JPH06172243A - Production of 4'-bromobiphenyl-4-ol - Google Patents
Production of 4'-bromobiphenyl-4-olInfo
- Publication number
- JPH06172243A JPH06172243A JP4351148A JP35114892A JPH06172243A JP H06172243 A JPH06172243 A JP H06172243A JP 4351148 A JP4351148 A JP 4351148A JP 35114892 A JP35114892 A JP 35114892A JP H06172243 A JPH06172243 A JP H06172243A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- bromobiphenyl
- dibromobiphenyl
- bbph
- amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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]
【産業上の利用分野】本発明は4’−ブロモビフェニル
−4−オール(以下BBPHと略記する)の製造方法に
関する。BBPHはそれ自体又はその誘導体が、スーパ
ーエンジニアリングプラスチックスのモノマー又はスー
パーエンジニアリングプラスチックスの改質添加剤とし
て、また染料、農薬、医薬等の原料として有用な化合物
である。FIELD OF THE INVENTION The present invention relates to a method for producing 4'-bromobiphenyl-4-ol (hereinafter abbreviated as BBPH). BBPH itself or a derivative thereof is a compound useful as a monomer for super engineering plastics or a modifying additive for super engineering plastics, and as a raw material for dyes, agricultural chemicals, pharmaceuticals and the like.
【0002】[0002]
【従来の技術】従来、BBPHの製造方法としては、次
のような方法が知られている。 1)4−ブロモー4’−ニトロビフェニルを還元して4
−ブロモ−4’アミノビフェニルとし、次いでジアゾ
化、分解してBBPHを得る[J.Chem.So
c.,1952,pp.1959〜60]。 2)4−アセトキシビフェニルを四塩化炭素中で塩基性
炭酸鉛の共存下にヨウ素を触媒として臭素と反応させた
後、加水分解してBBPHを得る[Proc.Loui
siana Acad.Sci.,10,205〜9
(1947)]。 3)4−アセトキシビフェニルを無水酢酸と酢酸との混
合溶剤中でヨウ素を触媒として、大過剰の臭素と反応さ
せた後、加水分解してBBPHを得る[J.Cem.S
oc.,1956,3243〜5]。 4)4−ベゾイルオキシビフェニルを氷酢酸中で鉄粉を
触媒とし、臭素と反応させた後、加水分解してBBPH
を得る[J.A.C.S.,61,1447,3037
(1939)]。 5)ビス(ビフェニル)カーボネートと臭素とを、不活
性媒体中で反応させた後、加水分解してBBPHを得る
[特開平4−244048号公報]。2. Description of the Related Art Conventionally, the following method has been known as a method for manufacturing BBPH. 1) 4-bromo-4'-nitrobiphenyl is reduced to 4
-Bromo-4'aminobiphenyl, followed by diazotization and decomposition to obtain BBPH [J. Chem. So
c. , 1952 , pp. 1959-60]. 2) 4-acetoxybiphenyl is reacted with bromine in the presence of basic lead carbonate in carbon tetrachloride in the presence of basic lead carbonate, and then hydrolyzed to obtain BBPH [Proc. Loui
siana Acad. Sci. , 10 , 205-9
(1947)]. 3) 4-acetoxybiphenyl is reacted with a large excess of bromine in a mixed solvent of acetic anhydride and acetic acid with iodine as a catalyst, and then hydrolyzed to obtain BBPH [J. Cem. S
oc. , 1956 , 3243-5]. 4) 4-bezoyloxybiphenyl was reacted with bromine in glacial acetic acid using iron powder as a catalyst, and then hydrolyzed to BBPH.
[J. A. C. S. , 61 , 1447, 3037
(1939)]. 5) Bis (biphenyl) carbonate and bromine are reacted in an inert medium and then hydrolyzed to obtain BBPH [JP-A-4-244048].
【0003】これらの従来技術では、工業的見地から使
用する溶剤、特殊薬品、触媒等について安全、衛生ある
いは公害防止等に種々の対策が必要であり、さらに目的
物の収率が十分でない等多くの問題点を有している。更
に各方法の原料はいずれも4−フェニルフェノールから
の誘導体であり、この4−フェニルフェノールは一般的
にはビフェニルのモノスルホン化、アルカリ溶融反応に
より得られる化合物で、比較的高価な化合物である。From the industrial viewpoint, these conventional techniques require various measures for safety, hygiene, pollution prevention, etc. for solvents, special chemicals, catalysts, etc., and the yield of the desired product is not sufficient. Has the problem of. Further, the raw materials for each method are all derivatives from 4-phenylphenol, and this 4-phenylphenol is generally a compound obtained by monosulfonation of biphenyl and an alkali melting reaction, and is a relatively expensive compound. .
【0004】また4、4’−ジブロモビフェニルをアル
カリと反応させてビフェニル−4、4’−ジオールを製
造する方法(特開昭54−22347号公報)は知られ
ているが、部分加水分解して、4’−ブロモビフェニル
−4−オールを効率良く製造する方法は知られていな
い。A method for producing biphenyl-4,4'-diol by reacting 4,4'-dibromobiphenyl with an alkali (Japanese Patent Laid-Open No. 54-22347) is known, but it is partially hydrolyzed. Therefore, a method for efficiently producing 4'-bromobiphenyl-4-ol is not known.
【0005】[0005]
【発明が解決しようとする課題】本発明者らは、かかる
問題点を解決するため種々研究を重ねた結果、比較的容
易に、安価に入手可能な原料を使用し、特殊な装置や薬
品を必要とせず、作業環境、公害防止等の観点からも、
操作上、収率、品質上からも有利にBBPHを製造する
方法を開発するに到った。DISCLOSURE OF THE INVENTION The present inventors have conducted various studies in order to solve such problems, and as a result, relatively easily and inexpensively used raw materials were used, and special equipment and chemicals were used. It is not necessary, and from the viewpoint of work environment and pollution prevention,
We have developed a method for producing BBPH, which is advantageous in terms of operation, yield and quality.
【0006】[0006]
【課題を解決するための手段】即ち、本発明に従って、
4、4’−ジブロモビフェニル(以下DBBPと略記す
る)と、モル比で該DBBPの2〜5倍量の水酸化ナト
リウム、水酸化カリウム又はこれらの混合物とを、反応
溶媒として水5〜25重量%を含有するメタノール、エ
タノール又はプロパノールから選ばれる少なくとも1種
を重量比で該DBBPの10〜30倍量使用し、触媒と
して銅化合物を使用し、加圧下に150〜200℃で反
応させて4’−ブロモビフェニル−4−オールを製造す
る方法が提供される。That is, according to the present invention,
5 to 25 parts by weight of water, 4,4′-dibromobiphenyl (hereinafter abbreviated as DBBP) and a molar ratio of 2 to 5 times the amount of sodium hydroxide, potassium hydroxide or a mixture thereof, as a reaction solvent % Of at least one selected from methanol, ethanol or propanol is used in a weight ratio of 10 to 30 times the DBBP, a copper compound is used as a catalyst, and the reaction is carried out at 150 to 200 ° C. under pressure. Methods of making'-bromobiphenyl-4-ol are provided.
【0007】以下本発明について更に詳細に説明する:
本発明の原料であるDBBPは、工業的にビフェニルと
臭素との反応により高純度、高収率で製造される;反応
溶媒として、水5〜25重量%を含有するメタノール、
エタノール又はプロパノール(ノルマル及びイソ)から
選ばれる少なくとも1種を重量比で該DBBPの10〜
30倍量使用する。ブタノールを用いた場合には反応
率、選択率ともに好ましくない。含水率が5重量%未満
になると反応率が十分でなくなり、また25重量%を越
える場合には選択率が十分でなくなる。使用量が10倍
量未満になると選択率が不十分となり、また30倍量を
越えると反応率及び反応効率が低下する;水酸化ナトリ
ウム、水酸化カリウム又はそれらの混合物の使用量は、
モル比でDBBPの2〜5倍量が適当である。2倍量未
満では反応率が低くなり、また5倍量を越えると選択率
が十分でなくなる;DBBPに対する反応溶媒及びアル
カリの使用量が一定範囲内に定められるので、溶媒中の
アルカリの反応初期濃度は当然に一定範囲内に定まる;
触媒の銅化合物としては、酸化物、ハロゲン化物、無機
又は有機酸塩が使用される。その使用量はDBBPのモ
ル基準で0.5〜15%である;反応は加圧下で実施さ
れ、反応温度は150〜200℃である。150℃未満
では反応率が十分でなく、200℃を越えると選択率が
低下する;反応時間は通常2〜25時間である;反応は
非酸化系、例えば窒素雰囲気下で行なわれるのが好まし
い;反応終了後、反応混合物を冷却し、アルコール分を
留去し、適当な抽出溶剤を加えて抽出処理後、水相を酸
性化して目的物を析出させ、必要なら適当な溶剤から再
結晶精製する。The present invention will be described in more detail below:
DBBP, which is a raw material of the present invention, is industrially produced in a high purity and a high yield by a reaction of biphenyl and bromine; methanol containing 5 to 25% by weight of water as a reaction solvent,
At least one selected from ethanol and propanol (normal and iso) is used in a weight ratio of 10 to 10 of the DBBP.
Use 30 times the amount. When butanol is used, both the reaction rate and the selectivity are unfavorable. When the water content is less than 5% by weight, the reaction rate becomes insufficient, and when it exceeds 25% by weight, the selectivity becomes insufficient. If the amount used is less than 10 times, the selectivity becomes insufficient, and if it exceeds 30 times, the reaction rate and reaction efficiency decrease; the amount of sodium hydroxide, potassium hydroxide or a mixture thereof is
A molar ratio of 2 to 5 times that of DBBP is suitable. If the amount is less than 2 times, the reaction rate will be low, and if it exceeds 5 times, the selectivity will not be sufficient; since the amount of the reaction solvent and alkali used for DBBP is set within a certain range, the initial reaction of the alkali in the solvent Concentration naturally falls within a certain range;
As the copper compound of the catalyst, oxides, halides, inorganic or organic acid salts are used. The amount used is 0.5-15% on a molar basis of DBBP; the reaction is carried out under pressure and the reaction temperature is 150-200 ° C. If the temperature is lower than 150 ° C., the reaction rate is not sufficient, and if it exceeds 200 ° C., the selectivity is lowered; the reaction time is usually 2 to 25 hours; the reaction is preferably performed in a non-oxidizing system, for example, in a nitrogen atmosphere; After the completion of the reaction, the reaction mixture is cooled, the alcohol content is distilled off, an appropriate extraction solvent is added and the extraction treatment is carried out, the aqueous phase is acidified to precipitate the desired product, and if necessary, recrystallized and purified from a suitable solvent. .
【0008】[0008]
【実施例】以下に本発明の実施例について説明する。た
だしここで、%は特に注記しない限り重量基準で示す。EXAMPLES Examples of the present invention will be described below. However,% is shown here by weight unless otherwise specified.
【0009】実施例 1 300ml容のステンレス製オートクレーブに、DBB
P18.7gr,80%エタノール水溶液152gr,
15%水酸化ナトリウム水溶液48gr及び酸化第一銅
0.15grを仕込み、オートクレーブ内を窒素置換し
た後密封し、160℃に昇温し、この温度に8時間保っ
た。アルコール濃度79%、反応圧力11Kg/cm2・
G.。Example 1 A DBB was placed in a 300 ml autoclave made of stainless steel.
P18.7 gr, 80% ethanol aqueous solution 152 gr,
A 15% aqueous sodium hydroxide solution (48 gr) and cuprous oxide (0.15 gr) were charged, and the inside of the autoclave was replaced with nitrogen and then sealed, the temperature was raised to 160 ° C, and this temperature was maintained for 8 hours. Alcohol concentration 79%, reaction pressure 11 kg / cm 2 ·
G. .
【0010】反応終了後の混合物からのサンプル中の有
機物のガスクロマトグラフ分析の結果は、BBPH 6
5.2%、DBBP 19.7%,4−ブロモビフェニ
ル(以下MBDPと略記する)1.8%、ビフェニル−
4.4’−ジオール(以下DODと略記する)0%、4
−ブロモ−4’−エトキシビフェニル(以下BEOBP
と略記する)11.6%、ビフェニル−4−オール(以
下P−PPと略記する)1.5%であった。この結果か
ら明らかなように反応率は80%、選択率は81%であ
った。The result of gas chromatographic analysis of organic matter in the sample from the mixture after the reaction was BBPH 6
5.2%, DBBP 19.7%, 4-bromobiphenyl (hereinafter abbreviated as MBDP) 1.8%, biphenyl-
4.4'-diol (hereinafter abbreviated as DOD) 0%, 4
-Bromo-4'-ethoxybiphenyl (hereinafter BEOBP
11.6% and biphenyl-4-ol (hereinafter abbreviated as P-PP) 1.5%. As is clear from this result, the reaction rate was 80% and the selectivity was 81%.
【0011】反応終了後の混合物を取り出し、少量の水
を加えてエタノールを蒸留流出させた後、水とベンゼン
を加えて抽出処理を行ない、さらに2回ベンゼン抽出を
行なった。水相を硫酸で弱酸性とし、析出した結晶を濾
取、水洗、乾燥して淡褐色粉末9.8grを得た。粗収
率は67%であった。ガスクロマトグラフにより求めた
純度は93%であった。この粗製品をエタノールから再
結晶精製したものは、白色結晶性粉末で融点は164〜
166℃(文献値164〜165℃)、純度は99%で
あった。After the completion of the reaction, the mixture was taken out, a small amount of water was added to distill off ethanol, water and benzene were added to carry out an extraction treatment, and benzene extraction was further performed twice. The aqueous phase was made weakly acidic with sulfuric acid, and the precipitated crystals were collected by filtration, washed with water and dried to obtain 9.8 gr of a light brown powder. The crude yield was 67%. The purity determined by gas chromatography was 93%. This crude product was recrystallized and purified from ethanol and was a white crystalline powder with a melting point of 164-
The temperature was 166 ° C. (literature value: 164-165 ° C.), and the purity was 99%.
【0012】なお4−ブロモ−4’−エトキシビフェニ
ルは臭化水素酸で加水分解すれば、目的物のBBPHが
得られる。If 4-bromo-4'-ethoxybiphenyl is hydrolyzed with hydrobromic acid, the desired BBPH can be obtained.
【0013】実施例 2〜16、比較例1〜3 実施例1と同様に操作し、DBBPを18.7gr、触
媒を0.3gr用いた以外は表1に示すように水酸化ナ
トリウムのモル比、銅化合物の種類、アルコールの種類
及び濃度、反応温度及び反応時間を変えて反応を行なっ
た。表1中の反応溶媒についての倍率は重量比での4、
4’−ジブロモビフェニル量に対する反応溶媒量の倍率
である。Examples 2 to 16 and Comparative Examples 1 to 3 The same operation as in Example 1 was repeated except that DBBP was used at 18.7 gr and the catalyst was used at 0.3 gr, and the molar ratio of sodium hydroxide was as shown in Table 1. The reaction was carried out by changing the type of copper compound, the type and concentration of alcohol, the reaction temperature and the reaction time. Magnifications for reaction solvents in Table 1 are 4, by weight ratio,
It is the ratio of the amount of reaction solvent to the amount of 4'-dibromobiphenyl.
【0014】実施例1と同様にして、反応終了後の混合
物からのサンプル中の有機物をガスクロマトグラフ分析
した。その結果を表2に示す。表2中の反応生成物中の
有機成分の分析結果の欄のその他はそのほとんどが使用
した反応溶媒のアルコールと反応して生じたアルキルエ
ーテル(4−アルコキシビフェニル−4−オール)であ
り、このものは臭化水素酸で加水分解することにより、
目的物のBBPHが得られる。更に実施例1と同様にし
て、反応終了後の混合物からBBDHを回収した。その
収量及び収率を表2に示す。In the same manner as in Example 1, gas chromatographic analysis was conducted on the organic substances in the sample from the mixture after the reaction. The results are shown in Table 2. Almost all of the others in the column of the analysis result of the organic component in the reaction product in Table 2 are the alkyl ether (4-alkoxybiphenyl-4-ol) produced by the reaction with the alcohol of the reaction solvent used. By hydrolyzing things with hydrobromic acid,
The target BBPH is obtained. Further, in the same manner as in Example 1, BBDH was recovered from the mixture after completion of the reaction. The yield and yield are shown in Table 2.
【0015】[0015]
【表1】 [Table 1]
【0016】[0016]
【表2】 [Table 2]
【0017】[0017]
【発明の効果】本発明の製造方法によれば、特殊な装置
や薬品等を使用する必要がなく、作業環境、公害防止等
の観点からも、また収率、品質上からも工業的に有利に
4、4’−ジブロモビフェニルから4’−ブロモビフェ
ニル−4−オールを製造することができる。Industrial Applicability According to the production method of the present invention, it is not necessary to use a special device or chemicals, and it is industrially advantageous from the viewpoints of working environment, pollution prevention, etc., and from the viewpoint of yield and quality. In addition, 4'-bromobiphenyl-4-ol can be produced from 4,4'-dibromobiphenyl.
Claims (1)
比で該4、4’−ジブロモビフェニルの2〜5倍量の水
酸化ナトリウム、水酸化カリウム又はこれらの混合物と
を、反応溶媒として水5〜25重量%を含有するメタノ
ール、エタノール又はプロパノールから選ばれる少なく
とも1種を重量比で該4、4’−ジブロモビフェニルの
10〜30倍量使用し、触媒として銅化合物を使用し、
加圧下に150〜200℃で反応させることを特徴とす
る、4’−ブロモビフェニル−4−オールの製造方法。1. A reaction solvent containing 4,4′-dibromobiphenyl and sodium hydroxide, potassium hydroxide or a mixture thereof in a molar ratio of 2 to 5 times the molar amount of 4,4′-dibromobiphenyl. At least one selected from methanol, ethanol or propanol containing 5 to 25% by weight is used in a weight ratio of 10 to 30 times the amount of 4,4′-dibromobiphenyl, and a copper compound is used as a catalyst,
A method for producing 4′-bromobiphenyl-4-ol, which comprises reacting at 150 to 200 ° C. under pressure.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4351148A JPH06172243A (en) | 1992-12-07 | 1992-12-07 | Production of 4'-bromobiphenyl-4-ol |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4351148A JPH06172243A (en) | 1992-12-07 | 1992-12-07 | Production of 4'-bromobiphenyl-4-ol |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH06172243A true JPH06172243A (en) | 1994-06-21 |
Family
ID=18415375
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4351148A Pending JPH06172243A (en) | 1992-12-07 | 1992-12-07 | Production of 4'-bromobiphenyl-4-ol |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH06172243A (en) |
-
1992
- 1992-12-07 JP JP4351148A patent/JPH06172243A/en active Pending
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