JP6288101B2 - テトラヒドロミルセノールの合成 - Google Patents
テトラヒドロミルセノールの合成 Download PDFInfo
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- JP6288101B2 JP6288101B2 JP2015543481A JP2015543481A JP6288101B2 JP 6288101 B2 JP6288101 B2 JP 6288101B2 JP 2015543481 A JP2015543481 A JP 2015543481A JP 2015543481 A JP2015543481 A JP 2015543481A JP 6288101 B2 JP6288101 B2 JP 6288101B2
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- JP
- Japan
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- WRFXXJKURVTLSY-UHFFFAOYSA-N 2,6-dimethyloctan-2-ol Chemical compound CCC(C)CCCC(C)(C)O WRFXXJKURVTLSY-UHFFFAOYSA-N 0.000 title description 6
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 238000003786 synthesis reaction Methods 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 28
- 238000007142 ring opening reaction Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- 230000002829 reductive effect Effects 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 150000002170 ethers Chemical class 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical group 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- -1 THF) Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- XSDYMDMXNRPZHU-UHFFFAOYSA-N 2-ethynyl-2,6,6-trimethyloxane Chemical compound CC1(C)CCCC(C)(C#C)O1 XSDYMDMXNRPZHU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000001371 (5E)-3,5-dimethylocta-1,5,7-trien-3-ol Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241000745768 Pluchea carolinensis Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000020971 citrus fruits Nutrition 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
- 238000001914 filtration Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- 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
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
-
- 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
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
-
- 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
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
で表される化合物であるテトラヒドロミルセノール(CAS番号:18479−57−7)は、香味および香料工業界ではよく知られた化合物である。それは多くの用途で広く使用されている。それは、嗅覚的には、「テルペンをベースに、新鮮で、全体的に柑橘系の花のような甘い香り」と表現される。
で表される化合物の還元的開環が、テトラヒドロミルセノールの優れた選択率および収率をもたらすことを見出した。還元的開環が、すなわち
などの望ましくない副生物を生成しない(または、極めて僅かな量しか生成しない)ことは驚くべきことである。
で表される化合物をもたらすであろう。
1〜20bar、好ましくは3〜15barの圧力のH2ガス下、
15〜100℃、好ましくは20〜80℃の温度で、
かつ、溶媒、または溶媒の混合物(好ましくは、アルコール、炭化水素、エステル、エーテルおよび塩素化炭化水素)中で
行われることを特徴とする方法に関する。
1〜20bar、好ましくは3〜15barの圧力のH2ガス下、
15〜100℃、好ましくは20〜80℃の温度で、
溶媒、または溶媒の混合物(好ましくは、アルコール、炭化水素、エステル、エーテルおよび塩素化炭化水素)中、かつ
10重量%(式(II)で表される化合物の全重量に対して)まで、好ましくは5重量%までの少なくとも1種の触媒(好ましくは、支持材料上の遷移金属、より好ましくはPd/C)の存在下に
行われることを特徴とする方法に関する。
3〜20bar、好ましくは3〜15barの圧力のH2ガス下、
15〜100℃、好ましくは20〜80℃の温度で、
溶媒、または溶媒の混合物(好ましくは、アルコール、炭化水素、エステル、エーテルおよび塩素化炭化水素)中、かつ
触媒(好ましくは、支持材料上の遷移金属、より好ましくはPd/C)の存在下、そして
有機酸および/または無機酸、ならびにこれらの混合物(好ましくは、HCl、H2SO4、p−トルエンスルホン酸)の存在下に
行われることを特徴とする方法に関する。
[実施例1]
8mgの触媒(Pd/C)を8mlのガラス製反応器に入れ、2−エチニル−2,6,6−トリメチル−テトラヒドロピラン(210mg、95%)を加えた。ヘプタン(1.5g)と濃塩酸(10μl)を加え、反応器を密閉した。反応器をアルゴンで3回パージ(5barに加圧後、圧力を解放)し、水素で3回(5barまで加圧後、解放)行った。反応混合物を50℃に加熱し、10barの水素に加圧し、水素の消費が観察されなくなるまで撹拌し、その後、さらに30〜60分間撹拌した。撹拌を中止し、反応物を室温まで冷却した。
Claims (7)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12194596 | 2012-11-28 | ||
EP12194596.8 | 2012-11-28 | ||
PCT/EP2013/075003 WO2014083121A1 (en) | 2012-11-28 | 2013-11-28 | Synthesis of tetrahydromyrcenol |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2015535527A JP2015535527A (ja) | 2015-12-14 |
JP6288101B2 true JP6288101B2 (ja) | 2018-03-07 |
Family
ID=47263156
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2015543481A Active JP6288101B2 (ja) | 2012-11-28 | 2013-11-28 | テトラヒドロミルセノールの合成 |
Country Status (7)
Country | Link |
---|---|
US (1) | US9249074B2 (ja) |
EP (1) | EP2925711B1 (ja) |
JP (1) | JP6288101B2 (ja) |
CN (1) | CN104822645B (ja) |
ES (1) | ES2619528T3 (ja) |
MX (1) | MX360018B (ja) |
WO (1) | WO2014083121A1 (ja) |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL216144A (ja) * | 1956-04-09 | |||
DE1118190B (de) | 1958-09-10 | 1961-11-30 | Int Flavors & Fragrances Inc | Verfahren zur Herstellung von Terpenalkoholen der empirischen Formel C H O und ihrenDerivaten mit besonderen Riechstoffeigenschaften |
DE1196177B (de) * | 1963-07-30 | 1965-07-08 | Basf Ag | Verfahren zur Herstellung von 2-Hydroxy-2, 3-dihydrocitral |
IT1058547B (it) | 1976-03-26 | 1982-05-10 | Snam Progetti | Procedimento di ciclizzazione del deidrolinalolo e prodotti ottenuti con tale procedimento |
DE60102272T2 (de) * | 2000-09-06 | 2005-02-24 | Dsm Ip Assets B.V. | Verfahren zu Herstellung von substituierten Pyranen |
US7829342B2 (en) * | 2007-10-03 | 2010-11-09 | The Board Of Trustees Of The Universiy Of Illinois | Selective aliphatic C-H oxidation |
-
2013
- 2013-11-28 JP JP2015543481A patent/JP6288101B2/ja active Active
- 2013-11-28 MX MX2015006537A patent/MX360018B/es active IP Right Grant
- 2013-11-28 US US14/647,636 patent/US9249074B2/en active Active
- 2013-11-28 EP EP13798647.7A patent/EP2925711B1/en active Active
- 2013-11-28 CN CN201380061702.4A patent/CN104822645B/zh active Active
- 2013-11-28 ES ES13798647.7T patent/ES2619528T3/es active Active
- 2013-11-28 WO PCT/EP2013/075003 patent/WO2014083121A1/en active Application Filing
Also Published As
Publication number | Publication date |
---|---|
EP2925711A1 (en) | 2015-10-07 |
EP2925711B1 (en) | 2016-12-21 |
CN104822645B (zh) | 2016-09-14 |
MX360018B (es) | 2018-10-10 |
JP2015535527A (ja) | 2015-12-14 |
ES2619528T3 (es) | 2017-06-26 |
US9249074B2 (en) | 2016-02-02 |
US20150329451A1 (en) | 2015-11-19 |
CN104822645A (zh) | 2015-08-05 |
MX2015006537A (es) | 2015-07-23 |
WO2014083121A1 (en) | 2014-06-05 |
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