JP4913962B2 - Process for producing phenylethynylphthalic anhydride derivative - Google Patents
Process for producing phenylethynylphthalic anhydride derivative Download PDFInfo
- Publication number
- JP4913962B2 JP4913962B2 JP2001260980A JP2001260980A JP4913962B2 JP 4913962 B2 JP4913962 B2 JP 4913962B2 JP 2001260980 A JP2001260980 A JP 2001260980A JP 2001260980 A JP2001260980 A JP 2001260980A JP 4913962 B2 JP4913962 B2 JP 4913962B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- aromatic hydrocarbon
- anhydride
- organic solvent
- represented
- 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
Description
【０００１】
【発明の属する技術分野】
本発明は、炭素−炭素３重結合を有するフタル酸無水物の製造方法に関し、特に、高純度フェニルエチニルフタル酸無水物誘導体を、工業的に効率良く高収率で得ることができる製造方法に関する。
【０００２】
【従来の技術】
フェニルエチニルフタル酸無水物誘導体は、ポリイミド分野で必要とされている接着性、耐熱性、機械強度を兼ね備えた材料であり、極めて利用価値が高い。
このフェニルエチニルフタル酸無水物誘導体の製造方法について、これまでにいくつかの方法が知られている。これらの製造方法は、いずれも反応後塩酸水溶液にて目的物の酸無水物を一旦、開環させ、再度、無水酢酸又は熱閉環により酸無水物としている。例えば、P. M. Hergenrotherらは、Polymer, 35巻(22号), 4857-(1994）において、エチニルベンゼンとブロモフタル酸無水物を大過剰の塩基性有機物存在下で反応後、副生塩をろ過し、水で晶析して最後に熱閉環によりフェニルエチニルフタル酸無水物を得ている（収率：６７％）。G. W. Meyerらは、HighPerform. Polym. 6巻, 423-(1994）において、ＤＭＡｃ中でエチニルベンゼンとブロモフタル酸無水物反応後、塩酸晶析、熱閉環、昇華によりフェニルエチニルフタル酸無水物を得ている（収率：８４％）。また、特開平１１−１８０９７０号公報には、過剰の塩基性有機物存在下で反応後、水で晶析後塩酸洗浄し無水酢酸で閉環しフェニルエチニルフタル酸無水物を得る方法が開示されている。工業的プロセスを考慮すると、酸無水物を開環して固液分離し、再度閉環することは生産性低下となり、工業プロセスとしては効率が悪い。
【０００３】
【課題を解決するための手段】
本発明（１）は、式（１）
【０００４】
【化４】
（式中、ｎは、１〜３の整数を表し、Ｒは、相互に独立して、水素原子、炭素数１〜４のアルキル基、アルコキシ基、フェニル基、フェノキシ基又はシアノ基を表す）で示されるエチニルベンゼン誘導体と
式（２）
【０００６】
【化５】
（式中、Ｘは、塩素、臭素又はヨウ素原子を表す）で示されるハロ無水フタル酸とを、触媒及び脱ハロゲン化剤の存在下、有機溶媒中で反応させた後、該有機溶媒を留去し、次いで芳香族系炭化水素又はハロゲン化芳香族系炭化水素溶媒を添加し、加熱溶解後、熱ろ過する方法により
式（３）
【０００８】
【化６】
（式中、Ｒ及びｎは、前記の通りである）で示されるフェニルエチニルフタル酸無水物誘導体を製造する方法である。
【００１０】
また、本発明（２）は、該有機溶媒が、アセトニトリル、テトラヒドロフラン（ＴＨＦ）、ベンゼン、トルエン、キシレン、ヘプタン、オクタン及びジオキサンから選択される、前記発明（１）の方法である。
【００１１】
更に、本発明（３）は、該芳香族系炭化水素又はハロゲン化芳香族炭化水素溶媒が、沸点が１００〜２５０℃、常温・常圧下で液体である、前記発明（１）又は（２）の方法である。
【００１２】
【発明の実施の形態】
まず、本発明に係る製造方法での使用原料等につき説明する。まず、第一の原料である式（１）で示されるエチニルベンゼン誘導体に関しては、ｎは、１〜３の整数を表し、Ｒは、相互に独立して、水素原子、炭素数１〜４のアルキル基、アルコキシ基、フェニル基、フェノキシ基又はシアノ基を表す。ここで、「相互に独立して」は、Ｒが複数存在する場合には同種でも異種でもよいことを意味する。また、Ｒが複数存在する場合、ベンゼン環上でのそれらの置換位置は特に限定されない。具体的には、エチニルベンゼン、２−メチルフェニルアセチレン、３−メチルフェニルアセチレン、４−メチルフェニルアセチレン、２，４−ジメチルフェニルアセチレン、４−メトキシフェニルアセチレン、４−フェノキシフェニルアセチレン、４−シアノフェニルアセチレンなどが挙げられる。
【００１３】
第二の原料である式（２）で示されるハロフタル酸無水物に関しては、Ｘは、塩素、臭素、ヨウ素を表す。具体的には、３−又は４−クロロフタル酸無水物、３−又は４−ブロモフタル酸無水物などが挙げられる。また、ベンゼン核上でのＸの置換位置は特に限定されない。
【００１４】
次に、本発明の製造方法で用いられる触媒は、例えば、２価又は０価のパラジウム錯体であり、好適なものを式（４）又は（５）に示す。
ＰｄＬ2Ｙ2 式（４）
ＰｄＬ4 式（５）
【００１５】
ここでＹとしては、例えば、塩素、臭素又はヨウ素原子、或いは、ＣＨ3ＣＯＯ−、Ｃ2Ｈ5ＣＯＯ−、Ｃ3Ｈ7ＣＯＯ−、Ｃ4Ｈ9ＣＯＯ−などが挙げられる。また、Ｌとしては、例えば、Ｐ、Ａｓ、Ｓｂの各原子を含む配位子が挙げられる。具体例としては、Ｒ3Ｐが挙げられ、ここで、Ｒは、例えば、ＣＨ3、Ｃ2Ｈ5、Ｃ3Ｈ7、Ｃ4Ｈ9、Ｃ5Ｈ11、Ｃ6Ｈ13、Ｃ7Ｈ15、Ｃ8Ｈ17などのアルキル基、Ｃ6Ｈ5、ＣｌＣ6Ｈ4、ＢｒＣ6Ｈ4、ＣＨ3ＯＣ6Ｈ4、Ｃ6Ｈ5ＣＨ2、などの芳香族化合物である。更に、Ｐ原子をＡｓ原子やＳｂ原子で置換した化合物も挙げられる。式（４）で示されるパラジウム錯体は、ＰｄＹ2で表わされる化合物と配位子Ｌとの混合物として使用しても構わない。
【００１６】
次に、本発明で使用する脱ハロゲン化剤は、好適には塩基性有機物質である。例えば、ジエチルアミン、トリエチルアミン、ピリジンなどが挙げられ、好ましくはトリエチルアミンである。脱ハロゲン化剤は、単独でも２種類以上を組み合わせて使用してもよい。
【００１７】
本発明で使用する有機溶媒は、特に限定されないが、反応後の溶媒留去を容易にするため、常圧での沸点が５０〜１００℃付近の有機溶媒が好適である。具体的には、例えば、アセトニトリル、テトラヒドロフラン（ＴＨＦ）、ベンゼン、トルエン、キシレン、ジオキサン、ヘプタン、オクタンが挙げられ、特にテトラヒドロフラン（ＴＨＦ）、アセトニトリルが好ましい。有機溶媒は、単独でも２種類以上を組み合わせて使用してもよい。また、反応前に溶媒を窒素やアルゴンなどの不活性ガスを反応系に導入することで、系内の酸素が除去され副反応を抑えることができる。
【００１８】
なお、従来の方法（従来技術の欄参照）では、いずれもハロゲン化銅を助触媒として使用している。しかしながら、３重結合化合物のアセチレンは銅と反応して、爆発性の不安定化合物である銅アセチリドを形成する。そのため、安全性等の観点から、場合によっては、ハロゲン化銅を使用しない方が好ましい。本発明の方法では、このような危険性のあるハロゲン化銅を使用せずに反応することができる。但し、使用しても反応はよりスムーズに進行する。ハロゲン化銅としては、塩化銅、臭化銅、ヨウ化銅が挙げられ、ヨウ化銅が好適である。
【００１９】
本発明で使用する芳香族系炭化水素又はハロゲン化芳香族系炭化水素溶媒は、式（３）のフェニルエチニルフタル酸の熱ろ過に使用しうるものであれば、特に限定されない。５０〜１００℃で熱ろ過でき、沸点が１００〜２５０℃で且つ常温・常圧下で液体の芳香族有機溶媒が好適である。具体的には、例えば、トルエン、キシレン、モノクロロベンゼン、ジクロロベンゼン、トリクロロベンゼン、ジクロロトルエン等が挙げられる。なお、この溶媒は、単独でも２種以上混合して使用してもよい。
【００２０】
なお、熱ろ過時に使用する芳香族系炭化水素又はハロゲン化芳香族系炭化水素溶媒を、反応時に使用する有機溶媒と同一のものを使用する場合（例えば、両方ともトルエンやキシレンを使用）には、反応と熱ろ過が同一溶媒となり、これらより沸点の低い塩基性有機溶媒を使用する場合、濃縮時により有効に塩基性有機溶媒を留去できる。
【００２１】
本発明により製造されるフェニルエチニルフタル酸無水物誘導体は、用いる原料により決まるが、具体的には、４−フェニルエチニルフタル酸無水物、３−フェニルエチニルフタル酸無水物、４−（２−メチルフェニルエチニル）フタル酸無水物、３−（２−メチルフェニルエチニル）フタル酸無水物、４−（３−メチルフェニルエチニル）フタル酸無水物、３−（３−メチルフェニルエチニル）フタル酸無水物、４−（４−メトキシフェニルエチニル）フタル酸無水物、３−（４−メトキシフェニルエチニル）フタル酸無水物、４（４−シアノフェニルエチニル）フタル酸無水物、３−（４−シアノフェニルエチニル）フタル酸無水物などである。
【００２２】
次に、本発明の製造方法における各種条件を説明する。まず、式（１）で示されるエチニルベンゼン誘導体と式（２）で示されるハロフタル酸無水物とのモル比に関しては、特に限定されないが、生成物の精製の容易さから考慮して、式（１）で示されるエチニルベンゼン誘導体を、式（２）で示されるハロフタル酸無水物に対し、１〜２当量で使用することが好適であり、１〜１．５当量で使用することが更に好適である。
【００２３】
次に、脱ハロゲン化剤として塩基性有機物を用いた場合、その使用量は少しの過剰量でよい。この点、大過剰量必要な従来技術とは異なる。好適量は、式（２）で示されるハロフタル酸無水物に対して１．０〜２．０当量であり、１．１〜１．５当量が更に好適である。
【００２４】
有機溶媒に関しては、その溶媒量は、特に限定されないが、好適には、反応全原料に対して、５０〜５００重量％の範囲である。
【００２５】
触媒としてパラジウム錯体を用いた場合、その使用量は、一般式（２）で示されるハロフタル酸無水物のモル数の０．１×１０-5〜０．１×１０-1倍の範囲が好適である。
【００２６】
ハロゲン化銅を使用する場合は、その使用量は、式（２）で示されるハロフタル酸無水物のモル数の０．１×１０-6〜０．１×１０-1倍の範囲が好適である。
【００２７】
反応条件は、圧力に関しては常圧で、また、反応温度に関しては室温〜１００℃の範囲で反応は進行する。なお、５０〜８０℃の範囲に設定すれば２０時間以内に反応は終了するので好ましい。反応後に有機溶媒を留去する。具体的には、例えば、減圧下、１００℃以下で濃縮する。この場合、使用した有機溶媒量に対し、好適には９０％、更に好適には９５％の有機溶媒を留去する。濃縮後、この系に芳香族有機溶媒又はハロゲン化芳香族有機溶媒を添加し、５０〜１００℃で熱ろ過する。その使用量は、一般式（３）で示されるフェニルエチニルフタル酸無水物の理論収量に対して、好適には１００〜６００重量％、より好適には２００〜４００重量％である。ろ過されたろ液を、室温まで冷却、固液分離することにより、一般式（３）で示されるフェニルエチニルフタル酸無水物を得ることができる。
【００２８】
【発明の効果】
本発明によれば、工業的に少ない工程で効率良く、高純度、高収率でフェニルエチニルフタル酸無水物誘導体を得ることができる。
【００２９】
【実施例】
以下、実施例により、更に具体的に発明の製造方法について述べるが、本発明はこれらの実施例に限定されるものではない。
【００３０】
実施例１
窒素導入管を備えた反応器に４−ブロモ無水フタル酸６８．１ｇ（０．３０モル）及びアセトニトリル１００ｇ、トリエチルアミン３６．４ｇ（０．３６モル）、ビストリフェニルホスフィンジクロロパラジウム０．３１ｇ（０．４５×１０-3モル）を反応器に入れ、６０℃に加熱した。次にフェニルアセチレン３３．７ｇ（０．３３モル）を２０分間にわたって投入した。投入後、１５時間熟成した。反応後、減圧下、６０℃にてアセトニトリルを９０％留去した。次に、混合キシレン１００ｇを入れ８０℃に加熱し、加圧熱ろ過した。ろ液を室温まで冷却し固液分離した。得られた結晶物を、キシレン洗浄、減圧乾燥してフェニルエチニルフタル酸無水物を得た。
６７．０ｇ（９０．０％収率）、融点１５２．０−１５２．７℃
【００３１】
実施例２
窒素導入管を備えた反応器に４−ブロモ無水フタル酸６８．１ｇ（０．３０モル）、テトラヒドロフラン１００ｇ、トリエチルアミン３６．４ｇ（０．３６モル）、トリフェニルホスフィン０．６０ｇ（０．２２×１０-2モル）、塩化パラジウム０．０７ｇ（０．４０×１０-3モル）、ヨウ化銅０．１０ｇ（０．５３×１０-3モル）を反応器に入れ、５０℃に加熱した。次に、４−シアノフェニルアセチレン４２．０ｇ（０．３３モル）、を２０分間にわたって投入した。投入後、１５時間熟成した。反応後、減圧下、４０℃にてテトラヒドロフランを９０％留去した。次に、モノクロロベンゼン１００ｇを入れ８０℃に加熱し、加圧熱ろ過した。ろ液を室温まで冷却し固液分離した。得られた結晶物をキシレン洗浄、乾燥して４−シアノフェニルエチニルフタル酸無水物を得た。
７４．６ｇ（９１．０％収率）、融点２２１．５−２２２．３℃[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a phthalic anhydride having a carbon-carbon triple bond, and particularly relates to a production method capable of industrially efficiently obtaining a high-purity phenylethynylphthalic anhydride derivative in a high yield. .
[0002]
[Prior art]
The phenylethynylphthalic anhydride derivative is a material having adhesiveness, heat resistance, and mechanical strength required in the polyimide field, and has extremely high utility value.
There have been known several methods for producing this phenylethynylphthalic anhydride derivative. In any of these production methods, after the reaction, the target acid anhydride is once opened with an aqueous hydrochloric acid solution, and the acid anhydride is again formed by acetic anhydride or thermal ring closure. For example, PM Hergenrother et al. In Polymer, Vol. 35 (No. 22), 4857- (1994), reacted ethynylbenzene and bromophthalic anhydride in the presence of a large excess of basic organic substances, and then filtered the by-product salt. Crystallization with water and finally phenylethynylphthalic anhydride is obtained by thermal ring closure (yield: 67%). GW Meyer et al. In HighPerform. Polym. 6, 423- (1994) obtained phenylethynylphthalic anhydride by reaction with ethynylbenzene and bromophthalic anhydride in DMAc, followed by hydrochloric acid crystallization, thermal ring closure and sublimation. (Yield: 84%). Japanese Patent Application Laid-Open No. 11-180970 discloses a method of obtaining phenylethynylphthalic anhydride by reacting in the presence of an excess of a basic organic substance, crystallization with water, washing with hydrochloric acid, and ring-closing with acetic anhydride. . In consideration of an industrial process, opening the acid anhydride, solid-liquid separation, and closing the ring again results in a decrease in productivity, which is inefficient as an industrial process.
[0003]
[Means for Solving the Problems]
The present invention (1) has the formula (1)
[0004]
[Formula 4]
(In the formula, n represents an integer of 1 to 3, and R independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a phenyl group, a phenoxy group, or a cyano group.) And an ethynylbenzene derivative represented by the formula (2)
[0006]
[Chemical formula 5]
(Wherein, X represents a chlorine, bromine or iodine atom) is reacted with an organic solvent in the presence of a catalyst and a dehalogenating agent, and then the organic solvent is distilled. Then, an aromatic hydrocarbon or halogenated aromatic hydrocarbon solvent is added, dissolved by heating, and then heated and filtered.
[0008]
[Chemical 6]
(Wherein R and n are as defined above), and a phenylethynylphthalic anhydride derivative.
[0010]
The present invention (2) is the method of the above invention (1), wherein the organic solvent is selected from acetonitrile, tetrahydrofuran (THF), benzene, toluene, xylene, heptane, octane and dioxane.
[0011]
Furthermore, the present invention (3) is the invention (1) or (2), wherein the aromatic hydrocarbon or halogenated aromatic hydrocarbon solvent is a liquid at a boiling point of 100 to 250 ° C. at room temperature and normal pressure. It is a method.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
First, raw materials used in the production method according to the present invention will be described. First, regarding the ethynylbenzene derivative represented by the formula (1) as the first raw material, n represents an integer of 1 to 3, and R is independently a hydrogen atom or a carbon atom having 1 to 4 carbon atoms. Represents an alkyl group, an alkoxy group, a phenyl group, a phenoxy group or a cyano group; Here, “independently” means that when a plurality of R exist, they may be the same or different. Moreover, when two or more R exists, those substitution positions on a benzene ring are not specifically limited. Specifically, ethynylbenzene, 2-methylphenylacetylene, 3-methylphenylacetylene, 4-methylphenylacetylene, 2,4-dimethylphenylacetylene, 4-methoxyphenylacetylene, 4-phenoxyphenylacetylene, 4-cyanophenyl Examples include acetylene.
[0013]
With respect to the halophthalic anhydride represented by the formula (2) as the second raw material, X represents chlorine, bromine or iodine. Specific examples include 3- or 4-chlorophthalic anhydride and 3- or 4-bromophthalic anhydride. Moreover, the substitution position of X on the benzene nucleus is not particularly limited.
[0014]
Next, the catalyst used in the production method of the present invention is, for example, a divalent or zero-valent palladium complex, and a suitable one is represented by formula (4) or (5).
PdL 2 Y 2 formula (4)
PdL 4 formula (5)
[0015]
Examples of Y include a chlorine, bromine or iodine atom, or CH 3 COO—, C 2 H 5 COO—, C 3 H 7 COO—, C 4 H 9 COO—, and the like. Moreover, as L, the ligand containing each atom of P, As, Sb is mentioned, for example. Specific examples include R 3 P, where R is, for example, CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 , C 5 H 11 , C 6 H 13 , C 7. It is an aromatic compound such as an alkyl group such as H 15 and C 8 H 17 , C 6 H 5 , ClC 6 H 4 , BrC 6 H 4 , CH 3 OC 6 H 4 , and C 6 H 5 CH 2 . Furthermore, the compound which substituted P atom by As atom and Sb atom is also mentioned. The palladium complex represented by the formula (4) may be used as a mixture of the compound represented by PdY 2 and the ligand L.
[0016]
Next, the dehalogenating agent used in the present invention is preferably a basic organic substance. For example, diethylamine, triethylamine, pyridine and the like can be mentioned, and triethylamine is preferable. The dehalogenating agents may be used alone or in combination of two or more.
[0017]
Although the organic solvent used by this invention is not specifically limited, In order to make the solvent distillation after reaction easy, the organic solvent whose boiling point in a normal pressure is 50-100 degreeC vicinity is suitable. Specific examples include acetonitrile, tetrahydrofuran (THF), benzene, toluene, xylene, dioxane, heptane, and octane. Tetrahydrofuran (THF) and acetonitrile are particularly preferable. The organic solvent may be used alone or in combination of two or more. Further, by introducing an inert gas such as nitrogen or argon into the reaction system before the reaction, oxygen in the system is removed and side reactions can be suppressed.
[0018]
Note that all of the conventional methods (see the prior art column) use copper halide as a promoter. However, the triple bond compound acetylene reacts with copper to form copper acetylide, an explosive unstable compound. Therefore, from the viewpoint of safety and the like, it is preferable not to use copper halide in some cases. In the method of the present invention, the reaction can be performed without using such a dangerous copper halide. However, the reaction proceeds more smoothly even when used. Examples of the copper halide include copper chloride, copper bromide, and copper iodide, with copper iodide being preferred.
[0019]
The aromatic hydrocarbon or halogenated aromatic hydrocarbon solvent used in the present invention is not particularly limited as long as it can be used for hot filtration of phenylethynylphthalic acid of the formula (3). An aromatic organic solvent that can be filtered at 50 to 100 ° C., has a boiling point of 100 to 250 ° C., and is liquid at normal temperature and normal pressure is suitable. Specific examples include toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, dichlorotoluene and the like. In addition, you may use this solvent individually or in mixture of 2 or more types.
[0020]
In addition, when using the same aromatic hydrocarbon or halogenated aromatic hydrocarbon solvent used during hot filtration as the organic solvent used during the reaction (for example, both toluene and xylene are used) When the basic organic solvent having a boiling point lower than these is used, the basic organic solvent can be distilled off more effectively during the concentration.
[0021]
The phenylethynylphthalic anhydride derivative produced according to the present invention is determined by the raw materials used, and specifically, 4-phenylethynylphthalic anhydride, 3-phenylethynylphthalic anhydride, 4- (2-methyl) Phenylethynyl) phthalic anhydride, 3- (2-methylphenylethynyl) phthalic anhydride, 4- (3-methylphenylethynyl) phthalic anhydride, 3- (3-methylphenylethynyl) phthalic anhydride, 4- (4-methoxyphenylethynyl) phthalic anhydride, 3- (4-methoxyphenylethynyl) phthalic anhydride, 4 (4-cyanophenylethynyl) phthalic anhydride, 3- (4-cyanophenylethynyl) Such as phthalic anhydride.
[0022]
Next, various conditions in the production method of the present invention will be described. First, the molar ratio between the ethynylbenzene derivative represented by the formula (1) and the halophthalic anhydride represented by the formula (2) is not particularly limited, but considering the ease of purification of the product, the formula ( The ethynylbenzene derivative represented by 1) is preferably used in an amount of 1 to 2 equivalents, more preferably 1 to 1.5 equivalents based on the halophthalic anhydride represented by the formula (2). It is.
[0023]
Next, when a basic organic substance is used as the dehalogenating agent, the amount used may be a slight excess. This is different from the prior art that requires a large excess. The preferred amount is 1.0 to 2.0 equivalents, more preferably 1.1 to 1.5 equivalents, based on the halophthalic anhydride represented by the formula (2).
[0024]
With respect to the organic solvent, the amount of the solvent is not particularly limited, but is preferably in the range of 50 to 500% by weight based on the total reaction raw material.
[0025]
When a palladium complex is used as the catalyst, the amount used is preferably in the range of 0.1 × 10 −5 to 0.1 × 10 −1 times the number of moles of the halophthalic anhydride represented by the general formula (2). It is.
[0026]
When copper halide is used, the amount used is preferably in the range of 0.1 × 10 −6 to 0.1 × 10 −1 times the number of moles of halophthalic anhydride represented by formula (2). is there.
[0027]
The reaction proceeds under normal pressure with respect to pressure, and the reaction proceeds in the range of room temperature to 100 ° C. with respect to the reaction temperature. In addition, since it will complete | finish reaction within 20 hours if it sets to the range of 50-80 degreeC, it is preferable. After the reaction, the organic solvent is distilled off. Specifically, for example, concentration is performed at 100 ° C. or lower under reduced pressure. In this case, 90%, more preferably 95% of the organic solvent is distilled off with respect to the amount of the organic solvent used. After the concentration, an aromatic organic solvent or a halogenated aromatic organic solvent is added to this system, followed by hot filtration at 50 to 100 ° C. The amount used is preferably 100 to 600% by weight, more preferably 200 to 400% by weight, based on the theoretical yield of phenylethynylphthalic anhydride represented by the general formula (3). The filtered filtrate is cooled to room temperature and solid-liquid separated to obtain phenylethynylphthalic anhydride represented by the general formula (3).
[0028]
【Effect of the invention】
According to the present invention, a phenylethynylphthalic anhydride derivative can be obtained efficiently and with high purity and high yield in a small number of industrial processes.
[0029]
【Example】
EXAMPLES Hereinafter, the production method of the invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
[0030]
Example 1
A reactor equipped with a nitrogen inlet tube was charged with 68.1 g (0.30 mol) of 4-bromophthalic anhydride and 100 g of acetonitrile, 36.4 g (0.36 mol) of triethylamine, 0.31 g (0.001 mol) of bistriphenylphosphine dichloropalladium. 45 × 10 −3 mol) was charged to the reactor and heated to 60 ° C. Next, 33.7 g (0.33 mol) of phenylacetylene was added over 20 minutes. After the addition, the mixture was aged for 15 hours. After the reaction, 90% of acetonitrile was distilled off at 60 ° C. under reduced pressure. Next, 100 g of mixed xylene was added and heated to 80 ° C., followed by pressure hot filtration. The filtrate was cooled to room temperature and solid-liquid separated. The obtained crystal was washed with xylene and dried under reduced pressure to obtain phenylethynylphthalic anhydride.
67.0 g (90.0% yield), mp 152.0-152.7 ° C
[0031]
Example 2
In a reactor equipped with a nitrogen introduction tube, 68.1 g (0.30 mol) of 4-bromophthalic anhydride, 100 g of tetrahydrofuran, 36.4 g (0.36 mol) of triethylamine, 0.60 g of triphenylphosphine (0.22 × 10 −2 mol), 0.07 g (0.40 × 10 −3 mol) of palladium chloride, and 0.10 g (0.53 × 10 −3 mol) of copper iodide were placed in the reactor and heated to 50 ° C. Next, 42.0 g (0.33 mol) of 4-cyanophenylacetylene was charged over 20 minutes. After the addition, the mixture was aged for 15 hours. After the reaction, 90% of tetrahydrofuran was distilled off at 40 ° C. under reduced pressure. Next, 100 g of monochlorobenzene was added and heated to 80 ° C., followed by hot filtration under pressure. The filtrate was cooled to room temperature and solid-liquid separated. The obtained crystal was washed with xylene and dried to obtain 4-cyanophenylethynylphthalic anhydride.
74.6 g (91.0% yield), mp 221.5-222.3 ° C.
Claims (4)
式（２）
式（３）
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001260980A JP4913962B2 (en) | 2001-08-30 | 2001-08-30 | Process for producing phenylethynylphthalic anhydride derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001260980A JP4913962B2 (en) | 2001-08-30 | 2001-08-30 | Process for producing phenylethynylphthalic anhydride derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003073372A JP2003073372A (en) | 2003-03-12 |
| JP4913962B2 true JP4913962B2 (en) | 2012-04-11 |
Family
ID=19088091
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001260980A Expired - Fee Related JP4913962B2 (en) | 2001-08-30 | 2001-08-30 | Process for producing phenylethynylphthalic anhydride derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4913962B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4574403B2 (en) | 2004-03-25 | 2010-11-04 | 富士フイルム株式会社 | Arylethynylphthalic acid derivative and method for producing the same |
| EP1586569B1 (en) * | 2004-03-25 | 2012-06-06 | FUJIFILM Corporation | Aryl ethynyl phthalic acid derivative and method for producing the same |
| JP5485890B2 (en) * | 2008-07-31 | 2014-05-07 | マナック株式会社 | Method for producing phthalic anhydride derivative |
| ES2523824T3 (en) * | 2012-04-20 | 2014-12-01 | Nexam Chemical Ab | Process for the production of (etino-1,2-diyl) bis (isobenzofuran-1,3-dione) |
| JPWO2015125734A1 (en) * | 2014-02-24 | 2017-03-30 | マナック株式会社 | Halohexahydrophthalic acid derivatives |
| CN109111416B (en) * | 2018-08-24 | 2022-03-29 | 吉林大学 | Diether dianhydride monomer with phenylethynyl-containing side group and preparation method and application thereof |
| CN113024496A (en) * | 2021-03-24 | 2021-06-25 | 天津市泰合利华材料科技有限公司 | Method for preparing 4-p-trifluoromethyl phenyl alkynyl phthalic anhydride |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2550201B1 (en) * | 1983-08-05 | 1986-02-28 | Charbonnages Ste Chimique | CHIRAL PHOSPHORUS LIGANDS, THEIR MANUFACTURING PROCESS FROM NATURAL AMINOACIDS AND THEIR APPLICATION TO THE CATALYSIS OF ENANTIOSELECTIVE SYNTHESIS REACTIONS |
| JPH05331157A (en) * | 1992-05-26 | 1993-12-14 | Mitsubishi Rayon Co Ltd | Ascorbic acid ester |
| US5493002A (en) * | 1994-07-06 | 1996-02-20 | Virginia Tech Intellectual Properties, Inc. | Aryl ethynyl phthalic anhydrides and polymers with terminal or pendant amines prepared with aryl ethynyl phthalic anhydrides |
| US5567800A (en) * | 1994-10-28 | 1996-10-22 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Imide oligomers endcapped with phenylethynyl phthalic anhydrides and polymers therefrom |
| DE19515444C1 (en) * | 1995-04-27 | 1996-11-14 | Hoechst Ag | Process for the preparation of aromatic acetylenes using palladium cycles as catalysts |
-
2001
- 2001-08-30 JP JP2001260980A patent/JP4913962B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003073372A (en) | 2003-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR19980018923A (en) | METHOD FOR PREPARING AROMATIC COMPOUNDS | |
| JP2012102146A (en) | Method for preparing oxydiphthalic anhydrides using guanidinium salt as catalyst | |
| JP4913962B2 (en) | Process for producing phenylethynylphthalic anhydride derivative | |
| JP5485890B2 (en) | Method for producing phthalic anhydride derivative | |
| WO2012046857A1 (en) | 3,4-dialkylbiphenyldicarboxylic acid compound, 3,4-dicarboalkoxybiphenyl-3',4'-dicarboxylic acid and corresponding acid anhydrides, and processes for producing these compounds | |
| US6727370B1 (en) | Method for preparing oxydiphthalic anhydrides using bicarbonate as catalyst | |
| CN108047089B (en) | Preparation method of 4-tert-butyl phthalonitrile | |
| JP3433482B2 (en) | Method for producing bismaleimide | |
| JP4698421B2 (en) | Process for producing 2,3,6,7,10,11-hexahydroxytriphenylene | |
| RU2314301C2 (en) | Method of producing and cleaning pyromellitic anhydrite | |
| CN108069845B (en) | One-step preparation method of bromo-1, 4-naphthoquinone | |
| JPS61267538A (en) | Production of 2-alkyl-6-acylnaphthalene | |
| JP3543585B2 (en) | Method for producing 2,2 ', 5,5', 6,6'-hexafluorobiphenyl-3,3 ', 4,4'-tetracarboxylic acid precursor | |
| JP4493805B2 (en) | Method for producing high-purity benzoic acid derivative | |
| JP5577821B2 (en) | Method for producing phthalic acid compound with chlorinated aromatic ring | |
| JP4143295B2 (en) | Method for producing 9,9-disubstituted-2,3,6,7-xanthenetetracarboxylic dianhydride | |
| JP2006151904A (en) | Method for producing ethynylphthalic anhydride derivative and ethynylphthalic acid derivative | |
| KR101174848B1 (en) | Preparaion method for iso-phthalic acid | |
| JPH0557971B2 (en) | ||
| JP2022001559A (en) | Aromatic ketone compound and method for producing the same | |
| JPH0377845A (en) | Production of acylated naphthalenes | |
| JP2003171332A (en) | Method for producing bisbenzyl compound | |
| JPH05125013A (en) | Selective production of benzophenone dicarboxylic acid | |
| JPS62155237A (en) | 2-(p-bromomethylphenyl)propionic acid and production thereof | |
| JPH05221920A (en) | Production of 2,2-bis@(3754/24)coarboxyphenyl)propane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20060315 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080613 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110308 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110309 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110427 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20111018 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20111213 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120117 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120120 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 4913962 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150127 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |