JPS5965031A - Preparation of 2-cis-tert-butylcyclohexanol - Google Patents
Preparation of 2-cis-tert-butylcyclohexanolInfo
- Publication number
- JPS5965031A JPS5965031A JP57173966A JP17396682A JPS5965031A JP S5965031 A JPS5965031 A JP S5965031A JP 57173966 A JP57173966 A JP 57173966A JP 17396682 A JP17396682 A JP 17396682A JP S5965031 A JPS5965031 A JP S5965031A
- Authority
- JP
- Japan
- Prior art keywords
- cis
- butylcyclohexanol
- tert
- formula
- hydrogen
- 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
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)
Abstract
Description
【発明の詳細な説明】
本発明は、香料物質として重装な公知化合物２−シス−
ｔ−ブチルシクロヘキサノールの製法に関し、従来法に
比して顕著に改善された収率をもって、トランス一体に
比して香気的に遥かに優れたシス一体を選択的に生成せ
しめることのできる、オル）−１−ブチルフェノールの
接触水素還元による２−シス−ｔ−ブチルシクロヘキサ
ノールの選択的製法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides the use of heavy known compounds 2-cis-
Regarding the method for producing t-butylcyclohexanol, it is possible to selectively produce cis-monochrome which has a significantly improved yield compared to conventional methods and which has a far superior aroma compared to trans-monolysis. )-1-Butylphenol selectively produced by catalytic hydrogen reduction of 2-cis-t-butylcyclohexanol.
更に詳しくは、本発明は下記式（２）
で表わされるオルト−６−ブチルフェノールを、ラネー
コバルト触媒の存在下に、接触水素還元することを特徴
とする下記式（１）
０１１
で表わされる２−シス−ｔ−ブチルシクロヘキサノール
の製法に関する。More specifically, the present invention is characterized in that ortho-6-butylphenol represented by the following formula (2) is subjected to catalytic hydrogen reduction in the presence of a Raney cobalt catalyst. The present invention relates to a method for producing cis-t-butylcyclohexanol.
上記式（１）で表わされる２−シス−ｔ−ブチルシクロ
ヘキサノールは、その異性体である２−トランス−ｔ−
ブチルシクロヘキサノールに較べて香気的に遥かに優れ
た香料物質である。又、該式（１）化合物は例えば２−
シス−ｔ−ブチルシクロヘキシルアセテートの如き他の
香料物質の製造原料としても軍費な化合物である。2-cis-t-butylcyclohexanol represented by the above formula (1) is its isomer 2-trans-t-
It is a fragrance substance with a far superior aroma compared to butylcyclohexanol. Further, the compound of formula (1) is, for example, 2-
It is also an expensive compound as a raw material for the production of other fragrance substances such as cis-t-butylcyclohexyl acetate.
従って、式（２）オル）−１−ブチルフェノールを接触
水素還元して式（１）化合物を製造するに際し、トラン
ス一体の生成を抑制し、シス一体の生成を選択的に進行
させることができれば、すなわち、工業的に分離困難な
トランス一体の生成を回避し、香気的に優れたシス一体
を選択的に生成させることが可能な方法が開発できれば
、工業的に極めて有利である。Therefore, when producing the compound of formula (1) by catalytic hydrogen reduction of (ol)-1-butylphenol (formula (2)), if it is possible to suppress the formation of trans-integrated structures and selectively promote the formation of cis-integrated ones, That is, it would be extremely advantageous industrially if a method could be developed that can selectively produce cis-integrated products that are superior in aroma while avoiding the production of trans-integrated products that are difficult to separate industrially.
製造することは行われている。そして該接触水素還元反
応に用いる触媒としてラネーニッケルが専ら利用され、
他に、より高価につくがノクラヅウムカーテン、ロソウ
ムカーボン、白金カーボンナトの資金属カーがン触媒の
使用も知られている。Manufacturing is being done. Raney nickel is exclusively used as a catalyst for the catalytic hydrogen reduction reaction,
Other metal carbon catalysts, although more expensive, are also known, such as nocladium curtain, lotum carbon, and platinum carbonate.
しかしながら、上記従来法に於てはシス一体とトランス
一体との生成割合は、シス：トランス＝５０〜８０：５
０〜２０程度が普通であって、最もよくてもシス一体の
選択率は高さ８０％前後である。斯くて、得られる生成
物は、実質的に香気に悪影響を与える量のトランス一体
を含有する混合物の形でしか得られず、このトランス一
体は工業的に実施可能なｌ’４製方法では分離できない
ため、香気的に満足し得る目的物を製、農することは極
めて困雛である。However, in the above conventional method, the production ratio of cis-integrated and trans-integrated is cis:trans = 50 to 80:5.
It is usually about 0 to 20, and at best the cis selectivity is around 80%. The resulting product is thus obtained only in the form of a mixture containing substantially aroma-adverse amounts of trans-integrates, which cannot be separated in industrially viable l'4 production processes. Therefore, it is extremely difficult to produce and farm products that are aromatically satisfying.
本発明者等は、式（２）化合物から式（１）シス一体を
選択的に製造できる方法を開発すべく研究を行ってきた
。The present inventors have conducted research to develop a method for selectively producing the cis monomer of formula (1) from the compound of formula (2).
その結果、従来全く使用されたことがないし、その使用
が示唆されたこともないシネ−コバルト触媒を用いて上
記の接触水素還元反応を行うことによって、約９８％以
上の格段に優れた選択率をもって高収率で、実質的に不
都合なトランス一体を含有しない香気的に遥かに優れ７
’（２−シス−ｔ−ブチルシクロヘキサノールが製造で
きることを発見した。As a result, by carrying out the above catalytic hydrogen reduction reaction using a cine-cobalt catalyst, which has never been used in the past and whose use has never been suggested, an extremely excellent selectivity of about 98% or more was achieved. It has a high yield and does not substantially contain any undesirable trans components and has a much superior aroma7.
(We discovered that 2-cis-t-butylcyclohexanol can be produced.
従って、本発明の目的は式（１）２−シス−ｔ−ブチル
シクロヘキサノールを製造する改善方法を提供するにあ
る。Accordingly, it is an object of the present invention to provide an improved method for producing 2-cis-t-butylcyclohexanol of formula (1).
本発明の上記目的及び史に多くの他の目的ならびに利点
は、以下の記載から一層明らかとなるであろう。The above objects and numerous other objects and advantages of the present invention will become more apparent from the following description.
本発明方法によれば、上記式（２）で表わされるオルト
−ｔ−ブチルフェノールをラネーコバルト触媒の存在下
に、接触水素還元して、９８％以上の高選択率をもって
上記式（１）で表わされる２−シス−ｔ−ブチルシクロ
ヘキサノールを高収率で容易に製造することが出来る。According to the method of the present invention, ortho-t-butylphenol represented by the above formula (2) is catalytically reduced with hydrogen in the presence of a Raney cobalt catalyst, and the ortho-t-butylphenol represented by the above formula (1) is reduced with a high selectivity of 98% or more. 2-cis-t-butylcyclohexanol can be easily produced in high yield.
本発明方法実施の一態様によれば、例えばオートクレー
ブ中、上記式（２）で表わされるオル）−１−ブチルフ
ェノールを好ましくは不活性有機浴媒中、ラネーコバル
ト触媒の存在下に水素と接触せしめて上記式（１）で表
わされる２−シス−ｔ−ブチルシクロヘキサノールに容
易に変換できる。According to one embodiment of the method of the invention, or)-1-butylphenol of formula (2) above is contacted with hydrogen in the presence of a Raney cobalt catalyst, preferably in an inert organic bath medium, for example in an autoclave. It can be easily converted into 2-cis-t-butylcyclohexanol represented by the above formula (1).
上記反応に於ける水素圧としては、例えば約１ｋｌ？Ｚ
ｃ１１〜約１００ｋｌＦ／ｃｄ程度の範囲好ましくけ約
ｓ ｋｇ ／ ａｌ 〜約５０ ｋｙ ／ ｃｄ程度の
範囲が例示でき、又、反応温度としては、例えば約１０
０Ｃ〜約２００Ｃ程度の範囲好ましくは約１２０Ｃ〜約
１８０Ｃ程度の範囲の温度を例示することができる。The hydrogen pressure in the above reaction is, for example, about 1 kl? Z
The range of c11 to about 100 klF/cd, preferably about s kg/al to about 50 ky/cd, is exemplified, and the reaction temperature is, for example, about 10 klF/cd.
For example, the temperature may be in the range of about 0C to about 200C, preferably about 120C to about 180C.
又、不活性有機溶媒を用いて反応を行う場合の溶媒とし
ては、例えばヘキサン、ベンゼン、トルエン、メタノー
ル、エタノール、などの如キ炭化水素類、アルコール類
などを例示できる。これらの有機溶媒の使用量には特別
な制約はないが、例えば上記式（２）化合物に対し、約
１〜約２００重量％稈度の範囲が例示できる。Further, examples of the solvent when carrying out the reaction using an inert organic solvent include hydrocarbons such as hexane, benzene, toluene, methanol, and ethanol, and alcohols. There is no particular restriction on the amount of these organic solvents used, but for example, the culm may be in the range of about 1 to about 200% by weight based on the compound of formula (2) above.
又、ラネーコバルト触媒の使用量としては、式（２）化
合物に対し、例えば、約０．０１〜約１０重量％程度、
好ましくは、約０．５〜約５重量％程度の範囲が例示で
きる。又、炭酸水素ナトリウム、炭酸ナトリウム等の弱
′アルカリ性物質を原料に対して、たとえば約０．１％
〜約５重量％程度の量で反応素に添加して接触還元する
こともできる。Further, the amount of Raney cobalt catalyst used is, for example, about 0.01 to about 10% by weight, based on the compound of formula (2),
Preferably, the range is about 0.5 to about 5% by weight. In addition, a weakly alkaline substance such as sodium hydrogen carbonate or sodium carbonate may be added to the raw material by approximately 0.1%, for example.
Catalytic reduction can also be carried out by adding it to the reactant in an amount of about 5% by weight.
反応時間は、理論量の水素を吸収した時点で終了すれば
良く、水素圧、温度などによっても適宜に選択されるが
、例えば、約１〜約８時間程度の範囲を好ましく例示す
ることができる。The reaction time may be terminated when the theoretical amount of hydrogen is absorbed, and is appropriately selected depending on the hydrogen pressure, temperature, etc., and is preferably in the range of about 1 to about 8 hours, for example. .
反応終了後は、触媒を除去して、例えば減圧蒸留の如き
精製手段により高純度、高収率で上記式（１）化合物を
容易に得ることができる。After the reaction is completed, the catalyst is removed and the compound of formula (1) can be easily obtained with high purity and high yield by purification means such as vacuum distillation.
以下実施例により、本発明方法製飾の数例について更に
詳細に説明する。Hereinafter, several examples of the decoration method of the present invention will be explained in more detail with reference to Examples.
実施例１
０．３１オートクレーブに、ｏ−ｔ−ブチルフェノール
＝５０ｆ及びラネーコバルト触媒：ｔ、ｏｆを仕込む。Example 1 A 0.31-liter autoclave was charged with o-t-butylphenol = 50f and Raney cobalt catalyst: t, of.
水素圧ｉ ５０ ｋｇ／ｃｒｌ、温度；ｔｓｏｃの条件
で接触木酢反応を行った。約２時間で理論量の水素を吸
収した。反応容器内よシ生成物を取り出しガスクロマ、
トゲラフイーで分析すると９＆５％の２−シス−ｔ−ブ
チルシクロヘキサノールと１．５％の２−トランス−ｔ
−ブチルシクロヘキサノールを含有している事が判明し
た。上記反応物をトルエンに溶解し、触媒を炉別した後
溶媒を回収し、２−シス−ｔ−ブチルシクロヘキサノー
ル４９２（収率：９４％）を得た。The catalytic wood vinegar reaction was carried out under the conditions of hydrogen pressure i 50 kg/crl and temperature tsoc. The theoretical amount of hydrogen was absorbed in about 2 hours. Remove the product from the reaction vessel and use a gas chroma.
Analysis by Togelafy shows 9&5% 2-cis-t-butylcyclohexanol and 1.5% 2-trans-t.
- It was found that it contained butylcyclohexanol. The above reaction product was dissolved in toluene, the catalyst was removed in a furnace, and the solvent was recovered to obtain 2-cis-t-butylcyclohexanol 492 (yield: 94%).
実施例２
実ｉ崩例１のオートクレーブに、ｏ−ｔ−ブチルフェノ
ール：２５ｆＸｎ−ヘキサン：２５ｆ及びラネーコバル
ト触媒：ｏ、ｓｔを仕込む。実施例１と同、俺の条件で
接触水添を行った。１．５時間で理論量の水素を吸収し
た。触媒を炉別した後溶媒を１１ｆｉ！収Ｌ、２−シス
−ｔ−ブチルシクロヘキサノール：２４Ｆを得た。この
方法による２−シス−ｔ−ブチルシクロヘキサノールの
純度はガスクロマトグラフィー分析により９８．７％で
あった。Example 2 Example I Reconstruction The autoclave of Example 1 was charged with o-t-butylphenol: 25fXn-hexane: 25f and Raney cobalt catalyst: o, st. Catalytic hydrogenation was carried out under the same conditions as in Example 1. The theoretical amount of hydrogen was absorbed in 1.5 hours. After the catalyst was separated from the furnace, the solvent was heated to 11fi! 2-cis-t-butylcyclohexanol:24F was obtained. The purity of 2-cis-t-butylcyclohexanol obtained by this method was 98.7% by gas chromatography analysis.
比較例１
実施例１に於いて、ラネーコ・ぐルト触媒の代りにラネ
ーニッケル触媒を用いた他は、実施例１と全く同一方法
によシ実施した。その結果、２−シス−ｔ−ブチルシク
ロヘキサノールを５０ ｒ 得た。Comparative Example 1 This was carried out in exactly the same manner as in Example 1, except that a Raney nickel catalyst was used in place of the Raneyco-Gult catalyst. As a result, 50 r of 2-cis-t-butylcyclohexanol was obtained.
このものの純度は、ガスクロマトグラフィー分析により
７９％であった。The purity of this product was 79% by gas chromatography analysis.
特許出願人 長谷川香料株式会社 代 理 人 弁理士 小田島 平 吉 （ほか１名）Patent applicant: Hasegawa Fragrance Co., Ltd. Representative Patent Attorney Taikichi Odashima (1 other person)
Claims (1)
コバルト触媒の存在下に、接触水素還元することを特徴
とする下記式（１） で表わされる２−シス−ｔ−ブチルシクロヘキサノール
の製法。[Scope of Claims] 1. 2 represented by the following formula (1), characterized in that or)-1-butylphenol represented by the following formula (2) is subjected to catalytic hydrogen reduction in the presence of a Raney cobalt catalyst. -Production method of cis-t-butylcyclohexanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57173966A JPS5965031A (en) | 1982-10-05 | 1982-10-05 | Preparation of 2-cis-tert-butylcyclohexanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57173966A JPS5965031A (en) | 1982-10-05 | 1982-10-05 | Preparation of 2-cis-tert-butylcyclohexanol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5965031A true JPS5965031A (en) | 1984-04-13 |
| JPS6355498B2 JPS6355498B2 (en) | 1988-11-02 |
Family
ID=15970332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57173966A Granted JPS5965031A (en) | 1982-10-05 | 1982-10-05 | Preparation of 2-cis-tert-butylcyclohexanol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5965031A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002309286A (en) * | 2001-04-17 | 2002-10-23 | Kao Corp | Perfume composition |
| US6489520B2 (en) | 2000-12-11 | 2002-12-03 | Haarmann & Reimer Gmbh | Process for the preparation of cis-2-tertiary-butylcyclohexanol by catalytic hydrogenation of 2-tertiary-butylphenol |
| JP2003055312A (en) * | 2001-08-10 | 2003-02-26 | Kao Corp | Optically active ester |
-
1982
- 1982-10-05 JP JP57173966A patent/JPS5965031A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6489520B2 (en) | 2000-12-11 | 2002-12-03 | Haarmann & Reimer Gmbh | Process for the preparation of cis-2-tertiary-butylcyclohexanol by catalytic hydrogenation of 2-tertiary-butylphenol |
| JP2002309286A (en) * | 2001-04-17 | 2002-10-23 | Kao Corp | Perfume composition |
| JP2003055312A (en) * | 2001-08-10 | 2003-02-26 | Kao Corp | Optically active ester |
| JP4707281B2 (en) * | 2001-08-10 | 2011-06-22 | 花王株式会社 | Optically active ester |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6355498B2 (en) | 1988-11-02 |
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