JP2000239203A - Production of phenol condensate - Google Patents
Production of phenol condensateInfo
- Publication number
- JP2000239203A JP2000239203A JP11040551A JP4055199A JP2000239203A JP 2000239203 A JP2000239203 A JP 2000239203A JP 11040551 A JP11040551 A JP 11040551A JP 4055199 A JP4055199 A JP 4055199A JP 2000239203 A JP2000239203 A JP 2000239203A
- Authority
- JP
- Japan
- Prior art keywords
- phenol
- organic solvent
- water
- dimer compound
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はフェノール縮合物の
製造方法に関する。[0001] The present invention relates to a method for producing a phenol condensate.
【０００２】[0002]
【従来の技術】フェノールの酸化カップリングにより得
られる低分子量縮合物、特にフェノール二量体化合物
は、エンジニアリングプラスチック、エポキシ樹脂、フ
ォトレジスト、酸化防止剤等の合成原料として幅広い分
野に応用されている。2. Description of the Related Art Low molecular weight condensates obtained by oxidative coupling of phenol, especially phenol dimer compounds, are widely used as synthetic raw materials for engineering plastics, epoxy resins, photoresists, antioxidants and the like. .
【０００３】フェノールの酸化カップリング法として、
生体酵素を用いる方法も報告されているが、一般に遷移
金属化合物を用いる方法が安価で有用な方法である。こ
の際、遷移金属化合物は酸化剤または触媒として使用さ
れる。しかし、フェノール二量体化合物の製造におい
て、一般に、生成したフェノール二量体化合物がフェノ
ールよりも酸化されやすく、フェノール二量体化合物が
生成しても高分子量化してしまうという問題があった。As a method for oxidative coupling of phenol,
Although a method using a biological enzyme has been reported, a method using a transition metal compound is generally an inexpensive and useful method. At this time, the transition metal compound is used as an oxidizing agent or a catalyst. However, in the production of the phenol dimer compound, generally, there has been a problem that the generated phenol dimer compound is more easily oxidized than phenol, and even if the phenol dimer compound is formed, the molecular weight is increased.
【０００４】これに対して、フェノール二量体化合物は
水に対する溶解性が低いので、遷移金属化合物を用いた
フェノールの酸化カップリング反応を水溶媒中で行わせ
る方法は、フェノール二量体で反応を停止する方法とし
て期待されていた。On the other hand, since the phenol dimer compound has low solubility in water, the method of conducting the oxidative coupling reaction of phenol using a transition metal compound in an aqueous solvent is a method using the phenol dimer. Was expected as a way to stop.
【０００５】J. Chem. Soc. Perkin Trans. II, 563 (1
983)には、遷移金属化合物を用いたフェノールの酸化カ
ップリングとして、溶媒としては有機溶媒のみを用いる
例の他に、溶媒として水のみを用いる例が記載されてい
る。また、本発明者らが提案した特開平１０−３６３０
２号公報には、溶媒としては水のみを用いて包接化合物
を共存させる実施例が記載されている。しかし、これら
の方法によってもフェノール二量体化合物の収率はまだ
十分とは言えない。[0005] J. Chem. Soc. Perkin Trans. II, 563 (1
983) describes, as an oxidative coupling of phenol using a transition metal compound, an example using only water as a solvent in addition to an example using only an organic solvent as a solvent. Further, Japanese Patent Application Laid-Open No. 10-3630 proposed by the present inventors.
No. 2 describes an example in which an inclusion compound is coexisted using only water as a solvent. However, even with these methods, the yield of the phenol dimer compound is not yet sufficient.
【０００６】一方、本発明者らは遷移金属錯体触媒と過
酸化水素水溶液を用い、有機溶媒中でフェノールの酸化
カップリング方法をいくつか提案している。これらの方
法では、過酸化水素水溶液由来の水が共存するため、反
応開始時より有機溶媒と水の混合溶媒系となっていた。On the other hand, the present inventors have proposed several methods for oxidative coupling of phenol in an organic solvent using a transition metal complex catalyst and an aqueous solution of hydrogen peroxide. In these methods, since water derived from an aqueous hydrogen peroxide solution coexists, a mixed solvent system of an organic solvent and water was used from the start of the reaction.
【０００７】これらで用いた有機溶媒としては、特開平
８−５３５４５号公報にはエチレングリコールジメチル
エーテルまたはトルエンを、特開平１０−４５９０２号
公報にはトルエンを、特開平１０−１７６０５０号公報
にはジオキサン/アセトニトリル混合溶媒を用いた例を
記載している。また、特開平９−２８６８５４号公報に
はトルエンまたは１，２−ジクロロベンゼンを用いた実
施例が記載されている。しかし、これらの方法によって
も得られるフェノール二量体化合物の収率は満足できる
ものではなかった。As the organic solvent used in these, ethylene glycol dimethyl ether or toluene is described in JP-A-8-53545, toluene is described in JP-A-10-45902, and dioxane is described in JP-A-10-176050. An example using a mixed solvent of / acetonitrile is described. Japanese Patent Application Laid-Open No. 9-286854 describes an example using toluene or 1,2-dichlorobenzene. However, the yield of the phenol dimer compound obtained by these methods was not satisfactory.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、低分子量フ
ェノール縮合物、特にフェノール二量体化合物を高収率
で製造することのできるフェノール縮合物の製造方法を
提供することをその目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a phenol condensate which can produce a low molecular weight phenol condensate, particularly a phenol dimer compound, in a high yield. .
【０００９】[0009]
【課題を解決するための手段】本研究者らは上記課題を
解決すべく鋭意研究を行った結果、遷移金属化合物を用
いてフェノールを酸化カップリング反応させるに当り、
反応を難水溶性または非水溶性で、かつフェノール二量
体化合物抽出能力の高い有機溶媒と水との混合溶媒中で
行わせることによって、目的のフェノールの二量体化が
効率良く進み、かつ、生成したフェノール二量体化合物
の高分子量化も抑制しうることを見出し、この知見に基
づき本発明を完成するに至った。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, when conducting oxidative coupling reaction of phenol using a transition metal compound,
By performing the reaction in a poorly water-soluble or water-insoluble and mixed solvent of water and an organic solvent having a high phenol dimer compound extraction ability, the dimerization of the objective phenol proceeds efficiently, and They have also found that the phenol dimer compound produced can also suppress the increase in the molecular weight, and have completed the present invention based on this finding.
【００１０】すなわち、本発明は、遷移金属化合物を用
いてフェノールを酸化カップリング反応させるに当り、
難水溶性または非水溶性で、かつフェノール二量体化合
物の抽出係数が４０％以上の有機溶媒と水との混合溶媒
中で反応させることを特徴とするフェノール縮合物の製
造方法。（ここで、有機溶媒のフェノール二量体化合物
抽出係数とは次のようにして求めたものである。有機溶
媒（通常５ｍｌ）にｐ，ｐ’−ビフェノールを１０ｍｇ
／ｍｌとなるように加え、有機溶媒と同体積量の水を加
え、十分に振とうする。これを静置し、二層に分離させ
た後、有機溶媒中に抽出されたｐ，ｐ’−ビフェノール
の割合をこの有機溶媒のフェノール二量体化合物の抽出
係数（％）とする。）である。次に本発明を詳細に説明
する。That is, the present invention provides an oxidative coupling reaction of phenol using a transition metal compound.
A method for producing a phenol condensate, which comprises reacting a poorly water-soluble or water-insoluble phenol dimer compound in a mixed solvent of water and an organic solvent having an extraction coefficient of 40% or more. (Here, the extraction coefficient of the phenol dimer compound in the organic solvent is determined as follows. 10 mg of p, p'-biphenol is added to the organic solvent (usually 5 ml).
/ Ml, add water in the same volume as the organic solvent, and shake well. After allowing this to stand and separating it into two layers, the ratio of p, p'-biphenol extracted in the organic solvent is defined as the extraction coefficient (%) of the phenol dimer compound in this organic solvent. ). Next, the present invention will be described in detail.
【００１１】[0011]
【発明の実施の形態】本発明においては、遷移金属化合
物を用いてフェノールの酸化カップリング反応を行う
が、遷移金属化合物は酸化剤または触媒として作用す
る。ここで遷移金属化合物とは周期律表（ＩＵＰＡＣ無
機化学命名法改訂版１９８９）の第３〜１２族の元素の
化合物であり、生体酵素は含まないものとする。このよ
うな遷移元素としてはスカンジウム、チタン、バナジウ
ム、クロム、マンガン、鉄、コバルト、ニッケル、銅、
イットリウム、ジルコニウム、ニオブ、モリブデン、テ
クネテウム、ルテニウム、ロジウム、パラジウム、銀、
セリウム、白金、金などが例示されるがこれに限定され
ない。DETAILED DESCRIPTION OF THE INVENTION In the present invention, oxidative coupling of phenol is carried out using a transition metal compound. The transition metal compound acts as an oxidizing agent or a catalyst. Here, the transition metal compound is a compound of an element belonging to Groups 3 to 12 of the Periodic Table (IUPAC Revised Edition of Inorganic Chemical Nomenclature, 1989), and does not include biological enzymes. Such transition elements include scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper,
Yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver,
Examples include, but are not limited to, cerium, platinum, and gold.
【００１２】本発明において遷移金属化合物を酸化剤と
して作用させる場合、遷移金属化合物としては、フェノ
ールを酸化する能力があればよく、通常標準酸化還元電
位（２５℃）が０.１V以上であればよい。具体的には、
日本化学会編「改訂４版化学便覧基礎編ＩＩ」Ｐ４６５
−４６８表１２・４０記載の水溶液中における標準電極
電位（２５℃）が０.１V以上である遷移金属化合物及び
遷移金属イオンを含む化合物等が挙げられる。好ましい
具体例としては、５価バナジウムイオン、３価マンガン
イオン、３価鉄イオン、３価コバルトイオン、２価銅イ
オン、１価銀イオン、１価金イオン、４価セリウムイオ
ン等の遷移金属イオンと、フッ化物イオン、塩化物イオ
ン、臭化物イオン、ヨウ化物イオン、硫酸イオン、硝酸
イオン、炭酸イオン、過塩素酸イオン、テトラフルオロ
ボーレートイオン、ヘキサフルオロホスフェイトイオ
ン、メタンスルホン酸イオン、トリフルオロメタンスル
ホン酸イオン、トルエンスルホン酸イオン、酢酸イオ
ン、トリフルオロ酢酸イオン、プロピオン酸イオン、安
息香酸イオン、水酸化物イオン、酸化物イオン、メトキ
サイドイオン、エトキサイドイオン等のカウンターアニ
オンと、アルカリ金属イオン、アルカリ土類金属イオ
ン、アンモニウムイオン等のカウンターカチオンからな
る遷移金属化合物を挙げることができる。In the present invention, when a transition metal compound is allowed to act as an oxidizing agent, the transition metal compound only needs to have the ability to oxidize phenol, and usually has a standard oxidation-reduction potential (25 ° C.) of 0.1 V or more. Good. In particular,
The Chemical Society of Japan, “Revised 4th Edition, Handbook of Chemistry II,” P465
-468 Transition metal compounds and compounds containing transition metal ions having a standard electrode potential (25 ° C.) of 0.1 V or more in the aqueous solution described in Tables 12 and 40 are exemplified. Preferred specific examples are transition metal ions such as pentavalent vanadium ion, trivalent manganese ion, trivalent iron ion, trivalent cobalt ion, divalent copper ion, monovalent silver ion, monovalent gold ion and tetravalent cerium ion. And fluoride, chloride, bromide, iodide, sulfate, nitrate, carbonate, perchlorate, tetrafluoroborate, hexafluorophosphate, methanesulfonate, trifluoromethanesulfone Counter anions such as acid ions, toluenesulfonic acid ions, acetate ions, trifluoroacetate ions, propionate ions, benzoate ions, hydroxide ions, oxide ions, methoxide ions, ethoxide ions, and alkali metal ions; Alkaline earth metal ion, ammonium It can be exemplified transition metal compounds comprising a counter cation such as ions.
【００１３】本発明の遷移金属化合物を酸化剤とする場
合の該遷移金属化合物の標準酸化還元電位（２５℃）と
して、好ましくは０．２V以上であり、より好ましくは
０．５V以上であり、さらに好ましくは１．０V以上であ
る。When the transition metal compound of the present invention is used as an oxidizing agent, the standard oxidation-reduction potential (25 ° C.) of the transition metal compound is preferably 0.2 V or more, more preferably 0.5 V or more; More preferably, it is 1.0 V or more.
【００１４】本発明の遷移金属化合物を酸化剤とする場
合その使用量に特に制限はないが、フェノール１モルに
対して０．５〜３モルが好ましく、０．６〜２モルがよ
り好ましく、０．７〜１．５モルがさらに好ましい。When the transition metal compound of the present invention is used as an oxidizing agent, its use amount is not particularly limited, but is preferably 0.5 to 3 mol, more preferably 0.6 to 2 mol per mol of phenol. 0.7-1.5 mol is more preferred.
【００１５】本発明において遷移金属化合物を触媒とす
る場合には、通常の酸化剤を共存させることにより反応
を行わせることができる。触媒として用いられる遷移金
属化合物の例としては、特開平１０−５３６４９号公報
記載の単座配位子／遷移金属錯体；特開平１０−１６８
１７９号公報記載の二座配位子／遷移金属錯体；特開平
９−１４４４４９号公報、特開平１０−４５９０４号公
報、特開平９−３２４０４０号公報記載の三座配位子／
遷移金属錯体；特開平９−３２４０４２号公報記載の四
座または五座配位子／遷移金属錯体；特開平９−３２４
０４３号公報記載の六座以上の配位子／遷移金属錯体；
特開平９−３２４０４５号公報記載のメタロセン錯体等
が挙げられる。該遷移金属化合物の触媒としての使用量
に特に限定はないが、フェノールに対して通常、０．０
０１〜２０モル％、好ましくは０．０１〜１０モル％使
用する。In the present invention, when a transition metal compound is used as a catalyst, the reaction can be carried out by coexisting a usual oxidizing agent. Examples of the transition metal compound used as a catalyst include a monodentate ligand / transition metal complex described in JP-A-10-53649;
179, a bidentate ligand / transition metal complex; a tridentate ligand described in JP-A-9-144449, JP-A-10-45904, and JP-A-9-324040.
Transition metal complex; tetradentate or pentadentate ligand / transition metal complex described in JP-A-9-32442; JP-A-9-324
A hexadentate or higher ligand / transition metal complex described in JP-A-043;
Metallocene complexes described in JP-A-9-324045 are exemplified. Although the amount of the transition metal compound used as a catalyst is not particularly limited, it is usually 0.0
It is used in an amount of from 0.01 to 20 mol%, preferably from 0.01 to 10 mol%.
【００１６】本発明において遷移金属化合物を触媒とし
て用いる場合に共存させる酸化剤としては、酸素または
パーオキサイドが挙げられる。酸素は不活性ガスとの混
合物であってもよく、空気でもよい。またパーオキサイ
ドの例としては、過酸化水素、ｔ−ブチルハイドロパー
オキサイド、ジ−ｔ−ブチルパーオキサイド、クメンハ
イドロパーオキサイド、ジクミルパーオキサイド、過酢
酸、過安息香酸等を示すことができる。該酸化剤の使用
量に特に限定はないが、酸素を用いる場合はフェノール
１モルに対して通常、０．１５モル以上大過剰に使用
し、パーオキサイドを用いる場合はフェノール１モルに
対して通常、０．３〜１モルを使用する。In the present invention, when a transition metal compound is used as a catalyst, the coexisting oxidizing agent includes oxygen or peroxide. Oxygen may be a mixture with an inert gas or air. Examples of the peroxide include hydrogen peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, peracetic acid, and perbenzoic acid. There is no particular limitation on the amount of the oxidizing agent, but when oxygen is used, it is usually used in a large excess of 0.15 mol or more per mol of phenol, and when peroxide is used, it is usually used per mol of phenol. , 0.3-1 mol.
【００１７】本発明においては、反応溶媒として、難水
溶性または非水溶性で、かつフェノール二量体化合物の
抽出係数が４０％以上の有機溶媒と水の混合溶媒を用い
る。In the present invention, as the reaction solvent, a mixed solvent of water and an organic solvent which is hardly water-soluble or water-insoluble and has an extraction coefficient of a phenol dimer compound of 40% or more is used.
【００１８】ここでいう難水溶性または非水溶性の有機
溶媒とは、水と任意の割合で相溶することのない有機溶
媒のことであり、少なくとも、反応に用いるため所定の
有機溶媒／水の体積比となるように水と混合した時に水
と相溶することのない有機溶媒である。このような有機
溶媒は通常、水１００ｍｌに対する溶解度が４０ｍｌ以
下である。また有機溶媒のフェノール二量体化合物の抽
出係数とは次のようにして求められる値である。まず、
有機溶媒に対しｐ，ｐ’−ビフェノールが１０ｍｇ／ｍ
ｌとなるように加え、有機溶媒と同体積量の水を加え、
十分に振とうする。次に、これを静置し（通常一夜
間）、二層に分離させる。このとき、有機溶媒中に抽出
されたｐ，ｐ’−ビフェノールの割合をこの有機溶媒の
フェノール二量体化合物の抽出係数とする。この分析は
通常室温（約２５℃）で行う。The term "poorly water-soluble or water-insoluble organic solvent" as used herein means an organic solvent which is not compatible with water at an arbitrary ratio, and at least a predetermined organic solvent / water for use in the reaction. It is an organic solvent that is not compatible with water when mixed with water so as to have a volume ratio of Such an organic solvent usually has a solubility in 100 ml of water of 40 ml or less. The extraction coefficient of the phenol dimer compound in the organic solvent is a value determined as follows. First,
10 mg / m of p, p'-biphenol with respect to the organic solvent
and the same volume of water as the organic solvent is added,
Shake well. This is then allowed to stand (usually overnight) and separated into two layers. At this time, the ratio of p, p'-biphenol extracted into the organic solvent is defined as the extraction coefficient of the phenol dimer compound in the organic solvent. This analysis is usually performed at room temperature (about 25 ° C.).
【００１９】有機溶媒として、水と任意の割合で相溶す
る水溶性の有機溶媒を用いた場合、フェノール二量体化
合物の総収率が低いので好ましくない。また、難水溶性
または非水溶性であっても、フェノール二量体化合物の
抽出係数が４０％未満の有機溶媒を用いた場合は、フェ
ノール二量体化合物の総収率が十分でないので好ましく
ない。有機溶媒として、難水溶性または非水溶性で、か
つフェノール二量体化合物の抽出係数が４０％以上の有
機溶媒を用いることにより、フェノール縮合物の高分子
量化を抑制し、低分子量フェノール縮合物、特にフェノ
ール二量体化合物の収率を高めることができる。It is not preferable to use a water-soluble organic solvent which is compatible with water at an arbitrary ratio as the organic solvent, since the total yield of the phenol dimer compound is low. In addition, even if the organic solvent is poorly water-soluble or water-insoluble, the use of an organic solvent having an extraction coefficient of the phenol dimer compound of less than 40% is not preferable because the total yield of the phenol dimer compound is not sufficient. . By using an organic solvent that is poorly water-soluble or water-insoluble and has an extraction coefficient of the phenol dimer compound of 40% or more, the phenol condensate is prevented from becoming high molecular weight, and the low molecular weight phenol condensate is used. In particular, the yield of the phenol dimer compound can be increased.
【００２０】本発明に用いる難水溶性または非水溶性有
機溶媒のフェノール二量体化合物の抽出係数として、好
ましくは６０％以上であり、より好ましくは８０％以上
であり、さらに好ましくは９５％以上である。特に好ま
しくは９９％以上である。The extraction coefficient of the phenol dimer compound of the poorly water-soluble or water-insoluble organic solvent used in the present invention is preferably at least 60%, more preferably at least 80%, further preferably at least 95%. It is. It is particularly preferably at least 99%.
【００２１】本発明に用いる有機溶媒としては、具体的
にはシクロヘキサノン、アセトフェノン、フェネチルア
ルコール、n-プロピオン酸メチル、酢酸エチル、テトラ
ヒドロピラン、シクロヘキサノン、2-ブタノン、酢酸n-
ブチル、酢酸メチル、ベンゾニトリル、安息香酸メチ
ル、酢酸ベンジル、酢酸フェニル、ジイソプロピルエー
テル等が挙げられる。Examples of the organic solvent used in the present invention include cyclohexanone, acetophenone, phenethyl alcohol, methyl n-propionate, ethyl acetate, tetrahydropyran, cyclohexanone, 2-butanone, and n-acetate.
Butyl, methyl acetate, benzonitrile, methyl benzoate, benzyl acetate, phenyl acetate, diisopropyl ether and the like.
【００２２】本発明の混合溶媒において、該有機溶媒と
水の割合に特に制限はないが、反応開始時に該有機溶媒
／水の体積比が１／９９〜９９／１であることが好まし
く、１０／９０〜９８／２であることがより好ましく、
２０／８０〜９７／３であることがさらに好ましい。４
０／６０〜９６／４であることが特に好ましい。本発明
において、この混合溶媒を用い、反応液の撹拌下に反応
を行う。In the mixed solvent of the present invention, the ratio of the organic solvent to water is not particularly limited, but the volume ratio of the organic solvent / water at the start of the reaction is preferably from 1/99 to 99/1, preferably from 10/99 to 99/1. / 90 to 98/2, more preferably
The ratio is more preferably 20/80 to 97/3. 4
It is particularly preferably 0/60 to 96/4. In the present invention, the reaction is carried out using this mixed solvent while stirring the reaction solution.
【００２３】本発明の混合溶媒は任意の量で用いること
ができるが、フェノールの濃度が０．０１〜５００g／L
となるのが好ましく、０．０５〜３００g／Lとなるのが
より好ましく、０．１〜２００g／Lとなるのがさらに好
ましい。The mixed solvent of the present invention can be used in any amount, but the phenol concentration is 0.01 to 500 g / L.
It is preferably 0.05 to 300 g / L, more preferably 0.1 to 200 g / L.
【００２４】本発明において、実施する反応温度に特に
限定はなく、有機溶媒または水の沸点以上の場合には加
圧下で反応を行えばよい。好ましい温度範囲は０℃〜１
００℃であり、より好ましくは５℃〜８０℃であり、さ
らに好ましくは１０℃〜６０℃である。本発明方法によ
りフェノール二量体化合物が高収率で得られる。ここで
フェノール二量体化合物としては、ｐ，ｐ’−ビフェノ
ール、p,o’-ビフェノール、o,o’-ビフェノールなどの
ビフェノール類（ジオキシビフェニル類）及び、o-フェ
ノキシフェノール、p-フェノキシフェノールなどのフェ
ノキシフェノール類が挙げられる。フェノール二量体化
合物の相互の分離は常法により、例えば蒸留、昇華、再
沈殿化、抽出、クロマト等の精製法を単独または組み合
わせて行うことができる。In the present invention, the reaction temperature to be carried out is not particularly limited, and the reaction may be carried out under pressure when the temperature is higher than the boiling point of the organic solvent or water. The preferred temperature range is 0 ° C to 1 ° C.
00 ° C., more preferably 5 ° C. to 80 ° C., and still more preferably 10 ° C. to 60 ° C. According to the method of the present invention, a phenol dimer compound is obtained in high yield. Here, the phenol dimer compound includes biphenols (dioxybiphenyls) such as p, p'-biphenol, p, o'-biphenol and o, o'-biphenol, and o-phenoxyphenol and p-phenoxy. Phenoxyphenols such as phenol are exemplified. The phenol dimer compounds can be separated from each other by a conventional method, for example, a purification method such as distillation, sublimation, reprecipitation, extraction, and chromatography can be used alone or in combination.
【００２５】[0025]
【実施例】以下に、実施例を挙げて本発明を更に詳細に
説明するが、本発明はこれらの実施例によりその範囲を
限定されるものではない。The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited by these examples.
【００２６】参考例１ 有機溶媒の二量体化合物抽出係数（E(p,p-2)）：２０ｍ
ｌサンプル管に有機溶媒５ｍｌにフェノール、ｐ，ｐ’
−ビフェノール（p,p-2）及びp-フェノキシフェノール
（p-2）をそれぞれ５０ｍｇづつ加え、よく振とうした
後、水５ｍｌを加え、再度十分に振とうした。（不溶部
のある場合には、不溶部をろ過して除いた。）この溶液
を１日静置し、二層に分離させた。なお、この抽出試験
は、室温（約２５℃）で行った。この有機層及び水層を
それぞれ２μＬサンプリングし、ガスクロマトグラフィ
−（Hewlett Packard社HP-6890を用い、 Hewlett Packa
rd社HP-5(30mx0.32mm)をカラムとし、 50℃から250℃ま
で10℃/minで昇温して、FID検出により分析）でp,p-2及
びp-2をそれぞれ定量し、有機層中のそれらの量をA(p,p
-2)及びA(p-2)とし、水層中のそれらの量をB(p,p-2)及
びB(p-2)とした。（なお、２０ｍｌサンプル管で酢酸エ
チル５ｍｌにｐ，ｐ’−ビフェノール（p,p-2）及びp-
フェノキシフェノール（p-2）をそれぞれ５０ｍｇづつ
加え、均一にした。この溶液を２μＬサンプリングし、
ガスクロマトグラフィ−で同様にp,p-2及びp-2を定量
し、C(p,p-2)及びC(p-2)とした。） 不溶部のない場合は、E＝A／（A＋B）x１００で求めら
れるEを、p,p-2及びp-2につきそれぞれのE(p,p-2)及びE
(p-2)とした。（不溶部のある場合は、E＝A／Cx１００
で求められるEを、p,p-2及びp-2につきそれぞれのE(p,p
-2)及びE(p-2)とした。）各有機溶媒のE(p,p-2)及びE(p
-2)を求めた結果を表１に示すが、E(p,p-2)をフェノー
ル二量体化合物の抽出係数とする。Reference Example 1 Extraction coefficient of dimer compound of organic solvent (E (p, p-2)): 20 m
l Phenol, p, p 'in 5 ml of organic solvent in the sample tube
-Biphenol (p, p-2) and p-phenoxyphenol (p-2) were added in an amount of 50 mg each, and after shaking well, 5 ml of water was added, followed by sufficient shaking again. (If there was an insoluble portion, the insoluble portion was removed by filtration.) The solution was allowed to stand for 1 day to separate into two layers. The extraction test was performed at room temperature (about 25 ° C.). The organic layer and the aqueous layer were each sampled at 2 μL, and subjected to gas chromatography (using Hewlett Packard HP-6890, Hewlett Packa).
rd company HP-5 (30mx0.32mm) was used as a column, and the temperature was raised from 50 ° C to 250 ° C at 10 ° C / min, and analyzed by FID detection. A (p, p
-2) and A (p-2), and their amounts in the aqueous layer were B (p, p-2) and B (p-2). (Note that p, p'-biphenol (p, p-2) and p-p-phenol were added to 5 ml of ethyl acetate in a 20 ml sample tube.
Phenoxyphenol (p-2) was added in an amount of 50 mg each for homogenization. 2 μL of this solution was sampled,
Similarly, p, p-2 and p-2 were quantified by gas chromatography and defined as C (p, p-2) and C (p-2). ) If there is no insoluble part, E obtained by E = A / (A + B) × 100 is calculated as E (p, p-2) and E for p, p-2 and p-2 respectively.
(p-2). (If there is an insoluble part, E = A / Cx100
The E obtained in the above is calculated as E (p, p
-2) and E (p-2). ) E (p, p-2) and E (p
-2) is shown in Table 1, where E (p, p-2) is the extraction coefficient of the phenol dimer compound.
【００２７】[0027]
【表１】 [Table 1]
【００２８】実施例１ 電磁撹拌機を備えたフラスコ中で、フェノール９４mg
（１mmol）をシクロヘキサノン２５mlに溶解した。これ
にCe(NH４)２(NO３)６ ４８２mg（０．８８mmol）を蒸
留水５mlに溶解させたものを加えて、室温（約２５℃）
で激しく撹拌して反応を開始した。２４hr反応させた
後、ジフェニルエーテル６０mg及びメタノール１００ml
を加え、不溶物をろ過し、そのろ液を高速液体クロマト
グラフィー（ポンプ：東ソー社製ＳＣ８０２０システ
ム、検出器：東ソー社製ＰＤ−８０２０、検出波長：２
７８ｎｍ、カラム：ＹＭＣ社製ＯＤＳ−ＡＭ、展開溶
媒：メタノール／水）で分析した。フェノールの転化率
はジフェニルエーテルを内部標準として定量した。フェ
ノール二量体：ｐ，ｐ’−ビフェノール（p,p-2）、p,
o’-ビフェノール（p,o-2）、o,o’-ビフェノール（o,o
-2）、p-フェノキシフェノール（p-2）、o-フェノキシ
フェノール（o-2）は、J.Chem.Soc.Perkin Trans., II,
563 (1983)を参考にして、ジフェニルエーテルを内部
標準として定量し、各々の収率および総収率（Yield）
をフェノール転化率（Conv.）を基準として求めた。結
果を表２に示す。Example 1 In a flask equipped with a magnetic stirrer, 94 mg of phenol was added.
(1 mmol) was dissolved in 25 ml of cyclohexanone. A solution obtained by dissolving 482 mg (0.88 mmol) of Ce (NH 4 ) 2 (NO 3 ) 6 in 5 ml of distilled water was added thereto, and the mixture was added at room temperature (about 25 ° C.).
The reaction was started by vigorous stirring. After reacting for 24 hours, diphenyl ether 60 mg and methanol 100 ml
, And the insolubles are filtered. The filtrate is subjected to high performance liquid chromatography (pump: SC8020 system manufactured by Tosoh Corporation, detector: PD-8020 manufactured by Tosoh Corporation, detection wavelength: 2)
78 nm, column: ODS-AM manufactured by YMC, developing solvent: methanol / water). The conversion of phenol was determined using diphenyl ether as an internal standard. Phenol dimer: p, p'-biphenol (p, p-2), p, p
o'-biphenol (p, o-2), o, o'-biphenol (o, o
-2), p-phenoxyphenol (p-2) and o-phenoxyphenol (o-2) are available from J. Chem. Soc. Perkin Trans., II,
With reference to 563 (1983), diphenyl ether was quantified as an internal standard, and each yield and total yield (Yield)
Was determined based on the phenol conversion (Conv.). Table 2 shows the results.
【００２９】実施例２〜９および比較例１〜３ 有機溶媒、有機溶媒量、水量を表２に示すように変えた
以外は、実施例１と同様にして重合を実施した。表１に
結果を示す。Examples 2 to 9 and Comparative Examples 1 to 3 Polymerization was carried out in the same manner as in Example 1 except that the amount of the organic solvent, the amount of the organic solvent and the amount of water were changed as shown in Table 2. Table 1 shows the results.
【００３０】実施例に示されるように難水溶性または非
水溶性で、かつフェノール二量体化合物の抽出係数が４
０％以上の有機溶媒を用いると、比較例１のように難水
溶性または非水溶性ではあるが、フェノール二量体化合
物の抽出係数が４０％未満（E(p,p-2)=0）の有機溶媒を
用いた場合や、比較例２のように水溶性有機溶媒を用い
た場合や、比較例３のように有機溶媒を全く用いない場
合よりも、二量体化合物の総収率がはるかに高くなっ
た。As shown in the examples, the compound is poorly water-soluble or water-insoluble and has an extraction coefficient of 4 for the phenol dimer compound.
When 0% or more of the organic solvent is used, it is poorly water-soluble or water-insoluble as in Comparative Example 1, but the extraction coefficient of the phenol dimer compound is less than 40% (E (p, p-2) = 0). ), The water-soluble organic solvent used in Comparative Example 2, or the total yield of the dimer compound as compared to the case where no organic solvent is used as in Comparative Example 3. Became much higher.
【００３１】[0031]
【表２】 [Table 2]
【００３２】[0032]
【発明の効果】以上のように、遷移金属化合物を用いて
フェノールを酸化カップリングする際に、難水溶性また
は非水溶性で、かつフェノール二量体化合物の抽出係数
が４０％以上の有機溶媒と水との混合溶媒を用いること
により、低分子量フェノール縮合物、特にフェノール二
量体化合物を非常に高い収率で合成することができる。As described above, when oxidatively coupling phenol with a transition metal compound, an organic solvent which is poorly water-soluble or water-insoluble and has an extraction coefficient of a phenol dimer compound of 40% or more. By using a mixed solvent of water and water, a low molecular weight phenol condensate, particularly a phenol dimer compound, can be synthesized in a very high yield.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ (72)発明者 諸岡 良彦 神奈川県横浜市青葉区藤が丘２丁目41番21 東工大宿舎404 (72)発明者 小林 四郎 茨城県つくば市東１丁目１番 工業技術院 物質工学工業技術研究所内 Ｆターム(参考） 4H006 AA02 AC23 AC43 BA05 BA08 BA10 BA12 BA14 BA16 BA19 BA20 BA21 BA23 BA24 BA25 BA26 BA34 BB10 BB16 BB17 BB25 BB31 BB49 BE30 BE32 FC52 FE13 GN05 GP06 GP12 4H039 CA41 CA61 CD10 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) // C07B 61/00 300 C07B 61/00 300 (72) Inventor Yoshihiko Morooka 2 Fujigaoka, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Chome 41-21 Tokyo Tech University 404 (72) Inventor Shiro Kobayashi 1-1-1 Higashi, Tsukuba, Ibaraki Pref. BA23 BA24 BA25 BA26 BA34 BB10 BB16 BB17 BB25 BB31 BB49 BE30 BE32 FC52 FE13 GN05 GP06 GP12 4H039 CA41 CA61 CD10
Claims (3)
化カップリング反応させるに当り、難水溶性または非水
溶性で、かつフェノール二量体化合物の抽出係数が４０
％以上の有機溶媒と水との混合溶媒中で反応させること
を特徴とするフェノール縮合物の製造方法。（ここで、
有機溶媒のフェノール二量体化合物抽出係数とは次のよ
うにして求める。有機溶媒にｐ，ｐ’−ビフェノールを
１０ｍｇ／ｍｌとなるように加え、有機溶媒と同体積量
の水を加え、十分に振とうする。これを静置し、二層に
分離させた後、有機溶媒中に抽出されたｐ，ｐ’−ビフ
ェノールの割合をこの有機溶媒のフェノール二量体化合
物の抽出係数（％）とする。）1. An oxidative coupling reaction of phenol with a transition metal compound, wherein the phenol dimer compound is poorly water-soluble or water-insoluble and has an extraction coefficient of 40.
%. A method for producing a phenol condensate, characterized in that the reaction is carried out in a mixed solvent of at least% of an organic solvent and water. (here,
The extraction coefficient of the phenol dimer compound in the organic solvent is determined as follows. Add p, p'-biphenol to the organic solvent to a concentration of 10 mg / ml, add water in the same volume as the organic solvent, and shake well. After allowing this to stand and separating into two layers, the ratio of p, p'-biphenol extracted into the organic solvent is defined as the extraction coefficient (%) of the phenol dimer compound in this organic solvent. )
体化合物の抽出係数が６０％以上であることを特徴とす
る請求項１記載のフェノール縮合物の製造方法。2. The method for producing a phenol condensate according to claim 1, wherein the extraction coefficient of the phenol dimer compound in the organic solvent is 60% or more.
体積比１／９９〜９９／１であることを特徴とする請求
項１または２記載のフェノール縮合物の製造方法。3. The process for producing a phenol condensate according to claim 1, wherein the ratio of the organic solvent and water is 1/99 to 99/1 by volume at the start of the reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11040551A JP3032780B1 (en) | 1999-02-18 | 1999-02-18 | Method for producing phenol condensate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11040551A JP3032780B1 (en) | 1999-02-18 | 1999-02-18 | Method for producing phenol condensate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP3032780B1 JP3032780B1 (en) | 2000-04-17 |
| JP2000239203A true JP2000239203A (en) | 2000-09-05 |
Family
ID=12583598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11040551A Expired - Fee Related JP3032780B1 (en) | 1999-02-18 | 1999-02-18 | Method for producing phenol condensate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3032780B1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009028724A1 (en) * | 2007-08-31 | 2009-03-05 | Sumitomo Chemical Company, Limited | Method for producing phenol dimer |
| JP2009057296A (en) * | 2007-08-30 | 2009-03-19 | Sumitomo Chemical Co Ltd | Method for producing dimer of phenol |
-
1999
- 1999-02-18 JP JP11040551A patent/JP3032780B1/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009057296A (en) * | 2007-08-30 | 2009-03-19 | Sumitomo Chemical Co Ltd | Method for producing dimer of phenol |
| WO2009028724A1 (en) * | 2007-08-31 | 2009-03-05 | Sumitomo Chemical Company, Limited | Method for producing phenol dimer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3032780B1 (en) | 2000-04-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bortolini et al. | Metal catalysis in oxidation by peroxides. Part 25. Molybdenum-and tungsten-catalyzed oxidations of alcohols by diluted hydrogen peroxide under phase-transfer conditions | |
| Kirillov et al. | Mild Peroxidative Oxidation of Cyclohexane Catalyzed by Mono‐, Di‐, Tri‐, Tetra‐and Polynuclear Copper Triethanolamine Complexes | |
| De Bruin et al. | Functional Models for Rhodium‐Mediated Olefin‐Oxygenation Catalysis | |
| Himeda | Conversion of CO2 into formate by homogeneously catalyzed hydrogenation in water: tuning catalytic activity and water solubility through the acid–base equilibrium of the ligand | |
| Chowdhury et al. | An iron catalyzed regioselective oxidation of terminal alkenes to aldehydes | |
| Hollis et al. | Homogeneous catalysis.[TiCp2 (CF3SO3) 2] and [ZrCp2 (CF3SO3) 2THF], fast and efficient catalysts for the Mukaiyama cross-aldol reaction | |
| Khenkin et al. | Aerobic Oxidation of Vicinal Diols Catalyzed by an Anderson‐Type Polyoxometalate,[IMo6O24] 5– | |
| Belokon’ et al. | Mechanistic investigation of the asymmetric addition of trimethylsilyl cyanide to aldehydes catalysed by dinuclear chiral (salen) titanium complexes | |
| Zhang et al. | Highly efficient chiral metal cluster systems derived from Ru 3 (CO) 12 and chiral diiminodiphosphines for the asymmetric transfer hydrogenation of ketones | |
| Zanardo et al. | Kinetic study of the epoxidation of 1-octene with hydrogen peroxide catalyzed by platinum (II) complexes. Evidence of the involvement of two metal species in the oxygen-transfer step | |
| Zsigmond et al. | Ruthenium-catalyzed aerobic oxidation of alcohols on zeolite-encapsulated cobalt salophen catalyst | |
| CN109922882A (en) | Make the hydroformylation catalyst solution regeneration method of inactivation | |
| Komiya et al. | Water-soluble diruthenium complexes bearing acetate and carbonate bridges: highly efficient catalysts for aerobic oxidation of alcohols in water | |
| US6680385B2 (en) | Catalytic preparation of aryl methyl ketones using a molecular oxygen-containing gas as the oxidant | |
| CN105837416A (en) | Method for preparing aldehyde or ketone by alcohol selective oxidation under catalysis of copper complex | |
| CN103467434B (en) | Method for preparing eta-caprolactone by composite catalysis | |
| Ajjou | First example of water-soluble transition-metal catalysts for Oppenauer-type oxidation of secondary alcohols | |
| JP3032780B1 (en) | Method for producing phenol condensate | |
| Kodama et al. | Tetranuclear vanadium complex,(VO) 4 (hpic) 4: A recyclable catalyst for oxidation of benzyl alcohols with molecular oxygen | |
| JPH0193556A (en) | Production of 3, 5, 5-trimethylcyclohexa-2-ene-1, 4-dione | |
| JP2790885B2 (en) | Oxygen oxidation of olefins by halogenated porphyrin complex catalysts | |
| Drymona et al. | An In‐Situ‐Formed Copper‐Based Perfluorinated Catalytic System for the Aerobic Oxidation of Alcohols | |
| US20040242922A1 (en) | Method of oxidising hydrocarbons to acids | |
| Lau et al. | Oxidation of C2, C3 and higher alkanes by a ruthenium–oxo system | |
| US6586643B2 (en) | One-step production of 1,3-propanediol from ethylene oxide and syngas with a catalyst with a N-heterocyclic ligand |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313118 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| 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 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080218 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090218 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100218 Year of fee payment: 10 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100218 Year of fee payment: 10 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110218 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120218 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120218 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130218 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140218 Year of fee payment: 14 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| LAPS | Cancellation because of no payment of annual fees | ||
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| R370 | Written measure of declining of transfer procedure |
Free format text: JAPANESE INTERMEDIATE CODE: R370 |