JP2017039717A - (e)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート化合物及びその製造方法並びにこれを用いた(e)−2−イソプロピル−5−メチル−3,5−ヘキサジエノール及び(e)−2−イソプロピル−5−メチル−3,5−ヘキサジエニル=カルボキシレートの製造方法 - Google Patents
(e)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート化合物及びその製造方法並びにこれを用いた(e)−2−イソプロピル−5−メチル−3,5−ヘキサジエノール及び(e)−2−イソプロピル−5−メチル−3,5−ヘキサジエニル=カルボキシレートの製造方法 Download PDFInfo
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- JP2017039717A JP2017039717A JP2016160053A JP2016160053A JP2017039717A JP 2017039717 A JP2017039717 A JP 2017039717A JP 2016160053 A JP2016160053 A JP 2016160053A JP 2016160053 A JP2016160053 A JP 2016160053A JP 2017039717 A JP2017039717 A JP 2017039717A
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- Prior art keywords
- methyl
- isopropyl
- group
- compound
- 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.)
- Granted
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- -1 (e)-2-isopropyl-5-methyl-3,5-hexadienoate compound Chemical class 0.000 title claims abstract description 210
- WLEKYECALOWNBL-AATRIKPKSA-N (3E)-5-methyl-2-propan-2-ylhexa-3,5-dien-1-ol Chemical compound C(C)(C)C(CO)\C=C\C(=C)C WLEKYECALOWNBL-AATRIKPKSA-N 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 150000007942 carboxylates Chemical class 0.000 title abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 5
- VJJVHLTWXZDALF-AATRIKPKSA-N (3E)-5-methyl-2-propan-2-ylhexa-3,5-dienoic acid Chemical compound C(C)(C)C(C(=O)O)\C=C\C(=C)C VJJVHLTWXZDALF-AATRIKPKSA-N 0.000 abstract description 37
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 11
- GRCMQBWPXLXKFG-UHFFFAOYSA-N 3-hydroxy-5-methyl-2-propan-2-ylhex-4-enoic acid Chemical compound CC(C)C(C(O)C=C(C)C)C(O)=O GRCMQBWPXLXKFG-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003016 pheromone Substances 0.000 abstract description 7
- 125000004453 alkoxycarbonyl group Chemical group 0.000 abstract description 3
- 230000001568 sexual effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 73
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 56
- 239000000047 product Substances 0.000 description 48
- 238000004817 gas chromatography Methods 0.000 description 46
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 37
- 239000002904 solvent Substances 0.000 description 35
- 238000006297 dehydration reaction Methods 0.000 description 34
- 239000000543 intermediate Substances 0.000 description 32
- 238000003786 synthesis reaction Methods 0.000 description 32
- 239000002585 base Substances 0.000 description 29
- 230000015572 biosynthetic process Effects 0.000 description 29
- 239000000203 mixture Substances 0.000 description 26
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- 239000002253 acid Substances 0.000 description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 20
- 239000011541 reaction mixture Substances 0.000 description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 19
- 150000002430 hydrocarbons Chemical group 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 18
- 150000004820 halides Chemical class 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical group CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 17
- 239000000758 substrate Substances 0.000 description 17
- 238000006722 reduction reaction Methods 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- 238000003379 elimination reaction Methods 0.000 description 15
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 15
- 229910052708 sodium Inorganic materials 0.000 description 14
- 239000011734 sodium Substances 0.000 description 14
- 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 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 13
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 13
- 238000009835 boiling Methods 0.000 description 13
- 239000012024 dehydrating agents Substances 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 13
- 125000001424 substituent group Chemical group 0.000 description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 11
- 229910052700 potassium Inorganic materials 0.000 description 11
- 239000011591 potassium Substances 0.000 description 11
- 229960003975 potassium Drugs 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 10
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 10
- 239000003638 chemical reducing agent Substances 0.000 description 10
- ASVAMZWCDMQNGW-UHFFFAOYSA-N ethyl 3-hydroxy-5-methyl-2-propan-2-ylhex-4-enoate Chemical compound OC(C(C(=O)OCC)C(C)C)C=C(C)C ASVAMZWCDMQNGW-UHFFFAOYSA-N 0.000 description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 10
- 239000012044 organic layer Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 150000002170 ethers Chemical class 0.000 description 9
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical group [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 9
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical group CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- 239000000877 Sex Attractant Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- VJJVHLTWXZDALF-WAYWQWQTSA-N (3Z)-5-methyl-2-propan-2-ylhexa-3,5-dienoic acid Chemical compound CC(C)C(\C=C/C(C)=C)C(O)=O VJJVHLTWXZDALF-WAYWQWQTSA-N 0.000 description 7
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical group CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 7
- 239000002841 Lewis acid Substances 0.000 description 7
- 150000008065 acid anhydrides Chemical class 0.000 description 7
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 7
- 229940092714 benzenesulfonic acid Drugs 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 7
- 238000002955 isolation Methods 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- 150000007517 lewis acids Chemical class 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 238000005809 transesterification reaction Methods 0.000 description 7
- BUWXUSLQPDDDSD-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-yloxy)butane Chemical group CCC(C)(C)OC(C)(C)CC BUWXUSLQPDDDSD-UHFFFAOYSA-N 0.000 description 6
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 235000011054 acetic acid Nutrition 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- 239000012230 colorless oil Substances 0.000 description 6
- 229940098779 methanesulfonic acid Drugs 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 238000004809 thin layer chromatography Methods 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 6
- YCDBFNRXRVEKST-AATRIKPKSA-N (E)-5-hydroxy-5-methyl-2-propan-2-ylhex-3-enoic acid Chemical compound CC(C)C(\C=C\C(C)(C)O)C(O)=O YCDBFNRXRVEKST-AATRIKPKSA-N 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 5
- 229910015900 BF3 Inorganic materials 0.000 description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910021623 Tin(IV) bromide Inorganic materials 0.000 description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 5
- 239000003377 acid catalyst Substances 0.000 description 5
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 5
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 5
- 230000008030 elimination Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000001282 iso-butane Substances 0.000 description 5
- 150000007522 mineralic acids Chemical class 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 5
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 4
- SEPQTYODOKLVSB-UHFFFAOYSA-N 3-methylbut-2-enal Chemical compound CC(C)=CC=O SEPQTYODOKLVSB-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- HTEAHIBOWDLHQZ-VOTSOKGWSA-N [(3E)-5-methyl-2-propan-2-ylhexa-3,5-dienyl] acetate Chemical compound C(C)(=O)OCC(\C=C\C(=C)C)C(C)C HTEAHIBOWDLHQZ-VOTSOKGWSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000012280 lithium aluminium hydride Substances 0.000 description 4
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 4
- 229910001623 magnesium bromide Inorganic materials 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
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- VJJVHLTWXZDALF-UHFFFAOYSA-N CC(C)C(C=CC(C)=C)C(O)=O Chemical compound CC(C)C(C=CC(C)=C)C(O)=O VJJVHLTWXZDALF-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
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- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical group C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- GMARCGBNZNYETI-UHFFFAOYSA-N aluminum;oxygen(2-);propan-2-olate Chemical group [O-2].[Al+3].CC(C)[O-] GMARCGBNZNYETI-UHFFFAOYSA-N 0.000 description 1
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- 150000008064 anhydrides Chemical class 0.000 description 1
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 1
- LZVHZSVLWDUFIR-UHFFFAOYSA-N aniline;n,n-diethylethanamine Chemical compound CCN(CC)CC.NC1=CC=CC=C1 LZVHZSVLWDUFIR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 229940088623 biologically active substance Drugs 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- VHAXQSFPTJUMLT-UHFFFAOYSA-N bis(3-methylbutan-2-yl)boron Chemical compound CC(C)C(C)[B]C(C)C(C)C VHAXQSFPTJUMLT-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical compound [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- BTAIYFXXVQLQAP-UHFFFAOYSA-N boric acid;oxolane Chemical compound OB(O)O.C1CCOC1 BTAIYFXXVQLQAP-UHFFFAOYSA-N 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 150000001649 bromium compounds Chemical group 0.000 description 1
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 description 1
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- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 description 1
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- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 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
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- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- PBGGNZZGJIKBMJ-UHFFFAOYSA-N di(propan-2-yl)azanide Chemical group CC(C)[N-]C(C)C PBGGNZZGJIKBMJ-UHFFFAOYSA-N 0.000 description 1
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- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- ZXDVQYBUEVYUCG-UHFFFAOYSA-N dibutyltin(2+);methanolate Chemical compound CCCC[Sn](OC)(OC)CCCC ZXDVQYBUEVYUCG-UHFFFAOYSA-N 0.000 description 1
- NFDFQCUYFHCNBW-SCGPFSFSSA-N dienestrol Chemical compound C=1C=C(O)C=CC=1\C(=C/C)\C(=C\C)\C1=CC=C(O)C=C1 NFDFQCUYFHCNBW-SCGPFSFSSA-N 0.000 description 1
- BYQFBFWERHXONI-UHFFFAOYSA-N diethyl 2-propan-2-ylpropanedioate Chemical compound CCOC(=O)C(C(C)C)C(=O)OCC BYQFBFWERHXONI-UHFFFAOYSA-N 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
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- YFHLIHJIWGFFRC-UHFFFAOYSA-N ethyl 5-methyl-3-oxo-2-propan-2-ylhex-4-enoate Chemical compound C(C)(C)C(C(=O)OCC)C(C=C(C)C)=O YFHLIHJIWGFFRC-UHFFFAOYSA-N 0.000 description 1
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- 208000015181 infectious disease Diseases 0.000 description 1
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- 230000009545 invasion Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
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- 239000012948 isocyanate Substances 0.000 description 1
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- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- IZDROVVXIHRYMH-UHFFFAOYSA-N methanesulfonic anhydride Chemical compound CS(=O)(=O)OS(C)(=O)=O IZDROVVXIHRYMH-UHFFFAOYSA-N 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- TWTZVVVTZXJEIE-UHFFFAOYSA-N methyl 3-hydroxy-5-methyl-2-propan-2-ylhex-4-enoate Chemical compound OC(C(C(=O)OC)C(C)C)C=C(C)C TWTZVVVTZXJEIE-UHFFFAOYSA-N 0.000 description 1
- YUJHFGTXVYEJQC-UHFFFAOYSA-N methyl hepta-4,6-dienoate Chemical compound COC(=O)CCC=CC=C YUJHFGTXVYEJQC-UHFFFAOYSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 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 description 1
- VBTQNRFWXBXZQR-UHFFFAOYSA-N n-bromoacetamide Chemical compound CC(=O)NBr VBTQNRFWXBXZQR-UHFFFAOYSA-N 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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- GKKCIDNWFBPDBW-UHFFFAOYSA-M potassium cyanate Chemical compound [K]OC#N GKKCIDNWFBPDBW-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- 150000003455 sulfinic acids Chemical class 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001926 trapping method Methods 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 238000002096 two-dimensional nuclear Overhauser enhancement spectroscopy Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/587—Monocarboxylic acid esters having at least two carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
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Abstract
Description
GPMBの性フェロモン合成例としては、非特許文献1において、ジエチル=イソプロピルマロネートを出発原料とし、2−ホルミル−3−メチルブチル=アセテートと2−メチルプロペニルトリフェニルホスホニウム=ブロミドから得られるイリド試薬とのWittig反応を最終工程とした4工程での合成が挙げられる。
また、A.Kaufmannらには、H.L.Simonらによる香料であるラバンジュロール(Lavandulol)の異性体の合成として、2−イソプロピル−5−メチル−3,5−ヘキサジエノエート及び2−イソプロピル−5−メチル−3,5−ヘキサジエノールの合成が記載されている(非特許文献2)。
本発明は、上記事情に鑑みなされたもので、幾何異性体と光学異性体の誘引活性を踏まえ、生物学的研究、農学的研究や実際の応用や利用等に必要な十分量のGPMBの性フェロモン(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエニル=アセテートの(±)−体の幾何選択的な製造方法を提供する。また、GPMBフェロモンの合成中間体として有用な(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート化合物及びその製造方法を提供する。更に、ラバンジュロール(Lavandulol)の異性体の一つで香料等として有用な(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノールの製造方法を提供することを目的とする。
本発明の一つの態様では、下記一般式(2)で表される(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート化合物が提供される。
本発明の別の態様では、下記一般式(1)で表される3−ヒドロキシ―2−イソプロピル−5−メチル−4−ヘキセノエート化合物を脱水反応することにより、下記一般式(2)で表される(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート化合物を得る工程を少なくとも含む(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート化合物の製造方法が提供される。
本発明の他の態様では、下記一般式(2)で表される(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート化合物のアルコキシカルボニル基を還元することにより、下記式(3)で表される(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノールを得る工程を少なくとも含む(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノールの製造方法を提供する。
本発明の他の態様では、下記一般式(2)で表される(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート化合物のアルコキシカルボニル基を還元することにより、下記式(3)で表される(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノールを得る工程と、得られた(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノールをエステル化して、下記一般式(4)で表される(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエニル=カルボキシレート化合物を得る工程を少なくとも含む(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエニル=カルボキシレート化合物の製造方法を提供する。
本発明の出発原料である3−ヒドロキシ―2−イソプロピル−5−メチル−4−ヘキセノエート化合物は、下記一般式(1)で表される。
脱水反応は、種々の条件を適用し得るが、基本的には水酸基を有する化合物(1)を脱離基Xを有する中間体(1x)に変換し、次いで、中間体(1x)からのHXを脱離させる工程である。
中間体(1x)は不安定な反応遷移状態の中間体である場合もあるし、単離できる安定な化合物である場合もある。後者の場合、中間体(1x)は単離せずそのまま脱離に用いてもよいし、段階的に中間体(1x)を単離した後に脱離に供してもよい[段階的脱水反応(Stepwise dehydration)]。また、(1x)はアリル転位により、二重結合と置換基Xの位置が動いた中間体(1xr)であってもよい。
酸を用いる脱水反応(i)において、中間体(1x)中の置換基Xは、プロトン酸やルイス酸で活性化された水酸基である。例えば、用いる酸がプロトン酸の場合は、Xはプロトン化された水酸基、すなわち、X=H2O+である。通常、酸を用いる脱水反応の場合、中間体(1x)は単離せず、直接(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート化合物(2)が得られる。
脱水剤を用いる脱水反応(ii)における脱水剤の使用量は、基質や脱水剤の種類によって種々ことなるが、基質の化合物(1)1モルに対して好ましくは0.0001モルから10,000モル、より好ましくは0.001モルから1,000モル、更に好ましくは0.001モルから100モルである。
脱水反応に用いる溶媒としては、例えば、水、液体アンモニア、メタノール、エタノール等のアルコール類、ジエチル=エーテル、ジ−n−ブチル=エーテル、テトラヒドロフラン、1,4−ジオキサン等のエーテル類、ヘキサン、ヘプタン、ベンゼン、トルエン、キシレン、クメン等の炭化水素類、アセトン、2−ブタノン等のケトン類、ギ酸エチル、酢酸メチル、酢酸エチル、酢酸ブチル、酢酸n−アミル等のエステル類、N,N-ジメチルホルムアミド、1,3−ジメチル−2−イミダゾリジノン、ジメチル=スルホキシド、ヘキサメチルホスホリック=トリアミド等の非プロトン性極性溶媒類、アセトニトリル、プロピオニトリル等のニトリル類、ピリジン、エチルアミン、ジエチルアミン、トリエチルアミン、アニリン、ジメチルアニリン等のアミン類を挙げることができ、これらを単独または混合して用いることができる。
加水分解に用いる塩類としては、例えば、ヨウ化リチウム、臭化リチウム、ヨウ化トリメチルシリル、臭化トリメチルシリル等のハロゲン化物類(好ましくはアルカリ金属ハロゲン化物)を挙げることができる。
反応の後処理、目的物の単離や精製は、減圧蒸留や各種クロマトグラフィー等の通常の有機合成における精製方法から便宜選択して用いることができる。また、目的物が十分な純度を有している場合には、粗生成物のまま次の工程に用いてもよい。
この還元反応には、公知のカルボン酸エステルまたはカルボン酸からアルコールへの還元反応を適用できる。還元反応は、通常溶媒中、必要に応じて冷却または加熱しながら反応基質を還元剤と反応させる。反応基質としては、用いる還元剤の種類や反応条件にも依存するが、例えば、エステル中のRaが一級または二級のアルキル基である場合は、(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート化合物(2)をそのまま還元の基質として用いることが好ましく、Raが三級であって、特にその立体障害が大きい場合には、二重結合の還元等の副反応が起こる場合がある。このような場合には、前述の方法により予め(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエン酸に変換して還元の基質として用いることが好ましい。
還元反応における溶媒は、用いられる還元剤の種類によって適切なものを選択して用いる。例えば、還元剤と溶媒の好ましい組み合わせとしては、還元剤として水素化ホウ素リチウムを用いる場合には、エーテル類、エーテル類とアルコール類との混合溶媒またはエーテル類と炭化水素類との混合溶媒等、還元剤として水素化アルミニウムリチウムを用いる場合には、エーテル類またはエーテル類と炭化水素類との混合溶媒等が挙げられる。
Rbは、前記Raと同様の置換基が挙げられ、特に、メチル基、エチル基、n−プロピル基、イソプロピル基、イソブチル基、sec−ブチル基、4−メチルペンチル基、2−メチル−1−プロペニル基、2−メチル−2−プロペニル基が好ましい。
アシル化剤との反応に用いる溶媒としては、好ましくは塩化メチレン、クロロホルム、トリクロロエチレン等の塩素系溶剤類、へキサン、ヘプタン、ベンゼン、トルエン、キシレン、クメン等の炭化水素類、ジエチル=エーテル、ジブチル=エーテル、ジエチレングリコール=ジエチル=エーテル、ジエチレングリコール=ジメチル=エーテル、テトラヒドロフラン、1,4−ジオキサン等のエーテル類、アセトニトリル等のニトリル類、アセトン、2−ブタノン等のケトン類、酢酸エチル、酢酸n−ブチル等のエステル類、N,N−ジメチルホルムアミド、ジメチルスルホキシド、ヘキサメチルホスホリックトリアミド等の非プロトン性極性溶媒類から選択した単独あるいは2種類以上の混合溶媒が挙げられる。
アシル化剤としては、好ましくはカルボン酸クロリド、カルボン酸ブロミド、カルボン酸無水物、カルボン酸トリフルオロ酢酸混合酸無水物、カルボン酸メタンスルホン酸混合酸無水物、カルボン酸トリフルオロメタンスルホン酸混合酸無水物、カルボン酸ベンゼンスルホン酸混合酸無水物、カルボン酸p−トルエンスルホン酸混合酸無水物、カルボン酸p−ニトロフェニル等が挙げられる。
塩基類としては、好ましくはトリエチルアミン、ジイソプロピルエチルアミン、N,N−ジメチルアニリン、ピリジン、4−ジメチルアミノピリジン等が挙げられる。
反応温度は、用いるアシル化剤の種類や反応条件により適切な反応温度を選択できるが、一般的には−50℃から溶媒の沸点温度が好ましく、−20℃から室温(5℃から35℃、以下同様)が更に好ましい。アシル化剤の使用量は、原料の化合物(3)1モルに対して好ましくは1から500モル、より好ましくは1〜50モル、更に好ましくは1〜5モルの範囲である。
化合物(3)とカルボン酸との反応に用いる酸触媒の例として、例えば、塩酸、臭化水素酸、硫酸、硝酸等の無機酸類、シュウ酸、トリフルオロ酢酸、メタンスルホン酸、ベンゼンスルホン酸、p−トルエンスルホン酸等の有機酸類、三塩化アルミニウム、アルミニウム=エトキシド、アルミニウム=イソプロポキシド、酸化アルミニウム、三フッ化ホウ素、三塩化ホウ素、三臭化ホウ素、塩化マグネシウム、臭化マグネシウム、ヨウ化マグネシウム、塩化亜鉛、臭化亜鉛、ヨウ化亜鉛、四塩化錫、四臭化錫、二塩化ジブチル錫、ジブチル錫=ジメトキシド、ジブチル錫=オキシド、四塩化チタン、四臭化チタン、チタン(IV)メトキシド、チタン(IV)=エトキシド、チタン(IV)=イソプロポキシド、酸化チタン(IV)等のルイス酸(Lewis acid)類を例示でき、これらは単独または混合して用いられる。酸触媒の使用量は、原料の化合物(3)1モルに対して好ましくは0.0001から100モル、より好ましくは0.001〜1モル、更に好ましくは0.01〜0.05モルの触媒量である。
化合物(3)とカルボン酸との反応に用いる溶媒としては、上記アシル化剤との反応に挙げたものと同様のものを例示できる。
化合物(3)とカルボン酸との反応温度は、カルボン酸の種類や反応条件により適切な反応温度を選択できるが、一般的には−50℃から溶媒の沸点温度が好ましく、室温から溶媒の沸点温度が更に好ましい。へキサン、ヘプタン、ベンゼン、トルエン、キシレン、クメン等の炭化水素類を含む溶媒を用いて、生じる水を共沸により系外に除去しながら反応を進行させるのもよい。この場合、常圧で溶媒の沸点で還流しながら水を留去してもよいが、減圧下に沸点より低い温度で水の留去を行ってもよい。
エステル交換反応に用いる触媒としては、例えば、塩酸、臭化水素酸、硫酸、硝酸等の無機酸類、シュウ酸、トリフルオロ酢酸、メタンスルホン酸、ベンゼンスルホン酸、p−トルエンスルホン酸等の有機酸類、ナトリウム=メトキシド、ナトリウム=エトキシド、カリウム=t−ブトキシド、4−ジメチルアミノピリジン等の塩基類、青酸ナトリウム、青酸カリウム、酢酸ナトリウム、酢酸カリウム、酢酸カルシウム、酢酸錫、酢酸アルミニウム、アセト酢酸アルミニウム、アルミナ等の塩類、三塩化アルミニウム、アルミニウム=エトキシド、アルミニウム=イソプロポキシド、酸化アルミニウム、三フッ化ホウ素、三塩化ホウ素、三臭化ホウ素、塩化マグネシウム、臭化マグネシウム、ヨウ化マグネシウム、塩化亜鉛、臭化亜鉛、ヨウ化亜鉛、四塩化錫、四臭化錫、二塩化ジブチル錫、ジブチル錫=ジメトキシド、ジブチル錫=オキシド、四塩化チタン、四臭化チタン、チタン(IV)メトキシド、チタン(IV)=エトキシド、チタン(IV)=イソプロポキシド、酸化チタン(IV)等のルイス酸(Lewis acid)類を挙げることができ、これらは単独または混合して用いられる。触媒の使用量は、原料の化合物(3)1モルに対して好ましくは0.0001から100モル、より好ましくは0.001〜1モル、更に好ましくは0.01〜0.05モルの触媒量である。
エステル交換反応は、無溶媒(反応試薬であるカルボン酸アルキル自身を溶媒として用いてもよい)で行うことができ、余計な濃縮や溶媒回収等の操作を必要としないので好ましいが、溶媒を補助的に用いることも可能である。この場合、溶媒として、例えば、へキサン、ヘプタン、ベンゼン、トルエン、キシレン、クメン等の炭化水素類、ジエチル=エーテル、ジブチルエーテル、ジエチレングリコール=ジエチル=エーテル、ジエチレングリコール=ジメチル=エーテル、テトラヒドロフラン、1,4−ジオキサン等のエーテル類の単独または混合使用が好ましい。反応温度は用いるカルボン酸アルキルの種類や反応条件により適切な反応温度を選択できるが、通常、加熱下に行われ、エステル交換反応で生じる低沸点の低級アルコール、即ち、メタノール、エタノール、1−プロパノール等の沸点付近で反応を行い、生じる低級アルコールを留去しながら行うのがよい結果を与える。減圧下に沸点より低い温度でアルコールの留去を行ってもよい。
なお、原料、生成物、中間体の純度としてガスクロマトグラフィー(GC)分析によって得られた値を用い%GCと表記する。GC条件: GC: Shimazdu GC−14A、Column: 5%Ph−Me silicone 0.25mmφx25m、Carrier gas: He、Detector: FID。
反応に用いられる原料及び反応で得られる生成物は100%純度であるとは限らないので、収率は%GCに基づく下記換算収率の値で表す。
化合物によっては、ガスクロマトグラフィーの感度が異なるため、特に原料や生成物が粗生成物の場合には、換算収率が100%を超えることもあり得る。
参考例1
エチル=3−ヒドロキシ―2−イソプロピル−5−メチル−4−ヘキセノエート[一般式(1)において、Ra=CH3CH2=Etの場合]の合成例
淡黄色油状物(yellowish oil)
IR(D−ATR):ν=3432(br.),2963,2935,2875,1731,1373,1239,1178,1154,1029cm-1。
1H−NMR(500MHz,CDCl3):δ=0.96(3H,d,J=6.1Hz),0.97(3H,d,J=5.7Hz),1.23(3H,t,J=7.3Hz),1.70(3H,d,J=1.5Hz),1.71(3H,d,J=1.1Hz),2.03(1H,s,OH),2.05−2.14(2H,m),2.41(1H,dd,J=6.5,7.7Hz),4.11(2H,q,J=7.3Hz),4.59(1H,dd,J=7.6,9.2Hz),5.34(1H,dq−様,J=9.6,1.5Hz)ppm。
13C−NMR(125MHz,CDCl3):δ=14.30,18.20,19.28,21.32,25.88,27.16,57.92,59.94,67.50,124.84,137.02,173.22ppm。
GC−MS(EI,70eV):29,41,55,69,85(ベースピーク),101,115,130,153,171,199,214(M+)。
実施例1
エチル=(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート[一般式(2)において、Ra=CH3CH2=Etの場合]の合成例1
無色から淡黄色油状物(colorless−yellowish oil)
沸点:74−80℃/400Pa
IR(D−ATR):ν=2963,2873,1732,1467,1370,1236,1176,1152,1032,969,888cm-1。
1H−NMR(500MHz,CDCl3):δ=0.87(3H,d,J=6.9Hz),0.92(3H,d,J=6.5Hz),1.25(3H,t,J=7.3Hz),1.84(3H,s),1.95−2.06(1H,m),2.70(1H,t,J=8.9Hz),4.08−4.18(2H,m),4.92(1H,br.s),4.93(1H,br.s),5.62(1H,dd,J=9.6,15.7Hz),6.17(1H,d,J=15.7Hz)ppm。
2D−NOESY: NOE(核オーバーハウザー効果:Nuclear Overhauser Effect)の相関(Correlation)を下図の両側向き矢印で示す。
GC−MS(EI,70eV):41,53,67,81(ベースピーク),91,111,123,139,154,181,196(M+)。
GC−MS(CI,イソブタン):123,197[(M+H)+]。
エチル=(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート[一般式(2)において、Ra=CH3CH2=Etの場合]の合成例2
エチル=(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート[一般式(2)において、Ra=CH3CH2=Etの場合]の合成例3
エチル=(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート[一般式(2)において、Ra=CH3CH2=Etの場合]の合成例4
エチル=(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート[一般式(2)において、Ra=CH3CH2=Etの場合]の合成例5
エチル=(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート[一般式(2)において、Ra=CH3CH2=Etの場合]の合成例6
GC−MS(EI,70eV):41,53,67,81(ベースピーク),111,123,139,154,181,196(M+)。
エチル=(E)−5−ヒドロキシ−2−イソプロピル−5−メチル−3−ヘキセノエート
GC−MS(EI,70eV):43,55,69,81,97,111,125,139,153,171,199,214(M+)。
エチル=(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート[一般式(2)において、Ra=CH3CH2=Etの場合]の合成例7
なお、下記反応式に示すように、エチル=3−ヒドロキシ−2,5−ジメチル−4−ヘキセノエートを原料として、本実施例と同様な条件の下で脱水反応を実施すると、エチル=2,5−ジメチル−2,4−ヘキサジエノエートが得られることが報告されており[井上、化学の領域、9、531(1955)及び井上ら、防虫科学、20、102(1955)、但し、原料及び生成物の立体化学については明記されていない。]、2−位の置換基の違いによる選択性の差が明らかとなった。
メチル=(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート[一般式(2)において、Ra=CH3=Meの場合]の合成例1
無色油状物(colorless oil)
IR(D−ATR):ν=2961,2873,1737,1435,1240,1154,969,888cm-1。
1H−NMR(500MHz,CDCl3):δ=0.87(3H,d,J=6.9Hz),0.92(3H,d,J=6.5Hz),1.84(3H,s),1.95−2.06(1H,m),2.74(1H,t,J=9.1Hz),3.67(3H,s),4.93(1H,br.s),4.94(1H,br.s),5.61(1H,dd,J=9.6,15.7Hz),6.18(1H,d,J=15.7Hz)ppm。
13C−NMR(125MHz,CDCl3):δ=18.56,19.83,20.75,31.18,51.55,57.09,116.23,126.63,135.97,141.50,174.46ppm。
GC−MS(EI,70eV):41,53,67,81(ベースピーク),91,107,125,140,182(M+)。
GC−MS(CI,イソブタン):115,123,183[(M+H)+]。
メチル=(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート[一般式(2)において、Ra=CH3=Meの場合]の合成例2
実施例9−1
GC: 保持時間=5.00分、GC条件: GC: Shimazdu GC−14A、Column: 5%Ph−Me silicone 0.25mmφx25m、Carrier gas: He、Detector: FID。
GC−MS(EI,70eV):41,55,69,85(ベースピーク),101,116,157,185,200(M+)。
GC: 保持時間=5.81分、GC条件: GC: Shimazdu GC−14A、Column: 5%Ph−Me silicone 0.25mmφx25m、Carrier gas: He、Detector: FID。
GC−MS(EI,70eV):41,55,69,85(ベースピーク),101,116,157,185,200(M+)。
無色油状物(colorless oil)
IR(D−ATR):ν=3464,2968,2934,2874,1737,1722,1435,1370,1244,1195,1153,975cm-1。
1H−NMR(500MHz,CDCl3):δ=0.85(3H,d,J=6.9Hz),0.88(3H,d,J=6.9Hz),1.29(3H,s),1.79(1H,br.),1.91−2.01(1H,m),2.65(1H,t−like,J=8.8Hz),3.65(3H,s),5.61(1H,dd,J=9.1,15.7Hz),5.67(1H,d,J=15.7Hz)ppm。
1H−NMRデカップリング(decoupling):2−位のH、δ=2.65を照射(irradiation)によりデカップリングすると3−位のHδ=5.61がt,J=15.7Hzに変化し、3−位と4−位の1H−1H結合定数Jが15.7Hzであることが確認された。
13C−NMR(125MHz,CDCl3):δ=19.65,20.67,29.57,29.76,30.88,51.51,56.41,70.60,123.43,141.67,174.59pm。
GC−MS(EI,70eV):43,55,69,81,97,111(ベースピーク),125,140,153,168,185,200(M+)。
GC−MS(CI,イソブタン):183[(M+H−H2O)+]。
イソブチル=(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート[一般式(2)において、Ra=(CH3)2CHCH2の場合]の合成例
黄色油状物(yellow oil)
IR(D−ATR):ν=2962,2874,1733,1469,1370,1284,1234,1151,1006,968cm-1。
1H−NMR(500MHz,CDCl3):δ=0.88(3H,d,J=6.9Hz),0.92(3H,s),0.93(3H,s),0.93(3H,d,J=6.5Hz),1.84(3H,s),1.88−1.98(1H,m),1.98−2.07(1H,m),2.74(1H,t,J=9.1Hz),3.81−3.91(2H,m),4.92(1H,br.s),4.93(1H,br.s),5.63(1H,dd,J=9.5,15.7Hz),6.18(1H,d,J=15.7Hz)ppm。
13C−NMR(125MHz,CDCl3):δ=18.57,19.05,19.04,19.87,20.78,27.70,31.15,57.38,70.49,116.07,126.90,135.82,141.56,174.02ppm。
GC−MS(EI,70eV):29,41,57,81(ベースピーク),93,111,123,153,168,224(M+)。
GC−MS(CI,イソブタン):123,169,225[(M+H)+]。
ベンジル=(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート[一般式(2)において、Ra=C6H5CH2の場合]の合成例
無色油状物(colorless oil)
IR(D−ATR):ν=3032,2962,2872,1732,1455,1231,1214,1148,970cm-1。
1H−NMR(500MHz,CDCl3):δ=0.89(3H,d,J=6.9Hz),0.93(3H,d,J=6.5Hz),1.86(3H,s),2.00−2.11(1H,m),2.81(1H,t,J=9.0Hz),4.94(1H,br.s),4.96(1H,br.s),5.11(1H,d,J=12.2Hz),5.16(1H,d,J=12.2Hz),5.66(1H,dd,J=9.6,15.7Hz),6.21(1H,d,J=15.3Hz),7.30−7.40(5H,m)ppm。
13C−NMR(125MHz,CDCl3):δ=18.55,19.81,20.72,31.20,57.11,66.14,116.24,126.51,128.06,128.10,128.46,136.00,136.08,141.50,173.80ppm。
GC−MS(EI,70eV):43,65,81,91(ベースピーク),107,123,258(M+)。
実施例12
(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノールの合成例
窒素雰囲気下、水素化アルミニウムリチウム2.23gとテトラヒドロフラン50mlの混合物に、氷冷しながら実施例1で得たエチル=(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート7.98g(84.2%GC)とテトラヒドロフラン40mlの混合物を滴下した。反応混合物を氷冷下100分間かき混ぜ、次いで氷冷したまま、水2.23g、15%水酸化ナトリウム水溶液2.23g、水6.69gを順次加えた。発熱が止んだ後、反応混合物をかき混ぜながら室温まで上げた。生じた沈殿をろ別し、ろ液を減圧濃縮して目的物6.23g(85.3%GC、定量的収率)を得た。
無色油状物(colorless oil)
IR(D−ATR):ν=3350,2958,2929,2873,1609,1464,1386,1368,1061,1037,968cm-1。
1H−NMR(500MHz,CDCl3):δ=0.86(3H,d,J=6.9Hz),0.91(3H,d,J=6.9Hz),1.48−1.55(1H,br.),1.65−1.75(1H,m),1.85(3H,s),2.02−2.09(1H,m),3.46(1H,br.t−like,J=10〜11Hz),3.65‐3.72(1H,m),4.92(2H,br.s),5.44(1H,dd,J=9.6,15.7Hz),6.22(1H,d,J=15.7Hz)ppm。
13C−NMR(125MHz,CDCl3):δ=18.64,19.57,20.82,29.00,52.58,64.22,115.55,129.46,136.35,141.56pm。
GC−MS(EI,70eV):41,55,67,81(ベースピーク),93,109,123,139,154(M+)。
これらのスペクトルデータは、J.Tabataら、J.Chem.Ecol.,41,194(2015)のものと良く一致していた。
(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエニル=アセテート[一般式(4)において、Rb=CH3の場合]の合成例
無色油状物(colorless oil)
沸点:56−59℃/400Pa
IR(D−ATR):ν=2960,2874,1742,1464,1382,1368,1234,1034,969cm-1。
1H−NMR(500MHz,CDCl3):δ=0.86(3H,d,J=6.9Hz),0.91(3H,d,J=6.5Hz),1.72−1.80(1H,m),1.82(3H,s),2.01(3H,s),2.20−2.27(1H,m),4.08(2H,d,J=6.9Hz),4.89(2H,br.s),5.44(1H,dd,J=9.2,15.7Hz),6.14(1H,d,J=15.7Hz)ppm。
13C−NMR(125MHz,CDCl3):δ=18.61,18.89,20.68,20.94,28.06,48.26,65.95,115.19,128.48,135.32,141.81,171.11ppm。
GC−MS(EI,70eV):43,55,67,79,93,107,121(ベースピーク),136,196(M+)。
GC−MS(CI,イソブタン):81,137[(M+H)+]。
これらのスペクトルデータは、J.Tabataら、J.Chem.Ecol.,41,194(2015)のものと良く一致していた。
Claims (4)
- 下記一般式(2):
で表される(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエノエート化合物のアルコキシカルボニル基を還元することにより、下記式(3):
で表される(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエニル=カルボキシレート化合物を得る工程を少なくとも含む(E)−2−イソプロピル−5−メチル−3,5−ヘキサジエニル=カルボキシレート化合物の製造方法。
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