JPH09169673A - Production of 3,5-bis(trifluoromethyl)bromobenzene - Google Patents
Production of 3,5-bis(trifluoromethyl)bromobenzeneInfo
- Publication number
- JPH09169673A JPH09169673A JP33440495A JP33440495A JPH09169673A JP H09169673 A JPH09169673 A JP H09169673A JP 33440495 A JP33440495 A JP 33440495A JP 33440495 A JP33440495 A JP 33440495A JP H09169673 A JPH09169673 A JP H09169673A
- Authority
- JP
- Japan
- Prior art keywords
- bis
- trifluoromethyl
- sulfuric acid
- reaction
- brominating
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、以下の反応式で示
される１，３−ビス（トリフルオロメチル）ベンゼン
（以下、ＢＴＦＢと略記する。）をＮ−ブロムイミド型
ブロム化剤を用いて３，５ビス（トリフルオロメチル）
ブロムベンゼン（以下、ＢＴＦＢＢと略記する。）の製
造法に関する。TECHNICAL FIELD The present invention relates to the use of 1,3-bis (trifluoromethyl) benzene (hereinafter abbreviated as BTFB) represented by the following reaction formula by using an N-bromimide type brominating agent. , 5 bis (trifluoromethyl)
The present invention relates to a method for producing brombenzene (hereinafter abbreviated as BTFBB).
【０００２】[0002]
【化１】 Embedded image
【０００３】ＢＴＦＢＢは、近年医薬・農薬等に代表さ
れる有機化学品の中間体として重要になって来ている。BTFBB has recently become important as an intermediate for organic chemicals represented by pharmaceuticals and agricultural chemicals.
【０００４】[0004]
【従来の技術】これまで、ＢＴＦＢＢを得た例は、次の
２例がある。 ブルティン・オブ・ケミカル・ソサイヤティ・ジャパ
ン１９８８年６１巻５号１６２５−３１頁（Ｂｕｌｌ．
Ｃｈｅｍ．Ｓｏｃ．Ｊｐｎ．（１９８８），６１
（５），１６２５−３１）；原料ＢＴＦＢをリチオ化し
た後に臭素によってブロム化する方法。この方法では、
１−ブロム−２，４−，−２，６−，−３，５−ビス
（トリフルオロメチル）ベンゼンが、それぞれ３５，３
１，８％の収率で得られた。即ち、目的とするＢＴＦＢ
Ｂの収率は、わずかでありかつ高価なリチオ化を経てい
る。2. Description of the Related Art There are the following two examples of obtaining BTFBB. Bulletin of Chemical Society Japan 1988 Vol. 61 No. 5 1625-31 (Bull.
Chem. Soc. Jpn. (1988), 61.
(5), 1625-31); A method of brominating with bromine after lithiating the raw material BTFB. in this way,
1-Brom-2,4-,-2,6-,-3,5-bis (trifluoromethyl) benzene are respectively 35,3
Obtained in a yield of 1.8%. That is, the target BTFB
The yield of B has undergone a slight and expensive lithiation.
【０００５】ゼェ・プリクル・キィム１９７３年４６
巻９号２０１２−１６頁（Ｚｈ．Ｐｒｉｋｌ．Ｋｈｉ
ｍ．（１９７３），４６（９），２０１２−１６）ＢＴ
ＦＢを５塩化アンチモンの存在下オートクレーブ中高温
高圧の臭化塩素によって反応させ、（転化率不明）選択
率で７４．１％のＢＴＦＢＢと２４．６％の３，５−ビ
ス（トリフルオロメチル）クロルベンゼンを得ている。
この方法では、高価な耐酸性用オートクレーブが必要で
あり、また５塩化アンチモンの廃棄処理の問題、さら
に、副生するクロル化物の分離精製の問題も抱え実用的
方法とはなり得ない。Ze Purikle Kim 1973 46
Volume 9, Pages 2012-16 (Zh. Prikl. Khi
m. (1973), 46 (9), 2012-16) BT
FB was reacted with chlorine bromide at high temperature and high pressure in an autoclave in the presence of antimony pentachloride, and the selectivity (conversion unknown) was 74.1% BTFBB and 24.6% 3,5-bis (trifluoromethyl). You are getting chlorobenzene.
This method requires an expensive acid-resistant autoclave, has a problem of waste disposal of antimony pentachloride, and has a problem of separation and purification of a chlorinated product produced as a by-product, and cannot be a practical method.
【０００６】[0006]
【発明が解決しようとする課題】高価な反応装置を用い
ず、かつ温和な反応条件で反応を行うことができ、また
多量の廃金属がなく、高収率でＢＴＦＢＢを生成する製
造法の提供を目的とする。DISCLOSURE OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION It is possible to carry out the reaction under mild reaction conditions without using an expensive reactor, and to provide a production method for producing BTFBB in a high yield without a large amount of waste metal. With the goal.
【０００７】[0007]
【課題を解決するための手段】本発明者は、簡便でかつ
温和な反応条件で、ＢＴＦＢＢを高収率で得られる条件
を鋭意検討した結果、濃度８１％以上の硫酸の存在下に
Ｎ−ブロムイミド型ブロム化剤を用いてブロム化するこ
とにより高収率で目的とするＢＴＦＢＢを得ることがで
きることを見出し、本発明を完成させた。Means for Solving the Problems The present inventor diligently studied the conditions for obtaining BTFBB in a high yield under simple and mild reaction conditions, and as a result, N-in the presence of sulfuric acid having a concentration of 81% or more, We have found that the desired BTFBB can be obtained in high yield by brominating using a bromimide type brominating agent, and completed the present invention.
【０００８】即ち、本発明は、１，３−ビス（トリフル
オロメチル）ベンゼンを濃度８５％以上の硫酸の存在下
に、Ｎ−ブロムイミド型ブロム化剤を用いることを特徴
とする３，５−ビス（トリフルオロメチル）ブロムベン
ゼンの製造法に関する。That is, the present invention is characterized in that an N-bromimide type brominating agent is used in the presence of sulfuric acid having a concentration of 85% or more and 1,3-bis (trifluoromethyl) benzene. It relates to a method for producing bis (trifluoromethyl) bromobenzene.
【０００９】[0009]
【発明の実施の形態】以下、本発明を詳細に説明する。
まず原料の１，３−ビス（トリフルオロメチル）ベンゼ
ンは、通常入手できる純度のものをそのまま使用でき
る。本発明の第１の特徴は、ブロム化剤である。下記構
造式で表されるＮ−ブロムイミド型ブロム化剤を用いる
ところにある。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
First, as the raw material 1,3-bis (trifluoromethyl) benzene, a commercially available one having a purity that is generally available can be used as it is. The first feature of the present invention is a brominating agent. An N-bromimide type brominating agent represented by the following structural formula is used.
【００１０】[0010]
【化２】 Embedded image
【００１１】具体的には、Ｎ−ブロムサクシイミド、Ｎ
−ブロムグルタルイミド、１，３−ジブロム−５，５−
ジメチルヒダントイン、Ｎ，Ｎ′，Ｎ″−トリブロムイ
ソシアヌール酸、Ｎ，Ｎ′−ジブロムイソヌール酸ナト
リウム及びＮ，Ｎ′−ジブロムイソシアヌール酸カリウ
ムを挙げることができる。これらの中で、入手容易なＮ
−ブロムサクシイミドが特に好ましい。Specifically, N-bromosuccinimide, N
-Brom glutarimide, 1,3-dibromo-5,5-
Mention may be made of dimethylhydantoin, N, N ', N "-tribrom isocyanuric acid, sodium N, N'-dibromo isocyanurate and potassium N, N'-dibromo isocyanurate. , Easily available N
-Bromsuccinimide is particularly preferred.
【００１２】その使用量は、原料ＢＴＦＢに対し、ブロ
ム原子で当量以上あれば充分であり、通常１．０〜１．
５当量使用するのが好ましい。次に本発明の第２の特徴
は、溶媒にある。即ち濃度８５％以上の硫酸から１１０
％硫酸（三酸化硫黄濃度が１０％までの発煙硫酸）を用
いることことができる。発煙硫酸を用いると副生物が生
成する場合もあり、好ましくは硫酸濃度９０％より１０
０％で迅速にかつ選択的に目的とするＢＴＦＢＢが得ら
れる。より好ましい硫酸濃度は９５％から１００％であ
る。硫酸濃度８５％未満では、反応速度が遅くなり好ま
しくない。The amount used is sufficient if the amount of bromine atoms is equal to or more than that of the raw material BTFB, and it is usually 1.0 to 1.
It is preferable to use 5 equivalents. Next, the second feature of the present invention lies in the solvent. That is, from sulfuric acid with a concentration of 85% or more,
% Sulfuric acid (fuming sulfuric acid with a sulfur trioxide concentration of up to 10%) can be used. When fuming sulfuric acid is used, a by-product may be generated, and it is preferable that the concentration of sulfuric acid is 90% to 10
At 0%, the desired BTFBB can be obtained rapidly and selectively. A more preferable sulfuric acid concentration is 95% to 100%. If the sulfuric acid concentration is less than 85%, the reaction rate becomes slow, which is not preferable.
【００１３】その使用量は、原料ＢＴＦＢに対し１〜５
０重量部が好ましい。使用量が多い方が原料ＢＴＦＢ及
びブロム化剤が溶解するところから反応が速くなるが、
経済的には、通常３〜１０重量倍の範囲で行うのが好ま
しい。本反応の反応温度は、−１０〜１００℃間で行う
のが好ましいが、特には０〜７０℃間がＢＴＦＢＢの選
択性と転化率との兼合いから好ましい。The amount used is 1 to 5 with respect to the raw material BTFB.
0 parts by weight is preferred. The higher the amount used, the faster the reaction because the raw material BTFB and the brominating agent are dissolved.
Economically, it is usually preferable to carry out the treatment in a range of 3 to 10 times by weight. The reaction temperature of this reaction is preferably from -10 to 100 ° C, and particularly preferably from 0 to 70 ° C in view of the selectivity of BTFBB and the conversion rate.
【００１４】反応時間は、ガスクロマトグラフィー又は
液体クロマトガラフィー等で反応進跡することにより決
定することができる。反応終了後は、反応液の有機分を
有機溶媒で抽出した後、水洗、濃縮してから蒸留するこ
とにより目的生成物ＢＴＦＢＢを得ることができる。以
下、実施例によってさらに具体的に説明するが、本発明
は、これらによって限定されるものではない。The reaction time can be determined by tracing the reaction by gas chromatography or liquid chromatography. After completion of the reaction, the target product BTFBB can be obtained by extracting the organic content of the reaction solution with an organic solvent, washing with water, concentrating and distilling. Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.
【００１５】実施例１ １，３−ビス（トリフルオロメチル）ベンゼン（ＢＴＦ
Ｂ）１０．７ｇ（５０ｍｍｏｌ）、Ｎ−ブロムサクシイ
ミド９．８ｇ（５５ｍｍｏｌ）及び９７％硫酸５３．５
ｇを反応フラスコに仕込み４０℃で６時間３０分攪拌し
た。反応終了後、室温に戻してから１，２−ジクロロエ
タン（ＥＤＣ）で抽出した。このＥＤＣ層を水洗、１０
％ＮａＯＨ水溶液洗さらに水洗を行った後、芒硝で脱水
した。その後この含水芒硝をろ別後ＥＤＣ溶液を蒸留に
供した。常圧で１５１〜１５２℃の主留分９．８ｇが得
られた。Example 1 1,3-bis (trifluoromethyl) benzene (BTF
B) 10.7 g (50 mmol), N-bromosuccinimide 9.8 g (55 mmol) and 97% sulfuric acid 53.5.
g was placed in a reaction flask and stirred at 40 ° C. for 6 hours and 30 minutes. After completion of the reaction, the temperature was returned to room temperature and then extracted with 1,2-dichloroethane (EDC). Wash this EDC layer with water, 10
After being washed with an aqueous solution of 10% NaOH and further washed with water, it was dehydrated with sodium sulfate. Then, the water-containing Glauber's salt was filtered off, and the EDC solution was subjected to distillation. 9.8g of main distillates of 151-152 degreeC were obtained at normal pressure.
【００１６】この主留分を、ＭＡＳＳ及び 1Ｈ−ＮＭＲ
から分析の結果、目的とする１，３−ビス（トリフルオ
ロメチル）ブロムベンゼン（ＢＴＦＢＢ）であることを
確認した。なお、反応直後のＥＤＣ抽出液をガスクロマ
トグラフィー内標法で定量した結果、ＢＴＦＢＢ収率は
９２．１％であった。This main fraction was subjected to MASS and 1 H-NMR.
As a result of analysis, it was confirmed that the target substance was 1,3-bis (trifluoromethyl) brombenzene (BTFBB). The EDC extract immediately after the reaction was quantified by the gas chromatography internal standard method, and as a result, the BTFBB yield was 92.1%.
【００１７】実施例２〜６及び比較例１〜３ 実施例１に於て、Ｎ−ブロムサクシイミド（ＮＢＳ）、
溶媒、温度及び時間等を変えて、反応を行い、得られた
反応液からＥＤＣ抽出し、ＥＤＣ溶液を内標法で定量し
た結果を、次表に示す。尚、原料のＢＴＦＢは、2.14ｇ
(10mmol)を用いた。Examples 2 to 6 and Comparative Examples 1 to 3 In Example 1, N-bromosuccinimide (NBS),
The following table shows the results of carrying out the reaction by changing the solvent, temperature, time and the like, extracting the reaction solution by EDC, and quantifying the EDC solution by the internal standard method. The raw material BTFB is 2.14 g.
(10 mmol) was used.
【００１８】[0018]
【表１】 [Table 1]
【００１９】実施例７ ＢＴＦＢ２．１４ｇ（１０ｍｍｏｌ）、Ｎ，Ｎ′，Ｎ″
−トリブロムイソシアヌール酸１．８ｇ（５ｍｍｏｌ）
及び９７％硫酸１２ｇを４０℃で５時間攪拌した。この
反応液を室温に戻してからＥＤＣ抽出し、得られたＥＤ
Ｃ溶液を定量した。未反応ＢＴＦＢ３２．０％、生成Ｂ
ＴＦＢＢ収率５１．１％であった。Example 7 2.14 g (10 mmol) of BTFB, N, N ', N "
-Tribrom isocyanuric acid 1.8 g (5 mmol)
And 12 g of 97% sulfuric acid were stirred at 40 ° C. for 5 hours. The reaction solution was returned to room temperature and then EDC extracted to obtain the ED
The C solution was quantified. Unreacted BTFB 32.0%, product B
The TFBB yield was 51.1%.
【００２０】[0020]
【発明の効果】濃度８１％以上の硫酸の存在下にＮ−ブ
ロムイミド型ブロム化剤を用いて、１，３−ビス（トリ
フルオロメチル）ベンゼンをブロム化することにより高
収率で、３，５−ビス（トリフルオロメチル）ブロムベ
ンゼンを得ることができる。EFFECTS OF THE INVENTION By brominating 1,3-bis (trifluoromethyl) benzene with an N-bromimide type brominating agent in the presence of sulfuric acid having a concentration of 81% or more, a high yield of 3,3-bis (trifluoromethyl) benzene can be obtained. 5-bis (trifluoromethyl) bromobenzene can be obtained.
Claims (3)
ンゼンを濃度８５％以上の硫酸の存在下に、Ｎ−ブロム
イミド型ブロム化剤を用いることを特徴とする３，５−
ビス（トリフルオロメチル）ブロムベンゼンの製造法。1. An N-bromimide type brominating agent is used in the presence of sulfuric acid containing 1,3-bis (trifluoromethyl) benzene at a concentration of 85% or more.
Process for producing bis (trifluoromethyl) brombenzene.
ブロムサクシイミド、Ｎ−ブロムグルタルイミド、１，
３−ジブロム−５，５−ジメチルヒダントイン又はＮ，
Ｎ′，Ｎ″−トリブロムイソシアヌール酸であることを
特徴とする請求項１記載の３，５−ビス（トリフルオロ
メチル）ブロムベンゼンの製造法。2. The method according to claim 1, wherein the N-bromoimide type brominating agent is N-bromoimide.
Bromsuccinimide, N-bromoglutarimide, 1,
3-dibromo-5,5-dimethylhydantoin or N,
The method for producing 3,5-bis (trifluoromethyl) bromobenzene according to claim 1, which is N ', N "-tribromoisocyanuric acid.
とする請求項１又は請求項２記載の３，５−ビス（トリ
フルオロメチル）ブロムベンゼンの製造法。3. The method for producing 3,5-bis (trifluoromethyl) bromobenzene according to claim 1 or 2, wherein the reaction temperature is 0 to 70 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33440495A JP3806962B2 (en) | 1995-12-22 | 1995-12-22 | Method for producing 3,5-bis (trifluoromethyl) bromobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33440495A JP3806962B2 (en) | 1995-12-22 | 1995-12-22 | Method for producing 3,5-bis (trifluoromethyl) bromobenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09169673A true JPH09169673A (en) | 1997-06-30 |
| JP3806962B2 JP3806962B2 (en) | 2006-08-09 |
Family
ID=18276995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33440495A Expired - Fee Related JP3806962B2 (en) | 1995-12-22 | 1995-12-22 | Method for producing 3,5-bis (trifluoromethyl) bromobenzene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3806962B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6255545B1 (en) | 1999-06-11 | 2001-07-03 | Merck & Co., Inc. | Process for the synthesis of 3,5-bis(trifluoromethyl)-bromobenzene |
| US6350915B1 (en) | 1999-06-11 | 2002-02-26 | Merck & Co., Inc. | Process for the synthesis of 1-(3,5-bis(trifluoromethyl)-phenyl)ethan-1-one |
| WO2002024615A1 (en) * | 2000-09-23 | 2002-03-28 | Synprotec Limited | 1,3-bis(trifluoromethyl)benzene derivatives |
| EP1192116A4 (en) * | 1999-06-11 | 2002-10-24 | Merck & Co Inc | Process for the synthesis of 3,5-bis(trifluoromethyl)-bromobenzene |
| US6506951B1 (en) | 1999-04-20 | 2003-01-14 | Central Glass Company, Limited | Process for producing brominated trifluoromethylbenzenes |
-
1995
- 1995-12-22 JP JP33440495A patent/JP3806962B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6506951B1 (en) | 1999-04-20 | 2003-01-14 | Central Glass Company, Limited | Process for producing brominated trifluoromethylbenzenes |
| US6255545B1 (en) | 1999-06-11 | 2001-07-03 | Merck & Co., Inc. | Process for the synthesis of 3,5-bis(trifluoromethyl)-bromobenzene |
| US6350915B1 (en) | 1999-06-11 | 2002-02-26 | Merck & Co., Inc. | Process for the synthesis of 1-(3,5-bis(trifluoromethyl)-phenyl)ethan-1-one |
| EP1192116A4 (en) * | 1999-06-11 | 2002-10-24 | Merck & Co Inc | Process for the synthesis of 3,5-bis(trifluoromethyl)-bromobenzene |
| WO2002024615A1 (en) * | 2000-09-23 | 2002-03-28 | Synprotec Limited | 1,3-bis(trifluoromethyl)benzene derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3806962B2 (en) | 2006-08-09 |
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