JPS6152138B2 - - Google Patents
Info
- Publication number
- JPS6152138B2 JPS6152138B2 JP633377A JP633377A JPS6152138B2 JP S6152138 B2 JPS6152138 B2 JP S6152138B2 JP 633377 A JP633377 A JP 633377A JP 633377 A JP633377 A JP 633377A JP S6152138 B2 JPS6152138 B2 JP S6152138B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- dihydroxydiphenylamine
- aminophenol
- para
- sulfate
- 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
Links
- YRUPBAWWCPVHFT-UHFFFAOYSA-N 4-(4-hydroxyanilino)phenol Chemical compound C1=CC(O)=CC=C1NC1=CC=C(O)C=C1 YRUPBAWWCPVHFT-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000012043 crude product Substances 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000012264 purified product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229950000244 sulfanilic acid Drugs 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 para-aminophenol hydrochloric acid Salt Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は４・4′−ジヒドロキシジフエニルアミ
ンの精製法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for purifying 4,4'-dihydroxydiphenylamine.
４・4′−ジヒドロキシジフエニルアミンは有機
物質の酸化防止剤として用いられるほか、農薬、
医薬、ポリマー、その他有機合成の中間体として
有用な物質である。 4,4'-Dihydroxydiphenylamine is used as an antioxidant for organic substances, as well as for agricultural chemicals,
It is a substance useful as an intermediate in pharmaceuticals, polymers, and other organic synthesis.
４・4′−ジヒドロキシジフエニルアミンはパラ
アミノフエノールの２分子より脱アンモニア縮合
反応により製造することができる化合物であり、
この方法で製造された粗製品には、原料のパラア
ミノフエノールの他に構造不明の高分子物が不純
物として含まれる。 4,4'-dihydroxydiphenylamine is a compound that can be produced from two molecules of para-aminophenol by deammonia condensation reaction,
The crude product produced by this method contains a polymer of unknown structure as an impurity in addition to the raw material para-aminophenol.
４・4′−ジヒドロキシジフエニルアミンの精製
法として、従来水またはその他の溶剤を用いて、
この化合物自体を再結晶させる方法が行われて来
たが、水を用いる場合には４・4′−ジヒドロキシ
ジフエニルアミンが水に対して難溶性であるため
極めて多量の水を必要とする不便があり、また、
有機溶剤を用いる場合には、４・4′−ジヒドロキ
シジフエニルアミンが、溶液状態で極めて酸化さ
れやすいため、厳重に酸素を排除しなければなら
ないという欠点がある。 Conventional methods for purifying 4,4'-dihydroxydiphenylamine include using water or other solvents.
A method of recrystallizing this compound itself has been carried out, but when using water, it is inconvenient that an extremely large amount of water is required because 4,4'-dihydroxydiphenylamine is poorly soluble in water. There is, and also,
When an organic solvent is used, there is a drawback that oxygen must be strictly excluded because 4,4'-dihydroxydiphenylamine is extremely easily oxidized in a solution state.
また水に対して溶解度を高めるため無機塩にし
て再結晶させる方法も考えられるが、４・4′−ジ
ヒドロキシジフエニルアミン中に含まれる不純物
のパラアミノフエノールは、４・4′−ジヒドロキ
シジフエニルアミンより造塩しやすく、水に対す
る溶解度が大きい。したがつて、無機酸の中でも
造塩しやすい塩酸などを用いて塩酸塩にして再結
晶させた場合は、再結晶時のロスを少なくして高
純度の精製物を得ようとしてもパラアミノフエノ
ール塩酸塩の混入は避けられない。 In addition, in order to increase the solubility in water, a method of recrystallizing the inorganic salt may be considered, but the impurity para-aminophenol contained in 4,4'-dihydroxydiphenylamine is It is easier to form salt and has high solubility in water. Therefore, when recrystallizing the hydrochloride salt using hydrochloric acid, which is easy to form salts among inorganic acids, para-aminophenol hydrochloric acid Salt contamination is unavoidable.
本発明者らは、４・4′−ジヒドロキシジフエニ
ルアミンの硫酸塩が再結晶に隆し結晶化しやす
く、かつ空気に対して比較的安定であることに着
目し、検討を重ねた結果、該硫酸塩を水より再結
晶させ、次で中和する方法が簡便かつすぐれた精
製方法であることを見出し、本発明に到達した。 The present inventors focused on the fact that the sulfate of 4,4'-dihydroxydiphenylamine is easily crystallized by recrystallization, and is relatively stable against air. We have discovered that a method of recrystallizing sulfate from water and then neutralizing it is a simple and excellent purification method, and have arrived at the present invention.
本発明の方法によつて精製される４・4′−ジヒ
ドロキシジフエニルアミンの粗製品としては、例
えばパラアミノフエノールの脱アンモニア縮合反
応を経て得られる、未反応原料およびタール状物
等の不純物を多量含む混合物の反応マスを直接用
いてもよいが、また、一旦反応マス中に比較的多
量に含まれるパラアミノフエノールを塩酸塩とし
て固液分離、中和して予じめ大部分の不純物を除
去した後に得られる比較的不純物が少ない製品を
用いてもよい。 The crude product of 4,4'-dihydroxydiphenylamine purified by the method of the present invention contains a large amount of impurities such as unreacted raw materials and tar-like substances obtained through the deammonia condensation reaction of para-aminophenol. Although the reaction mass of the mixture containing p-aminophenol may be used directly, it is also possible to remove most of the impurities in advance by solid-liquid separation and neutralization of para-aminophenol, which is contained in a relatively large amount in the reaction mass, as a hydrochloride. The relatively impurity-free product obtained later may also be used.
本発明の方法を実施するには、４・4′−ジヒド
ロキシジフエニルアミンの粗製品を1.0ないし5.0
当量の硫酸を含む水溶液３部ないし10部に加え、
通常80〜90℃まで加熱溶解し、この温度でタール
状の高分子不純物を活性炭などの吸着剤を用いて
脱色した後、冷却して結晶を析出させる。これを
固液分離することにより、不純物のパラアミノフ
エノールは硫酸塩として母液に移行させて除去さ
れるが、なお微量のパラアミノフエノール硫酸塩
が結晶に付着しているので少量の水で洗つたの
ち、水に懸濁させ、中和してPH６ないし８とし、
過して水洗し、乾燥すればよい。 To carry out the process of the present invention, the crude product of 4,4'-dihydroxydiphenylamine is mixed between 1.0 and 5.0
In addition to 3 to 10 parts of an aqueous solution containing an equivalent amount of sulfuric acid,
Usually, it is heated and dissolved to 80-90°C, and at this temperature, tar-like polymer impurities are decolorized using an adsorbent such as activated carbon, and then cooled to precipitate crystals. By solid-liquid separation, the impurity para-aminophenol is transferred to the mother liquor as sulfate and removed, but since a trace amount of para-aminophenol sulfate is still attached to the crystals, after washing with a small amount of water, Suspend in water and neutralize to pH 6 to 8,
Just wash it with water and dry it.
これらの操作は、酸化による不純物の生成を避
けるため、不活性気体の雰囲気下で手早く行うの
が望ましい。 It is desirable that these operations be carried out quickly under an inert gas atmosphere in order to avoid the formation of impurities due to oxidation.
また、４・4′−ジヒドロキシジフエニルアミン
はパラアミノフエノール含量が少ない場合は、た
とえば反応マスを直接硫酸に排出し、得られた硫
酸塩を析出させ単離後、この硫酸塩を用いること
も勿論可能である。 In addition, if 4,4'-dihydroxydiphenylamine has a low para-aminophenol content, it is of course possible to discharge the reaction mass directly into sulfuric acid, precipitate the resulting sulfate, isolate it, and then use this sulfate. It is possible.
中和には通常用いられるアルカリを使用するこ
とができ、例えば、水酸化ナトリウム、水酸化カ
リウム、炭酸ナトリウム、炭酸カリウム、アンモ
ニア、水酸化アンモニウム等が用いられる。 A commonly used alkali can be used for neutralization, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia, ammonium hydroxide, and the like.
粗製品からの回収率は通常充分高いが、硫酸塩
の母液を濃縮再使用することにより、回収率を更
に向上させることが可能である。 Although the recovery rate from the crude product is usually sufficiently high, it is possible to further improve the recovery rate by concentrating and reusing the sulfate mother liquor.
本発明の方法によつて得られる精製品は無色
で、パラアミノフエノールを事実上含まないこと
がガスクロマトグラフイーによりたしかめられて
いる。 The purified product obtained by the method of the present invention is colorless and virtually free of para-aminophenol, as confirmed by gas chromatography.
次に実施例により、本発明の方法を詳しく説明
する。 Next, the method of the present invention will be explained in detail with reference to Examples.
実施例 １
パラアミノフエノール6.0ｇおよびスルフアニ
ル酸0.2ｇを混合し、窒素雰囲気中、210℃で１時
間撹拌したのち、反応混合物を30mlの５％塩酸中
に排出し、活性炭で脱色し、水酸化ナトリウム水
溶液で中和した。析出した沈澱を過し、水洗
し、乾燥して４・4′−ジヒドロキシジフエニルア
ミンの粗製品3.42ｇを得た。融点は158〜164℃
（文献値169゜、174゜）であつた。この粗製品は
淡い青紫色を呈し、ガスクロマトグラフイーによ
り、約0.3％のパラアミノフエノールを含むこと
が判つた。Example 1 6.0 g of para-aminophenol and 0.2 g of sulfanilic acid were mixed and stirred at 210°C for 1 hour in a nitrogen atmosphere. The reaction mixture was then discharged into 30 ml of 5% hydrochloric acid, decolorized with activated carbon, and diluted with sodium hydroxide. Neutralized with aqueous solution. The precipitate was filtered, washed with water, and dried to obtain 3.42 g of a crude product of 4,4'-dihydroxydiphenylamine. Melting point is 158-164℃
(Reference values: 169°, 174°). This crude product had a pale blue-purple color and was found to contain approximately 0.3% para-aminophenol by gas chromatography.
この粗製品を3.5％硫酸25mlに加えて加熱溶解
させ、そのまま約１ｇの活性炭でタール分を脱色
したのち冷却して析出した結晶を過し、約５ml
の水で付着のパラアミノフエノール硫酸塩を手早
く洗い、ただちに50mlの水に懸濁させ、水酸化ナ
トリウム水溶液で中和して析出した白色の固体を
過し、水洗し、乾燥した。精製品の収量は2.80
ｇで、粗製品からの回収率は82％であつた。 This crude product was added to 25 ml of 3.5% sulfuric acid, heated and dissolved, and after decolorizing the tar with about 1 g of activated carbon, it was cooled and the precipitated crystals were filtered, and about 5 ml
The attached para-aminophenol sulfate was quickly washed with water, immediately suspended in 50 ml of water, neutralized with an aqueous sodium hydroxide solution, and the precipitated white solid was filtered, washed with water, and dried. The yield of purified product is 2.80
g, and the recovery rate from the crude product was 82%.
このようにして精製された４・4′−ジヒドロキ
シジフエニルアミンは無色の微粉末状固体で、ガ
スクロマトグラフイーによる分析ではパラアミノ
フエノールその他の不純物は検出されなかつた。
融点は168〜９℃で文献値と一致した。元素分析
値（炭素71.67％、水素5.45％、窒素6.90％）は計
算値（炭素71.63％、水素5.51％、窒素6.96％）と
よく一致した。 The thus purified 4,4'-dihydroxydiphenylamine was a colorless finely powdered solid, and no para-aminophenol or other impurities were detected when analyzed by gas chromatography.
The melting point was 168-9°C, consistent with literature values. The elemental analysis values (carbon 71.67%, hydrogen 5.45%, nitrogen 6.90%) were in good agreement with the calculated values (carbon 71.63%, hydrogen 5.51%, nitrogen 6.96%).
実施例 ２
実施例１に従つて反応および精製を行つたが、
塩酸および硫酸の中和には水酸化ナトリウム水溶
液のかわりにアンモニア水を用いたところ、実施
例１と本質的に同様の結果が得られた。即ち、粗
製品の収量3.29ｇ、精製品の収量2.80ｇ、粗製品
よりの精製品の回収率85％であつた。Example 2 The reaction and purification were carried out according to Example 1, but
When aqueous ammonia was used instead of an aqueous sodium hydroxide solution to neutralize hydrochloric acid and sulfuric acid, essentially the same results as in Example 1 were obtained. That is, the yield of the crude product was 3.29 g, the yield of the purified product was 2.80 g, and the recovery rate of the purified product from the crude product was 85%.
実施例 ３
パラアミノフエノール6.0ｇおよびスルフアニ
ル酸0.2ｇを混合し、窒素雰囲気中、210℃で１時
間撹拌した。この反応混合物を５％硫酸30ml中に
加え、80〜90℃で活性炭を用いて溶液が透明な暗
褐色を呈するまで脱色し、放冷した。Example 3 6.0 g of para-aminophenol and 0.2 g of sulfanilic acid were mixed and stirred at 210° C. for 1 hour in a nitrogen atmosphere. The reaction mixture was added to 30 ml of 5% sulfuric acid, decolorized using activated carbon at 80-90°C until the solution became clear and dark brown, and allowed to cool.
析出した結晶を過し、約５mlの水で手早く洗
滌したのち、50mlの水に懸濁させて炭酸ナトリウ
ム水溶液で中和した。析出した結晶を過し、水
洗し、乾燥した結果、無色の粉末2.59ｇが得られ
た。このものの融点は167〜９℃であり、ガスク
ロマトグラフイーでは、パラアミノフエノール等
の不純物は検出されなかつた。 The precipitated crystals were filtered and briefly washed with about 5 ml of water, then suspended in 50 ml of water and neutralized with an aqueous sodium carbonate solution. The precipitated crystals were filtered, washed with water, and dried to obtain 2.59 g of colorless powder. The melting point of this product was 167-9°C, and no impurities such as para-aminophenol were detected by gas chromatography.
実施例 ４
パラアミノフエノール6.0ｇおよびスルフアニ
ル酸0.2ｇを混合し、窒素雰囲気中、210℃で１時
間撹拌した。この反応混合物を25mlの５％硫酸中
に排出し、90℃に加熱し、室温まで放冷し、析出
した暗褐色の結晶を過し、約５mlの水で手早く
洗滌した。こうして得られた４・4′−ジヒドロキ
シジフエニルアミン硫酸塩の粗結晶をただちに25
mlの3.5％硫酸中に加え、80〜90℃に加温して溶
解させ、約0.2ｇの活性炭を加えて約30分間撹拌
した。得られた淡褐色の水溶液を放冷し、析出し
た結晶を過し、約５mlの水で手早く洗滌した
後、50mlの水に懸濁させて水酸化ナトリウム水溶
液で中和した。析出した沈澱を過、水洗し、乾
燥して無色の４・4′−ジヒドロキシジフエニルア
ミン2.55ｇを得た。この精製品の融点は168〜９
℃であつた。Example 4 6.0 g of para-aminophenol and 0.2 g of sulfanilic acid were mixed and stirred at 210° C. for 1 hour in a nitrogen atmosphere. The reaction mixture was poured into 25 ml of 5% sulfuric acid, heated to 90° C., allowed to cool to room temperature, and the dark brown crystals that had precipitated were filtered off and washed briefly with about 5 ml of water. The crude crystals of 4,4′-dihydroxydiphenylamine sulfate thus obtained were immediately
ml of 3.5% sulfuric acid, heated to 80-90°C to dissolve, added about 0.2 g of activated carbon, and stirred for about 30 minutes. The resulting pale brown aqueous solution was allowed to cool, and the precipitated crystals were filtered and washed quickly with about 5 ml of water, suspended in 50 ml of water, and neutralized with an aqueous sodium hydroxide solution. The precipitate was filtered, washed with water, and dried to obtain 2.55 g of colorless 4,4'-dihydroxydiphenylamine. The melting point of this purified product is 168-9
It was warm at ℃.
Claims (1)
硫酸塩にして加熱溶解させた水溶液を、吸着剤の
存在下処理した後、再結晶して４・4′−ジヒドロ
キシジフエニルアミン硫酸塩を単離し、次で中和
することを特徴とする４・4′−ジヒドロキシジフ
エニルアミンの精製方法。1 4,4'-dihydroxydiphenylamine,
4, characterized in that an aqueous solution prepared by heating and dissolving the sulfate is treated in the presence of an adsorbent, recrystallized to isolate 4,4'-dihydroxydiphenylamine sulfate, and then neutralized.・Method for purifying 4'-dihydroxydiphenylamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP633377A JPS5392722A (en) | 1977-01-25 | 1977-01-25 | Purification of 4,4'-dihydroxydiphenylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP633377A JPS5392722A (en) | 1977-01-25 | 1977-01-25 | Purification of 4,4'-dihydroxydiphenylamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5392722A JPS5392722A (en) | 1978-08-15 |
| JPS6152138B2 true JPS6152138B2 (en) | 1986-11-12 |
Family
ID=11635424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP633377A Granted JPS5392722A (en) | 1977-01-25 | 1977-01-25 | Purification of 4,4'-dihydroxydiphenylamine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5392722A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2001253147A1 (en) | 2000-04-03 | 2001-10-15 | Phycogen, Inc. | Generation of combinatorial synthetic libraries and screening for proadhesins and nonadhesins |
| CN103992233B (en) * | 2014-05-16 | 2016-06-08 | 常州大学 | A kind of method of synthesis 2-(arylamino) phenol of ferrum catalysis |
-
1977
- 1977-01-25 JP JP633377A patent/JPS5392722A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5392722A (en) | 1978-08-15 |
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