JP2515354B2 - Process for producing 3,3-bis (4-hydroxyphenyl) -cyclohexanol - Google Patents

Process for producing 3,3-bis (4-hydroxyphenyl) -cyclohexanol

Info

Publication number
JP2515354B2
JP2515354B2 JP62318704A JP31870487A JP2515354B2 JP 2515354 B2 JP2515354 B2 JP 2515354B2 JP 62318704 A JP62318704 A JP 62318704A JP 31870487 A JP31870487 A JP 31870487A JP 2515354 B2 JP2515354 B2 JP 2515354B2
Authority
JP
Japan
Prior art keywords
hydroxyphenyl
bis
cyclohexanol
reaction
producing
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 - Lifetime
Application number
JP62318704A
Other languages
Japanese (ja)
Other versions
JPH01160932A (en
Inventor
徹 三浦
勝 和田
政幸 古屋
輝幸 永田
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.)
Mitsui Toatsu Chemicals Inc
Original Assignee
Mitsui Toatsu Chemicals Inc
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 Mitsui Toatsu Chemicals Inc filed Critical Mitsui Toatsu Chemicals Inc
Priority to JP62318704A priority Critical patent/JP2515354B2/en
Publication of JPH01160932A publication Critical patent/JPH01160932A/en
Application granted granted Critical
Publication of JP2515354B2 publication Critical patent/JP2515354B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime 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

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は3,3−ビス（４−ヒドロキシフェニル）−シ
クロヘキサノールの製造方法に関する。さらに詳細には
３−ヒドロキシフェニルシクロヘキサノンをフェノール
と縮合反応させることを特徴とする3,3−ビス（４−ヒ
ドロキシフェニル）−シクロヘキサノールの製造方法に
関する。TECHNICAL FIELD The present invention relates to a method for producing 3,3-bis (4-hydroxyphenyl) -cyclohexanol. More specifically, it relates to a method for producing 3,3-bis (4-hydroxyphenyl) -cyclohexanol, which comprises subjecting 3-hydroxyphenylcyclohexanone to a condensation reaction with phenol.

3,3−ビス（４−ヒドロキシフェニル）−シクロヘキ
サノールは新規な化合物であり、3,4−ジヒドロキシビ
フェニル等の前駆体として有用である。3,3-bis (4-hydroxyphenyl) -cyclohexanol is a novel compound and is useful as a precursor of 3,4-dihydroxybiphenyl and the like.

〔従来の技術〕[Conventional technology]

1,1−ビス（４−ヒドロキシフェニル）−シクロヘキ
サン、または４−メチル−1,1−ビス（４−ヒドロキシ
フェニル）−シクロヘキサン等のようなシクロヘキサン
環にアルキル基を持つ化合物は公知である。例えば、1,
1−ビス（４−ヒドロキシフェニル）−シクロヘキサン
は融点184℃を有する結晶であり、４−メチル−1,1−ビ
ス（４−ヒドロキシフェニル）−シクロヘキサンおよび
3,5−ジメチル−1,1−ビス（４−ヒドロキシフェニル）
−シクロヘキサンは、それぞれ融点180℃および174℃を
有する結晶である。〔メトーデンデル オルガニイシェ
ン ヒイミー（Methoden der organishen Chemie,Vol
6,No.2,1028）〕 〔目的及びこれを達成するための手段〕 3,3−ビス（４−ヒドロキシフェニル）−シクロヘキ
サノールについては、これまで全く知られていなかった
のであるが、本発明者等は、その合成に成功し、本発明
はこの新規な化合物の製造方法を例供するものである。Compounds having an alkyl group on the cyclohexane ring such as 1,1-bis (4-hydroxyphenyl) -cyclohexane, 4-methyl-1,1-bis (4-hydroxyphenyl) -cyclohexane and the like are known. For example, 1,
1-Bis (4-hydroxyphenyl) -cyclohexane is a crystal with a melting point of 184 ° C., 4-methyl-1,1-bis (4-hydroxyphenyl) -cyclohexane and
3,5-dimethyl-1,1-bis (4-hydroxyphenyl)
-Cyclohexane is a crystal with melting points of 180 ° C and 174 ° C, respectively. [Methoden der organishen Chemie, Vol
6, No. 2, 1028)] [Objectives and means for achieving the same] 3,3-bis (4-hydroxyphenyl) -cyclohexanol has not been known at all until now. The inventors have succeeded in its synthesis, and the present invention exemplifies a method for producing this novel compound.

即ち、本発明は３−ヒドロキシシクロヘキサノンをフ
ェノールと縮合反応させることを特徴とする3,3−ビス
（４−ヒドロキシフェニル）−シクロヘキサノールの製
造方法である。That is, the present invention is a method for producing 3,3-bis (4-hydroxyphenyl) -cyclohexanol, which comprises subjecting 3-hydroxycyclohexanone to a condensation reaction with phenol.

本発明反応において原料として使用される３−ヒドロ
キシシクロヘキサノンはレゾルシンの還元、シクロヘキ
セン−３−オンの水付加反応、あるいは1,3−シクロヘ
キサンジオールの酸化等の方法により得ることができ
る。3-Hydroxycyclohexanone used as a raw material in the reaction of the present invention can be obtained by a method such as reduction of resorcin, water addition reaction of cyclohexen-3-one, or oxidation of 1,3-cyclohexanediol.

本発明反応は通常、触媒の存在下に行われる。例えば
塩酸、塩化水素のガスのほか、硫酸、リン酸、トルエン
スルホン酸、BF3、ZnCl2、AlCl3、SnCl4及び移動酸性基
を有する陽イオン交換樹脂などが挙げられる。これらの
触媒の使用量は３−ヒドロキシシクロヘキサノン100重
量部あたり0.1〜30重量部の範囲である。また、助触媒
の添加により反応速度を高めることも可能であり、メチ
ルメルカプタン、エチルメルカプタン、ｎ−プロピルメ
ルカプタン、イソプロピルメルカプタン、ｎ−ブチルメ
ルカプタン、イソブチルメルカプタン、ｔ−ブチルメル
カプタンの如きアルキルメルカプタン又は高分子量アル
キルメルカプタンなどが活性な助触媒である。The reaction of the present invention is usually carried out in the presence of a catalyst. Examples thereof include hydrochloric acid and hydrogen chloride gas, as well as sulfuric acid, phosphoric acid, toluenesulfonic acid, BF 3 , ZnCl 2 , AlCl 3 , SnCl 4 and cation exchange resins having a mobile acidic group. The amount of these catalysts used is in the range of 0.1 to 30 parts by weight per 100 parts by weight of 3-hydroxycyclohexanone. It is also possible to increase the reaction rate by adding a cocatalyst, and alkyl mercaptans such as methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, isobutyl mercaptan, t-butyl mercaptan or high molecular weight compounds. Alkyl mercaptans are active cocatalysts.

また硫化水素、チオフェノール、チオアルコール、チ
オ酸、重合体チオアセトン、ジアルキルスルフィドの如
き他のイオウ化合物やこれらと類似のセレン化合物もま
た用いることができる。Further, other sulfur compounds such as hydrogen sulfide, thiophenol, thioalcohol, thioacid, polymer thioacetone, dialkyl sulfide and selenium compounds similar to these can also be used.

本発明反応においては、芳香族炭化水素、塩素化脂肪
族炭化水素、氷酢酸などのような反応に悪影響を及ぼさ
ない触媒を用いて行うこともできる。The reaction of the present invention can be carried out using a catalyst such as aromatic hydrocarbon, chlorinated aliphatic hydrocarbon, glacial acetic acid, etc., which does not adversely affect the reaction.

しかしながら、生成物の収率を高め、かつ副反応を最
少にするには過剰量のフェノールを溶媒とするのが望ま
しい。使用するフェノールの量は３−ヒドロキシシクロ
ヘキサノン１重量部あたり２重量部から10重量部が適当
である。However, it is desirable to use an excess of phenol as solvent to increase product yield and minimize side reactions. The amount of phenol used is suitably 2 to 10 parts by weight per 1 part by weight of 3-hydroxycyclohexanone.

また、本発明における反応温度は30℃から100℃の範
囲で、好ましくは40℃から80℃の範囲である。反応温度
が高いと副生物が増え、収率が低下する傾向にある。The reaction temperature in the present invention is in the range of 30 ° C to 100 ° C, preferably 40 ° C to 80 ° C. When the reaction temperature is high, by-products tend to increase and the yield tends to decrease.

本反応によって生成した3,3−ビス（４−ヒドロキシ
フェニル）−シクロヘキサノールは、例えばベンゼンな
どの本発明の化合物を溶解し難い溶媒に、反応マスを排
出し、冷却晶出させることにより、あるいは触媒は除去
したのち脱フェノールすること等によって取り出すこと
ができる。The 3,3-bis (4-hydroxyphenyl) -cyclohexanol produced by this reaction can be obtained by discharging the reaction mass into a solvent in which the compound of the present invention is difficult to dissolve, such as benzene, and cooling crystallization, or The catalyst can be taken out by removing and then dephenoling.

また過剰に使用したフェノールは、減圧下で蒸留する
などの方法によって回収、再使用することができる。The phenol used in excess can be recovered and reused by a method such as distillation under reduced pressure.

以下実施例により本発明を具体的に説明する。 The present invention will be specifically described below with reference to examples.

〔実施例〕〔Example〕

100ml反応フラスコに３−ヒドロキシシクロヘキサノ
ン11.4g（0.10モル）、フェノール47.1g（0.50モル）、
36％塩酸3ml、ｎ−ブチルメルカプタン0.5mlを仕込み40
℃で６時間反応させた。反応終了後トルエン200ml、水5
0mlの混合液中に排出し、一昼夜放置した。晶出した結
晶を濾別洗浄して乾燥し、白色結晶21.6gを得た。液体
クロマトグラフィーによる3,3−ビス（４−ヒドロキシ
フェニル）−シクロヘキサノールの純度80％であった。
収率は61％であった。3-hydroxycyclohexanone 11.4 g (0.10 mol), phenol 47.1 g (0.50 mol) in a 100 ml reaction flask,
Charge 36% hydrochloric acid 3 ml, n-butyl mercaptan 0.5 ml 40
The reaction was carried out at 0 ° C for 6 hours. After completion of the reaction, 200 ml of toluene, 5 water
The mixture was discharged into 0 ml of the mixed solution, and left overnight. The crystallized crystals were separated by filtration, washed and dried to obtain 21.6 g of white crystals. The purity of 3,3-bis (4-hydroxyphenyl) -cyclohexanol measured by liquid chromatography was 80%.
The yield was 61%.

Claims (1)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】３−ヒドロキシシクロヘキサノンをフェノ
ールと縮合反応させることを特徴とする3,3−ビス（４
−ヒドロキシフェニル）−シクロヘキサノールの製造方
法。1. A 3,3-bis (4) compound characterized by reacting 3-hydroxycyclohexanone with phenol.
-Hydroxyphenyl) -cyclohexanol production method.
JP62318704A 1987-12-18 1987-12-18 Process for producing 3,3-bis (4-hydroxyphenyl) -cyclohexanol Expired - Lifetime JP2515354B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP62318704A JP2515354B2 (en) 1987-12-18 1987-12-18 Process for producing 3,3-bis (4-hydroxyphenyl) -cyclohexanol

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP62318704A JP2515354B2 (en) 1987-12-18 1987-12-18 Process for producing 3,3-bis (4-hydroxyphenyl) -cyclohexanol

Publications (2)

Publication Number Publication Date
JPH01160932A JPH01160932A (en) 1989-06-23
JP2515354B2 true JP2515354B2 (en) 1996-07-10

Family

ID=18102064

Family Applications (1)

Application Number Title Priority Date Filing Date
JP62318704A Expired - Lifetime JP2515354B2 (en) 1987-12-18 1987-12-18 Process for producing 3,3-bis (4-hydroxyphenyl) -cyclohexanol

Country Status (1)

Country Link
JP (1) JP2515354B2 (en)

Also Published As

Publication number Publication date
JPH01160932A (en) 1989-06-23

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