第四級アン
モニウム塩あるいは第四級ホスホニウム塩が適
し、代表的なものを例示するならば、テトラメチ
ルアンモニウムクロライド、テトラエチルアンモ
ニウムプロマイド、テトラブチルアンモニウムア
イオダイド、ステアリルトリメチルアンモニウム
クロライド、ラウリルトリメチルアンモニウムク
ロライド、ベンジルトリメチルアンモニウムクロ
ライド、ベンジルトリエチルアンモニウムアイオ
ダイド、トリメチルフエニルアンモニウムアイオ
ダイド、ｍ―トルフルオロメチルフエニルトリメ
チルアンモニウムアイオダイド、テトラエチルア
ンモニウムハイドロオキサイド、テトラブチルア
ンモニウムハイドロオキサイド、ベンジルトリメ
チルアンモニウムハイドロオオキサイド、ｍ―ト
ルフルオロメチルフエニルトリメチルアンモニウ
ムハイドロオキサイドなどの第四級アンモニウム
塩、ならびに第四級アンモニウム型イオン交換樹
脂（好ましくはポーラス型、ハイポーラス型）た
とえばアンバリストＡ―26，Ａ―27，Ａ―29（ロ
ームアンドハース社製）ダイヤイオンHPA型PA
型（三菱化成工業KK製）およびアミルトリフエ
ニルホスホニウムブロマイド、ベンジルトリフエ
ニルホスホニウムクロライド、トリブチルヘキサ
デシルホスホニウムアイオダイド、トリシクロヘ
キシルエチルホスホニウムブロマイドなどの第四
級ホスホニウム塩であるが、ここに記載の化合物
のみに限定されるものではない。これら窒素塩基
ならびにリン塩基は２種以上を混合して使用して
もよい。
本発明に於いて用いられるアルコールとしては
メタノール、エタノール、ｎ―プロパノール、
iso―プロパノール、ｎ―ブタノール、sec―ブタ
ノール、tert―ブタノール、ｎ―ペンタノール、
ｎ―ヘキサノールなどの低級アルコールが実用上
好ましい。
また、本発明方法ではアルカリ性物質の共存が
必要であるが、このアルカリ性物質としてはリチ
ウム、ナトリウム、カリウムなどのアルカリ金属
及びマグネシウム、カルシウムなどのアルカリ土
類金属の水酸化物、金属酸化物、炭酸塩、アルコ
キシド、アミド等を挙げることができる。
本発明を実施するに当たつては、通常低級アル
コールを溶媒として用いる以外、溶媒は必ずしも
必要ではないが、ｎ―ヘキサン、シクロヘキサン
の如き脂肪族炭化水素、ベンゼン、トルエンの如
き芳香族炭化水素、ジエチルエーテル、テトラヒ
ドロフランの如きエーテル類などの不活性の溶媒
を使用することもできる。
又、本発明に於いて、水の存在は必要ではない
が、水が存在してもさしつかえない。
本発明の実施に当りアルカリの使用量は多くて
もさしつかえないが、通常テルペン系アルコール
のカルボン酸エステル１モルに対し、0.01〜1.0
モルで反応は完結する。尚、反応速度及び経剤性
の面から0.1〜0.5モル範囲を推奨することがこ範
囲に限定されるものではない。
低級アルコールは、普通反応試験剤兼溶媒とし
て使用し、テルペン系アルコールのカルボン酸エ
ステル１モルに対し通例１〜10モルを使用する。
触媒として用いる窒素塩基あるいはリン塩基は
テルプン系アルコールのカルボン酸エステル１モ
ル対し、0.001〜1.0モル範囲が通例であるが、特
に0.005〜0.1モルの範囲が好ましい。
本反応の反応温度は常温から200℃程合温度範
囲で行なう事ができるが、反応速度点で50〜150
℃範囲で実施する事が好ましい。また、低級アル
コールの還流下にて反応を行なつても良いが、通
常、反応の進行につれて生成する低級アルコール
のカルボン酸エステルを留去しつつ反応する事が
好ましい。この反応は空気中で実施しても良が通
例は不活性ガス雰囲気下に於て行なうが好まし。
更に２，６―ジ―tert―ブチル―ｐ―クレゾール
の如き抗酸化剤の共存下に反応を行なつてもよ
い。尚、原料の仕込み方法について特に制限はな
く、仕込割合は上記範囲内の限定されるものでは
ない。
以上、詳述した如く本発明の方法は従来法に比
して副生成物が少なくより高収率で目的物を得る
事ができ、工業的にも優れた方法である。
以下に本発明を実施例により更に具体的に説明
し、本発明の効果をより明らかにするが、これら
の実施例によつて本発明の範囲が限定されるもの
ではない。
実施例 １
撹拌機、温度計、窒素ガス導入管、ヴイグリユ
ー分留管及び蒸留装置を備えた200ml四ツ口フラ
スコにプレニルアセテート13.0ｇ（0.1モル）、ベ
ンジルトリメチルアンモニウムヒドロキシド（40
％水溶液）2.1ｇ（0.005モル）、水酸化ナトリウ
ム（フレーク）1.2ｇ（0.003mol）及びメタノー
ル64.1ｇを仕込み、生成する酢酸メチルをメタノ
ール共沸で留去しつつ65℃て５時間反応を行なつ
た。反応終了液よりメタノールを留去し、釜残に
ｎ―ヘキサンを加え、水洗を行なつた。水洗した
油層より、ｎ―ヘキサンを減圧留去し、粗プレノ
ールを8.7ｇ得た。ガスクロマトグラフイーにて
分析を行なつたところ、プレノールを7.91ｇを含
有していた（収率91.8mol％）。
実施例２〜５及び比較例１〜２
種々の触媒及びアルカリを用いて、実施例１と
同様に反応を行ない、テルペン系アルコールを製
造した。その結果を第１表に示す。[Formula] Isoprenoid group represented by (n=1-10), 2
A polybond-transferred isoprenoid group, a cyclized isoprenoid group, or a partially or completely hydrogenated product thereof, and R 2 is a hydrogen atom, a vinyl group, an ethynyl group, or a straight-chain or branched alkyl group having 10 or less carbon atoms. , R 3 is a hydrogen atom or a linear or branched alkyl group having 10 or less carbon atoms, and R 4 represents an ethyl group, a vinyl group, or an ethynyl group. ] Specific examples thereof include prenol, linalool, dehydrolinalool, tetrahydrolinalool, geraniol, nerol, nerolidol, and farnesol. Further, as the carboxylic acid ester of terpene alcohol, formic acid of the terpene alcohol,
Examples include lower carboxylic acid esters such as acetic acid, propionic acid, and butyric acid. As the nitrogen base or phosphorus base, quaternary ammonium salts or quaternary phosphonium salts are suitable, and typical examples include tetramethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium iodide, and stearyltrimethylammonium chloride. , lauryltrimethylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium iodide, trimethylphenylammonium iodide, m-trifluoromethylphenyltrimethylammonium iodide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium Hydrooxide, quaternary ammonium salts such as m-trifluoromethylphenyltrimethylammonium hydroxide, and quaternary ammonium type ion exchange resins (preferably porous type, hyperporous type) such as Amberlyst A-26, A -27, A-29 (manufactured by Rohm and Haas) Diamond Ion HPA type PA
type (manufactured by Mitsubishi Kasei KK) and quaternary phosphonium salts such as amyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tributylhexadecylphosphonium iodide, tricyclohexylethylphosphonium bromide, but only the compounds listed here. It is not limited to. Two or more of these nitrogen bases and phosphorus bases may be used in combination. Alcohols used in the present invention include methanol, ethanol, n-propanol,
iso-propanol, n-butanol, sec-butanol, tert-butanol, n-pentanol,
Lower alcohols such as n-hexanol are practically preferred. In addition, the method of the present invention requires the coexistence of alkaline substances, and these alkaline substances include hydroxides, metal oxides, and carbonates of alkali metals such as lithium, sodium, and potassium, and alkaline earth metals such as magnesium and calcium. Salts, alkoxides, amides, etc. can be mentioned. In carrying out the present invention, solvents are not necessarily required other than lower alcohols, but aliphatic hydrocarbons such as n-hexane and cyclohexane, aromatic hydrocarbons such as benzene and toluene, Inert solvents such as ethers such as diethyl ether and tetrahydrofuran can also be used. Further, in the present invention, the presence of water is not necessary, but there is no problem even if water is present. In carrying out the present invention, the amount of alkali used may be large, but it is usually 0.01 to 1.0 per mole of carboxylic acid ester of terpene alcohol.
The reaction is completed in moles. Incidentally, from the viewpoint of reaction rate and administration properties, a range of 0.1 to 0.5 mol is recommended, but the range is not limited to this range. The lower alcohol is usually used as a reaction test agent and solvent, and is usually used in an amount of 1 to 10 moles per mole of the carboxylic acid ester of the terpene alcohol. The nitrogen base or phosphorus base used as a catalyst is generally in the range of 0.001 to 1.0 mole, and particularly preferably in the range of 0.005 to 0.1 mole, per mole of the carboxylic acid ester of the terpenic alcohol. The reaction temperature of this reaction can be carried out in the temperature range from room temperature to about 200℃, but the reaction rate is 50 to 150℃.
It is preferable to carry out the test in the °C range. Although the reaction may be carried out under reflux of the lower alcohol, it is usually preferable to carry out the reaction while distilling off the carboxylic acid ester of the lower alcohol produced as the reaction progresses. Although this reaction may be carried out in air, it is usually preferably carried out under an inert gas atmosphere.
Furthermore, the reaction may be carried out in the presence of an antioxidant such as 2,6-di-tert-butyl-p-cresol. Note that there is no particular restriction on the method of charging the raw materials, and the charging ratio is not limited within the above range. As described above in detail, the method of the present invention produces fewer by-products and can obtain the desired product in a higher yield than conventional methods, and is an excellent method from an industrial perspective. EXAMPLES The present invention will be described in more detail below with reference to examples to further clarify the effects of the present invention, but the scope of the present invention is not limited by these examples. Example 1 Prenyl acetate 13.0 g (0.1 mol), benzyltrimethylammonium hydroxide (40 g
% aqueous solution), 1.2 g (0.003 mol) of sodium hydroxide (flake), and 64.1 g of methanol, and the reaction was carried out at 65°C for 5 hours while distilling off the generated methyl acetate by methanol azeotrope. Summer. Methanol was distilled off from the reaction solution, and n-hexane was added to the residue, followed by washing with water. From the water-washed oil layer, n-hexane was distilled off under reduced pressure to obtain 8.7 g of crude prenol. Analysis by gas chromatography revealed that it contained 7.91 g of prenol (yield: 91.8 mol%). Examples 2 to 5 and Comparative Examples 1 to 2 Terpene alcohols were produced by carrying out reactions in the same manner as in Example 1 using various catalysts and alkalis. The results are shown in Table 1.
【表】【table】
Claims (1)
を窒素塩基あるいはリン塩基触媒及びそれ以外の
アルカリ性物質の存在下、アルコール分解する事
を特徴とするテルペン系アルコールの製造方法。1. A method for producing a terpene alcohol, which comprises alcohol decomposing a carboxylic acid ester of a terpene alcohol in the presence of a nitrogen base or phosphorus base catalyst and other alkaline substances.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56088882A JPS57206628A (en) | 1981-06-11 | 1981-06-11 | Preparation of terpenic alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56088882A JPS57206628A (en) | 1981-06-11 | 1981-06-11 | Preparation of terpenic alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57206628A JPS57206628A (en) | 1982-12-18 |
| JPH0139409B2 true JPH0139409B2 (en) | 1989-08-21 |
Family
ID=13955360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56088882A Granted JPS57206628A (en) | 1981-06-11 | 1981-06-11 | Preparation of terpenic alcohol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57206628A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1234837A (en) * | 1983-06-28 | 1988-04-05 | Robert J. Knopf | Continuous process for producing linear, secondary, aliphatic alcohols |
| CN112739675B (en) | 2018-09-18 | 2023-11-28 | 巴斯夫欧洲公司 | Method for recovering high quality 3-methyl-but-3-en-1-ol |
-
1981
- 1981-06-11 JP JP56088882A patent/JPS57206628A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57206628A (en) | 1982-12-18 |
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