JPS6245555A - Production of cinnamic acid - Google Patents
Production of cinnamic acidInfo
- Publication number
- JPS6245555A JPS6245555A JP60185907A JP18590785A JPS6245555A JP S6245555 A JPS6245555 A JP S6245555A JP 60185907 A JP60185907 A JP 60185907A JP 18590785 A JP18590785 A JP 18590785A JP S6245555 A JPS6245555 A JP S6245555A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- cinnamic acid
- reaction
- cinnamic
- alkyl
- 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は桂皮酸アルキルエステル類の加水分解による桂
皮酸類の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing cinnamic acids by hydrolysis of cinnamic acid alkyl esters.
桂皮酸類は香料または感光性樹脂の原料など、工業的に
重要な化合物である。Cinnamic acids are industrially important compounds, such as raw materials for perfumes and photosensitive resins.
（従来の技術）
桂皮酸類の合成方法としては、これまで種々の方法が知
ら肛ている。例えば、ベンズアルデヒドを原料として、
Ｐｅｒｋｉｎ反応、にｎｏｅｖｅｎａｇｅ１反応、Ｃ１
ａｉｓｅｎ縮合、ベンゼンやベンゼン誘導体とアクリル
酸エステルを原料とする方法などが知られている（例え
ば、特公昭４７−５（Ｈ；１１ 、特開昭５８−５９９
２７、米国特許３７８３１４０ 、同３９２２２９９な
ど）ａまた、スチレンまたはその誘導体と一酸化炭素、
アルコールおよび酸素を触媒の存在下に反応させる方法
も最近提案されている（例えば、特公昭５９−５５７０
、同６０−２３６６１など）。(Prior Art) Various methods have been known for synthesizing cinnamic acids. For example, using benzaldehyde as a raw material,
Perkin reaction, noevenage1 reaction, C1
Aisen condensation, a method using benzene or a benzene derivative and an acrylic ester as raw materials, etc. are known (for example, Japanese Patent Publication No. 47-5 (H;
27, U.S. Pat. No. 3,783,140, U.S. Pat. No. 3,922,299, etc.)
Recently, a method of reacting alcohol and oxygen in the presence of a catalyst has also been proposed (for example, Japanese Patent Publication No. 59-5570
, 60-23661, etc.).
これらの方法のうち、ベンズアルデヒドと酎：酸エステ
ルを用いるＣ１ａｉｓｅｎ縮合や、ベンゼンまたはベン
ゼン誘導体と、アクリル酸エステルをＪｊλ！十とする
方法、スチレン類またはその誘導体と一酸化炭素、アル
コールおよび酸素を原料とする方法などは、いずれも、
一旦桂皮酸エステルが生成するので遊離の桂皮酸を得る
にはエステルを加水分解する必要がある。Among these methods, C1aisen condensation using benzaldehyde and chuan acid ester, and Jjλ! Methods using styrenes or their derivatives, carbon monoxide, alcohol and oxygen as raw materials, etc.
Once the cinnamic acid ester is formed, it is necessary to hydrolyze the ester to obtain free cinnamic acid.
カルボン酸エステル類を酸またはアルカリを用いて加水
分解して遊離のカルボン酸類を得る方法は公知である。A method of hydrolyzing carboxylic acid esters using acid or alkali to obtain free carboxylic acids is known.
しかし、一般に桂皮酸エステル類の加水分解はアルコー
ル、ジオキサン、アセトンなどとの水溶液中で水酸化ナ
トリウムなどのアルカリを用いて均−系で行なわれてい
る（例えば、特開昭４９−１０２６１４）。また、最近
、酸を触媒として加水分解する方法も提案されている（
特開昭６Ｏ−１１２７３６）。However, the hydrolysis of cinnamic acid esters is generally carried out homogeneously using an alkali such as sodium hydroxide in an aqueous solution of alcohol, dioxane, acetone, etc. (for example, JP-A-49-102614). Recently, a method of hydrolysis using acid as a catalyst has also been proposed (
JP-A No. 6O-112736).
（発明が解決しようとする問題点）
桂皮酸エステル類のアルカリ分解によって桂皮酸類を得
る場合には、桂皮酸エステル類に対して等モル以上のア
ルカリを必要とし、さらに得らｉｂだ桂皮酸アルカリ塩
を中和するためにアルカリと等モル以上の酸が必要とな
る。(Problems to be Solved by the Invention) When obtaining cinnamic acids by alkaline decomposition of cinnamic acid esters, it is necessary to use an alkali in an amount equal to or more than the mole of the cinnamic acid esters. In order to neutralize the salt, more than the same molar amount of acid as the alkali is required.
アルカリを用いずに、酸を触媒として用いてエステルを
分解する方法は、一般のエステル加水分解法として公知
であるが、桂皮酸エステル類の場合には反応が遅く、未
反応原料が残ることが多く目的物の収率および品質が劣
り、さらに精製が必要となる。例えば、前述の特開昭Ｇ
ｏ−１１２７３６にはｐＫａが ２．０以下の酸を用い
る方法が開示されているが、耐水ｌ′１１液を用いた場
合には反応は遅く、桂皮酸エステル類の転化率は、２３
．２％で、未反応原料が多く残存している。また、この
方法では固体１’１２触媒を用いる方法が例示されてい
るが、この場合には生成する桂皮酸類を抽出などの方法
で固体酸から分にしなければならない。The method of decomposing esters using an acid as a catalyst without using an alkali is known as a general ester hydrolysis method, but in the case of cinnamic acid esters, the reaction is slow and unreacted raw materials may remain. In many cases, the yield and quality of the desired product are poor, and further purification is required. For example, the aforementioned JP-A-Sho G
O-112736 discloses a method using an acid with a pKa of 2.0 or less, but when a water-resistant l'11 liquid is used, the reaction is slow and the conversion rate of cinnamic acid esters is 2.3
．． At 2%, a large amount of unreacted raw material remains. Further, this method exemplifies a method using a solid 1'12 catalyst, but in this case, the produced cinnamic acids must be separated from the solid acid by a method such as extraction.
（問題を屏決するための手段）
本発明者らは、桂皮酸エステル類の酸水溶液による加水
分解について鋭意検討の結果、特定の条件および方法を
用いることにより、高い反応速度で反応が進み、温和な
条件下で短時間で反応を実施でき、しかも、高品質の桂
皮酸類が容易な操作で反応系から高収率で分離、取得で
きることを見出し本発明に到達した。(Means for resolving the problem) As a result of intensive studies on the hydrolysis of cinnamic acid esters with an aqueous acid solution, the present inventors found that by using specific conditions and methods, the reaction proceeds at a high reaction rate and is mild. The present invention was achieved by discovering that the reaction can be carried out in a short time under suitable conditions, and that high-quality cinnamic acids can be separated and obtained from the reaction system in high yield with easy operations.
本発明は桂皮酸エステル類を酸の存在下で加水分屏して
桂皮酸類を製造する方法において、水溶性の酸を用い、
桂皮酸エステル類を桂皮酸エステル類の融点以」−１対
応する桂皮酸類の融点以下の温度で、酸水溶液と桂皮酸
エステル類からなる不均一、二液系で反応せしめ、生成
する桂皮酸類を固体として析出させ、分離することを特
徴とする桂皮酸類の製造法である。The present invention provides a method for producing cinnamic acids by hydrolyzing cinnamic acid esters in the presence of an acid, using a water-soluble acid,
Cinnamic acid esters are reacted in a heterogeneous, two-component system consisting of an acid aqueous solution and a cinnamic acid ester at a temperature below the melting point of the corresponding cinnamic acid, and the resulting cinnamic acid is This is a method for producing cinnamic acids, which is characterized by precipitating and separating them as a solid.
本発明方法で用いら才する原料の桂皮酸エステル類は、
一般式
（式中、Ｒは、水素または芳香環上の少なくとも１種以
上の［汀換基であり、ハロゲン、水酸基、炭素数１−４
のアルキル基、または炭素数１−４のアルコキシ基を表
わす。Ｒ２およびＲ３はそれぞ、ｆＬ同種または異種の
基であり、水素、炭素数１＝６のアルキル基を表わす。The raw material cinnamic acid esters used in the method of the present invention are:
General formula (wherein, R is hydrogen or at least one [sulfate substituent group] on an aromatic ring, halogen, hydroxyl group, carbon number 1-4
represents an alkyl group or an alkoxy group having 1 to 4 carbon atoms. R2 and R3 are the same or different groups as fL, and each represents hydrogen or an alkyl group having 1=6 carbon atoms.
Ｒ４は置換または未置換のアルキルもしくはアルケニル
基を表わす）で示される桂皮酸エステル類であり、具体
的には桂皮酸メチル、桂皮酸エチル、桂皮酸プロピル。R4 represents a substituted or unsubstituted alkyl or alkenyl group); specific examples include methyl cinnamate, ethyl cinnamate, and propyl cinnamate.
桂皮酸ブチル、Ｃヌーメチルーβ−フェニルアクリル酸
エヂル、ｄ−プロピル−β−クロロフェニルアクリル酸
メチル、／１３−３．４−ジメトキシフェニルアクリル
酸メチル、／、４−メｌ〜キシフェニルアクリル酸メチ
ル、桂皮酸ベンジル、桂皮酸シンナミル、桂皮酸グアヤ
コールなどがあげられる。Butyl cinnamate, C-numethyl-β-phenylacrylate methyl d-propyl-β-chlorophenylacrylate, /13-3.4-dimethoxyphenylacrylate methyl, /,4-mel-xyphenylacrylate methyl, Examples include benzyl cinnamate, cinnamyl cinnamate, and guaiacol cinnamate.
これらの桂皮酸エステル類は各種の方法で製造すること
ができる。例えば、前述のようにベンズアアルデヒドと
酢酸エステルからＣ１ａｉｓｅｎ縮合、あるいはベンゼ
ンまたはベンゼン誘導体とアクリル酸エステルとの反応
、さらには、スチレンの酸化的カルボニル化反応等で製
造することができる。These cinnamic acid esters can be produced by various methods. For example, as described above, it can be produced by C1aisen condensation from benzaldehyde and acetate, reaction between benzene or a benzene derivative and acrylic ester, or oxidative carbonylation reaction of styrene.
また天然物の蘇合香浦などから分離することもできる。It can also be isolated from natural products such as Soaikaura.
このような方法で得られたものがいず汎も使用できる。Any product obtained by such a method can be used.
本発明で７＋１いら４しる酸は、水に溶けて水溶液とし
て使用できる酸である。水に不溶性のＭ＋よ、［ｊ約物
の桂皮酸類の結晶との分離が必要となり好ましくない。In the present invention, the 7+1 acid is an acid that dissolves in water and can be used as an aqueous solution. M+, which is insoluble in water, is not preferred because it requires separation from the cinnamic acid crystals.
また、桂皮酸類と反応するおそれのある酸は好ましくな
い。Furthermore, acids that may react with cinnamic acids are not preferred.
好ましい酸としては、たとえば 塩酸、硫酸、燐酸、二
燐酸、フォスフイン酸、フォスフオン酸トリポリ燭酸、
ＨｌＳ、０７． Ｈ２Ｓ２０１Ｂ ＋ Ｈ２Ｓ２０１Ｂ
の化学式で表わされるポリ硫酸、過塩素酸、１−リ：フ
ルオロ酢酸、パラトルエンスルフォン酸、フルオロスル
フォン酸、トリフルオロメタンスルフォン酸などのいわ
ゆる超強酸などが使用できる。また、フルオロスルフォ
ン酸と五フッ化アンチモンなどとの組合わせで作られる
マジック酸と呼ばれる酸も使用できる。Preferred acids include, for example, hydrochloric acid, sulfuric acid, phosphoric acid, diphosphoric acid, phosphinic acid, phosphonic acid, tripolysulfuric acid,
HLS, 07. H2S201B + H2S201B
So-called superacids such as polysulfuric acid, perchloric acid, 1-li:fluoroacetic acid, para-toluenesulfonic acid, fluorosulfonic acid, and trifluoromethanesulfonic acid represented by the chemical formula can be used. An acid called magic acid, which is made from a combination of fluorosulfonic acid and antimony pentafluoride, can also be used.
これらの酸は、単独で用いてもよいが、２種以上の混合
酸の形でも使用できる。These acids may be used alone or in the form of a mixed acid of two or more.
特開昭６０−１１２７３６で使用できる酸としてあげら
れている硝酸、フッ化水素酸、臭化水素酸、ヨウ化水素
酸は、反応が極めて遅いか、または、原料の桂皮酸エス
テル類や、生成物の桂皮酸類と反応して、目的物以外の
生成物を生じるので５本発明方法には不適当である。Nitric acid, hydrofluoric acid, hydrobromic acid, and hydroiodic acid listed as usable acids in JP-A No. 60-112736 either react extremely slowly or react poorly with cinnamic acid esters as raw materials or It is unsuitable for the method of the present invention because it reacts with cinnamic acids to produce products other than the desired product.
本発明方法では、桂皮酸エステル類を加水分解する場合
、実質上工業的に有効な反応速度を得るためには、反応
系内の酸度関数（Ｈｏ）を、−１以下の状態に保ちなが
ら反応させることが好ましい。ここで、酸度関数（Ｈ８
）とは、改訂３版化学便覧 基礎編 ＩＩ ３４３−
３４．５ページに記されているように、塩基１３とその
共役酸Ｉ３１！”の活旦系数をそれぞれｙ８− ｙＢＨ
＋、水素イオン■Ｉ＋の情景をａＦ１士とすると
で定義される物性値であり、代表的な数値は上記のペー
ジに記さｈている。In the method of the present invention, when hydrolyzing cinnamic acid esters, in order to obtain a substantially industrially effective reaction rate, it is necessary to maintain the acidity function (Ho) in the reaction system at -1 or less. It is preferable to let Here, the acidity function (H8
) is the revised 3rd edition Chemistry Handbook Basic Edition II 343-
As noted on page 34.5, base 13 and its conjugate acid I31! ”, respectively y8− yBH
It is a physical property value defined by assuming that the scene of +, hydrogen ion ■I+ is aF1, and typical values are listed on the above page.
酸度関数を一１以下に保ちながら反応しようとすれば、
例えば、塩酸水ｉ８液を使用する場合は、約１０ｆｆｌ
量％以上の濃度を保つ必要があり、硫酸水溶液の場合は
、約２０％以上の濃度が必要となる。酸度関数が一１以
上の状態で反応した場合には、比較例で後述するように
、反応が極めて遅くなる。If you try to react while keeping the acidity function below 11,
For example, when using hydrochloric acid solution I8, approximately 10ffl
It is necessary to maintain a concentration of % or more, and in the case of an aqueous sulfuric acid solution, a concentration of about 20% or more is required. When the reaction occurs in a state where the acidity function is 11 or more, the reaction becomes extremely slow as will be described later in the comparative example.
加水分留の温度は、原料の桂皮酸エステル類の融点以上
から、対応する桂皮酸類の融点以下の範囲で行われる。The temperature of the hydrolysis is carried out in a range from above the melting point of the raw cinnamic acid ester to below the melting point of the corresponding cinnamic acid.
例えば、桂皮酸メチルの加水分解では、３６６Ｃ−１３
６°Ｃの温度範囲で、桂皮酸エチルの加水分解では、約
ｔｏ’ Ｃ−１３６６Ｃの温度範囲で行われる。桂皮酸
エステル類の融点以Ｆでも反応は進行するが非常に遅く
、また、桂皮酸エステル類が固体であるため良好な攪拌
ができない。For example, in the hydrolysis of methyl cinnamate, 366C-13
In a temperature range of 6°C, the hydrolysis of ethyl cinnamate is carried out in a temperature range of about to'C-1366C. Although the reaction proceeds at temperatures above the melting point of the cinnamic acid esters, it is very slow and, since the cinnamic acid esters are solid, good stirring is not possible.
また、桂皮酸の融点以上では、生成した桂皮酸が油状に
なり、取り扱い上不利である。Furthermore, if the temperature is above the melting point of cinnamic acid, the produced cinnamic acid becomes oily, which is disadvantageous in terms of handling.
反応圧力は通常、常圧で実施されるが、場合によっては
若干加圧または減圧で行うこともできる本発明の特徴は
、桂皮酸エステル類の融点以上の温度で酸水溶液を用い
、酸水溶液と桂皮酸エステル類からなる不均一、二液系
で反応を行うことであり、本発明方法によれば、反応の
進行につれて目的生成物の桂皮酸類が固体となって反応
系に析出してくる。そのため高い反応速度で反応が進行
し、しかも、反応後結晶を濾過または遠心公正などの通
常の固液分前操作で容易に、しかも損失なく、高収率で
得ることができ、得られた固体はそのまま、または、簡
単な精製で、例えば水洗、乾燥するのみで高品質の桂皮
酸を得ることができる。The reaction pressure is usually carried out at normal pressure, but the feature of the present invention is that it can be carried out under slightly increased or reduced pressure in some cases. The reaction is carried out in a heterogeneous, two-liquid system consisting of cinnamic acid esters, and according to the method of the present invention, as the reaction progresses, the desired product, cinnamic acid, becomes solid and precipitates in the reaction system. Therefore, the reaction proceeds at a high reaction rate, and the crystals after the reaction can be easily obtained in high yield without any loss through ordinary solid-liquid separation procedures such as filtration or centrifugation. High-quality cinnamic acid can be obtained as is or by simple purification, such as washing with water and drying.
不均一、二液系で加水分解するという本発明の効果を損
なわない限り、少量のケトン類、ニーチル、炭化水素類
などを系内に存在させて使用することができる。As long as the effect of the present invention of hydrolyzing in a heterogeneous, two-component system is not impaired, small amounts of ketones, nityl, hydrocarbons, etc. may be present in the system.
本発明方法は、反応中に生成するアルコールを系外に留
出させながら加水分解を行うことにより反応をさらに促
進させることができる。In the method of the present invention, the reaction can be further accelerated by performing hydrolysis while distilling the alcohol produced during the reaction out of the system.
アルコールを系外に留出させる手段として１次の方法が
有効である。例えば、反応液中へ不活性ガスを吹き込み
ながら生成するアルコールを川伝ガスと共に系外に留去
させる方法、加水分解の反応温度以下の沸点の不活性溶
媒を反応系に滴下し発生する蒸気と共に生成するアルコ
ールを系外に留出させる方法などが有効である。The first method is effective as a means for distilling alcohol out of the system. For example, there is a method in which the alcohol produced is distilled out of the system together with Kawaden gas while blowing an inert gas into the reaction solution, or a method in which an inert solvent with a boiling point below the hydrolysis reaction temperature is dropped into the reaction system together with the generated vapor. An effective method is to distill the alcohol produced out of the system.
また、反応を促進させるために、テトラフェニルポウ化
すトリウムなどの相聞移！ＦＩｌ＋ 溶媒や、１−デシ
ルベンゼンスルフォン酸などの界面活性剤５ｉ （ｊ４
用することもできる。In addition, to accelerate the reaction, phase transfer such as thorium to tetraphenylpolymerate! FIl+ Solvent and surfactant such as 1-decylbenzenesulfonic acid 5i (j4
It can also be used.
本発明方法は、原料、および酸水溶液を−・括して反応
器に仕込んで反応させる回分式でも、そ扛らの１部を少
しずつ滴下しながら行う半回分式でも、また、原料およ
び酸水溶液を連続的に仕込み反応液を連続的に■ト出さ
せる連続式反応のいずれの方法でも実施できる。The method of the present invention can be carried out either by a batch method in which raw materials and an aqueous acid solution are charged into a reactor and reacted together, or by a semi-batch method in which a portion of the raw materials and an acid aqueous solution are added dropwise little by little. Any continuous reaction method in which an aqueous solution is continuously charged and a reaction solution is continuously taken out can be carried out.
加水分解によって生成したアルコールは５反応後、反応
液から蒸留または抽出などの方法で容易に回収すること
ができるが、前述のように不活性ガスや不活性溶媒の使
用などにより、反応中にアルコールを留去させながら加
水分解を行う方法では、反応後９反応液から回収する必
要はなく、必要に応じて留出液から回収す４しばよい。Alcohol produced by hydrolysis can be easily recovered from the reaction solution by distillation or extraction after the reaction, but as mentioned above, alcohol can be recovered during the reaction by using an inert gas or an inert solvent. In a method in which hydrolysis is carried out while distilling off the reaction mixture, it is not necessary to recover it from the reaction solution after the reaction, but it is only necessary to recover it from the distillate as necessary.
また、反応中に系外レコ排出されるガスを適当に分縮す
ることにより分離することもできる。It is also possible to separate the gas discharged outside the system during the reaction by appropriately partial condensation.
このように、目的物の桂皮酸類および生成したアルコー
ルを容易に分離して取得できることは、反応の促進およ
び完結と共に本発明方法の大きな利点の１つである。Thus, the ability to easily separate and obtain the target cinnamic acids and the produced alcohol is one of the great advantages of the method of the present invention, as well as the promotion and completion of the reaction.
（発明の効果）
本発明によれば、桂皮酸エステル類の酸による加水分解
が、温和な条件下で、高い反応速度で進行し、簡単な操
作で、高品質の桂皮酸類を分離することができる。さら
に、生成するアルコールの回収も容易であり、工業的に
極めて有利な桂皮酸類の製造法となる。(Effects of the Invention) According to the present invention, acid hydrolysis of cinnamic acid esters proceeds at a high reaction rate under mild conditions, and high-quality cinnamic acids can be separated with a simple operation. can. Furthermore, the alcohol produced is easy to recover, making it an extremely industrially advantageous method for producing cinnamic acids.
（実施例）
以下、実施例および比較例により本発明を其体的に説明
する。(Examples) Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples.
実施例 １
攪拌装は、温度計、留出物冷却用のリービッヒ冷却管を
とりつけたセパラブルフラスコに桂皮酸メチル ８．１
ｇ （０，０５モル）と、５５重旦％ゲ（酸（酸度関
数 −３，９） １．２５ ｍ ｌを仕込み、激し
く攪拌しながら１００°Ｃに加熱した。反応開始約３０
分後から結晶が析出しはじめた。２．０時間後、反応液
を室温まで冷却し結晶を；戸別し、水洗して減圧下に乾
燥した。その結果７．４ｇの結晶が得られ液体クロマト
グラフィーによる分析の結果、結晶中には桂皮酸以外の
成分は認められなかった。Example 1 Methyl cinnamate was added to a separable flask equipped with a thermometer and a Liebig condenser for cooling the distillate.
g (0.05 mol) and 1.25 ml of 55% acid (acidity function -3.9) were charged and heated to 100°C with vigorous stirring. Approximately 30 minutes after the start of the reaction.
Crystals began to precipitate after a few minutes. After 2.0 hours, the reaction solution was cooled to room temperature, and the crystals were separated, washed with water, and dried under reduced pressure. As a result, 7.4 g of crystals were obtained, and as a result of analysis by liquid chromatography, no components other than cinnamic acid were found in the crystals.
ろ液を減圧下で１００°Ｃに加熱し、２０．０ ｇの留
出液をえた。反応中の少量の留出液とあわせてガスクロ
マ１−グラフィーで分析した結果、１．３ｇのメタノー
ルが回収されていた。結晶を戸別する前の反応液を同様
に蒸留すると、１．４ｇのメタノールを含む溜出水が回
収された。The filtrate was heated to 100°C under reduced pressure, yielding 20.0 g of distillate. As a result of analysis by gas chromatography together with a small amount of distillate from the reaction, 1.3 g of methanol was recovered. When the reaction solution before the crystals were separated was similarly distilled, distilled water containing 1.4 g of methanol was recovered.
比較例 １
実施例１において、５５重景％硫酸の代わりに、１５％
硫酸（酸度関数−（１，８） １２５ｍ１を用い、１
０５°Ｃで２時間反応させたほかは実施例１と同様に反
応させた。得られた結晶は７．９ｇで分析の結果、これ
は２．Ｏｇの桂皮酸と５．９ｇの桂皮酸メチルの混合物
であった。Comparative Example 1 In Example 1, 15% sulfuric acid was used instead of 55% sulfuric acid.
Sulfuric acid (acidity function - (1,8) using 125ml, 1
The reaction was carried out in the same manner as in Example 1, except that the reaction was carried out at 05°C for 2 hours. The obtained crystals were 7.9 g, and the analysis showed that this was 2.9 g. It was a mixture of Og of cinnamic acid and 5.9g of methyl cinnamate.
比較例 ２
実施例１において ５５重景％硫ｒｆ１１２５ｍｌの代
わりに 同３１度の硫酸 ｓｏｍｌ（硫酸 ０．３６モ
ル）用いて同様の反応を行ったところ、得られた結晶は
７．７ｇで、桂皮酸 ３．７ｇと桂皮酸メチル ４．
０ｇの８２合物であった。Comparative Example 2 In Example 1, a similar reaction was carried out using 31 degree sulfuric acid soml (0.36 mol of sulfuric acid) instead of 1125 ml of 55% sulfur rf, and the obtained crystals weighed 7.7 g. 3.7 g of acid and methyl cinnamate 4.
It was 0g of compound 82.
実施例 ２
実施例１と同し装置に空気吹き込み管および、リービッ
ヒ冷却管の後段にドライアイス−メタノールで冷却した
コールドトラップをとり付け、桂皮酸メチル ３２．４
ｇおよび ５５重景％硫ｉ’１２５００ｍ１を仕込み
、反応中、空気を５００ ｍ ｌ ／分の土量で液中に
吹き込み、１００°Ｃで１．５時間反応し実施例１と同
様に反応液を処理した。その結果、２８．５ｇの桂皮酸
が得られた。結晶、！−１１には桂皮酸メチルは認めら
れなかった。この反応で ６０ｇの留出液が得らオし、
その中にメタノールが ５．７ｇ含まれていた。Example 2 The same equipment as in Example 1 was equipped with an air blowing tube and a cold trap cooled with dry ice-methanol at the downstream stage of the Liebig cooling tube, and methyl cinnamate 32.4
During the reaction, air was blown into the solution at a volume of 500 ml/min, and the reaction was carried out at 100°C for 1.5 hours. processed. As a result, 28.5 g of cinnamic acid was obtained. crystal,! No methyl cinnamate was observed in -11. This reaction yielded 60g of distillate,
It contained 5.7g of methanol.
実施例 ３
実施例１の装置に）４下ロートを取り付け、桂皮酸メチ
ル １６．２ ｇ と ５５％硫酸２５（ｌ ｍ ｌ
を仕込み、激しく ｂ’Ｊ １Ｔ Ｌながら滴下ロート
から、１，２−ジメトキシエタンを５０ｇ／Ｈｒの速度
で心下しほぼ同じ速度で留出液を得た。Ｌ、５時間後滴
下を止め、暫く留去を続けた後冷却し、水溶液中の結晶
を炉別、水洗して、減圧下に乾燥した。その結果、１４
．２ ｇの桂皮酸が得られ、分析の結果成分は桂皮酸の
みであった。Example 3 A lower funnel was attached to the apparatus of Example 1, and 16.2 g of methyl cinnamate and 25 (l ml) of 55% sulfuric acid were added.
was charged, and 1,2-dimethoxyethane was added from the dropping funnel at a rate of 50 g/Hr while vigorously b'J 1T L was added to obtain a distillate at approximately the same rate. After 5 hours, the dropping was stopped, and after continued distillation for a while, it was cooled, and the crystals in the aqueous solution were separated from the furnace, washed with water, and dried under reduced pressure. As a result, 14
．． 2 g of cinnamic acid was obtained, and analysis revealed that cinnamic acid was the only component.
実施例 ４
実施例１１コおいて、５５重景％硫酸水溶液３３０．１
ｌ−ｆ景％塩酸（酸度関数−３，３）に、反応時間を１
時間に変更した以外は実施例１と同様に反応を行った。Example 4 In Example 11, 55% sulfuric acid aqueous solution 330.1
l-f ratio hydrochloric acid (acidity function -3,3), reaction time 1
The reaction was carried out in the same manner as in Example 1 except that the time was changed.
その結果、７．４ｇの桂皮酸が得られ、結＋’ｉ？＋
１には桂皮酸メチルは認められなかった。As a result, 7.4 g of cinnamic acid was obtained. +
No methyl cinnamate was observed in sample No. 1.
比較例 ３
実施例４において、 ３０重量％塩酸の代わりに、５重
量％塩酸（酸度間１１−０．５ ） ２５０ ｍ ｌ用
い、ｔｏｏ ’ ｃ″Ｃ″１５時間反応させたほかは実
施例４と同様に反応を行った。得られた結晶は７．８ｇ
であり、桂皮酸１．２ｇと桂皮酸メチル６．６ｇの混合
物であった。Comparative Example 3 Example 4 except that 250 ml of 5 wt% hydrochloric acid (acidity range: 11-0.5) was used instead of 30 wt% hydrochloric acid, and the reaction was carried out for 15 hours. The reaction was carried out in the same manner. The obtained crystals weighed 7.8g.
It was a mixture of 1.2 g of cinnamic acid and 6.6 g of methyl cinnamate.
実施例 ５
実施例２において、５５重量％硫酸水溶液を６０重量％
ｔ＃酸（酸度関数−１，５）に、反応温度を１２０に、
反応時間を３時間に変更した以外は実施例２と同様に反
応を行った。その結果、２８．０ｇの結晶が得られ結晶
中には桂皮酸メチルは認められなかった。Example 5 In Example 2, 60% by weight of the 55% by weight sulfuric acid aqueous solution
t# acid (acidity function -1,5), reaction temperature 120,
The reaction was carried out in the same manner as in Example 2 except that the reaction time was changed to 3 hours. As a result, 28.0 g of crystals were obtained, and no methyl cinnamate was observed in the crystals.
実施例 ６
実施例１において、桂皮酸メチルを桂皮酸エチル ８．
８ ｇ （０，０５モル）反応時間を３時間に変更した
以外はｙ：前例１と同様に反応を行った。その結果、７
．３ｇの結晶が得られ、結晶中には桂皮酸エチルは認め
られなかった。Example 6 In Example 1, methyl cinnamate was replaced with ethyl cinnamate 8.
8 g (0.05 mol) The reaction was carried out in the same manner as in Example 1 except that the reaction time was changed to 3 hours. As a result, 7
．． 3 g of crystals were obtained, and no ethyl cinnamate was observed in the crystals.
Claims (1)
酸類を製造する方法において、水溶性の酸を用い、桂皮
酸エステル類を桂皮酸エステル類の融点以上、対応する
桂皮酸類の融点以下の温度で、酸水溶液と桂皮酸エステ
ル類からなる不均一二液系で反応せしめ、生成する桂皮
酸類を固体として析出させ、分離することを特徴とする
桂皮酸類の製造法。1) In a method for producing cinnamic acids by hydrolyzing cinnamic esters in the presence of an acid, a water-soluble acid is used, and the cinnamic esters are heated to a temperature higher than the melting point of the cinnamic acid ester, and the melting point of the corresponding cinnamic acid is A method for producing cinnamic acids, which comprises reacting in a heterogeneous two-liquid system consisting of an acid aqueous solution and cinnamic acid esters at the following temperature, and precipitating and separating the produced cinnamic acids as a solid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60185907A JPH0615499B2 (en) | 1985-08-26 | 1985-08-26 | Method for producing cinnamic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60185907A JPH0615499B2 (en) | 1985-08-26 | 1985-08-26 | Method for producing cinnamic acids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6245555A true JPS6245555A (en) | 1987-02-27 |
| JPH0615499B2 JPH0615499B2 (en) | 1994-03-02 |
Family
ID=16178967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60185907A Expired - Lifetime JPH0615499B2 (en) | 1985-08-26 | 1985-08-26 | Method for producing cinnamic acids |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0615499B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1591435A3 (en) * | 2004-03-26 | 2007-11-28 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Method for preparing 2,6-Naphtalene dicarboxyclic acid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60112736A (en) * | 1983-11-22 | 1985-06-19 | Mitsubishi Chem Ind Ltd | Production of cinnamic acid |
-
1985
- 1985-08-26 JP JP60185907A patent/JPH0615499B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60112736A (en) * | 1983-11-22 | 1985-06-19 | Mitsubishi Chem Ind Ltd | Production of cinnamic acid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1591435A3 (en) * | 2004-03-26 | 2007-11-28 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Method for preparing 2,6-Naphtalene dicarboxyclic acid |
| US7355071B2 (en) | 2004-03-26 | 2008-04-08 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Method for preparing 2,6-naphthalene dicarboxylic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0615499B2 (en) | 1994-03-02 |
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