JPS63154642A - Purification of meta-bromobenzoic acid - Google Patents
Purification of meta-bromobenzoic acidInfo
- Publication number
- JPS63154642A JPS63154642A JP29956486A JP29956486A JPS63154642A JP S63154642 A JPS63154642 A JP S63154642A JP 29956486 A JP29956486 A JP 29956486A JP 29956486 A JP29956486 A JP 29956486A JP S63154642 A JPS63154642 A JP S63154642A
- Authority
- JP
- Japan
- Prior art keywords
- mbba
- acid
- meta
- crude
- 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.)
- Granted
Links
- VOIZNVUXCQLQHS-UHFFFAOYSA-N 3-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC(Br)=C1 VOIZNVUXCQLQHS-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000000746 purification Methods 0.000 title description 5
- 239000013078 crystal Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 4
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000010979 pH adjustment Methods 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 12
- 239000012535 impurity Substances 0.000 abstract description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052794 bromium Inorganic materials 0.000 abstract description 4
- 229910052740 iodine Inorganic materials 0.000 abstract description 4
- 239000011630 iodine Substances 0.000 abstract description 4
- 239000000725 suspension Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract 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 28
- 238000011084 recovery Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003756 stirring Methods 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
- 239000003513 alkali Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、農薬、染料等の中間体として有用なメタブロ
モ安息香酸（以下、ＭＢＥＡと言う）の精製方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for purifying metabromobenzoic acid (hereinafter referred to as MBEA), which is useful as an intermediate for agricultural chemicals, 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
これを濾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シ、ＭＢＢＡの純度ｇコ〜ｇ６
チに対し不純物の量がＢＡ？〜ｑ％、ＤＢＢＡ７〜？チ
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. This is then filtered to recover crude MBBA crystals. However, in this case, there is a tendency for unreacted raw material BA and overreacted product dibromobenzoic acid (hereinafter referred to as DBBA) to be mixed into the crystals obtained, and the purity of MBBA is from g to g6.
Is the amount of impurities BA compared to Q? ~q%, DBBA7~? It will be about 100%. Therefore, it is necessary to purify and remove these.
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
かった。Conventionally, distillation is generally known as a method for purifying MBBA, but it has the following drawbacks and is not yet satisfactory as an industrially inexpensive and advantageous method.
（１）’ Ｍ Ｂ Ｂ Ａは高沸点（ｂ、ｐ、 ／り
３℃ａｔ ２０ｍＨｇ）であるため蒸留時の熱源費が高
価となる。(1)' M B B A has a high boiling point (b, p, /3°C at 20 mHg), so the heat source cost during distillation is high.
（２） ＭＢＢＡは高融点（ｍ、ｐ、 ／ ！ｒ 左℃
）であシ、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、また取扱い
が煩雑である。(2) MBBA has a high melting point (m, p, / !r left °C
), it is necessary to heat piping, tanks, etc. to prevent blockages. 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、１
）。(3) The boiling point difference between the target substance MBBA and DBBA in the impurity to be separated is small (DBBA b, 1
).
／７り℃ａｔ ２０ｗｎＨｇ）蒸留分離が困難である。/7℃at 20wnHg) Distillation separation is difficult.
（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ＭＢＢＡの結晶を水中に懸濁させた後、ｐＨを調整す
ることによりネ細物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光
成した。(Problems to be Solved by the Invention) In view of the above-mentioned circumstances, the present inventors have conducted various studies to provide a method for obtaining high-purity MBBA at low cost and with ease.
The inventors have discovered that by suspending crude MBBA crystals in water and then adjusting the pH, it is possible to remove the fine particles BA and DBBA, thereby achieving the object of the present invention.
（問題点を解決するだめの手段）
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／〜−〇Ｍ量倍の水中に懸濁させ１
．２０〜ｉｏｏ℃の温度下ｐＨ，？Ｊ〜乙に調整、保持
し、次いで濾別することよシなるＭＢＢＡの精製方法に
存する。(Means for Solving the Problems) The gist of the present invention is to suspend crude MBBA crystals obtained by brominating BA in water with an amount of /~-0M times the crystals.
．． pH at a temperature of 20~ioo℃, ? The present invention consists in a method for purifying MBBA, which involves adjusting and retaining it to J to B, and then filtering it.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
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ＭＢＢ
Ａの結晶を析出させ、次いでこれを濾過することにより
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 produce MBB.
Crystals of A are precipitated and then filtered to recover crude MBBA crystals.
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／
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Ｍａｉｌ 、 ＫＯＨ等のアルカリが
使用される。According to the method of the present invention, the crude MBBA crystals obtained are suspended in water again, and the impurities BA and DBBA are removed by adjusting the pH of the suspension within a certain range. In this case, the pH when the crude MBBA crystals are suspended in water is due to the adhesion of sulfuric acid used during the reaction.
Therefore, in order to adjust the pH to a specific pH range according to the present invention, an alkali such as Mail or KOH is used as an adjusting agent.
本発明のｐＨの範囲としては、３．５〜乙、好ましくは
ダ〜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−
０ｇ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Ｏ
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。The pH range of the present invention is from 3.5 to O, preferably from Da to 5. Here, when pure MBBA crystals with no sulfuric acid attached are suspended in water, the pH is approximately -
However, in the present invention, by adjusting this to be slightly alkaline, impurities BA and DBBA can be made preferentially water-soluble and MBBA can be purified. Removal is not sufficient, while impurities can be removed above this range, but the recovery rate of the target MBBA is significantly lowered, so both are unfavorable.
水中懸濁時の粗ＭＢＢＡに対する水の使用量は７〜２０
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。The amount of water used for crude MBBA when suspended in water is 7 to 20
The amount is preferably 3 to 10 times the weight. If the amount used is too small, removal of impurities will not be sufficient and problems will arise in the stirrability of the suspension. On the other hand, if the amount used is too large, impurities can be removed, but the recovery rate of the target MBBA decreases, and the processing equipment becomes larger due to the increase in the amount of liquid, which is disadvantageous.
ｐＨ調整後の保持時間は Ｏ，Ｓ〜コ時間である。The retention time after pH adjustment is O,S~co time.
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、−１２時間以上保持しても精製効果の向上は期
待できない。If the holding time is too short, impurities may not be sufficiently dissolved, and even if the holding time is held for -12 hours or more, no improvement in the purification effect can be expected.
ｐＨ調整及び保持の温度としては、２０〜１００℃、好
ましくはグθ〜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 maintenance is in the range of 20 to 100°C, preferably in the range of θ to 60°C. If the temperature is too low, the removal of impurities will not be sufficient, whereas if the temperature is too high, the impurities can be removed, but the recovery rate of the target MBBA will decrease.
以−百σ′り本発明によるＭＢＢＡ精製時の各種条件は
、粗ＭＢＢＡ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。Hereinafter, various conditions during MBBA purification according to the present invention include the quality of crude MBBA, the required quality of purified MBBA,
Optimum conditions are appropriately set within a range that satisfies the above requirements depending on 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 explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.
実施例／〜Ｓ
還流冷却管及び攪拌機の付いたコルベン中に、９ｇ％硫
酸／！ｒ、３９１１、ＢＡダ左ｏｇ、沃素２コ、ｒｔｔ
、臭素、２９．５〜、コＩを仕込み、ダθ℃に昇温溶解
後３！ｒ％過酸化水素水／−テ、θｇを３時間かけて滴
下した。得られた反応液を水／２．９Ｋｑ中へ放出し、
次いでこれを沖過することにより第１表に示す品質の粗
ＭＢＢＡの結晶３０ 左、ＩＩ９を得た。Examples/~S In a Kolben equipped with a reflux condenser and a stirrer, 9 g% sulfuric acid/! r, 3911, BA da left og, iodine 2 pieces, rtt
, Bromine, 29.5~, CoI was prepared, heated to θ℃, and dissolved after 3! r% hydrogen peroxide/-te, θg was added dropwise over 3 hours. The resulting reaction solution was discharged into water/2.9Kq,
This was then filtered to obtain crude MBBA crystal 30, II9 having the quality shown in Table 1.
次に、攪拌機の付いたビーカーに上記粗ＭＢＢＡｙｏｇ
及び第２表に示す割合の水を添加し、攪拌上第コ表に示
す所定温度に調節する。このとき懸濁液のｐＩ（は全て
／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７時間その温度
を保持し攪拌を続ける。次いで、これを濾過し、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, add the above crude MBBAyog to a beaker equipped with a stirrer.
Then, add water in the proportion shown in Table 2, and adjust the temperature to the predetermined temperature shown in Table 1 while stirring. At this time, the pI of the suspension is all/below, and then the pH is adjusted to the predetermined pH shown in Table 2 by adding 25% NaOH aqueous solution, and the temperature is maintained for another 7 hours and stirring is continued. By filtering and drying the obtained crystals, purified MBBA crystals were obtained.
得られた結晶は高速液体クロマトグラフィーにて分析し
、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／
実施例／の方法において１．２３％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った場
合の結果を第二表に示す。Table 2 shows the results obtained when purification was carried out in exactly the same manner as in Comparative Example/Example, except that the addition of the 1.23% NaOH aqueous solution was omitted.
比較例コ
実施例／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った場合の結果を第２表
に示す。Table 2 shows the results when purification was carried out in exactly the same manner as in Comparative Example/Example, except that the pH was adjusted to 6.5.
（発明の効果）
本発明方法によれば粕ＭＢＢＡを水中に懸濁し、ｐＨを
特定範凹に醐整するという極めて簡便な方法によりネ細
物を優先的に溶解させｐ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。(Effects of the Invention) According to the method of the present invention, fines can be preferentially dissolved and separated by an extremely simple method of suspending MBBA lees in water and adjusting the pH to a specific range. This is an industrially useful method that allows the target MBBA to be easily recovered with high purity and high yield.
第１表 ＝ ７− 第２表 出 願 人 三菱化成工業株式会社 代 理 人 弁理士長香川 （ほか７名）Table 1 =7- Table 2 Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Naga Kagawa (7 others)
Claims (3)
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、次いで濾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) Crystals of crude metabromobenzoic acid obtained by brominating benzoic acid are suspended in 1 to 20 times the weight of the crystals in water, and the pH is adjusted to 3.5 to 6 at a temperature of 20 to 100°C. A method for purifying metabromobenzoic acid, the method comprising obtaining highly pure metabromobenzoic acid by retaining and then filtering it.
請求の範囲第（１）項記載の方法。(2) The method according to claim (1), wherein the pH is adjusted with NaOH or KOH.
特許請求の範囲第（１）項記載の方法。(3) The method according to claim (1), wherein the holding 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 true JPS63154642A (en) | 1988-06-27 |
| JPH07116099B2 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH028323A (en) * | 1988-06-27 | 1990-01-11 | Nippon Steel Corp | Production of good magnetic steel plate |
| US8022247B2 (en) | 2005-04-06 | 2011-09-20 | Chugai Seiyaku Kabushiki Kaisha | Process for production of 2,3,4-trifluoro-5-(iodo or bromo)-benzoic acid |
-
1986
- 1986-12-16 JP JP29956486A patent/JPH07116099B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH028323A (en) * | 1988-06-27 | 1990-01-11 | Nippon Steel Corp | Production of good magnetic steel plate |
| US8022247B2 (en) | 2005-04-06 | 2011-09-20 | Chugai Seiyaku Kabushiki Kaisha | Process for production of 2,3,4-trifluoro-5-(iodo or bromo)-benzoic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07116099B2 (en) | 1995-12-13 |
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