JPH0768171B2 - Process for producing 4-acyloxy-4'-bromobiphenyl - Google Patents
Process for producing 4-acyloxy-4'-bromobiphenylInfo
- Publication number
- JPH0768171B2 JPH0768171B2 JP62327362A JP32736287A JPH0768171B2 JP H0768171 B2 JPH0768171 B2 JP H0768171B2 JP 62327362 A JP62327362 A JP 62327362A JP 32736287 A JP32736287 A JP 32736287A JP H0768171 B2 JPH0768171 B2 JP H0768171B2
- Authority
- JP
- Japan
- Prior art keywords
- bromobiphenyl
- acyloxy
- general formula
- producing
- acetoxy
- 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 - Fee Related
Links
- 238000000034 method Methods 0.000 title description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 235000010216 calcium carbonate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- MISFQCBPASYYGV-UHFFFAOYSA-N (4-phenylphenyl) acetate Chemical group C1=CC(OC(=O)C)=CC=C1C1=CC=CC=C1 MISFQCBPASYYGV-UHFFFAOYSA-N 0.000 description 11
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 9
- 229910052794 bromium Inorganic materials 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- PZPSICDSQWAIBR-UHFFFAOYSA-N [4-(4-bromophenyl)phenyl] acetate Chemical group C1=CC(OC(=O)C)=CC=C1C1=CC=C(Br)C=C1 PZPSICDSQWAIBR-UHFFFAOYSA-N 0.000 description 8
- 239000002609 medium Substances 0.000 description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- YSQFVAIHOFDARU-UHFFFAOYSA-N (2-bromo-4-phenylphenyl) acetate Chemical group C1=C(Br)C(OC(=O)C)=CC=C1C1=CC=CC=C1 YSQFVAIHOFDARU-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 238000006640 acetylation reaction Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CINHWMYRCOGYIX-UHFFFAOYSA-N (4-phenylphenyl) benzoate Chemical group C=1C=CC=CC=1C(=O)OC(C=C1)=CC=C1C1=CC=CC=C1 CINHWMYRCOGYIX-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- -1 4-acetoxy-3,6,4 ' Tribrombiphenyl Chemical group 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
- TWASDZSEWLGVOQ-UHFFFAOYSA-N [2-bromo-4-(4-bromophenyl)phenyl] acetate Chemical group C(C)(=O)OC1=C(C=C(C=C1)C1=CC=C(C=C1)Br)Br TWASDZSEWLGVOQ-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は４−アシロキシビフェニルを臭素化して４−ア
シロキシ−４′−ブロムビフェニルを選択的に且つ収率
良く製造する方法に関する。TECHNICAL FIELD The present invention relates to a method for brominating 4-acyloxybiphenyl to selectively produce 4-acyloxy-4′-bromobiphenyl with good yield.
４−アシロキシ−４′−ブロムビフェニルは医薬、農
薬、液晶電子材料、液晶高分子化合物、高耐熱性高分子
化合物等の原料として近年特に注目を集めている化合物
である。4-Acyloxy-4′-bromobiphenyl is a compound that has been particularly attracting attention in recent years as a raw material for medicines, agricultural chemicals, liquid crystal electronic materials, liquid crystal polymer compounds, highly heat-resistant polymer compounds and the like.
従来その製造方法として次のような方法が提案されてい
る。Conventionally, the following method has been proposed as a manufacturing method thereof.
（１） ４−ベンゾイルオキシビフェニルを氷酢酸中で
鉄粉を触媒として臭素化する方法。（収率82％）〔J.A.
C.S.,61,pp.1447,3037（1939）〕 （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化する方
法。（収率52％）〔Proc.Louisiana Acad.Sci.,10,pp.2
05〜９（1947）,C.A.,42,1919C〕 （３） ４−アセトキシビフェニルを無水酢酸と酢酸と
の混合溶媒中でヨウ素を触媒として大過剰の臭素（53倍
モル）により臭素化する方法。（収率15％）〔J.Chem.S
oc.,1956,pp 3243〜５〕 しかしながら、これら従来技術は工業的見地からみると
使用溶媒（特に酢酸系）の臭気や回収、特殊な薬品の使
用等のほか、目的化合物の収率が十分でない等遠くの問
題点を有している。(1) A method of brominating 4-benzoyloxybiphenyl in glacial acetic acid using iron powder as a catalyst. (Yield 82%) [JA
CS, 61 , pp.1447, 3037 (1939)] (2) A method of brominating 4-acetoxybiphenyl in carbon tetrachloride in the presence of basic lead carbonate using iodine as a catalyst. (Yield 52%) [Proc. Louisiana Acad. Sci., 10 , pp.2
05-9 (1947), CA, 42 , 1919C] (3) A method of brominating 4-acetoxybiphenyl in a mixed solvent of acetic anhydride and acetic acid with a large excess of bromine (53 times mol) using iodine as a catalyst. (Yield 15%) [J.Chem.S
oc., 1956 , pp 3243-5] However, from an industrial point of view, these conventional techniques have sufficient yields of the target compound in addition to the odor and recovery of the solvent used (especially acetic acid type) and the use of special chemicals. It has a distant problem such as not.
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、特殊な装置や薬品等に頼ることなく、作業環
境、公害防止等の観点からも、目的物の収率、品質上か
らも工業的に有利に４−アシロキシ−４′−ブロムビフ
ェニルを製造する方法を完成した。The inventors of the present invention have conducted various researches to solve such a problem, and without relying on a special device or chemicals, work environment, pollution prevention, etc. Also completed a method for producing 4-acyloxy-4'-bromobiphenyl in an industrially advantageous manner.
すなわち本発明は、一般式（II） 〔一般式（II）で、Ｒは低級アルキル基を示す。〕で表
わされる４−アシロキシビフェニルを、臭素と反応させ
て、一般式（Ｉ） 〔一般式（Ｉ）で、Ｒは一般式（II）における定義に同
じ。〕 で表わされる４−アシロキシ−４′−ブロムビフェニル
を製造するに当り、不活性媒体中で水酸化カルシウム、
炭酸ナトリウム、炭酸カルシウム、重炭酸ナトリウム及
び酢酸ナトリウムの１種又は２種以上の共存下で反応さ
せることを特徴とする、４−アシロキシ−４′−ブロム
ビフェニルの製造方法を提供する。That is, the present invention has the general formula (II) [In the general formula (II), R represents a lower alkyl group. ] 4-acyloxybiphenyl represented by the formula: [In the general formula (I), R is the same as the definition in the general formula (II). ] In producing 4-acyloxy-4'-bromobiphenyl represented by the following formula, calcium hydroxide in an inert medium,
Provided is a method for producing 4-acyloxy-4'-bromobiphenyl, which comprises reacting in the presence of one or more of sodium carbonate, calcium carbonate, sodium bicarbonate and sodium acetate.
以下、本発明についてさらに詳細に説明する。Hereinafter, the present invention will be described in more detail.
本発明に用いる４−アシロキシビフェニルは、従来公知
の方法により、４−ヒドロキシビフェニルをアシル化剤
と反応させることにより容易に製造することができる。
例えば４−ヒドロキシビフェニルを無水酢酸、塩化アセ
チル又はジケテン等と反応させて４−アセトキシビフェ
ニルを殆ど定量的に製造し得る。The 4-acyloxybiphenyl used in the present invention can be easily produced by reacting 4-hydroxybiphenyl with an acylating agent by a conventionally known method.
For example, 4-hydroxybiphenyl can be reacted with acetic anhydride, acetyl chloride, diketene or the like to produce 4-acetoxybiphenyl almost quantitatively.
又不活性媒体としては、水、ハロゲン化水素酸酸性水、
硫酸、ハロゲン化炭化水素等が挙げられ、なかでもハロ
ゲン化炭化水素特に1,2−ジクロルエタン、クロロホル
ム、四塩化炭素、トリクロルエタン、テトラクロルエチ
レン等が好適である。その使用量は４−アシロキシビフ
ェニルの0.5〜10倍量、好ましくは１〜５倍量である。As the inert medium, water, hydrohalic acid acid water,
Sulfuric acid, halogenated hydrocarbons and the like can be mentioned, and among them, halogenated hydrocarbons, especially 1,2-dichloroethane, chloroform, carbon tetrachloride, trichloroethane, tetrachloroethylene and the like are preferable. The amount used is 0.5 to 10 times, preferably 1 to 5 times the amount of 4-acyloxybiphenyl.
反応時に共存せしめる水酸化カルシウム、炭酸ナトリウ
ム、炭酸カルシウム、重炭酸ナトリウム、酢酸ナトリウ
ムの使用量は４−アシロキシビフェニルに対し0.5〜10
モル比、好ましくは１〜４モル比相当量である。The amount of calcium hydroxide, sodium carbonate, calcium carbonate, sodium bicarbonate, and sodium acetate that are allowed to coexist during the reaction is 0.5 to 10 relative to 4-acyloxybiphenyl.
A molar ratio, preferably 1 to 4 molar ratio equivalent amount.
臭素の使用量は４−アシロキシビフェニルに対し0.8〜
３モル比、好ましくは1.0〜1.5モル比相当量であり、臭
素を直接反応系に添加してもよく、又不活性媒体に溶解
したものを添加してもよい。The amount of bromine used is 0.8-based on 4-acyloxybiphenyl
The amount is 3 mol ratio, preferably 1.0 to 1.5 mol ratio, and bromine may be added directly to the reaction system or may be dissolved in an inert medium.
反応温度は用いられる不活性媒体の沸点以下で、５〜10
0℃、通常30〜60℃である。反応時間は使用する不活性
媒体や共存化合物の種類、量、反応温度等により異なる
が、臭素添加時間を含め１〜15時間、通常５〜10時間で
ある。The reaction temperature is below the boiling point of the inert medium used,
0 ° C, usually 30-60 ° C. The reaction time varies depending on the type and amount of the inert medium and the coexisting compound used, the reaction temperature, etc., but is 1 to 15 hours including the bromine addition time, and usually 5 to 10 hours.
反応終了後室温まで冷却し、不活性媒体としてハロゲン
化炭化水素等を用いた場合には、必要により該媒体を追
加して、過することにより、添加共存化合物及び反応
により副生する化合物を除去することができる。不活性
媒体として水系を使用した場合は、水と混合せず４−ア
シロキシ−４′−ブロムビフェニルを溶解する不活性有
機溶媒を加えて目的物を抽出する。After the completion of the reaction, the reaction mixture is cooled to room temperature, and when a halogenated hydrocarbon or the like is used as an inert medium, the medium is added as necessary, and by passing, the coexisting compound added and the compound by-produced by the reaction are removed. can do. When an aqueous medium is used as the inert medium, the desired product is extracted by adding an inert organic solvent which does not mix with water and dissolves 4-acyloxy-4′-bromobiphenyl.
かくして得られる有機溶媒中の４−アシロキシビフェニ
ルのブロム化生成物は、４−アシロキシ−４′−ブロム
ビフェニルを高率に含有しており、常法により溶媒を除
去することにより高収率で高純度の目的物を得ることが
出来る。さらに高純度の目的物を必要とする場合はベン
ゼン、トルエン、キシレン、アルコールなど適当な溶媒
により再結晶精製を行なう。The brominated product of 4-acyloxybiphenyl in the organic solvent thus obtained contains 4-acyloxy-4′-bromobiphenyl at a high rate, and a high yield can be obtained by removing the solvent by a conventional method. It is possible to obtain a high-purity target product. When a highly pure target substance is required, recrystallization purification is performed using a suitable solvent such as benzene, toluene, xylene, alcohol.
４−アシロキシビフェニルと臭素との反応は、前述した
通り一般的にヨウ素又は鉄を触媒として行なわれるが、
この場合、相当量の異性体（特に４−アシロキシ−３−
ブロムビフェニル）やポリブロム化物の副生が避け難
い。本発明方法によれば、ヨウ素、鉄等の触媒を必要と
せず、温和な条件で、高反応率、高選択率で目的の４−
アシロキシ−４′−ブロムビフェニルを製造することが
できる。The reaction of 4-acyloxybiphenyl with bromine is generally carried out using iodine or iron as a catalyst as described above,
In this case, a considerable amount of isomers (especially 4-acyloxy-3-
Brombiphenyl) and polybrominated products are difficult to avoid. According to the method of the present invention, a catalyst such as iodine and iron is not required, and the desired 4- and high-reactivity can be obtained under mild conditions.
Acyloxy-4'-bromobiphenyl can be prepared.
次に本発明の実施例について説明する。 Next, examples of the present invention will be described.
実施例１ 100ml容反応フラスコに、４−アセトキシビフェニル15.
0g（0.07モル）、1,2−ジクロルエタン25g及び炭酸ナト
リウム22.3g（0.21モル）を仕込み、撹拌下で50℃付近
に保温しながら、滴下漏斗から臭素18g（0.1モル）を1,
2−ジクロルエタン25gに溶解したものを６時間で添加し
た。添加終了後、同温度に４時間保ったのち、反応混合
液試料を採り、ガスクロマトグラフ（G.C.）分析を行な
ったところ、４−アセトキシ−４′−ブロムビフェニル
96.8％、４−アセトキシ−３−ブロムビフェニル0.5
％、４−アセトキシビフェニル2.7％であった。反応混
合法を過して固形物を除去した液から溶媒を留去さ
せて、４−アセトキシ−４′−ブロムビフェニルの黄白
色結晶20.2gを得た。収率98％。（G.C.分析による）純
度96.0％。Example 1 4-acetoxybiphenyl 15.
0 g (0.07 mol), 1,2-dichloroethane 25 g and sodium carbonate 22.3 g (0.21 mol) were charged, and while maintaining the temperature at around 50 ° C under stirring, 18 g (0.1 mol) of bromine was added from a dropping funnel.
What was dissolved in 25 g of 2-dichloroethane was added over 6 hours. After the addition was completed, the temperature was kept at the same temperature for 4 hours, and then a sample of the reaction mixture was sampled and analyzed by gas chromatography (GC). As a result, 4-acetoxy-4′-bromobiphenyl was obtained.
96.8%, 4-acetoxy-3-bromobiphenyl 0.5
%, And 4-acetoxybiphenyl was 2.7%. The solvent was distilled off from the liquid obtained by removing the solid matter by passing through the reaction mixing method, to obtain 20.2 g of 4-acetoxy-4'-bromobiphenyl yellowish white crystals. Yield 98%. Purity 96.0% (by GC analysis).
このものをトルエン38gを用いて再結晶精製し、白色結
晶16.5gを得た。収率80％。融点130〜131℃。純度99.8
％。This product was recrystallized and purified using 38 g of toluene to obtain 16.5 g of white crystals. Yield 80%. Melting point 130-131 ° C. Purity 99.8
%.
実施例２ 実施例１と同様に操作して、４−アセトキシビフェニル
15.0g、1,2−ジクロルエタン25g及び酢酸ナトリウム17.
2g（0.21モル）の混合物に、臭素18.0g（0.1モル）と1,
2−ジクロルエタンの混合物を添加して反応、熟成、冷
却、過、溶媒除去を行ない、４−アセトキシ−４′−
ブロムビフェニルの黄白色結晶17.2gを得た。収率83.5
％。純度97.4％（４−アセトキシ−３−ブロムビフェニ
ル2.4％、４−アセトキシビフェニル0.2％）。Example 2 In the same manner as in Example 1, 4-acetoxybiphenyl was used.
15.0 g, 1,2-dichloroethane 25 g and sodium acetate 17.
In a mixture of 2g (0.21mol), 18.0g (0.1mol) of bromine and 1,
2-dichloroethane mixture was added to carry out reaction, aging, cooling, excess, solvent removal, 4-acetoxy-4'-
17.2 g of yellow-white crystals of brombiphenyl were obtained. Yield 83.5
%. Purity 97.4% (4-acetoxy-3-bromobiphenyl 2.4%, 4-acetoxybiphenyl 0.2%).
実施例３ 実施例１における炭酸ナトリウム22.3gの代りに水酸化
カルシウム15.5g（0.21モル）を使用したこと以外は実
施例１と同様に操作して、４−アセトキシ−４′−ブロ
ムビフェニルの黄白色結晶17.0gを得た。収率82.5％。
純度84.2％（４−アセトキシ−３−ブロムビフェニル1
4.4％、４−アセトキシビフェニル1.4％）。Example 3 4-acetoxy-4'-bromobiphenyl yellow was prepared in the same manner as in Example 1 except that 15.5 g (0.21 mol) of calcium hydroxide was used instead of 22.3 g of sodium carbonate. 17.0 g of white crystals were obtained. Yield 82.5%.
Purity 84.2% (4-acetoxy-3-bromobiphenyl 1
4.4%, 4-acetoxybiphenyl 1.4%).
実施例４ 実施例１における炭酸ナトリウム22.3gの代りに炭酸カ
ルシウム23g（0.23モル）を使用したこと以外は実施例
１と同様に操作して、４−アセトキシ−４′−ブロムビ
フェニルの黄白色結晶17.8gを得た。収率86.4％。純度8
3.5％。Example 4 The yellow-white crystals of 4-acetoxy-4'-bromobiphenyl were prepared in the same manner as in Example 1 except that 23 g (0.23 mol) of calcium carbonate was used instead of 22.3 g of sodium carbonate in Example 1. 17.8 g was obtained. Yield 86.4%. Purity 8
3.5%.
実施例５ 実施例１における炭酸ナトリウム22.3gの代りに重炭酸
ナトリウム29.4g（0.35モル）を使用したこと以外は実
施例１と同様に操作して、４−アセトキシ−４′−ブロ
ムビフェニルの黄白色結晶17.5gを得た。収率84.9％。
純度81.8％。Example 5 4-acetoxy-4'-bromobiphenyl yellow was prepared in the same manner as in Example 1 except that 29.4 g (0.35 mol) of sodium bicarbonate was used instead of 22.3 g of sodium carbonate in Example 1. 17.5 g of white crystals were obtained. Yield 84.9%.
Purity 81.8%.
実施例６ 本例では４−ヒドロキシビフェニルを出発原料とし、ア
セチル化、ブロム化反応を一貫して行なう場合について
説明する。Example 6 In this example, the case where 4-hydroxybiphenyl is used as the starting material and the acetylation and bromination reactions are carried out consistently will be described.
100ml容反応フラスコに４−ヒドロキシビフェニル10.0g
（0.059モル）と無水酢酸9.0g（0.0885モル）を仕込
み、約140℃の還流下アセチル化反応を行なった。G.C.
分析でアセチル化反応の完結を確認した後、℃以下に冷
却し、1,2−ジクロルエタン38gを加えた。内容物が均一
になってから炭酸ナトリウム12.4g（0.117モル）を少量
ずつ添加した後、温度を50℃付近に保ちながら臭素12.3
g（0.0683モル）を約６時間で添加した。添加終了後４
時間熟成を行なったところで反応混合物試料を採り、G.
C.分析を行なったところ、４−アセトキシ−４′−ブロ
ムビフェニル97.2％、４−アセトキシ−３−ブロムビフ
ェニル2.4％、４−アセトキシビフェニル0.4％であっ
た。反応混合物を実施例１と同様に処理して溶媒を除去
し、４−アセトキシ−４′−ブロムビフェニルの黄白色
結晶16.8gを得た。収率98.2％（対４−ヒドロキシビフ
ェニル）。純度97.8％。4-hydroxybiphenyl 10.0 g in a 100 ml reaction flask
(0.059 mol) and acetic anhydride 9.0 g (0.0885 mol) were charged, and the acetylation reaction was carried out under reflux at about 140 ° C. GC
After confirming the completion of the acetylation reaction by analysis, the mixture was cooled to below ° C and 38 g of 1,2-dichloroethane was added. After the contents became uniform, 12.4 g (0.117 mol) of sodium carbonate was added little by little, and bromine 12.3 was added while keeping the temperature near 50 ° C.
g (0.0683 mol) was added in about 6 hours. 4 after addition
After aging for a while, take a sample of the reaction mixture and
C. Analysis revealed that it was 97.2% 4-acetoxy-4′-bromobiphenyl, 2.4% 4-acetoxy-3-bromobiphenyl and 0.4% 4-acetoxybiphenyl. The reaction mixture was treated in the same manner as in Example 1 to remove the solvent, and 16.8 g of a yellowish white crystal of 4-acetoxy-4′-bromobiphenyl was obtained. Yield 98.2% (vs. 4-hydroxybiphenyl). Purity 97.8%.
比較例 100ml容反応フラスコに、４−アセトキシビフェニル15.
0g（0.07モル）、1,2−ジクロルエタン25g及び鉄粉0.5g
を仕込み、撹拌下で50℃付近に保温しながら、滴下漏斗
から臭素18.0g（0.1モル）と1,2−ジクロルエタン25gの
混合液を６時間で添加した。添加終了後同温度で４時間
熟成した後、反応混合液試料を採りG.C.分析したとこ
ろ、４−アセトキシ−４′−ブロムビフェニル0.6％、
４−アセトキシ−３−ブロムビフェニル44.0％、４−ア
セトキシビフェニル15.7％、４−アセトキシ−3,4′−
ジブロムビフェニル24.4％、４−アセトキシ−3,6,4′
−トリブロムビフェニル15.3％であった。Comparative Example 4-acetoxybiphenyl 15.
0g (0.07mol), 1,2-dichloroethane 25g and iron powder 0.5g
Was charged, and a mixture of 18.0 g (0.1 mol) of bromine and 25 g of 1,2-dichloroethane was added over 6 hours from the dropping funnel while maintaining the temperature at about 50 ° C. under stirring. After aging at the same temperature for 4 hours after the addition was completed, a sample of the reaction mixture was taken and analyzed by GC. As a result, 4-acetoxy-4′-bromobiphenyl 0.6%,
4-acetoxy-3-bromobiphenyl 44.0%, 4-acetoxybiphenyl 15.7%, 4-acetoxy-3,4'-
Dibromobiphenyl 24.4%, 4-acetoxy-3,6,4 '
Tribrombiphenyl 15.3%.
本発明の製造方法によれば、特殊な装置や薬品等に頼る
ことなく、作業環境、公害防止の観点からも、収率およ
び品質上からも工業的に有利に４−アシロキシ−４′−
ブロムビフェニルを製造することができる。According to the production method of the present invention, 4-acyloxy-4′-is industrially advantageous from the viewpoints of working environment, pollution prevention, yield and quality without relying on a special device or chemicals.
Brombiphenyl can be produced.
Claims (3)
させて一般式（Ｉ） 〔一般式（Ｉ）で、Ｒは一般式（II）における定義と同
じ。〕 で表わされる４−アシロキシ−４′−ブロムビフェニル
を製造するに当り、不活性媒体中で水酸化カルシウム、
炭酸ナトリウム、炭酸カルシウム、重炭酸ナトリウム及
び酢酸ナトリウムの１種又は２種以上の共存下で反応さ
せることを特徴とする、４−アシロキシ−４′−ブロム
ビフェニルの製造方法。1. General formula (II) [In the general formula (II), R represents a lower alkyl group. ] 4-acyloxybiphenyl represented by the formula: [In the general formula (I), R is the same as the definition in the general formula (II). ] In producing 4-acyloxy-4'-bromobiphenyl represented by the following formula, calcium hydroxide in an inert medium,
A method for producing 4-acyloxy-4′-bromobiphenyl, which comprises reacting in the presence of one or more of sodium carbonate, calcium carbonate, sodium bicarbonate and sodium acetate.
がメチル基である特許請求の範囲第１項記載の４−アシ
ロキシ−４′−ブロムビフェニルの製造方法。2. R in general formula (II) and general formula (I)
The method for producing 4-acyloxy-4'-bromobiphenyl according to claim 1, wherein is a methyl group.
許請求の範囲第１項記載の４−アシロキシ−４′−ブロ
ムビフェニルの製造方法。3. The method for producing 4-acyloxy-4′-bromobiphenyl according to claim 1, wherein the inert medium is a halogenated alkane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62327362A JPH0768171B2 (en) | 1987-12-25 | 1987-12-25 | Process for producing 4-acyloxy-4'-bromobiphenyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62327362A JPH0768171B2 (en) | 1987-12-25 | 1987-12-25 | Process for producing 4-acyloxy-4'-bromobiphenyl |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01172361A JPH01172361A (en) | 1989-07-07 |
| JPH0768171B2 true JPH0768171B2 (en) | 1995-07-26 |
Family
ID=18198297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62327362A Expired - Fee Related JPH0768171B2 (en) | 1987-12-25 | 1987-12-25 | Process for producing 4-acyloxy-4'-bromobiphenyl |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0768171B2 (en) |
-
1987
- 1987-12-25 JP JP62327362A patent/JPH0768171B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01172361A (en) | 1989-07-07 |
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