JP2002220361A - Method for producing macrocyclic ketone compound - Google Patents
Method for producing macrocyclic ketone compoundInfo
- Publication number
- JP2002220361A JP2002220361A JP2001017711A JP2001017711A JP2002220361A JP 2002220361 A JP2002220361 A JP 2002220361A JP 2001017711 A JP2001017711 A JP 2001017711A JP 2001017711 A JP2001017711 A JP 2001017711A JP 2002220361 A JP2002220361 A JP 2002220361A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- producing
- cycloalkenone
- hydroxycyclopentadecanone
- mixture
- 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
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、香料等の原体やそ
の中間体として利用される大環状ケトン化合物を高効率
で製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a macrocyclic ketone compound to be used as a base such as a fragrance or an intermediate thereof with high efficiency.
【０００２】[0002]
【従来の技術】大環状ケトン、例えば、次の化学式
（1）で示されるシクロペンタデカノンや化学式（２）
で示される3-メチルシクロペンタデカノン、いわゆるム
スコンは麝香の香気成分として知られ、非常に高価で取
引されている。2. Description of the Related Art Macrocyclic ketones such as cyclopentadecanone represented by the following chemical formula (1) and chemical formula (2)
3-methylcyclopentadecanone, so-called muscone, which is known as a scent component of musk, is very expensive and traded.
【化1】 [Formula 1]
【０００３】このうちのシクロペンタデカノンの工業的
な製造方法の一つとして、ペンタデカン二酸ジエステル
をアシロイン縮合させて得られた2-ヒドロキシシクロペ
ンタデカノンを原料とし、亜鉛と所定濃度の硫酸などの
鉱酸の存在下に有機溶媒中で還元を行いシクロペンタデ
カノンとする方法が知られている（特許第3087921号公
報など）。この方法は2-ヒドロキシシクロペンタデカノ
ンを収率良く還元できる優れた方法であるが、この方法
では還元が金属表面でおこるために、鉱酸水溶液と有機
溶媒との２相中に亜鉛を高分散させることが必要であ
り、十分な分散に必要な撹拌を得るためには比較的小容
積の反応器を使用する必要があり、生産効率を向上させ
るためにスケールアップを考えた場合には問題があっ
た。As one of the industrial methods for producing cyclopentadecanone, 2-hydroxycyclopentadecanone obtained by subjecting pentadecane diacid diester to acyloin condensation is used as a raw material, and zinc and sulfuric acid having a predetermined concentration are used. Such a method is known in which reduction is carried out in an organic solvent in the presence of a mineral acid such as the above to give cyclopentadecanone (Japanese Patent No. 3087921). This method is an excellent method that can reduce 2-hydroxycyclopentadecanone in good yield, but in this method, since the reduction occurs on the metal surface, zinc is highly contained in two phases of a mineral acid aqueous solution and an organic solvent. It is necessary to disperse, and it is necessary to use a reactor with a relatively small volume in order to obtain the stirring required for sufficient dispersion, which is a problem when scaling up to improve production efficiency. was there.
【０００４】また、2-ヒドロキシシクロペンタデカノン
のカルボニル基を保護した後、ヒドロキシル基をトシル
基などの脱離基に変換し、塩基の存在下に引き抜くこと
により二重結合を生成させ、カルボニル基を脱保護する
ことにより、2-シクロペンタデセノンを合成する方法が
公知であり（特公平7-108876号公報）、この2-シクロペ
ンタデセノンを水素化してシクロペンタデカノンが得ら
れるだろうと述べられている（Alvin S. Williams, Syn
thesis, (1999), 10, 1707-1723）。しかし、この2-シ
クロペンタデセノン合成方法は多段階の反応工程が必要
であり、経済性に問題がある。In addition, after protecting the carbonyl group of 2-hydroxycyclopentadecanone, the hydroxyl group is converted to a leaving group such as a tosyl group, and the resulting compound is extracted in the presence of a base to form a double bond. A method of synthesizing 2-cyclopentadecenone by deprotecting a group is known (Japanese Patent Publication No. 7-108876), and hydrogenating this 2-cyclopentadecenone gives cyclopentadecanone. (Alvin S. Williams, Syn
thesis, (1999), 10, 1707-1723). However, this method for synthesizing 2-cyclopentadecenone requires a multi-step reaction process, and has a problem in economics.
【０００５】さらに、2-ヒドロキシシクロペンタデカノ
ンを原料とし、気相反応でアルミナを触媒として脱水
し、直接、2-シクロペンタデセノンに導く方法（Stoll,
M.; Commarmont, A. Helv. Chim. Acta 1948, 31, 55
4）が知られ、これを水素化すればシクロペンタデカノ
ンが得られることは予測される。しかし、気相反応の採
用は装置及び操作上必ずしも簡単ではない。Further, a method of dehydrating 2-hydroxycyclopentadecanone as a raw material using alumina as a catalyst in a gas phase reaction to directly lead to 2-cyclopentadecenone (Stoll,
M .; Commarmont, A. Helv. Chim. Acta 1948, 31, 55
4) is known, and it is expected that hydrogenation of this will yield cyclopentadecanone. However, adoption of a gas phase reaction is not always simple in terms of equipment and operation.
【０００６】一方、3-メチルシクロペンタデカノンの合
成法として、2-ヒドロキシシクロペンタデカノンのカル
ボニル基を保護した後、ヒドロキシル基をトシル基など
の脱離基に変換し、塩基の存在下に引き抜くことにより
二重結合を生成させ、カルボニル基を脱保護することで
得た2-シクロペンタデセノンを常法によりメチル化する
合成法が知られている（特公平7-108876号公報）。しか
し、この方法は2-シクロペンタデセノンを得るまでに長
い工程が必要であり、経済的ではない。On the other hand, as a method for synthesizing 3-methylcyclopentadecanone, after protecting the carbonyl group of 2-hydroxycyclopentadecanone, the hydroxyl group is converted to a leaving group such as a tosyl group and the like. A double bond is formed by extracting the carbonyl group, and 2-cyclopentadecenone obtained by deprotecting the carbonyl group is methylated by a conventional method (Japanese Patent Publication No. 7-108876). . However, this method requires a long process to obtain 2-cyclopentadecenone, and is not economical.
【０００７】また、シクロペンタデカノンを原料とし、
この2位にハロゲン等の脱離基を導入し、塩基の存在下
に引き抜くことにより二重結合を生成させることで得
た、2-シクロペンタデセノンを常法によりメチル化する
合成法やその変法（Journal ofthe Korean Chemical So
ciety, 40, 4, 243 (1996)など）も知られている。しか
し、この方法も、シクロペンタデカノンが2-ヒドロキシ
シクロペンタデカノンから合成されていることを考える
と、必ずしも経済性に優れているとは言いがたい。[0007] Also, using cyclopentadecanone as a raw material,
A synthetic method for methylating 2-cyclopentadecenone obtained by introducing a leaving group such as halogen at the 2-position and generating a double bond by withdrawing in the presence of a base. Modified method (Journal of the Korean Chemical So
ciety, 40, 4, 243 (1996)). However, this method cannot always be said to be excellent in economical efficiency considering that cyclopentadecanone is synthesized from 2-hydroxycyclopentadecanone.
【０００８】[0008]
【発明が解決しようとする課題】本発明は上記課題を解
決するもので、本発明の目的は液相反応において、効率
的にシクロアルケノンを製造する方法、このシクロアル
ケノンを原料として水素化してシクロアルカノンを製造
する方法、及びシクロアルケノンへアルキル基を導入す
ることにより、アルキルシクロアルカノンを製造する方
法を提供することにある。An object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to provide a method for efficiently producing cycloalkenone in a liquid phase reaction. An object of the present invention is to provide a method for producing an alkanone, and a method for producing an alkylcycloalkanone by introducing an alkyl group into cycloalkenone.
【０００９】[0009]
【課題を解決するための手段】本発明者は、スケールア
ップによる生産効率向上に好ましく、かつ、短い反応工
程で良く、さらには、汎用性のある装置での製造が容易
な液相反応が可能な、2-ヒドロキシシクロアルカノンを
原料とした脱水反応によるシクロアルケノンの合成方法
について、鋭意、研究を進めた結果、酸触媒を存在させ
ることにより、驚くべきことに液相反応においても保護
基を導入する必要がなく、高収率で脱水反応が進行する
こと、得られたシクロアルケノンは還元により容易にシ
クロアルカノンにできること、シクロアルケノン中の2-
シクロアルケノンは常法によりアルキル化でき、経済的
に3-アルキルシクロアルカノンに導けることを見出し、
本発明に想到した。SUMMARY OF THE INVENTION The present inventor has found that the present invention is preferable for improving the production efficiency by scale-up, requires only a short reaction step, and enables a liquid phase reaction which can be easily manufactured with a versatile apparatus. Furthermore, as a result of diligent studies on a method for synthesizing cycloalkenones by a dehydration reaction using 2-hydroxycycloalkanone as a raw material, surprisingly, the presence of an acid catalyst makes it possible to surprisingly protect a protective group even in a liquid phase reaction. No introduction is required, the dehydration reaction proceeds in high yield, the obtained cycloalkenones can be easily converted to cycloalkanone by reduction, and 2-
It has been found that cycloalkenones can be alkylated by conventional methods and can be economically led to 3-alkylcycloalkanones.
The present invention has been made.
【００１０】すなわち、本発明の大環状ケトン化合物の
製造方法は、 １）炭素数12〜18の2−ヒドロキシシクロアルカノン、
特に好ましくは2−ヒドロキシシクロペンタデカノンを
液相で酸触媒、特にはリン酸類または固体酸類の存在下
に脱水させてシクロアルケノン、特にはシクロペンタデ
セノンを製造する方法、 ２）上記方法で得られたシクロアルケノン、特にはシク
ロペンタデセノンを還元してシクロアルカノン、特にシ
クロペンタデカノンを製造する方法、 ３）上記方法で得られたシクロアルケノン、特には2−
シクロペンタデセノンをアルキル化、特にはメチル化し
てアルキルシクロアルカノン、特には3−メチルシクロ
ペンタデカンを製造する方法、を含むものである。That is, the method for producing the macrocyclic ketone compound of the present invention comprises the following steps: 1) 2-hydroxycycloalkanone having 12 to 18 carbon atoms;
Particularly preferably, 2-hydroxycyclopentadecanone is dehydrated in a liquid phase in the presence of an acid catalyst, particularly phosphoric acids or solid acids, to produce cycloalkenones, particularly cyclopentadecenone. A method for producing a cycloalkanone, particularly cyclopentadecanone by reducing the obtained cycloalkenone, particularly cyclopentadecenone; 3) a cycloalkenone obtained by the above method, particularly 2-
A process for alkylating, especially methylating, cyclopentadecenone to produce an alkylcycloalkanone, especially 3-methylcyclopentadecane.
【００１１】[0011]
【発明の実施の態様】本発明の原料である炭素数12〜18
の2-ヒドロキシシクロアルカノンは、対応する炭素数の
直鎖アルカンジカルボン酸ジエステルを有機溶媒中で金
属ナトリウムの存在下にアシロイン縮合させることによ
り、容易に合成できる。BEST MODE FOR CARRYING OUT THE INVENTION The raw material of the present invention has 12 to 18 carbon atoms.
Can be easily synthesized by subjecting a straight-chain alkanedicarboxylic acid diester having the corresponding carbon number to acyloin condensation in an organic solvent in the presence of sodium metal.
【００１２】これらの2-ヒドロキシシクロアルカノンを
原料として、酸触媒の存在下、必要に応じて溶媒を用い
て、加熱して脱水反応を行う。この場合、酸触媒として
は、リン酸類、例えばオルトリン酸、メタリン酸、ピロ
リン酸等のポリリン酸、あるいは固体酸類、例えば、シ
リカアルミナ、ゼオライト、ジルコニアおよび／または
アルミナに硫酸を担持させた硫酸ジルコニアまたは硫酸
ジルコニアアルミナ等（特公昭59−6181号公報、特開平
11−809727号公報等参照）が好ましい。これらの触媒の
使用量は、触媒の種類によって異なるが、例えばリン酸
類の場合は、2-ヒドロキシシクロアルカノン1モルに対
して0.01〜0.5モル、固体酸類の場合は、2-ヒドロキシ
シクロアルカノン1重量部当たり0.01〜1重量部の範囲か
ら適宜選定することが好ましい。Using these 2-hydroxycycloalkanone as a raw material, a dehydration reaction is carried out by heating in the presence of an acid catalyst, if necessary, using a solvent. In this case, examples of the acid catalyst include phosphoric acids, for example, polyphosphoric acid such as orthophosphoric acid, metaphosphoric acid, and pyrophosphoric acid, or solid acids, for example, silica alumina, zeolite, zirconia, and / or zirconia sulfate obtained by supporting sulfuric acid on alumina or Zirconia sulfate alumina and the like (Japanese Patent Publication No. 59-6181,
11-809727). The amount of these catalysts varies depending on the type of the catalyst.For example, in the case of phosphoric acids, 0.01 to 0.5 mol per 1 mol of 2-hydroxycycloalkanone, in the case of solid acids, 2-hydroxycycloalkanone It is preferable to appropriately select from the range of 0.01 to 1 part by weight per 1 part by weight.
【００１３】この反応において溶媒を用いて行う場合、
当該溶媒は本反応に不活性なものであれば特に支障なく
使用できるが、安定性の面から飽和炭化水素、芳香族炭
化水素を用いることが好ましい。この場合の溶媒の使用
量は多すぎると反応が遅くなり、一定容積当たりの反応
効率が悪くなるなどの不都合を生じるため、2-ヒドロキ
シシクロアルカノンの濃度が0.1モル/リットル以上にな
るような範囲から適宜選定すると良い。When the reaction is carried out using a solvent,
The solvent can be used without any particular problem as long as it is inert to the reaction, but it is preferable to use a saturated hydrocarbon or an aromatic hydrocarbon from the viewpoint of stability. In this case, if the amount of the solvent used is too large, the reaction is slowed down, and the reaction efficiency per fixed volume becomes inferior.In such a case, the concentration of 2-hydroxycycloalkanone becomes 0.1 mol / liter or more. It is good to select appropriately from the range.
【００１４】反応温度は100〜400℃、好ましくは150〜3
00℃とすると良く、低沸点の溶媒を用いる場合には、オ
ートクレーブ中で加圧反応として実施してもよい。The reaction temperature is 100-400 ° C., preferably 150-3.
The temperature is preferably set to 00 ° C. When a solvent having a low boiling point is used, the reaction may be carried out as a pressurized reaction in an autoclave.
【００１５】反応時間は選定した反応液の濃度、反応温
度などを勘案して決定される。The reaction time is determined in consideration of the concentration of the selected reaction solution, the reaction temperature, and the like.
【００１６】このような脱水反応では異性化等も同時に
起こるため、反応生成物であるシクロアルケノンは、主
に2-シクロアルケノンと3-シクロアルケノンからなって
いる。これらの混合物は、触媒を利用した水素化反応等
によって、容易にシクロアルカノンとすることができ
る。この水素化反応に使用できる触媒としては、ニッケ
ル触媒、コバルト触媒、銅触媒、パラジウム触媒、白金
触媒、ルテニウム触媒、ロジウム触媒等が例示できる。
これらの触媒の使用量は、触媒の種類、活性度によって
異なるが、シクロアルケノン1重量部当たり0.001〜0.1
重量部の範囲から適宜選定することが好ましい。In such a dehydration reaction, isomerization and the like also occur at the same time, so that the cycloalkenone, which is a reaction product, is mainly composed of 2-cycloalkenones and 3-cycloalkenones. These mixtures can be easily converted to cycloalkanone by a hydrogenation reaction using a catalyst or the like. Examples of the catalyst that can be used in the hydrogenation reaction include a nickel catalyst, a cobalt catalyst, a copper catalyst, a palladium catalyst, a platinum catalyst, a ruthenium catalyst, and a rhodium catalyst.
The amount of these catalysts varies depending on the type and activity of the catalyst, but is preferably 0.001 to 0.1 per part by weight of cycloalkenone.
It is preferable to appropriately select from the range of parts by weight.
【００１７】この反応は溶媒を用いて溶液の形態で行う
ことが好ましく、当該溶媒は本反応に不活性なものであ
れば特に支障なく使用できるが、脱水反応において使用
しているために利便性の面から飽和炭化水素、芳香族炭
化水素を用いることが、特に好ましい。この場合、シク
ロアルケノンの濃度が0.1モル/リットル以上になるよう
にすると効率よく反応を行うことができる。This reaction is preferably carried out in the form of a solution using a solvent. The solvent can be used without any particular problem as long as it is inert to the reaction, but it is convenient because it is used in the dehydration reaction. It is particularly preferable to use a saturated hydrocarbon or an aromatic hydrocarbon in view of the above. In this case, if the concentration of cycloalkenones is adjusted to 0.1 mol / liter or more, the reaction can be performed efficiently.
【００１８】反応温度は0〜400℃、好ましくは室温〜10
0℃とすると良く、常圧の水素ガス封入下で行うのが簡
便であるが、水素ガスをバブリングしてもよく、また、
オートクレーブを用いて、0〜30kg/cm2の水素加圧下で
実施してもよい。さらには、充填した触媒中を反応液と
水素ガスを並流させる流通方式で行ってもよい。The reaction temperature is 0 to 400 ° C, preferably room temperature to 10 ° C.
The temperature is preferably set to 0 ° C., and it is convenient to carry out the reaction under hydrogen gas filling at normal pressure, but hydrogen gas may be bubbled,
It may be carried out using an autoclave under a hydrogen pressure of 0 to 30 kg / cm 2 . Further, the reaction may be carried out by a flow system in which the reaction liquid and the hydrogen gas flow in the charged catalyst in parallel.
【００１９】得られた水素化反応生成物は蒸留等の常法
で精製することができる。The obtained hydrogenation reaction product can be purified by a conventional method such as distillation.
【００２０】一方、上述の脱水反応で得られた反応生成
物の主として2-シクロアルケノンと3-シクロアルケノン
の混合物を直接に、あるいは必要に応じて、2-シクロア
ルケノンを蒸留やクロマトグラフィー等の常法により分
離した後に、例えば、銅試薬、グリニアル試薬の存在下
にマイケル反応などの常法によって、3-アルキル化シク
ロアルカノンとすることができる（Journal of the Kor
ean Chemical Society, 40, 4, 243 (1996)を参照）。On the other hand, a mixture of 2-cycloalkenones and 3-cycloalkenones, which is a reaction product obtained by the above-mentioned dehydration reaction, is directly or, if necessary, is subjected to distillation, chromatography or the like. After separation by a conventional method, 3-alkylated cycloalkanone can be obtained by a conventional method such as a Michael reaction in the presence of a copper reagent or a Grignard reagent (Journal of the Kor
ean Chemical Society, 40, 4, 243 (1996)).
【００２１】以下に、具体例を挙げ、本発明を説明する
が、本発明の範囲はこれらに限定されるものではない。Hereinafter, the present invention will be described with reference to specific examples, but the scope of the present invention is not limited thereto.
【００２２】[0022]
【実施例】（実施例１）100ml容３つ口フラスコに、温
度計、冷却管をセットしたところに、2-ヒドロキシシク
ロペンタデカノン6.0g、シリカアルミナ触媒（触媒化成
社製HA）1.0g、テトラデカン54.0gを加え、マグネチッ
クスターラーで撹拌しながら、マントルヒーターで加熱
し、反応液温220℃で7時間反応させた。反応液に内部標
準物質としてエイコサンを加え、ガスクロマトグラフィ
ーで定量したところ、2-ヒドロキシシクロペンタデカノ
ンに対して、収率85％でシクロペンタデセノン混合物を
得た。[Example] (Example 1) A thermometer and a cooling tube were set in a 100 ml three-necked flask. Then, 6.0 g of 2-hydroxycyclopentadecanone and 1.0 g of a silica-alumina catalyst (HA manufactured by Catalyst Kasei Co., Ltd.) were used. And 54.0 g of tetradecane, and the mixture was heated with a mantle heater while stirring with a magnetic stirrer, and reacted at a reaction liquid temperature of 220 ° C. for 7 hours. Eicosane was added to the reaction solution as an internal standard substance, and the mixture was quantified by gas chromatography. As a result, a cyclopentadecenone mixture was obtained at a yield of 85% with respect to 2-hydroxycyclopentadecanone.
【００２３】（実施例２）200ml容オートクレーブに、2
-ヒドロキシシクロペンタデカノン6.0g、シリカアルミ
ナ触媒（触媒化成社製HA）1.0g、トルエン54.0gを加
え、マグネチックスターラーで撹拌しながら、オイルバ
ス温240℃で5時間反応させた。反応液に内部標準物質と
してエイコサンを加え、ガスクロマトグラフィーで定量
したところ、2-ヒドロキシシクロペンタデカノンに対し
て、収率90％でシクロペンタデセノン混合物を得た。Example 2 In a 200 ml autoclave, 2
6.0 g of -hydroxycyclopentadecanone, 1.0 g of a silica-alumina catalyst (HA, manufactured by Catalyst Kasei Co., Ltd.) and 54.0 g of toluene were added, and the mixture was reacted at an oil bath temperature of 240 ° C for 5 hours while stirring with a magnetic stirrer. Eicosane was added to the reaction solution as an internal standard substance, and the mixture was quantified by gas chromatography. As a result, a cyclopentadecenone mixture was obtained in a yield of 90% with respect to 2-hydroxycyclopentadecanone.
【００２４】（実施例３）100ml容３つ口フラスコに、
温度計、冷却管をセットしたところに、2-ヒドロキシシ
クロペンタデカノン6.0g、シリカアルミナ触媒（触媒化
成社製LA）0.5g、テトラデカン12.0gを加え、200℃で1
時間反応させた。反応液に内部標準物質としてエイコサ
ンを加え、ガスクロマトグラフィーで定量したところ、
2-ヒドロキシシクロペンタデカノンに対して、収率11％
でシクロペンタデセノン混合物を得た。Example 3 In a 100 ml three-necked flask,
At the place where a thermometer and a cooling tube were set, 6.0 g of 2-hydroxycyclopentadecanone, 0.5 g of a silica-alumina catalyst (LA, manufactured by Kasei Kasei Co., Ltd.) and 12.0 g of tetradecane were added.
Allowed to react for hours. Eicosane was added as an internal standard substance to the reaction solution, and quantified by gas chromatography.
11% yield based on 2-hydroxycyclopentadecanone
To obtain a cyclopentadecenone mixture.
【００２５】（実施例４）100ml容３つ口フラスコに、
温度計、冷却管をセットしたところに、2-ヒドロキシシ
クロペンタデカノン6.0g、ゼオライト触媒（Zeolyst社
製CBV720）1.0g 、テトラデカン12.0gを加え、マグネチ
ックスターラーで撹拌しながら、マントルヒーターで加
熱し、200℃で12時間反応させた。反応液に内部標準物
質としてエイコサンを加え、ガスクロマトグラフィーで
定量したところ、2-ヒドロキシシクロペンタデカノンに
対して、収率41％でシクロペンタデセノン混合物を得
た。Example 4 In a 100 ml three-necked flask,
After setting the thermometer and cooling tube, add 6.0 g of 2-hydroxycyclopentadecanone, 1.0 g of zeolite catalyst (CBV720 manufactured by Zeolyst) and 12.0 g of tetradecane, and heat with a mantle heater while stirring with a magnetic stirrer. Then, the reaction was performed at 200 ° C. for 12 hours. Eicosan was added to the reaction solution as an internal standard substance, and the mixture was quantified by gas chromatography. As a result, a cyclopentadecenone mixture was obtained at a yield of 41% based on 2-hydroxycyclopentadecanone.
【００２６】（実施例５）100ml容３つ口フラスコに、
温度計、冷却管をセットしたところに、2-ヒドロキシシ
クロペンタデカノン6.0g、硫酸ジルコニアアルミナ（特
開平11−809727号公報記載の方法で調製したもの）5.0
g、テトラデカン54.0gを加え、マグネチックスターラー
で撹拌しながら、マントルヒーターで加熱し、200℃で4
時間反応させた。反応液に内部標準物質としてエイコサ
ンを加え、ガスクロマトグラフィーで定量したところ、
2-ヒドロキシシクロペンタデカノンに対して、収率73％
でシクロペンタデセノン混合物を得た。Example 5 In a 100 ml three-necked flask,
After setting a thermometer and a cooling tube, 6.0 g of 2-hydroxycyclopentadecanone, zirconia alumina sulfate (prepared by the method described in JP-A-11-809727) 5.0
g, 54.0 g of tetradecane, and heating with a mantle heater while stirring with a magnetic stirrer.
Allowed to react for hours. When eicosane was added to the reaction solution as an internal standard, and quantified by gas chromatography,
73% yield based on 2-hydroxycyclopentadecanone
To obtain a cyclopentadecenone mixture.
【００２７】（実施例6）100ml容３つ口フラスコに、温
度計、冷却管をセットしたところに、2-ヒドロキシシク
ロペンタデカノン6.0g、H3PO4 0.1gを加え、マグネチッ
クスターラーで撹拌しながら、マントルヒーターで加熱
し、240℃で20分間反応させた。反応液に内部標準物質
としてエイコサンを加え、ガスクロマトグラフィーで定
量したところ、2-ヒドロキシシクロペンタデカノンに対
して、収率64％でシクロペンタデセノン混合物を得た。(Example 6) A thermometer and a cooling tube were set in a 100 ml three-necked flask, 6.0 g of 2-hydroxycyclopentadecanone and 0.1 g of H 3 PO 4 were added, and the mixture was stirred with a magnetic stirrer. While stirring, the mixture was heated with a mantle heater and reacted at 240 ° C. for 20 minutes. Eicosan was added to the reaction solution as an internal standard substance, and the mixture was quantified by gas chromatography. As a result, a cyclopentadecenone mixture was obtained at a yield of 64% based on 2-hydroxycyclopentadecanone.
【００２８】（実施例7）100ml容３つ口フラスコに、温
度計、冷却管をセットしたところに、2-ヒドロキシシク
ロペンタデカノン6.0g、H4P2O7 0.1gを加え、マグネチ
ックスターラーで撹拌しながら、マントルヒーターで加
熱し、240℃で20分間反応させた。反応液に内部標準物
質としてエイコサンを加え、ガスクロマトグラフィーで
定量したところ、2-ヒドロキシシクロペンタデカノンに
対して、収率65％でシクロペンタデセノン混合物を得
た。Example 7 A thermometer and a cooling tube were set in a 100 ml three-necked flask, and 6.0 g of 2-hydroxycyclopentadecanone and 0.1 g of H 4 P 2 O 7 were added. While stirring with a stirrer, the mixture was heated with a mantle heater and reacted at 240 ° C. for 20 minutes. Eicosan was added to the reaction mixture as an internal standard substance, and the mixture was quantified by gas chromatography. As a result, a cyclopentadecenone mixture was obtained in a yield of 65% based on 2-hydroxycyclopentadecanone.
【００２９】（実施例8）100ml容３つ口フラスコに、温
度計、冷却管をセットしたところに、2-ヒドロキシシク
ロペンタデカノン6.0g、HPO3 0.5g、テトラデカン18.0g
を加え、マグネチックスターラーで撹拌しながら、マン
トルヒーターで加熱し、250℃で6時間反応させた。反応
液に内部標準物質としてエイコサンを加え、ガスクロマ
トグラフィーで定量したところ、2-ヒドロキシシクロペ
ンタデカノンに対して、収率63％でシクロペンタデセノ
ン混合物を得た。(Example 8) A thermometer and a cooling tube were set in a 100 ml three-necked flask, whereupon 6.0 g of 2-hydroxycyclopentadecanone, 0.5 g of HPO 3 and 18.0 g of tetradecane
Was added and heated with a mantle heater while stirring with a magnetic stirrer, and reacted at 250 ° C. for 6 hours. Eicosane was added to the reaction solution as an internal standard substance, and the mixture was quantified by gas chromatography. As a result, a cyclopentadecenone mixture was obtained with a yield of 63% based on 2-hydroxycyclopentadecanone.
【００３０】（実施例9）100ml容３つ口フラスコに、温
度計、冷却管をセットしたところに、2-ヒドロキシシク
ロトリデカノン6.0g、シリカアルミナ触媒（触媒化成社
製HA）1.0g、テトラデカン54.0gを加え、マグネチック
スターラーで撹拌しながら、マントルヒーターで加熱
し、反応液温220℃で7時間反応させた。反応液に内部標
準物質としてエイコサンを加え、ガスクロマトグラフィ
ーで定量したところ、2-ヒドロキシシクロトリデカノン
に対して、収率81％でシクロトリデセノン混合物を得
た。Example 9 A thermometer and a cooling tube were set in a 100 ml three-necked flask, and 6.0 g of 2-hydroxycyclotridecanone, 1.0 g of a silica-alumina catalyst (HA, manufactured by Catalyst Kasei Co., Ltd.), tetradecane 54.0 g was added, and the mixture was heated with a mantle heater while stirring with a magnetic stirrer, and reacted at a reaction liquid temperature of 220 ° C. for 7 hours. Eicosan was added to the reaction solution as an internal standard substance, and the mixture was quantified by gas chromatography. As a result, a cyclotridecenone mixture was obtained with a yield of 81% based on 2-hydroxycyclotridecanone.
【００３１】（実施例10）100ml容ナスフラスコに、シ
クロペンタデセノン混合物2.0g、5％Pd/C 0.1g、トルエ
ン18.0gを加え、水素雰囲気下、室温で3時間反応させ
た。反応液に内部標準物質としてエイコサンを加え、ガ
スクロマトグラフィーで定量したところ、水素化収率10
0％でシクロペンタデカノンを得た。Example 10 A 100 ml eggplant-shaped flask was charged with 2.0 g of a cyclopentadecenone mixture, 0.1 g of 5% Pd / C, and 18.0 g of toluene, and reacted at room temperature under a hydrogen atmosphere for 3 hours. Eicosane was added as an internal standard substance to the reaction mixture, and the mixture was quantified by gas chromatography.
Cyclopentadecanone was obtained at 0%.
【００３２】（実施例11）100ml容３つ口フラスコに、
温度計、滴下漏斗をセットし、フラスコに無水CuCl 0.4
4g、CH3MgIのエーテル溶液（0.84mol/l）1.3ml、乾燥エ
ーテル15mlを加え、氷浴で冷やしながら、滴下漏斗のシ
クロペンタデセノン混合物（脱水反応生成物をカラム精
製して得た。2-シクロペンタデセノン62％を含む。）1.
2g、乾燥エーテル5ml溶液を、約1時間かけてゆっくり滴
下した。滴下終了後反応液温を10℃にあげ、さらに2時
間撹拌を続けた。氷冷しながら、10％塩酸水溶液10mlを
滴下し、有機相を分相した。水相をジクロロメタンで抽
出したものをこの有機相に混ぜ、飽和炭酸水素ナトリウ
ム水溶液、水で洗った後に、無水MgSO4で乾燥させた。
濃縮して、黄色い粗生成物0.98gを得た。シリカゲルカ
ラム精製により、3-メチルシクロペンタデカノン0.72g
を得た。2-シクロペンタデセノンに対して、収率68％で
あった。(Example 11) In a 100 ml three-necked flask,
Set a thermometer and a dropping funnel, and put anhydrous CuCl 0.4
4 g, 1.3 ml of a CH 3 MgI ether solution (0.84 mol / l) and 15 ml of dry ether were added, and the mixture was cooled in an ice bath, and a cyclopentadecenone mixture (a dehydration reaction product was obtained by column purification from a dropping funnel). It contains 62% of 2-cyclopentadecenone.) 1.
A solution of 2 g and 5 ml of dry ether was slowly added dropwise over about 1 hour. After completion of the dropwise addition, the temperature of the reaction solution was raised to 10 ° C., and stirring was continued for another 2 hours. While cooling with ice, 10 ml of a 10% aqueous hydrochloric acid solution was added dropwise, and the organic phase was separated. The aqueous phase was extracted with dichloromethane, mixed with the organic phase, washed with a saturated aqueous solution of sodium hydrogen carbonate and water, and dried over anhydrous MgSO 4 .
Concentration gave 0.98 g of a yellow crude product. 0.72 g of 3-methylcyclopentadecanone by silica gel column purification
I got The yield was 68% based on 2-cyclopentadecenone.
【００３３】[0033]
【発明の効果】本発明は、短い反応工程で、しかも汎用
性のある装置により工業的に効率よくシクロアルケノン
を、またこのシクロアルケノンから効率的にシクロアル
カノンを、さらには、アルキルシクロアルカノンを製造
することができるという格別の効果を奏する。Industrial Applicability According to the present invention, a cycloalkenone can be industrially efficiently used in a short reaction step and using a versatile apparatus, and a cycloalkanone can be efficiently produced from the cycloalkenone. Is produced.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) // C07B 61/00 300 C07B 61/00 300
Claims (6)
ルカノンを液相で酸触媒の存在下に脱水させることを特
徴とするシクロアルケノンの製造方法。1. A process for producing cycloalkenones, comprising dehydrating 2-hydroxycycloalkanone having 12 to 18 carbon atoms in a liquid phase in the presence of an acid catalyst.
は固体酸類であることを特徴とするシクロアルケノンの
製造方法。2. A process for producing cycloalkenones, wherein the acid catalyst according to claim 1 is a phosphoric acid or a solid acid.
ルカノンを液相で酸触媒の存在下に脱水させ、得られた
シクロアルケノンを還元することを特徴とするシクロア
ルカノンの製造方法。3. A process for producing cycloalkanone, comprising dehydrating a 2-hydroxycycloalkanone having 12 to 18 carbon atoms in a liquid phase in the presence of an acid catalyst, and reducing the resulting cycloalkenone.
ルカノンを液相で酸触媒の存在下に脱水させ、得られた
シクロアルケノンをアルキル化することを特徴とするア
ルキルシクロアルカノンの製造方法。4. A method for producing an alkylcycloalkanone, comprising dehydrating a 2-hydroxycycloalkanone having 12 to 18 carbon atoms in a liquid phase in the presence of an acid catalyst, and alkylating the resulting cycloalkenone. Method.
液相で酸触媒の存在下に脱水させ、得られたシクロペン
タデセノンを還元することを特徴とするシクロペンタデ
カノンの製造方法。5. A process for producing cyclopentadecanone, comprising dehydrating 2-hydroxycyclopentadecanone in a liquid phase in the presence of an acid catalyst to reduce the obtained cyclopentadecenone.
液相で酸触媒の存在下に脱水させ、得られた2−シクロ
ペンタデセノンをメチル化することを特徴とする3-メチ
ルシクロペンタデカノンの製造方法。6. 3-Methylcyclopentadecanone comprising dehydrating 2-hydroxycyclopentadecanone in a liquid phase in the presence of an acid catalyst, and methylating the resulting 2-cyclopentadecenone. Manufacturing method.
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| JP2001017711A JP4649743B2 (en) | 2001-01-26 | 2001-01-26 | Process for producing macrocyclic ketone compounds |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1440963A1 (en) * | 2003-01-24 | 2004-07-28 | Japan Energy Corporation | Production method of ketone compound |
| JP2008100951A (en) * | 2006-10-19 | 2008-05-01 | Kawaguchi Yakuhin Kk | Method for preparing 2-cyclopentadecenone |
| JPWO2006051595A1 (en) * | 2004-11-11 | 2008-05-29 | 高砂香料工業株式会社 | Process for producing macrocyclic ketones and intermediates thereof |
| CN101979367A (en) * | 2010-10-22 | 2011-02-23 | 高旌 | Preparation method of trimethyl macrocyclic ketone |
| JP4929402B2 (en) * | 2009-03-27 | 2012-05-09 | 正晴 銅谷 | Method for producing 3-methyl-cyclopentadecenones, method for producing R / S-muscone and method for producing optically active muscone |
| CN104560359A (en) * | 2014-12-24 | 2015-04-29 | 江南大学 | Method for catalyzing cellulose to be liquefied into biological oil by using magnetic solid acid |
| CN106946679A (en) * | 2017-05-08 | 2017-07-14 | 苏州碳壹科技有限公司 | A kind of preparation method of the cyclopentadecylene ketone of E 2 |
| CN114621069A (en) * | 2022-03-16 | 2022-06-14 | 山东宏济堂制药集团股份有限公司 | Method for preparing macrocyclic ketone by using binary composite solvent system |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2656391A (en) * | 1947-10-07 | 1953-10-20 | Firmenich & Co | Processes for the preparation of alpha-beta unsaturated cyclopolymethylenic ketones |
| JPS5148635A (en) * | 1974-10-16 | 1976-04-26 | Toray Industries | Daikanjoketonno seizoho |
| JPH04139144A (en) * | 1990-09-29 | 1992-05-13 | Nippon Zeon Co Ltd | Production of large ring ketones |
| JPH05155802A (en) * | 1991-12-02 | 1993-06-22 | Nikko Kyodo Co Ltd | Production of large cyclic ketone |
| JPH11315044A (en) * | 1998-02-12 | 1999-11-16 | Basf Ag | Production of 2-cycloalkenone |
-
2001
- 2001-01-26 JP JP2001017711A patent/JP4649743B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2656391A (en) * | 1947-10-07 | 1953-10-20 | Firmenich & Co | Processes for the preparation of alpha-beta unsaturated cyclopolymethylenic ketones |
| JPS5148635A (en) * | 1974-10-16 | 1976-04-26 | Toray Industries | Daikanjoketonno seizoho |
| JPH04139144A (en) * | 1990-09-29 | 1992-05-13 | Nippon Zeon Co Ltd | Production of large ring ketones |
| JPH05155802A (en) * | 1991-12-02 | 1993-06-22 | Nikko Kyodo Co Ltd | Production of large cyclic ketone |
| JPH11315044A (en) * | 1998-02-12 | 1999-11-16 | Basf Ag | Production of 2-cycloalkenone |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1440963A1 (en) * | 2003-01-24 | 2004-07-28 | Japan Energy Corporation | Production method of ketone compound |
| US7034188B2 (en) | 2003-01-24 | 2006-04-25 | Japan Energy Corporation | Production method of ketone compound |
| JPWO2006051595A1 (en) * | 2004-11-11 | 2008-05-29 | 高砂香料工業株式会社 | Process for producing macrocyclic ketones and intermediates thereof |
| JP4860481B2 (en) * | 2004-11-11 | 2012-01-25 | 高砂香料工業株式会社 | Process for producing macrocyclic ketones and intermediates thereof |
| JP2008100951A (en) * | 2006-10-19 | 2008-05-01 | Kawaguchi Yakuhin Kk | Method for preparing 2-cyclopentadecenone |
| JP4929402B2 (en) * | 2009-03-27 | 2012-05-09 | 正晴 銅谷 | Method for producing 3-methyl-cyclopentadecenones, method for producing R / S-muscone and method for producing optically active muscone |
| CN101979367A (en) * | 2010-10-22 | 2011-02-23 | 高旌 | Preparation method of trimethyl macrocyclic ketone |
| CN104560359A (en) * | 2014-12-24 | 2015-04-29 | 江南大学 | Method for catalyzing cellulose to be liquefied into biological oil by using magnetic solid acid |
| CN106946679A (en) * | 2017-05-08 | 2017-07-14 | 苏州碳壹科技有限公司 | A kind of preparation method of the cyclopentadecylene ketone of E 2 |
| CN106946679B (en) * | 2017-05-08 | 2020-07-31 | 苏州碳壹科技有限公司 | Preparation method of E-2-cyclopentadecanone |
| CN114621069A (en) * | 2022-03-16 | 2022-06-14 | 山东宏济堂制药集团股份有限公司 | Method for preparing macrocyclic ketone by using binary composite solvent system |
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