JPH0419987B2 - - Google Patents
Info
- Publication number
- JPH0419987B2 JPH0419987B2 JP16013482A JP16013482A JPH0419987B2 JP H0419987 B2 JPH0419987 B2 JP H0419987B2 JP 16013482 A JP16013482 A JP 16013482A JP 16013482 A JP16013482 A JP 16013482A JP H0419987 B2 JPH0419987 B2 JP H0419987B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- reaction
- disulfonic acid
- dinitronaphthalene
- disulfonic
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 239000002253 acid Substances 0.000 claims description 37
- 238000004519 manufacturing process Methods 0.000 claims description 24
- 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 description 12
- 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 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 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 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims description 5
- -1 1-nitronaphthalene- 1,8-dinitronaphthalene Chemical compound 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 230000000802 nitrating effect Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000005070 ripening Effects 0.000 claims description 2
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 claims 1
- 230000002250 progressing effect Effects 0.000 claims 1
- 239000000543 intermediate Substances 0.000 description 14
- 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 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 238000006396 nitration reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000004811 liquid chromatography Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 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 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-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
- 238000001816 cooling Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 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 2
- 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 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 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
- 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000987 azo dye Substances 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
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- OESVLPLHBXKGGT-UHFFFAOYSA-L disodium 4,5-diaminonaphthalene-2,7-disulfonate Chemical compound [Na+].NC1=CC(=CC2=CC(=CC(=C12)N)S(=O)(=O)[O-])S(=O)(=O)[O-].[Na+] OESVLPLHBXKGGT-UHFFFAOYSA-L 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003792 electrolyte 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
- 238000009776 industrial production Methods 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
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 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 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 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)
Description
＜産業上の利用分野＞
本発明は１・８−ジニトロナフタレン−３・６
−ジスルホン酸の製造法に関する。より詳細に
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）を製造する際の中間
体として有用な１・８−ジニトロナフタレン−
３・６−ジスルホン酸の製造法に関する。
＜従来の技術及び発明が解決しようとする課題＞
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
言つても過言ではない。
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時間加熱撹拌し、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−ジスルホン酸が得られ
（DRP.A.O.1430）、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、放冷することによつて針状微黄
色のＨ酸アンモニウム塩が得られる
（DRP67062）、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。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
であつた。
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）によつて得られる高純度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、ニトロ化、還
元、加水分解の各工程について鋭意検討をかさね
た結果、高純度のＨ酸を高収率で得られる方法を
見出した。本発明はかかるＨ酸の製法において、
中間体として有用な１・８−ジニトロナフタレン
−３・６−ジスルホン酸の製造法を提供するもの
である。
＜課題を解決するための手段＞
本発明は２・７−ナフタレンジスルホン酸を出
発物質とし、特定の条件下でニトロ化をおこなう
１・８−ジニトロナフタレン−３・６−ジスルホ
ン酸の製造法である。より詳細には、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いだし、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、本発明を完成した。
本発明を更に具体的に述べるならば、
１ ２・７−ナフタレンジスルホン酸を硫酸溶媒
中、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方法
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−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
トロ化剤滴下終了後、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つてか
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ことを特徴とする１・
８−ジニトロナフタレン−３・６−ジスルホン
酸の製造法。
２ 脱水値を８乃至12にして、ジニトロ化反応を
おこなわせることを特徴とする上記１）記載の
製造法。
３ 反応温度を−10℃乃至25℃の範囲で、ジニト
ロ化反応をおこなわせることを特徴とする上記
１）又は２）記載の製造法。
４ 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、８モ
ル乃至12モルを用いて、ジニトロ化反応をおこ
なわせることを特徴とする上記１）、２）又は
３）記載の製造法。
５ ジニトロ化反応を熟成・完成させる際、該反
応温度を50℃乃至沸点以下でおこなうことを特
徴とする上記１）、２）、３）又は４）記載の製
造法。
本発明は上記の構成からなり、２・７−ナフタ
レンジスルホン酸をニトロ化して１−ニトロナフ
タレン−３・６−ジスルホン酸を生成させ、２・
７−ナフタレンジスルホン酸が消失しモノニトロ
化が完了した後の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−ジスルホン酸へのジニトロ化反応時に
おける反応系内条件として特定の条件を採用する
ものである。
上記の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−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。
しかしながら、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つた時点
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。
本発明の方法により得られた１・８−ジニトロ
ナフタレン−３・６−ジスルホン酸は、還元して
１・８−ジアミノナフタレン−３・６−ジスルホ
ン酸とし、次いでモノ加水分解することによりＨ
酸を得ることができる。特に、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
て塩化アンモニアを含む水溶液中、80℃以上の温
度で鉄粉を用いて還元して１・８−ジアミノナフ
タレン−３・６−ジスルホン酸とし、次いで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重量％の硫酸又は塩
酸溶液１モル以上を使用して100℃乃至沸点でモ
ノ加水分解することにより高収率且つ高純度でＨ
酸を得ることができる。
＜発明の効果＞
本発明によれば特定の条件下でニトロ化反応が
おこなわれており、硫酸の使用量を著しく低減で
きるとと共に高収率の高純度の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
できるという効果を奏する。
＜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時間撹拌し、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
御しながら撹拌反応をおこない、１−ニトロナフ
タレン−３・６−ジスルホン酸の消失を液体クロ
マトグラフイーで確認した。
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、硝酸濃度
を50％に希釈し、90℃乃至95℃の範囲で約２時間
同温度で保温撹拌を続けた。
冷却後、液体クロマトグラフイーで分析した結
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％であつた。
常法に準じて、上記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191.7ｇ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
ジナトリウムを得た。尚、液体クロマトグラフイ
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。
実施例 ２
96.21％の硫酸71.50ｇ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＝１／１（重
量比で）の混酸29.46ｇ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時間撹拌した後、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
時間保温撹拌した（硫酸モル比8.07、脱水値12）。
液体クロマトグラフイーで分析した結果、中間
化合物5.7％、１・８−ジニトロナフタレン−
３・６−ジスルホン酸87.6％を含み、１−ニトロ
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
間保温撹拌した。
液体クロマトグラフイーで分析した結果、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
れていなかつた。
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。結果は以下の表に示した。
<Industrial Application Field> The present invention relates to 1,8-dinitronaphthalene-3,6
-Relating to a method for producing disulfonic acid. More specifically, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (hereinafter referred to as H acid) is produced from naphthalene-2,7-disulfonic acid through the steps of nitration, reduction, and hydrolysis. 1,8-dinitronaphthalene useful as an intermediate in the production of
The present invention relates to a method for producing 3,6-disulfonic acid. <Prior art and problems to be solved by the invention> H acid is a famous dye intermediate, and is one of the most important intermediates for azo dyes such as direct or acid dyes, and is currently used in many countries around the world. At the same time, technical improvements related to the production of these H acids have been actively made, and many research reports and patent applications have been filed. However, there are no literatures on the production method or improvement method of these H acids.
It is only about a method that goes through the steps of nitration, reduction, and alkaline hydrolysis of 6-trisulfonic acid,
It is no exaggeration to say that there are no recent known documents regarding a method for producing H acid from naphthalene-2,7-disulfonic acid. Publicly known documents regarding the method for producing H acid from naphthalene-2,7-disulfonic acid include naphthalene-2,7-disulfonic acid.
Dipotassium 2,7-disulfonic acid salt was mononitrated with 1.08 molar ratio of nitric acid (mixed acid) in 18 molar amount of concentrated sulfuric acid in the range of 0°C to 5°C, then 1.44 molar ratio of potassium nitrate was added, and the mixture was heated at 80°C to 90°C. After heating and stirring at ℃ for 1 to 2 hours, the obtained 1,8-dinitronaphthalene-3,6-disulfonic acid was reduced using iron powder and nitric acid to obtain the corresponding 1,8-diaminonaphthalene-3,6. -Disulfonic acid was obtained (DRP.AO1430), and 1,8-diaminonaphthalene-3,6-disulfonic acid was added to a 10% aqueous sulfuric acid solution containing about equimolar sulfuric acid, and the mixture was heated at 110°C for about 6 hours.
There is a description that a acicular slightly yellow ammonium salt of H-acid can be obtained by heating at 120° C. and then allowing it to cool (DRP67062), but there is no description of the quality, yield, etc. of this method. 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 unusable as it was, and the yield was also unsatisfactory. It was hot. Under these circumstances, the present inventors have developed highly pure 2,7-naphthalenedisulfonic acid, which can be obtained by the already completed method for producing 2,7-naphthalenedisulfonic acid (Japanese Patent Application Laid-open No. 77254/1983).
We started research on an industrial production method for producing H-acid using naphthalenedisulfonic acid, and after intensive study of each step of nitration, reduction, and hydrolysis, we were able to produce high-purity H-acid in high yield. I found a way to get it. The present invention provides a method for producing such H acid,
The present invention provides a method for producing 1,8-dinitronaphthalene-3,6-disulfonic acid, which is useful as an intermediate. <Means for Solving the Problems> The present invention is a method for producing 1,8-dinitronaphthalene-3,6-disulfonic acid, which uses 2,7-naphthalenedisulfonic acid as a starting material and performs nitration under specific conditions. be. More specifically, we found that when dinitration reaction is carried out with a mixed acid using 2,7-naphthalenedisulfonic acid, the reaction progresses from a mononitrated product to a dinitrated product via an intermediate compound. It has been found that when an 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 reducing the use of sulfuric acid solvent used as a reaction solvent by half, and completed the present invention. To describe the present invention more specifically, in a method for producing 1,8-dinitronaphthalene-3,6-disulfonic acid by nitrating 12,7-naphthalenedisulfonic acid with a mixed acid in a sulfuric acid solvent, the reaction is 1-nitronaphthalene-3.
The reaction system conditions at the time when 6-disulfonic acid progresses to 1,8-dinitronaphthalene-3,6-disulfonic acid are such that the dehydration value is 5 to 5.
27. Nitric acid or mixed acid was used at a reaction temperature of -20°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 nitrating agent, 1-nitronaphthalene-
After 3,6-disulfonic acid is no longer detected, it is discharged into water and heated and aged for 0.5 hours or more with the sulfuric acid concentration diluted to 80% or less to complete the dinitration reaction. Do 1・
Method for producing 8-dinitronaphthalene-3,6-disulfonic acid. 2. The production method described in 1) above, characterized in that the dinitration reaction is carried out at a dehydration value of 8 to 12. 3. The production method described in 1) or 2) above, wherein the dinitration reaction is carried out at a reaction temperature in the range of -10°C to 25°C. 4. The dinitration reaction is carried out using 8 to 12 moles of sulfuric acid as a reaction solvent per mole of 1-nitronaphthalene-3,6-disulfonic acid, or 1) or 2) above. 3) Manufacturing method described. 5. The production method described in 1), 2), 3), or 4) above, wherein the reaction temperature is 50°C to below the boiling point when ripening and completing the dinitration reaction. The present invention has the above configuration, in which 2,7-naphthalenedisulfonic acid is nitrated to produce 1-nitronaphthalene-3,6-disulfonic acid, and 2.
1-Nitronaphthalene-3.6 after 7-naphthalenedisulfonic acid disappears and mononitration is completed
-Specific conditions are employed as conditions within the reaction system during the dinitration reaction from -disulfonic acid to 1,8-dinitronaphthalene-3,6-disulfonic acid. In the above dinitration step, if the dehydration value [dehydration value = (weight of sulfuric acid in the final reaction system)/(weight of water in the final reaction system)] is 5 or less, many unreacted substances remain;
As a result, the quality of the final H acid deteriorates, and if it is 12 or more, the selectivity increases slightly, but no significant economic effect can be expected due to an increase in the amount of waste acid. Furthermore, when the reaction temperature is -20°C or lower, 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.
Furthermore, at temperatures above 40°C, there is a large loss of nitric acid due to decomposition and evaporation, which requires an excess of nitric acid.
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 Quality 1.8
-Dinitronaphthalene-3,6-disulfonic acid can be obtained in high yield. However, even in the reaction under these reaction conditions, if the reaction is allowed to proceed until the end of the dinitration, as in a normal dinitration reaction, the reaction system will not produce the dinitration. Near the end point, the mass becomes highly viscous, making it difficult to discharge it out of the reaction system, and abnormal reactions also proceed, 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. When 1-nitronaphthalene-3,6-disulfonic acid no longer exists in the reaction system, the reaction mass is discharged into water, the temperature is raised to 50℃ or higher, preferably 80℃ or higher, and By keeping the amount of sulfuric acid as a solvent for 0.5 hours or more, preferably 1 hour or more, high yield and high quality 1.8-
The above-mentioned effect of being able to obtain dinitronaphthalene-3,6-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. The 1,8-dinitronaphthalene-3,6-disulfonic acid obtained by the method of the present invention is reduced to 1,8-diaminonaphthalene-3,6-disulfonic acid, and then monohydrolyzed into H
Acid can be obtained. In particular, 1,8-diaminonaphthalene-3,6-disulfonic acid is reduced using iron powder at a temperature of 80°C or higher in an aqueous solution containing ammonia chloride as an electrolyte. disulfonic acid, then 1.
High yield and high yield can be obtained by monohydrolyzing at 100°C to boiling point using 1 mol or more of 15 wt% to 50 wt% sulfuric acid or hydrochloric acid solution per 1 mol of 8-diaminonaphthalene-3,6-disulfonic acid. H in purity
Acid can be obtained. <Effects of the Invention> According to the present invention, the nitration reaction is carried out under specific conditions, which makes it possible to significantly reduce the amount of sulfuric acid used, and to produce highly purified 1,8-dinitronaphthalene-3 in high yield. The effect is that 6-disulfonic acid can be obtained. <Examples> In order to explain the present invention in more detail, Examples will be 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 prepared.
was added dropwise over a period of 1 hour in the range of 0 to 3℃, stirred for 1 hour at the same temperature, then 70 g of 99% nitric acid was added dropwise over a period of 1 hour at the same temperature, and then the temperature was controlled for an additional 3 hours. The reaction was carried out with stirring, and the disappearance of 1-nitronaphthalene-3,6-disulfonic acid was confirmed by liquid chromatography. The liquid chromatogram at this point shows that the intermediate compound was 7.4%, 1,8-dinitronaphthalene-3,
It was confirmed that it contained 84.4% of 6-disulfonic acid. The reaction mass was discharged into 935.7 g of water, the nitric 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, 1,8-dinitronaphthalene-
The yield of 3,6-disulfonic acid was 91.7%. According to a conventional method, 191.7 g of 48% sodium hydroxide solution was added to the above 1,8-dinitronaphthalene-3,6-disulfonic acid solution to precipitate crystals.
Disodium 8-dinitronaphthalene-3,6-disulfonate was obtained. It was confirmed by liquid chromatography and atomic absorption analysis that it was a disodium salt. Example 2 A solution of 0.105 mol of 2,7-naphthalenedisulfonic acid was prepared in 71.50 g of 96.21% sulfuric acid,
After cooling to 15℃, 1/2 of 29.46g of mixed acid of 98% sulfuric acid/99% nitric acid = 1/1 (weight ratio) was added to the reaction system for 1 hour while controlling the temperature at 15℃±2℃. Dropwise, then after stirring at the same temperature for 1 hour, the remaining mixed acid was added dropwise at the same temperature for 1 hour.
The mixture was kept warm and stirred for an hour (sulfuric acid molar ratio 8.07, dehydration value 12). As a result of liquid chromatography analysis, the intermediate compound was 5.7%, 1,8-dinitronaphthalene.
It was confirmed that it contained 87.6% of 3,6-disulfonic acid and did not contain 1-nitronaphthalene-3,6-disulfonic acid. The reaction mass was discharged into 28.73 g of water (sulfuric acid concentration 70
%), the temperature was raised to 90°C, and the mixture was stirred at a temperature in the range of 90°C to 95°C for 3 hours. As a result of liquid chromatography analysis, the target product, 1,8-dinitronaphthalene-3,6-
It contained 89.2% disulfonic acid and no intermediate compounds. Examples 3 to 8 According to Examples 1 and 2, nitration was carried out using nitric acid or a mixed acid, and the method was carried out by changing each condition. The results are shown in the table below.
【表】
参考例 １
水１中に塩化アンモニウム0.4モルを加え、
更に鉄粉376.65ｇを加え、撹拌しながら98℃に昇
温、98℃〜100℃で30分保温撹拌した。
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
422.3ｇを沸点下、１時間を要して投入、更に同
温度で１時間撹拌し、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
1070ｇ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時間加熱撹拌した。
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、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。[Table] Reference example 1 Add 0.4 mol of ammonium chloride to 1 mol of water,
Furthermore, 376.65 g of iron powder was added, and the temperature was raised to 98° C. while stirring, and the mixture was stirred at a temperature of 98° C. to 100° C. for 30 minutes. Next, 1,8-dinitronaphthalene-3,6-disulfonic acid disodium salt obtained in Example 1
422.3g was added over a period of 1 hour at the boiling point, stirred for another 1 hour at the same temperature, then cooled to 70℃, iron powder was separated, and 1,8-diaminonaphthalene-3,6-disulfonic acid disodium salt was obtained. Solution containing 0.965 mol
Obtained 1070g. 178g of sulfuric acid prepared by adjusting 107g of the solution to 42.5% with water
When mixed with 1,8-diaminonaphthalene-
3,6-disulfonic acid monosodium salt was precipitated, but it took 30 minutes to raise the temperature to 120℃ in a suspended state.
The mixture was heated and stirred at ±2°C for 17.5 hours. After that, the precipitated H acid monosodium salt was collected, washed with water, and dried at 100°C for 10 hours to obtain 1,8-diaminonaphthalene-3,6-
H containing 3.0% disulfonic acid monosodium salt
The acid monosodium salt was obtained in a yield of 88.6% based on 1,8-dinitronaphthalene-3,6-disulfonic acid.
Claims (1)
中、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方法にお
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−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、且つニトロ化剤滴下終了後、
１−ニトロナフタレン−３・６−ジスルホン酸が
検出されなくなつてから、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ことを
特徴とする１・８−ジニトロナフタレン−３・６
−ジスルホン酸の製造法。 ２ 脱水値を８乃至12にして、ジニトロ化反応を
おこなわせることを特徴とする特許請求の範囲第
１項記載の製造法。 ３ 反応温度を−10℃乃至25℃の範囲で、ジニト
ロ化反応をおこなわせることを特徴とする特許請
求の範囲第１項又は第２項記載の製造法。 ４ 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、８モル
乃至12モルを用いて、ジニトロ化反応をおこなわ
せることを特徴とする特許請求の範囲第１項乃至
第３項のいずれかに記載の製造法。 ５ ジニトロ化反応を熟成・完成させる際、該反
応温度を50℃乃至沸点以下でおこなうことを特徴
とする特許請求の範囲第１項乃至第４項のいずれ
かに記載の製造法。[Claims] 1. A method for producing 1,8-dinitronaphthalene-3,6-disulfonic acid by nitrating 2,7-naphthalenedisulfonic acid with a mixed acid in a sulfuric acid solvent, in which the reaction is 1-nitronaphthalene- 1,8-dinitronaphthalene from 3,6-disulfonic acid
The conditions in the reaction system at the time of progressing to 3,6-disulfonic acid were: dehydration value of 5 to 27, reaction temperature of -20°C to 40°C, and sulfuric acid as a reaction solvent of 1-
Nitronaphthalene-3,6-disulfonic acid is nitrated with nitric acid or mixed acid under conditions of 6 to 15 moles per mole of 3,6-disulfonic acid, and after completion of dropping the nitrating agent,
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 while the sulfuric acid concentration was diluted to 80% or less to complete the dinitration reaction. 1,8-dinitronaphthalene-3,6 characterized by
-Production method of disulfonic acid. 2. The production method according to claim 1, characterized in that the dinitration reaction is carried out at a dehydration value of 8 to 12. 3. The production method according to claim 1 or 2, characterized in that the dinitration reaction is carried out at a reaction temperature in the range of -10°C to 25°C. 4. Claim 1, characterized in that the dinitration reaction is carried out using 8 to 12 moles of sulfuric acid as a reaction solvent per 1 mole of 1-nitronaphthalene-3,6-disulfonic acid. The manufacturing method according to any one of Items 3 to 3. 5. The production method according to any one of claims 1 to 4, characterized in that when ripening and completing the dinitration reaction, the reaction temperature is from 50°C to below the boiling point.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16013482A 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16013482A 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 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5406491A Division JPH04210954A (en) | 1991-02-25 | 1991-02-25 | Production of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5951253A JPS5951253A (en) | 1984-03-24 |
| JPH0419987B2 true JPH0419987B2 (en) | 1992-03-31 |
Family
ID=15708602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16013482A Granted 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 |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5951253A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256302B (en) * | 2019-06-27 | 2020-07-17 | 山东创蓝垚石环保技术有限公司 | Method for producing H acid by complex extraction |
| CN112774616A (en) * | 2020-12-18 | 2021-05-11 | 尹诺士国际股份有限公司 | Process for the preparation of dinitronaphthalenes |
-
1982
- 1982-09-14 JP JP16013482A patent/JPS5951253A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5951253A (en) | 1984-03-24 |
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