JP3210148B2 - Method for hydrogenating dialkyl naphthalenedicarboxylate - Google Patents
Method for hydrogenating dialkyl naphthalenedicarboxylateInfo
- Publication number
- JP3210148B2 JP3210148B2 JP19959293A JP19959293A JP3210148B2 JP 3210148 B2 JP3210148 B2 JP 3210148B2 JP 19959293 A JP19959293 A JP 19959293A JP 19959293 A JP19959293 A JP 19959293A JP 3210148 B2 JP3210148 B2 JP 3210148B2
- Authority
- JP
- Japan
- Prior art keywords
- ndce
- catalyst
- tdce
- dialkyl
- naphthalenedicarboxylate
- 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
【０００１】[0001]
【産業上の利用分野】本発明は、ナフタレンジカルボン
酸ジアルキルエステル（以後ＮＤＣＥと略称する）を水
素化しテトラリンジカルボン酸シアルキルエステル（以
後ＴＤＣＥと略称する）を合成する技術に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technology for synthesizing a dialkyl tetralin dicarboxylate (hereinafter abbreviated as TDCE) by hydrogenating a dialkyl naphthalene dicarboxylate (hereinafter abbreviated as NDCE).
【０００２】[0002]
【発明の背景】ＮＤＣＥを原料とするポリ（アルキレン
ナフタレンジカルボキシレート）とりわけポリ（エチレ
ン―２，６―ナフタレンジカルボキシレート）は、ポリ
（エチレンテレフタレート）と較べて耐熱性、機械的特
性、ガスバリアー性が優れており、繊維、フィルム、ボ
トル及び工業用樹脂用の高機能性材料として利用されて
いる。しかしながら、そのガラス転移点が高いために例
えばボトル等の成形加工条件の設定が難しい。その点を
解決するために、ＴＤＣＥがポリマー原料またはポリ
（エチレン―２，６―ナフタレンジカルボキシレート）
の改質剤として注目されている。本発明はこのＴＤＣＥ
を製造する方法に関するものである。BACKGROUND OF THE INVENTION Poly (alkylene naphthalenedicarboxylate) derived from NDCE, especially poly (ethylene-2,6-naphthalenedicarboxylate), has higher heat resistance, mechanical properties and gaseous properties than poly (ethylene terephthalate). It has excellent barrier properties and is used as a highly functional material for fibers, films, bottles and industrial resins. However, since the glass transition point is high, it is difficult to set molding processing conditions for, for example, bottles. To solve the problem, TDCE is used as a polymer raw material or poly (ethylene-2,6-naphthalenedicarboxylate).
Has attracted attention as a modifier. The present invention uses this TDCE
And a method for producing the same.
【０００３】[0003]
【従来の技術及び課題】ＴＤＣＥを合成する方法とし
て、以下の２手段が知られている。先ず、特開昭５１―
１２７０５８号公報に開示されている方法は、１―テト
ラロン―３，７―ジカルボン酸またはそのアルキルエス
テルを水素化してテトラリン―２，６―ジカルボン酸ま
たはその２，６―アルキルエステルを得るものである。2. Description of the Related Art The following two methods are known as methods for synthesizing TDCE. First, JP-A-51-
The method disclosed in Japanese Patent No. 127058 is a method in which 1-tetralone-3,7-dicarboxylic acid or its alkyl ester is hydrogenated to obtain tetralin-2,6-dicarboxylic acid or its 2,6-alkyl ester. .
【０００４】また、米国特許第３５３４００２号明細書
には、２，６―ナフタレンジカルボン酸ジアルキルエス
テル（以下２，６―ＮＤＣＥと略記する）をニッケル触
媒の存在下で水素化し、テトラリン―２，６―ジカルボ
ン酸ジアルキルエステル（以下２，６―ＴＤＣＥと略記
する）を得る方法が記載されている。Further, US Pat. No. 3,534,002 discloses that 2,6-naphthalenedicarboxylic acid dialkyl ester (hereinafter abbreviated as 2,6-NDCE) is hydrogenated in the presence of a nickel catalyst to give tetralin-2,6 A method for obtaining a dialkyl dicarboxylate (hereinafter abbreviated as 2,6-TDCE) is described.
【０００５】そこで、上記の２手段を検討すると、前者
の技術は原料テトラロンジカルボン酸またはそのアルキ
ルエステルを得るのに数次の工程を経る合成方法である
から、ＮＤＣＥ原料の入手が困難な場合はともかく、入
手可能ならば工業的に有利な合成方法とは云えない。ま
た後者の合成手段はニッケル触媒を用いて約３５〜７０
０ｋｇ／ｃｍ2 Ｇの高圧下で２，６―ＮＤＣＥを水素化
するものであるから、高圧下の水素の取扱いの危険性が
無視できず、しかも生成物の収率も満足できるものでは
ないことから、精製効率も低く、経済性に欠ける。In consideration of the above two measures, the former technique is a synthesis method that requires several steps to obtain the starting tetralone dicarboxylic acid or its alkyl ester. Anyway, if available, it is not an industrially advantageous synthesis method. The latter means for synthesizing is about 35-70 using a nickel catalyst.
Since 2,6-NDCE is hydrogenated under high pressure of 0 kg / cm 2 G, the danger of handling hydrogen under high pressure cannot be ignored, and the yield of the product is not satisfactory. Therefore, the purification efficiency is low and the economy is low.
【０００６】[0006]
【課題を解決するための手段】ニッケル触媒はその活性
が低いため、ＮＤＣＥを水素化してＴＤＣＥを得るため
には、反応圧力を約３５乃至７００ｋｇ／ｃｍ2 Ｇ、実
際には１００ｋｇ／ｃｍ2 Ｇ以上、反応温度を１５０℃
以上にする必要があるが、高圧下の水素を取り扱う点、
安全上課題が残るとともに、デカリンジカルボン酸ジア
ルキルへの過剰水素化反応が避け難く、収率の低下を招
いていた。一方、パラジウム、ルテニウム、ロジウムは
その水素化活性が高い為に、ＮＤＣＥを水素化してデカ
リンジカルボン酸ジアルキルを合成する触媒として知ら
れていたが、部分水素化してＴＤＣＥを得るための触媒
としては、認識されていなかった（Ｊ．Ｃｈｅｍ．Ｅｎ
ｇ．Ｄａｔａ，１４（４），４８９―９０及び英国特許
第１０２４４８１号明細書参照）。SUMMARY OF THE INVENTION Since the activity of nickel catalyst is low, in order to hydrogenate NDCE to obtain TDCE, the reaction pressure should be about 35 to 700 kg / cm 2 G, and actually 100 kg / cm 2 G. As described above, the reaction temperature was set to 150 ° C.
Although it is necessary to do above, the point of handling hydrogen under high pressure,
While safety issues remain, excessive hydrogenation reaction to dialkyl decalin dicarboxylate is difficult to avoid, resulting in a decrease in yield. On the other hand, palladium, ruthenium, and rhodium have been known as catalysts for synthesizing dialkyl decalin dicarboxylate by hydrogenating NDCE because of their high hydrogenation activity, but as catalysts for obtaining TDCE by partially hydrogenating, (J. Chem. En)
g. Data, 14 (4), 489-90 and GB 1024441).
【０００７】発明者は、これらの課題を解決する為に、
鋭意検討した結果、本件発明に達し課題を解決するに至
った。The inventor has set out to solve these problems.
As a result of intensive studies, the present inventors have reached the present invention and have solved the problem.
【０００８】即ち、本発明は、パラジウム、ルテニウ
ム、ロジウム及び白金から成る群から選ばれる少なくと
も１種の触媒の存在下にＮＤＣＥに、その反応条件にお
いて少なくとも部分的に可溶である溶媒を使用して、水
素圧力３５ｋｇ／ｃｍ2 Ｇ以下で水素を作用させテトラ
リンジカルボン酸ジアルキルエステルを合成することか
らなるナフタレンジカルボン酸ジアルキルエステルの水
素化方法である。That is, the present invention uses a solvent which is at least partially soluble in NDCE under the reaction conditions in the presence of at least one catalyst selected from the group consisting of palladium, ruthenium, rhodium and platinum. Then, hydrogen is acted at a hydrogen pressure of 35 kg / cm 2 G or less to synthesize a dialkyl tetralin dicarboxylate, thereby hydrogenating a dialkyl naphthalenedicarboxylate.
【０００９】本発明を以下に説明する。The present invention will be described below.
【００１０】本発明におけるＮＤＣＥは、ジ置換体であ
ればその位置は限定されないが、ポリ（エチレン―２，
６―ナフタレンジカルボキシレート）の原料として入手
可能な２，６―ＮＤＣＥを用いることができれば、本発
明を有利に実施できる。The position of NDCE in the present invention is not limited as long as it is a di-substituted product.
The present invention can be advantageously carried out if 2,6-NDCE available as a raw material for 6-naphthalenedicarboxylate) can be used.
【００１１】本発明におけるＮＤＣＥはジアルキルエス
テル体であり、具体的に例えばジメチルエステル体、ジ
エチルエステル体、ジイソプロピルエステル体が挙げら
れる。さらにこれらのモノアルキルエステル体でも本発
明における原料として使用でき、入手可能なジメチルエ
ステル体を使用した場合も本発明を実施できる。The NDCE in the present invention is a dialkyl ester, and specific examples include a dimethyl ester, a diethyl ester and a diisopropyl ester. Further, these monoalkyl esters can also be used as a raw material in the present invention, and the present invention can be carried out using an available dimethyl ester.
【００１２】本発明において用いる触媒パラジウム、ル
テニウム、ロジウム又は白金を支持する担体は一般的に
用いられる活性炭、珪藻土、アルミナ、シリカ、チタニ
ア、マグネシウム及びゼオライト等であり、担体として
は何ら限定されないが、比較的比表面積の大きい活性炭
が好ましいものである。The carrier for supporting the catalyst palladium, ruthenium, rhodium or platinum used in the present invention is generally used activated carbon, diatomaceous earth, alumina, silica, titania, magnesium, zeolite and the like, and the carrier is not limited at all. Activated carbon having a relatively large specific surface area is preferred.
【００１３】本発明で用いる溶媒は、水素化反応に不活
性なものであれば特に限定されない。水素化反応条件に
おいてＮＤＣＥが少なくとも部分的に可溶である溶媒で
あって、具体例としては、酢酸、メタノール、エタノー
ル、イソプロパノール、シクロヘキサン等が挙げられ
る。[0013] The solvent used in the present invention is not particularly limited as long as it is inert to the hydrogenation reaction. A solvent in which NDCE is at least partially soluble under hydrogenation reaction conditions, and specific examples include acetic acid, methanol, ethanol, isopropanol, cyclohexane and the like.
【００１４】本発明において、ＮＤＣＥを水素化させる
際の水素圧力は重要であり３５ｋｇ／ｃｍ2 Ｇ以下で水
素を作用させることが必要である。特に好ましくは、５
乃至３５ｋｇ／ｃｍ2 Ｇであり、水素圧力が３５ｋｇ／
ｃｍ2 Ｇを超えるとデカリンジカルボン酸またはデカリ
ンジカルボン酸ジアルキルへの過剰水素化反応が進行
し、ＴＤＣＥの収率が低下する。５ｋｇ／ｃｍ2 Ｇ未満
でも特に支障はないが反応速度が低下し、反応に長時間
を要し工業的規模で行う場合好ましくない。In the present invention, the hydrogen pressure at the time of hydrogenating NDCE is important, and it is necessary to apply hydrogen at 35 kg / cm 2 G or less. Particularly preferably, 5
To 35 kg / cm 2 G, and the hydrogen pressure is 35 kg / cm 2 G.
If it exceeds cm 2 G, excessive hydrogenation reaction to decalin dicarboxylic acid or dialkyl decalin dicarboxylate proceeds, and the yield of TDCE decreases. Even if it is less than 5 kg / cm 2 G, there is no particular problem, but the reaction rate decreases, and the reaction requires a long time, which is not preferable when the reaction is performed on an industrial scale.
【００１５】本発明におけるＮＤＣＥの水素化反応の適
用温度は０〜１５０℃である。好ましくは５０〜１２０
℃であり１５０℃を超えるとデカリンジカルボン酸ジア
ルキルへの過剰水素化反応が進行し、ＴＤＣＥの収率が
低下する。５０℃未満でも特に支障はないが反応速度が
低下し、反応に長時間を必要とし工業的規模で行う場合
好ましくない。[0015] The application temperature of the hydrogenation reaction of NDCE in the present invention is 0 to 150 ° C. Preferably 50 to 120
When the temperature exceeds 150 ° C., the excess hydrogenation to dialkyl decalin dicarboxylate proceeds, and the yield of TDCE decreases. Even if the temperature is lower than 50 ° C., there is no particular problem, but the reaction rate is lowered, and the reaction requires a long time, which is not preferable when the reaction is carried out on an industrial scale.
【００１６】本発明におけるＮＤＣＥと溶媒との重量比
は、ＮＤＣＥが少なくとも部分的に可溶である状態がよ
く、 原料合計量／溶媒合計量重量比＝０．０１乃至１．０ の範囲で実施するとよい。In the present invention, the weight ratio of NDCE to the solvent is preferably such that NDCE is at least partially soluble, and the weight ratio of the total amount of raw materials / the total amount of solvent is in the range of 0.01 to 1.0. Good to do.
【００１７】本発明で触媒とＮＤＣＥとの重量比は、特
に限定されないが、例えば活性炭に５重量％含むパラジ
ウム、ルテニウム、ロジウム及び白金のいずれか１つの
触媒の場合には、 担体を含めた触媒合計量／原料合計重量比＝０．００５
乃至０．５ の範囲で実施するのが好ましい。この値が０．００５未
満の場合は反応時間が長くなり効率的ではなく、０．５
を超える場合はデカリンジカルボン酸ジアルキルへの過
剰水素化反応が進行し、ＴＤＣＥの収率が低下する。In the present invention, the weight ratio of the catalyst to NDCE is not particularly limited. For example, in the case of any one of palladium, ruthenium, rhodium and platinum containing 5% by weight in activated carbon, the catalyst including the carrier Total amount / total weight ratio of raw materials = 0.005
It is preferable to carry out in the range of 0.5 to 0.5. If this value is less than 0.005, the reaction time becomes longer and it is not efficient.
When it exceeds, the excess hydrogenation reaction to the dialkyl decalin dicarboxylate proceeds, and the yield of TDCE decreases.
【００１８】本発明の水素化反応方法としては、水素化
触媒を溶液中に懸濁させて行う所謂懸濁床による方法、
あるいは、水素化触媒を固定してこれに溶液を流す所謂
固定床による通常の方法が採用できる。さらに例えば懸
濁床に於いては、耐圧容器に水素化触媒、原料のＮＤＣ
Ｅ及び溶媒を仕込み、空間を水素で置換した後、所定温
度で所定時間攪拌する方法、又は水素ガスを反応溶液中
に吹き込む方法がある。また、例えば固定床に於いて
は、水素化触媒を充填した層（例えば充填塔）に原料の
ＮＤＣＥを溶媒に完全溶解した溶液と水素ガスを並流で
通じる方法などがあり、本発明方法においてはこれらの
如何なる方法をも用いることができる。As the hydrogenation reaction method of the present invention, a method using a so-called suspended bed in which a hydrogenation catalyst is suspended in a solution,
Alternatively, an ordinary method using a so-called fixed bed in which a hydrogenation catalyst is fixed and a solution is passed through the fixed catalyst can be adopted. Further, for example, in a suspension bed, a hydrogenation catalyst and NDC as a raw material
After charging E and a solvent and replacing the space with hydrogen, there is a method of stirring at a predetermined temperature for a predetermined time, or a method of blowing hydrogen gas into the reaction solution. Further, for example, in a fixed bed, there is a method in which a solution in which the raw material NDCE is completely dissolved in a solvent and a hydrogen gas are passed in parallel to a layer (for example, a packed tower) packed with a hydrogenation catalyst. Can use any of these methods.
【００１９】本発明方法で水素化して得られたＴＤＣＥ
の粗生成物は触媒を濾過により除去した後、蒸留を経て
触媒を完全に除去し、ついで溶媒再結晶或いは溶融再結
晶により精製できる。例えば、２，６―ＴＤＣＥ（ジメ
チルエステル体）は１０ｍｍＨｇの減圧下、２０８℃で
蒸留できる。さらに、本発明方法で得られた粗２，６―
ＴＤＣＥは不純物含量が低い為に、メタノール再結晶に
より簡単に純度９９．９％以上に精製できる。TDCE obtained by hydrogenation according to the method of the present invention
The crude product can be purified by removing the catalyst by filtration, removing the catalyst completely by distillation, and then recrystallizing the solvent or melting. For example, 2,6-TDCE (dimethyl ester) can be distilled at 208 ° C. under a reduced pressure of 10 mmHg. Furthermore, the crude 2,6-
Since TDCE has a low impurity content, it can be easily purified to a purity of 99.9% or more by recrystallization from methanol.
【００２０】[0020]
【発明の効果】本発明によれば、従来の方法に比較し
て、ＮＤＣＥの水素化反応圧力を大幅に低下でき、製造
する際の効率及び安全性が格段向上する。さらに、ＮＤ
ＣＥの水素化反応温度も低下できることにより反応が穏
やかに進行し副反応が制御でき、ＴＤＣＥへの選択性も
大幅に向上する。According to the present invention, as compared with the conventional method, the hydrogenation reaction pressure of NDCE can be greatly reduced, and the efficiency and safety in production are greatly improved. Further, ND
Since the hydrogenation reaction temperature of CE can be lowered, the reaction proceeds gently and side reactions can be controlled, and the selectivity to TDCE is greatly improved.
【００２１】[0021]
【実施例】次に、本発明を実施例によりさらに詳細に説
明する。尚、以下の実施例の２，６―ＮＤＣＥ転化率及
び２，６―ＴＤＣＥ選択率は下記の式に基いて算出した
ものである。Next, the present invention will be described in more detail with reference to examples. The 2,6-NDCE conversion and the 2,6-TDCE selectivity in the following examples were calculated based on the following equations.
【００２２】[0022]
【数１】 (Equation 1)
【００２３】[0023]
【実施例１】１０ｇの原料２，６―ＮＤＣＥ（ジメチル
エステル体、純度９９．９％以上）を内容積５００ｃｃ
の攪拌機付きハステロイ製オートクレーブの中に、市販
の５％パラジウムを活性炭に担持させた触媒２ｇを１０
０ｇの酢酸と共に入れた。次にオートクレーブ内の空気
を窒素と置換し、さらに窒素を水素と置き換えた後に、
オートクレーブを水素で５ｋｇ／ｃｍ2Ｇに加圧した。
次に攪拌機を起動し回転速度を５００ｒｐｍに調整し、
２０分間かけてオートクレーブ内温を８０℃まで上げた
後、オートクレーブ内圧を水素で１０ｋｇ／ｃｍ2まで
上げ、その状態で６０分間保った。そこで水素の吸収が
無くなったのでオートクレーブを冷却し水素を放出し
た。オートクレーブから取り出した生成物をガスクロマ
トグラフィーで分析し原料が完全に消費された事を確認
した後、Ｎｏ．５Ｃの濾紙を用い５０℃において濾過
し、さらに濾紙上の触媒を５０℃の酢酸１００ｇで洗浄
した。この生成物の分離濾液と洗浄濾液とを併せた後、
溶媒の酢酸をエバポレーターで蒸発させ１０．１ｇの粗
生成物を得た。その組成を分析した結果、２，６―デカ
リンジカルボン酸ジメチル（以後２，６―ＤＤＣＥと略
称する）幾何異性体を全て併せた量で１．４０重量％含
まれている以外は目的物２，６―ＴＤＣＥ（ジメチルエ
ステル体）のみであった。この２，６―ＴＤＣＥ（ジメ
チルエステル体）の選択率は９８．６モル％であった。Example 1 10 g of raw material 2,6-NDCE (dimethyl ester, purity 99.9% or more) was charged to an internal volume of 500 cc.
Of in a stirred Hastelloy autoclave, the catalysts 2g of a commercially available 5% palladium was responsible lifting the activated carbon 10
Charged with 0 g acetic acid. Next, after replacing the air in the autoclave with nitrogen and further replacing nitrogen with hydrogen,
The autoclave was pressurized with hydrogen to 5 kg / cm 2 G.
Next, start the stirrer and adjust the rotation speed to 500 rpm.
After the internal temperature of the autoclave was raised to 80 ° C. over 20 minutes, the internal pressure of the autoclave was raised to 10 kg / cm 2 with hydrogen, and the state was maintained for 60 minutes. Then, since the absorption of hydrogen was lost, the autoclave was cooled to release hydrogen. The product taken out of the autoclave was analyzed by gas chromatography to confirm that the raw materials were completely consumed. The mixture was filtered at 50 ° C. using a 5C filter paper, and the catalyst on the filter paper was washed with 100 g of acetic acid at 50 ° C. After combining the separated filtrate and the washing filtrate of this product,
The solvent acetic acid was evaporated by an evaporator to obtain 10.1 g of a crude product. As a result of analyzing the composition, the target compound 2, except that it contained 1.40% by weight of all geometric isomers of dimethyl 2,6-decalin dicarboxylate (hereinafter abbreviated as 2,6-DDCE), was added. It was only 6-TDCE (dimethyl ester). The selectivity for this 2,6-TDCE (dimethyl ester) was 98.6 mol%.
【００２４】[0024]
【実施例２〜４】原料２，６―ＮＤＣＥの仕込み量およ
び５％パラジウムを活性炭に担持した触媒の仕込量以外
は実施例１の方法を繰り返した。その結果を表１に記載
した。Examples 2 to 4 The procedure of Example 1 was repeated except for the amount of the starting materials 2,6-NDCE and the amount of the catalyst having 5% palladium supported on activated carbon. The results are shown in Table 1.
【００２５】[0025]
【表１】 [Table 1]
【００２６】[0026]
【実施例５〜７】触媒として、５％ルテニウムを活性炭
に担持した触媒、５％ロジウムを活性炭に担持した触媒
および５％白金を活性炭に担持した触媒としたこと以外
は実施例１の方法を繰り返した。その結果を表２に記載
した。 As Example 5-7] catalysts, 5% ruthenium supported on activated carbon catalyst, <br/> except that the supported catalyst and 5% platinum on activated carbon 5% rhodium was catalysts carried on active carbon The method of Example 1 was repeated. The results are shown in Table 2.
【００２７】[0027]
【表２】 [Table 2]
【００２８】[0028]
【実施例８】溶媒がメタノールであること以外は実施例
１の方法を繰り返した。その結果を表３に記載した。Example 8 solvent is except that it is methanol The method of Example 1 was repeated. The results are shown in Table 3.
【００２９】[0029]
【実施例９】溶媒がメタノールであること以外は実施例
４の方法を繰り返した。その結果を実施例８と併せて表
３に記載した。Example 9 except that the solvent is methanol was repeated process of Example 4. The results are shown in Table 3 together with Example 8.
【００３０】[0030]
【比較例１】触媒が市販のラネーニッケル触媒であるこ
と以外は実施例８の方法を繰り返した。その結果を実施
例８，９と併せて表３に記載した。全く水素化反応は起
こらなかった。Comparative Example 1 The procedure of Example 8 was repeated except that the catalyst was a commercially available Raney nickel catalyst. The results are shown in Table 3 together with Examples 8 and 9 . All Ku hydrogenation reaction did not occur.
【００３１】[0031]
【表３】 [Table 3]
【００３２】[0032]
【比較例２】触媒が市販のラネーニッケル触媒であるこ
と、反応温度が１５０℃、反応圧力が１０５ｋｇ／ｃｍ
2 Ｇであること以外は実施例８の方法を繰り返した。そ
の結果は２，６―ＤＤＣＥが幾何異性体を全て併せた量
で９．５重量％含まれていて、原料の２，６―ＮＤＣＥ
が１．０％残っていた。この時の２，６―ＴＤＣＥの選
択率は９１．３％であった。Comparative Example 2 The catalyst was a commercially available Raney nickel catalyst, the reaction temperature was 150 ° C., and the reaction pressure was 105 kg / cm.
It is except that it is 2 G was repeated process of Example 8. As a result, it was found that 2,6-DDCE contained 9.5% by weight in a combined amount of all geometric isomers, and the raw material 2,6-NDCE was contained.
1.0% remained. At this time, the selectivity of 2,6-TDCE was 91.3%.
【００３３】[0033]
【実施例１０】２７０ｇの原料２，６―ＮＤＣＥ（ジメ
チルエステル体、純度９９．９％以上）を内容積３００
０ｃｃの攪拌機付きハステロイ製オートクレーブの中
に、市販の５％パラジウムを活性炭担持した触媒１８ｇ
及び９００ｇのメタノールと共に入れ、実施例１と同様
な条件で反応し、濾過により大方の触媒を除去し、さら
に溶媒を蒸発させ２７３ｇの粗生成物を得た。その組成
を分析した結果、２，６―ＤＤＣＥが幾何異性体を全て
併せた量で１．９４重量％含まれている他は目的物２，
６―ＴＤＣＥ（ジメチルエステル体）のみであった。こ
の２，６―ＴＤＣＥ（ジメチルエステル体）の選択率は
９８．１モル％であった。EXAMPLE 10 270 g of a raw material 2,6-NDCE (dimethyl ester, purity 99.9% or more) was added to an internal volume of 300.
In a 0 cc Hastelloy autoclave equipped with a stirrer, 18 g of a commercially available catalyst carrying 5% palladium on activated carbon was used.
And 900 g of methanol, and reacted under the same conditions as in Example 1. Most of the catalyst was removed by filtration, and the solvent was evaporated to obtain 273 g of a crude product. As a result of analyzing the composition, it was confirmed that the target compound 2 was obtained except that 2,6-DDCE contained 1.94% by weight in a combined amount of all geometric isomers.
It was only 6-TDCE (dimethyl ester). The selectivity of this 2,6-TDCE (dimethyl ester) was 98.1 mol%.
【００３４】この粗生成物を、２０ｃｍビグリューカラ
ムの装填した蒸留装置で塔頂圧力１０ｍｍＨｇ、塔頂温
度２０８℃そして蒸留釜の温度２２０℃の条件で蒸留
し、２６６ｇ（蒸留率９７．４％）の蒸留品を得た。さ
らに、この蒸留品２５０ｇに５００ｇのメタノールを加
え、５５℃まで加温しその後５℃まで冷却し析出した結
晶を濾過分離した。さらに５℃のメタノール２００ｇで
洗浄後室温で真空乾燥し２２５ｇ（回収率９０％）の純
度９９．９２％の２，６―ＴＤＣＥを得た。The crude product was distilled in a distillation apparatus equipped with a 20 cm Vigreux column under the conditions of a top pressure of 10 mmHg, a top temperature of 208 ° C., and a distillation pot temperature of 220 ° C., and 266 g (distillation rate: 97.4%) ) Was obtained. Further, 500 g of methanol was added to 250 g of the distilled product, heated to 55 ° C., cooled to 5 ° C., and the precipitated crystals were separated by filtration. Further, after washing with 200 g of methanol at 5 ° C., it was vacuum-dried at room temperature to obtain 225 g (recovery rate 90%) of 2,6-TDCE having a purity of 99.92%.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平７−53458（ＪＰ，Ａ) 特開 平６−199705（ＪＰ，Ａ) 特開 平６−157406（ＪＰ，Ａ) 特開 昭51−125265（ＪＰ，Ａ) 特開 昭47−12320（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 67/303 C07C 69/74 C07C 69/75 C07C 69/753 C07C 69/76 C07B 61/00 300 B01J 23/40 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-7-53458 (JP, A) JP-A-6-199705 (JP, A) JP-A-6-157406 (JP, A) JP-A-51- 125265 (JP, A) JP 47-12320 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C07C 67/303 C07C 69/74 C07C 69/75 C07C 69/753 C07C 69/76 C07B 61/00 300 B01J 23/40
Claims (2)
白金から成る群から選ばれる少なくとも１種の触媒の存
在下に、ナフタレンジカルボン酸ジアルキルエステル
に、その反応条件においてナフタレンジカルボン酸ジア
ルキルエステルが少なくとも部分的に可溶である溶媒を
用い、３５ｋｇ／ｃｍ2Ｇ以下の圧力下で水素を作用さ
せテトラリンジカルボン酸ジアルキルエステルを合成す
ることからなるナフタレンジカルボン酸ジアルキルエス
テルの水素化方法。1. A palladium, ruthenium, in the presence of at least one catalyst selected from the group consisting of rhodium and platinum, naphthalene dicarboxylic acid dialkyl esters, naphthalene dicarboxylic acid diaryl Te reaction conditions odor
Even alkyl ester is no less using a solvent which is partially soluble, hydrogenation of naphthalene dicarboxylic acid dialkyl ester which comprises synthesizing tetralindicarboxylic acid dialkyl ester by the action of hydrogen under a pressure of less than 35 kg / cm 2 G Method.
６―ナフタレンジカルボン酸ジアルキルである請求項１
に記載の水素化方法。2. The method according to claim 1, wherein the alkyl naphthalenedicarboxylate is 2,2.
2. A dialkyl 6-naphthalenedicarboxylate.
The hydrogenation method according to 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19959293A JP3210148B2 (en) | 1993-08-11 | 1993-08-11 | Method for hydrogenating dialkyl naphthalenedicarboxylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19959293A JP3210148B2 (en) | 1993-08-11 | 1993-08-11 | Method for hydrogenating dialkyl naphthalenedicarboxylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0753467A JPH0753467A (en) | 1995-02-28 |
| JP3210148B2 true JP3210148B2 (en) | 2001-09-17 |
Family
ID=16410418
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19959293A Expired - Fee Related JP3210148B2 (en) | 1993-08-11 | 1993-08-11 | Method for hydrogenating dialkyl naphthalenedicarboxylate |
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| Country | Link |
|---|---|
| JP (1) | JP3210148B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7257734B2 (en) | 2017-04-05 | 2023-04-14 | 株式会社Adeka | Plastic water-in-oil emulsified fat composition for bakery |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4788019B2 (en) * | 2000-06-14 | 2011-10-05 | Ｄｉｃ株式会社 | Method for producing fluorotetrahydronaphthalene derivative |
| JP4788021B2 (en) * | 2000-06-26 | 2011-10-05 | Ｄｉｃ株式会社 | Method for producing 1,2,3,4-tetrahydronaphthalene derivative |
| JPWO2014051021A1 (en) * | 2012-09-28 | 2016-08-22 | 三菱瓦斯化学株式会社 | 1,4-Tetralindicarboxylic acid dialkyl ester and process for producing the same |
| JP6206659B2 (en) * | 2013-09-20 | 2017-10-04 | 三菱瓦斯化学株式会社 | Method for producing 2,6-tetralindicarboxylic acid dialkyl ester |
-
1993
- 1993-08-11 JP JP19959293A patent/JP3210148B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7257734B2 (en) | 2017-04-05 | 2023-04-14 | 株式会社Adeka | Plastic water-in-oil emulsified fat composition for bakery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0753467A (en) | 1995-02-28 |
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