JP2004149449A - Method for producing alicyclic dicarboxylic acid diester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for economically producing a dialkyl tetracyclo[5,4,1,0<SP>2,6</SP>,0<SP>8,11</SP>]dodeca-3,9-diene-9,10-dicarboxylate (DATD) useful as a monomer for polyesters, polyamides, polyepoxy resins, and the like which utilize the specificity of the skeleton of dicyclopentadine (DCPD) and have improved physical properties such as heat resistance, light transmissivity and electric characteristics, or as an intermediate for them, from dicyclopentadiene (DCPD) as a raw material. <P>SOLUTION: This method for producing DATD represented by formula [2] (R<SP>1</SP>and R<SP>2</SP>are each independently a 1 to 10C alkyl group or a 5 to 6C cycloalkyl group), comprising addition-reacting DCPD with a dialkyl acetylenedicarboxylate represented by formula [1] in the presence of a group 8 metal in the periodic table as a catalyst, is characterized by using a ruthenium metal salt as the catalyst and not using a solvent or using at least one solvent selected from oxygen-containing and/or nitrogen-containing hydrocarbon compounds. <P>COPYRIGHT: (C)2004,JPO

Description

【０００８】
（式中、Ｒ^１、Ｒ^２はそれぞれ独立して炭素数１〜１０のアルキル基、炭素数５又は６のシクロアルキル基を表す。）
で表されるアセチレンジカルボン酸ジアルキルを周期律表第８族金属を触媒とし付加反応させ、式［２］
【０００９】
【化５】

【００１０】
（式中、Ｒ^１、Ｒ^２は前記と同じ意味を表す。）
で表されるジアルキルテトラシクロ［５．４．１．０^２，６．０^８，１１］ドデカ−３，９−ジエン−９，１０−ジカルボキシレートの製造法において、ルテニウム金属塩を触媒とし、無溶媒下または含酸素及び含窒素炭化水素化合物の中から選ばれた少なくとも１種の溶媒を用いることを特徴とするジアルキルテトラシクロ［５．４．１．０^２，６．０^８，１１］ドデカ−３，９−ジエン−９，１０−ジカルボキシレートの製造法に関する。以下本発明を詳細に説明する。
【００１１】
【発明の実施の形態】
本発明のジアルキルテトラシクロ［５．４．１．０^２，６．０^８，１１］ドデカ−３，９−ジエン−９，１０−ジカルボキシレート（ＤＡＴＤ）の製造法は、下記のルートで表される。
【００１２】
【化６】

【００１３】
（式中、Ｒ^１、Ｒ^２及びＸは前記と同じ意味を表す。）
ジシクロペンタジエン（以下ＤＣＰＤと略す）は、市販品をそのまま使用することができる。アセチレンジカルボン酸ジアルキル化合物（以下ＤＭＡ化合物と略す）としては、種々の化合物が使用できる。
【００１４】
ＤＭＡ化合物のＲ^１、Ｒ^２は炭素数１〜１０のアルキル基、炭素数５又は６のシクロアルキル基を表すが、例えば、具体的には、ジメチルアセチレンジカルボキシレート、ジエチルアセチレンジカルボキシレート、ジプロピルアセチレンジカルボキシレート、ジブチルアセチレンジカルボキシレート、ジペンチルアセチレンジカルボキシレート、ジヘキシルアセチレンジカルボキシレート、ジシクロペンチルアセチレンジカルボキシレート及びジシクロヘキシルアセチレンジカルボキシレート等が挙げられる。
【００１５】
本反応において、本触媒存在下では、ＤＭＡ化合物が特に重合し易く、ＤＭＰ化合物の３量体であるヘキサ（メトキシカルボニル）ベンゼンが副生するので、ＤＣＰＤの転化率を上げるためには過剰量仕込むことが必要である。ＤＭＡ化合物の仕込み量は、ＤＣＰＤに対して１〜３モル当量が好ましく、更には１．２〜２．５モル当量が好ましい。ＤＭＡ化合物の仕込み法は、５０〜８０℃でＤＣＰＤ、溶媒及び触媒の混合液中に０．５〜１０時間かけて分割滴下することにより重合物の副生を抑制しつつ本反応を進行させることができる。ＤＣＰＤが残余しＤＭＡ化合物が消失された場合は、ＤＭＡ化合物を追加滴下し反応を完結させることができる。
【００１６】
本発明では、ルテニウム金属塩を用いて、溶媒種の選択や、上記したＤＭＡ化合物の仕込み方法を改良することにより目的物が高収率で得られる。
【００１７】
触媒のルテニウム金属塩としては、ルテニウムの塩酸、硫酸、硝酸及び燐酸等の鉱酸塩、蟻酸、酢酸及びプロピオン酸等の有機酸塩が挙げられる。具体的には例えば、三塩化ルテニウム、三臭化ルテニウム、三沃化ルテニウム、硫酸ルテニウム、硝酸ルテニウム、リン酸ルテニウム、蟻酸テニウム、酢酸ルテニウム及びプロピオン酸ルテニウムが挙げられる。実用的には最も経済的な三塩化ルテニウム及び三臭化ルテニウム等が好ましい。
【００１８】
その使用量は、原料のＤＣＰＤに対し、０．１〜３０モル％、特には、０．５〜１０モル％が好ましい。三塩化ルテニウム及び三臭化ルテニウムは、トリフェニルホスフィン存在下で使用することもできる。その際のトリフェニルホスフィンの添加量は、トリハロゲン化ルテニウムに対して１〜１０モル当量が好ましく、特には３〜６モル当量が好ましい。
【００１９】
本発明で重要なのが溶媒の選択である。本反応では溶媒を使用しなくとも、反応は進行するが、溶媒を使用することが好ましい。無溶媒で反応すると、その進行に従い生成物が多くなると反応液の粘度が上がり攪拌が低下し原料ＤＣＰＤが未反応のままで残余する。溶媒を使用することにより、ＤＣＰＤの転化率が上がり、また特定の溶媒を使用することにより目的物ＤＡＤＴの選択率及び収率が向上する。その溶媒としては例えば、含酸素及び又は含窒素炭化水素化合物であり触媒を溶解する極性溶媒が好ましい。具体的には脂肪族エーテル化合物、脂肪族ケトン化合物、低級アルコール化合物、脂肪族カルボン酸化合物、脂肪族エステル化合物、脂肪族ニトリル化合物、脂肪族アミド化合物、脂肪族ラクトン化合物、脂肪族ラクタム化合物、脂肪族ニトロ化合物及び脂肪族スルホン化合物等が挙げられる。
【００２０】
更に、具体的には脂肪族エーテル化合物としては、１，２−ジメトキシエタン及びジエチレングリコールジメチルエーテル（ジグライム）等の鎖状エーテル類、１，４−ジオキサン、１２−クラウン−４−エーテル、１５−クラウン−５−エーテル、１８−クラウン−６−エーテル及びジベンゾ−１８−クラウン−６−エーテル等の環状エーテル類等、脂肪族ケトン化合物としては、アセトン、メチルエチルケトン及びメチルイソブチルケトン等、低級アルコール化合物としては、メタノール、エタノール、ｎ−プロパノール、ｉｓｏ−プロパノール、ｎ−ブタノール、ｉｓｏ−ブタノール、ｓｅｃ−ブタノール及びｔｅｒｔーブタノール等、脂肪族カルボン酸化合物としては、蟻酸、酢酸及びプロピオン酸等、脂肪族エステル化合物としては、酢酸エチル、酢酸プロピル、プロピオン酸メチル及びプロピオン酸エチル等、脂肪族ニトリル化合物としては、アセトニトリル、プロピオニトリル、ブチロニトリル及びバレロニトリル等、脂肪族アミド化合物としては、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）、Ｎ−メチルピロリドン（ＮＭＰ）及び１，３−ジメチル−２−イミダゾリジノン（ＤＭＩ）等、脂肪族ラクトン化合物としては、β−プロピオラクトン、β−ブチロラクトン及びδ−ブチロラクトン等、脂肪族ラクタム化合物としては、β−ブチロラクタム及びδ−バレロラクタム等、脂肪族ニトロ化合物としては、ニトロメタン、ニトロエタン及びニトロプロパン等、脂肪族スルホン化合物がジメチルスルホキシド及びスルホラン等が一例として挙げられる。
【００２１】
特には、脂肪族エーテル化合物が、１，２−ジメトキシエタン、ジエチレングリコールジメチルエーテル（ジグライム）、１，４−ジオキサン、１５−クラウン−５−エーテル、脂肪族ケトン化合物がメチルイソブチルケトン、脂肪族カルボン酸化合物が酢酸、脂肪族エステル化合物が酢酸エチル、脂肪族アミド化合物がＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）、Ｎ−メチルピロリドン（ＮＭＰ）及び１，３−ジメチル−２−イミダゾリジノン（ＤＭＩ）並びに脂肪族ニトロ化合物がニトロメタン及びニトロエタン並びに脂肪族スルホン化合物がジメチルスルホキシド等が好ましい。
【００２２】
特に好ましい溶媒は、１，２−ジメトキシエタン、ジクライム、メチルイソブチルケトン、ＤＭＦ、ＮＭＰ及びニトロメタンが挙げられる。
【００２３】
又これらの溶媒を組み合わせて使用することもできる。更には、脂肪族ニトロ化合物が、副生物が抑制され目的化合物の選択率及び収率が高く特に優れている。
【００２４】
その使用量は、溶媒量が多くなると反応進行が遅くなるが、無溶媒では、反応進行に伴い高粘稠になることから、溶媒量はＤＣＰＤに対し１〜２０質量倍、特には１〜１０質量倍が経済的にも好ましい。
【００２５】
ＤＭＡ化合物の滴下終了後、昇温し未反応ＤＣＰＤの反応を完結させることができる。本発明で重要なのが溶媒の選択に加えて反応温度の設定である。高温ほど反応が速いが重合等の副反応を伴うので、通常５０〜１８０℃の範囲が好ましく、特には６０〜１５０℃の範囲で行うのが好ましい。
【００２６】
また、本反応の原料であるＤＣＰＤやＤＭＰ化合物の重合を抑制するために重合禁止剤を添加することもできる。
【００２７】
重合禁止剤としては例えば、ジフェニルピクリルヒドラジン、トリ−ｐ−ニトロフェニルメチル、Ｎ−（３−Ｎ−オキシアニリノ−１，３−ジメチルブチリデン）アニリンオキシド、ｐ−ベンゾキノン、ｐ−ｔｅｒｔ−ブチルカテコール、ニトロベンゼン、ピクリン酸、ジチオベンゾイルジスルフィド、ヒドロキノン、ｐ−メトキシフェノール、２，４−ジ−ｔ−ブチル−４−メチルフェノール及び塩化銅（ＩＩ）等が挙げられる。
【００２８】
重合禁止剤の添加量は、ＤＣＰＤやＤＭＰ化合物に対して０．０１〜１モル％が好ましい。
【００２９】
反応時間は、ガスクロマトグラフィー（ＧＣ）や液体クロマトグラフィー（ＬＣ）で反応追跡して決定することができるが、通常４〜３０時間で終了させることができる。本反応は、常圧又は加圧で行うこともでき、又回分式あるいは連続式でも可能である。
【００３０】
反応生成物の単離は、濾過により触媒を分離した後、溶媒を濃縮留去させてから、蒸留法又はカラムクロマトグラフィー法で行うことができる。
【００３１】
以下に実施例を挙げ、本発明を更に具体的に説明するが、本発明はこれらに限定されるものではない。
【００３２】
【実施例】
実施例１
１００ｍｌ耐熱ガラス製４つ口反応フラスコにＤＣＰＤ１３．２ｇ（１００ｍｍｏｌ）、三塩化ルテニウム・三水塩（ＲｕＣｌ_{３ ・}３Ｈ_２Ｏ）１．０ｇ（４ｍｍｏｌ）、ニトロメタン６６．０ｇを仕込み、攪拌しながら７５℃に昇温してアセチレンジカルボン酸ジメチル（ＤＭＡ）２１．３ｇ（１５０ｍｍｏｌ）を１時間３０分かけて滴下した。７５℃で１時間攪拌を続けてから９０℃に昇温し５時間攪拌を続け、反応液を、ガスクロマトグラフィー（ＧＣ）で分析した結果、未反応ＤＣＰＤが８．２面積％残余し、新たなピークが７８．６面積％生成していることが解った。そのまま更に１０時間攪拌してから再度ＧＣ分析した結果、未反応ＤＣＰＤが２．３面積％残余し、新たなピークが８２．５面積％生成していることが解った。冷却後、触媒を濾過除去し、濃縮してからシリカゲルカラムクロマトグラフィー（溶離液：酢酸エチル／ｎ−ヘプタン＝１／５〜１／１）で精製すると油状物２１．５ｇ（収率７８．３％）が得られた。この油状物をＭＡＳＳ、^１ＨＮＭＲ、^１３ＣＮＭＲで分析の結果、下記の分析値よりジメチルテトラシクロ［５．４．１．０^２，６．０^８，１１］ドデカ−３，９−ジエン−９，１０−ジカルボキシレート（ＤＭＤＥ）であることを確認した。
【００３３】
ＭＡＳＳ（ＦＡＢ^＋，ｍ／ｅ（％））：２７５（［Ｍ＋Ｈ］^＋，６０），２４３（５０），１７６（１００），１６３（３８），１４９（４８）．
^１ＨＮＭＲ（ＣＤＣｌ_３，δｐｐｍ）：１．２２（ｄ，Ｊ＝１１．０Ｈｚ，１Ｈ），１．３９（ｄ，Ｊ＝１０．７Ｈｚ，１Ｈ），２．１７（ｄ，Ｊ＝４．８９Ｈｚ，１Ｈ），２．１８−２．２０（ｍ，２Ｈ），２．２９（ｄ，Ｊ＝５．１９Ｈｚ，１Ｈ），２．６２−２．６５（ｍ，２Ｈ），２．７２（ｄ，Ｊ＝３．３６Ｈｚ，１Ｈ），３．０９−３．１３（ｍ，１Ｈ），３．６９（ｓ，６Ｈ），５．４６−５．４８（ｍ，１Ｈ），５．５６−５．５８（ｍ，１Ｈ）．
^１３ＣＮＭＲ（ＣＤＣｌ_３，δｐｐｍ）：３０．９９，３３．６３，３５．５９，３７．３８，４１．１０，４１．４１，４４．０５，５１．５１（２Ｃ），５２．０３，１３０．４７，１３１．４５，１４１．１９，１４２．３４，１６１．２８，１６１．３１．
【００３４】
実施例２〜８
５０ｍｌ耐熱ガラス製４つ口反応フラスコにＤＣＰＤ１．３２ｇ（１０ｍｍｏｌ）、三塩化ルテニウム・三水塩（ＲｕＣｌ_３・３Ｈ_２Ｏ）、１，４−ジオキサ６．６ｇを仕込み、攪拌しながら６０℃に昇温してＤＭＡ２．１３ｇ（１５ｍｍｏｌ）を３０分かけて滴下した。続いて所望の温度に昇温して攪拌を続けて反応させた。触媒量、反応温度、反応時間を変えて得られた反応液を、ガスクロマトグラフィーで分析した結果を表１に示す。
【００３５】
【表１】

【００３６】
実施例９〜２６及び比較例１、２
５０ｍｌ耐熱ガラス製４つ口反応フラスコにＤＣＰＤ１．３２ｇ（１０ｍｍｏｌ）、三塩化ルテニウム・三水塩（ＲｕＣｌ_３・３Ｈ_２Ｏ） ０．０１ｇ（０．４ｍｍｏｌ）、溶媒６．６ｇを仕込み、攪拌しながら７０℃に昇温してＤＭＡ２．１３ｇ（１５ｍｍｏｌ）を３０分かけて滴下した。そのまま７０℃で１時間攪拌を続けてから、所望の温度に昇温して攪拌を続けて反応させた。溶媒種、反応温度、反応時間を変えて得られた反応液を、ガスクロマトグラフィーで分析した結果を表２に示す。
【００３７】
【表２】

【００３８】
【発明の効果】
耐熱性、光透過性、電気特性（絶縁性、誘電率）、吸水性及び有機溶媒溶解性等の諸物性の改良されたポリエステル、ポリアミド、ポリアクリレート及びポリエポキシ樹脂等のモノマー又はその中間体として有用なジアルキルテトラシクロ［５．４．１．０^２，６．０^８，１１］ドデカ−３，９−ジエン−９，１０−ジカルボキシレート（ＤＡＴＤ）が安価な触媒で高収率で得られる。[0001]
TECHNICAL FIELD OF THE INVENTION
In the present invention, dicyclopentadiene and dialkyl acetylenedicarboxylate are used as a catalyst with a ruthenium metal salt as a catalyst, or in the absence of a solvent or with an oxygen-containing and / or nitrogen-containing hydrocarbon compound as a solvent, and dialkyltetracyclo [5.4.1.0 ^{2, 6} . 0 ^8,11] (abbreviated as DATD) dodeca-3,9-diene-9,10-dicarboxylate comprising the preparation of cycloaliphatic dicarboxylic acid diester related.
[0002]
DATD is expected to have a new use as a monomer such as polyester, polyamide, polyacrylate and polyepoxy resin or an intermediate thereof in terms of heat resistance and light transmittance.
[0003]
[Prior art]
Conventionally, a polyester having a norbornane skeleton has a high glass transition temperature and excellent dimensional stability, and is used as a base of a photographic film (Non-Patent Document 1). In the past, synthesis of polycyclic compounds having a norbornane skeleton required many steps in many cases, and was disadvantageous in terms of production cost. DATD has obtained DATD in a high yield as a novel and excellent monomer in which the polymer is expected to have improved heat resistance and high light transmittance as compared with conventional products (Patent Document 1).
[0004]
However, the production catalyst is dihydridotetrakis (triphenylphosphine) ruthenium, dihydridocarbonyltris (triphenylphosphine) ruthenium, dichlorotris (triphenylphosphine) ruthenium, or the like. In addition to the complicated handling, the catalyst is expensive and industrially unsuitable, and therefore has the problem of cost reduction.
[0005]
[Non-patent document 1]
JOURNAL OF POLYMER SCIENCE: Polymer Chemistry Edition, vol. 10, p. 3191-3204 (1972). Journal of Polymer Science: Polymer Chemistry Edition.
[Patent Document 1]
Japanese Patent Application Laid-Open No. 09-077721 [Problems to be Solved by the Invention]
Using dicyclopentadiene as a raw material, which has high industrial economic value, various properties such as heat resistance, light transmittance, electrical properties (insulation and dielectric constant), water absorption and organic solvent solubility, etc. It is an object of the present invention to provide an economical method for producing a monomer such as polyester, polyamide, polyacrylate and polyepoxy resin having improved physical properties, or an alicyclic dicarboxylic diester as an intermediate thereof.
[0006]
Means for Solving the Invention
The present inventor has conducted intensive studies to solve the above-mentioned problems, and as a result, in one step, by using ruthenium metal salt as a Group 8 metal catalyst of the periodic table from dicyclopentadiene and dialkyl acetylenedicarboxylate, The resulting dialkyltetracyclo [5.4.1.0 ^2,6 . 0 ^8,11] found an industrially feasible economical method for producing dodeca-3,9-diene-9,10-dicarboxylate (DATD). That is, the present invention relates to dicyclopentadiene and formula [1]
[0007]
Embedded image

[0008]
(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms.)
Is subjected to an addition reaction using a group 8 metal of the periodic table as a catalyst to give a dialkyl acetylenedicarboxylate represented by the formula [2]
[0009]
Embedded image

[0010]
(In the formula, R ¹ and R ² represent the same meaning as described above.)
The dialkyltetracyclo [5.4.1.0 ^2,6 . In 0 ^8,11] dodeca-3,9-diene-9,10-dicarboxylate process, the ruthenium metal salt as a catalyst, selected from among without a solvent or oxygen-containing and nitrogen-containing hydrocarbon compound A dialkyltetracyclo [5.4.1.0 ^2,6 ... Characterized by using at least one solvent. 0 ^8,11] dodeca-3,9-diene-9,10-di-carboxylate Method for. Hereinafter, the present invention will be described in detail.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
The dialkyltetracyclo [5.4.1.0 ^2,6 . 0 ^8,11] preparation of dodeca-3,9-diene-9,10-dicarboxylate (DATD) is represented by the following route.
[0012]
Embedded image

[0013]
(In the formula, R ¹ , R ² and X represent the same meaning as described above.)
As dicyclopentadiene (hereinafter abbreviated as DCPD), a commercially available product can be used as it is. Various compounds can be used as the dialkyl acetylenedicarboxylate compound (hereinafter abbreviated as DMA compound).
[0014]
R ¹ and R ² of the DMA compound each represent an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms. For example, specifically, dimethyl acetylenedicarboxylate, diethyl acetylenedicarboxylate, Examples thereof include dipropyl acetylene dicarboxylate, dibutyl acetylene dicarboxylate, dipentyl acetylene dicarboxylate, dihexyl acetylene dicarboxylate, dicyclopentyl acetylene dicarboxylate, and dicyclohexyl acetylene dicarboxylate.
[0015]
In the present reaction, in the presence of the present catalyst, the DMA compound is particularly easily polymerized, and hexa (methoxycarbonyl) benzene which is a trimer of the DMP compound is by-produced. Therefore, an excess amount is charged in order to increase the conversion of DCPD. It is necessary. The amount of the DMA compound charged is preferably 1 to 3 molar equivalents, more preferably 1.2 to 2.5 molar equivalents, with respect to DCPD. The method of charging the DMA compound is to allow the reaction to proceed while suppressing the by-product of the polymer by dividing and dropping into a mixture of DCPD, a solvent and a catalyst at 50 to 80 ° C. over 0.5 to 10 hours. Can be. When DCPD remains and the DMA compound disappears, the reaction can be completed by adding an additional drop of the DMA compound.
[0016]
In the present invention, the target product can be obtained in a high yield by using a ruthenium metal salt and improving the selection of the solvent type and the above-described method of charging the DMA compound.
[0017]
Examples of the ruthenium metal salt of the catalyst include mineral salts of ruthenium, such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and organic acid salts, such as formic acid, acetic acid, and propionic acid. Specific examples include ruthenium trichloride, ruthenium tribromide, ruthenium triiodide, ruthenium sulfate, ruthenium nitrate, ruthenium phosphate, ruthenium formate, ruthenium acetate and ruthenium propionate. Practically, ruthenium trichloride and ruthenium tribromide, which are the most economical, are preferred.
[0018]
The amount used is preferably 0.1 to 30 mol%, particularly preferably 0.5 to 10 mol%, based on DCPD of the raw material. Ruthenium trichloride and ruthenium tribromide can also be used in the presence of triphenylphosphine. The amount of triphenylphosphine to be added at this time is preferably 1 to 10 molar equivalents, particularly preferably 3 to 6 molar equivalents, based on ruthenium trihalide.
[0019]
What is important in the present invention is the choice of solvent. In this reaction, the reaction proceeds without using a solvent, but it is preferable to use a solvent. When the reaction is carried out without a solvent, if the amount of products increases with the progress of the reaction, the viscosity of the reaction solution increases, the stirring decreases, and the raw material DCPD remains unreacted. The use of a solvent increases the conversion of DCPD, and the use of a specific solvent improves the selectivity and yield of the target product, DADT. As the solvent, for example, a polar solvent which is an oxygen-containing and / or nitrogen-containing hydrocarbon compound and dissolves the catalyst is preferable. Specifically, aliphatic ether compounds, aliphatic ketone compounds, lower alcohol compounds, aliphatic carboxylic acid compounds, aliphatic ester compounds, aliphatic nitrile compounds, aliphatic amide compounds, aliphatic lactone compounds, aliphatic lactam compounds, fatty acids Nitro compounds and aliphatic sulfone compounds.
[0020]
More specifically, examples of the aliphatic ether compound include chain ethers such as 1,2-dimethoxyethane and diethylene glycol dimethyl ether (diglyme), 1,4-dioxane, 12-crown-4-ether, and 15-crown-ether. As aliphatic ketone compounds such as cyclic ethers such as 5-ether, 18-crown-6-ether and dibenzo-18-crown-6-ether, acetone, methyl ethyl ketone and methyl isobutyl ketone, and lower alcohol compounds such as As aliphatic carboxylic acid compounds such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol and tert-butanol, formic acid, acetic acid and propionic acid, etc. , Ethyl acetate, propyl acetate, methyl propionate and ethyl propionate; aliphatic nitrile compounds such as acetonitrile, propionitrile, butyronitrile and valeronitrile; aliphatic amide compounds such as N, N-dimethylformamide (DMF ), N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone (DMI), such as β-propiolactone, β Aliphatic lactam compounds such as -butyrolactone and δ-butyrolactone; β-butyrolactam and δ-valerolactam; aliphatic nitro compounds such as nitromethane, nitroethane and nitropropane; and aliphatic sulfone compounds such as dimethyl sulfoxide and sulfolate. And the like as an example.
[0021]
In particular, the aliphatic ether compound is 1,2-dimethoxyethane, diethylene glycol dimethyl ether (diglyme), 1,4-dioxane, 15-crown-5-ether, the aliphatic ketone compound is methyl isobutyl ketone, the aliphatic carboxylic acid compound Is acetic acid, the aliphatic ester compound is ethyl acetate, and the aliphatic amide compound is N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and 1,3-dimethyl- 2-imidazolidinone (DMI) and the aliphatic nitro compound are preferably nitromethane and nitroethane, and the aliphatic sulfone compound is preferably dimethyl sulfoxide.
[0022]
Particularly preferred solvents include 1,2-dimethoxyethane, diclime, methyl isobutyl ketone, DMF, NMP and nitromethane.
[0023]
Further, these solvents can be used in combination. Furthermore, aliphatic nitro compounds are particularly excellent because the by-products are suppressed and the selectivity and yield of the target compound are high.
[0024]
The amount of the solvent used is such that the reaction progresses slowly when the amount of the solvent increases, but in the absence of a solvent, the viscosity increases with the progress of the reaction. Therefore, the amount of the solvent is 1 to 20 times, preferably 1 to 10 times the mass of DCPD. A mass-fold is economically preferable.
[0025]
After the completion of the dropwise addition of the DMA compound, the temperature is raised to complete the reaction of unreacted DCPD. What is important in the present invention is the setting of the reaction temperature in addition to the selection of the solvent. The higher the temperature is, the faster the reaction is, but it involves a side reaction such as polymerization.
[0026]
Further, a polymerization inhibitor may be added to suppress polymerization of DCPD or DMP compound which is a raw material of this reaction.
[0027]
Examples of the polymerization inhibitor include diphenylpicrylhydrazine, tri-p-nitrophenylmethyl, N- (3-N-oxyanilino-1,3-dimethylbutylidene) aniline oxide, p-benzoquinone, and p-tert-butylcatechol. Nitrobenzene, picric acid, dithiobenzoyl disulfide, hydroquinone, p-methoxyphenol, 2,4-di-t-butyl-4-methylphenol, copper (II) chloride and the like.
[0028]
The addition amount of the polymerization inhibitor is preferably 0.01 to 1 mol% based on DCPD or DMP compound.
[0029]
The reaction time can be determined by pursuing the reaction by gas chromatography (GC) or liquid chromatography (LC), but can usually be completed in 4 to 30 hours. This reaction can be carried out at normal pressure or under pressure, and can also be carried out batchwise or continuously.
[0030]
Isolation of the reaction product can be carried out by separating the catalyst by filtration, concentrating and distilling off the solvent, and then performing a distillation method or a column chromatography method.
[0031]
Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.
[0032]
【Example】
Example 1
DCPD13.2g in 100ml heat-resistant glass-made 4-neck reaction flask (100 mmol), ruthenium trichloride trihydrate _{(RuCl 3 · 3H 2 O)} 1.0g (4mmol), were charged nitromethane 66.0 g, stirring 75 After the temperature was raised to 2 ° C., 21.3 g (150 mmol) of dimethyl acetylenedicarboxylate (DMA) was added dropwise over 1 hour and 30 minutes. After stirring at 75 ° C. for 1 hour, the temperature was raised to 90 ° C., and stirring was continued for 5 hours. As a result of analyzing the reaction solution by gas chromatography (GC), 8.2 area% of unreacted DCPD remained, and It was found that 78.6 area% of a peak was generated. The mixture was stirred for another 10 hours and subjected to GC analysis again. As a result, it was found that 2.3 area% of unreacted DCPD remained and 82.5 area% of a new peak was generated. After cooling, the catalyst was removed by filtration, concentrated, and then purified by silica gel column chromatography (eluent: ethyl acetate / n-heptane = 1/5 to 1/1) to give 21.5 g of an oily substance (yield: 78.3). %)was gotten. As a result of analyzing this oily substance by MASS, ¹ HNMR, and ¹³ CNMR, dimethyltetracyclo [5.4.1.0 ^2,6 . 0 ^8,11] was confirmed to be dodeca-3,9-diene-9,10-dicarboxylate (DMDE).
[0033]
MASS (FAB ⁺ , m / e (%)): 275 ([M + H] ⁺ , 60), 243 (50), 176 (100), 163 (38), 149 (48).
¹ H NMR (CDCl ₃ , δ ppm): 1.22 (d, J = 11.0 Hz, 1H), 1.39 (d, J = 10.7 Hz, 1H), 2.17 (d, J = 4.89 Hz) , 1H), 2.18-2.20 (m, 2H), 2.29 (d, J = 5.19 Hz, 1H), 2.62-2.65 (m, 2H), 2.72 (d , J = 3.36 Hz, 1H), 3.09-3.13 (m, 1H), 3.69 (s, 6H), 5.46-5.48 (m, 1H), 5.56-5. .58 (m, 1H).
¹³ C NMR (CDCl ₃ , δ ppm): 30.99, 33.63, 35.59, 37.38, 41.10, 41.41, 44.05, 51.51 (2C), 52.03, 130. 47, 131.45, 141.19, 142.34, 161.28, 161.31.
[0034]
Examples 2 to 8
1.32 g (10 mmol) of DCPD, ruthenium trichloride / trihydrate (RuCl ₃ .3H ₂ O) and 6.6 g of 1,4-dioxa were charged into a 50 ml heat-resistant glass four-necked reaction flask, and the mixture was heated to 60 ° C. with stirring. The temperature was raised and 2.13 g (15 mmol) of DMA was added dropwise over 30 minutes. Subsequently, the temperature was raised to a desired temperature and stirring was continued to cause a reaction. The reaction liquid obtained by changing the amount of the catalyst, the reaction temperature and the reaction time was analyzed by gas chromatography, and the results are shown in Table 1.
[0035]
[Table 1]

[0036]
Examples 9 to 26 and Comparative Examples 1 and 2
1.32 g (10 mmol) of DCPD, 0.01 g (0.4 mmol) of ruthenium trichloride / trihydrate (RuCl ₃ .3H ₂ O), and 6.6 g of a solvent were charged into a 50 ml heat-resistant glass four-necked reaction flask and stirred. While the temperature was raised to 70 ° C., 2.13 g (15 mmol) of DMA was added dropwise over 30 minutes. After stirring at 70 ° C. for 1 hour as it was, the temperature was raised to a desired temperature and stirring was continued to cause a reaction. Table 2 shows the results of gas chromatography analysis of the reaction solution obtained by changing the solvent type, reaction temperature, and reaction time.
[0037]
[Table 2]

[0038]
【The invention's effect】
As monomers or intermediates of polyesters, polyamides, polyacrylates and polyepoxy resins, etc. with improved properties such as heat resistance, light transmittance, electrical properties (insulation, dielectric constant), water absorption and solubility in organic solvents Useful dialkyltetracyclo [5.4.1.0 ^2,6 . 0 ^8,11] dodeca-3,9-diene-9,10-dicarboxylate (DATD) in high yields at low catalyst.

Claims (5)

Dicyclopentadiene and formula [1]

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms.)
Is subjected to an addition reaction using a group 8 metal of the periodic table as a catalyst to give a dialkyl acetylenedicarboxylate represented by the formula [2]

(In the formula, R ¹ and R ² represent the same meaning as described above.)
The dialkyltetracyclo [5.4.1.0 ^2,6 . In 0 ^8,11] production process for obtaining a dodeca-3,9-diene-9,10-dicarboxylate, ruthenium metal salt as a catalyst, among the solvent-free or under an oxygen-containing and / or nitrogen-containing hydrocarbon compound A dialkyltetracyclo [5.4.1.0 ^2,6 ... Characterized by using at least one selected solvent. 0 ^8,11] dodeca-3,9 preparation of diene-9,10-dicarboxylate. The ruthenium metal salt has the formula [3]

(In the formula, X represents a halogen atom.)
3. The dialkyltetracyclo [5.4.1.0 ^2,6 .3] according to claim 1, which is a trihalogenorthenium represented by the formula: 0 ^8,11] dodeca-3,9 preparation of diene-9,10-dicarboxylate. 3. The dialkyltetracyclo [5.4.1.0 ^2,6 .3] according to claim 1 or 2, wherein the ruthenium metal salt is ruthenium trichloride. ^08,11 ], 9-diene-9,10-dicarboxylate. The oxygen-containing and / or nitrogen-containing hydrocarbon compound is an aliphatic ether compound, an aliphatic ketone compound, an aliphatic carboxylic acid compound, an aliphatic ester compound, an aliphatic nitrile compound, an aliphatic amide compound, an aliphatic lactone compound, an aliphatic lactam. 4. The dialkyltetracyclo [5.4.1.0 ^2,6 .4] according to any one of claims 1 to 3, which is a compound, an aliphatic nitro compound and an aliphatic sulfone compound. 0 ^8,11] dodeca-3,9 preparation of diene-9,10-dicarboxylate. The dialkyl acetylenedicarboxylate is used in an amount of 1 to 3 molar equivalents with respect to dicyclopentadiene, and the mixture is added dropwise at 50 to 80 ° C. in a mixture of dicyclopentadiene and a catalyst over 0.5 to 10 hours. The dialkyltetracyclo [5.4.1.0 ^2,6 . 0 ^8,11] dodeca-3,9 preparation of diene-9,10-dicarboxylate.