JPS62234042A - Production of 4,4'-(p-hydroxybenzoyl)diphenyl ether - Google Patents
Production of 4,4'-(p-hydroxybenzoyl)diphenyl etherInfo
- Publication number
- JPS62234042A JPS62234042A JP61075591A JP7559186A JPS62234042A JP S62234042 A JPS62234042 A JP S62234042A JP 61075591 A JP61075591 A JP 61075591A JP 7559186 A JP7559186 A JP 7559186A JP S62234042 A JPS62234042 A JP S62234042A
- Authority
- JP
- Japan
- Prior art keywords
- diphenyl ether
- liquid hydrogen
- hydrogen fluoride
- reaction
- diphenoxycarbonyl
- 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
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000007788 liquid Substances 0.000 claims abstract description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- 238000004821 distillation Methods 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 2
- 238000005618 Fries rearrangement reaction Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 18
- 239000012429 reaction media Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 5
- -1 that is Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006462 rearrangement reaction Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- WKFQMDFSDQFAIC-UHFFFAOYSA-N 2,4-dimethylthiolane 1,1-dioxide Chemical compound CC1CC(C)S(=O)(=O)C1 WKFQMDFSDQFAIC-UHFFFAOYSA-N 0.000 description 1
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- PBWZKZYHONABLN-UHFFFAOYSA-N difluoroacetic acid Chemical compound OC(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- KALNIDZIJNJFPI-UHFFFAOYSA-N gold hydrofluoride Chemical compound F.[Au] KALNIDZIJNJFPI-UHFFFAOYSA-N 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の利用技術分野〕
本発明は、耐熱性ポリマーの原料として重要な４．４’
−（パラヒドロキシベンゾイル）ジフェニルエーテルの
製造法に関する。Detailed Description of the Invention [Technical Field of Application of the Invention] The present invention is directed to the use of 4.4'
-Regarding a method for producing (parahydroxybenzoyl)diphenyl ether.
従来、４．４’−（パラヒドロキシベンゾイル）ジフェ
ニルエーテルは、４．４’−（シカル＆ ＋ シ）ジフ
ェニルエーテルをトリフルオロメタ／スルホン酸の存在
下にフェノールと反応させる方法が知られている（ｑ＃
開昭５８−６２１３２）。すなわち、この方法を反応式
で示せば次のように表わされる。Conventionally, 4.4'-(parahydroxybenzoyl)diphenyl ether is produced by a method in which 4.4'-(cical & + cy)diphenyl ether is reacted with phenol in the presence of trifluorometa/sulfonic acid (q #
1986-62132). That is, this method can be expressed as a reaction formula as follows.
しかしながら、この方法においては、水が化学量論量だ
け副生じ、この水は反応溶媒であるトリフルオロメタン
スルホン酸と水和物を形成するために、トリフルオロメ
タンスルホン酸を再使用するには、この水和水の分離と
いうやつり憧つ費用がかかる工程を要する。また、トリ
フルオロメタンスルホン酸は、高価である。さらにこの
方法で杜、水が存在するために４．４’−（ジカルボキ
シ）ジフェニルエーテルとフェノールから中間体として
の４ 、４’−（？／フェノキシカルボニル）ジフェニ
ルエーテルが生成する反応と、中間体である４、４’−
（ジフエノキシカルボニル）ジフェニルエーテルが加水
分解反応により４．４’−＜ジカルボキシ）ジフェニル
エーテルとフェノールに戻る反応との平衡反応となシ、
結果として、目的物である４、４’−（パラヒドロキシ
ベンゾイル）ジフェニルエーテルの収率が低い。However, in this method, a stoichiometric amount of water is produced as a by-product, and this water forms a hydrate with trifluoromethanesulfonic acid, which is a reaction solvent. Separating the hydration water requires an expensive process. Additionally, trifluoromethanesulfonic acid is expensive. Furthermore, in this method, due to the presence of water, a reaction occurs in which 4,4'-(dicarboxy)diphenyl ether and phenol form 4,4'-(?/phenoxycarbonyl)diphenyl ether as an intermediate, and the intermediate certain 4, 4'-
(Diphenoxycarbonyl)diphenyl ether returns to 4.4'-<dicarboxy)diphenyl ether and phenol through a hydrolysis reaction.
As a result, the yield of the target product, 4,4'-(parahydroxybenzoyl)diphenyl ether, is low.
〔間趙点を解決するための手段及び作用〕そこで本発明
者らは、４．４’−（パラヒドロキシベンゾイル）ジフ
ェニルエーテルを反応速度が速く、高収率で製造でキ、
シかも、目的とする生成物と反応媒体との分離が容易で
あって、反応媒体の再使用が容易である方法を開発すべ
く鋭意検討した結果、本発明を完成するに至った。[Means and effects for solving the problem of the Zhao point] Therefore, the present inventors have developed a method for producing 4,4'-(parahydroxybenzoyl)diphenyl ether with a high reaction rate and high yield.
However, as a result of intensive studies to develop a method that allows easy separation of the desired product from the reaction medium and easy reuse of the reaction medium, the present invention has been completed.
すなわち本発明は、液状７フ化水素の存在下に４．４’
−（シフエノキシカルボニル）ジフェニルエーテルを温
度−２０〜８０℃で、７リ一ス転位させることｔ−特徴
とする４、４’−（パラヒドロキシベンゾイル）ジフェ
ニルエーテルの製造方法である。That is, in the present invention, 4.4'
- A method for producing 4,4'-(parahydroxybenzoyl) diphenyl ether, characterized by subjecting (siphenoxycarbonyl) diphenyl ether to 7 Lith rearrangement at a temperature of -20 to 80°C.
発明の方法を形式的に示せば次のように表わされる。The method of the invention can be formally expressed as follows.
従って本発明の方法では、４．４’−（シフエノキシカ
ルボニル）ジフェニルエーテルの７リ一ス転位反応の反
応媒体として特定の反応媒体、すなわち液状７ツ化水素
を用い、さらＫａ度−２０〜８０℃で反応させることに
よって、４．４’−（パラヒドロキシベンゾイル）ジフ
ェニルエーテルが、反応速度が速く、高収率で得られる
ことが特徴である。Therefore, in the method of the present invention, a specific reaction medium, that is, liquid hydrogen heptathide, is used as the reaction medium for the 7-lis rearrangement reaction of 4,4'-(siphenoxycarbonyl)diphenyl ether, and the Ka degree is -20 to By reacting at 80°C, 4,4'-(parahydroxybenzoyl)diphenyl ether is characterized by a fast reaction rate and a high yield.
さらに本発明の方法では、水が全く副生じない上に液状
７ツ化水素は常圧で約２０℃の沸点を有していることか
ら、該液状フッ化水素は蒸留によって反応生成物から容
易に分離でき、回収・再使用が容易にできることも特徴
である。しかも安価であるのでさらに有利である。Furthermore, in the method of the present invention, water is not produced as a by-product at all, and liquid hydrogen heptadide has a boiling point of about 20°C at normal pressure. Therefore, liquid hydrogen fluoride can be easily extracted from the reaction product by distillation. Another feature is that it can be separated into two parts, making it easy to collect and reuse. Moreover, it is further advantageous because it is inexpensive.
本発明に用いる４、４’−（ジフェノキシカルボニル）
ジフェニルエーテルは、遷移金属化合物を含有する触媒
の存在下、４ 、４’−ゾジードジ７ユニルエーテル又
ハ４．４’−シフロムジフェニルエーテルにフェノール
と一酸化炭素とを反応させることによシ製造される。4,4'-(diphenoxycarbonyl) used in the present invention
Diphenyl ether is produced by reacting 4,4'-zozido di7unyl ether or 4,4'-sifurom diphenyl ether with phenol and carbon monoxide in the presence of a catalyst containing a transition metal compound. .
得られた４、４’−（シフエノキシカルボニル）ジフェ
ニルエーテルは、反応液の蒸留、抽出、再結晶等の通常
の方法によシ単隙・精製され、本反応の原料に供せられ
る。The obtained 4,4'-(siphenoxycarbonyl)diphenyl ether is purified to a single point by a conventional method such as distillation of the reaction solution, extraction, recrystallization, etc., and is used as a raw material for this reaction.
本発明？！−実施するに当り、４．４’−（パラヒドロ
キシベンゾイル）ジフェニルエーテルｔＡ収率で得るた
めに反応温度は一２０〜８０℃で行な５ことが好ましい
が、さらに好ましくは０〜５０℃の範囲内である。Invention? ! - In order to obtain a high yield of 4.4'-(parahydroxybenzoyl)diphenyl ether tA, the reaction temperature is preferably -20 to 80°C, more preferably in the range of 0 to 50°C. It is within.
本ＩＡ、４ 、４’−（ジフェノキシカルボニル）ジフ
ェニルエーテルの７リ一ス転位反応においては、温度が
一２０℃より低い場合では、該４．４’−（シフエノキ
シカルボニル）ジフェニルエーテルの反応率が極端に下
がる。また、温度８０℃を越えると、４．４’−（オル
トヒｒロキシベンゾイル）ジフェニルエーテル等の副生
物のために、目的とする４、４’−（パラヒドロキシベ
ンゾイル）ジフェニルエーテルの選択率が下がる。In the present IA, 4, 7 Lith rearrangement reaction of 4'-(diphenoxycarbonyl) diphenyl ether, when the temperature is lower than 120°C, the reaction rate of the 4,4'-(siphenoxycarbonyl) diphenyl ether is drops dramatically. Moreover, when the temperature exceeds 80°C, the selectivity of the target 4,4'-(parahydroxybenzoyl) diphenyl ether decreases due to by-products such as 4,4'-(orthohydroxybenzoyl) diphenyl ether.
本発明の方法において、液状フッ化水素と４゜４’−（
？／フェノキシカルボニル）ジフェニルエーテルの量比
は、通常、４．４’−（シフエノキシカルボニル）ジフ
ェニルエーテル１モル当Ｄ、７ツ化水素が１〜１０００
モルの範囲で実施される。In the method of the present invention, liquid hydrogen fluoride and 4°4'-(
? /phenoxycarbonyl)diphenyl ether is usually 4.4'-(siphenoxycarbonyl)diphenyl ether per mole of D and hydrogen heptaternide of 1 to 1000.
Performed in the molar range.
液状フツ化水素ｔ−溶媒ｔ−兼ねる反応媒体として用い
ることも好ましい方法である。また、必要に応じて反応
に悪影響を及ぼさない、本反応に対して、実質的に不活
性な溶媒音用いて笑施することもできる。It is also a preferable method to use liquid hydrogen fluoride as a reaction medium that also serves as a solvent. Furthermore, if necessary, a substantially inert solvent may be used for this reaction without adversely affecting the reaction.
このような溶媒としては例えば、ペンタン、ヘキサン、
ヘゾタン、オクタン、ノナン、デカン、ｎ−へキサデカ
ン、シクロペンタン、シクロヘキサンなどの脂肪族また
は脂環族炭化水素類；クロロホルム、塩化メチレン、四
塩化炭素、ジクロルエタン、トリクロルエタン、テトラ
クロルエタン、クロルペンゼ／、ジクロルベンゼン、ブ
ロムベンゼン、ブロムナフタリンなどのノ・ロダン化炭
化水素類； ベンゼン、トルエン、キシレン、エチルベ
ンゼンなどの芳香族炭化水素類；ニトロベンゼン、ニト
ロトルエンなどの芳香族ニトロ化合物類；スルホラン、
３−メチルスルホラン、２，４−ジメチルスルホランな
どのスルホラン類；酢酸、ゾロピオン酸、モノクロル酢
酸、ジクロル酢酸、フルオロ酢酸、ジフルオロ酢酸、ト
リフルオロ酢酸などのカルボン酸類などが用いられる。Examples of such solvents include pentane, hexane,
Aliphatic or alicyclic hydrocarbons such as hezotane, octane, nonane, decane, n-hexadecane, cyclopentane, cyclohexane; chloroform, methylene chloride, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, chlorpenze/, Rodanized hydrocarbons such as dichlorobenzene, bromobenzene, and bromnaphthalene; Aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; Aromatic nitro compounds such as nitrobenzene and nitrotoluene; Sulfolane,
Sulfolanes such as 3-methylsulfolane and 2,4-dimethylsulfolane; carboxylic acids such as acetic acid, zolopionic acid, monochloroacetic acid, dichloroacetic acid, fluoroacetic acid, difluoroacetic acid, and trifluoroacetic acid, and the like are used.
また、本発明方法の反応時間は、反応温度、液状フッ化
水素の量、他の溶媒の有無及び量、反応方法などの他の
反応条件によって異なるが、通常数分〜数十時間である
。Further, the reaction time of the method of the present invention varies depending on other reaction conditions such as the reaction temperature, the amount of liquid hydrogen fluoride, the presence/absence and amount of other solvents, and the reaction method, but is usually from several minutes to several tens of hours.
ｆ７’？、本発明の反応方式としては、特に制限はなく
、回分式、連続式、牛連続式、及びこれらを組合わせ九
ものなど、どのような方式でもよく、反応装置も特に制
限されるものではない。f7'? The reaction method of the present invention is not particularly limited, and any method may be used, such as a batch method, a continuous method, a cow continuous method, and nine combinations thereof, and the reaction apparatus is not particularly limited. .
以上述べてきた様に、本発明によれば、−４、４’−（
シフエノキシカルボニル）ジフェニルエーテルの７リ一
ス転位反応の反応媒体として液状フッ化水素を用い、さ
らに温度−２０℃〜８０℃で反応させることによって、
４．４’−（シフエノキシカルボニル）ジフェニルエー
テルの反応時間が従来、数日間要したものが数十時間以
内に短縮され、４．４’−（パラヒドロキシベンゾイル
）ジフエニ ・ルエーテルが高収率で得られる。As described above, according to the present invention, -4, 4'-(
By using liquid hydrogen fluoride as the reaction medium for the 7-liss rearrangement reaction of (siphenoxycarbonyl) diphenyl ether, and further reacting at a temperature of -20°C to 80°C,
The reaction time for 4.4'-(siphenoxycarbonyl) diphenyl ether, which conventionally required several days, has been shortened to within tens of hours, and 4.4'-(parahydroxybenzoyl) diphenyl ether can be produced in high yield. can get.
さらに本発明の方法では、水が全く副生しないことから
、反応媒体である液状７ツ化水素は、蒸留によって反応
生成物から容易に分離でき、回収・再使用が安働で容易
にできる。Furthermore, in the method of the present invention, since no water is produced as a by-product, liquid hydrogen heptadide, which is a reaction medium, can be easily separated from the reaction product by distillation, and recovery and reuse can be performed safely and easily.
以下、実施例によｐ本発明をさらに説明するが、本発明
はこれらの実施例に限定されるものではない。The present invention will be further explained below with reference to Examples, but the present invention is not limited to these Examples.
実施例１
４．４’−（シフエノキシカルボニル）ゾ７工二ルエー
テル２５１１液状フッ化水素１５０ｇを還流冷却器付？
リエチレーン製フラスコに入れ、攪拌下−１０〜０℃で
２０時間、反応させた。反応後２０〜４０℃に上げ、液
状フッ化水゛素を蒸留によって回収した。得られ九残渣
を少量の希アルカリ水及び、ＷｗＩ水で洗浄した後、減
圧下に乾燥しな。Example 1 150 g of 4.4'-(siphenoxycarbonyl)zo7-dyl ether 2511 liquid hydrogen fluoride with a reflux condenser?
The mixture was placed in a Liethylane flask and reacted with stirring at -10 to 0°C for 20 hours. After the reaction, the temperature was raised to 20-40°C, and liquid hydrogen fluoride was recovered by distillation. The resulting residue was washed with a small amount of dilute alkaline water and WWI water, and then dried under reduced pressure.
生成物をガスクロマトグラフィー、液体クロマトグラフ
ィー、ＮＭＲにて分析し九結果、４．４’−（シフエノ
キシカルボニル）ジフェニルエーテルの反応率は、９８
％で、４．４’−（パラヒドロキシベンゾイル）ジフェ
ニルエーテルが収率９６ ％。The product was analyzed by gas chromatography, liquid chromatography, and NMR, and the reaction rate of 4.4'-(siphenoxycarbonyl)diphenyl ether was 98.
%, yield of 4.4'-(parahydroxybenzoyl)diphenyl ether is 96%.
選択ｙ４９８％で生成していた。異性体である４゜４’
−（オルトヒドロキシベンゾイル）ジフェニルエーテル
は、選択率２俤しか検出されなかった。It was generated with selection y498%. 4゜4' which is an isomer
-(Orthohydroxybenzoyl)diphenyl ether was detected with a selectivity of only 2.
また、液状フッ化水素の回収率は９８％であった。Moreover, the recovery rate of liquid hydrogen fluoride was 98%.
実施例２
実施例１で回収した液状フッ化水素１００９．４．４’
−（シフエノキシカルボニル）ジフェニルエーテル２０
９’ｌ用い実施例１と同様な方法により、−１０〜０“
Ｃで２００時間反応せた結果、４．４’−（シフエノキ
シカルボニル）ジフェニルエーテルの反応率は９８％で
、４．４’−（パラヒドロキシベンゾイル）ジフェニル
エーテルカ収率９７鋒で得られた。Example 2 Liquid hydrogen fluoride recovered in Example 1 1009.4.4'
-(siphenoxycarbonyl)diphenyl ether 20
-10 to 0" by the same method as in Example 1 using 9'l
As a result of the reaction at C for 200 hours, the reaction rate of 4.4'-(siphenoxycarbonyl)diphenyl ether was 98%, and the yield of 4.4'-(parahydroxybenzoyl)diphenyl ether was 97%.
実施例３
４．４’−（シフエノキシカルボニル）゛ジフェニルエ
ーテル２５ｇ１液状７ツ化水素ｉ ｓｏｇｔ−８ＵＳ製
オートクレーブに入れ、攪拌下５０℃で５時間反応させ
た。反応後、系内ｔ５０℃まで下げ、オートクレーブの
パルプｔ−開放し液状フッ化水素金回収した。得られた
残渣を少量の希アルカリ水及び蒸留水で洗浄した後、減
圧下に乾燥した。Example 3 25 g of 4.4'-(siphenoxycarbonyl)diphenyl ether and 1 liquid hydrogen heptafluoride was placed in a sogt-8 US autoclave and reacted at 50° C. for 5 hours with stirring. After the reaction, the temperature inside the system was lowered to 50° C., and the autoclave was opened to recover liquid hydrogen fluoride gold. The resulting residue was washed with a small amount of dilute alkaline water and distilled water, and then dried under reduced pressure.
生成物を分析した結果、４．４’−（シフエノキシカル
ボニル）ジフェニルエーテルの反応”１Ｆ−１ａ９９％
で、４．４’−（パラヒドロキシベンゾイル）ジフェニ
ルエーテルが選択率９７％で得られ次。As a result of analyzing the product, the reaction of 4.4'-(siphenoxycarbonyl)diphenyl ether"1F-1a99%
Then, 4.4'-(parahydroxybenzoyl)diphenyl ether was obtained with a selectivity of 97%.
Claims (1)
テルを液状フッ化水素の存在下に、温度−２０〜８０℃
で処理することを特徴とする４，４′−（パラヒドロキ
シベンゾイル）ジフェニルエーテルの製造法。4,4'-(diphenoxycarbonyl)diphenyl ether in the presence of liquid hydrogen fluoride at a temperature of -20 to 80°C.
A method for producing 4,4'-(parahydroxybenzoyl)diphenyl ether, which comprises treating with.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61075591A JPS62234042A (en) | 1986-04-03 | 1986-04-03 | Production of 4,4'-(p-hydroxybenzoyl)diphenyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61075591A JPS62234042A (en) | 1986-04-03 | 1986-04-03 | Production of 4,4'-(p-hydroxybenzoyl)diphenyl ether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62234042A true JPS62234042A (en) | 1987-10-14 |
Family
ID=13580593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61075591A Pending JPS62234042A (en) | 1986-04-03 | 1986-04-03 | Production of 4,4'-(p-hydroxybenzoyl)diphenyl ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62234042A (en) |
-
1986
- 1986-04-03 JP JP61075591A patent/JPS62234042A/en active Pending
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