JPH0892168A - Production of aromatic carbonic acid ester - Google Patents

Production of aromatic carbonic acid ester

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Publication number
JPH0892168A
JPH0892168A JP6226935A JP22693594A JPH0892168A JP H0892168 A JPH0892168 A JP H0892168A JP 6226935 A JP6226935 A JP 6226935A JP 22693594 A JP22693594 A JP 22693594A JP H0892168 A JPH0892168 A JP H0892168A
Authority
JP
Japan
Prior art keywords
palladium
component
compound
aromatic
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP6226935A
Other languages
Japanese (ja)
Inventor
Katsufumi Kujira
勝文 鯨
Masatoshi Takagi
雅敏 高木
Hidekazu Miyagi
秀和 宮城
Hideto Hayashi
英人 林
Yuji Okago
祐二 大篭
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Chemical Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsubishi Chemical Corp filed Critical Mitsubishi Chemical Corp
Priority to JP6226935A priority Critical patent/JPH0892168A/en
Publication of JPH0892168A publication Critical patent/JPH0892168A/en
Pending legal-status Critical Current

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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

Abstract

PURPOSE: To simply obtain the simple ester useful as a raw material for polycarbonate, etc., in a high yield by reacting an aromatic hydroxy compound with carbon monoxide and oxygen using a specific simple catalyst system. CONSTITUTION: This method for producing an aromatic carbonic acid ester is to add a catalyst system comprising (D). (i) one or more kinds of compounds selected from a Pd and a Pd compound (preferably an organic acid salt of Pd, especially palladium acetate), (ii) one or more kinds of inorganic halides selected from alkali earth metal halides (preferably chloride and bromide, especially preferably cesium chloride or cesium bromide) and (iii) an activated carbon to a reactional system comprising (A) an aromatic hydroxy compound (especially preferably phenol), (B) carbon monoxide and (C) oxygen and react the component A with the components B and C. Furthermore, the catalyst component (i) is preferably used in a molar ratio of 10<-6> to 1 based on the component A and the component (ii) is preferably used in a molar ratio of 10<-2> to 10<3> based on the component (ii) and the component (iii) is preferably used in a weight ratio of 20-200g based on 1g of the Pd metal of the component (i).

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、特定の触媒系を用いた
芳香族炭酸エステルの製造方法に関するものである。芳
香族炭酸エステル、特に炭酸ジフェニルは、ポリカーボ
ネート等の原料として有用なものである。FIELD OF THE INVENTION The present invention relates to a method for producing an aromatic carbonic acid ester using a specific catalyst system. Aromatic carbonic acid esters, especially diphenyl carbonate, are useful as raw materials for polycarbonate and the like.

【０００２】[0002]

【従来の技術】従来、芳香族炭酸エステルの製造法とし
ては、芳香族ヒドロキシ化合物とホスゲンを反応させる
方法が用いられてきた。しかし、ホスゲンは毒性が強い
ため、この方法は好ましくない。そこで、ホスゲンを用
いない方法として、芳香族ヒドロキシ化合物と一酸化炭
素及び酸素とから芳香族炭酸エステルを製造する方法が
提案されている。2. Description of the Related Art Conventionally, a method of reacting an aromatic hydroxy compound with phosgene has been used as a method for producing an aromatic carbonic acid ester. However, this method is not preferable because phosgene is highly toxic. Therefore, as a method that does not use phosgene, a method of producing an aromatic carbonic acid ester from an aromatic hydroxy compound and carbon monoxide and oxygen has been proposed.

【０００３】この方法における触媒として、特公昭56ー3
8144号公報には、パラジウム化合物と周期律表のIII
Ａ、IVＡ、VＡ、VIＡ、IＢ、IIＢ、VIＢまたはVIIＢ族
の金属を含む化合物及び塩基を用いる方法が記載されて
いる。また、特公昭56-38145号公報には、パラジウム化
合物、マンガン錯体またはコバルト錯体、塩基及び乾燥
剤を用いる方法；特開平1-165551号公報には、パラジウ
ム化合物、ヨウ素及びゼオライト類を用いる方法；特開
平2-104564号公報には、パラジウム化合物、二価または
三価のマンガン化合物、テトラアルキルアンモニウムハ
ライド及びキノン類を用いる方法；特開平2-142754号公
報には、パラジウム化合物、二価または三価のコバルト
化合物、テトラアルキルアンモニウムハライド及びキノ
ン類を用いる方法；特開平5-25095号公報には、パラジ
ウム化合物、コバルト化合物、有機または無機ハロゲン
化物及び塩基性化合物を用いる方法；特開平5-58961号
公報には、パラジウム化合物、コバルト化合物及びアル
カリ金属ハロゲン化物を用いる方法が記載されている。
また、特開平5-97775号公報には、パラジウム化合物
と、コバルト、鉄、セリウム、マンガン、モリブデン、
サマリウム、バナジウム、クロム、銅から選ばれた無機
化合物の助触媒と、芳香族ケトン、脂肪族ケトン、芳香
族多環式炭化水素から選ばれた有機の助触媒と、４級ア
ンモニウム塩からなる混合物を用いる方法が記載されて
いる。As a catalyst in this method, Japanese Examined Patent Publication No. 56-3
No. 8144 discloses a palladium compound and III of the periodic table.
Methods of using compounds and bases containing metals of group A, IVA, VA, VIA, IB, IIB, VIB or VIIB are described. Further, JP-B-56-38145 discloses a method using a palladium compound, a manganese complex or cobalt complex, a base and a desiccant; JP-A-1-165551 discloses a method using a palladium compound, iodine and zeolites; JP-A-2-104564 discloses a method using a palladium compound, a divalent or trivalent manganese compound, a tetraalkylammonium halide and quinones; JP-A-2-142754 discloses a palladium compound, a divalent or trivalent compound. -Valent cobalt compounds, tetraalkylammonium halides and quinones; JP-A-525095 discloses a method using palladium compounds, cobalt compounds, organic or inorganic halides and basic compounds; JP-A-5-58961. The publication describes a method using a palladium compound, a cobalt compound and an alkali metal halide. Has been.
Further, in JP-A-5-97775, a palladium compound, cobalt, iron, cerium, manganese, molybdenum,
Mixture of a cocatalyst of an inorganic compound selected from samarium, vanadium, chromium and copper, an organic cocatalyst selected from an aromatic ketone, an aliphatic ketone and an aromatic polycyclic hydrocarbon, and a quaternary ammonium salt. Is described.

【０００４】[0004]

【発明が解決しようとする課題】芳香族炭酸エステルを
製造するための従来の触媒系は、収率向上のために高価
で複雑な塩基、４級アンモニウム塩、助触媒などを必要
とし、またマンガン、銅、コバルト、セリウムなどの金
属イオンを含むレドックス剤の使用が必須であることな
ど、反応系が複雑で、生成物である芳香族炭酸エステル
の分離、精製が煩雑であった。また、従来の方法におけ
る芳香族炭酸エステル収率はさほど高くなく、実用化の
ためには触媒成分の回収が必須であるが、特に４級アン
モニウム塩などは、反応条件下において不安定であり、
例えば臭素化フェノールが多量に生成するなど、従来の
複雑な触媒系では該成分の回収操作が非常に煩雑なもの
となる。本発明の課題は、従来よりも単純な触媒系を用
いて、目的とする芳香族炭酸エステルを高い収率で製造
する方法を提供することである。Conventional catalyst systems for producing aromatic carbonates require expensive and complex bases, quaternary ammonium salts, co-catalysts, etc. to improve yields, and manganese. Since the use of a redox agent containing a metal ion such as copper, cobalt, or cerium is essential, the reaction system is complicated, and the separation and purification of the product aromatic carbonate ester is complicated. Further, the yield of aromatic carbonate ester in the conventional method is not so high, and recovery of the catalyst component is essential for practical use, but especially quaternary ammonium salts are unstable under the reaction conditions,
For example, in the conventional complicated catalyst system, the recovery operation of the component becomes very complicated, for example, a large amount of brominated phenol is produced. An object of the present invention is to provide a method for producing a target aromatic carbonic acid ester in a high yield by using a catalyst system simpler than conventional ones.

【０００５】[0005]

【課題を解決するための手段】本発明者らは、レドック
ス作用を行う金属イオンを含む化合物や、複雑な塩基お
よび助触媒などを用いない簡単な触媒系で、芳香族炭酸
エステルを高収率、高選択率で得られる方法を開発する
ため鋭意検討を行った結果、下記の特定の触媒系を用い
ることにより、上記目的が達成されることを見いだし本
発明を完成した。即ち、本発明は、芳香族ヒドロキシ化
合物と一酸化炭素及び酸素を反応させて、芳香族炭酸エ
ステルを製造する方法において、（Ａ）パラジウム及び
パラジウム化合物から選ばれた一種以上、（Ｂ）アルカ
リ金属ハロゲン化物及びアルカリ土類金属ハロゲン化物
から選ばれた無機ハロゲン化物の一種以上、および
（Ｃ）活性炭を存在させて、該反応を行うことを特徴と
する芳香族炭酸エステルの製造方法である。The present inventors have developed a high yield of aromatic carbonate with a simple catalyst system that does not use a compound containing a metal ion that performs a redox action or a complicated base and cocatalyst. As a result of earnest studies to develop a method with high selectivity, it was found that the above object can be achieved by using the following specific catalyst system, and the present invention has been completed. That is, the present invention provides a method for producing an aromatic carbonic acid ester by reacting an aromatic hydroxy compound with carbon monoxide and oxygen, wherein (A) one or more selected from palladium and a palladium compound, and (B) an alkali metal. A method for producing an aromatic carbonic acid ester, characterized in that the reaction is carried out in the presence of at least one inorganic halide selected from halides and alkaline earth metal halides, and (C) activated carbon.

【０００６】［発明の具体的説明］ １．反応原料 （１）芳香族ヒドロキシ化合物 本発明に用いられる芳香族ヒドロキシ化合物は、芳香族
モノまたはポリヒドロキシ化合物であり、例えばフェノ
ール；クレゾール、キシレノール、トリメチルフェノー
ル、テトラメチルフェノール、エチルフェノール、プロ
ピルフェノール、メトキシフェノール、エトキシフェノ
ール、クロロフェノール、ジクロロフェノール、ブロモ
フェノール、ジブロモフェノールなどの置換フェノール
類及びそれらの異性体；ナフトール、メチルナフトー
ル、エチルナフトール、クロロナフトール、ブロモナフ
トールなどの置換ナフトール類及びそれらの異性体；
２，２−ビス（４−ヒドロキシフェニル）プロパンなど
の各種ビスフェノール類；各種ビフェノール類；各種ヘ
テロ芳香族ヒドロキシ化合物及びそれらの異性体、さら
にそれらのアルキル、ハロゲンなどによる置換体などで
ある。これらの中でフェノールが特に好ましい。[Detailed Description of the Invention] 1. Reaction Raw Materials (1) Aromatic Hydroxy Compound The aromatic hydroxy compound used in the present invention is an aromatic mono- or polyhydroxy compound, for example, phenol; cresol, xylenol, trimethylphenol, tetramethylphenol, ethylphenol, propylphenol, Substituted phenols such as methoxyphenol, ethoxyphenol, chlorophenol, dichlorophenol, bromophenol, dibromophenol and their isomers; substituted naphthols such as naphthol, methylnaphthol, ethylnaphthol, chloronaphthol, bromonaphthol and their isomers body;
Various bisphenols such as 2,2-bis (4-hydroxyphenyl) propane; various biphenols; various heteroaromatic hydroxy compounds and their isomers, and their substitution products with alkyl, halogen and the like. Of these, phenol is particularly preferred.

【０００７】（２）一酸化炭素 本発明に用いられる一酸化炭素は、高純度のものはもと
より、窒素、アルゴン、二酸化炭素、水素など反応に悪
影響をおよぼさない他のガスで希釈されているものでも
使用することができる。(2) Carbon monoxide Carbon monoxide used in the present invention is not only highly pure, but also diluted with other gases such as nitrogen, argon, carbon dioxide and hydrogen, which do not adversely affect the reaction. You can use it even if there is.

【０００８】（３）酸素 本発明に用いられる酸素は、高純度のものはもとより、
空気、または窒素、アルゴン、二酸化炭素、水素など反
応に悪影響をおよぼさない他のガスで希釈されているも
のでも使用することができる。(3) Oxygen The oxygen used in the present invention is not only high-purity oxygen,
It is also possible to use one diluted with air or another gas that does not adversely influence the reaction, such as nitrogen, argon, carbon dioxide, or hydrogen.

【０００９】２．触媒 本発明の反応に使用される触媒は、下記の（Ａ）〜
（Ｃ）の３成分を含有するものである。 （Ａ）パラジウムまたはパラジウム化合物 本発明に用いられるパラジウムまたはパラジウム化合物
は、パラジウム黒；パラジウム／カーボン、パラジウム
／アルミナ、パラジウム／シリカなどの担持パラジウ
ム；塩化パラジウム、臭化パラジウム、ヨウ化パラジウ
ム、硫酸パラジウム、硝酸パラジウムなどのパラジウム
の無機塩類；酢酸パラジウム、シュウ酸パラジウム、ギ
酸パラジウム、安息香酸パラジウムなどのパラジウムの
有機酸塩類等である。またパラジウム（II）アセチルア
セトナートや、パラジウムに一酸化炭素、ニトリル類、
アミン類、ホスフィン類、オレフィン類などが配位した
パラジウムの錯化合物、例えばＰｄＣｌ2（ＰｈＣ
Ｎ）2、ＰｄＣｌ2（ＰＰｈ3）2、Ｐｄ（ＣＯ）（ＰＰｈ
3）3、［Ｐｄ（ＮＨ3）4］Ｃｌ2、Ｐｄ（Ｃ2Ｈ4）（Ｐ
Ｐｈ3）2など、あるいはそれら錯化合物が反応系中で生
成されるような化合物類とパラジウムとの混合物を使用
することもできる。これらの中で、パラジウムの有機酸
塩類が好ましく、特に酢酸パラジウムが好ましい。反応
に用いられるパラジウム成分の量は、芳香族ヒドロキシ
化合物に対してモル比で１０-6〜１の範囲であることが
好ましく、特に１０-5〜１０-1の範囲であることが特に
好ましい。2. Catalyst The catalyst used in the reaction of the present invention is (A) to
It contains three components (C). (A) Palladium or palladium compound Palladium or palladium compound used in the present invention is palladium black; supported palladium such as palladium / carbon, palladium / alumina, palladium / silica; palladium chloride, palladium bromide, palladium iodide, palladium sulfate. Inorganic salts of palladium such as palladium nitrate; organic acid salts of palladium such as palladium acetate, palladium oxalate, palladium formate and palladium benzoate. Palladium (II) acetylacetonate, palladium on carbon monoxide, nitriles,
Palladium complex compounds coordinated with amines, phosphines, olefins, etc., such as PdCl 2 (PhC
N) 2 , PdCl 2 (PPh 3 ) 2 , Pd (CO) (PPh
3 ) 3 , [Pd (NH 3 ) 4 ] Cl 2 , Pd (C 2 H 4 ) (P
It is also possible to use a mixture of palladium with Ph 3 ) 2 or the like, or a compound such that a complex compound thereof is formed in the reaction system. Among these, organic acid salts of palladium are preferable, and palladium acetate is particularly preferable. The amount of the palladium component used in the reaction is preferably in the range of 10 -6 to 1 with respect to the aromatic hydroxy compound, and particularly preferably in the range of 10 -5 to 10 -1 .

【００１０】（Ｂ）無機ハロゲン化物 本発明に用いられる無機ハロゲン化物は、アルカリ金属
またはアルカリ土類金属のハロゲン化物である。ハロゲ
ン化物としては、塩化物および臭化物が好ましく、例え
ば、塩化リチウム、塩化セシウム、臭化ナトリウム、臭
化カリウム、臭化ルビジウム、臭化セシウム、臭化バリ
ウム等が上げられ、これらの中で特に塩化セシウム、臭
化セシウムが好ましい。反応に用いられる無機ハロゲン
化物の量は特に制限はないが、パラジウム成分（Ａ）に
対してモル比で１０-2〜１０3の範囲であることが好ま
しく、特に１０-1〜１０2の範囲であることが好まし
い。(B) Inorganic Halide The inorganic halide used in the present invention is an alkali metal or alkaline earth metal halide. As the halide, chloride and bromide are preferable, and examples thereof include lithium chloride, cesium chloride, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, barium bromide, and the like. Cesium and cesium bromide are preferred. The amount of the inorganic halide used in the reaction is not particularly limited, but it is preferably in the range of 10 -2 to 10 3 with respect to the palladium component (A), and particularly in the range of 10 -1 to 10 2 . Is preferred.

【００１１】（Ｃ）活性炭 本発明に用いられる活性炭は、市販のいかなるものでも
よく、原料も木質系、ヤシ殻系、石炭系、ピッチ系等の
全てを使用することができる。反応に用いられる活性炭
の量は、特に制限はないが、パラジウム金属に対して重
量で２０〜２００倍、特に５０〜１５０倍の範囲である
ことが好ましい。(C) Activated Carbon The activated carbon used in the present invention may be any commercially available one, and the raw material may be wood-based, coconut shell-based, coal-based, pitch-based or the like. The amount of activated carbon used in the reaction is not particularly limited, but it is preferably in the range of 20 to 200 times, particularly 50 to 150 times by weight of palladium metal.

【００１２】３．反応条件 反応は上記芳香族ヒドロキシ化合物と、上記成分
（Ａ）、（Ｂ）および（Ｃ）からなる触媒とを反応装置
に仕込み、一酸化炭素および酸素により加圧し、加温下
に行われる。反応圧力は１０-2〜５０ＭＰａ、好ましく
は１０-1〜２５ＭＰａの範囲である。一酸化炭素と酸素
の組成比は、安全性の観点から、その燃焼範囲からはず
れた組成比であることが好ましい。反応温度は２０〜３
００℃、好ましくは６０〜２５０℃、より好ましくは８
０〜１３０℃の範囲である。反応時間は数分から数時間
である。反応系中にモレキュラーシーブのような乾燥剤
を添加することや、反応系から生成する水を抜きながら
反応を実施することも効果的である。反応に際しては、
溶媒として、例えばヘキサン、ヘプタン、シクロヘキサ
ン、ベンゼン、トルエン、キシレン、塩化メチレン、ク
ロロホルム、クロロベンゼン、ジエチルエーテル、ジフ
ェニルエーテル、テトラヒドロフラン、ジオキサン、酢
酸エチル、ギ酸メチル、アセトニトリルなどの不活性な
溶媒を用いることができる。なお、原料の芳香族ヒドロ
キシ化合物が反応溶媒となる場合もあるので、このとき
は特に他の溶媒を用いる必要はない。3. Reaction conditions The reaction is carried out by heating the aromatic hydroxy compound and the catalyst comprising the components (A), (B) and (C) in a reactor, pressurizing with carbon monoxide and oxygen, and heating. The reaction pressure is in the range of 10 -2 to 50 MPa, preferably 10 -1 to 25 MPa. From the viewpoint of safety, the composition ratio of carbon monoxide and oxygen is preferably outside the combustion range. Reaction temperature is 20-3
00 ° C, preferably 60 to 250 ° C, more preferably 8
It is in the range of 0 to 130 ° C. The reaction time is a few minutes to a few hours. It is also effective to add a desiccant such as molecular sieve to the reaction system or carry out the reaction while removing water generated from the reaction system. In the reaction,
As the solvent, for example, an inert solvent such as hexane, heptane, cyclohexane, benzene, toluene, xylene, methylene chloride, chloroform, chlorobenzene, diethyl ether, diphenyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl formate, acetonitrile can be used. . Since the starting aromatic hydroxy compound may serve as the reaction solvent, it is not necessary to use another solvent at this time.

【００１３】[0013]

【実施例】以下に実施例および比較例を挙げて本発明を
詳細に説明する。 実施例１ 容量３０mlのハステロイ製オートクレーブにフェノール
３.０ｇ（３２mmol）、酢酸パラジウム２.７mg(０.０１
２mmol Pd)、塩化セシウム４０mg（０.２３８mmol）、
活性炭［二村化学工業社製「太閤Ｐ」］１００mg（Ｃ／
Ｐｄ＝７７重量比）を入れ、系内を一酸化炭素で置換し
た後、一酸化炭素６ＭＰａ、乾燥空気３ＭＰａを導入
し、１００℃で３時間反応させ、反応液をガスクロマト
グラフィーにより分析した。その結果、炭酸ジフェニル
が収率４.８７％（０.７８mmol）で得られた。また、副
生成物としてサリチル酸フェニルは０.０９％（０.０１
４mmol）、ｐ−フェノキシフェノールは０.３７％（０.
０５９mmol）生成した。The present invention will be described in detail below with reference to examples and comparative examples. Example 1 3.0 g (32 mmol) of phenol and 2.7 mg (0.01 of palladium acetate) were placed in a Hastelloy autoclave having a volume of 30 ml.
2 mmol Pd), cesium chloride 40 mg (0.238 mmol),
Activated carbon ["Taiko P" manufactured by Nimura Chemical Co., Ltd.] 100 mg (C /
(Pd = 77 weight ratio) was charged and the system was replaced with carbon monoxide, then carbon monoxide (6 MPa) and dry air (3 MPa) were introduced, reacted at 100 ° C. for 3 hours, and the reaction solution was analyzed by gas chromatography. As a result, diphenyl carbonate was obtained with a yield of 4.87% (0.78 mmol). In addition, as a by-product, phenyl salicylate was 0.09% (0.01
4 mmol), p-phenoxyphenol 0.37% (0.3.
059 mmol) was produced.

【００１４】実施例２ 反応時間を５時間に変更した以外は実施例１と同様に反
応を行った結果、炭酸ジフェニルが収率５.８４％（０.
９３mmol）で得られた。Example 2 The reaction was carried out in the same manner as in Example 1 except that the reaction time was changed to 5 hours. As a result, the yield of diphenyl carbonate was 5.84% (0.8%).
93 mmol).

【００１５】実施例３ 活性炭の使用量を１２０mg（Ｃ／Ｐｄ＝９２重量比）に
変更した以外は実施例１と同様に反応を行った結果、炭
酸ジフェニルが収率５.２７％（０.８４mmol）で得られ
た。Example 3 The reaction was carried out in the same manner as in Example 1 except that the amount of activated carbon used was changed to 120 mg (C / Pd = 92 weight ratio). As a result, the yield of diphenyl carbonate was 5.27% (0.2 84 mmol).

【００１６】比較例１ 容量３０mlのハステロイ製オートクレーブにフェノール
３.０ｇ（３２mmol）、酢酸パラジウム２.７mg(０.０１
２mmol Pd)、酢酸セリウム（III）・１水和物４.１mg
（０.０１２mmol）、塩化セシウム４０mg（０.２３８ m
mol）を入れ、系内を一酸化炭素で置換した後、一酸化
炭素６ＭＰａ、乾燥空気３ＭＰａを導入し、１００℃で
３時間反応させ、反応液をガスクロマトグラフィーによ
り分析した。その結果、炭酸ジフェニルが収率４.２２
％（０.６８mmol）で得られた。また、副生成物として
サリチル酸フェニルは０.２６％（０.０４２mmol）、ｐ
−フェノキシフェノールは０.４６％（０.０７４mmol）
生成した。Comparative Example 1 3.0 g (32 mmol) of phenol and 2.7 mg (0.01 of palladium acetate) were placed in a Hastelloy autoclave having a volume of 30 ml.
2mmol Pd), cerium (III) acetate monohydrate 4.1mg
(0.012 mmol), 40 mg of cesium chloride (0.238 m)
mol) was added and the inside of the system was replaced with carbon monoxide, then carbon monoxide 6 MPa and dry air 3 MPa were introduced, the reaction was carried out at 100 ° C. for 3 hours, and the reaction liquid was analyzed by gas chromatography. As a result, the yield of diphenyl carbonate was 4.22.
% (0.68 mmol). In addition, phenyl salicylate as a by-product is 0.26% (0.042 mmol), p
-Phenoxyphenol is 0.46% (0.074 mmol)
Generated.

【００１７】比較例２ 比較例１よりレドックス剤である酢酸セリウムを除き、
触媒を酢酸パラジウム２.７mg、塩化セシウム４０mgだ
けにした。その他は比較例１と同様の条件で反応を行っ
た結果、炭酸ジフェニルが収率０.４４％（０.０７０mm
ol）で得られた。COMPARATIVE EXAMPLE 2 From Comparative Example 1, the redox agent cerium acetate was removed,
The catalyst was only 2.7 mg of palladium acetate and 40 mg of cesium chloride. Other than that, the reaction was conducted under the same conditions as in Comparative Example 1, and as a result, the yield of diphenyl carbonate was 0.44% (0.070 mm).
ol).

【００１８】[0018]

【発明の効果】上記の結果から明らかなように、本発明
の触媒系においては、蒸留分離の困難な副生物の生成が
抑制されるので、工業的価値の高い方法であるというこ
とができる。As is clear from the above results, in the catalyst system of the present invention, the production of by-products which are difficult to separate by distillation is suppressed, and therefore it can be said to be a method of high industrial value.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ０７Ｂ 61/00 ３００ (72)発明者 林 英人 茨城県稲敷郡阿見町中央８丁目３番１号 三菱油化株式会社筑波総合研究所内 (72)発明者 大篭 祐二 茨城県稲敷郡阿見町中央８丁目３番１号 三菱油化株式会社筑波総合研究所内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Reference number within the agency FI technical display location // C07B 61/00 300 (72) Inventor Hideto Hayashi 8-3 Chuo, Ami-cho, Inashiki-gun, Ibaraki No. 1 Mitsubishi Petrochemical Co., Ltd. Tsukuba Research Institute (72) Inventor Yuji Ogaki 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Prefecture Mitsubishi Petrochemical Co., Ltd. Tsukuba Research Institute

Claims (4)

【特許請求の範囲】[Claims] 【請求項１】 芳香族ヒドロキシ化合物と一酸化炭素及
び酸素を反応させて芳香族炭酸エステルを製造する方法
において、反応系に（Ａ）パラジウム及びパラジウム化
合物から選ばれた一種以上、（Ｂ）アルカリ金属ハロゲ
ン化物及びアルカリ土類金属ハロゲン化物から選ばれた
無機ハロゲン化物の一種以上、および（Ｃ）活性炭を存
在させて、該反応を行うことを特徴とする芳香族炭酸エ
ステルの製造方法。1. A method for producing an aromatic carbonic acid ester by reacting an aromatic hydroxy compound with carbon monoxide and oxygen, wherein the reaction system comprises one or more selected from (A) palladium and a palladium compound, and (B) an alkali. A process for producing an aromatic carbonic acid ester, which comprises carrying out the reaction in the presence of at least one inorganic halide selected from metal halides and alkaline earth metal halides, and (C) activated carbon. 【請求項２】 前記パラジウム化合物がパラジウムの有
機酸塩である請求項１記載の方法。2. The method according to claim 1, wherein the palladium compound is an organic acid salt of palladium. 【請求項３】 前記無機ハロゲン化物が塩化物または臭
化物である請求項１記載の方法。3. The method according to claim 1, wherein the inorganic halide is chloride or bromide. 【請求項４】 前記無機ハロゲン化物が塩化セシウムま
たは臭化セシウムである請求項１記載の方法。4. The method according to claim 1, wherein the inorganic halide is cesium chloride or cesium bromide.
JP6226935A 1994-09-21 1994-09-21 Production of aromatic carbonic acid ester Pending JPH0892168A (en)

Priority Applications (1)

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JPH0892168A true JPH0892168A (en) 1996-04-09

Family

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