JPS63301837A - Production of high-purity 4,4'-biphenols - Google Patents
Production of high-purity 4,4'-biphenolsInfo
- Publication number
- JPS63301837A JPS63301837A JP62138635A JP13863587A JPS63301837A JP S63301837 A JPS63301837 A JP S63301837A JP 62138635 A JP62138635 A JP 62138635A JP 13863587 A JP13863587 A JP 13863587A JP S63301837 A JPS63301837 A JP S63301837A
- Authority
- JP
- Japan
- Prior art keywords
- biphenol
- reaction
- biphenols
- tert
- butyl
- 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
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical class C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000003377 acid catalyst Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 abstract description 14
- 230000006210 debutylation Effects 0.000 abstract description 12
- 239000000047 product Substances 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 229920006351 engineering plastic Polymers 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000010926 purge Methods 0.000 abstract description 2
- LYQIPMLFCQTVQK-UHFFFAOYSA-N 3,5-ditert-butyl-4-(2,6-ditert-butyl-4-hydroxyphenyl)phenol Chemical compound CC(C)(C)C1=CC(O)=CC(C(C)(C)C)=C1C1=C(C(C)(C)C)C=C(O)C=C1C(C)(C)C LYQIPMLFCQTVQK-UHFFFAOYSA-N 0.000 abstract 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 abstract 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract 1
- 238000004040 coloring Methods 0.000 abstract 1
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 239000000178 monomer Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- CZFAFXQXFPWGTF-UHFFFAOYSA-N 2-tert-butyl-4-(4-hydroxyphenyl)phenol Chemical compound C1=C(O)C(C(C)(C)C)=CC(C=2C=CC(O)=CC=2)=C1 CZFAFXQXFPWGTF-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- -1 but fyK Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 238000010555 transalkylation reaction Methods 0.000 description 2
- VHNKTXXKQBOFGI-UHFFFAOYSA-N 2-butyl-4-(4-hydroxyphenyl)phenol Chemical group C1=C(O)C(CCCC)=CC(C=2C=CC(O)=CC=2)=C1 VHNKTXXKQBOFGI-UHFFFAOYSA-N 0.000 description 1
- HSGGHYHJWNCYIA-UHFFFAOYSA-N 3,4,5-tritert-butyl-2-(2-hydroxyphenyl)phenol Chemical compound CC(C)(C)C1=C(C(C)(C)C)C(C(C)(C)C)=CC(O)=C1C1=CC=CC=C1O HSGGHYHJWNCYIA-UHFFFAOYSA-N 0.000 description 1
- NWFCWGXMDAJKLT-UHFFFAOYSA-N 3-ethyl-4-(2-ethyl-4-hydroxyphenyl)phenol Chemical compound CCC1=CC(O)=CC=C1C1=CC=C(O)C=C1CC NWFCWGXMDAJKLT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- OPSWAWSNPREEFQ-UHFFFAOYSA-K triphenoxyalumane Chemical class [Al+3].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 OPSWAWSNPREEFQ-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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
【発明の詳細な説明】
産業上の利用分野
本発明は少なくとも１個の第三ブチル基を有するアルキ
ルビフェノール類（以後、第三ブチル基置換アルキルビ
フェノールと呼ぶ）を有機溶媒中で脱ブチル化すること
により高純度の４，４′−ビフェノール類を製造する方
法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention deals with the debutylation of alkylbiphenols having at least one tert-butyl group (hereinafter referred to as tert-butyl-substituted alkylbiphenols) in an organic solvent. In particular, it relates to a method for producing highly pure 4,4'-biphenols.
本発明の方法により製造される４、４′−ビフェノール
類は、近年、耐熱性エンジニアリングプラスチックの出
発原料として脚光をあびており、本発明の方法により、
当該ポリマー用原料として供するに足りる高純度の４．
４′−ビフェノール類を高収率で製造することが出来る
。4,4'-biphenols produced by the method of the present invention have recently been in the spotlight as starting materials for heat-resistant engineering plastics.
4. of sufficient purity to serve as a raw material for the polymer.
4'-biphenols can be produced in high yield.
従来の技術
４．４′−ビフェノールの製造方法として、Ｌ３’１５
、Ｓ′−テトラ第三ブチル−４，４′−ビフェノールを
酸触媒により脱ブチル化する方法が知られてｈるが、こ
の反応は逐次的であるため、中間生成物（モノ−、ジー
、トリー第三ブチルビフェノール）が反応溶液中に残存
し易い。Conventional technology 4. As a method for producing 4'-biphenol, L3'15
A method of debutylating S'-tetra-tert-butyl-4,4'-biphenol using an acid catalyst is known, but since this reaction is sequential, intermediate products (mono-, di-, tri-tert-butylbiphenol) tends to remain in the reaction solution.
特開昭５８−１８９１２７号公報では、３．３’。In JP-A-58-189127, it is 3.3'.
５、Ｓ′−テトラ第三ブチル−４，４′−ビフェノール
をアルキル基またはアルコキシ基で置換されたフェノー
ル溶媒中、硫酸またはスルホン酸を触媒として脱ブチル
化し４，４′−と、フェノールを製造する方法を報告し
ているが、この方法では、置換フェノール類へのトラン
スアルキル化が起こり易いために溶媒のリサイクルが困
難であり、また、−換フエノール類の融点が高いため生
成物は熱時ろ過にて分離しなければならないという欠点
がある。一方、特開昭６０−２３３３８号公報及び特開
昭６１−２００９３５号公報では、同様の反応を高沸点
化合物であるジフェニルエーテルを溶媒として少量のｐ
−）ルエンスルホン酸触媒により脱ブチル化しているが
、中間生成物であるモノ第三ブチルビフェノール等の脱
ブチル化が起こりにくく、反応を完結させるためには２
５０℃もの高温に加熱することが必要となっている。ま
た、この方法においても熱時ろ過を必要としている。5. Debutylation of S'-tetra-tert-butyl-4,4'-biphenol in a phenol solvent substituted with an alkyl or alkoxy group using sulfuric acid or sulfonic acid as a catalyst to produce 4,4'- and phenol. However, in this method, it is difficult to recycle the solvent because transalkylation to substituted phenols easily occurs, and because the melting point of -substituted phenols is high, the product cannot be heated when heated. It has the disadvantage that it must be separated by filtration. On the other hand, in JP-A-60-23338 and JP-A-61-200935, similar reactions were carried out using diphenyl ether, a high boiling point compound, as a solvent and a small amount of p.
-) Although debutylation is carried out using a toluenesulfonic acid catalyst, debutylation of intermediate products such as mono-tert-butyl biphenol is difficult to occur, and in order to complete the reaction, it is necessary to
It is now necessary to heat it to a high temperature of 50°C. In addition, this method also requires filtration while hot.
発明が解決しようとする問題点
上記のように、酸触媒によ、る脱ブチル化反応は逐次的
であるため、中間生成物が残存し易く、高純度の４，４
′−ビフェノール類を得ることは難しい〇このことを回
避するため２００℃以上の高温で反応を行うと、酸ある
いは熱により生成物が劣化し、着色した生成物しか得ら
れない。本発明らが、２００℃で実験を行ったところ、
生成物は著しく着色し潰延する結果は得られなかった（
比較例２′）Ｑ更に、得られる４、４′−ビフェノール
類は高融点化合物であり、且つ、はとんどの有機溶媒に
難溶性であるため４，４−ビフェノール類を蒸留、或は
、再結晶の方法で精製する場合には、極めて高温で蒸留
するか、或は、多量の溶媒中での再結晶となるため非効
率的であるばかりでなく、工業的操作自体が極めて厄介
であり、経済的に白色で高純度の４．４′−ビフェノー
ル類を得ることは非常に困難となっている。Problems to be Solved by the Invention As mentioned above, since the acid-catalyzed debutylation reaction is sequential, intermediate products tend to remain, and highly pure 4,4
It is difficult to obtain '-biphenols. To avoid this problem, if the reaction is carried out at a high temperature of 200°C or higher, the product will deteriorate due to acid or heat, and only colored products will be obtained. When the present inventors conducted an experiment at 200°C,
The product was significantly colored and no results were obtained that caused it to crumble (
Comparative Example 2') Q Furthermore, since the obtained 4,4'-biphenols are high melting point compounds and are poorly soluble in most organic solvents, 4,4-biphenols were distilled or When purifying by recrystallization, it is not only inefficient because it requires distillation at extremely high temperatures or recrystallization in a large amount of solvent, but also the industrial operation itself is extremely troublesome. It has become very difficult to economically obtain white and highly pure 4,4'-biphenols.
問題を解決するだめの手段
本発明者らは、上述の先行技術の欠点を解決すべく鋭意
検討を行った結果本発明に至った。Means for Solving the Problem The inventors of the present invention have conducted intensive studies to solve the above-mentioned drawbacks of the prior art, and as a result, have arrived at the present invention.
即ち、本発明は、第三ブチル基置換ビフェノールを有機
溶媒中、酸触媒存在下で脱ブチル化反応により４．４′
−ビフェノール類を製造する方法に於て、前記の酸触媒
を逐次添加し脱ブチル化することにより高純度の４．４
′−ビフェノール類を製造する工業的に有利な方法を提
供するものである。That is, the present invention provides tertiary-butyl group-substituted biphenol with 4.4'
- In a method for producing biphenols, high purity 4.4
The present invention provides an industrially advantageous method for producing '-biphenols.
本発明に利用できる基質としては、少なくとも１個の第
三ブチル基を有するアルキルビフェノール（第三ブチル
基置換ビフェノール）であればよく第三ブチル基の置換
位置は厳しく限定されない。The substrate that can be used in the present invention may be any alkyl biphenol having at least one tert-butyl group (tert-butyl group-substituted biphenol), and the substitution position of the tert-butyl group is not strictly limited.
又、少なくとも１個の第三ブチル基の他に０１〜ＣＩＯ
の直鎮めるいは側鎖を有するアルキル置換基を有してい
るものでもよい。In addition to at least one tert-butyl group, 01 to CIO
It may have an alkyl substituent having a direct substitution or a side chain.
用いられる代表的な第三ブチル基置換ビフェノールとし
ては、３ ＋ ３’：５ ＊ダーテトラ第三ブチルー４
゜４′−ビフェノール、３．３′−ジメチル−５，５′
−第三プチル−４，４′−ビフェノール、及び、３．３
′−ジエチル−５，５′−第三プチル−４，４′−ビフ
ェノール等が挙げられ、４．４’−ビフェノール類とし
てそれぞれ４，４′−ビフェノール、３．３′−ジメチ
ル−４＋４’−ビフェノール、３．３′−ジエチル−４
，４′−ビフェノールが得られる。Typical tert-butyl group-substituted biphenols used include 3 + 3':5 * tert-tert-butyl-4
゜4'-biphenol, 3,3'-dimethyl-5,5'
-tertiary butyl-4,4'-biphenol, and 3.3
'-diethyl-5,5'-tert-butyl-4,4'-biphenol, etc., and 4,4'-biphenols include 4,4'-biphenol and 3,3'-dimethyl-4+4'-, respectively. Biphenol, 3,3'-diethyl-4
, 4'-biphenol are obtained.
本発明の方法において、用いることができる有機溶媒の
種類は、反応温度条件下で第三ブチル基置換ビフェノー
ルを溶解するものであればよく、厳しく限定されるもの
ではない。しかし、次に述べる理由により、特に、アル
キルベンゼン類が好ましい。In the method of the present invention, the type of organic solvent that can be used is not strictly limited as long as it dissolves the tert-butyl group-substituted biphenol under the reaction temperature conditions. However, for the following reasons, alkylbenzenes are particularly preferred.
１）反応は少なくとも１００℃以上で行う必要があるた
めこれ以上の沸点を有していること、２）トランスアル
キル化が起こり難いこと（溶媒がブチル化され難いこと
）、３） ４．４’−ビフェノール類の溶解度が、第
三ブチル基置臭ビフェノールのそれに較べて著しく小さ
く、室温で生成物をろ過しても中間生成物であるアルキ
ルビフェノール類の混入が殆どなく、高純度の４，４′
−ビフェノール類が容易に得られること等があげられる
。1) The reaction must be carried out at at least 100°C or higher, so the boiling point should be higher than this, 2) Transalkylation should be difficult to occur (the solvent should be difficult to be butylated), 3) 4.4' - The solubility of biphenols is significantly lower than that of tertiary-butyl-based odoriferous biphenols, and even if the product is filtered at room temperature, there is almost no contamination of the intermediate alkyl biphenols, resulting in high purity 4,4 ′
- Biphenols can be easily obtained.
具体的ニハ、トルエン、キシレン、エチルベンゼン、イ
ンプロピルベンゼン、第三フ′チルベンゼン、ジエチル
ベンゼン、ジインプロピルベンゼン等が例示されるが、
特に、ジエチルベンゼンを用いることが好ましい。Specific examples include nipropylene, toluene, xylene, ethylbenzene, inpropylbenzene, tertiary methylbenzene, diethylbenzene, diimpropylbenzene, etc.
In particular, it is preferable to use diethylbenzene.
本発明の方法では、１００℃〜２００℃の温度範囲で反
応を実施することが出来るが、１５０℃〜１８０℃の範
囲で行うことが好ましい。これより低い温度では反応時
間が長くなるだけでアリ、また、これより高い温度で反
応を行うと生成物が劣化、着色し、高純度で、且つ、白
色の４．４′−ビフェノール類を得ることは非常に困難
となる。In the method of the present invention, the reaction can be carried out at a temperature range of 100°C to 200°C, but it is preferably carried out at a temperature range of 150°C to 180°C. If the temperature is lower than this, the reaction time will only become longer, and if the reaction is carried out at a temperature higher than this, the product will deteriorate and become colored, yielding highly pure and white 4,4'-biphenols. That becomes extremely difficult.
また、脱ブチル化反応により副生じたインブテレンガス
を強制的に系外へ排出させるために、Ｎ雪、Ｃｏｗ等の
不活性ガスにより系内をパージすることは逆反応（イン
ブチレンによや再びブチル化でれる）を防止する上で極
めて有効でるる。In addition, purging the system with an inert gas such as N snow or Cow in order to forcibly discharge imbutylene gas, which is a by-product of the debutylation reaction, may cause a reverse reaction (inbutylene and butylene gas may regenerate into butylene). It is extremely effective in preventing oxidation.
本発明の方法において、脱ブチル化触媒として用イル酸
触媒は、公知のＨ２ＳＯ４、ベンゼンスルホン酸類、ア
ルミニウムフェノキシト類等も用い得るが、着色性物質
の副生を抑えるという点から、ｆｙＫ、ｐ−トルエンス
ルホン酸、または、硫酸が好ましい。In the method of the present invention, known H2SO4, benzenesulfonic acids, aluminum phenoxides, etc. can be used as the debutylation catalyst, but fyK, p -Toluenesulfonic acid or sulfuric acid is preferred.
本発明の方法では、上記酸触媒の必要量を一度に加える
のではなく、逐次添加していく方法で行うものである。In the method of the present invention, the required amount of the acid catalyst is not added all at once, but is added sequentially.
触媒の必要量は第三ブチル基置換ビフェノールに対して
、１０〜０．０１ ｗｔ％、好ましくは、８〜２ ｗｔ
％を添加するのが良く、これより少ない触媒量では反応
が完全に進行せず、また、これより多い量では酸により
生成物が劣化、着色し、いずれの場合にも高純度の４，
４′−ビフェノール類を得ることができない。本発明に
おいて逐次とは２回以上であれば特に限定する必要はな
く、通常２〜５回に分けて触媒を添加する。逐次添加す
る量は触媒の必要量をＭ１分割回数をｎとすると、−回
に加えるｌ１ｍは、
ｍ＝Ｍ／ｎ （但し、２≦ｎ≦ｏｏ）と定義するこ
とが出来る。ζこで、ｎ＝■の場合は、連続フィードに
よる添加を意味するものである。この連続フィード以外
における、酸触媒の添加間隔ｔは、全反応時間の範囲で
適宜選ばれるが、この間隔ｔは一定である必要はなく反
応の進行状況に応じて添加する方が効果的である。The required amount of catalyst is 10 to 0.01 wt%, preferably 8 to 2 wt%, based on the tert-butyl group-substituted biphenol.
%. If the amount of catalyst is less than this, the reaction will not proceed completely, and if the amount is more than this, the product will be degraded and colored by the acid. In either case, highly pure 4,
4'-biphenols cannot be obtained. In the present invention, the term "sequentially" is not particularly limited as long as it is added twice or more, and the catalyst is usually added in 2 to 5 times. The amount to be added sequentially can be defined as m=M/n (however, 2≦n≦oo), where the required amount of catalyst is M1 and the number of divisions is n, and l1m added to - times can be defined as m=M/n (however, 2≦n≦oo). ζHere, when n=■, it means addition by continuous feeding. The addition interval t of the acid catalyst other than this continuous feeding is appropriately selected within the range of the total reaction time, but this interval t does not need to be constant, and it is more effective to add it according to the progress of the reaction. .
例えば、３，３１５，５′−テトラ第三ブチル−４１４
’−ビフェノールの脱ブチル化反応は逐次反応で６す、
特にモノ第三ブデルー４．４′−ビフェノールの脱ブチ
ル化が律速的でろるため、反応液中の主成分がモノ第三
ブチル−４，４′−ビフェノールとなった時点、即ち少
量の４．４′−ビフェノールの析出が始まった時点で次
の酸触媒を添加すると効果的である。For example, 3,315,5'-tetra-tert-butyl-414
'-The debutylation reaction of biphenol is a sequential reaction6.
In particular, since the debutylation of mono-tert-butyl-4,4'-biphenol is rate-limiting and slow, the time when the main component in the reaction solution becomes mono-tert-butyl-4,4'-biphenol, that is, a small amount of 4.4'-biphenol. It is effective to add the following acid catalyst at the point when the precipitation of 4'-biphenol begins.
発明の効果
第三ブチル基を有するアルキルビフェノール類の脱ブチ
ル化反応に於て酸触媒を従来法のように一括添加するの
ではなく、逐次添加する本発明の方法により４，４′−
ビフェノールの収率が著しく向上し、同時に、生成物の
着色、劣化をも抑えることが出来、高純度で且つ白色の
４．４′−ビフェノール類が容易に製造可能となった。Effects of the Invention In the debutylation reaction of alkylbiphenols having a tert-butyl group, the method of the present invention, in which an acid catalyst is added sequentially instead of all at once as in the conventional method, allows 4,4'-
The yield of biphenol was significantly improved, and at the same time, coloration and deterioration of the product could be suppressed, making it possible to easily produce highly pure and white 4,4'-biphenols.
実施例
以下、実施例をもって本発明の詳細な説明を行うが、本
発明はこれらの実施例に限定されるものではない。EXAMPLES Hereinafter, the present invention will be explained in detail using Examples, but the present invention is not limited to these Examples.
実施例１
２ｔの４つ口丸底フラスコに、３１３’１５１５’−テ
トラ第三ブチル−４，４′−ビフェノール３００ｆ（０
゜７３ ｍｏｌ！ ）、ｐ−トルエンスルホン酸４．Ｏ
ｆ （０゜０２１ ｍｏｌ ）、ジエチルベンゼン４５
０ ｔ （３，３６ｍ０Ｌ）を添加し、温度計、窒素ガ
ス導入管、攪拌羽根、冷却管を取り付は窒素気流下、１
６５℃で１．５時間ｆｉ拌した後、ｐ−）ルエンスルホ
ン酸４、Ｏｆ （０，０２１ｍｏｊ＆ ）を追加しくｐ
−トルエンスルホン酸の全添加ｉ８．Ｏｆ）、更に２．
５時間攪拌を続は合計４時間反応を行った。反応終了後
、反応液を室温まで冷却し４，４′−ビフェノールの結
晶をろ過し、水／メタノールの１／ １ ｖｏｌｔ ａ
合溶媒により生成物を洗浄し、乾燥を行ったところ白
色の４，４′−ビフェノールの結晶１２！Ｍ（対理論収
率９２％）が得られた。その生成物をガスクロマトグラ
フにより分析を行ったところその純度は９９．３％であ
った。Example 1 313'1515'-tetra-tert-butyl-4,4'-biphenol 300f (0
゜73 mol! ), p-toluenesulfonic acid 4. O
f (0°021 mol), diethylbenzene 45
Add 0 t (3.36 m0L) and install a thermometer, nitrogen gas introduction tube, stirring blade, and cooling tube under a nitrogen stream.
After stirring for 1.5 h at 65 °C, add p-)luenesulfonic acid 4, Of (0,021 moj & ).
- total addition of toluenesulfonic acid i8. Of), further 2.
After stirring for 5 hours, the reaction was continued for a total of 4 hours. After the reaction, the reaction solution was cooled to room temperature, the 4,4'-biphenol crystals were filtered, and the mixture was diluted with 1/1 volt a of water/methanol.
When the product was washed with a mixed solvent and dried, 12 white crystals of 4,4'-biphenol were obtained! M (92% of theoretical yield) was obtained. When the product was analyzed by gas chromatography, its purity was found to be 99.3%.
実施例２
実施例１において、追加するＰ−）ルエンスルホン酸を
１６５℃で１．５時間攪拌した後２．Ｏｆ （０，０１
１ｍｏｌ！ ）、更に１．５時間後に２．Ｏｙ （ｏ、
。Example 2 In Example 1, after stirring the added P-)luenesulfonic acid at 165°C for 1.5 hours, 2. Of (0,01
1 mol! ), and after another 1.5 hours, 2. Oy (o,
.
１１ ｍｄ ）とした他は実施例１と同様に行ったとこ
ろ、白色の４．４′−ビフェノールの結晶１２９ｆ（対
理論収率９５％）が得られ、そのガスクロ純度は９９．
７％でろ？た。11 md) was carried out in the same manner as in Example 1, and white crystals of 4,4'-biphenol 129f (95% of theoretical yield) were obtained, with a gas chromatography purity of 99.
Is it 7%? Ta.
実施例３
実施例ＩＫ於て３＊ ３’ｓ ５ Ｈ５’−テトラ第三
ブチル−４，４′−ビフェノールの代わりに３．３′−
ジメチル−５，５′−ジ第三ブチルー４．４′−ビフェ
ノール１５６ｆ （０，７３ｍｏｚ ）を用いた以外は
、実施例１と同一方法及び同一条件下で実施したところ
、白色の３．３′−ジメチル−４，４′−ビフェノール
が１４５１（収率９３％）得られ、その純度は９９．３
％であった。Example 3 In Example IK, 3* 3's 5 H5'-tetra-tert-butyl-4,4'-biphenol was replaced by 3,3'-
The process was carried out in the same manner and under the same conditions as in Example 1, except that dimethyl-5,5'-ditert-butyl-4,4'-biphenol 156f (0.73 moz) was used. As a result, a white 3.3'-Dimethyl-4,4'-biphenol was obtained in 1451 (yield 93%) with a purity of 99.3.
%Met.
実施例４
２ｔの４つ口丸底フラスコに、３．３’、５．５’−テ
トラ第三ブチル−４，４′−ビフェノール２ Ｑ ＯＰ
（０，４９ｍａｉｌ ）、ジエチルベンゼン３００
？ （２，２４ｒｎＱＩｌ ）を添加し、温度計、窒素
ガス導入管、攪拌羽根、冷却管を取ね付は窒素気流下で
昇温し、液温か１２０℃になった時点でｐ−）ルエンス
ルホン酸２．６ｆ（０，０１４ｍｍｏｊ＋）を添加した
。反応温度を１７０℃まで昇温しながら１．５時間攪拌
したのちｐ−）ルエンスルホン酸２．６ ｆ （０，０
１４ｍｍｏｆ ）を追加しくｐ−）ルエンスルホン酸の
全添加量５．２ ｔ ）更に２．５時間攪拌を続け、合
計４時間反応を行った。実施例１と同様の後処理を行っ
たところ、白色の４，４′−ビフェノール８８Ｆ（収率
９７％）が得られ、その純度は９９．７％でめった。Example 4 3.3', 5.5'-tetra-tert-butyl-4,4'-biphenol 2 Q OP was placed in a 2 t four-necked round bottom flask.
(0.49mail), diethylbenzene 300
? (2,24rnQIl) was added, and a thermometer, nitrogen gas introduction tube, stirring blade, and cooling tube were attached.The temperature was raised under a nitrogen stream, and when the liquid temperature reached 120℃, p-)luenesulfonic acid 2.6f (0,014 mmoj+) was added. After stirring for 1.5 hours while raising the reaction temperature to 170°C, 2.6 f (0,0
14 mmof) was added, and the total amount of p-)luenesulfonic acid added was 5.2 t). Stirring was continued for an additional 2.5 hours, and the reaction was carried out for a total of 4 hours. When the same post-treatment as in Example 1 was carried out, white 4,4'-biphenol 88F (yield 97%) was obtained, with a purity of 99.7%.
比較例１
２ｔの４つ口丸底フラスコに、３１３’＃５１５’−テ
トラ第三ブチル−４，４′−ビフェノール３００ ｔ
（０，７３ｒｒｙｏｉｔ ）、Ｐ−）Ａ−エンスルホン
酸８．Ｏｆ （０，０２１ｍｏｊｌ ）、ジエチルベン
ゼン４５０ ｆ （３，３６ｍｏｎ）を添加し、温度計
、窒素ガス導入管、攪拌羽根、冷却管を増す付は窒素気
流下、１７５℃で４時間攪拌し念後、室温まで冷却し生
成物をろ過、洗浄を行い乾燥したところ、赤紫色に着色
劣化した４゜４′−ビフェノールが１１６１Ｆ（収率８
５ ％ ）得られ、その純度は９２．８％でめった。Comparative Example 1 300 t of 313'#515'-tetra-tert-butyl-4,4'-biphenol was placed in a 2 t four-necked round bottom flask.
(0,73rryoit), P-)A-enesulfonic acid8. Of (0,021 mojl), diethylbenzene 450 f (3,36 mon) were added, and a thermometer, nitrogen gas introduction tube, stirring blade, and cooling tube were added. After stirring at 175°C for 4 hours under a nitrogen stream, When the product was cooled to room temperature, filtered, washed, and dried, 1161F (yield: 8
5%) with a purity of 92.8%.
比較例２
比較例１において溶媒でめるジエチルベンゼンの代わり
にジフェニルエーテルを用い、ｐ−）ルエンスルホン酸
３．Ｏｆ （０，０１６ｍｍｏβ）を添加し、２００Ｃ
にて同様に反応を行なった。反応終了（＆、４．４’−
ビフェノールの結晶を１００℃にて熱時濾過し、トルエ
ン洗浄後乾燥したところ、灰紫色に着色した４、４′−
ビフェノール１０４ｆ（収率７６％）が得られ、その純
度は９８．２％であつた。Comparative Example 2 In Comparative Example 1, diphenyl ether was used instead of diethylbenzene in the solvent, and p-)luenesulfonic acid 3. Added Of (0,016 mmoβ) and heated at 200C
The reaction was carried out in the same manner. Reaction completed (&, 4.4'-
When the biphenol crystals were filtered hot at 100°C, washed with toluene and dried, the 4,4'-
Biphenol 104f (yield 76%) was obtained, and its purity was 98.2%.
Claims (1)
ノールを有機溶媒中、酸触媒存在下で脱ブチル化反応に
より４，４′−ビフェノール類を製造する方法に於て、
前記の酸触媒を逐次添加することを特徴とする高純度４
，４′−ビフェノール類の製造方法。In a method for producing 4,4'-biphenols by debutylating an alkylbiphenol having at least one tert-butyl group in an organic solvent in the presence of an acid catalyst,
High purity 4 characterized by sequentially adding the above acid catalyst
, 4'-biphenol production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62138635A JP2524594B2 (en) | 1987-06-02 | 1987-06-02 | Method for producing high-purity 4,4'-biphenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62138635A JP2524594B2 (en) | 1987-06-02 | 1987-06-02 | Method for producing high-purity 4,4'-biphenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63301837A true JPS63301837A (en) | 1988-12-08 |
| JP2524594B2 JP2524594B2 (en) | 1996-08-14 |
Family
ID=15226653
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62138635A Expired - Fee Related JP2524594B2 (en) | 1987-06-02 | 1987-06-02 | Method for producing high-purity 4,4'-biphenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2524594B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0432782A2 (en) * | 1989-12-15 | 1991-06-19 | Mitsubishi Petrochemical Co., Ltd. | Process for preparing 4,4'-dihydroxybiphenyl |
| EP0571947A1 (en) * | 1992-05-29 | 1993-12-01 | Mitsubishi Chemical Corporation | Method for preparing 4,4'-biphenol |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4268810B2 (en) | 2003-01-23 | 2009-05-27 | 本州化学工業株式会社 | Method for producing 4,4'-biphenol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5271422A (en) * | 1975-12-05 | 1977-06-14 | Bayer Ag | Method of dealkylating terttalkyllsubstituted phenols |
| JPS58189127A (en) * | 1982-04-30 | 1983-11-04 | Showa Denko Kk | Preparation of p,p-biphenol |
| JPS61200935A (en) * | 1985-03-04 | 1986-09-05 | Honsyu Kagaku Kogyo Kk | Production of p,p'-biphenol |
-
1987
- 1987-06-02 JP JP62138635A patent/JP2524594B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5271422A (en) * | 1975-12-05 | 1977-06-14 | Bayer Ag | Method of dealkylating terttalkyllsubstituted phenols |
| JPS58189127A (en) * | 1982-04-30 | 1983-11-04 | Showa Denko Kk | Preparation of p,p-biphenol |
| JPS61200935A (en) * | 1985-03-04 | 1986-09-05 | Honsyu Kagaku Kogyo Kk | Production of p,p'-biphenol |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0432782A2 (en) * | 1989-12-15 | 1991-06-19 | Mitsubishi Petrochemical Co., Ltd. | Process for preparing 4,4'-dihydroxybiphenyl |
| EP0571947A1 (en) * | 1992-05-29 | 1993-12-01 | Mitsubishi Chemical Corporation | Method for preparing 4,4'-biphenol |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2524594B2 (en) | 1996-08-14 |
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