JPS591444A - Preparation of bis(2-chloro-4-trifluoromethylphenyl) carbonate - Google Patents
Preparation of bis(2-chloro-4-trifluoromethylphenyl) carbonateInfo
- Publication number
- JPS591444A JPS591444A JP57109965A JP10996582A JPS591444A JP S591444 A JPS591444 A JP S591444A JP 57109965 A JP57109965 A JP 57109965A JP 10996582 A JP10996582 A JP 10996582A JP S591444 A JPS591444 A JP S591444A
- Authority
- JP
- Japan
- Prior art keywords
- carbonate
- bis
- trifluoromethylphenyl
- raw material
- chloro
- 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
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、ビス（４−トリフルオロメチルフェニル）カ
ーボネートの２位を選択的忙核塩素化することによって
、ビス（２−クロロ−４−トリフルオロメチルフェニル
）カーボネートを製ａする新規な方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides bis(2-chloro-4-trifluoromethylphenyl) carbonate by selectively chlorinating the 2-position of bis(4-trifluoromethylphenyl) carbonate. This invention relates to a novel method for producing a.
ビス（２−クロロ−４−トリフルオロメチルフェニル）
カーボネートは、医薬、染料および最近特に農薬の製造
原料として注目されている有用な化合物である。Bis(2-chloro-4-trifluoromethylphenyl)
Carbonates are useful compounds that have recently attracted attention as raw materials for the production of pharmaceuticals, dyes, and especially agricultural chemicals.
従来、ビス（２−クロロ−４−トリフルオロメチルフェ
ニル）カーボネートの合成法としては、ドイツ特許１．
２５７．７８４号公報に、トリフルオロメチルフェノー
ル類製造のＩａ駆体として、ヒス（２−クロロ−４−）
ＩＪ クロロメチルフェニル）カーボネー）１無水フ
ツ化水素酸（以下ＨＦと略称）と反応させ、ビス（２−
クロロ−４−トリフルオロフェニル）、カーボネートを
得る方法が記載されている。Conventionally, as a method for synthesizing bis(2-chloro-4-trifluoromethylphenyl) carbonate, German Patent No. 1.
No. 257.784 discloses that his(2-chloro-4-) is used as an Ia precursor for the production of trifluoromethylphenols.
IJ (chloromethylphenyl)carbonate) 1 was reacted with hydrofluoric anhydride (hereinafter abbreviated as HF) to form bis(2-
A method for obtaining chloro-4-trifluorophenyl), carbonate is described.
しかしこの方法は、出発原料となるビス（２−クロロ−
４−） ＩＪジクロロチルフェニル）カーボネートを得
るための２−クロロ−４−メチルフェノールは工業的に
入手が不可能な現状である。However, this method uses bis(2-chloro-
4-) 2-chloro-4-methylphenol for obtaining IJ dichlorotylphenyl) carbonate is currently not available industrially.
直接核塩素化反応によってビス（２−クロロ−４−トリ
フルオロメチルフェニル）カーボネートを得る方法につ
いてはこれまで全く報告されていない。There has been no report on a method for obtaining bis(2-chloro-4-trifluoromethylphenyl) carbonate by direct nuclear chlorination reaction.
本発明者等はこうした現状に鑑み工業化可能な製造法を
見い出すべく種々検討した結果、驚くベキコとに、ビス
（４−）リフルオロメチルフェニル）カーボネートを核
塩素化することにより、異性体および塩素置換数の異な
る副生成物を殆んど生成させずに、選択的にベンゼン核
の２位に、塩素ｆｔ換したビス（２−クロロ−４−トリ
フルオロことを見い出し本発明を完成した。In view of the current situation, the present inventors conducted various studies in order to find a production method that can be industrialized, and were surprised to discover that by nuclear chlorination of bis(4-)lifluoromethylphenyl) carbonate, isomers and chlorine The present invention was completed by discovering that bis(2-chloro-4-trifluoro) is selectively substituted with chlorine at the 2-position of the benzene nucleus without producing any by-products with different numbers of substitutions.
すなわち本発明は、ビス（４−トリフルオロメチルフェ
ニル）カーボネートを不活性有機溶剤に溶解し、ルイス
酸触媒存在下に塩素ガスと反応させ１選択的にビス（２
−クロロ−４−トリフルオロメチルフェニル）カーボネ
ートを得ることを特徴とするビス（２−クロロ−４−ト
リフルオロメチルフェニル）カーボネートの製造法であ
る。That is, in the present invention, bis(4-trifluoromethylphenyl) carbonate is dissolved in an inert organic solvent and reacted with chlorine gas in the presence of a Lewis acid catalyst to selectively produce bis(2).
This is a method for producing bis(2-chloro-4-trifluoromethylphenyl) carbonate, which is characterized by obtaining -chloro-4-trifluoromethylphenyl) carbonate.
本発明の出発原料であるビス（４−トリフルオロメチル
フェニル）カーボネートは、４−メチルフェノールをホ
スゲンまたはトリクロロメチルクロロホーメートと反応
させ、ビス（４−メチルフェニル）カーボネートとし１
次いで側鎖塩素化し、得られたビス（４−トリクロロメ
チルフェニル）゛カーボネートをＨＦでフッ素化する通
常の方法で容易に高収率で得ることが出来る。Bis(4-trifluoromethylphenyl) carbonate, which is the starting material of the present invention, is produced by reacting 4-methylphenol with phosgene or trichloromethyl chloroformate to form bis(4-methylphenyl) carbonate.
Next, the side chain is chlorinated, and the resulting bis(4-trichloromethylphenyl)carbonate is fluorinated with HF, which can be easily obtained in a high yield by a conventional method.
本発明に使用される不活性有機溶媒としては、例えば四
塩化炭素、１，１．１− ）リクロロエタン、１．１．
２．２−テトラクロロエタン、ペンタクロロエタン、フ
゛ロモホルム、１．２−シフ゛ロモエタン、ニトロベン
ゼンなどがあげられる。Examples of the inert organic solvent used in the present invention include carbon tetrachloride, 1,1.1-)lichloroethane, 1.1.
Examples include 2.2-tetrachloroethane, pentachloroethane, fluoroform, 1.2-cyfuromoethane, and nitrobenzene.
不活性有機溶剤の蓄はビス（４−トリフルオロメチルフ
ェニル）カーボネートを溶解し、均−系で反応を進める
ことができる量の２〜２０重舊部が用いられる。The amount of inert organic solvent used is from 2 to 20 parts, which is sufficient to dissolve bis(4-trifluoromethylphenyl) carbonate and allow the reaction to proceed homogeneously.
ビス（４−）リフルオロメチルフェニル）カーボネート
は上記溶媒に溶解させ、次いでルイス酸触媒を添加し、
この混合液中に塩素ガスを導入して反応を行なうが、ル
イス酸触媒としては例えば。Bis(4-)lifluoromethylphenyl) carbonate is dissolved in the above solvent, then a Lewis acid catalyst is added,
Chlorine gas is introduced into this mixed solution to carry out the reaction, and as a Lewis acid catalyst, for example.
ＡｔＣ２Ｂ、ＦｅＣｌ３．５ｂｃｚ３．５ｂｃｔ、、８
ｎ（１４、ＴａＣ４、Ｎｄｃｔ、、ＭｏＣｔｌ、、Ｍｏ
Ｆ３ 、 ＳｂＦ５などがあげられる。AtC2B, FeCl3.5bcz3.5bct, 8
n(14, TaC4, Ndct, , MoCtl, , Mo
Examples include F3 and SbF5.
しくはｃＬ５〜１．５％である。ルイス酸触媒の添加は
分割または一括して添加することができる。Preferably, cL is 5 to 1.5%. The Lewis acid catalyst can be added in portions or all at once.
反応温度は６０〜１５０℃、好ましくは７０〜１１０℃
である。塩素ガス導入速度は、この温度な保つよう塩素
ガスの逸散をおさえることができる範囲で調節される。Reaction temperature is 60-150°C, preferably 70-110°C
It is. The rate of chlorine gas introduction is adjusted within a range that can suppress the escape of chlorine gas so as to maintain this temperature.
その導入量は、ビス（４−トリフルオロメチルフェニル
）カーボネート１モルに対して反応にあずかった塩素が
２．０モル忙なった所で終了することが収率および純度
の点で好ましい。このようにして得られたビス（２−ク
ロロ−４−トリフルオロメチルフェニル）カーボネート
は、収率９５％以上、純度９５％以上で得られ工業的に
容易かつ安価にｍ造できる。From the viewpoints of yield and purity, it is preferable that the amount of introduction be stopped at 2.0 moles of chlorine participating in the reaction per mole of bis(4-trifluoromethylphenyl) carbonate. The bis(2-chloro-4-trifluoromethylphenyl) carbonate thus obtained is obtained in a yield of 95% or more and a purity of 95% or more, and can be manufactured industrially easily and inexpensively.
以下本発明を実施例により詳細に説明する。The present invention will be explained in detail below using examples.
実施例１
温度計、コンデンサー、かきまぜ機および塩素導入管す
付した２ｔの四ツロフラスコに３５０部のビス（４−ト
リフルオロメチルフェニル）カーボネートと８７５部の
１．１，２．２−テトラクロロエタンな仕込み、かきま
ぜ下に溶解させる。この中に５５部の無水塩化第２鉄（
ＦｅＣ１ｍ ）な添加し。Example 1 350 parts of bis(4-trifluoromethylphenyl) carbonate and 875 parts of 1,1,2,2-tetrachloroethane were placed in a 2-t four-ton flask equipped with a thermometer, condenser, stirrer and chlorine inlet tube. Prepare and stir to dissolve. In this, 55 parts of anhydrous ferric chloride (
FeC1m) was added.
９５〜１００℃を保って塩素ガスを２９．８部／時間の
速度で５時間導入した。発生塩酸中の未反応塩素外は４
．７モル％であった。導入終了後、窒素抜気を１時間行
なった。反応液を室温まで冷却し、５％塩酸水および水
で洗浄後、脱水した後１，１，２゜２−テトラクロロエ
タンを留去し、４１部１部のビス（２−クロロ−４−）
ＩＪフルオロメチルフェニル）カーボネートな得た。While maintaining the temperature at 95 to 100°C, chlorine gas was introduced at a rate of 29.8 parts/hour for 5 hours. The amount of unreacted chlorine in the generated hydrochloric acid is 4.
．． It was 7 mol%. After the introduction, nitrogen was vented for 1 hour. The reaction solution was cooled to room temperature, washed with 5% hydrochloric acid and water, dehydrated, 1,1,2°2-tetrachloroethane was distilled off, and 41 parts and 1 part of bis(2-chloro-4-)
IJ fluoromethylphenyl) carbonate was obtained.
ガスクロマドクラフィーにより分析した結果、純度９９
５％、収率９９３％を得た。元素分析値は次忙示す結果
を得た。As a result of gas chromatography analysis, the purity was 99.
5%, yield of 993% was obtained. The elemental analysis values obtained showed the following results.
ＣＨＣｔＦ
理論値 ４２．９６％ １．４３％ １６．９５％ ２
１２１％実測値 ４２．９５ １．４４ １７．００
２７．２０実施例２
塩素化触媒を５ｂＣｔ５に代えた他は実施例１と同様に
反応して、４１部６部のビス（２−クロロ−４−トリフ
ルオロメチルフェニル）カーボネートを得た。ガスクロ
マトグラフィーにより分析した結果、純度９９．１％、
収率９９．０％を得た。CHCtF Theoretical value 42.96% 1.43% 16.95% 2
121% actual value 42.95 1.44 17.00
27.20 Example 2 The reaction was carried out in the same manner as in Example 1 except that the chlorination catalyst was replaced with 5bCt5 to obtain 41 parts and 6 parts of bis(2-chloro-4-trifluoromethylphenyl) carbonate. As a result of gas chromatography analysis, the purity was 99.1%.
A yield of 99.0% was obtained.
実施例３
実施例１と同じ装置を用い、６５０部のビス（４−トリ
フルオロメチルフェニル）カーボネートと１．１２０部
の四塩化炭素とを仕込み、かきまぜ下に溶解させる。こ
の中に３，５部の無水塩化第２鉄（Ｆｅｃｔａ ） ヲ
添加し、７０〜７５ｃを保って塩素ガスを７．４５部／
時間の速度で２０時間導入した。発生塩酸中の未反応塩
素弁は４，５モル％であった。以下実施し１」１と同様
に処理し、４１７．７部のビス（２−クロロ−４−）
ＩＪフルオロメチルフェニル）カーボネートを得た。Example 3 Using the same equipment as in Example 1, 650 parts of bis(4-trifluoromethylphenyl) carbonate and 1.120 parts of carbon tetrachloride are charged and dissolved with stirring. Add 3.5 parts of anhydrous ferric chloride (Fecta) to this, maintain the temperature of 70-75c, and add 7.45 parts/chlorine gas.
It was introduced at a rate of 20 hours. The amount of unreacted chlorine in the generated hydrochloric acid was 4.5 mol%. The following procedure was carried out in the same manner as in 1, and 417.7 parts of bis(2-chloro-4-)
IJ fluoromethylphenyl) carbonate was obtained.
ガスクロマトグラフィーにより分析した結果、純度９８
．８％、収率は９部５％であった。As a result of gas chromatography analysis, the purity was 98.
．． The yield was 9 parts, 5%.
保土谷化学工業林式会社Hodogaya Chemical Industrial Forest Company
Claims (1)
ートな不活性有機溶剤に溶解し、ルイス酸触媒存在下に
塩素ガスと反応させ、選択的にビス（２−クロロ−４−
）リフルオロメチルフェニル）カーボネートを得ること
を特許とするビス（２−クロロ−４−）リフルオロメチ
ルフェニル）カーボネートの製造法。Bis(2-chloro-4-
) A patented process for producing bis(2-chloro-4-)lifluoromethylphenyl)carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57109965A JPS591444A (en) | 1982-06-28 | 1982-06-28 | Preparation of bis(2-chloro-4-trifluoromethylphenyl) carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57109965A JPS591444A (en) | 1982-06-28 | 1982-06-28 | Preparation of bis(2-chloro-4-trifluoromethylphenyl) carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS591444A true JPS591444A (en) | 1984-01-06 |
| JPH0235744B2 JPH0235744B2 (en) | 1990-08-13 |
Family
ID=14523636
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57109965A Granted JPS591444A (en) | 1982-06-28 | 1982-06-28 | Preparation of bis(2-chloro-4-trifluoromethylphenyl) carbonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS591444A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2701230A4 (en) * | 2011-04-22 | 2014-10-15 | Ube Industries | NONAQUEOUS ELECTROLYTE SOLUTION, ELECTRICITY STORAGE DEVICE USING THE SAME, AND TRIFLUOROMETHYLBENZENE COMPOUND |
-
1982
- 1982-06-28 JP JP57109965A patent/JPS591444A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2701230A4 (en) * | 2011-04-22 | 2014-10-15 | Ube Industries | NONAQUEOUS ELECTROLYTE SOLUTION, ELECTRICITY STORAGE DEVICE USING THE SAME, AND TRIFLUOROMETHYLBENZENE COMPOUND |
| US9472828B2 (en) | 2011-04-22 | 2016-10-18 | Ube Industries, Ltd. | Nonaqueous electrolyte solution, electricity storage device using same, and trifluoromethylbenzene compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0235744B2 (en) | 1990-08-13 |
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