CN1085210A - 1，4-二氨基蒽醌-2，3-二磺酸和1，4-二氨基蒽醌-2，3-二腈的制备 - Google Patents
1，4-二氨基蒽醌-2，3-二磺酸和1，4-二氨基蒽醌-2，3-二腈的制备 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- VZXITARXQRMVGJ-UHFFFAOYSA-N 1,4-diamino-9,10-dioxoanthracene-2,3-disulfonic acid Chemical compound C1=CC=C2C(=O)C3=C(N)C(S(O)(=O)=O)=C(S(O)(=O)=O)C(N)=C3C(=O)C2=C1 VZXITARXQRMVGJ-UHFFFAOYSA-N 0.000 title claims description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 24
- 150000004056 anthraquinones Chemical class 0.000 claims abstract description 16
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000009835 boiling Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 5
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- 238000000034 method Methods 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 150000004996 alkyl benzenes Chemical group 0.000 claims description 8
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- 239000011541 reaction mixture Substances 0.000 claims description 5
- WETZVVQTMWRYHU-UHFFFAOYSA-N 1,4-diamino-2,3-dibromoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=C(Br)C(Br)=C2N WETZVVQTMWRYHU-UHFFFAOYSA-N 0.000 claims description 3
- KZYAYVSWIPZDKL-UHFFFAOYSA-N 1,4-diamino-2,3-dichloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=C(Cl)C(Cl)=C2N KZYAYVSWIPZDKL-UHFFFAOYSA-N 0.000 claims description 3
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- 235000010338 boric acid Nutrition 0.000 description 9
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000006277 sulfonation reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- -1 alkali metal sulfite Chemical class 0.000 description 2
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- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
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- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- PLUFITIFLBGFPN-UHFFFAOYSA-N 1,2-dichloroanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=C(Cl)C(Cl)=CC=C3C(=O)C2=C1 PLUFITIFLBGFPN-UHFFFAOYSA-N 0.000 description 1
- FBMQNRKSAWNXBT-UHFFFAOYSA-N 1,4-diaminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=CC=C2N FBMQNRKSAWNXBT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
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- 238000003916 acid precipitation Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
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- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
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- 239000000049 pigment Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/33—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of six-membered aromatic rings being part of condensed ring systems
- C07C309/38—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of six-membered aromatic rings being part of condensed ring systems formed by at least three rings
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
- C09B1/22—Dyes with unsubstituted amino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/16—Preparation of carboxylic acid nitriles by reaction of cyanides with lactones or compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
- C09B1/22—Dyes with unsubstituted amino groups
- C09B1/24—Dyes with unsubstituted amino groups sulfonated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/24—Anthracenes; Hydrogenated anthracenes
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Abstract
1，4-二氨基蒽醌-2，3-二磺酸(I)的制备方法，
即在惰性有机溶剂中将1，4-二氨基-2，3-二卤代蒽
醌(II)与硼酸反应，然后使所得反应产物(IIa)进一
步与亚硫酸钠溶液反应，其中所用的惰性有机溶剂是
沸点≥130℃并且粘度≤0.95g/cm3的非极性溶
剂。1，4-二氨基蒽酯-2，3-二磺酸(I)与氰化物反
应，可制得1，4-二氨基蒽酯-2，3-二腈(III)。
Description
本发明涉及1，4-二氨基蒽醌-2，3-二磺酸（Ⅰ）的改进的制备方法，即在惰性溶剂中使1，4-二氨基-2，3-二卤代蒽醌（Ⅱ）与硼酸反应，并使所得反应产物与亚硫酸盐溶液进一步反应。
本发明还涉及1，4-二氨基蒽醌-2，3-腈（Ⅲ）的制备方法，即使本发明得到的1，4-二氨基蒽醌-2，3-二磺酸（Ⅰ）与氰化物反应。
1，4-二氨基蒽醌-2，3-二磺酸（Ⅰ）和1，4-二氨基蒽醌-2，3-二腈（Ⅲ）是制备兰色分散染料（如C.I.分散兰60）的有用中间体，其结构式如下：
US-A-4279825公开了从1，4-二氨基-2，3-二氯代蒽醌制备1，4-二氨基蒽醌-2，3-二磺酸的方法。其中，首先在硝基苯存在下将二氯蒽醌与硼酸反应，反应中所形成的水以其与硝基苯的混合物形式完全蒸除。蒽醌和硼酸的反应产物（Ⅱa）以中间体的形式被分离出来，然后与亚硫酸盐水溶液反应得到二磺酸。
该方法的缺点是在蒸除硝基苯和水的同时，过量使用的挥发性硼酸也被排出，有时会导致特定设备的故障。当使用US-A-4279825推荐的划槽式干燥器来干燥中间体（Ⅱa）时，由于反应混合物的高度腐蚀作用还会引起其它问题。
然后，使二磺酸（Ⅱ）与氰化物反应，将（Ⅱ）转变为二腈（Ⅲ）例如US-A-4279825所述。
本发明的目的是从过程工程的角度提供经济、简便的制备1，4-二氨基蒽醌-2，3-二磺酸（Ⅰ）的方法，该方法无上述缺点，产率高，纯度高。从而对制备1，4-二氨基蒽醌-2，3-二腈（Ⅲ）有利。
我们发现，上述目的可通过下述1，4-二氨基蒽醌-2，3-二磺酸（Ⅰ）的制备方法而达到，即在惰性有机溶剂中将1，4-二氨基-2，3-二卤代蒽醌（Ⅱ）与硼酸反应，然后使所得反应产物（Ⅱa）进一步与亚硫酸钠溶液反应，其中所用的惰性有机溶剂是沸点≥130℃并且粘度≤0.95g/cm3的非极性溶剂。
按照本发明制得的1，4-二氨基蒽醌-2，3-二磺酸（Ⅰ）可与氰化物反应，转变为1，4-二氨基蒽醌-2，3-二腈（Ⅲ）。
适用于1，4-二氨基-2，3-二卤代蒽醌（Ⅱ）与硼酸的反应的非极性有机溶剂通常沸点≥130℃。
除了可商购的脂肪族烃类或其混合物（例如：商标为Exsol
的产品，Esso Chemie生产）外，还特别优选芳香族烃类，尤其是在130℃以上沸腾的烷基苯。特别优选的烷基苯的例子有间二甲苯、对二甲苯和邻二甲苯及其混合物、乙苯和异丙苯。采用适当的烷基萃混合物（例如：Esso Chemie生产的商品Solvesso
）特别有利。非常特别优选沸点为180-200℃密度约为0.90g/cm3（Solvesso 150）的混合物。
所用溶剂的沸点原则上没有上限，但由于实践上的原因，不使用沸点高于约250℃的烃类作为反应介质，这是因为其粘度太高。也可以使用130℃以下、尤其是140℃以下沸腾的烷基苯，但在这种情况下反应温度必须相应地降低，导致反应速度不经济地降低。因此，一般来说特别优选沸点为160-220℃的溶剂。
此外，溶剂的密度应低于水相的密度，尤其在磺化反应中，例如密度通常应低于或等于0.95g/cm3。
在本发明中，使用溶剂的特别有利之处在于它们不必在磺化反应之前分离，但从蒽醌（Ⅱ）和硼酸得到的中间体（Ⅱa）可不经中间体分离而直接以所得反应混合物的形式与亚硫酸盐反应得到二磺酸（Ⅰ）。然后可简单地将溶剂轻相分离出来，再作溶剂使用。US-A-4279825所述问题在本新方法中根本不出现，这是由于可以免除中间体（Ⅱa）的分离。
本发明中溶剂（尤其是烷基苯）用量本身并不严格，通常每公斤（Ⅱ）加入5Kg溶剂。
该反应的过程条件亦可选用于其它反应。
优选的原料化合物（Ⅱ）是：
1，4-二氨基-2，3-二氯蒽醌，和
1，4-二氨基-2，3-二溴蒽醌。
硼酸可以是偏硼酸（HBO2）或优选的原硼酸（H3BO3）形式。
通常，硼酸的用量是每摩尔（Ⅱ），2-10mol，优选6-8mol。
在本发明的一种较好的方法中，将1，4-二氨基-2，3-二卤代蒽醌（Ⅱ）、硼酸和溶剂在1-3小时加热至120-180℃，必要时，在惰性气氛中进行，例如充入氮气流。在该过程中反应产生的一部分水和一部分溶剂以恒沸混合物的形式蒸出。经2-3小时的反应，形成囟代蒽醌（Ⅱ）和硼酸的反应产物（Ⅱa），然后将反应混合物通常冷却至90-95℃，不必进一步处理直接用于二磺酸（Ⅰ）的制备。
磺化反应本身也可类似地按常规方法进行。
特别适宜的亚硫酸盐水溶液是碱金属亚硫酸盐，如亚硫酸钾（尤其是亚硫酸钠）和亚硫酸铵溶液。
亚硫酸铵的用量通常为每摩尔（Ⅱ）约2.2-2.6mol，以浓度为8-10%的水溶液形式使用。
在将所得反应混合物加到热至90-95℃的亚硫酸盐溶液中时，最好同时计量加入碱，例如氢氧化钠溶液或氢氧化钾溶液，以保持PH值为7.5-8.5。
该反应通常进行30-60分钟。
在本新方法中，仍残留的非极性溶剂随后以轻相的形式从含有溶解的盐的形式的二磺酸（Ⅰ）的下层水相中被分离出来，这一步骤最好在整批物料过滤澄清后进行。
这样便省去了用酸沉淀、过滤、洗涤和干燥来分离1，4-二氨基蒽醌-2，3-二磺酸（Ⅰ）的步骤，而分离的水相可方便地直接用于随后的水性介质中的反应，例如1，4-二氨基蒽醌-2，3-二腈（Ⅲ）。
制备1，4-二氨基蒽醌-2，3-二磺酸（Ⅰ）的新方法可连续或间歇地进行。
借助于该方法，可简单、经济地得到高产率高纯度的1，4-二氨基蒽醌-2，3-二磺酸，这点也反映在二步产物上。
就制得1，4-二氨基蒽醌-2，3-二腈（Ⅲ）的进一步反应而言，可按照US-A-42879825所述的常规方式，加入碱金属氰化物例如氰化钾或尤其是氰化钠，加入量通常为每摩尔（Ⅰ）2.2-4mol，于90-95℃下加热所得混合物3-5小时，并用过氧化氢破坏过量的氰化物。
也可以得到如此高纯度的1，4-二氨基蒽醌-2，3-二腈（Ⅲ），以致于它们可被直接用于进一步的用途，例如颜料制备。
制备1，4-二氨基蒽醌2，3-二腈（Ⅲ）的较好的合成路线是用新的磺化方法将1，4-二氨基-2，3-二囟代蒽醌（Ⅱ）磺化，随后将所得1，4-二氨基蒽醌-2，3-二磺酸（Ⅰ）与氰化物反应。
实施例1
a）1，4-二氨基蒽醌-2，3-二磺酸（Ⅰ）的制备
在缓慢的氮气流下，用3小时的时间将400g Solvesso 150，103g（0.26mol）1，4-二氨基-2，3-二溴蒽醌（计算为100%）和139g（2.24mol）原硼酸的混合物加热至160-165℃。缓慢蒸去水/Solvesso 150混合物。
两小时后，将悬浮液冷却至90℃，将其滴加到90℃的80g亚硫酸钠溶于1200ml水的溶液中，同时滴加浓度为50%（重量）的氢氧化钠溶液以保持在引入悬浮液的整个过程中溶液的PH值为8-8.5。
于90℃下搅拌30分钟后，将全部反应物料过滤澄清，用相分离法分出溶剂。所得水溶液含有1，4-二氨基蒽醌-2，3-二磺酸。
b）进一步反应制得1，4-二氨基蒽醌-2，3-二腈（Ⅲ）
加入36g（0.73mol）氰化钠后，将水相于90-95℃加热3小时，冷却至80℃后，滴加120ml浓度为30%（重量）的过氧化氢以除去过量氰化物。
趁热过滤所得沉淀，用热水洗涤，干燥，得65.3g纯度为91.4%的1，4-二氨基蒽醌-2，3-二腈，产率对应地为79.5%。
实施例2
将80.0g（0.26mol）1，4-二氨基-2，3-二氯蒽醌（计算为100%）在480g Solvesso 150中类似于实施例1进行反应。
将所得1，4-二氨基蒽醌-2，3-二磺酸进一步反应，得64g纯度为96%的1，4-二氨基蒽醌-2，3-二腈，对应产率为77%。
Claims (6)
1、1，4-二氨基蒽醌-2，3-二磺酸(Ⅰ)的制备方法，即在惰性有机溶剂中将1，4-二氨基-2，3-二卤代蒽醌(Ⅱ)与硼酸反应，然后使所得反应产物(Ⅱa)进一步与亚硫酸钠溶液反应，其中所用的惰性有机溶剂是沸点≥130℃并且粘度≤0.95g/cm3的非极性溶剂。
2、按照权利要求1所述的方法，其中所用溶剂是烷基苯或烷基苯混合物。
3、按照权利要求1所述的方法，其中反应产物（Ⅱa）不经过中间体分离，以所得反应混合物的形式直接与亚硫酸盐反应，然后相分离除去有机溶剂。
4、按照权利要求1所述的方法，其中所用的1，4-二氨基-2，3-二卤代蒽醌（Ⅱ）是1，4-二氨基-2，3-二氯蒽醌或1，4-二氨基-2，3-二溴蒽醌。
5、制备1，4-二氨基蒽醌-2，3-二腈（Ⅲ）的方法，即
a）在惰性有机溶剂中，将1，4-二氨基-2，3-二卤代蒽醌（Ⅱ）与硼酸反应，再使所得反应产物进一步与亚硫酸盐水溶液反应，并且
b）随后将所得1，4-二氨基蒽醌-2，3-二磺酸（Ⅰ）与氰化物反应，
其中步骤a）所用的惰性有机溶剂是沸点≥130℃且密度≤0.95g/cm3的非极性溶剂。
6、按照权利要求5所述的方法，其中所用溶剂是烷基苯或烷基苯混合物。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4222302A DE4222302A1 (de) | 1992-07-08 | 1992-07-08 | Verfahren zur Herstellung von 1,4-Diaminoanthrachinon-2,3-disulfonsäure und 1,4-Diaminoanthrachinon-2,3-dinitril |
| DEP4222302.4 | 1992-07-08 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98115677A Division CN1079392C (zh) | 1992-07-08 | 1998-07-03 | 1,4－二氨基蒽醌－2,3－二腈的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1085210A true CN1085210A (zh) | 1994-04-13 |
| CN1052719C CN1052719C (zh) | 2000-05-24 |
Family
ID=6462681
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93108509A Expired - Fee Related CN1052719C (zh) | 1992-07-08 | 1993-07-08 | 1,4－二氨基蒽醌－2,3－二磺酸的制备方法 |
| CN98115677A Expired - Fee Related CN1079392C (zh) | 1992-07-08 | 1998-07-03 | 1,4－二氨基蒽醌－2,3－二腈的制备方法 |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98115677A Expired - Fee Related CN1079392C (zh) | 1992-07-08 | 1998-07-03 | 1,4－二氨基蒽醌－2,3－二腈的制备方法 |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5386042A (zh) |
| EP (1) | EP0582079B1 (zh) |
| JP (1) | JPH06179647A (zh) |
| KR (1) | KR100268980B1 (zh) |
| CN (2) | CN1052719C (zh) |
| DE (2) | DE4222302A1 (zh) |
| ES (1) | ES2098596T3 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069896C (zh) * | 1997-01-28 | 2001-08-22 | 常州市合成材料厂 | 1,4-二氨基-2,3-二氰基蒽醌的制备工艺 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242208B (zh) * | 2013-05-03 | 2015-01-07 | 盐城市瓯华化学工业有限公司 | 烟酸法制备1,4-二氨基蒽醌-2,3-二磺酸的工艺 |
| CN115521636B (zh) * | 2022-10-24 | 2023-06-30 | 浙江博澳新材料股份有限公司 | 一种含双氰基耐晒型蒽醌分散染料及其制备方法 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1975386A (en) * | 1932-03-26 | 1934-10-02 | Gen Aniline Works Inc | Process of preparing 1.4-diamino-anthraquinone-2.3-disulphonic acid |
| US2795593A (en) * | 1953-07-22 | 1957-06-11 | Du Pont | Process for preparing alkali metal salts of 1, 4-diamino-2, 3-anthraquinone-disulfonic acid |
| DE2524748C3 (de) * | 1975-06-04 | 1980-06-04 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Herstellung von 1 ^-Diaminoanthrachinon^-dinitril |
| DE2846622A1 (de) * | 1978-10-26 | 1980-05-08 | Bayer Ag | Verfahren zur herstellung von 1,4-diaminoanthrachinon-2,3-disulfonsaeure |
| JPS57158261A (en) * | 1981-03-26 | 1982-09-30 | Sumitomo Chem Co Ltd | Preparation of 1,4-diamino anthraquinone-2,3-disulfonic acid |
| JPS58172364A (ja) * | 1982-04-02 | 1983-10-11 | Sumitomo Chem Co Ltd | １，４−ジアミノアントラキノン−２，３−ジスルホン酸の製造方法 |
| GB2185035B (en) * | 1986-01-07 | 1989-11-08 | Sumitomo Chemical Co | Process for preparing 1,4-diaminoanthraquinone-2,3-disubstituted compound |
-
1992
- 1992-07-08 DE DE4222302A patent/DE4222302A1/de not_active Withdrawn
-
1993
- 1993-06-26 EP EP93110227A patent/EP0582079B1/de not_active Expired - Lifetime
- 1993-06-26 ES ES93110227T patent/ES2098596T3/es not_active Expired - Lifetime
- 1993-06-26 DE DE59305709T patent/DE59305709D1/de not_active Expired - Fee Related
- 1993-07-01 KR KR1019930012243A patent/KR100268980B1/ko not_active IP Right Cessation
- 1993-07-07 JP JP5167815A patent/JPH06179647A/ja not_active Withdrawn
- 1993-07-08 CN CN93108509A patent/CN1052719C/zh not_active Expired - Fee Related
- 1993-07-08 US US08/088,740 patent/US5386042A/en not_active Expired - Fee Related
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1998
- 1998-07-03 CN CN98115677A patent/CN1079392C/zh not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069896C (zh) * | 1997-01-28 | 2001-08-22 | 常州市合成材料厂 | 1,4-二氨基-2,3-二氰基蒽醌的制备工艺 |
Also Published As
| Publication number | Publication date |
|---|---|
| US5386042A (en) | 1995-01-31 |
| DE4222302A1 (de) | 1994-01-13 |
| CN1218798A (zh) | 1999-06-09 |
| DE59305709D1 (de) | 1997-04-17 |
| CN1079392C (zh) | 2002-02-20 |
| CN1052719C (zh) | 2000-05-24 |
| KR100268980B1 (en) | 2000-10-16 |
| KR940005563A (ko) | 1994-03-21 |
| EP0582079A1 (de) | 1994-02-09 |
| ES2098596T3 (es) | 1997-05-01 |
| EP0582079B1 (de) | 1997-03-12 |
| JPH06179647A (ja) | 1994-06-28 |
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