JPH08198800A - Production of 3-substituted-3-methylbutanoic acid - Google Patents
Production of 3-substituted-3-methylbutanoic acidInfo
- Publication number
- JPH08198800A JPH08198800A JP7024689A JP2468995A JPH08198800A JP H08198800 A JPH08198800 A JP H08198800A JP 7024689 A JP7024689 A JP 7024689A JP 2468995 A JP2468995 A JP 2468995A JP H08198800 A JPH08198800 A JP H08198800A
- Authority
- JP
- Japan
- Prior art keywords
- hydroxy
- methyl
- acid
- methylbutanoic acid
- reaction
- 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
【０００１】[0001]
【産業上の利用分野】本発明は３−ヒドロキシ−３−メ
チルブタン酸及び／又は３−メチル−３−メトキシブタ
ン酸の製造方法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing 3-hydroxy-3-methylbutanoic acid and / or 3-methyl-3-methoxybutanoic acid.
【０００２】本発明により提供される３−ヒドロキシ−
３−メチルブタン酸及び／又は３−メチル−３−メトキ
シブタン酸（以下、３−ヒドロキシ−３−メチルブタン
酸及び／又は３−メチル−３−メトキシブタン酸を３−
置換−３−メチルブタン酸と称することがある）は、例
えば、脱水反応あるいは脱メタノール反応に付すること
によりセネシオン酸に誘導でき、医薬、香料、農薬など
の合成原料などとして有用である。3-Hydroxy-provided by the present invention
3-methylbutanoic acid and / or 3-methyl-3-methoxybutanoic acid (hereinafter 3-hydroxy-3-methylbutanoic acid and / or 3-methyl-3-methoxybutanoic acid
Substituted-3-methylbutanoic acid) may be converted into senecioic acid by subjecting it to dehydration reaction or demethanol reaction, and is useful as a synthetic raw material for medicines, fragrances, agricultural chemicals and the like.
【０００３】[0003]
【従来の技術】従来、３−ヒドロキシ−３−メチルブタ
ン酸の製造方法として下記のような方法が知られてい
る。すなわち、 ４，４−ジメチル−１，３−ジオキサンを、硝酸触媒
下で酸化反応する方法（Ａｒｍ．Ｋｈｉｍ．Ｚｈ．，４
４（７−８），４４３，（１９９１）） ３−メチル−３−ブテン−１−オールを、硝酸触媒下
で水和反応及び酸化反応する方法（Ｋｈｉｍ．Ｐｒｉ
ｒ．Ｓｏｅｄｉｎ．，（３），３１３，１９９１） ４−ヒドロキシ−４−メチル−２−ペンタノンを、次
亜塩素酸ソーダで酸化反応する方法（米国特許第４９９
２４７０号明細書） ４−ヒドロキシ−４−メチル−１−ペンテンを、過マ
ンガン酸カリウムで酸化反応する方法（Ｊ．Ｐｒａｋ
ｔ．Ｃｈｅｍ．，（２）２３（１８８１）２０６） アセトンとクロロ酢酸エチルを亜鉛触媒下に縮合反応
し、続いてアルカリ加水分解する方法（Ｚｈ．Ｒｕｓ
ｓ．Ｆｉｚ．−Ｋｈｉｍ．Ｏ−ｖａ．２２（１８９０）
４７） ｔ−ブタノール、一酸化炭素及び過酸化水素の混合物
を、硫酸鉄存在下に反応する方法（Ｊ．Ａｍ．Ｃｈｅ
ｍ．Ｓｏｃ．，（１９５８）８０，２８８２） アセトンとケテンの反応でβ−イソバレロラクトンを
得、続いてこのラクトン環を開く方法（Ｊ．Ａｍ．Ｃｈ
ｅｍ．Ｓｏｃ．，（１９５４）７６，４８６）等が知ら
れている。2. Description of the Related Art Conventionally, the following method has been known as a method for producing 3-hydroxy-3-methylbutanoic acid. That is, a method of oxidizing 4,4-dimethyl-1,3-dioxane under a nitric acid catalyst (Arm. Khim. Zh., 4
4 (7-8), 443, (1991)) 3-Methyl-3-buten-1-ol is subjected to a hydration reaction and an oxidation reaction under a nitric acid catalyst (Khim. Pri.
r. Soedin. , (3), 313, 1991) A method of oxidizing 4-hydroxy-4-methyl-2-pentanone with sodium hypochlorite (US Pat. No. 499).
No. 2470) Method for oxidizing 4-hydroxy-4-methyl-1-pentene with potassium permanganate (J. Prak)
t. Chem. , (2) 23 (1881) 206) A method of subjecting acetone and ethyl chloroacetate to a condensation reaction in the presence of a zinc catalyst, followed by alkali hydrolysis (Zh. Rus
s. Fiz. -Khim. O-va. 22 (1890)
47) A method of reacting a mixture of t-butanol, carbon monoxide and hydrogen peroxide in the presence of iron sulfate (J. Am. Che.
m. Soc. , (1958) 80 , 2882) β-isovalerolactone is obtained by the reaction of acetone with ketene, and then the lactone ring is opened (J. Am. Ch.
em. Soc. , (1954) 76 , 486) and the like are known.
【０００４】[0004]
【発明が解決しようとする課題】上記のように、３−ヒ
ドロキシ−３−メチルブタン酸の製造方法は数多く知ら
れている。しかしながら、、の方法は、酸化反応触
媒として硝酸を用いるため、反応装置の腐食、酸化窒素
の副生等種々の危険性をはらんでいる。、、の方
法は、原料が高価であり、特に、及びでは多量の有
毒重金属を使用しなくてはならない。の方法は、一酸
化炭素を用いるので非常に危険であり、また収率も低
い。更に、の方法は、原料のケテンが常温常圧で気体
であり、取り扱いが難しい。As described above, many methods for producing 3-hydroxy-3-methylbutanoic acid are known. However, since the method of (1) uses nitric acid as the oxidation reaction catalyst, there are various risks such as corrosion of the reactor and by-product of nitric oxide. In the methods of ,, and, the raw materials are expensive, and particularly in and, a large amount of toxic heavy metals must be used. Since the method of (1) uses carbon monoxide, it is very dangerous and the yield is low. Further, in the method (1), the ketene as a raw material is a gas at room temperature and atmospheric pressure, and is difficult to handle.
【０００５】このように、従来の製造方法はそれぞれ問
題点を有しており、３−ヒドロキシ−３−メチルブタン
酸の製法として満足のいく製造方法が確立していないの
が現状である。As described above, each of the conventional production methods has problems, and at present, a satisfactory production method for 3-hydroxy-3-methylbutanoic acid has not been established.
【０００６】また、３−メチル−３−メトキシブタン酸
は、医薬、農薬、例えば第一菊酸の原料であるセネシオ
ン酸の中間体化合物として有用であるにもかかわらず、
その合成法は知られておらず、新規な化合物である。Although 3-methyl-3-methoxybutanoic acid is useful as an intermediate compound for senecioic acid, which is a raw material for pharmaceuticals and agricultural chemicals such as primary chrysanthemic acid,
The synthetic method is unknown and it is a novel compound.
【０００７】本発明の課題は、工業的に入手可能な原料
から、安価に、しかも容易な製造方法で工業的に有用性
の高い、３−置換−３−メチルブタン酸、及びその製造
方法を提供することである。An object of the present invention is to provide a 3-substituted-3-methylbutanoic acid, which is industrially useful with a low-cost and easy production method, from a commercially available raw material, and a production method thereof. It is to be.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、上記課題
を解決するために鋭意検討を重ねた結果、３−ヒドロキ
シ−３−メチルブタノール及び／又は３−メチル−３−
メトキシブタノールを水の存在下に白金系あるいはパラ
ジウム系触媒により酸素酸化することにより、３−ヒド
ロキシ−３−メチルブタン酸及び／又は３−メチル−３
−メトキシブタン酸を高収率で容易に製造しうることを
見出し、本発明に至った。The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, 3-hydroxy-3-methylbutanol and / or 3-methyl-3-
3-hydroxy-3-methylbutanoic acid and / or 3-methyl-3 can be obtained by oxidizing methoxybutanol with oxygen in the presence of water using a platinum-based or palladium-based catalyst.
The inventors have found that -methoxybutanoic acid can be easily produced in high yield, and have reached the present invention.
【０００９】本発明において原料として用いられる３−
ヒドロキシ−３−メチルブタノール及び／又は３−メチ
ル−３−メトキシブタノール（以下、３−ヒドロキシ−
３−メチルブタノール及び／又は３−メチル−３−メト
キシブタノールを３−置換−３−メチルブタノールある
いは基質と称することがある）は、イソブテンとホルム
アルデヒドとから合成される４，４−ジメチル−１，３
−ジオキサンをイオン交換樹脂の存在下メタノールを溶
媒に用いて分解することにより容易に製造することがで
きる（特開昭５３−１２４２０５号公報）し、またイソ
ブテンとホルマリンから工業的に製造され、市販されて
いる。（昭和５２年度第２回新製品・新技術紹介発表講
演会 講演要旨「３−メチル−３−メトキシブタノール
新規なグリコールエーテル系溶剤“ソルフィッ
ト”」） 本発明は、３−置換−３−メチルブタノールを水の存在
下に白金系あるいはパラジウム系触媒により酸素酸化す
る方法に関するものであるが、本発明において使用する
酸化反応触媒としては、白金、あるいはパラジウムの単
独、あるいは白金、あるいはパラジウムのいずれかと、
他の金属、例えば鉛、テルル、ビスマス、ルテニウム、
セレン、セリウムが一種もしくはそれ以上で同時に担持
されているものが使用できる。金属の担体としては、活
性炭、アルミナ等があげられる。3 used as a raw material in the present invention
Hydroxy-3-methylbutanol and / or 3-methyl-3-methoxybutanol (hereinafter 3-hydroxy-
3-methylbutanol and / or 3-methyl-3-methoxybutanol may be referred to as 3-substituted-3-methylbutanol or a substrate) is 4,4-dimethyl-1, which is synthesized from isobutene and formaldehyde. Three
-Dioxane can be easily produced by decomposing methanol in a solvent in the presence of an ion exchange resin (JP-A-53-124205), and is industrially produced from isobutene and formalin, and is commercially available. Has been done. (Summary of the 2nd New Product / New Technology Presentation Lecture in 1977) "3-Methyl-3-methoxybutanol New glycol ether solvent" Solfit "") The present invention is 3-substituted-3-methyl. The present invention relates to a method of oxygen-oxidizing butanol in the presence of water with a platinum-based or palladium-based catalyst, and the oxidation reaction catalyst used in the present invention includes platinum or palladium alone, or platinum or palladium. ,
Other metals such as lead, tellurium, bismuth, ruthenium,
It is possible to use one in which selenium and cerium are supported alone or in combination. Examples of the metal carrier include activated carbon and alumina.
【００１０】白金あるいはパラジウムの担持量は、１〜
１０重量％の範囲が好ましい。白金あるいはパラジウム
のいずれかと他の金属を同時に担持する場合、白金ある
いはパラジウムの担持量は、１〜１０重量％の範囲が好
ましく、他の金属の担持量は、１〜１０重量％の範囲が
好ましい。The amount of platinum or palladium supported is 1 to
A range of 10% by weight is preferred. When either platinum or palladium and another metal are supported simultaneously, the supported amount of platinum or palladium is preferably in the range of 1 to 10% by weight, and the supported amount of the other metal is preferably in the range of 1 to 10% by weight. .
【００１１】酸化反応触媒の量は反応液に対して好まし
くは０．０１〜１０重量％の範囲、より好ましくは１〜
５重量％の範囲が適当である。The amount of the oxidation reaction catalyst is preferably in the range of 0.01 to 10% by weight, more preferably 1 to 10% by weight based on the reaction solution.
A range of 5% by weight is suitable.
【００１２】本発明における酸素酸化反応では、水の存
在が必須である。用いる水の量は、基質に対して９重量
倍〜０．２５重量倍の範囲が好ましく、より好ましくは
９重量倍〜１重量倍の範囲である。The presence of water is essential for the oxygen oxidation reaction in the present invention. The amount of water used is preferably in the range of 9 times to 0.25 times the weight of the substrate, more preferably in the range of 9 times to 1 times the weight.
【００１３】本発明は酸素ガス雰囲気下で行なう。酸素
源としては純酸素の他に窒素あるいはアルゴン等の不活
性ガスと酸素の混合ガスも用いることが出来る。なお、
混合ガスを用いる場合、不活性ガスを系外に排出する必
要がある。The present invention is carried out in an oxygen gas atmosphere. As the oxygen source, a mixed gas of oxygen and an inert gas such as nitrogen or argon can be used in addition to pure oxygen. In addition,
When using a mixed gas, it is necessary to discharge the inert gas out of the system.
【００１４】酸素酸化反応の温度は５０〜１２０℃の範
囲が好ましく、より好ましくは７０〜９０℃の範囲であ
る。また酸素酸化反応の圧力は、１〜３０ｋｇ／ｃｍ2
の範囲が好ましく、より好ましくは１〜１０ｋｇ／ｃｍ
2 の範囲である。The temperature of the oxygen oxidation reaction is preferably in the range of 50 to 120 ° C, more preferably 70 to 90 ° C. The pressure of the oxygen oxidation reaction is 1 to 30 kg / cm 2
Is preferable, and more preferably 1 to 10 kg / cm
It is in the range of 2 .
【００１５】反応の追跡は、反応液をそのままＧＬＣ分
析することで可能である。The reaction can be traced by GLC analysis of the reaction solution as it is.
【００１６】上記の方法で生成した目的物は、反応液か
ら酸化反応触媒をろ別した後に、副生成物を有機溶媒を
用いて抽出分離し、水を蒸留分離することにより単離さ
れる。このようにして単離された目的物は、段数を有す
る蒸留塔で減圧蒸留することによって更に高純度化する
事が出来る。The target product produced by the above method is isolated by filtering off the oxidation reaction catalyst from the reaction solution, extracting and separating the by-product with an organic solvent, and separating water by distillation. The target product thus isolated can be further purified by vacuum distillation in a distillation column having a plate number.
【００１７】[0017]
【実施例】以下、実施例により本発明を具体的に説明す
るが、本発明はこれらの実施例に限定されるものではな
い。EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.
【００１８】実施例１ ３−ヒドロキシ−３−メチルブタノール３０ｇ（２８８
ｍｍｏｌ）、蒸留水２７０ｇ、５％Ｐｔ、５％Ｂｉ／カ
ーボン３ｇを５００ｍｌ、ＳＵＳ製オートクレーブに仕
込み、空気圧９ｋｇ／ｃｍ2 、８０℃で２０時間撹拌を
行なった。この時、排気は１０Ｌ／ｈｒで行なった。反
応終了後冷却し、触媒を濾別し、更に水をエヴァポレー
ターで留去することにより粗３−ヒドロキシ−３−メチ
ルブタン酸４２．４ｇ（反応収率９７％）を得た。Example 1 30 g (288) of 3-hydroxy-3-methylbutanol
mmol), distilled water 270 g, 5% Pt, 5% Bi / carbon 3 g, 500 ml, were charged into an SUS autoclave and stirred at 80 ° C. for 20 hours at an air pressure of 9 kg / cm 2 . At this time, evacuation was performed at 10 L / hr. After completion of the reaction, the mixture was cooled, the catalyst was filtered off, and water was distilled off by an evaporator to obtain 42.4 g of crude 3-hydroxy-3-methylbutanoic acid (reaction yield 97%).
【００１９】なお、組成生物４０．０ｇをビブリュウ塔
（論理段数約３段）で減圧蒸留を行ない、沸点１１３〜
１１８℃／２〜４ｍｍＨｇを有する純度９７％の目的物
２７．６ｇを得た。このものはＮＭＲ分析の結果から、
３−ヒドロキシ−３−メチルブタン酸であることを確認
した。It is to be noted that 40.0 g of the composition organisms was subjected to vacuum distillation in a Bibreu tower (about 3 logical stages) to obtain a boiling point of 113-
27.6 g of a target substance having a purity of 97% and having 118 ° C./2 to 4 mmHg was obtained. This is the result of NMR analysis,
It was confirmed to be 3-hydroxy-3-methylbutanoic acid.
【００２０】1Ｈ−ＮＭＲ（ＣＤＣｌ3 ，ｐｐｍ）：
１．３４０（ｓ，６Ｈ）、２．５６３（ｓ，２Ｈ） 1 H-NMR (CDCl 3 , ppm):
1.340 (s, 6H), 2.563 (s, 2H)
【００２１】実施例２ ３−メチル−３−メトキシブタノール３０ｇ（２５４ｍ
ｍｏｌ）、蒸留水２７０ｇ、５％Ｐｔ、５％Ｂｉ／カー
ボン３ｇを５００ｍｌ、ＳＵＳ製オートクレーブに仕込
み、空気圧９ｋｇ／ｃｍ2 、８０℃で２０時間撹拌を行
なった。この時、排気は１０Ｌ／ｈｒで行なった。反応
終了後冷却し、触媒を濾別し、更に水をエヴァポレータ
ーで留去することにより、粗３−メチル−３−メトキシ
ブタン酸４０．７ｇ（反応収率９５％）を得た。Example 2 30 g (254 m of 3-methyl-3-methoxybutanol)
mol), distilled water 270 g, 5% Pt, 5% Bi / carbon 3 g, 500 ml, were charged into an SUS autoclave and stirred at 80 ° C. for 20 hours at an air pressure of 9 kg / cm 2 . At this time, evacuation was performed at 10 L / hr. After completion of the reaction, the mixture was cooled, the catalyst was filtered off, and water was distilled off by an evaporator to obtain 40.7 g of crude 3-methyl-3-methoxybutanoic acid (reaction yield 95%).
【００２２】なお、組成生物３５．０ｇをビブリュウ塔
（論理段数約３段）で減圧蒸留を行ない、沸点９９〜１
０１℃／２〜４ｍｍＨｇを有する純度９８％以上の目的
物２５．２ｇを得た。このものはＮＭＲ分析の結果か
ら、３−メチル−３−メトキシブタン酸であることを確
認した。It should be noted that 35.0 g of the compositional organism was subjected to vacuum distillation in a Bibreu tower (about 3 logical stages), and the boiling point was 99-1.
25.2 g of a target substance having a purity of 98% or more and having 01 ° C./2 to 4 mmHg was obtained. It was confirmed from the result of NMR analysis that this was 3-methyl-3-methoxybutanoic acid.
【００２３】1Ｈ−ＮＭＲ（ＣＤＣｌ3 ，ｐｐｍ）：
１．３２８（ｓ，６Ｈ）、２．５６６（ｓ，２Ｈ）、
３．３０７（ｓ，３Ｈ） 1 H-NMR (CDCl 3 , ppm):
1.328 (s, 6H), 2.566 (s, 2H),
3.307 (s, 3H)
【００２４】実施例３ ３−ヒドロキシ−３−メチルブタノール２５０ｇ（２．
４０ｍｏｌ）、蒸留水２５０ｇ、５％Ｐｔ、５％Ｂｉ／
カーボン５ｇを１Ｌ、ガラス製オートクレーブに仕込
み、空気圧９ｋｇ／ｃｍ2 、８０℃で５０時間撹拌を行
なった。この時、排気は１０Ｌ／ｈｒで行なった。反応
終了後冷却し、触媒を濾別した。このろ液６７４．３ｇ
中には、原料の３−ヒドロキシ−３−メチルブタノール
が２９．９ｇ（転化率８８％）、目的物の３−ヒドロキ
シ−３−メチルブタン酸が９２．３ｇ（収率３２．６
％）、中間体の３−ヒドロキシ−３−メチルブタノール
が４５．３ｇ（収率１８．５％）そして、副生成物の
４，４−ジメチル−２−（２−ヒドロキシ−２−メチル
プロピル）−１，３−ジオキサンが４３．８ｇ（収率１
９．４％）含まれていた。このろ液に対して、トルエン
３００ｇで３回洗浄を行なった結果、４，４−ジメチル
−２−（２−ヒドロキシ−２−メチルプロピル）−１，
３−ジオキサン４２．９ｇと３−ヒドロキシ−３−メチ
ルブタナール３１．３ｇが油層側に抽出された。水層側
をヘリパック充填塔（理論段数１２段）で蒸留を行なう
ことによって純度９７％異常の目的物６４．５ｇが得ら
れた。Example 3 250 g of 3-hydroxy-3-methylbutanol (2.
40 mol), distilled water 250 g, 5% Pt, 5% Bi /
5 L of carbon (1 L) was placed in a glass autoclave and stirred at 80 ° C. for 50 hours at an air pressure of 9 kg / cm 2 . At this time, evacuation was performed at 10 L / hr. After completion of the reaction, the mixture was cooled and the catalyst was filtered off. 674.3 g of this filtrate
Among them, the raw material 3-hydroxy-3-methylbutanol was 29.9 g (conversion rate 88%), and the target 3-hydroxy-3-methylbutanoic acid was 92.3 g (yield 32.6).
%), 45.3 g of the intermediate 3-hydroxy-3-methylbutanol (yield 18.5%), and the by-product 4,4-dimethyl-2- (2-hydroxy-2-methylpropyl). 43.8 g of -1,3-dioxane (yield 1
9.4%) was included. As a result of washing the filtrate with 300 g of toluene three times, 4,4-dimethyl-2- (2-hydroxy-2-methylpropyl) -1,
42.9 g of 3-dioxane and 31.3 g of 3-hydroxy-3-methylbutanal were extracted on the oil layer side. By distilling the water layer side in a helipack packed column (12 theoretical plates), 64.5 g of the desired product having a purity of 97% was obtained.
【００２５】実施例４ ３−ヒドロキシ−３−メチルブタノール３０ｇ（２８８
ｍｍｏｌ）、蒸留水２７０ｇ、５％Ｐｔ、５％Ｂｉ／カ
ーボン３ｇを５００ｍｌ、ＳＵＳ製オートクレーブに仕
込み、空気圧９ｋｇ／ｃｍ2 、８０℃で２０時間撹拌を
行なった。この時、排気は１０Ｌ／ｈｒで行なった。反
応終了後冷却し、触媒を濾別し、更に、水をエヴァポレ
ーターで留去することにより粗３−ヒドロキシ−３−メ
チルブタン酸４２．４ｇ（反応収率９７％）を得た。Example 4 30 g of 3-hydroxy-3-methylbutanol (288)
mmol), distilled water 270 g, 5% Pt, 5% Bi / carbon 3 g, 500 ml, were charged into an SUS autoclave and stirred at 80 ° C. for 20 hours at an air pressure of 9 kg / cm 2 . At this time, evacuation was performed at 10 L / hr. After completion of the reaction, the mixture was cooled, the catalyst was filtered off, and water was distilled off with an evaporator to obtain 42.4 g of crude 3-hydroxy-3-methylbutanoic acid (reaction yield 97%).
【００２６】得られた溶液にメタノール２６．８ｇ、硫
酸１．４ｇを加え２時間加熱還流を行なった。その後、
硫酸を塩基で中和し、塩を濾過した。更に、得られた濾
液からエヴァポレーターでメタノールを留去し、粗３−
ヒドロキシ−３−メチルブタン酸メチルエステル３８．
２ｇ（反応収率９９％）を得た。このものはＮＭＲ分析
の結果から、３−ヒドロキシ−３−メチルブタン酸メチ
ルエステルであることを確認した。Methanol (26.8 g) and sulfuric acid (1.4 g) were added to the resulting solution, and the mixture was heated under reflux for 2 hours. afterwards,
The sulfuric acid was neutralized with base and the salts were filtered. Further, methanol was distilled off from the obtained filtrate with an evaporator to obtain crude 3-
Hydroxy-3-methylbutanoic acid methyl ester 38.
2 g (reaction yield 99%) was obtained. From the result of NMR analysis, this was confirmed to be 3-hydroxy-3-methylbutanoic acid methyl ester.
【００２７】1Ｈ−ＮＭＲ（ＣＤＣｌ3 、ｐｐｍ）：
１．２９１（ｓ，６Ｈ）、２．５１０（ｓ，２Ｈ）、
３．７２５（ｓ，３Ｈ） 得られた溶液に、硫酸水素カリウム０．４ｇを加え、６
００Ｔｏｒｒの減圧下、１５０℃で反応蒸留を行なうこ
とにより、セネシオン酸メチル１０．０ｇ（収率３２
％）とβ，γ−不飽和エステル１４．９ｇ（収率４７
％）の混合液を留出として得た。この留出液にパラトル
エンスルホン酸０．４ｇを加え、１２０℃で２０時間加
熱した。酸を中和し、塩を濾別した後、濾液について常
圧蒸留を行なうことにより、沸点１３４〜１３９℃をも
つ純度９４％のセネシオン酸メチル２０．２ｇ（収率８
５％）を得た。このものはＮＭＲ分析の結果から、セネ
シオン酸メチルであることを確認した。 1 H-NMR (CDCl 3 , ppm):
1.291 (s, 6H), 2.510 (s, 2H),
3.725 (s, 3H) To the resulting solution was added 0.4 g of potassium hydrogensulfate, 6
By performing reactive distillation at 150 ° C. under a reduced pressure of 00 Torr, 10.0 g of methyl senecionate (yield 32
%) And 14.9 g of β, γ-unsaturated ester (yield 47
%) Was obtained as a distillate. 0.4 g of paratoluenesulfonic acid was added to this distillate and heated at 120 ° C. for 20 hours. After the acid was neutralized and the salt was filtered off, the filtrate was subjected to atmospheric distillation to obtain 20.2 g of methyl senesionate having a boiling point of 134 to 139 ° C. and a purity of 94% (yield 8
5%). From the result of NMR analysis, this was confirmed to be methyl senecionate.
【００２８】1Ｈ−ＮＭＲ（ＣＤＣｌ3 、ｐｐｍ）：
１．９００（ｄ，３Ｈ）、２．１７４（ｄ，３Ｈ）、
３．６８１（ｓ，３Ｈ）、５．６８２（ｔ，１Ｈ） 1 H-NMR (CDCl 3 , ppm):
1.900 (d, 3H), 2.174 (d, 3H),
3.681 (s, 3H), 5.682 (t, 1H)
【００２９】実施例５ ３−ヒドロキシ−３−メチルブタノール３０ｇ（２８８
ｍｍｏｌ）、蒸留水２７０ｇ、５％Ｐｔ、５％Ｂｉ／カ
ーボン３ｇを５００ｍｌ、ＳＵＳ製オートクレーブに仕
込み、空気圧９ｋｇ／ｃｍ2 、８０℃で２０時間撹拌を
行なった。この時、排気は１０Ｌ／ｈｒで行なった。反
応終了後冷却し、触媒を濾別し、更に、水をエヴァポレ
ーターで留去することにより粗３−ヒドロキシ−３−メ
チルブタン酸４２．４ｇ（反応収率９７％）を得た。Example 5 30 g (288) of 3-hydroxy-3-methylbutanol
mmol), distilled water 270 g, 5% Pt, 5% Bi / carbon 3 g, 500 ml, were charged into an SUS autoclave and stirred at 80 ° C. for 20 hours at an air pressure of 9 kg / cm 2 . At this time, evacuation was performed at 10 L / hr. After completion of the reaction, the mixture was cooled, the catalyst was filtered off, and water was distilled off with an evaporator to obtain 42.4 g of crude 3-hydroxy-3-methylbutanoic acid (reaction yield 97%).
【００３０】この液に、硫酸５．５ｇを加え９５℃で６
時間加熱した後に、塩化メチレン抽出を行ない塩化メチ
レンをエヴァポレーターにて留去することで、セネシオ
ン酸２７．０ｇ（収率８２％）β，γ−不飽和カルボン
酸３．０ｇ（収率９％）を得た。この不飽和カルボン酸
にメタノール６９．１ｇと硫酸０．４ｇを加え、５０時
間加熱還流した。酸を中和し、塩を濾別した後、濾液か
らメタノール留去することで、セネシオン酸メチル２
９．９ｇ（収率９７％）とβ，γ−不飽和エステル３．
３ｇ（収率９７％）の混合液を得た。この混合液に、パ
ラトルエンスルホン酸０．５ｇを加え、１２０℃で１０
時間加熱し、酸を中和し、塩をろ別した後に、濾液につ
いて常圧蒸留を行なうことにより、沸点１３４〜１３９
℃をもつ純度９２％のセネシオン酸メチル２８．９ｇ
（収率８７％）を得た。To this solution, 5.5 g of sulfuric acid was added, and the mixture was mixed at 95 ° C for 6
After heating for a period of time, methylene chloride extraction was carried out and methylene chloride was distilled off with an evaporator to obtain 27.0 g of senecioic acid (yield 82%) and 3.0 g of β, γ-unsaturated carboxylic acid (yield 9 %) Was obtained. To this unsaturated carboxylic acid, 69.1 g of methanol and 0.4 g of sulfuric acid were added, and the mixture was heated under reflux for 50 hours. After neutralizing the acid and filtering off the salt, methanol was distilled off from the filtrate.
9.9 g (yield 97%) and β, γ-unsaturated ester 3.
3 g (yield 97%) of a mixed solution was obtained. To this mixed solution, 0.5 g of paratoluenesulfonic acid was added, and the mixture was mixed at 120 ° C for 10
After heating for an hour to neutralize the acid and filtering out the salt, the filtrate is subjected to atmospheric distillation to give a boiling point of 134 to 139.
28.9 g of methyl senecionate having a purity of 92% and having a temperature of ℃
(Yield 87%) was obtained.
【００３１】[0031]
【発明の効果】本発明の方法によれば、工業的に安価に
入手できる３−置換−３−メチルブタノールを用い、香
料、医薬、あるいは農薬中間体などとして有用な３−置
換−メチルブタン酸を効果的、且つ、経済的に製造する
ことが出来る。Industrial Applicability According to the method of the present invention, 3-substituted-3-methylbutanol, which is industrially available at low cost, is used to obtain 3-substituted-methylbutanoic acid useful as a fragrance, a drug, an intermediate for agricultural chemicals, or the like. It can be manufactured effectively and economically.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location // C07B 61/00 300
Claims (2)
及び／又は３−メチル−３−メトキシブタノールを水の
存在下に白金系あるいはパラジウム系触媒により酸素酸
化することを特徴とする３−ヒドロキシ−３−メチルブ
タン酸及び／又は３−メチル−３−メトキシブタン酸の
製造方法。1. 3-Hydroxy-3, which is characterized in that 3-hydroxy-3-methylbutanol and / or 3-methyl-3-methoxybutanol is oxygen-oxidized in the presence of water by a platinum-based or palladium-based catalyst. -A method for producing methylbutanoic acid and / or 3-methyl-3-methoxybutanoic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02468995A JP3529876B2 (en) | 1995-01-19 | 1995-01-19 | 3-methyl-3-methoxybutanoic acid. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02468995A JP3529876B2 (en) | 1995-01-19 | 1995-01-19 | 3-methyl-3-methoxybutanoic acid. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08198800A true JPH08198800A (en) | 1996-08-06 |
| JP3529876B2 JP3529876B2 (en) | 2004-05-24 |
Family
ID=12145144
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02468995A Expired - Fee Related JP3529876B2 (en) | 1995-01-19 | 1995-01-19 | 3-methyl-3-methoxybutanoic acid. |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3529876B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6090978A (en) * | 1996-07-19 | 2000-07-18 | Met-Rx Usa, Inc. | Process for manufacturing 3-hydroxy-3-methylbutanoic acid |
| CN111039774A (en) * | 2018-10-15 | 2020-04-21 | 捷恩智株式会社 | Process for producing aliphatic carboxylic acid compound and pyridine compound adduct of aliphatic ketone compound |
-
1995
- 1995-01-19 JP JP02468995A patent/JP3529876B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6090978A (en) * | 1996-07-19 | 2000-07-18 | Met-Rx Usa, Inc. | Process for manufacturing 3-hydroxy-3-methylbutanoic acid |
| US6248922B1 (en) | 1996-07-19 | 2001-06-19 | Met-Rx Usa Inc. | Process for manufacturing 3-hydroxy-3-Methylbutanoic acid |
| US6392092B2 (en) | 1996-07-19 | 2002-05-21 | Met-Rx Usa, Inc. | Process for manufacturing 3-hydroxy-3-methylbutanoic acid |
| CN111039774A (en) * | 2018-10-15 | 2020-04-21 | 捷恩智株式会社 | Process for producing aliphatic carboxylic acid compound and pyridine compound adduct of aliphatic ketone compound |
| JP2020063240A (en) * | 2018-10-15 | 2020-04-23 | Jnc株式会社 | Manufacturing method of aliphatic carboxylic acid compound, and pyridine compound addition product of aliphatic ketone compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3529876B2 (en) | 2004-05-24 |
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