JP3555201B2 - Method for producing alicyclic diketone compound - Google Patents

Description

［式中、Ｘは単結合、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−又は−ＳＯ_２−を表す。Ｒ^１、Ｒ^２は同一又は異なって、水素又は炭素数１〜６のアルキル基を表す。ｍ、ｎは同一又は異なって、０〜２の整数を表す。］
【００１３】

［式中、Ｘ、Ｒ^１、Ｒ^２、ｍ及びｎは一般式（Ｉ）と同義である。］
【００１４】
一般式（Ｉ）で表されるビスフェノール化合物として、具体的には、ビス（４−ヒドロキシフェニル）、ビス（２−メチル−４−ヒドロキシフェニル）、ビス（２−ヒドロキシフェニル）、ビス（４−ヒドロキシフェニル）メタン、ビス（２−エチル−４−ヒドロキシフェニル）メタン、ビス（２−ヒドロキシフェニル）メタン、２−ヒドロキシフェニル−４−ヒドロキシフェニルメタン、ビスフェノールＡ、２，２−ビス（２−メチル−４−ヒドロキシフェニル）プロパン、２，２−ビス（３−メチル−４−ヒドロキシフェニル）プロパン、２，２−ビス（２−ヒドロキシフェニル）プロパン、２−（２−ヒドロキシフェニル）−２−（４−ヒドロキシフェニル）プロパン、ビス（４−ヒドロキシフェニル）エーテル、ビス（２−ヒドロキシフェニル）エーテル、ビス（４−ヒドロキシフェニル）スルホン（以下「ビスフェノールＳ」と略記する。）、ビス（２−メチル−４−ヒドロキシフェニル）スルホン等が例示され、特にビス（４−ヒドロキシフェニル）、ビスフェノールＡ、ビス（４−ヒドロキシフェニル）エーテル、２，２−ビス（３−メチル−４−ヒドロキシフェニル）プロパン、ビスフェノールＳ等が効果的な原料として推奨される。
【００１５】
尚、本発明に係る水素化反応の原料としては、上記ビスフェノール化合物のみならず、当該ビスフェノール化合物と上記化合物２に例示される一方のヒドロキシフェニル基のみがオキソシクロヘキシル基に水素化されてなる化合物との混合物も適用される。
【００１６】
本発明に係る水素化触媒は、１種又は２種以上のパラジウム系触媒である。
【００１７】
上記パラジウム系触媒としては、水素化触媒を調製するために通常使用される担体にパラジウム金属、パラジウム酸化物又はパラジウム水酸化物を担持してなる触媒が例示される。
【００１８】
かかる担体としては、カーボン、アルミナ、シリカ、シリカアルミナ、酸化ジルコニウム、酸化チタン、白土等が例示され、特にカーボンやアルミナが推奨される。
【００１９】
上記担体に担持されるパラジウム量としては、パラジウム金属換算で１〜１０重量％が推奨される。
【００２０】
パラジウム触媒の形態は、特に限定されず、その反応形態に応じて粉末状、タブレット状等適宜選択して使用される。
【００２１】
触媒の使用量としては、原料のビスフェノール化合物に対して０．５〜５重量％、好ましくは１〜３重量％が推奨される。０．５重量％未満では実用的な反応速度が得られにくく、５重量％を越えて適用しても顕著な効果の向上は認められず、経済的に不利である。
【００２２】
触媒は、繰り返し使用も可能である。
【００２３】
本発明において、アルカリ金属化合物の存在下で水素化することにより、高純度、高収率で目的とする脂環式ジケトン化合物を得ることができる。
【００２４】
アルカリ金属化合物としては、ナトリウム、カリウム等のアルカリ金属の水酸化物や炭酸塩等が例示され、中でも所定の炭酸塩が推奨される。
【００２５】
アルカリ金属化合物の適用量としては、原料のビスフェノール系化合物に対し０．０１〜０．５重量％が好ましく、特に０．０５〜０．２重量％が推奨される。０．０１重量％未満では所定の併用効果が得られにくく、０．５重量％を越えて配合したとしても顕著な併用効果の向上が認められにくい。
【００２６】
本発明に係る水素化反応は、無溶媒系、溶媒系のいずれも可能である。具体的には、例えば、低融点のビスフェノール化合物の場合には溶媒を使用せず、原料を溶融して反応に供することも可能であるが、一般に、触媒の活性を維持し、目的とする脂環式ジケトン化合物の収率を向上させるためには溶媒系で反応することが好ましい。
【００２７】
使用できる溶媒としては、反応に不活性で原料や生成物が溶解しやすい溶媒であれば足り、具体的にはエ−テル類、炭化水素類及びケトン類が例示される。
【００２８】
エ−テル類としては、例えば、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジプロピルエーテル、エチレングリコールジブチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジプロピルエーテルエチレングリコールジブチルエーテル、トリエチレングリコールジメチルエーテル等が挙げられ、特に工業的に入手が容易で、溶解性が大きいエチレングリコールジメチルエーテル及びジエチレングリコールジメチルエーテル（以下「ＤＭＤＧ」と略記する。）が推奨される。
【００２９】
炭化水素類としては、例えば、ベンゼン、トルエン、キシレン、メシチレン等のアルキルベンゼン及びポリアルキルベンゼン等の芳香族炭化水素；シクロヘキサン、メチルシクロヘキサン、ジメチルシクロヘキサン等のアルキルシクロヘキサン及びポリアルキルシクロヘキサン等の脂環式炭化水素が挙げられ、特に工業的に入手が容易で、取り扱いが容易なアルキルベンゼン、ポリアルキルベンゼン（例えば、商品名「ソルベッソ１５０」、エクソン化学社製）、アルキルシクロヘキサン及びポリアルキルシクロヘキサンが推奨される。
【００３０】
ケトン類としては、例えば、アセトン、メチルエチルケトン、ジエチルケトン、ジイソプロピルケトン、ジブチルケトン、ジイソブチルケトン、シクロヘキサノン及びそのアルキル（炭素数１〜４）置換体等が挙げられる。
【００３１】
溶媒の適当な使用量は、脂環式ジオール化合物に対して０．１〜５重量倍、好ましくは１〜３重量倍程度である。使用量が０．１重量倍未満では触媒の活性維持及び高融点原料の溶解性の面で不利となる傾向があり、一方、５重量倍を越える場合には経済的に不利となる傾向がある。
【００３２】
水素化反応の温度は、原料であるビスフェノール化合物の種類によって適宜選択できる。具体的には、例えば、ビスフェノールＡの水素化では１３０〜１９０℃が推奨され、ビフェノールの水素化では１００〜１８０℃が推奨される。一般に、上記所定の温度未満では実用的な反応速度が得られにくく、所定の温度を越えて反応した場合には副反応が顕著となり、いずれも好ましくない。
【００３３】
水素化圧力は、反応温度、反応溶媒、原料及び生成物等の種類により適宜選択されるが、基本的には加圧系であり、特に０．５〜１０ｋｇ／ｃｍ^２Ｇが推奨される。０．５ｋｇ／ｃｍ^２Ｇ未満では実用的な反応速度が得られにくく、１０ｋｇ／ｃｍ^２Ｇを越える圧力では目的物の選択率が低下する傾向が認められ好ましくない。
【００３４】
水素化反応に適用する水素は、特に限定されるものではなく、従来の水素化反応に用いられる水素で足りる。
【００３５】
反応時間は、反応条件によって適宜選択できるが、通常、２〜１０時間程度である。
【００３６】
水素化反応の形態としては、粉末触媒による回分式又は連続式の懸濁反応及びタブレット触媒等を用いた固定床反応としても行うことができる。
【００３７】
かくして得られた反応粗物は、必要に応じて蒸留や再結晶にて精製し、製品化される。
【００３８】
【実施例】
以下に実施例を掲げて本発明を詳しく説明する。尚、各例において得られた生成物中の目的物の純度は、ガスクロマトグラフィー（ＧＣ）による内部標準法により求めた。
【００３９】
実施例１
電磁攪拌装置、温度計及び水素導入口を備えた０．５リットルのオートクレーブにビスフェノールＡ７０ｇ（０．３１モル）、炭酸ナトリウム０．０７ｇ、５％パラジウム／カーボン及び「ソルベッソ１５０」１４０ｇを仕込み、１７０℃、５Ｋｇ／ｃｍ^２Ｇで３時間液相水素化した。その結果、反応率１００％で目的とする２，２−ビス（４−オキソシクロヘキシル）プロパンを純度８１．７％、選択率８１．７％で得た。
【００４０】
実施例２
水素化触媒を５％パラジウム／アルミナに代えた以外は実施例１と同様にしてビスフェノールＡを液相水素化した。その結果、反応率１００％で目的とする２，２−ビス（４−オキソシクロヘキシル）プロパンを純度８２．６％、選択率８２．６％で得た。
【００４１】
実施例３
反応溶媒をキシレンに代えた以外は実施例１と同様にしてビスフェノールＡを液相水素化した。その結果、反応率１００％で目的とする２，２−ビス（４−オキソシクロヘキシル）プロパンを純度７６．４％、選択率７６．４％で得た。
【００４２】
実施例４
反応溶媒をＤＭＤＧに代えた以外は実施例１と同様にしてビスフェノールＡを液相水素化した。その結果、反応率８９．８％で目的とする２，２−ビス（４−オキソシクロヘキシル）プロパンを純度６３．６％、選択率７０．５％で得た。
【００４３】
実施例５
実施例１と同様の装置にビフェノール７０ｇ（０．３８モル）、炭酸ナトリウム０．０４ｇ、５％パラジウム／カーボン１．４ｇ及び反応溶媒としてメシチレン１４０ｇを仕込み、１２０℃、０．５ｋｇ／ｃｍ^２Ｇの条件下で１２時間水素化した。その結果、反応率５６．８％で目的とする２，２−ビス（４−オキソシクロヘキシル）を純度５０．４％、選択率８８．７％で得た。
【００４４】
実施例６
実施例１と同様の装置にビスフェノールＳ７０ｇ（０．２８モル）、炭酸ナトリウム０．０７ｇ、５％パラジウム／カーボン２．１ｇ及び反応溶媒として「ソルベッソ１５０」１４０ｇを仕込み、１７０℃、５ｋｇ／ｃｍ^２Ｇの条件下で６時間水素化した。その結果、反応率８０．３％で目的とする２，２−ビス（４−オキソシクロヘキシル）スルホンを純度４６．２％、選択率５７．５％で得た。
【００４５】
実施例７
実施例１と同様の装置に２，２−ビス（３−メチル−４−ヒドロキシフェニル）プロパン７０ｇ（０．２７モル）、炭酸ナトリウム０．０７ｇ、５％パラジウム／カーボン２．１ｇ及び反応溶媒として「ソルベッソ１５０」１４０ｇを仕込み、１７０℃、５ｋｇ／ｃｍ^２Ｇの条件下で６時間水素化した。その結果、反応率９７．５％で目的とする２，２−ビス（３−メチル−４−オキソシクロヘキシル）プロパンを純度８０．７％、選択率８２．８％で得た。
【００４６】
比較例１
水素化触媒として５％ルテニウム／アルミナ２．１ｇを使用した以外は実施例１と同様にしてビスフェノールＡを液相水素化した。その結果、反応率２３．１％で目的とする２，２−ビス（４−オキソシクロヘキシル）プロパンは得られなかった。ちなみに、当該反応生成物中において、２−（４−オキソシクロヘキシル）−２−（４−ヒドロキシフェニル）プロパンが４．７重量％及び２−（４−オキソシクロヘキシル）−２−（４−ヒドロキシシクロヘキシル）プロパンが１８．４重量％の組成で認められた。
【００４７】
比較例２
水素化触媒として安定化ニッケル２．１ｇを使用した以外は実施例１と同様にしてビスフェノールＡを液相水素化した。その結果、反応率４２．５％で目的とする２，２−ビス（４−オキソシクロヘキシル）プロパンは得られなかった。ちなみに、当該反応生成物中において、ビスフェノールＡが３．１重量％、２−（４−オキソシクロヘキシル）−２−（４−ヒドロキシフェニル）プロパンが６．０重量％及び２−（４−オキソシクロヘキシル）−２−（４−ヒドロキシシクロヘキシル）プロパンが３９．４重量％の組成で認められた。
【００４８】
比較例３
アルカリ金属化合物を適用しない他は実施例１と同様にしてビスフェノールＡを水素化した。その結果、反応率６０．０％で目的とする２，２−ビス（３−メチル−４−オキソシクロヘキシル）プロパンの純度は１３．０％、選択率は２１．７％に留まった。
【００４９】
【発明の効果】
本発明の方法によれば、現在、工業的に用いられている試薬酸化法と異なって副生廃棄物が発生せず、汎用的な原料が適用可能であり、しかも安価に高選択、高収率で目的とする脂環式ジケトン化合物を工業的に有利な条件下で製造することができる。[0001]
[Industrial applications]
The present invention relates to a method for producing an alicyclic diketone compound inexpensively with high yield and high purity. The alicyclic diketone compound obtained by the present invention is a compound useful as an intermediate such as a pharmaceutical raw material, an industrial chemical raw material, a polymer raw material, a polymerization initiator raw material, an antioxidant, and a heat resistance improver.
[0002]
[Prior art]
As a method for producing an alicyclic diketone compound, a method in which an alicyclic diol is oxidized with a reagent is known. Specifically, 2,2-bis (4-hydroxycyclohexyl) propane (hereinafter referred to as “hydrogenated bisphenol A”) is used. ) With chromic acid (Bull. Chem. Soc. Japan, 39 (10), 2194 (1966)) or with hypochlorous acid (JP-A-4-59742). Illustrated. However, in these methods, expensive raw materials are used, and a large amount of waste is produced as a by-product, so that there is a problem as an industrial production method.
[0003]
The present inventors have previously proposed a method for dehydrogenating an alicyclic diol compound containing hydrogenated bisphenol A in the liquid phase in the presence of a copper-based catalyst and / or a Raney-based catalyst (Japanese Patent Application Hei 6-187441).
[0004]
On the other hand, a technique for producing an alicyclic diketone compound using a more general-purpose bisphenol compound as a raw material instead of the alicyclic diol is considered industrially useful, but such a technique has not been known so far.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel and useful method for producing an alicyclic diketone compound at low cost, with high yield and high purity from a general-purpose bisphenol compound as a raw material.
[0006]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found the following facts, and have completed the present invention based on such findings. That is,
[0007]
(1) Palladium-based catalysts have better catalytic activity at low temperatures than other hydrogenation catalysts, and are remarkably excellent in selectivity to alicyclic diketone compounds. Specifically, it is as follows.
[0008]
The reaction mechanism when bisphenol A (hereinafter abbreviated as “compound 1”) is hydrogenated using a palladium-based catalyst is estimated as follows. That is, first, one hydroxyphenyl group is hydrogenated to an oxocyclohexyl group to form 2- (4-oxocyclohexyl) -2- (4-hydroxyphenyl) propane (hereinafter abbreviated as “compound”), and then remains. The hydroxyphenyl group is also hydrogenated to obtain the desired 2,2-bis (4-oxocyclohexyl) propane (hereinafter abbreviated as “compound 3”) as a main reaction product. Further, a part of the compound 3 is further hydrogenated to hydrogenated bisphenol A via 2- (4-oxocyclohexyl) -2- (4-hydroxycyclohexyl) propane (hereinafter abbreviated as “compound 4”). .
[0009]
On the other hand, when a ruthenium-based catalyst or a nickel-based catalyst is applied, the reaction mechanism is different from that described above, and the compound 2 does not pass through the compound 3 but is converted from the compound 2 to 2- (4-hydroxycyclohexyl) -2- (4-hydroxyphenyl) propane. Or hydrogenated from compound 1 to hydrogenated bisphenol A via compound 4 directly.
[0010]
(2) A target alicyclic diketone compound (for example, compound 3) by using a palladium-based catalyst in combination with a specific compound as a reaction accelerator and performing liquid phase hydrogenation under heating and pressurizing conditions. Can be obtained with high purity and high yield.
[0011]
That is, the method for producing an alicyclic diketone compound represented by the general formula (II) according to the present invention comprises heating a bisphenol compound represented by the general formula (I) in the presence of a palladium-based catalyst and an alkali metal compound. And hydrogenation in the liquid phase under pressurized conditions.
[0012]

[Wherein, X is a single _{bond, -CH 2 -, - C (} CH 3) 2 -, - O- or -SO ₂ - represents a. R ¹ and R ² are the same or different and represent hydrogen or an alkyl group having 1 to 6 carbon atoms. m and n are the same or different and represent an integer of 0 to 2. ]
[0013]

[Wherein, X, R ¹ , R ² , m and n have the same meanings as in formula (I). ]
[0014]
As the bisphenol compound represented by the general formula (I), specifically, bis (4-hydroxyphenyl), bis (2-methyl-4-hydroxyphenyl), bis (2-hydroxyphenyl), bis (4-hydroxyphenyl) (Hydroxyphenyl) methane, bis (2-ethyl-4-hydroxyphenyl) methane, bis (2-hydroxyphenyl) methane, 2-hydroxyphenyl-4-hydroxyphenylmethane, bisphenol A, 2,2-bis (2-methyl -4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (2-hydroxyphenyl) propane, 2- (2-hydroxyphenyl) -2- ( 4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) ether, bis (2-hydroxy Phenyl) ether, bis (4-hydroxyphenyl) sulfone (hereinafter abbreviated as “bisphenol S”), bis (2-methyl-4-hydroxyphenyl) sulfone, and the like, particularly bis (4-hydroxyphenyl), Bisphenol A, bis (4-hydroxyphenyl) ether, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, bisphenol S and the like are recommended as effective raw materials.
[0015]
In addition, as a raw material of the hydrogenation reaction according to the present invention, not only the bisphenol compound but also a compound obtained by hydrogenating only one hydroxyphenyl group exemplified by the bisphenol compound and the compound 2 to an oxocyclohexyl group is used. Also apply.
[0016]
The hydrogenation catalyst according to the present invention is one or more palladium-based catalysts.
[0017]
Examples of the palladium-based catalyst include a catalyst obtained by supporting a palladium metal, a palladium oxide or a palladium hydroxide on a carrier usually used for preparing a hydrogenation catalyst.
[0018]
Examples of such a carrier include carbon, alumina, silica, silica-alumina, zirconium oxide, titanium oxide, clay and the like, and particularly, carbon and alumina are recommended.
[0019]
The amount of palladium supported on the carrier is preferably 1 to 10% by weight in terms of palladium metal.
[0020]
The form of the palladium catalyst is not particularly limited, and may be appropriately selected and used in a powder form, a tablet form, or the like according to the reaction form.
[0021]
The amount of the catalyst to be used is 0.5 to 5% by weight, preferably 1 to 3% by weight, based on the bisphenol compound as the raw material. If it is less than 0.5% by weight, it is difficult to obtain a practical reaction rate, and if it exceeds 5% by weight, no remarkable improvement in the effect is observed, which is economically disadvantageous.
[0022]
The catalyst can be used repeatedly.
[0023]
In the present invention, the desired alicyclic diketone compound can be obtained with high purity and high yield by hydrogenating in the presence of an alkali metal compound.
[0024]
Examples of the alkali metal compound include hydroxides and carbonates of alkali metals such as sodium and potassium, and among them, a predetermined carbonate is recommended.
[0025]
The application amount of the alkali metal compound is preferably 0.01 to 0.5% by weight, and particularly preferably 0.05 to 0.2% by weight, based on the bisphenol compound as the raw material. If the amount is less than 0.01% by weight, a predetermined combination effect is hardly obtained, and even if the amount exceeds 0.5% by weight, a remarkable improvement in the combination effect is hardly recognized.
[0026]
The hydrogenation reaction according to the present invention can be either a solventless system or a solvent system. Specifically, for example, in the case of a bisphenol compound having a low melting point, it is possible to melt the raw material and use it for the reaction without using a solvent, but in general, the activity of the catalyst is maintained and the desired oil is maintained. In order to improve the yield of the cyclic diketone compound, the reaction is preferably performed in a solvent system.
[0027]
As a solvent that can be used, any solvent that is inert to the reaction and easily dissolves the raw materials and products is sufficient, and specific examples thereof include ethers, hydrocarbons, and ketones.
[0028]
Examples of the ethers include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, ethylene glycol dibutyl ether, and triethylene glycol dimethyl ether. In particular, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether (hereinafter abbreviated as “DMDG”), which are easily available industrially and have high solubility, are recommended.
[0029]
Examples of the hydrocarbons include aromatic hydrocarbons such as alkylbenzene and polyalkylbenzene such as benzene, toluene, xylene and mesitylene; and alicyclic hydrocarbons such as alkylcyclohexane and polyalkylcyclohexane such as cyclohexane, methylcyclohexane and dimethylcyclohexane. Alkylbenzene, polyalkylbenzene (for example, trade name “Solvesso 150”, manufactured by Exxon Chemical Co., Ltd.), which is industrially easily available and easy to handle, alkylcyclohexane and polyalkylcyclohexane are particularly recommended.
[0030]
Examples of ketones include acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone, cyclohexanone, and alkyl (1 to 4 carbon) substituted products thereof.
[0031]
An appropriate amount of the solvent used is about 0.1 to 5 times, preferably about 1 to 3 times the weight of the alicyclic diol compound. If the amount used is less than 0.1% by weight, it tends to be disadvantageous in terms of maintaining the activity of the catalyst and the solubility of the raw material having a high melting point, while if it exceeds 5% by weight, it tends to be economically disadvantageous. .
[0032]
The temperature of the hydrogenation reaction can be appropriately selected depending on the kind of the bisphenol compound as a raw material. Specifically, for example, 130 to 190 ° C. is recommended for hydrogenation of bisphenol A, and 100 to 180 ° C. is recommended for hydrogenation of biphenol. Generally, when the temperature is lower than the predetermined temperature, a practical reaction rate is hardly obtained, and when the reaction is performed at a temperature higher than the predetermined temperature, side reactions become remarkable, and both are not preferable.
[0033]
The hydrogenation pressure is appropriately selected depending on the reaction temperature, reaction solvent, raw materials, products and the like, but is basically a pressurized system, and particularly, 0.5 to 10 kg / cm ² G is recommended. If the pressure is less than 0.5 kg / cm ² G, a practical reaction rate is hardly obtained, and if the pressure exceeds 10 kg / cm ² G, the selectivity of the target substance tends to decrease, which is not preferable.
[0034]
Hydrogen applied to the hydrogenation reaction is not particularly limited, and hydrogen used in a conventional hydrogenation reaction is sufficient.
[0035]
The reaction time can be appropriately selected depending on the reaction conditions, but is usually about 2 to 10 hours.
[0036]
The form of the hydrogenation reaction may be a batch or continuous suspension reaction using a powder catalyst, or a fixed bed reaction using a tablet catalyst or the like.
[0037]
The reaction crude thus obtained is purified by distillation or recrystallization if necessary, and commercialized.
[0038]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples. In addition, the purity of the target substance in the products obtained in each example was determined by an internal standard method using gas chromatography (GC).
[0039]
Example 1
170 g of bisphenol A (0.31 mol), 0.07 g of sodium carbonate, 140 g of 5% palladium / carbon and "Solvesso 150" were charged into a 0.5 liter autoclave equipped with a magnetic stirrer, a thermometer and a hydrogen inlet, and 170 Liquid phase hydrogenation was performed at 5 Kg / cm ² G for 3 hours. As a result, the target 2,2-bis (4-oxocyclohexyl) propane was obtained at a conversion of 100% with a purity of 81.7% and a selectivity of 81.7%.
[0040]
Example 2
Bisphenol A was subjected to liquid phase hydrogenation in the same manner as in Example 1 except that the hydrogenation catalyst was changed to 5% palladium / alumina. As a result, the target 2,2-bis (4-oxocyclohexyl) propane was obtained at a conversion of 100% with a purity of 82.6% and a selectivity of 82.6%.
[0041]
Example 3
Bisphenol A was liquid-phase hydrogenated in the same manner as in Example 1 except that xylene was used as the reaction solvent. As a result, the target 2,2-bis (4-oxocyclohexyl) propane was obtained at a conversion of 100% with a purity of 76.4% and a selectivity of 76.4%.
[0042]
Example 4
Bisphenol A was liquid-phase hydrogenated in the same manner as in Example 1 except that the reaction solvent was changed to DMDG. As a result, the target 2,2-bis (4-oxocyclohexyl) propane was obtained at a conversion of 89.8% with a purity of 63.6% and a selectivity of 70.5%.
[0043]
Example 5
The same apparatus as in Example 1 was charged with 70 g (0.38 mol) of biphenol, 0.04 g of sodium carbonate, 1.4 g of 5% palladium / carbon and 140 g of mesitylene as a reaction solvent, and 120 ° C., 0.5 kg / cm ² G For 12 hours. As a result, the target 2,2-bis (4-oxocyclohexyl) was obtained at a conversion of 56.8% with a purity of 50.4% and a selectivity of 88.7%.
[0044]
Example 6
The same apparatus as in Example 1 was charged with 70 g (0.28 mol) of bisphenol S, 0.07 g of sodium carbonate, 2.1 g of 5% palladium / carbon and 140 g of "Solvesso 150" as a reaction solvent, and 170 ° C., 5 kg / cm ^2. Hydrogenated under G conditions for 6 hours. As a result, the target 2,2-bis (4-oxocyclohexyl) sulfone was obtained at a conversion of 80.3% with a purity of 46.2% and a selectivity of 57.5%.
[0045]
Example 7
In the same apparatus as in Example 1, 70 g (0.27 mol) of 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 0.07 g of sodium carbonate, 2.1 g of 5% palladium / carbon, and as a reaction solvent 140 g of “Solvesso 150” was charged and hydrogenated at 170 ° C. and 5 kg / cm ² G for 6 hours. As a result, the target 2,2-bis (3-methyl-4-oxocyclohexyl) propane was obtained at a conversion of 97.5% with a purity of 80.7% and a selectivity of 82.8%.
[0046]
Comparative Example 1
Bisphenol A was liquid-phase hydrogenated in the same manner as in Example 1 except that 2.1 g of 5% ruthenium / alumina was used as a hydrogenation catalyst. As a result, the desired 2,2-bis (4-oxocyclohexyl) propane was not obtained at a conversion of 23.1%. Incidentally, in the reaction product, 4.7% by weight of 2- (4-oxocyclohexyl) -2- (4-hydroxyphenyl) propane and 2- (4-oxocyclohexyl) -2- (4-hydroxycyclohexyl) were used. ) Propane was found at a composition of 18.4% by weight.
[0047]
Comparative Example 2
Bisphenol A was liquid-phase hydrogenated in the same manner as in Example 1 except that 2.1 g of stabilized nickel was used as a hydrogenation catalyst. As a result, the desired 2,2-bis (4-oxocyclohexyl) propane was not obtained at a conversion of 42.5%. Incidentally, in the reaction product, bisphenol A was 3.1% by weight, 2- (4-oxocyclohexyl) -2- (4-hydroxyphenyl) propane was 6.0% by weight, and 2- (4-oxocyclohexyl). ) -2- (4-Hydroxycyclohexyl) propane was found in a composition of 39.4% by weight.
[0048]
Comparative Example 3
Bisphenol A was hydrogenated in the same manner as in Example 1 except that no alkali metal compound was used. As a result, the target 2,2-bis (3-methyl-4-oxocyclohexyl) propane had a purity of 13.0% and a selectivity of 21.7% at a reaction rate of 60.0%.
[0049]
【The invention's effect】
According to the method of the present invention, unlike the reagent oxidation method currently used industrially, by-product waste is not generated, general-purpose raw materials can be applied, and high-selection and high-yield can be achieved at low cost. The desired alicyclic diketone compound can be produced under industrially advantageous conditions.

Claims (1)

The bisphenol compound represented by the general formula (I) is hydrogenated in a liquid phase under the conditions of heating and pressurization in the presence of a palladium catalyst and an alkali metal compound in a liquid phase. For producing an alicyclic diketone compound to be used.

[Wherein, X is a single _{bond, -CH 2 -, - C (} CH 3) 2 -, - O- or -SO ₂ - represents a. R ¹ and R ² are the same or different and represent hydrogen or an alkyl group having 1 to 6 carbon atoms. m and n are the same or different and represent an integer of 0 to 2. ]

[Wherein, X, R ¹ , R ² , m and n have the same meanings as in formula (I). ]