JPH04210954A - Production of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid - Google Patents
Production of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acidInfo
- Publication number
- JPH04210954A JPH04210954A JP5406491A JP5406491A JPH04210954A JP H04210954 A JPH04210954 A JP H04210954A JP 5406491 A JP5406491 A JP 5406491A JP 5406491 A JP5406491 A JP 5406491A JP H04210954 A JPH04210954 A JP H04210954A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- disulfonic acid
- reaction
- disulfonic
- dinitronaphthalene
- 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 15
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 title claims abstract 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 20
- XFKRPUUIHKVIDM-UHFFFAOYSA-N 4,5-dinitronaphthalene-2,7-disulfonic acid Chemical compound [O-][N+](=O)C1=CC(S(O)(=O)=O)=CC2=CC(S(=O)(=O)O)=CC([N+]([O-])=O)=C21 XFKRPUUIHKVIDM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006722 reduction reaction Methods 0.000 claims abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 11
- VILFVXYKHXVYAB-UHFFFAOYSA-N naphthalene-2,7-disulfonic acid Chemical compound C1=CC(S(O)(=O)=O)=CC2=CC(S(=O)(=O)O)=CC=C21 VILFVXYKHXVYAB-UHFFFAOYSA-N 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006396 nitration reaction Methods 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 8
- 230000000802 nitrating effect Effects 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 239000002253 acid Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- VGHJNLKOGBNGTR-UHFFFAOYSA-N 4-nitronaphthalene-2,7-disulfonic acid Chemical compound [O-][N+](=O)C1=CC(S(O)(=O)=O)=CC2=CC(S(=O)(=O)O)=CC=C21 VGHJNLKOGBNGTR-UHFFFAOYSA-N 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 3
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000006277 sulfonation reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 13
- BRSYMBVQGUKXPE-UHFFFAOYSA-N 4,5-diaminonaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(N)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 BRSYMBVQGUKXPE-UHFFFAOYSA-N 0.000 abstract description 3
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 22
- 239000000543 intermediate Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 7
- -1 ammonium H acid salt Chemical class 0.000 description 6
- 238000004811 liquid chromatography Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- AVCSMMMOCOTIHF-UHFFFAOYSA-N 1,8-dinitronaphthalene Chemical compound C1=CC([N+]([O-])=O)=C2C([N+](=O)[O-])=CC=CC2=C1 AVCSMMMOCOTIHF-UHFFFAOYSA-N 0.000 description 1
- RJKGJBPXVHTNJL-UHFFFAOYSA-N 1-nitronaphthalene Chemical compound C1=CC=C2C([N+](=O)[O-])=CC=CC2=C1 RJKGJBPXVHTNJL-UHFFFAOYSA-N 0.000 description 1
- RWSMEUGBSLLVNA-UHFFFAOYSA-N 3,4-dinitronaphthalene-2,7-disulfonic acid Chemical compound [O-][N+](=O)C1=C([N+]([O-])=O)C(S(O)(=O)=O)=CC2=CC(S(=O)(=O)O)=CC=C21 RWSMEUGBSLLVNA-UHFFFAOYSA-N 0.000 description 1
- TZBROGJRQUABOK-UHFFFAOYSA-N 4-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=C2C(O)=CC(S(O)(=O)=O)=CC2=C1 TZBROGJRQUABOK-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- HLVXFWDLRHCZEI-UHFFFAOYSA-N chromotropic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(O)=CC(S(O)(=O)=O)=CC2=C1 HLVXFWDLRHCZEI-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- UTFRXVRPQCQDAD-UHFFFAOYSA-L dipotassium;naphthalene-2,7-disulfonate Chemical compound [K+].[K+].C1=CC(S([O-])(=O)=O)=CC2=CC(S(=O)(=O)[O-])=CC=C21 UTFRXVRPQCQDAD-UHFFFAOYSA-L 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- YZMHQCWXYHARLS-UHFFFAOYSA-N naphthalene-1,2-disulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C21 YZMHQCWXYHARLS-UHFFFAOYSA-N 0.000 description 1
- ZPBSAMLXSQCSOX-UHFFFAOYSA-N naphthalene-1,3,6-trisulfonic acid Chemical compound OS(=O)(=O)C1=CC(S(O)(=O)=O)=CC2=CC(S(=O)(=O)O)=CC=C21 ZPBSAMLXSQCSOX-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
［０００１］ [0001]
【産業上の利用分野】本発明は改良された１−アミノ８
−ヒドロキシナフタレン−３・６−ジスルホン酸（以下
、Ｈ酸という）の工業的製造法に関する。更に詳しくは
、ナフタレン−２・７−ジスルホン酸から、ニトロ化、
還元、加水分解の各工程を経て合成されるＨ酸の製造法
の工業的に改良された方法に関する。
［０００２］[Industrial Application Field] The present invention provides an improved 1-amino 8
-Relates to an industrial method for producing hydroxynaphthalene-3,6-disulfonic acid (hereinafter referred to as H acid). More specifically, from naphthalene-2,7-disulfonic acid, nitration,
This invention relates to an industrially improved method for producing H acid synthesized through reduction and hydrolysis steps. [0002]
【従来の技術】Ｈ酸は著名な染料中間体で、特に直接、
或いは酸性染料等のアゾ系染料の最も重要な中間物の一
つであり、現在、世界各国で多量生産され、同時にこれ
らＨ酸の製造に関する技術改良もさかんにおこなわれ、
更には研究報告或いは特許出願も多数おこなわれている
。しかしながら、これらＨ酸の製造方法、或いは改良方
法についての文献はナフタレン−１・３・６−トリスル
ホン酸のニトロ化、還元、アルカリ加水分解の工程を経
る方法についてだけであり、ナフタレン−２・７−ジス
ルホン酸からのＨ酸製造法についての最近の公知文献は
皆無である、と言っても過言ではない。ナフタレン２・
７−ジスルホン酸からのＨ酸製造方法についての公知文
献は、ナフタレン−２・７−ジスルホン酸ジカリウム塩
から１８モル倍量の濃硫酸中、０℃乃至５℃の範囲で１
．０８モル比の硝酸（混酸）でモノニトロ化し、次いで
硝酸カリウム１．４４モル比を加え、８０℃乃至９０℃
で１乃至２時間加熱攪拌し、得られた１・８−ジニトロ
ナフタレン３・６−ジスルホン酸を鉄粉及び硝酸を用い
て、還元し、対応する１・８−ジアミノナフタレン−３
・６−ジスルホン酸を得（ＤＲＰ、 Ａ、 ０．１４３
０） 、更に１・８ジアミノナフタレン−３・６−ジス
ルホン酸を約等モルの硫酸を含む１０％硫酸水溶液に加
え、約６時間１１０℃乃至１２０℃で加熱後、放冷する
ことによって針状微黄色のＨ酸アンモニウム塩が得られ
る（Ｄ ＲＰ ６７０６２） 、との記載があるが、該
方法における品質、収率等の記載はない。
［０００３］BACKGROUND OF THE INVENTION H-acid is a well-known dye intermediate, especially directly,
It is also one of the most important intermediates for azo dyes such as acid dyes, and is currently produced in large quantities in various countries around the world.
Furthermore, many research reports and patent applications have been filed. However, the literature on the production method or improvement method of these H acids is only about the method that goes through the steps of nitration, reduction, and alkaline hydrolysis of naphthalene-1,3,6-trisulfonic acid, and naphthalene-2. It is no exaggeration to say that there are no recent known documents regarding a method for producing H acid from 7-disulfonic acid. Naphthalene 2.
A known document on a method for producing H acid from 7-disulfonic acid states that naphthalene-2,7-disulfonic acid dipotassium salt is reacted with 18 moles of concentrated sulfuric acid at a temperature of 0°C to 5°C.
．． Mononitrate with 0.08 molar ratio of nitric acid (mixed acid), then add 1.44 molar ratio of potassium nitrate, and heat at 80°C to 90°C.
The resulting 1,8-dinitronaphthalene-3,6-disulfonic acid was reduced using iron powder and nitric acid to form the corresponding 1,8-diaminonaphthalene-3.
・6-disulfonic acid was obtained (DRP, A, 0.143
0), and further added 1,8 diamino naphthalene-3,6-disulfonic acid to a 10% aqueous sulfuric acid solution containing approximately equimolar sulfuric acid, heated at 110°C to 120°C for approximately 6 hours, and then allowed to cool to form needles. There is a description that a slightly yellow ammonium H acid salt is obtained (D RP 67062), but there is no description of the quality, yield, etc. of this method. [0003]
【発明が解決しようとする課題】本発明者等の該方法に
ついての追試結果によれば、異性体を多量に含んだＨ酸
が得られ、このままでは使用に耐えない品質であり、又
、収率的にも満足し得ないものであった。これらの状況
から、本発明者等はすでに完成した２・７−ナフタレン
ジスルホン酸の製法（特開昭５６−７７２５４号）によ
って得られる高純度２・７−ナフタレンジスルホン酸を
用いて、Ｈ酸を製造する工業的製造方法の研究に着手し
、鋭意検討をかさねた結果、本発明を完成したもので、
本発明は経済的であると共に高純度のＨ酸を高収率で得
られる方法を提供することを目的とする。
［０００４］[Problem to be Solved by the Invention] According to the results of a follow-up test of the method by the present inventors, H acid containing a large amount of isomers was obtained, and the quality was unsuitable for use as it was. The efficiency was also unsatisfactory. Under these circumstances, the present inventors used high-purity 2,7-naphthalenedisulfonic acid obtained by the already completed method for producing 2,7-naphthalenedisulfonic acid (Japanese Patent Application Laid-open No. 77254/1982) to produce H acid. We started research on industrial manufacturing methods and completed the present invention as a result of intensive study.
An object of the present invention is to provide a method that is economical and can obtain highly purified H acid in high yield. [0004]
【課題を解決するための手段】上記の課題を解決するた
め、本発明者らが鋭意検討したところ、２・７−ナフタ
レンジスルホン酸を用い、混酸でジニトロ化反応をおこ
なう場合、モノニトロ化物からジニトロ化物へ反応が進
行するに際し、中間化合物を経由して進行することを見
出し、且つ該中間化合物が系内に存在する場合、反応系
内の粘性増加を抑制することを見い出した。これらの性
質を巧みに利用することにより、反応溶媒として用いら
れている硫酸溶媒の使用を半減させることに成功した。
本発明者等は更に研究を進め、上記の方法よって、高収
率で得られる高品質の１・８−ジニトロナフタレン−３
・６−ジスルホン酸を用いての還元工程及び加水分解工
程についても鋭意検討を加えた結果、各工程においても
、成る限定された条件でのみ反応をおこなうことにより
、最終的に高収率で高品質のＨ酸を合成することに成功
した。
［０００５１本発明は上記の知見に基づいてなされたも
ので、更に具体的に述べるならば、ナフタレンのスルホ
ン化反応によって得たナフタレン−２・７−ジスルホン
酸を硫酸の存在下、ニトロ化剤を作用させ、■・８−ジ
ニトロナフタレン−３・６−ジスルホン酸を得、次いで
鉄粉を用いて還元し、１・８−ジアミノナフタレン−３
・６−ジスルホン酸を得、更に加水分解によってＨ酸を
製造する方法において、 （１）ナフタレン−２・７
ジスルホン酸を硫酸溶媒中、硝酸又は混酸でニトロ化し
、１・８−ジニトロナフタレン−３・６−ジスルホン酸
を製造する工程において、反応が１−ニトロナフタレン
−３・６−ジスルホン酸から１・８−ジニトロナフタレ
ン−３・６−ジスルホン酸へ進行する時点における反応
系内条件として、脱水値が５乃至２７、反応温度が一２
０℃乃至４０℃、反応溶媒としての硫酸を１−ニトロナ
フタレン−３・６−ジスルホン酸１モルに対し、６モル
乃至１５モルの条件下、硝酸又は混酸でニトロ化され、
且つニトロ止剤滴下終了後、１−ニトロナフタレン−３
・６ジスルホン酸が検出されなくなってから、水中に排
出し、硫酸濃度が８０％以下に希釈された状態で、０．
５時間以上昇温・熟成しジニトロ化反応を完成させる工
程。
（２）該ジニトロ化反応工程で得た１・８−ジニトロナ
フタレン−３・６−ジスルホン酸を、電解質として塩化
アンモニウムを０．２乃至３．０（モル／リットル−水
）含む水溶液中で、鉄粉を用いて８０℃以上の温度で還
元反応をおこなう工程。
（３）該還元工程で得た１・８−ジアミノナフタレン３
・６−ジスルホン酸１モル当り、１５重軍事乃至５０重
軍事の硫酸又は塩酸溶液１モル以上を使用し、１００℃
乃至沸点で加水分解をおこなう工程。の三工程を少くと
も含むＨ酸の製造法である。
［０００６］上記の構成からなる本発明について、更に
詳細に述べるならば、ジニトロ化工程において脱水値［
脱水値＝（反応最終系内硫酸重量）／（反応最終系内水
分重量）］が５以下では未反応物が多く残存し、その結
果最終Ｈ酸の品質悪化を招き、１２以上では選択性が若
干上昇するが、廃酸量の増大等、経済的に大きな効果は
望めない。又、反応温度については一２０℃以下では反
応系内の粘性が増加し、溶媒としての硫酸量を増加させ
なければ反応マスの系外への取出しが困難となり、経済
性を損う。又、４０℃以上では硝酸の分解、蒸発による
損失が大きく、そのために過剰の硝酸を必要とし、又、
異常反応による不明成分の増加を招き、好ましい結果は
得られない。以上のような理由により、本発明の限定さ
れた諸条件内でニトロ化反応を行なうことにより、溶媒
としての硫酸量を公知文献記載の方法と比較して、半減
し得る効果を得、同時に高品質な１・８−ジニトロナフ
タレン−３・６−ジスルホン酸を高収率で得られるとい
う効果を発現する。
［０００７］Ｌかしながら、これらの効果は該反応条件
内での反応においても、通常のジニトロ化反応の如く、
ジニトロ化の終了時点迄、反応を進行させた場合には発
現されず、むしろ反応系内はジニトロ化終点付近では高
粘性マスとなり、反応系外への排出も困難となり、又、
異常反応も進行して、そのために経済的に多大の損失を
招くことになる。本発明の他の特徴は上述した如く、モ
ノニトロ体よりジニトロ体に反応が進行するに際し、中
間化合物を経由し、該中間化合物の存在する反応系内の
粘性は低いという事実、更には該中間化合物は希釈され
た硫酸溶液においても、加熱することにより、容易に目
的物である１・８−ジニトロナフタレン−３・６−ジス
ルホン酸に反応が進むことを見い出したことにより、次
工程で好ましくない原因となる１−ニトロナフタレン３
・６−ジスルホン酸が反応系内に存在しなくなった時点
で、反応マスを水中に排出し、５０℃以上、好ましくは
８０℃以上に温度を高め、同温度で０．５時間以上、好
ましくは１時間以上保つことにより、溶媒としての硫酸
使用量を公知文献と比較して、半減した状態においても
、高収率で高品質な１・８−ジニトロナフタレン−３・
６ジスルホン酸を得ることができる、という上述した効
果が発現されるのである。又、熟成時間は該中間化合物
のジニトロ体への転移速度は速く、中間化合物が消失す
れば、それ以上の加熱は意味を有さない。又、硫酸の希
釈濃度は低くともジニトロ体への中間化合物からの転移
は進行するが、廃酸の再利用等を考慮した場合、系内の
異常反応は進行せず、転移反応のみが進行する濃度、即
ち、８０％以下の濃度で、実際的には可及的高濃度が好
ましい。
［０００８］該ニトロ化工程で得た１・８−ジニトロナ
フタレン−３・６−ジスルホン酸を鉄粉で還元する場合
、電解質として塩化アンモニア水溶液を用いるが、該濃
度を０．２（モル／リットル−水）以下の濃度では反応
も遅く、生産性が悪く、実際的ではない。又、３．０（
モル／リットル−水）以上は加えることの効果が生じな
い。 本発明者等は後述する如く、他の電解質の種類及
び該濃度における効果を種々検討したが、塩化アンモニ
ウムの該濃度範囲に調整することによってのみ、高収率
で還元をおこなうことができた。
［０００９］ これら還元工程で得られた１・８−ジア
ミノナフタレン−３・６−ジスルホン酸をモノ加水分解
によってＨ酸を製造する場合、文献記載の如く低濃度に
よる加水分解反応は、本発明者等の研究によれば、１０
％程度のクロモトロープ酸の生成を抑制することができ
ず、本発明の記載条件によってのみ、加水分解反応をお
こなわせることによって、予想以上の高収率、且つ高品
質のＨ酸を製造することができる。以上、本発明内容に
ついて詳細に説明してきた如く、各工程における製品の
品質の善し悪しが最終製品であるＨ酸の品質及び収率を
左右する。
［００１０１[Means for Solving the Problems] In order to solve the above problems, the present inventors have made extensive studies and found that when dinitration reaction is carried out with a mixed acid using 2,7-naphthalenedisulfonic acid, dinitration is The inventors have discovered that when the reaction progresses to a compound, the reaction proceeds via an intermediate compound, and that when the intermediate compound is present in the system, the increase in viscosity within the reaction system is suppressed. By skillfully utilizing these properties, we succeeded in halving the use of sulfuric acid as a reaction solvent. The present inventors have further conducted research and found that high quality 1,8-dinitronaphthalene-3 can be obtained in high yield by the above method.
・As a result of intensive studies on the reduction process using 6-disulfonic acid and the hydrolysis process, we found that by conducting the reaction only under limited conditions in each process, we finally achieved high yields and high yields. We succeeded in synthesizing high-quality H acid. [00051 The present invention has been made based on the above findings, and more specifically, naphthalene-2,7-disulfonic acid obtained by a naphthalene sulfonation reaction is treated with a nitrating agent in the presence of sulfuric acid. 1,8-dinitronaphthalene-3,6-disulfonic acid was obtained, which was then reduced using iron powder to obtain 1,8-diaminonaphthalene-3.
・In a method for obtaining 6-disulfonic acid and further producing H acid by hydrolysis, (1) Naphthalene-2.7
In the step of producing 1,8-dinitronaphthalene-3,6-disulfonic acid by nitrating disulfonic acid with nitric acid or a mixed acid in a sulfuric acid solvent, the reaction is to nitrate 1,8-dinitronaphthalene-3,6-disulfonic acid from 1-nitronaphthalene-3,6-disulfonic acid. -The conditions in the reaction system at the time of progressing to dinitronaphthalene-3,6-disulfonic acid are a dehydration value of 5 to 27, a reaction temperature of 12
Nitrated with nitric acid or mixed acid at 0°C to 40°C, using sulfuric acid as a reaction solvent in an amount of 6 mol to 15 mol per 1 mol of 1-nitronaphthalene-3,6-disulfonic acid,
And after finishing dropping the nitro stopper, 1-nitronaphthalene-3
・After 6-disulfonic acid is no longer detected, it is discharged into water and the sulfuric acid concentration is diluted to 80% or less.
A process of raising the temperature and aging for 5 hours or more to complete the dinitration reaction. (2) 1,8-dinitronaphthalene-3,6-disulfonic acid obtained in the dinitration reaction step in an aqueous solution containing 0.2 to 3.0 (mol/liter of water) ammonium chloride as an electrolyte, A process in which a reduction reaction is carried out using iron powder at a temperature of 80°C or higher. (3) 1,8-diaminonaphthalene 3 obtained in the reduction step
・Use 1 mole or more of a 15 to 50 strength sulfuric acid or hydrochloric acid solution per 1 mole of 6-disulfonic acid at 100°C.
A process in which hydrolysis is carried out at the boiling point. This is a method for producing H acid which includes at least the following three steps. [0006] To describe the present invention having the above configuration in more detail, the dehydration value [
If the dehydration value = (weight of sulfuric acid in the final reaction system)/(weight of water in the final reaction system) is less than 5, a large amount of unreacted substances will remain, resulting in deterioration of the quality of the final H acid, and if it is more than 12, the selectivity will decrease. Although it will increase slightly, no significant economic effects such as an increase in the amount of waste acid can be expected. Furthermore, when the reaction temperature is below -20°C, the viscosity within the reaction system increases, and unless the amount of sulfuric acid as a solvent is increased, it becomes difficult to take out the reaction mass from the system, which impairs economic efficiency. Moreover, at temperatures above 40°C, the loss due to decomposition and evaporation of nitric acid is large, which requires an excess of nitric acid, and
This will lead to an increase in unknown components due to abnormal reactions, making it impossible to obtain favorable results. For the reasons mentioned above, by carrying out the nitration reaction within the limited conditions of the present invention, it is possible to reduce the amount of sulfuric acid as a solvent by half compared to methods described in known literature, and at the same time achieve a high The effect is that high quality 1,8-dinitronaphthalene-3,6-disulfonic acid can be obtained in high yield. [0007]L However, these effects can be observed even in the reaction within the above reaction conditions, as in the usual dinitration reaction.
If the reaction is allowed to proceed until the end of dinitration, it will not be expressed; rather, the reaction system will become a highly viscous mass near the end of dinitration, and it will be difficult to discharge it out of the reaction system.
Abnormal reactions also progress, resulting in large economic losses. As mentioned above, another feature of the present invention is the fact that when the reaction progresses from a mononitro compound to a dinitro compound, the viscosity in the reaction system in which the intermediate compound exists is low, and furthermore, the viscosity of the reaction system in which the intermediate compound exists is low. discovered that even in a diluted sulfuric acid solution, the reaction easily progresses to the target product, 1,8-dinitronaphthalene-3,6-disulfonic acid, by heating, thereby eliminating undesirable causes in the next step. 1-nitronaphthalene 3
- When 6-disulfonic acid no longer exists in the reaction system, the reaction mass is discharged into water, the temperature is raised to 50°C or higher, preferably 80°C or higher, and the temperature is maintained at the same temperature for 0.5 hours or more, preferably By keeping it for more than 1 hour, even when the amount of sulfuric acid used as a solvent is halved compared to known literature, high yield and high quality 1,8-dinitronaphthalene-3.
The above-mentioned effect of being able to obtain 6-disulfonic acid is achieved. Furthermore, the rate of transition of the intermediate compound to the dinitro form is fast, and once the intermediate compound disappears, further heating is meaningless. In addition, even if the diluted concentration of sulfuric acid is low, the transfer from the intermediate compound to the dinitro form will proceed, but if the reuse of waste acid is taken into account, no abnormal reaction will proceed in the system, and only the transfer reaction will proceed. The concentration is 80% or less, preferably as high as possible in practice. [0008] When reducing 1,8-dinitronaphthalene-3,6-disulfonic acid obtained in the nitration step with iron powder, an aqueous ammonia chloride solution is used as an electrolyte, and the concentration is 0.2 (mol/liter). - water) or lower, the reaction is slow, productivity is poor, and it is not practical. Also, 3.0 (
(mol/liter - water), the addition has no effect. As will be described later, the present inventors have variously investigated the effects of other electrolyte types and concentrations, but were able to achieve high yield reduction only by adjusting the ammonium chloride concentration within the range. [0009] When producing H acid by monohydrolysis of the 1,8-diaminonaphthalene-3,6-disulfonic acid obtained in these reduction steps, the present inventors conducted a hydrolysis reaction at a low concentration as described in the literature. According to research by et al., 10
% of chromotropic acid, and by carrying out the hydrolysis reaction only under the conditions described in the present invention, H acid can be produced in a higher yield than expected and in high quality. I can do it. As described above in detail about the contents of the present invention, the quality of the product in each step influences the quality and yield of the final product, H acid. [00101
【発明の効果］本発明は、ナフタレン−２・７−ジスル
ホン酸を原料として用い、特定の条件下でニトロ化、還
元、加水分解の各工程をおこなうＨ酸の製造法であり、
高純度のＨ酸を高収率で得ることができる。また、ジニ
トロ化工程における硫酸使用量の低減など、Ｈ酸製造工
程の経済性、操作性を著しく改良することができる。
［００１１］
【実施例】本発明を更に詳細に説明するため、以下に実
施例をあげて説明するが、本発明の範囲はこれら実施例
のみに限定されるものではない。
実施例 １
９５、６８％の硫酸１０２４．２ｇ （１０モル）中に
１モルの２・７ナフタレンジスルホン酸が溶解した溶液
（脱水値１２）に調整し、冷却後、９９％硝酸７０ｇを
０〜３℃の範囲で１時間を要して滴下し、同温度で１時
間攪拌し、次いで９９％硝酸７０ｇを同温度で１時間を
要して滴下、後更に３時間同温度に制御しながら攪拌反
応をおこない、１−二ト口ナフタレン−３・６−ジスル
ホン酸の消失を液体クロマトグラフィーで確認した。こ
の時点での液体クロマトグラムから、中間化合物７．４
％、１・８−ジニトロナフタレン−３・６−ジスルホン
酸８４．４％を含有していたことを確認した。該反応マ
スを水９３５．７ｇ中に排出し、硫酸濃度を５０％に希
釈し、９０℃乃至９５℃の範囲で約２時間同温度で保温
攪拌を続けた。冷却後、液体クロマトグラフィーで分析
した結果、目的物である１・８−ジニトロナフタレン−
３・６−ジスルホン酸の収率は９１．７％であった。常
法に準じて、上記の１・８−ジニトロナフタレン−３・
６−ジスルホン酸溶液に４８％水酸化ナトリウム液１９
１．７ ｇを加えて結晶を析出させ、１・８−ジニトロ
ナフタレン−３・６−ジスルホン酸ジナトリウム塩を得
た。なお、液体クロマトグラフィー及び原子吸光分析に
よりジナトリウム塩であることを確認した。
［００１２］
実施例 ２
９６、２１％の硫酸７１．５０ ｇ中に２・７−ナフタ
レンジスルホン酸０．１０５モルが溶解した溶液に調整
し、１５℃に冷却後、９８％硫酸／９９％硝酸＝１７１
（軍事比で）の混酸２９、４６ ｇの１／２を１５℃
±２℃に反応系内を制御しながら１時間を要して滴下、
次いで同温度で１時間攪拌した後、残りの混酸を１時間
要して、同温度で滴下、滴下後、同温度で更に１時間保
温攪拌した（硫酸モル比８．０７、脱水値１２）。液体
クロマトグラフィーで分析した結果、中間化合物５．７
％、■・８−ジニトロナフタレン３・６−ジスルホン酸
８７．６％を含み、１−二ト口ナフタレン−３・６−ジ
スルホン酸を含まないことを確認した。該反応マスを水
２８．７３ｇ中に排出（硫酸濃度７０％）し、９０℃に
昇温、９０℃乃至９５℃の範囲で３時間保温攪拌した。
液体クロマトグラフィーで分析した結果、目的物である
１・８−ジニトロナフタレン−３・６−ジスルホン酸は
８９．２％含有し、中間化合物は含まれていなかった。
［００１３］
実施例 ３〜８
実施例１及び実施例２に準じ、硝酸又は混酸でニトロ化
をおこない、各条件を変えて該方法を実施した。結果は
以下の表１に示した。
［００１４］[Effects of the invention] The present invention is a method for producing H acid, which uses naphthalene-2,7-disulfonic acid as a raw material and performs the steps of nitration, reduction, and hydrolysis under specific conditions.
High purity H acid can be obtained in high yield. Furthermore, the economic efficiency and operability of the H acid production process can be significantly improved, such as by reducing the amount of sulfuric acid used in the dinitration process. [0011] [0011] In order to explain the present invention in more detail, Examples are given below, but the scope of the present invention is not limited only to these Examples. Example 1 A solution of 1 mole of 2.7 naphthalenedisulfonic acid dissolved in 1024.2 g (10 moles) of 95%, 68% sulfuric acid (dehydration value 12) was prepared, and after cooling, 70 g of 99% nitric acid was added to It was added dropwise over 1 hour at 3°C, stirred at the same temperature for 1 hour, then 70 g of 99% nitric acid was added dropwise at the same temperature over 1 hour, and then stirred for another 3 hours while controlling the same temperature. The reaction was carried out, and the disappearance of 1-dito-naphthalene-3,6-disulfonic acid was confirmed by liquid chromatography. From the liquid chromatogram at this point, intermediate compound 7.4
%, and 84.4% of 1,8-dinitronaphthalene-3,6-disulfonic acid. The reaction mass was discharged into 935.7 g of water, the sulfuric acid concentration was diluted to 50%, and stirring was continued at the same temperature for about 2 hours in the range of 90°C to 95°C. After cooling, analysis by liquid chromatography revealed that the target product was 1,8-dinitronaphthalene.
The yield of 3,6-disulfonic acid was 91.7%. According to a conventional method, the above 1,8-dinitronaphthalene-3.
48% sodium hydroxide solution in 6-disulfonic acid solution 19
1.7 g was added to precipitate crystals to obtain 1,8-dinitronaphthalene-3,6-disulfonic acid disodium salt. In addition, it was confirmed that it was a disodium salt by liquid chromatography and atomic absorption spectrometry. [0012] Example 2 A solution of 0.105 mol of 2,7-naphthalenedisulfonic acid dissolved in 71.50 g of 96.21% sulfuric acid was prepared, and after cooling to 15°C, 98% sulfuric acid/99% nitric acid was prepared. =171
1/2 of 29.46 g of mixed acid (military ratio) at 15℃
The reaction system was added dropwise over an hour while controlling the temperature at ±2°C.
Next, after stirring at the same temperature for 1 hour, the remaining mixed acid was added dropwise at the same temperature over a period of 1 hour, and after the dropwise addition, the mixture was further stirred at the same temperature for 1 hour (sulfuric acid molar ratio: 8.07, dehydration value: 12). As a result of liquid chromatography analysis, intermediate compound 5.7
It was confirmed that the sample contained 87.6% of 8-dinitronaphthalene-3,6-disulfonic acid and did not contain 1-ditoronaphthalene-3,6-disulfonic acid. The reaction mass was discharged into 28.73 g of water (sulfuric acid concentration: 70%), heated to 90°C, and stirred at a temperature in the range of 90°C to 95°C for 3 hours. As a result of analysis by liquid chromatography, it was found that the target product, 1,8-dinitronaphthalene-3,6-disulfonic acid, was contained in an amount of 89.2%, and no intermediate compound was contained. [0013] Examples 3 to 8 According to Examples 1 and 2, nitration was performed with nitric acid or mixed acid, and the method was carried out by changing each condition. The results are shown in Table 1 below. [0014]
【表１】
［００１５］
実施例 ９
水１リットル中に塩化アンモニウム０．４モルを加え、
更に鉄粉３７６、６５ ｇを加え、攪拌しながら９８℃
に昇温、９８℃〜１００℃で３０分保温攪拌した。次い
で実施例１で得た１・８−ジニトロナフタレン−３・６
−ジスルホン酸ジナトリウム塩４２２．３ ｇを沸点下
、１時間を要して投入、更に同温度で１時間攪拌し、後
７０℃に冷却、鉄粉を分離、１・８−ジアミノナフタレ
ン−３・６−ジスルホン酸ジナトリウム塩０．９６５モ
ルを含んだ溶液１０７０ ｇを得た。該溶液１０７ｇを
水で４２．５％に調整した硫酸１７８ｇと混合すると、
１・８−ジアミノナフタレン−３・６−ジスルホン酸モ
ノナトリウム塩が析出したが、懸濁状態で３０分を要し
て１２０℃迄昇温、１２０±２℃で１７．５時間加熱攪
拌した。
後、３時間を要して３０℃迄放冷、析出したＨ酸モノナ
トリウム塩を分取、水洗後１００℃で１０時間乾燥し、
■・８−ジアミノナフタレン−３・６−ジスルホン酸モ
ノナトリウム塩３．０％を含んだＨ酸モノナトリウム塩
を、１・８−ジニトロナフタレン−３・６−ジスルホン
酸に対して８８．６％の収率で得た。
［００１６］
実施例 １０
実施例９で得た還元液１０７ｇに３５％塩酸６０．３７
ｇを加えると、１・８−ジアミノナフタレン−３・６−
ジスルホン酸モノナトリウム塩が析出するが、そのまま
懸濁状態で攪拌しながら、３０分を要して１１５℃まで
昇温、１１５±２℃で２０時間保温攪拌した。後３時間
放冷し３０℃になったとき、析出しているＨ酸モノナト
リウム塩を分取し、２０ｍ１の水で水洗、乾燥し、■・
８−ジアミノナフタレン−３・６−ジスルホン酸モノナ
トリウム塩２．２％を含むＨ酸モノナトリウム塩をジニ
トロ体に対し、９０％の収率で得た。
［００１７］
実施例 １１
塩化アンモニウム溶液の濃度を変化させた以外は、実施
例９に準じて還元工程をおこない、表２に示される結果
を得た。
表２
［００１８］
実施例 １２〜１９
使用した硫酸及び塩酸の濃度、温度及び時間を変化させ
、実施例９．１０に準じて加水分解反応をおこなった。
その結果を表３に示す。
［００１９］[Table 1] [0015] Example 9 Adding 0.4 mol of ammonium chloride to 1 liter of water,
Add 376.65 g of iron powder and heat to 98°C while stirring.
The temperature was raised to 98°C to 100°C, and the mixture was stirred while keeping the temperature at 98°C to 100°C for 30 minutes. Next, 1,8-dinitronaphthalene-3,6 obtained in Example 1
- Added 422.3 g of disulfonic acid disodium salt at boiling point over 1 hour, stirred at the same temperature for 1 hour, then cooled to 70°C, separated iron powder, 1,8-diaminonaphthalene-3 - 1070 g of a solution containing 0.965 mol of 6-disulfonic acid disodium salt was obtained. When 107 g of this solution is mixed with 178 g of sulfuric acid adjusted to 42.5% with water,
Although 1,8-diaminonaphthalene-3,6-disulfonic acid monosodium salt precipitated, the temperature was raised to 120°C over 30 minutes in a suspended state, and the mixture was heated and stirred at 120±2°C for 17.5 hours. After that, it was left to cool to 30°C over a period of 3 hours, and the precipitated H acid monosodium salt was collected, washed with water, and dried at 100°C for 10 hours.
■H acid monosodium salt containing 3.0% of 8-diaminonaphthalene-3,6-disulfonic acid monosodium salt is 88.6% based on 1,8-dinitronaphthalene-3,6-disulfonic acid. It was obtained in a yield of . [0016] Example 10 Add 60.37 g of 35% hydrochloric acid to 107 g of the reducing solution obtained in Example 9.
When g is added, 1,8-diaminonaphthalene-3,6-
Disulfonic acid monosodium salt was precipitated, but the mixture was stirred in a suspended state, and the temperature was raised to 115° C. over 30 minutes, and the mixture was stirred at 115±2° C. for 20 hours. After cooling for 3 hours, when the temperature reached 30°C, the precipitated H acid monosodium salt was collected, washed with 20 ml of water, dried, and
H acid monosodium salt containing 2.2% of 8-diaminonaphthalene-3,6-disulfonic acid monosodium salt was obtained in a yield of 90% based on the dinitro form. [0017] Example 11 The reduction process was carried out in the same manner as in Example 9, except that the concentration of the ammonium chloride solution was changed, and the results shown in Table 2 were obtained. Table 2 [0018] Examples 12 to 19 A hydrolysis reaction was carried out according to Example 9.10 while changing the concentrations of sulfuric acid and hydrochloric acid used, temperature, and time. The results are shown in Table 3. [0019]
【表３】
［００２０１
参考例 １
電解質種を塩化アンモニウムに代えて、硫酸、塩酸、酢
酸、硫酸アンモニウム、硫酸ナトリウム等を用い、還元
条件を検討したが、いずれの場合にも９３％以上の１・
８−ジアミツナフタレン−３・６−ジスルホン酸を得る
ことができず、還元反応は成る程度進行するが、工業的
でないと判断した。
フロントページの続き[Table 3] [00201 Reference Example 1 Reduction conditions were investigated using sulfuric acid, hydrochloric acid, acetic acid, ammonium sulfate, sodium sulfate, etc. instead of ammonium chloride as the electrolyte species, but in all cases, 1.
8-diamitunaphthalene-3,6-disulfonic acid could not be obtained, and although the reduction reaction progressed to some extent, it was judged that it was not industrially practical. Continuation of front page
Claims (1)
て得たナフタレン−２・７−ジスルホン酸を硫酸の存在
下、ニトロ化剤を作用させ、１・８−ジニトロナフタレ
ン−３・６−ジスルホン酸を得、次いで鉄粉を用いて還
元し、■・８−ジアミノナフタレン−３・６−ジスルホ
ン酸を得、更に加水分解によって、１−アミノ−８−ヒ
ドロキシナフタレン−３・６−ジスルホン酸を製造する
方法において、 （１）ナフタレン−２・７−ジスルホン酸を硫酸溶媒中
、硝酸又は混酸でニトロ化し、１・８−ジニトロナフタ
レン−３・６−ジスルホン酸を製造する工程において、
反応が１−ニトロナフタレン−３・６−ジスルホン酸か
ら１・８−ジニトロナフタレン−３・６−ジスルホン酸
へ進行する時点における反応系内条件として、脱水値が
５乃至２７、反応温度が一２０℃乃至４０℃、反応溶媒
としての硫酸を１−ニトロナフタレン−３・６−ジスル
ホン酸１モルに対し、６モル乃至１５モルの条件下、硝
酸又は混酸でニトロ化され、且つニトロ止剤滴下終了後
、１ニトロナフタレン−３・６−ジスルホン酸が検出さ
れなくなってから、水中に排出し、硫酸濃度が８０％以
下に希釈された状態で０．５時間以上昇温・熟成しジニ
トロ化反応を完成させる工程。 （２）該ジニトロ化反応工程で得た１・８−ジニトロナ
フタレン−３・６−ジスルホン酸を、電解質として塩化
アンモニウムを０．２乃至３．０（モル／リットル−水
）含む水溶液中で、鉄粉を用いて８０℃以上の温度で還
元反応をおこなう工程。 （３）該還元工程で得た１・８−ジアミノナフタレン３
・６−ジスルホン酸１モル当り、１５重量％乃至５０重
軍事の硫酸又は塩酸溶液１モル以上を使用し、１００℃
乃至沸点で加水分解をおこなう工程。の三工程を少なく
とも含む１−アミノ−８−ヒドロキシナフタレン−３・
６ジスルホン酸の製造法。Claim 1: Naphthalene-2,7-disulfonic acid obtained by a sulfonation reaction of naphthalene is treated with a nitrating agent in the presence of sulfuric acid to obtain 1,8-dinitronaphthalene-3,6-disulfonic acid, Next, in a method for producing 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid by reduction using iron powder to obtain 1.8-diaminonaphthalene-3,6-disulfonic acid and further hydrolysis. (1) In the step of nitrating naphthalene-2,7-disulfonic acid with nitric acid or mixed acid in a sulfuric acid solvent to produce 1,8-dinitronaphthalene-3,6-disulfonic acid,
The conditions in the reaction system at the time when the reaction progresses from 1-nitronaphthalene-3,6-disulfonic acid to 1,8-dinitronaphthalene-3,6-disulfonic acid are as follows: dehydration value is 5 to 27, reaction temperature is -20 ℃ to 40℃, nitration is carried out with nitric acid or a mixed acid under conditions of 6 to 15 moles of sulfuric acid as a reaction solvent per 1 mole of 1-nitronaphthalene-3,6-disulfonic acid, and the dropwise addition of the nitration stopper is completed. After that, after 1-nitronaphthalene-3,6-disulfonic acid was no longer detected, it was discharged into water and heated and aged for more than 0.5 hours with the sulfuric acid concentration diluted to 80% or less to carry out the dinitration reaction. The process of completing it. (2) 1,8-dinitronaphthalene-3,6-disulfonic acid obtained in the dinitration reaction step in an aqueous solution containing 0.2 to 3.0 (mol/liter of water) ammonium chloride as an electrolyte, A process in which a reduction reaction is carried out using iron powder at a temperature of 80°C or higher. (3) 1,8-diaminonaphthalene 3 obtained in the reduction step
・Use 1 mole or more of 15% by weight to 50% sulfuric acid or hydrochloric acid solution per mole of 6-disulfonic acid, and heat at 100°C.
A process in which hydrolysis is carried out at the boiling point. 1-amino-8-hydroxynaphthalene-3, comprising at least three steps of
6. Method for producing disulfonic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5406491A JPH04210954A (en) | 1991-02-25 | 1991-02-25 | Production of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5406491A JPH04210954A (en) | 1991-02-25 | 1991-02-25 | Production of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16013482A Division JPS5951253A (en) | 1982-09-14 | 1982-09-14 | Novel preparation of 1,8-dinitronaphthalene-3,6-disulfonic acid, and preparation of high-purity 1-amino-8- hydroxynaphthalene-3,6-disulfonic acid using its method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04210954A true JPH04210954A (en) | 1992-08-03 |
| JPH0524146B2 JPH0524146B2 (en) | 1993-04-06 |
Family
ID=12960190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5406491A Granted JPH04210954A (en) | 1991-02-25 | 1991-02-25 | Production of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04210954A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775808A (en) * | 2012-08-23 | 2012-11-14 | 楚源高新科技集团股份有限公司 | Process for recycling ammonium sulfate and synthesizing acidic dye by T-acid mother liquor wastewater |
| CN102936213A (en) * | 2011-08-15 | 2013-02-20 | 中国中化股份有限公司 | Clean preparation method of 1, 8-dinitro-3, 6-naphthalenedisulfonic acid |
| CN106698744A (en) * | 2016-12-06 | 2017-05-24 | 浙江力禾集团有限公司 | Method for removing hydrazine hydrate in H acid waste water |
-
1991
- 1991-02-25 JP JP5406491A patent/JPH04210954A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936213A (en) * | 2011-08-15 | 2013-02-20 | 中国中化股份有限公司 | Clean preparation method of 1, 8-dinitro-3, 6-naphthalenedisulfonic acid |
| CN102775808A (en) * | 2012-08-23 | 2012-11-14 | 楚源高新科技集团股份有限公司 | Process for recycling ammonium sulfate and synthesizing acidic dye by T-acid mother liquor wastewater |
| CN106698744A (en) * | 2016-12-06 | 2017-05-24 | 浙江力禾集团有限公司 | Method for removing hydrazine hydrate in H acid waste water |
| CN106698744B (en) * | 2016-12-06 | 2019-10-18 | 浙江力禾集团有限公司 | A method of hydrazine hydrate in removal H acid waste water |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0524146B2 (en) | 1993-04-06 |
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