JP7148743B2 - (z)型ソラノン、その製造方法および使用 - Google Patents
(z)型ソラノン、その製造方法および使用 Download PDFInfo
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- JP7148743B2 JP7148743B2 JP2021568581A JP2021568581A JP7148743B2 JP 7148743 B2 JP7148743 B2 JP 7148743B2 JP 2021568581 A JP2021568581 A JP 2021568581A JP 2021568581 A JP2021568581 A JP 2021568581A JP 7148743 B2 JP7148743 B2 JP 7148743B2
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- PQDRXUSSKFWCFA-CFNZNRNTSA-N solanone Chemical compound CC(=O)CC[C@@H](C(C)C)\C=C\C(C)=C PQDRXUSSKFWCFA-CFNZNRNTSA-N 0.000 title claims description 21
- PQDRXUSSKFWCFA-UHFFFAOYSA-N solanone Natural products CC(=O)CCC(C(C)C)C=CC(C)=C PQDRXUSSKFWCFA-UHFFFAOYSA-N 0.000 title claims description 21
- 238000000034 method Methods 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- CZYSAVDTNMUQRT-SNVBAGLBSA-N CC(C)[C@H](CCC(=C=O)C)C=O Chemical compound CC(C)[C@H](CCC(=C=O)C)C=O CZYSAVDTNMUQRT-SNVBAGLBSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- KBPUBCVJHFXPOC-UHFFFAOYSA-N ethyl 3,4-dihydroxybenzoate Chemical compound CCOC(=O)C1=CC=C(O)C(O)=C1 KBPUBCVJHFXPOC-UHFFFAOYSA-N 0.000 claims description 6
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- CZYSAVDTNMUQRT-UHFFFAOYSA-N CC(C)C(CCC(=C=O)C)C=O Chemical compound CC(C)C(CCC(=C=O)C)C=O CZYSAVDTNMUQRT-UHFFFAOYSA-N 0.000 claims description 5
- CZYSAVDTNMUQRT-JTQLQIEISA-N CC(C)[C@@H](CCC(=C=O)C)C=O Chemical compound CC(C)[C@@H](CCC(=C=O)C)C=O CZYSAVDTNMUQRT-JTQLQIEISA-N 0.000 claims description 5
- NAVMMSRRNOXQMJ-UHFFFAOYSA-M iodomethyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CI)C1=CC=CC=C1 NAVMMSRRNOXQMJ-UHFFFAOYSA-M 0.000 claims description 5
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical group C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- CGUGCZSRPDCLBT-QGZVFWFLSA-N (2r)-2-[methoxy(diphenyl)methyl]pyrrolidine Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(OC)[C@H]1CCCN1 CGUGCZSRPDCLBT-QGZVFWFLSA-N 0.000 claims description 3
- CGUGCZSRPDCLBT-KRWDZBQOSA-N (2s)-2-[methoxy(diphenyl)methyl]pyrrolidine Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(OC)[C@@H]1CCCN1 CGUGCZSRPDCLBT-KRWDZBQOSA-N 0.000 claims description 3
- MMFXPSMSVKKMQF-UHFFFAOYSA-N CCCCC(C=O)=C=O Chemical compound CCCCC(C=O)=C=O MMFXPSMSVKKMQF-UHFFFAOYSA-N 0.000 claims description 3
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 claims description 3
- CGUGCZSRPDCLBT-UHFFFAOYSA-N 2-[methoxy(diphenyl)methyl]pyrrolidine Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(OC)C1CCCN1 CGUGCZSRPDCLBT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003426 co-catalyst Substances 0.000 claims description 2
- COPMASWDWLENMV-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-prop-1-enyl-1,3,2-dioxaborolane Chemical compound CC=CB1OC(C)(C)C(C)(C)O1 COPMASWDWLENMV-UHFFFAOYSA-N 0.000 claims 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 24
- 241000208125 Nicotiana Species 0.000 description 23
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000000796 flavoring agent Substances 0.000 description 9
- 239000000779 smoke Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 235000019504 cigarettes Nutrition 0.000 description 7
- 235000019634 flavors Nutrition 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SVSUYEJKNSMKKW-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-prop-1-en-2-yl-1,3,2-dioxaborolane Chemical compound CC(=C)B1OC(C)(C)C(C)(C)O1 SVSUYEJKNSMKKW-UHFFFAOYSA-N 0.000 description 2
- NCBKUTILUODENZ-UHFFFAOYSA-N 6-methyl-5-(4-methylfuran-2-yl)heptan-2-one Chemical compound CC(=O)CCC(C(C)C)C1=CC(C)=CO1 NCBKUTILUODENZ-UHFFFAOYSA-N 0.000 description 2
- 206010013911 Dysgeusia Diseases 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- PMOWTIHVNWZYFI-WAYWQWQTSA-N cis-2-coumaric acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1O PMOWTIHVNWZYFI-WAYWQWQTSA-N 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000036186 satiety Effects 0.000 description 2
- 235000019627 satiety Nutrition 0.000 description 2
- 230000001953 sensory effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AFPLNGZPBSKHHQ-UHFFFAOYSA-N Betulaprenol 9 Natural products CC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCO AFPLNGZPBSKHHQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000000626 Daucus carota Species 0.000 description 1
- 235000002767 Daucus carota Nutrition 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000745768 Pluchea carolinensis Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000019568 aromas Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RHMQSXRCGOZYND-UHFFFAOYSA-N ethyl 2,3-dihydroxybenzoate Chemical compound CCOC(=O)C1=CC=CC(O)=C1O RHMQSXRCGOZYND-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- -1 solanedione Chemical compound 0.000 description 1
- AFPLNGZPBSKHHQ-MEGGAXOGSA-N solanesol Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CO AFPLNGZPBSKHHQ-MEGGAXOGSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000019505 tobacco product Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/203—Unsaturated compounds containing keto groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/227—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing halogen
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/18—Treatment of tobacco products or tobacco substitutes
- A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
- A24B15/30—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances
- A24B15/32—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances by acyclic compounds
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B3/00—Preparing tobacco in the factory
- A24B3/12—Steaming, curing, or flavouring tobacco
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
であり、
名称が(S,Z)-5-イソプロピル-8-メチル-6,8-ジエン-2-オン、または(R,Z)-5-イソプロピル-8-メチル-6,8-ジエン-2-オンであることを特徴とする、(Z)型ソラノンが開示されている。
前記製造方法は、
原料であるイソアミルアルデヒド及びメチルビニルケトンを触媒及び共触媒の存在下で反応させ、化合物である(S)-2-イソプロピル-5-カルボニルヘキサナール、又は化合物である(R)-2-イソプロピル-5-カルボニルヘキサナールを得るステップ(1)と、
ステップ(1)で得られた(S)-2-イソプロピル-5-カルボニルヘキサナール又は(R)-2-イソプロピル-5-カルボニルヘキサナールをヨードメチル-トリフェニル-ホスホニウムヨージドと反応させ、(S,Z)-7-ヨード-5-イソプロピル-6-エン-2-オン又は(R,Z)-7-ヨード-5-イソプロピル-6-エン-2-オンを得るステップ(2)と、
ステップ(2)で得られた(S,Z)-7-ヨード-5-イソプロピル-6-エン-2-オン又は(R,Z)-7-ヨード-5-イソプロピル-6-エン-2-オンを触媒の存在下でイソプロペニルボロン酸ピナコールエステルと反応させ、前記(Z)型ソラノンとして(S,Z)-5-イソプロピル-8-メチル-6,8-ジエン-2-オン又は(R,Z)-5-イソプロピル-8-メチル-6,8-ジエン-2-オンを得るステップ(3)とを含み、
前記製造方法を示す反応式は、
である。
1、本発明に係る純粋の(Z)型ソラノン、すなわち、(S,Z)-5-イソプロピル-8-メチル-6,8-ジエン-2-オン、または(R,Z)-5-イソプロピル-8-メチル-6,8-ジエン-2-オンは初めて開示されており、新規な化合物である。
3,4-ジヒドロキシ安息香酸エチル73mg(約0.4mmol)を丸底フラスコに入れ、(S)-2-(メトキシベンズヒドリル)ピロリジン53.48mg(0.2mmol)、イソアミルアルデヒド215μL(約2mmol)及びメチルビニルケトン243μL(約3mmol)を順次加え、室温で撹拌して固形分を溶解させ、24時間撹拌して反応させた。
であった。分析結果は以下の通りである。
であった。分析結果は以下の通りである。
であった。分析結果は以下の通りである。
であった。分析結果は以下の通りである。
反応管に[1,1’-ビス(ジフェニルホスフィノ)フェロセン]ジクロロパラジウム731mg(約1mmol)を入れ、テトラヒドロフラン70mLを加えた。また、実施例2で得られた(S,Z)-7-ヨード-5-イソプロピル-6-エン-2-オン2802mg(約10mmol)とイソプロペニルボロン酸ピナコールエステル2.8mL(約15mmol)とをテトラヒドロフランに混合して混合溶液30mLを得た。この混合溶液30mLを前記反応管に加えた。最後に、2Mの水酸化ナトリウム水溶液10mL(約20mmol)を上記反応管に加えた。これらを60℃で5時間撹拌した。
であった。分析結果は以下の通りである。
であった。分析結果は以下の通りである。
中国雲南産の某ブランド品紙巻タバコのサンプルを試験対象とし、タバコ刻みの重量に基づいて香料の添加量を計算した。本発明により合成された2種の純粋の(Z)型ソラノン、すなわち、(S,Z)-5-イソプロピル-8-メチル-6,8-ジエン-2-オン(これを注入して加香したタバコはサンプル1とする)と(R,Z)-5-イソプロピル-8-メチル-6,8-ジエン-2-オン(これを注入して加香したタバコはサンプル2とする)をエタノールに溶解し、所定濃度のエタノール溶液となるように配合した。CIJECTORフレーバー・香料注入機を用い、タバコ刻みの重量に対して香料が0.005重量%となるように、上記のエタノール溶液を均一にタバコに注入した。同じ条件で同じ体積のエタノールを注入したタバコ(サンプル0)を対照サンプルとし、相対湿度60%、22℃で48時間平衡化し、三つのサンプルに対して中国タバコ産業標準「タバコ製品の官能評価方法」(YC/T415-2011)に準拠して官能比較評価を行った。その結果を下記表に示す。
Claims (5)
- 立体構造式が
であり、
名称が(S,Z)-5-イソプロピル-8-メチル-6,8-ジエン-2-オン、または(R,Z)-5-イソプロピル-8-メチル-6,8-ジエン-2-オンであることを特徴とする、(Z)型ソラノンであって、
原料であるイソアミルアルデヒド及びメチルビニルケトンを触媒及び共触媒の存在下で反応させ、化合物である(S)-2-イソプロピル-5-カルボニルヘキサナール、又は化合物である(R)-2-イソプロピル-5-カルボニルヘキサナールを得る、ステップ(1)と、
ステップ(1)で得られた(S)-2-イソプロピル-5-カルボニルヘキサナール、又は(R)-2-イソプロピル-5-カルボニルヘキサナールをヨードメチル-トリフェニル-ホスホニウムヨージドと反応させて(S,Z)-7-ヨード-5-イソプロピル-6-エン-2-オン、又は(R,Z)-7-ヨード-5-イソプロピル-6-エン-2-オンを得るステップ(2)と、
ステップ(2)で得られた(S,Z)-7-ヨード-5-イソプロピル-6-エン-2-オン又は(R,Z)-7-ヨード-5-イソプロピル-6-エン-2-オンを触媒の存在下でイソプロペニルボロン酸ピナコールエステルと反応させ、前記(Z)型ソラノンとして(S,Z)-5-イソプロピル-8-メチル-6,8-ジエン-2-オン又は(R,Z)-5-イソプロピル-8-メチル-6,8-ジエン-2-オンを得るステップ(3)とを含み、
前記製造方法を示す反応式は、
であることを特徴とする、(Z)型ソラノンの製造方法。 - ステップ(1)における前記触媒は、(S)-2-(メトキシベンズヒドリル)ピロリジンまたは(R)-2-(メトキシベンズヒドリル)ピロリジンであり、前記共触媒は、3,4-ジヒドロキシ安息香酸エチルであり、原料であるメチルビニルケトンとイソアミルアルデヒドとのモル比は、(1:1.0)~(1:2.0)であり、2-(メトキシベンズヒドリル)ピロリジンとイソアミルアルデヒドとのモル比は、(0.1:1.0)~(0.1:2.0)であり、3,4-ジヒドロキシ安息香酸エチルとイソアミルアルデヒドとのモル比は、(0.2:1.0)~(0.2:2.0)であり、反応温度は、-10℃~50℃であり、反応時間は、20~30時間であることを特徴とする、請求項1に記載の製造方法。
- ステップ(2)における反応は塩基性の溶媒の存在下、且つ添加剤を添加する条件で行われ、前記溶媒はテトラヒドロフランであり、塩基はヘキサメチルジシラザンナトリウムであり、前記添加剤はヘキサメチルリン酸トリアミドであり、2-イソプロピル-5-カルボニルヘキサナールとヨードメチル-トリフェニル-ホスホニウムヨージドとのモル比は(1:1.0)~(1:1.5)であり、2-イソプロピル-5-カルボニルヘキサナールとヘキサメチルジシラザンナトリウムとのモル比は(1:1.0)~(1:1.5)であり、2-イソプロピル-5-カルボニルヘキサナールとヘキサメチルリン酸トリアミドとのモル比は(1:4.0)~(1:5.0)であり、反応温度は-100℃~室温であり、反応時間は2~10時間であり、前記室温は40℃であることを特徴とする、請求項1に記載の製造方法。
- ステップ(3)で使用される触媒が、[1,1’-ビス(ジフェニルホスフィノ)フェロセン]ジクロロパラジウムであることを特徴とする、請求項1に記載の製造方法。
- ステップ(3)における反応は塩基性の溶媒の存在下で行われ、前記溶媒はテトラヒドロフランであり、塩基は水酸化ナトリウムであり、7-ヨード-5-イソプロピル-6-エン-2-オンとイソプロペニルボロン酸ピナコールエステルとのモル比は、(1:1.0)~(1:2.0)であり、7-ヨード-5-イソプロピル-6-エン-2-オンと水酸化ナトリウムとのモル比は、(1:1.5)~(1:2.5)であり、触媒と7-ヨード-5-イソプロピル-6-エン-2-オンとのモル比は、(0.05:1.0)~(0.05:2.0)であり、反応温度は0℃~100℃であり、反応時間は2~10時間であることを特徴とする、請求項1に記載の製造方法。
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