JPH04193858A - Production of 1,4-diaminobenzene-2,6-disulfonic acid and its purification - Google Patents
Production of 1,4-diaminobenzene-2,6-disulfonic acid and its purificationInfo
- Publication number
- JPH04193858A JPH04193858A JP32079590A JP32079590A JPH04193858A JP H04193858 A JPH04193858 A JP H04193858A JP 32079590 A JP32079590 A JP 32079590A JP 32079590 A JP32079590 A JP 32079590A JP H04193858 A JPH04193858 A JP H04193858A
- Authority
- JP
- Japan
- Prior art keywords
- diaminobenzene
- acid
- disulfonic acid
- water
- temperature
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- QGNJPFLIBOTDKU-UHFFFAOYSA-N 2,5-diaminobenzene-1,3-disulfonic acid Chemical compound NC1=CC(S(O)(=O)=O)=C(N)C(S(O)(=O)=O)=C1 QGNJPFLIBOTDKU-UHFFFAOYSA-N 0.000 title claims description 11
- 238000000746 purification Methods 0.000 title description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000007524 organic acids Chemical class 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- -1 alkali metal salt Chemical class 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 16
- IPOFQEDKXYAPBX-UHFFFAOYSA-N 1,4-diaminocyclohexa-2,4-diene-1-sulfonic acid Chemical compound NC1=CCC(N)(S(O)(=O)=O)C=C1 IPOFQEDKXYAPBX-UHFFFAOYSA-N 0.000 abstract description 9
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000975 dye Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 4
- 125000000542 sulfonic acid group Chemical group 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000012043 crude product Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- VOPSFYWMOIKYEM-UHFFFAOYSA-N 2,5-diaminobenzene-1,4-disulfonic acid Chemical compound NC1=CC(S(O)(=O)=O)=C(N)C=C1S(O)(=O)=O VOPSFYWMOIKYEM-UHFFFAOYSA-N 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- UGEHFOSBNBEWMP-UHFFFAOYSA-N 2,3-diaminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1N UGEHFOSBNBEWMP-UHFFFAOYSA-N 0.000 description 1
- AJMCQAZRSKYSAF-UHFFFAOYSA-N 2,6-diaminobenzene-1,4-disulfonic acid Chemical compound NC1=CC(S(O)(=O)=O)=CC(N)=C1S(O)(=O)=O AJMCQAZRSKYSAF-UHFFFAOYSA-N 0.000 description 1
- YADSWTKOIHUSDX-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-disulfonic acid Chemical compound NC1=CC(N)=C(S(O)(=O)=O)C=C1S(O)(=O)=O YADSWTKOIHUSDX-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material 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】
［産業上の利用分野コ
本発明は染料等の中間体として有用な、１，４−ジアミ
ノベンゼン−２，６−ジスルフ」ン酸の製造方法及び精
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 producing and purifying 1,4-diaminobenzene-2,6-disulfonic acid, which is useful as an intermediate for dyes and the like. be.
［従来の技術］
１．４−ジアミノベンゼン（モノ）スルフォン酸は染料
の中間体として工業的に利用価値の高いものであるが、
従来はパラニトロクロールベンゼンを原料として、これ
をスルフォン化し、ついでクロール基を高圧下でアミン
基に変え、さらに二１・四基を還元して、１，４−ジア
ミノベンゼンスルフ」ン酸を得ていた。しかしながらこ
の方法は、反応工程が多く、各工程毎に反応物を取り出
すため、廃液処理に困難な問題があり、且つ収率も高い
とは言えない等の問題が有った。[Prior Art] 1.4-Diaminobenzene (mono)sulfonic acid has high industrial utility value as an intermediate for dyes.
Conventionally, p-nitrochlorobenzene was used as a raw material, which was sulfonated, the chloro group was changed to an amine group under high pressure, and the 21,4 group was further reduced to produce 1,4-diaminobenzenesulfonic acid. I was getting it. However, this method involves many reaction steps and the reactants are taken out at each step, so there are problems in that waste liquid treatment is difficult and the yield cannot be said to be high.
［発明が解決しようとする課題］
本発明者らは、合成繊維原料として量産されている１、
４−ジアミノベンゼンを原料として用い、簡便に１．４
−ジアミノベンゼンスルフオン酸を製造する方法につい
て検討した。[Problem to be solved by the invention] The present inventors have discovered that 1, which is mass-produced as a synthetic fiber raw material,
Using 4-diaminobenzene as a raw material, 1.4
-A method for producing diaminobenzenesulfonic acid was studied.
その結果、１，４−ジアミノベンゼンを先ずジスルフォ
ン化した後、脱モノスルフォン化して１．４−ジアミノ
ベンゼンモノスルフォン酸とすれば良いことが分かった
。As a result, it was found that 1,4-diaminobenzene should first be disulfonated and then demonosulfonated to form 1,4-diaminobenzene monosulfonic acid.
しかしながらこの方法では、１．４−ジアミノベンゼン
−２，５−ジスルフォン酸は脱モノスルフォンできない
ため、中間体として１，４−ジアミノベンゼン−２，６
−ジスルフォン酸を経る必要が有る。However, in this method, 1,4-diaminobenzene-2,5-disulfonic acid cannot be demonosulfonated, so 1,4-diaminobenzene-2,6-disulfonic acid is used as an intermediate.
- It is necessary to pass through disulfonic acid.
従来のジスルフォン化物の製造方法としては、フリート
ランダース フォルトシュリッチ デア タールフア
ルペンファブリカチオン（Ｆｒｉｅｄｌａｅｎｄｅｒｓ
Ｆｏｒｔｓｃｈｒｉｔｔｅ ｄｅｒ Ｔｅｅｒｆａｒ
ｂｅｎｆａｂｒｉｋａｔｉｏｎ）第２巻３１２及びドイ
ツ特許箱４７．４２６号、第１．５４４，４４２号に、
■、４−ジアミノベンゼン硫酸塩に発煙硫酸を１４０℃
で作用させる方法が記載されている。前者は１，４−ジ
アミノベンゼン−２，６−ジスルフォン酸の製造方法と
して記載されているが、後者は１．４−ジアミノベンゼ
ン−２，５−ジスルフォン酸の製造方法であり、１，４
−ジアミノベンゼン−２，６−ジスルフォン酸はる液よ
り回収されると記載されている。Conventional methods for producing disulfonated products include
Fortschritte der Teerfar
benfabrikation) Volume 2 312 and German Patent Box No. 47.426, No. 1.544,442,
■ Add fuming sulfuric acid to 4-diaminobenzene sulfate at 140°C.
It describes how to make it work. The former is described as a method for producing 1,4-diaminobenzene-2,6-disulfonic acid, while the latter is a method for producing 1,4-diaminobenzene-2,5-disulfonic acid;
-Diaminobenzene-2,6-disulfonic acid is described as being recovered from the liquid.
しかしながらこれらの製造方法を実施してみると、１，
４−ジアミノベンゼン−２，５−ジスルフォン酸が反応
生成物の過半を占めることが確認された。However, when implementing these manufacturing methods, 1,
It was confirmed that 4-diaminobenzene-2,5-disulfonic acid accounted for the majority of the reaction products.
即ち、１．４−ジアミノベンゼン−２，６−ジスルフ］
ン酸の製造方法としては、収率が低く適していない。i.e., 1,4-diaminobenzene-2,6-disulf]
This method is not suitable as a method for producing phosphoric acid due to its low yield.
本発明の目的は、現在量産されている１、４−ジアミノ
ベンゼンを原料として、最終的には１，４−ジアミノベ
ンゼンモノスルフォン酸を得るために、１．４−ジアミ
ノベンゼン−２，６−ジスルフォン酸を製造する方法及
び精製方法を提供することである。The purpose of the present invention is to obtain 1,4-diaminobenzene-2,6- An object of the present invention is to provide a method for producing and purifying disulfonic acid.
［課題を解決するための手段及び作用］本発明者らは、
■、４−ジアミノベンゼンをスルフォン化する条件を鋭
意検討した結果、低温度で発煙硫酸を作用させることに
より２，６−ジスルフォン酸のみ高収率で得られること
を知見し、本発明を達成した。[Means and effects for solving the problem] The present inventors
(2) As a result of intensive study on the conditions for sulfonating 4-diaminobenzene, the inventors found that only 2,6-disulfonic acid could be obtained in high yield by reacting fuming sulfuric acid at low temperatures, and the present invention was achieved. .
即ち、第１の発明は、１．４−ジアミノベンゼンな８０
〜１２０℃の範囲の反応温度でジスルフォン化すること
を特徴とする１、４−ジアミノベンゼン−２，６−ジス
ルフォン酸の製造方法であり、さらに第２の発明は、不
純物を含有する１、４−ジアミノベンゼン−２，６−ジ
スルフォン酸をアルカリ金属塩として、水に溶解し、有
機酸で酸析することを特徴とする１、４−ジアミノベン
ゼン−２，６−ジスルフォン酸の精製方法である。That is, the first invention is based on 1,4-diaminobenzene 80
A second invention is a method for producing 1,4-diaminobenzene-2,6-disulfonic acid, characterized in that disulfonation is carried out at a reaction temperature in the range of ~120°C; - A method for purifying 1,4-diaminobenzene-2,6-disulfonic acid, which comprises dissolving diaminobenzene-2,6-disulfonic acid as an alkali metal salt in water and precipitating it with an organic acid. .
第１の発明において、反応温度の選択が重要である。本
発明において反応温度は８０〜１２０℃１好ましくは９
５〜１１０℃である。反応温度が１２０℃を越えると、
１．４−ジアミノベンゼン−２，５−ジスルフォン酸が
著しく増加し、好ましくない。また、発煙硫酸に１，４
−ジアミノベンゼンを添加する際には発熱するので冷却
して系の温度を制御するのが好ましい。In the first invention, selection of reaction temperature is important. In the present invention, the reaction temperature is 80 to 120°C, preferably 9
The temperature is 5 to 110°C. When the reaction temperature exceeds 120℃,
1,4-diaminobenzene-2,5-disulfonic acid increases significantly, which is not preferable. Also, oleum contains 1,4
- When adding diaminobenzene, it generates heat, so it is preferable to control the temperature of the system by cooling it.
また、使用する発煙硫酸は、市販のいずれの濃度のもの
でも良く、使用量は１．４−ジアミノベンゼン１モルに
対して、３モル未満の場合未反応物の残存量が増加する
傾向が認められ、これを防止するため反応時間を長くす
ると、１，４−ジアミノベンゼン−２，５−ジスルフォ
ン酸が増加し好ましくない。未反応物の残存量を極力少
なくし、反応時間を適切にする関係からみて、工業的に
は発煙硫酸の量は３モル以上が好ましい。Furthermore, the fuming sulfuric acid used may be of any commercially available concentration, and if the amount used is less than 3 mol per 1 mol of 1,4-diaminobenzene, there is a tendency for the residual amount of unreacted substances to increase. If the reaction time is increased to prevent this, 1,4-diaminobenzene-2,5-disulfonic acid will increase, which is not preferable. From the standpoint of minimizing the residual amount of unreacted substances and appropriate reaction time, the amount of fuming sulfuric acid is preferably 3 moles or more from an industrial perspective.
第１の発明で得られる１、４−ジアミノベンゼン−２，
６−ジスルフォン酸には未反応物や副生物が含まれるが
、第２の発明によりこれを生成し、さらに高純度の製品
とすることができる。1,4-diaminobenzene-2 obtained in the first invention,
Although 6-disulfonic acid contains unreacted substances and by-products, this can be produced according to the second invention and a product with even higher purity can be obtained.
即ち、生成した１、４−ジアミノベンゼン−２，６−ジ
スルフォン酸をアルカリ金属塩とし、水に溶解し、有機
酸で酸析する方法で、はとんど純粋な１．４−ジアミノ
ベンゼン−２，６−ジスルフォン酸が得られる。上記ア
ルカリ金属塩にするためには例えば、水酸化ナトリウム
等が好ましい。また酸析に使用する有機酸としては、蟻
酸、酢酸、プロピオン酸を用いることができ、特に酢酸
が好適である。無機酸では精製効果に劣り、使用に適さ
ない。That is, the produced 1,4-diaminobenzene-2,6-disulfonic acid is made into an alkali metal salt, dissolved in water, and acid-precipitated with an organic acid. 2,6-disulfonic acid is obtained. For example, sodium hydroxide or the like is preferable to form the above-mentioned alkali metal salt. Further, as the organic acid used for acid precipitation, formic acid, acetic acid, and propionic acid can be used, and acetic acid is particularly suitable. Inorganic acids have poor purification effects and are not suitable for use.
本発明において、酸析の他の条件は特に限定きれないが
、例えば、１．４−ジアミノベンゼン−２，６−ジスル
フォン酸を水に溶解した後、水酸化ナトリウムの水溶液
を添加してこれを中和し、有機酸を添加して目的の結晶
を析出させれば良い。In the present invention, other conditions for acid precipitation cannot be particularly limited, but for example, 1,4-diaminobenzene-2,6-disulfonic acid is dissolved in water, and then an aqueous solution of sodium hydroxide is added. What is necessary is to neutralize it and add an organic acid to precipitate the desired crystals.
本発明により得られた１、４−ジアミノベンゼン−２，
６−ジスルフォン酸は、粗製品の段階でも、また精製後
のものでも好適に次工程の１，４−ジアミノベンゼンス
ルフォン酸の製造に用いることができる。1,4-diaminobenzene-2 obtained according to the present invention,
6-disulfonic acid can be suitably used in the next step of producing 1,4-diaminobenzenesulfonic acid, either in the crude product stage or after purification.
１．４−ジアミノベンゼンスルフォン酸の製造方法とし
ては、例えば、１．４−ジアミノベンゼン−２，６−ス
ルフォン酸を濃度９０〜９８％の硫酸中で１２０〜１５
０℃で処理して脱モノスルフォン化するのが好ましい。As a method for producing 1.4-diaminobenzene sulfonic acid, for example, 1.4-diaminobenzene-2,6-sulfonic acid is mixed with 120 to 15
It is preferable to perform demonosulfonation by treatment at 0°C.
さらに好ましくは、硫酸の濃度は９５〜９８％、反応温
度は１３５〜１３７℃である。また、本発明筒１の工程
からそのまま続けて脱モノスルフォン化反応を行っても
良い。More preferably, the concentration of sulfuric acid is 95-98% and the reaction temperature is 135-137°C. Alternatively, the demonosulfonation reaction may be carried out directly from the step of the present invention cylinder 1.
こうして製造された１、４−ジアミノベンゼンスルフォ
ン酸はアルカリ金属塩として水に溶解し、有機酸、好ま
しくは酢酸で酸析することにより精製できる。The 1,4-diaminobenzenesulfonic acid thus produced can be purified as an alkali metal salt by dissolving it in water and precipitating it with an organic acid, preferably acetic acid.
本発明で得られる１、４−ジアミノベンゼン−２，６−
ジスルフォン酸は高純度であり、他の工業用途にも好適
に用いることができる。1,4-diaminobenzene-2,6- obtained by the present invention
Disulfonic acid has high purity and can be suitably used for other industrial applications.
［実施例コ
実施例１
２８％発煙硫酸２８５．７ｇ （１，０モル）を仕込ん
だ５００ ｍｌ四つロフラスコを２０℃の冷水で外部冷
却しながら、１，４−ジアミノベンゼン２７ｇ （０，
２５モル）を３５℃以下の温度で１時間かけて少量ずつ
加えた。１０５℃まで昇温し、そのまま１１時間撹拌し
て反応を終了した。生成物を４０℃まで冷却し、液温か
５０〜６０℃になるように注意しながら２６４ ｍｌの
水を１時間かけて注入し、結晶を析出させた。その後３
０℃に冷却して１時間熟成させ、ろ過し、水１２、５ｍ
ｌで洗浄した。この粗製品には、高速液体クロマトグラ
フィ （ＨＰＬＣ）により、未反応物０．６％、１．４
−ジアミノベンゼンモノスルフォン酸２．１％、■、４
−ジアミノベンゼンー２．５−ジスルフォン酸３．２％
が含まれていた。[Example Example 1 A 500 ml four-bottle flask containing 285.7 g (1.0 mol) of 28% oleum was cooled externally with cold water at 20°C, and 27 g (0,0 mol) of 1,4-diaminobenzene was added to the flask.
25 mol) was added in small portions over 1 hour at a temperature below 35°C. The temperature was raised to 105°C, and the reaction was completed by stirring for 11 hours. The product was cooled to 40°C, and 264 ml of water was poured over 1 hour, taking care to keep the liquid temperature at 50-60°C, to precipitate crystals. then 3
Cool to 0°C and mature for 1 hour, filter, and add 12.5 m of water.
Washed with l. This crude product was found to contain 0.6% unreacted material and 1.4% unreacted material by high performance liquid chromatography (HPLC).
-Diaminobenzene monosulfonic acid 2.1%, ■, 4
-Diaminobenzene-2.5-disulfonic acid 3.2%
was included.
次に、５００ｍ１ビーカーに水１２５ ｍｌを入れ、上
記粗製品を撹拌しながら投入し、４８％ＮａＯＨ溶液８
８ｇで中和した。中和後７０℃に昇温し、液温を７５℃
に保ちながら氷酢酸３０ｇを３０分かけて添加し、さら
に３０分間撹拌を続けて結晶を析出させた。その後、３
０℃まで冷却し、１時間撹拌後ろ過し、７５ｍ１の水で
洗浄して７０℃で乾燥し、１，４−ジアミノベンゼン−
２，６−ジスルフォン酸ケーキ６２８ｇを得た。Next, put 125 ml of water in a 500 ml beaker, add the above crude product while stirring, and add 8 ml of 48% NaOH solution.
Neutralized with 8g. After neutralization, raise the temperature to 70℃, and then reduce the liquid temperature to 75℃.
30 g of glacial acetic acid was added over a period of 30 minutes while maintaining the temperature at 100.degree. C., and stirring was continued for an additional 30 minutes to precipitate crystals. After that, 3
Cool to 0°C, stir for 1 hour, filter, wash with 75ml of water and dry at 70°C to obtain 1,4-diaminobenzene-
628 g of 2,6-disulfonic acid cake was obtained.
得られた生成物の純度をＨＰＬＣで測定したところ９８
．８％と高純度であり、未反応物０．０３％、■、４−
ジアミノベンゼンモノスルフォン酸０．３％、１，４−
ジアミノベンゼン−２，５−ジスルフォン酸痕跡が含有
されている程度であった。The purity of the obtained product was measured by HPLC and was found to be 98.
．． High purity of 8%, unreacted matter 0.03%, ■, 4-
Diaminobenzene monosulfonic acid 0.3%, 1,4-
It contained only traces of diaminobenzene-2,5-disulfonic acid.
この精製品３３ｇを９８％硫酸１００ｇに仕込み１３５
℃に昇温して、１３５〜１３８℃で２時間撹拌した後、
１００℃に冷却し、１００ｍ１の水を注入して１００〜
１１０℃とすると結晶が析出した。さらに３０℃に冷却
後、４０ｍ１の水で洗浄し、７０℃で乾燥すると、１８
、２ｇの１．４−ジアミノベンゼンスルフォン酸が得ら
れた。Add 33g of this purified product to 100g of 98% sulfuric acid and make 135
After raising the temperature to ℃ and stirring at 135 to 138℃ for 2 hours,
Cool to 100℃, pour 100ml of water and heat to 100~
When the temperature was set at 110°C, crystals precipitated. After further cooling to 30℃, washing with 40ml of water and drying at 70℃, 18
, 2 g of 1,4-diaminobenzenesulfonic acid were obtained.
実施例２
５００ｍ１四つロフラスコに２８％発煙硫酸２１４ｇ（
０，７５モル）を仕込み、２０ ’Ｃの冷水で外部冷却
して液温を３５℃以下に保ちながら、１，４−ジアミノ
ベンゼン２７ｇを１時間かけて少量ずつ加えた。次に徐
々に９８℃まで昇温してそのままで１８時間撹拌し、反
応させ、粗製品を得た。ＨＰＬＣ分析よりこの粗製品に
は不純物として１，４−ジアミノベンゼン２．８％、１
，４−ジアミノベンゼン−２，５−ジスルア２ン酸１０
．０％、１．４−ジアミノベンゼンモノスルフ月ン酸３
．５％が含まれていた。Example 2 214 g of 28% oleum was placed in a 500 m four-bottle flask (
0.75 mol) was added thereto, and 27 g of 1,4-diaminobenzene was added little by little over 1 hour while keeping the liquid temperature below 35°C by external cooling with cold water at 20'C. Next, the temperature was gradually raised to 98° C., and the mixture was stirred for 18 hours to react, and a crude product was obtained. HPLC analysis revealed that this crude product contained 2.8% of 1,4-diaminobenzene and 1 as impurities.
,4-diaminobenzene-2,5-disulfanoic acid 10
．． 0%, 1,4-diaminobenzene monosulfonic acid 3
．． It contained 5%.
以下実施例１と同様に処理して、１．４−ジアミノベン
ゼン−２，６−ジスルフォン酸精製ケーキ６０．０ｇを
得た。純度はＨＰＬＣによりほぼ１．００％、収率は７
３．７％であった。Thereafter, the same treatment as in Example 1 was carried out to obtain 60.0 g of a purified cake of 1,4-diaminobenzene-2,6-disulfonic acid. Purity is approximately 1.00% by HPLC, yield is 7.
It was 3.7%.
実施例３
２８％発煙硫酸４７１．４ｇ（１，６５モル）を仕込ん
だ１ｐ四つロフラスコを２０ ’Ｃの冷水で外部冷却し
て内部の系を３５℃以下に保ちながら、１．４−ジアミ
ノベンゼン５４ｇ （０，５モル）を１時間かけて加え
た。Example 3 A 1P four-bottle flask containing 471.4 g (1.65 mol) of 28% oleum was externally cooled with cold water at 20'C to maintain the internal system below 35°C, and 1,4-diamino 54 g (0.5 mol) of benzene were added over a period of 1 hour.
さらに徐々に１０５℃にまで昇温した後そのまま１１時
間撹拌し、１，４−ジアミノベンゼン−２，６−ジスル
フォン酸が主成分の反応生成物が得られた。これを９０
℃まで冷却し、冷却を続けながら、水２０ｍ１を滴下し
た。この間液温は１００℃以下であった。この水により
系内の硫酸濃度は１００％になった。次いで水２５ｍ１
を冷却せずに滴下すると液温は１３５℃付近まで上昇し
たので、１３５〜１３７℃で２時間撹拌した。次に冷却
しながら水４２５ｍ１を加え約３０℃まで達すると結晶
が析出し始めたのでその温度で１時間以上撹拌を続けた
後、１夜放置し、ろ過して水５０ｍ１にて洗浄し、粗製
の１，４−ジアミノベンゼンスルフォン酸を得た。この
粗製品の純度は８８２％、収率は８３．８％であった。The temperature was further gradually raised to 105° C. and the mixture was stirred for 11 hours to obtain a reaction product containing 1,4-diaminobenzene-2,6-disulfonic acid as the main component. This is 90
The mixture was cooled to 0.degree. C., and 20 ml of water was added dropwise while continuing to cool. During this time, the liquid temperature was below 100°C. This water brought the sulfuric acid concentration in the system to 100%. Then 25ml of water
When added dropwise without cooling, the liquid temperature rose to around 135°C, so the mixture was stirred at 135-137°C for 2 hours. Next, 425 ml of water was added while cooling, and when the temperature reached about 30°C, crystals started to precipitate, so after stirring at that temperature for more than 1 hour, it was left overnight, filtered, washed with 50 ml of water, and the crude 1,4-diaminobenzenesulfonic acid was obtained. The purity of this crude product was 882%, and the yield was 83.8%.
上記粗製品には加水分解されにくい１．４−ジアミノベ
ンゼン−２，５−ジスルフォン酸が含まれている。この
粗製品を水２５０ｍ１中に仕込み、常温で撹拌しながら
、４８％ＮａＯＨ溶液１６０ｇを滴下し、ｐＨ５付近で
０．５ｇのハイドロサルファイドを添加し、ｐＨ８まで
中和し、温度７０℃として完全に溶解したことを確認し
た後、氷酢酸８ｇを３０分かけて注入し、７０℃で撹拌
した。その後、３０℃まで冷却し、３０分以上撹拌して
から析出した結晶をろ過し、水］、 ５０ ｍ ｌで洗
浄し、７０℃で乾燥して、■、４−ジアミノベンゼンス
ルフォン酸７３．１ｇを得た。ＨＰＬＣによると純度は
９８％、収率は７６．２％であった。The above crude product contains 1,4-diaminobenzene-2,5-disulfonic acid, which is difficult to hydrolyze. This crude product was poured into 250 ml of water, and while stirring at room temperature, 160 g of 48% NaOH solution was added dropwise. At around pH 5, 0.5 g of hydrosulfide was added to neutralize to pH 8, and at a temperature of 70°C, completely After confirming that it had dissolved, 8 g of glacial acetic acid was injected over 30 minutes, and the mixture was stirred at 70°C. Thereafter, it was cooled to 30°C, stirred for 30 minutes or more, and the precipitated crystals were filtered, washed with 50 ml of water, and dried at 70°C to obtain 73.1 g of 4-diaminobenzenesulfonic acid. I got it. According to HPLC, the purity was 98% and the yield was 76.2%.
［発明の効果］
以上のように本発明によると、目的とするｌ、４−ジア
ミノベンゼン−２，６−ジスルフォン酸を高純度且つ高
収率で製造することができ、■、４−ジアミノベンゼン
スルフォン酸を製造する上で経済的効率が高（、工業的
にひじように有用である。[Effects of the Invention] As described above, according to the present invention, the target l,4-diaminobenzene-2,6-disulfonic acid can be produced with high purity and high yield; It has high economic efficiency in producing sulfonic acid and is very useful industrially.
Claims (1)
〜１２０℃の範囲の反応温度でジスルフォン化すること
を特徴とする１，４−ジアミノベンゼン−２，６−ジス
ルフォン酸の製造方法。 ２）１，４−ジアミノベンゼン２，６−ジスルフォン酸
をアルカリ金属塩として水に溶解し、有機酸で酸析する
ことを特徴とする１，４−ジアミノベンゼン−２，６−
ジスルフォン酸の精製方法。 ３）反応温度を９５〜１１０℃とする請求項第１項記載
の製造方法。 ４）発煙硫酸を１，４−ジアミノベンゼンに対し、モル
比で３以上使用する請求項第１又は第３項記載の製造方
法。[Claims] 1) 1,4-diaminobenzene is treated with 80% oleum using oleum.
1. A method for producing 1,4-diaminobenzene-2,6-disulfonic acid, comprising disulfonation at a reaction temperature in the range of ~120°C. 2) 1,4-diaminobenzene 1,4-diaminobenzene-2,6-, which is characterized by dissolving 2,6-disulfonic acid as an alkali metal salt in water and precipitating it with an organic acid.
Method for purifying disulfonic acid. 3) The manufacturing method according to claim 1, wherein the reaction temperature is 95 to 110°C. 4) The manufacturing method according to claim 1 or 3, wherein oleum is used in a molar ratio of 3 or more to 1,4-diaminobenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32079590A JPH0623167B2 (en) | 1990-11-27 | 1990-11-27 | Method for producing 1,4-diaminobenzene-2,6-disulphonic acid and purification method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32079590A JPH0623167B2 (en) | 1990-11-27 | 1990-11-27 | Method for producing 1,4-diaminobenzene-2,6-disulphonic acid and purification method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04193858A true JPH04193858A (en) | 1992-07-13 |
| JPH0623167B2 JPH0623167B2 (en) | 1994-03-30 |
Family
ID=18125330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32079590A Expired - Fee Related JPH0623167B2 (en) | 1990-11-27 | 1990-11-27 | Method for producing 1,4-diaminobenzene-2,6-disulphonic acid and purification method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0623167B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308296C (en) * | 2003-12-03 | 2007-04-04 | 上海化学试剂研究所 | Process for purifying 2,5 diamino phenyl-1,3-disulfonic acid |
-
1990
- 1990-11-27 JP JP32079590A patent/JPH0623167B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308296C (en) * | 2003-12-03 | 2007-04-04 | 上海化学试剂研究所 | Process for purifying 2,5 diamino phenyl-1,3-disulfonic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0623167B2 (en) | 1994-03-30 |
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