JPH07116099B2 - Purification method of meta-bromobenzoic acid - Google Patents
Purification method of meta-bromobenzoic acidInfo
- Publication number
- JPH07116099B2 JPH07116099B2 JP29956486A JP29956486A JPH07116099B2 JP H07116099 B2 JPH07116099 B2 JP H07116099B2 JP 29956486 A JP29956486 A JP 29956486A JP 29956486 A JP29956486 A JP 29956486A JP H07116099 B2 JPH07116099 B2 JP H07116099B2
- Authority
- JP
- Japan
- Prior art keywords
- mbba
- crystals
- meta
- impurities
- water
- 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 claims description 15
- VOIZNVUXCQLQHS-UHFFFAOYSA-N 3-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC(Br)=C1 VOIZNVUXCQLQHS-UHFFFAOYSA-N 0.000 title claims description 5
- 238000000746 purification Methods 0.000 title description 5
- 239000013078 crystal Substances 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010979 pH adjustment Methods 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- FEIWNULTQYHCDN-UHFFFAOYSA-N mbba Chemical compound C1=CC(CCCC)=CC=C1N=CC1=CC=C(OC)C=C1 FEIWNULTQYHCDN-UHFFFAOYSA-N 0.000 description 29
- 239000012535 impurity Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000011084 recovery Methods 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- YNVNFMCYBIBHLH-UHFFFAOYSA-N 2,3-dibromobenzoic acid Chemical compound OC(=O)C1=CC=CC(Br)=C1Br YNVNFMCYBIBHLH-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、農薬、染料等の中間体とてい有用なメタブロ
モ安息香酸（以下、MBBAと言う）の精製方法に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for purifying metabromobenzoic acid (hereinafter referred to as MBBA), which is useful as an intermediate for pesticides, dyes and the like.
（従来の技術） MBBAは、安息香酸（以下、BAと言う）と臭素とを硫酸
中、沃素触媒の存在下、反応させて得た後、その反応液
を水中に放出しMBBAの結晶を析出させ、次いでこれを
過することにより粗MBBAの結晶として回収される。しか
し、この場合得られる結晶中に未反応原料BAと過反応物
ジブロモ安息香酸（以下、DBBAと言う）が混入する傾向
にあり、MBBAの純度82〜86％に対し不純物の量がBA7〜
９％、DBBA7〜９％程度となる。そこで、これらを精製
し除去する必要がある。(Prior art) MBBA is obtained by reacting benzoic acid (hereinafter referred to as BA) with bromine in sulfuric acid in the presence of an iodine catalyst, and then releasing the reaction solution into water to precipitate MBBA crystals. The crude MBBA crystals are recovered by passing this over and then passing through. However, the unreacted raw material BA and the over-reacted product dibromobenzoic acid (hereinafter referred to as DBBA) tend to be mixed in the crystals obtained in this case, and the amount of impurities is BA7-
9% and DBBA 7-9%. Therefore, it is necessary to purify and remove them.
従来、MBBAの精製方法については蒸留による方法が一般
的に知られているが、次のような欠点を有し工業的に安
価で有利な方法としてはまだ満足できるものではなかつ
た。Conventionally, a method by distillation is generally known as a method for purifying MBBA, but it has not been satisfactory as an industrially inexpensive and advantageous method due to the following drawbacks.
（１）MBBAは高沸点（b.p.173℃ at 20mmHg）であるた
め蒸留時の熱源費が高価となる。(1) Since MBBA has a high boiling point (bp173 ° C at 20 mmHg), the heat source cost for distillation is expensive.
（２）MBBAは高融点（m.p.155℃）であり、その閉塞防
止のため配管、タンク等の加温が必要である。そのた
め、設備が高価となり、また取扱が煩雑である。(2) MBBA has a high melting point (mp155 ° C), and it is necessary to heat pipes, tanks, etc. to prevent its clogging. Therefore, the equipment is expensive and the handling is complicated.
（３）目的物MBBAと分離しようとする不純物中のDBBAと
の沸点差が小さく（DBBA b.p.177℃ at 20mmHg）蒸留分
離が困難である。(3) The boiling point difference between the target MBBA and DBBA in the impurities to be separated is small (DBBA bp 177 ° C at 20 mmHg), and thus it is difficult to separate by distillation.
（発明が解決しようとする問題点） 本発明者等は上記実情に鑑み、安価でかつ容易に高純度
のMBBAを得る方法を提供すべく種々検討した結果、粗MB
BAの結晶を水中に懸濁させた後、pHを調整することによ
り不純物BA及びDBBAの除去が可能となり本発明の目的が
達成されることを見い出し本発明を完成した。(Problems to be solved by the invention) In view of the above circumstances, the present inventors have conducted various studies to provide a method for obtaining high-purity MBBA inexpensively and easily
The present invention was completed by finding that the impurities BA and DBBA can be removed by suspending the BA crystals in water and then adjusting the pH, thereby achieving the object of the present invention.
（問題点を解決するための手段） 本発明の要旨は、BAを臭素化して得た粗MBBAの結晶を、
該結晶に対し１〜20重量倍の水中に懸濁させ、20〜100
℃の温度下pH3.5〜６に調整、保持し、次いで別する
ことよりなるMBBAの精製方法に存する。(Means for Solving Problems) The gist of the present invention is to provide a crude MBBA crystal obtained by brominating BA,
Suspended in 1 to 20 times by weight of water with respect to the crystals, 20 to 100
A method for purifying MBBA consists of adjusting and maintaining pH 3.5 to 6 at a temperature of ℃, and then separating.
以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
MBBAは、BAと臭素とを硫酸中、沃素触媒の存在下、反応
させて得た後、その反応液を水中に放出しMBBAの結晶を
析出させ、次いでこれを過することにより粗MBBAの結
晶として回収される。MBBA is obtained by reacting BA and bromine in sulfuric acid in the presence of an iodine catalyst, and then releasing the reaction solution into water to precipitate MBBA crystals, which are then passed through to obtain crude MBBA crystals. Will be collected as.
本発明方法によれば、得られた粗MBBAの結晶を再度水中
に懸濁させた後、その懸濁液のpHをある一定範囲内に調
整することにより不純物BA及びDBBAを除去する。この場
合、粗MBBAの結晶を水中に懸濁したときのpHは、反応時
に用いた硫酸が付着しているため１以下であるので、本
発明の特定のpH領域に調整のためには調整剤としてNaO
H,KOH等のアルカリが使用される。According to the method of the present invention, the obtained crude MBBA crystals are suspended again in water, and then the pH of the suspension is adjusted within a certain range to remove impurities BA and DBBA. In this case, the pH when the crystals of crude MBBA are suspended in water is 1 or less because the sulfuric acid used in the reaction adheres. As NaO
Alkali such as H and KOH is used.
本発明のpHの範囲としては、3.5〜６、好ましくは４〜
５の範囲である。ここで、硫酸の付着していない純粋な
MBBAの結晶を水中に懸濁したときのpHは約2.8である
が、本発明においてこれを若干アルカリ側に調整するこ
とにより、不純物であるBA及びDBBAを優先的に水溶性化
しMBBAを精製することができるのである。The pH range of the present invention is 3.5 to 6, preferably 4 to
The range is 5. Here, pure sulfuric acid is not attached
The pH of MBBA crystals when suspended in water is about 2.8, but by adjusting this slightly to the alkaline side in the present invention, the impurities BA and DBBA are preferentially water-solubilized to purify MBBA. It is possible.
pHがこの範囲以下では不純物の除去は十分でなく、一方
この範囲以上では不純物の除去はできるが、目的とする
MBBAの回収率が著しく低下するのでいずれも好ましくな
い。If the pH is below this range, the impurities will not be removed sufficiently. On the other hand, if the pH is above this range, the impurities can be removed.
Both are not preferable because the recovery rate of MBBA is significantly reduced.
水中懸濁時の粗MBBAに対する水の使用量は１〜20重量
倍、好ましくは３〜10重量倍の範囲である。使用量が少
な過ぎると不純物の除去は十分でなく、また懸濁液の攪
拌性に問題を生じる。逆に、使用量が多過ぎると不純物
の除去はできるが、目的とするMBBAの回収率が低下し、
また液量の増大により処理装置が大型化するので不利で
ある。When suspended in water, the amount of water used relative to the crude MBBA is in the range of 1 to 20 times by weight, preferably 3 to 10 times by weight. If the amount used is too small, the removal of impurities will not be sufficient and the stirring properties of the suspension will be problematic. On the contrary, if the amount used is too large, impurities can be removed, but the target MBBA recovery rate decreases,
Further, the processing apparatus becomes large due to the increase in the amount of liquid, which is disadvantageous.
pH調整後の保持時間は0.5〜２時間である。保持時間が
短か過ぎると不純物の溶解が十分でないことがあり、一
方２時間以上保持しても精製効果の向上は期待できな
い。The retention time after pH adjustment is 0.5 to 2 hours. If the holding time is too short, the dissolution of impurities may not be sufficient, while holding for 2 hours or more cannot be expected to improve the purification effect.
pH調整及び保持の温度としては20〜100℃、好ましくは4
0〜60℃の範囲である。温度が低いと不純物の除去は十
分でなく、逆に温度が高過ぎると不純物の除去はできる
が、目的とするMBBAの回収率が低下する。The temperature for pH adjustment and holding is 20 to 100 ° C, preferably 4
It is in the range of 0 to 60 ° C. If the temperature is low, the impurities will not be removed sufficiently. Conversely, if the temperature is too high, the impurities will be removed, but the target MBBA recovery rate will decrease.
以上により本発明によるMBBA精製時の各種条件は、粗MB
BAの品質及び精MBBAの要求される品質、回収率に応じて
上記要件を満たす範囲内に於て適宜最適条件が設定され
る。From the above, various conditions during MBBA purification according to the present invention are
Optimum conditions are appropriately set within the range satisfying the above requirements according to the quality of BA, the required quality of MBBA, and the recovery rate.
（実施例） 以下、本発明を実施例により更に詳細に説明するが、本
発明はその要旨を超えない限り以下の実施例に限定され
るものではない。(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded.
実施例１〜５ 還流冷却管及び攪拌機の付いたコルベン中に、98％硫酸
1539g、BA450g、沃素22.8g、臭素295.2gを仕込み、40℃
に昇温溶解後35％過酸化水素水69.0gを３時間かけて滴
下した。得られた反応液を水12.9Kg中へ放出し、次いで
これを過することにより第１表に示す品質の粗MBBAの
結晶305.4gを得た。Examples 1-5 98% sulfuric acid in Kolben equipped with reflux condenser and stirrer
Charge 1539g, BA450g, iodine 22.8g, bromine 295.2g, 40 ℃
After temperature rising dissolution, 69.0 g of 35% hydrogen peroxide solution was added dropwise over 3 hours. The obtained reaction solution was discharged into 12.9 Kg of water and then passed through it to obtain 305.4 g of crude MBBA crystals having the quality shown in Table 1.
次に、攪拌機の付いたビーカーに上記粗MBBA40g及び第
２表に示す割合の水を添加し、攪拌下第２表に示す所定
温度に調節する。このとき懸濁液のpHは全て１以下であ
り、その後25％NaOH水溶液の添加により第２表に示す所
定のpHに調整し更に１時間その温度を保持し攪拌を続け
る。次いで、これを過し、得られた結晶を乾燥するこ
とにより精MBBAの結晶を得た。Next, 40 g of the above crude MBBA and water in the proportion shown in Table 2 are added to a beaker equipped with a stirrer, and the temperature is adjusted to a predetermined temperature shown in Table 2 with stirring. At this time, the pH of the suspension is all less than 1, and then the pH is adjusted to the predetermined pH shown in Table 2 by adding a 25% NaOH aqueous solution, and the temperature is maintained for 1 hour and stirring is continued. Next, this was passed through and the obtained crystals were dried to obtain purified MBBA crystals.
得られた結晶は高速液体クロマトグラフイーにて分析
し、品質及び回収率を求めた。各実施例の結果を第２表
に示す。The obtained crystals were analyzed by high performance liquid chromatography to determine the quality and recovery rate. The results of each example are shown in Table 2.
比較例１ 実施例１の方法において、25％NaOH水溶液の添加を省略
した以外は全く同様の方法で精製を行なつた場合の結果
を第２表に示す。Comparative Example 1 Table 2 shows the results when purification was carried out in the same manner as in Example 1 except that the addition of the 25% NaOH aqueous solution was omitted.
比較例２ 実施例１の方法において、pHを6.5に調整した以外は全
く同様の方法で精製を行なつた場合の結果を第２表に示
す。Comparative Example 2 Table 2 shows the results when purification was carried out by the same method as in Example 1 except that the pH was adjusted to 6.5.
（発明の効果） 本発明方法によれば粗MBBAを水中に懸濁し、pHを特定範
囲に調整するという極めて簡便な方法により不純物を優
先的に溶解させ別することができるので、目的とする
MBBAを容易に高純度、かつ高収率で回収することができ
工業的に有用な方法である。(Effect of the invention) According to the method of the present invention, it is possible to preferentially dissolve and separate impurities by a very simple method of suspending crude MBBA in water and adjusting the pH to a specific range.
This is an industrially useful method because MBBA can be easily recovered in high purity and high yield.
Claims (3)
息香酸の結晶を、該結晶に対し１〜20重量倍の水中に懸
濁させ、20〜100℃の温度下pH3.5〜６に調整、保持し、
次いで別することにより高純度のメタブロモ安息香酸
を得ることを特徴とするメタブロモ安息香酸の精製方
法。1. A crystal of crude metabromobenzoic acid obtained by brominating benzoic acid is suspended in 1 to 20 times by weight of the crystal, and the pH is adjusted to 3.5 to 6 at a temperature of 20 to 100 ° C. Adjust, hold,
Then, a high-purity meta-bromobenzoic acid is obtained by separating, and a method for purifying meta-bromobenzoic acid.
求の範囲第（１）項記載の方法。2. The method according to claim 1, wherein the pH is adjusted with NaOH or KOH.
る特許請求の範囲第（１）項記載の方法。3. The method according to claim 1, wherein the retention time after pH adjustment is 0.5 to 2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29956486A JPH07116099B2 (en) | 1986-12-16 | 1986-12-16 | Purification method of meta-bromobenzoic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29956486A JPH07116099B2 (en) | 1986-12-16 | 1986-12-16 | Purification method of meta-bromobenzoic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63154642A JPS63154642A (en) | 1988-06-27 |
| JPH07116099B2 true JPH07116099B2 (en) | 1995-12-13 |
Family
ID=17874259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29956486A Expired - Fee Related JPH07116099B2 (en) | 1986-12-16 | 1986-12-16 | Purification method of meta-bromobenzoic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07116099B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USD595909S1 (en) | 2008-09-24 | 2009-07-07 | Chemical Specialties Manufacturing Corp. | Cleaning device |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0745689B2 (en) * | 1988-06-27 | 1995-05-17 | 新日本製鐵株式会社 | Manufacturing method of good electromagnetic thick plate |
| ES2346998T3 (en) | 2005-04-06 | 2010-10-22 | Chugai Seiyaku Kabushiki Kaisha | PROCEDURE FOR THE PRODUCTION OF ACID 2,3,4-TRIFLUORO-5- (IODINE OR SPRAY) BENZOIC. |
-
1986
- 1986-12-16 JP JP29956486A patent/JPH07116099B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USD595909S1 (en) | 2008-09-24 | 2009-07-07 | Chemical Specialties Manufacturing Corp. | Cleaning device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63154642A (en) | 1988-06-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |