JP3087921B2 - Method for producing macrocyclic ketone - Google Patents
Method for producing macrocyclic ketoneInfo
- Publication number
- JP3087921B2 JP3087921B2 JP03341750A JP34175091A JP3087921B2 JP 3087921 B2 JP3087921 B2 JP 3087921B2 JP 03341750 A JP03341750 A JP 03341750A JP 34175091 A JP34175091 A JP 34175091A JP 3087921 B2 JP3087921 B2 JP 3087921B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- sulfuric acid
- macrocyclic ketone
- acyloin
- producing
- 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.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【産業上の利用分野】本発明は炭素数１２〜１８の直鎖
アルカン二酸のジエステル化物をアシロイン縮合反応に
より分子内環化し、得られたアシロイン縮合反応生成物
を還元して炭素数１２〜１８の大環状ケトンを製造する
方法に関する。BACKGROUND OF THE INVENTION The present invention relates to an intramolecular cyclization of a diester of a linear alkane diacid having 12 to 18 carbon atoms by an acyloin condensation reaction, and reduction of the resulting acyloin condensation reaction product to thereby reduce the carbon number of the resulting acryloic acid. 18 relates to a method for producing a macrocyclic ketone.
【０００２】尚、炭素数１２〜１８の大環状ケトンはム
スク様の匂いを呈し、香料またはその調合基材として用
いられる。[0002] A macrocyclic ketone having 12 to 18 carbon atoms has a musk-like odor and is used as a perfume or a base material for preparing the fragrance.
【０００３】[0003]
【従来の技術】大環状ケトンの製造方法として、下記式
に示すように、直鎖アルカンジカルボン酸のジエステル
をアシロイン縮合反応により分子内環化し、還元する方
法が提案されている〔Helv. Chim. Acta.,30 P1741(194
7)〕。2. Description of the Related Art As a method for producing a macrocyclic ketone, a method has been proposed in which a diester of a linear alkanedicarboxylic acid is intramolecularly cyclized by an acyloin condensation reaction and reduced as shown in the following formula [Helv. Chim. Acta., 30 P1741 (194
7)].
【化１】 Embedded image
【０００４】上記製造方法のうちアシロインの還元反応
は、酢酸溶媒中で、塩酸と亜鉛の共存下に行われてい
る。また、この還元反応の改良方法として、沸点が６０
℃以上でかつ水と共沸する有機溶媒を使用する方法（特
開昭６１−５６１４６号公報）、表面酸化物を除去した
亜鉛を使用する方法（特開昭６１−５６１４７号公報）
等が提案されている。この方法では、亜鉛の他に、スズ
およびアルミニウム等の粉末が使用できることや、鉱酸
として、塩酸以外にも濃硫酸等をそのまま或いは水で適
宜希釈して使用できることも知られているが、使用量、
濃度等についての詳細な記述はされていない。[0004] Among the above production methods, the reduction reaction of acyloin is carried out in an acetic acid solvent in the presence of hydrochloric acid and zinc. As a method for improving this reduction reaction, a boiling point of 60
A method using an organic solvent which is azeotropic with water at a temperature of at least ℃ (JP-A-61-56146) and a method using zinc whose surface oxide has been removed (JP-A-61-56147)
Etc. have been proposed. In this method, in addition to zinc, it is known that powders such as tin and aluminum can be used, and that as a mineral acid, concentrated sulfuric acid or the like other than hydrochloric acid can be used as it is or appropriately diluted with water. amount,
No detailed description of the concentration etc. is given.
【０００５】上述の改良したアシロインの還元反応方法
においても、その収率は、７４.３〜８６.４％であり、
十分に高いとは言い難い。[0005] In the above-mentioned improved acyloin reduction reaction method, the yield is 74.3 to 86.4%.
It is hard to say that it is high enough.
【０００６】また、上述の還元反応方法によって得られ
た大環状ケトンは、黄色に着色しているために、このま
までは香料等としての品質を満足できるものではなく、
減圧蒸留および再結晶を行うことにより〔V.V.DHEKNE、
他、インデアン、ジャーナル、オブ、ケミストリー(IND
IAN J. CHEM.)4,p524〕あるいは、光照射することによ
り（特開昭６３−２４３０４９号公報参照）精製してい
たが、操作が煩雑であり、また歩留りが悪くなる等の問
題があった。Further, the macrocyclic ketone obtained by the above-mentioned reduction reaction method is colored in yellow, so that it cannot satisfy the quality as a fragrance or the like as it is.
By performing vacuum distillation and recrystallization, [VVDHEKNE,
Other, Indian, Journal, Ob, Chemistry (IND
IAN J. CHEM.) 4 , p524] Alternatively, purification was performed by light irradiation (see JP-A-63-243049). However, there were problems such as complicated operations and poor yield. Was.
【０００７】さらに、上述の還元反応方法において鉱酸
としての実施例が示されている塩酸は、反応機器等の腐
食を招きやすく、そのため当該反応機器材質には、特殊
かつ高価な材質を使用しなければいけなかった。Furthermore, hydrochloric acid, which is described as an example of a mineral acid in the above-mentioned reduction reaction method, is apt to cause corrosion of the reaction equipment and the like, and therefore, a special and expensive material is used for the reaction equipment. I had to.
【０００８】[0008]
【発明が解決しようとする課題】本発明は上記の課題を
解決するもので、本発明の目的は低腐食性の硫酸を使用
して、特別な精製工程が不必要な大環状ケトンを高収率
で製造する方法を提供することにある。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to use a low corrosive sulfuric acid to produce a macrocyclic ketone which does not require a special purification step. It is an object of the present invention to provide a method of manufacturing at a high rate.
【０００９】[0009]
【課題を解決するための手段】本発明は、炭素数１２〜
１８の直鎖アルカン二酸のジエステル化物をアシロイン
縮合反応により分子内環化し、得られたアシロイン縮合
反応生成物を還元して大環状ケトンを製造する方法にお
いて、前記還元に際し、１４規定以上２６規定未満の濃
度の硫酸と亜鉛末とを用いることを特徴とする大環状ケ
トンの製造方法である。Means for Solving the Problems The present invention provides a compound having 12 to 12 carbon atoms.
In a method for producing a macrocyclic ketone by intramolecularly cyclizing a diesterified product of a linear alkanediacid of No. 18 by an acyloin condensation reaction and reducing the obtained acyloin condensation reaction product, in the reduction, 14 N or more and 26 N or less. A method for producing a macrocyclic ketone, comprising using sulfuric acid and zinc dust at concentrations less than the above.
【００１０】本発明における還元する際の硫酸の濃度で
あるが、１４規定未満の濃度では反応速度が遅いため実
用的ではなく、また２６規定以上の濃度とすると、アシ
ロイン縮合反応生成物等の炭化などの副反応が生じ、反
応収率が低下する。In the present invention, the concentration of sulfuric acid at the time of reduction is not practical if the concentration is less than 14 N because the reaction rate is slow. If the concentration is 26 N or more, the concentration of sulfuric acid such as acyloin condensation reaction product is reduced. And other side reactions occur, and the reaction yield decreases.
【００１１】硫酸の使用量は、アシロイン縮合反応生成
物中に含有されるアシロインに対して（以下同様）１〜
２０モル倍、好ましくは３〜１０モル倍用いると良い。
等モル倍未満では反応が不十分であり、２０モル倍以上
加えると収率が減少する傾向にありあまり好ましくな
い。The amount of sulfuric acid used is 1 to 1 with respect to the acyloin contained in the acyloin condensation reaction product (the same applies hereinafter).
It is good to use 20 times, preferably 3 to 10 times.
If the molar ratio is less than equimolar, the reaction is insufficient, and if the molar ratio is 20 mol or more, the yield tends to decrease, which is not preferred.
【００１２】一方、亜鉛の量は、アシロインに対し、１
〜２０モル倍、好ましくは５〜１０モル倍とするとよ
い。等モル倍未満の添加量では反応が不十分であり、ま
た２０モル倍以上加えても添加量に見合うだけ収率が向
上しないため経済的でない。On the other hand, the amount of zinc is 1 to acyloin.
The molar ratio is preferably 20 to 20 times, preferably 5 to 10 times. If the amount is less than equimolar, the reaction is insufficient, and if the amount is more than 20 times, the yield is not improved as much as the amount added, which is not economical.
【００１３】反応溶媒に溶解させたアシロイン縮合反応
生成物に対して、亜鉛は、一度に全量を加えても、ある
いは、分割して加えても良いが、硫酸は少量ずつ分割し
て、あるいは滴下して加えるのが好ましい。これは、硫
酸を一度に大量に加えると、発生する反応熱のために反
応が暴走したり、あるいは好ましくない副反応を引き起
こしたりするおそれがあるためである。To the acyloin condensation reaction product dissolved in the reaction solvent, zinc may be added at once or in portions, but sulfuric acid may be added in small portions or in drops. It is preferable to add them. This is because if a large amount of sulfuric acid is added at one time, the reaction may run away due to the generated heat of reaction, or may cause an undesirable side reaction.
【００１４】この還元反応の際の温度は６０℃〜反応混
合物の還流温度範囲で行うことがよく、特に７０〜１４
０℃が好ましい。６０℃未満では反応の進行がおそく、
１４０℃以上では副反応の影響が大きくなるため好まし
くない。The temperature of the reduction reaction is preferably in the range of 60 ° C. to the reflux temperature of the reaction mixture.
0 ° C. is preferred. If the temperature is lower than 60 ° C, the reaction progresses slowly,
A temperature of 140 ° C. or higher is not preferred because the influence of side reactions increases.
【００１５】反応溶剤としては、亜鉛および硫酸と共存
させた時に不活性なものであれば何れも使用することが
可能であるが、アシロイン縮合反応をトルエン、キシレ
ン等の芳香族炭化水素中で行うことが多いため、これら
を使用するのが溶剤を置換する必要がなく、プロセス的
に好ましい。As the reaction solvent, any solvent can be used as long as it is inert when coexisting with zinc and sulfuric acid. The acyloin condensation reaction is carried out in an aromatic hydrocarbon such as toluene or xylene. Since these are often used, it is not necessary to replace the solvent, and it is preferable in terms of process.
【００１６】反応時間は、反応条件に従って適宜選定す
るとよい。The reaction time may be appropriately selected according to the reaction conditions.
【００１７】[0017]
【実施例】以下実施例により本発明方法を具体的に説明
する。本反応での生成物の同定および定量はガスクロマ
トグラフィーによって行った。また、着色度は、生成物
の５０wt％メタノール溶液を調製し、４３９nmでの吸光
度を１cmセルを用いて測定した。EXAMPLES The method of the present invention will be specifically described below with reference to examples. The product in this reaction was identified and quantified by gas chromatography. The degree of coloring was determined by preparing a 50 wt% methanol solution of the product and measuring the absorbance at 439 nm using a 1 cm cell.
【００１８】（実施例１）アシロイン１０.８g（４５mm
ol）を含有するアシロイン縮合反応生成物のトルエン溶
液４５.０gにガスクロ内部標準物質としてのエイコサン
５.０gおよび２２.６６g（３４７mmol）の亜鉛末を加え
た。(Example 1) 10.8 g of acyloin (45 mm)
ol) was mixed with 45.0 g of a toluene solution of an acyloin condensation reaction product containing 5.0 g of eicosane as an internal standard substance for gas chromatography and 22.66 g (347 mmol) of zinc dust.
【００１９】窒素通気下で撹拌しながら、反応液温が９
０℃に達したところで、２２規定濃度の硫酸２７.０ml
（２９７mmol）を１８ml／Hの速度で滴下した。滴下開
始から５時間後に加熱を止め、反応を停止した。While stirring under a stream of nitrogen, the temperature of the reaction solution is 9
When the temperature reached 0 ° C., 27.0 ml of 22N sulfuric acid was used.
(297 mmol) was added dropwise at a rate of 18 ml / H. Five hours after the start of the dropwise addition, the heating was stopped to stop the reaction.
【００２０】収率９２.８％でシクロペンタデカノンを
得た。 （実験例１〜６）Cyclopentadecanone was obtained with a yield of 92.8%. (Experimental Examples 1 to 6)
【００２１】２２規定濃度の硫酸の使用量を変えた以外
は実施例１と同様の実験を行った。結果を表１に示す。The same experiment as in Example 1 was conducted except that the amount of sulfuric acid having a specified concentration of 22 was changed. Table 1 shows the results.
【表１】 [Table 1]
【００２２】（実験例７〜１１） 硫酸の濃度を変化させ、０.５時間後のシクロペンタデ
カノン収率を測定した。硫酸の使用量は、常に２９７mm
olになるように、また、硫酸は全量を一時に加えた。上
記以外は実施例１と同様の方法で実験を行った。結果を
表２に示す。(Experimental Examples 7 to 11 ) The concentration of sulfuric acid was changed and the cyclopentadecanone yield after 0.5 hour was measured. The amount of sulfuric acid used is always 297mm
Also, the sulfuric acid was added all at once, so as to be ol. An experiment was conducted in the same manner as in Example 1 except for the above. Table 2 shows the results.
【表２】 [Table 2]
【００２３】（実施例１２〜１４） 亜鉛の使用量を変化させた以外は実施例１と同様の実験
を行った。結果を表３に示す。[0023] Except for changing the amount of (Example 1 2-1 4) zinc was subjected to the same experiment as in Example 1. Table 3 shows the results.
【表３】 [Table 3]
【００２４】（実施例２）アシロイン１２０.０g（５０
０mmol）を含有するアシロイン縮合反応生成物のトルエ
ン溶液５００.０gに２５１.８g（３８５０mmol）の亜鉛
末を加え、窒素通気下で撹拌（６００rpm）を行いなが
ら、反応液温が９０℃に達したところで、２２規定濃度
の硫酸３００ml（３３００mmol）を２００ml／Hの速度
で滴下した。滴下開始から６時間後に加熱を止め、反応
を停止し、反応液を分析したところ、収率９１.２％で
シクロペンタデカノンが生成していた。Example 2 120.0 g of acyloin (50
(25 mmol) of zinc powder was added to 500.0 g of a toluene solution of an acyloin condensation reaction product containing 0 mmol), and the temperature of the reaction solution reached 90 ° C. while stirring (600 rpm) under a nitrogen stream. By the way, 300 ml (3300 mmol) of 22N sulfuric acid was dropped at a rate of 200 ml / H. Six hours after the start of the dropwise addition, heating was stopped to stop the reaction, and the reaction solution was analyzed. As a result, cyclopentadecanone was produced in a yield of 91.2%.
【００２５】反応終了後、未反応の亜鉛と反応液とを瀘
別し、洗浄、濃縮して、粗シクロペンタデカノンを得
た。このシクロペンタデカノン純度は、９０.６％であ
った。After completion of the reaction, unreacted zinc and the reaction solution were separated by filtration, washed and concentrated to obtain crude cyclopentadecanone. The purity of this cyclopentadecanone was 90.6%.
【００２６】このシクロペンタデカノンの１０.０gをと
り、１mmHg以下の圧力で減圧蒸留した結果、着色度６.
２×１０-3のシクロペンタデカノン５.０２gを得た。The cyclopentadecanone (10.0 g) was subjected to distillation under reduced pressure at a pressure of 1 mmHg or less.
5.02 g of 2 × 10 -3 cyclopentadecanone was obtained.
【００２７】（比較例１）アシロイン縮合反応生成物５
３０.７ｋgおよびトルエン１０７８.４ｋgから成る還元
反応液に亜鉛粉末４５０ｋgを加えて撹拌した。窒素通
気下で、反応液温を７５℃とし、１２規定の塩酸１７２
０ｌを６４５ｌ／Hの速度で滴下した。滴下開始から１
６０分後の反応液を分析したところ、収率８２.４％で
シクロペンタデカノンが生成していた。この反応液から
未反応亜鉛を瀘別した後、反応液を洗浄、濃縮し、粗シ
クロペンタデカノンを得た。(Comparative Example 1) Acyloin condensation reaction product 5
450 kg of zinc powder was added to a reduction reaction solution consisting of 30.7 kg and 1078.4 kg of toluene, followed by stirring. The temperature of the reaction solution was set to 75 ° C. under a stream of nitrogen, and 172 of 12N hydrochloric acid was added.
0 l was added dropwise at a rate of 645 l / H. 1 from the start of dripping
Analysis of the reaction solution after 60 minutes revealed that cyclopentadecanone was produced in a yield of 82.4%. After unreacted zinc was filtered off from the reaction solution, the reaction solution was washed and concentrated to obtain crude cyclopentadecanone.
【００２８】この粗シクロペンタデカノンを１mmHg以下
の圧力で減圧蒸留することで着色度４１.６×１０-3の
シクロペンタデカノンを得た。このシクロペンタデカノ
ンは黄色に着色しているため、別途脱色処理を行うこと
が必要であった。The crude cyclopentadecanone was distilled under reduced pressure at a pressure of 1 mmHg or less to obtain cyclopentadecanone having a coloring degree of 41.6 × 10 −3 . Since this cyclopentadecanone was colored yellow, it was necessary to separately perform a decolorizing treatment.
【００２９】以上の結果から、１８規定以上２６規定未
満の濃度の硫酸を用いると還元収率が向上し、着色の問
題も解決できることが分かる。From the above results, it can be seen that the use of sulfuric acid having a concentration of 18 N or more and less than 26 N improves the reduction yield and solves the problem of coloring.
【００３０】[0030]
【発明の効果】本発明の方法は、着色度の低い大環状ケ
トンを高収率で合成することが可能であり、生産効率を
格段に高めることができる効果を奏するものである。According to the method of the present invention, it is possible to synthesize a macrocyclic ketone having a low degree of coloration at a high yield, and it is possible to significantly improve the production efficiency.
Claims (2)
ジエステル化物をアシロイン縮合反応により分子内環化
し、得られたアシロイン縮合反応生成物を還元して炭素
数１２〜１８の大環状ケトンを製造する方法において、
前記還元に際し、１４規定を超え２６規定未満の濃度の
硫酸と亜鉛末とを用いることを特徴とする大環状ケトン
の製造方法。1. A macrocyclic ketone having 12 to 18 carbon atoms by subjecting a diester of a linear alkane diacid having 12 to 18 carbon atoms to intramolecular cyclization by an acyloin condensation reaction and reducing the resulting acyloin condensation reaction product. In the method for producing
A method for producing a macrocyclic ketone, wherein sulfuric acid and zinc dust having a concentration of more than 14 N and less than 26 N are used in the reduction.
以上２２規定以下の濃度の硫酸を用いることを特徴とすCharacterized in that sulfuric acid having a concentration of at least 22 norm is used.
る大環状ケトンの製造方法。A method for producing a macrocyclic ketone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03341750A JP3087921B2 (en) | 1991-12-02 | 1991-12-02 | Method for producing macrocyclic ketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03341750A JP3087921B2 (en) | 1991-12-02 | 1991-12-02 | Method for producing macrocyclic ketone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05155802A JPH05155802A (en) | 1993-06-22 |
| JP3087921B2 true JP3087921B2 (en) | 2000-09-18 |
Family
ID=18348477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03341750A Expired - Fee Related JP3087921B2 (en) | 1991-12-02 | 1991-12-02 | Method for producing macrocyclic ketone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3087921B2 (en) |
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| US7034188B2 (en) | 2003-01-24 | 2006-04-25 | Japan Energy Corporation | Production method of ketone compound |
| JP2014040946A (en) * | 2012-08-21 | 2014-03-06 | Hoshizaki Electric Co Ltd | Cold/warm storage device |
| DE102015221529A1 (en) | 2015-11-03 | 2017-05-04 | Cht R. Beitlich Gmbh | Continuous process for reactions with finely divided alkali metal dispersions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4649743B2 (en) * | 2001-01-26 | 2011-03-16 | Ｊｘ日鉱日石エネルギー株式会社 | Process for producing macrocyclic ketone compounds |
| JP2008222596A (en) * | 2007-03-09 | 2008-09-25 | Asahi Kasei Chemicals Corp | Method for producing dicarboxylic acid derivative containing cis-double bond |
| CN102144778B (en) * | 2010-11-25 | 2015-08-05 | 高旌 | A kind of preparation method of mind-refreshing oral liquid |
-
1991
- 1991-12-02 JP JP03341750A patent/JP3087921B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6759557B2 (en) | 2001-06-08 | 2004-07-06 | Takasago International Corporation | Melanin production inhibitors and skincare products containing such inhibitors |
| US7034188B2 (en) | 2003-01-24 | 2006-04-25 | Japan Energy Corporation | Production method of ketone compound |
| JP2014040946A (en) * | 2012-08-21 | 2014-03-06 | Hoshizaki Electric Co Ltd | Cold/warm storage device |
| DE102015221529A1 (en) | 2015-11-03 | 2017-05-04 | Cht R. Beitlich Gmbh | Continuous process for reactions with finely divided alkali metal dispersions |
| WO2017076744A1 (en) | 2015-11-03 | 2017-05-11 | Cht R. Beitlich Gmbh | Continuous method for reactions with fine-particulate alkali metal dispersions |
| US10494486B2 (en) | 2015-11-03 | 2019-12-03 | CHT Germany GmbH | Continuous method for reactions with fine-particulate alkali metal dispersions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05155802A (en) | 1993-06-22 |
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