JP4929402B2 - 3−メチル−シクロペンタデセノン類の製造方法、r/s−ムスコンの製造方法および光学活性ムスコンの製造方法 - Google Patents
3−メチル−シクロペンタデセノン類の製造方法、r/s−ムスコンの製造方法および光学活性ムスコンの製造方法 Download PDFInfo
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
- B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
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- C—CHEMISTRY; METALLURGY
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- 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
- C07C45/62—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 hydrogenation of carbon-to-carbon double or triple bonds
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
- B01J2531/0266—Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Description
22mmφ、長さ40cmのカラムにおいて、3〜4mmφの磁製ラシヒ35mlを上部に充填し、触媒として元素周期律表第2族の化合物である3〜5mmφの酸化亜鉛ペレット50mlを下部に充填し、ラシヒ層温度が315℃となり、触媒層温度が360℃となるように加熱する。この加熱したカラムへ、不活性ガスとしての窒素(5L/hr)キャリア下にて、5重量%の2,15−ヘキサデカンジオンを溶解した容量比が1対3のトルエン/デカリン溶液を25g/hrの速度で導入して分子内縮合反応を行った。この反応生成物を30〜50℃へ冷却して捕集した。
触媒として元素周期律表第2族の化合物である酸化カルシウムまたは酸化マグネシウムを用いたこと以外は、上記実施例1と同様にして反応を行った。この結果を表1に示す。
触媒として、元素周期律表第2族ではない種々の化合物を用いたこと以外は、上記実施例1と同様にして反応を行った。この結果を表2に示す。
3〜4mmφの磁製ラシヒ50ml充填管(22mmφ、長さ30cm)であるラシヒ充填管を上部に配置し、触媒として元素周期律表第2族の化合物である3〜5mmφの酸化亜鉛ペレット80ml充填管(22mmφ、長さ40cm)である触媒充填管を下部に配置し、ラシヒ管を320℃に加熱し、触媒充填管を360℃に加熱した。また、ラシヒ充填管へ窒素(5L/hr)キャリア下にて、5重量%の2,15−ヘキサデカンジオンを溶解したn−デカン溶液を25g/hrの速度で導入して分子内縮合反応を行った。この反応生成物を30〜50℃へ冷却して捕集した。
実施例4にて得られた反応生成液を1200g採取し、20℃へ冷却し、析出する結晶を濾過分離して、3−メチル−シクロペンタデセノン類2.5重量%および未反応2,15−ヘキサデカンジオン0.1重量%含有液を1158g得た。回収した未反応2,15−ヘキサデカンジオンの結晶は、乾燥後20.4gであり、純度は95重量%であった。
上記実施例5にて得られた未反応2,15−ヘキサデカンジオン分離後の3−メチル−シクロペンタデセノン類含有液1100gを濃縮後、東科精機製回転バンド型精密蒸留塔(理論段数80段)を用いて、減圧度10〜2mmHg、還流比10〜100にて精密蒸留を行い、初留分カット後、減圧度2mmHg、140.5〜142℃の留分10.3gを得た。この留分をガスクロマトグラフィにて分析したところ、(Z)−3−メチル−2−シクロペンタデセノン含量が95.3重量%であった。
窒素で置換した100ml耐圧容器へ、上記実施例6にて得られた(Z)−3−メチル−2−シクロペンタデセノン留分2g、ルテニウム/光学活性錯体触媒としてのRu2Cl4[(R)−Tol−BINAP]2(NEt3)10mgおよび溶媒としてのメタノール15mlを添加し、50KG水素加圧下にて、25℃で24時間の振とう反応を行い、不斉水素化した。
Claims (5)
- 触媒として用いる元素周期律表第2族の単成分の金属酸化物の存在下にて、2,15−ヘキサデカンジオンを気相で分子内縮合反応する
ことを特徴とする3−メチル−シクロペンタデセノン類の製造方法。 - 金属酸化物は、酸化マグネシウム、酸化カルシウムおよび酸化亜鉛のいずれかである
ことを特徴とする請求項1記載の3−メチル−シクロペンタデセノン類の製造方法。 - 触媒として用いる元素周期律表第2族の単成分の金属酸化物の存在下にて、2,15−ヘキサデカンジオンを気相で分子内縮合反応して3−メチル−シクロペンタデセノン類含有液を生成し、
この3−メチル−シクロペンタデセノン類含有液を、触媒を用いて水素化する
ことを特徴とするR/S−ムスコンの製造方法。 - 触媒として用いる元素周期律表第2族の単成分の金属酸化物の存在下にて、2,15−ヘキサデカンジオンを気相で分子内縮合反応して、少なくとも(E)−3−メチル−2−シクロペンタデセノンおよび(Z)−3−メチル−2−シクロペンタデセノンを含有する3−メチル−シクロペンタデセノン類含有液を生成し、
この3−メチル−シクロペンタデセノン類含有液を精密蒸留にて各成分に分離する
ことを特徴とする3−メチル−シクロペンタデセノン類の製造方法。 - 触媒として用いる元素周期律表第2族の単成分の金属酸化物の存在下にて、2,15−ヘキサデカンジオンを気相で分子内縮合反応して、少なくとも(E)−3−メチル−2−シクロペンタデセノンおよび(Z)−3−メチル−2−シクロペンタデセノンを含有する3−メチル−シクロペンタデセノン類含有液を生成し、
この3−メチル−シクロペンタデセノン類含有液を精密蒸留にて各成分に分離し、
この精密蒸留による3−メチル−シクロペンタデセノン類留分を、ルテニウム/光学活性錯体触媒を用いて不斉水素化する
ことを特徴とする光学活性ムスコンの製造方法。
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PCT/JP2009/056302 WO2010109650A1 (ja) | 2009-03-27 | 2009-03-27 | 3-メチル-シクロペンタデセノン類の製造方法、r/s-ムスコンの製造方法および光学活性ムスコンの製造方法 |
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JP4929402B2 true JP4929402B2 (ja) | 2012-05-09 |
JPWO2010109650A1 JPWO2010109650A1 (ja) | 2012-09-27 |
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US (1) | US20110172465A1 (ja) |
EP (1) | EP2412696A4 (ja) |
JP (1) | JP4929402B2 (ja) |
WO (1) | WO2010109650A1 (ja) |
Families Citing this family (7)
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JP6219884B2 (ja) * | 2015-05-28 | 2017-10-25 | 株式会社 東邦アーステック | (z)−3−メチル−2−シクロペンタデセノンの製造方法および(r)−(−)−3−メチルシクロペンタデカノンの製造方法 |
JP6595377B2 (ja) * | 2016-03-14 | 2019-10-23 | 株式会社 東邦アーステック | 3−メチルシクロペンタデセノン類の製造方法 |
JP6502884B2 (ja) * | 2016-03-14 | 2019-04-17 | 株式会社 東邦アーステック | 3−メチルシクロアルケノン類の製造方法 |
JP2018087184A (ja) * | 2016-11-24 | 2018-06-07 | 国立大学法人 新潟大学 | (e)−3−メチル−2−シクロアルケノン化合物、3−ハロ−3−メチルシクロアルカノン化合物および(r)−3−メチルシクロアルカノン化合物の製造方法 |
CN108191622B (zh) * | 2017-12-15 | 2021-02-09 | 广东省石油与精细化工研究院 | 一种dl-麝香酮的连续制备方法 |
US11377411B2 (en) | 2018-09-25 | 2022-07-05 | Takasago International Corporation | Method for producing 3-methylcycloalkenone compound |
CN109678684B (zh) * | 2018-12-25 | 2022-11-04 | 万华化学集团股份有限公司 | 一种制备左旋麝香酮的方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0381242A (ja) * | 1989-06-02 | 1991-04-05 | Basf Ag | ムスコンの製法及び2個の不飽和結合を有する開鎖状2,15―ジケトン |
JPH06192161A (ja) * | 1992-12-25 | 1994-07-12 | Takasago Internatl Corp | 光学活性ムスコンの製造方法 |
JPH07267968A (ja) * | 1994-03-30 | 1995-10-17 | Takasago Internatl Corp | (z)−3−メチル−2−シクロペンタデセン−1−オンの製造法 |
JP2002220361A (ja) * | 2001-01-26 | 2002-08-09 | Japan Energy Corp | 大環状ケトン化合物の製造方法 |
Family Cites Families (2)
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JPS59157047A (ja) | 1983-02-28 | 1984-09-06 | Nippon Mining Co Ltd | デヒドロムスコンの製造方法 |
JP4540197B2 (ja) | 2000-08-30 | 2010-09-08 | 高砂香料工業株式会社 | (e)−3−メチル−2−シクロペンタデセノンの製造法 |
-
2009
- 2009-03-27 JP JP2010526494A patent/JP4929402B2/ja not_active Expired - Fee Related
- 2009-03-27 EP EP09842264A patent/EP2412696A4/en not_active Withdrawn
- 2009-03-27 US US13/063,541 patent/US20110172465A1/en not_active Abandoned
- 2009-03-27 WO PCT/JP2009/056302 patent/WO2010109650A1/ja active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0381242A (ja) * | 1989-06-02 | 1991-04-05 | Basf Ag | ムスコンの製法及び2個の不飽和結合を有する開鎖状2,15―ジケトン |
JPH06192161A (ja) * | 1992-12-25 | 1994-07-12 | Takasago Internatl Corp | 光学活性ムスコンの製造方法 |
JPH07267968A (ja) * | 1994-03-30 | 1995-10-17 | Takasago Internatl Corp | (z)−3−メチル−2−シクロペンタデセン−1−オンの製造法 |
JP2002220361A (ja) * | 2001-01-26 | 2002-08-09 | Japan Energy Corp | 大環状ケトン化合物の製造方法 |
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WO2010109650A1 (ja) | 2010-09-30 |
US20110172465A1 (en) | 2011-07-14 |
EP2412696A1 (en) | 2012-02-01 |
JPWO2010109650A1 (ja) | 2012-09-27 |
EP2412696A4 (en) | 2012-08-22 |
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