CN102993049A - Environment-friendly method for preparing 1,4-diamido-2,3-dicyano anthraquinone - Google Patents
Environment-friendly method for preparing 1,4-diamido-2,3-dicyano anthraquinone Download PDFInfo
- Publication number
- CN102993049A CN102993049A CN2012103271203A CN201210327120A CN102993049A CN 102993049 A CN102993049 A CN 102993049A CN 2012103271203 A CN2012103271203 A CN 2012103271203A CN 201210327120 A CN201210327120 A CN 201210327120A CN 102993049 A CN102993049 A CN 102993049A
- Authority
- CN
- China
- Prior art keywords
- diamino
- anthraquinone
- nitrae
- isosorbide
- sodium cyanide
- 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.)
- Pending
Links
Images
Abstract
The invention relates to a novel environment-friendly method for preparing 1,4-diamido-2,3-dicyano anthraquinone. The method comprises the following steps: using 1,4-diamido-2-sulfo anthraquinone as a raw material; using dimethylformamide and water mixed as a solvent, nitrobenzene as an oxidant, and acetic acid as an alkali constraining agent; cyaniding with sodium cyanide in a reaction device; and filtering, cleaning and drying to obtain 1,4-diamido-2,3-dicyano anthraquinone. Compared with the conventional processes, the preparation method provided by the invention has only one production step: cyaniding, so that the process flow is short, the operation is simpler, and the production period is greatly shortened. The mother liquid can be directly used, so that the trouble of distillation is avoided, and the energy consumption is reduced. As dimethylformamide can be directly circularly used, and excessive sodium cyanide can be directly circularly used, the use amount of hypertoxic sodium cyanide is reduced, the risk of single treatment is reduced, and the production cost is greatly lowered actually. With the increased use of the mother liquid, the yield of 1,4-diamido-2,3-dicyano anthraquinone can reach 120% maximally which is far higher than the theoretical yield as the product is reserved and accumulated when the mother liquid is used.
Description
Technical field
The invention belongs to chemical field, particularly, relate to a kind of eco-friendly preparation Isosorbide-5-Nitrae-diamino-2, the novel method of 3-dicyan anthraquinone.
Background technology
Isosorbide-5-Nitrae-diamino-2,3-dicyan anthraquinone are important dyestuff intermediates, are the dyestuff of synthetic many excellent propertys and the intermediate of pigment, are mainly used at present the production of Disperse Blue-60.Traditional synthetic method is take Isosorbide-5-Nitrae-diamino-anthraquinone leuco compound as raw material, makes Isosorbide-5-Nitrae-diamino-2 through chloro, the 3-dichloroanthraquinone, and then carry out sulfonation and obtain Isosorbide-5-Nitrae-diamino-2,3-disulfonic acid base anthraquinone, replace with sodium cyanide at last, obtain Isosorbide-5-Nitrae-diamino-2, the 3-dicyan anthraquinone.Carry out but the method must experience for two steps, technical process is long, and total recovery is low, and product is of poor quality, and mother liquor not realization directly apply mechanically, cause producing a large amount of waste water, the sewage disposal difficulty is larger.
US 4279825 discloses a kind of with 1,4-diamino-2, the 3-dichloroanthraquinone is raw material, is reaction medium at oil of mirbane, with acid reaction, make boric acid ester, then steam oil of mirbane, make Isosorbide-5-Nitrae-diamino-2 at the reactant aqueous solution with S-WAT, 3-disulfonic acid base anthraquinone, but the method reclaims relatively difficulty of solvent oil of mirbane, and oil of mirbane has the boiling point height, the distillation difficulty, and distillation is power consumption relatively, and the boric acid that adds in when reaction also can steam with oil of mirbane, and this can cause the oil of mirbane that reclaims impure, and can cause the fault such as equipment corrosion, the production cost of totally seeing this patented method is higher, and market competition advantage is not obvious.
CN 200610156081 discloses a kind of take orthodichlorobenzene as solvent, the Trace water that intensification is deviate from the system under negative pressure divides, again with chlorsulfonic acid with 1, the leuco compound oxidation of 4-diamino-anthraquinone and sulfonation, the gained material is after neutralization, distillation orthodichlorobenzene, filtering and impurity removing, acidification, the material of separating out is drained clean, the wet product filter cake 1 that obtains, 4-diamino-anthraquinone-2-sulfonic acid is in the presence of oxygenant and bundle alkaline agent, take the mixture of dimethyl formamide and water as solvent, use the sodium cyanide cyaniding, make Isosorbide-5-Nitrae-diamino-2,3-cyano group anthraquinone.Although the method only needs the synthetic purity higher Isosorbide-5-Nitrae-diamino-2,3-cyano group anthraquinone of just obtaining of two steps.But this patented method has the defective of himself, the production cost of the method is too high, its reason is that this patent (CN200610156081) method is not studied solvent dimethyl formamide (DMF) and reclaimed and to reuse, just simply carried dimethyl formamide through distillation recirculation use.
Dimethyl formamide is relatively more expensive organic solvent, report is produced one ton 1 in patent CN 200610156081, the amount that 4-diamino-2,3-cyano group anthraquinone need to consume dimethyl formamide is 2.65 tons, if not recycling use of dimethyl formamide, must cause 1,4-diamino-2,3-cyano group anthraquinone production cost improves greatly, and along with the discharging of waste water, must bring difficulty to wastewater treatment, cause environmental pollution; If the way with distillation reclaims dimethyl formamide in each mother liquor, because dimethyl formamide belongs to high boiling solvent, and can dissolve each other with water, by the Distillation recovery dimethyl formamide be relatively the difficulty, this must cause power consumption, complex operation, the cost compare that reclaims is high, dimethyl formamide can dissolve each other with water and form azeotropic in addition, the moisture content of the dimethyl formamide that therefore reclaims has uncertainty, and the expense of the consumption of the energy must improve like this, produces 1 thereby increased, 4-diamino-2, the cost of 3-cyano group anthraquinone.Next be exactly patent CN 200610156081 described method sodium cyanides be excessive, the method does not have recycling of real realization sodium cyanide.The excessive use of sodium cyanide if do not reach recycled, must contain a large amount of sodium cyanides, contaminate environment in the sewage.Therefore, the method does not have real reduction Isosorbide-5-Nitrae-diamino-2,3-cyano group anthraquinone production cost.For the method for applying mechanically again after this traditional rectifying, have following defective: 1, the cost of complex operation, power consumption, recovery is higher, and the production cost of product is high; The water content of the dimethyl formamide that 2, reclaims is still higher; 3, excessive sodium cyanide is processed relatively difficulty, and the waste resource; 4, the product that is partly dissolved in the solution can't be recycled; 5, the usage quantity of overall solvent is larger.
Summary of the invention
The eco-friendly preparation 1 that technical problem to be solved by this invention provides that a kind of technical process is short, mother liquor can be high, simple to operate by simple cycle time usefulness, good product quality, yield, production cost can decrease, 4-diamino-2, the novel method of 3-dicyan anthraquinone.
The present invention solves the problems of the technologies described above the technical scheme that adopts: a kind of eco-friendly preparation Isosorbide-5-Nitrae-diamino-2, the novel method of 3-dicyan anthraquinone, with 1,4-diamino-2-sulfonic group anthraquinone is raw material, is mixed into solvent with dimethyl formamide and water, and oil of mirbane is oxygenant, acetic acid is the bundle alkaline agent, in reaction unit, use the sodium cyanide cyaniding, after filtration, clean, oven dry, obtain 1,4-diamino-2, the 3-dicyan anthraquinone.Novel method of the present invention is single stage method, just can react generation Isosorbide-5-Nitrae-diamino-2 by this procedure of hydrogenation, the 3-dicyan anthraquinone, simplify technical process and greatly shortened the production cycle, adopt the production technique of this simplification, preparation Isosorbide-5-Nitrae-diamino-2, the yield of product is more than 90% during the 3-dicyan anthraquinone, prepared Isosorbide-5-Nitrae-diamino-2, the content of 3-dicyan anthraquinone is more than 95%.
With the sodium cyanide cyaniding time, in the used mixed solvent, the solvent quality that dimethyl formamide accounts for is 40-80%, and the mol ratio of the Isosorbide-5-Nitrae-diamino of sodium cyanide and drying-2-sulfonic group anthraquinone is 2.5-4:1; The mol ratio of the consumption of oil of mirbane and Isosorbide-5-Nitrae-diamino-2-sulfonic group anthraquinone is 0.7486-1.4996:1; The mol ratio of acetic acid consumption and Isosorbide-5-Nitrae-diamino-2-sulfonic group anthraquinone is 0.7306-0.7714:1; The cyaniding temperature is 70-75 ℃; The cyaniding temperature is 70-75 ℃.Further, proportioning when the present invention has optimized cyanogenation between each reactant, solvent, oxygenant, the bundle alkaline agent, adopt proportioning of the present invention, can direct circulation not be applied mechanically so that reacted mother liquor does not need through distillation, and the number of times of high recycled can reach 8 times.In the 8th time recycled, utilize the Isosorbide-5-Nitrae-diamino-2 of mother liquor preparation, the content of 3-dicyan anthraquinone still can reach 95%, and the yield of product is more than 90%.
The mother liquor of described filtration directly causes the reaction unit recycled by return line without distillation, as the reaction solvent of the 2nd cyaniding.
The mother liquor that filters behind described the 2nd cyanogenation is without distillation, directly cause the reaction unit recycled by return line, as the 3rd time reaction solvent, reacted mother liquor continues recycled, until the 7th recycled, as the reaction solvent of the 8th cyaniding.
The mother liquor that filters behind described the 2nd cyanogenation is without distillation, directly cause the reaction unit recycled by return line, as the 3rd time reaction solvent, reacted mother liquor continues recycled, until the 8th recycled, as the reaction solvent of the 9th cyaniding.
Described method prepares Isosorbide-5-Nitrae-diamino-2, and the purity of 3-dicyan anthraquinone is 95-99.9%.
Described mother liquor adds the sodium cyanide of anhydrous solid powder when recycled, the mol ratio of the Isosorbide-5-Nitrae-diamino of maintenance sodium cyanide and drying-2-sulfonic group anthraquinone is 2.0-2.5:1.
Of the present invention a kind of novel eco-friendly 1,4-diamino-2, the novel method of 3-dicyan anthraquinone is: take Isosorbide-5-Nitrae-diamino-2-sulfonic group anthraquinone as raw material, take dimethyl formamide as solvent, oil of mirbane is oxygenant, and acetic acid is used the sodium cyanide cyaniding for the bundle alkaline agent, after filtration or suction filtration, clean, oven dry, obtain Isosorbide-5-Nitrae-diamino-2, the 3-dicyan anthraquinone.Reaction mother liquor after the filtration can directly be applied mechanically, and the number of times of applying mechanically is Isosorbide-5-Nitrae-diamino-2, the number of times the when content of 3-dicyan anthraquinone to commodity require.Mother liquor after stopping to apply mechanically can reclaim dimethyl formamide by the method for distillation.
The main chemical reactions that relates in said new method is:
DMF in the reaction formula is dimethyl formamide.
The technical process figure that relates in said new method is as shown in Figure 1: in the figure, during first set reaction, ratio according to the ingredient requirement of first set reaction is carried out in reaction vessel, after reaction is finished, the ratio of ingredient requirement is carried out the reaction second time when adding recycled in the filtrate of gained in reaction vessel, then recycled filtrate is until the 8th secondary response of this technique finishes.
Preferred as novel method of the present invention, with 1,4-diamino-anthraquinone-2-sulfonic acid is raw material, take oil of mirbane as oxygenant, acetic acid is lower for the bundle alkaline agent exists, with the mixture of dimethyl formamide and water as solvent, use the sodium cyanide cyaniding, after filtration, the washing, the oven dry, make Isosorbide-5-Nitrae-diamino-2,3-cyano group anthraquinone, mother liquor after the filtration can directly be applied mechanically, and the number of times of applying mechanically is the number of times (can apply mechanically at most 8 times) when the purity drop to 94% of product, and then the mother liquor after repeatedly circulating reclaims dimethyl formamide through heavily steaming again.In this novel method, when using the sodium cyanide cyaniding, in the used mixed solvent, the mass percent that dimethyl formamide accounts for solvent is 60%, sodium cyanide and 1 during first set reaction, the mol ratio of 4-diamino-anthraquinone-2-sulfonic acid is 3:1, the mol ratio of the consumption of oil of mirbane and Isosorbide-5-Nitrae-diamino-anthraquinone-2-sulfonic acid is 0.7486-1.4996:1, the consumption of acetic acid and 1, the mol ratio of 4-diamino-anthraquinone-2-sulfonic acid is 0.7306-0.7714:1, and the cyaniding temperature is 75 ℃.In the Recycling Mother Solution cover time spent, the mol ratio of sodium cyanide consumption and Isosorbide-5-Nitrae-diamino-anthraquinone-2-sulfonic acid is 2.1:1, and other conditions are constant.Such cyanidation technology condition be more convenient for cyanogenation carrying out and reduce the harm of sodium cyanide.
In said new method, mother liquor can directly be applied mechanically behind filtering product, does not need to add dimethyl formamide and water.After the process time was used, when Isosorbide-5-Nitrae-diamino-2, when purity drop to the commodity of 3-cyano group anthraquinone required, mother liquor stopped to apply mechanically.
In said new method, when the sodium cyanide cyaniding, after mother liquor stopped to apply mechanically, the dimethyl formamide in the mother liquor can use through distillation recirculation.
In said new method, with the sodium cyanide cyaniding time, the consumption of sodium cyanide can be along with the suitable reduction of the increase of the number of times of applying mechanically, but the mol ratio of the consumption Isosorbide-5-Nitrae-diamino-anthraquinone of sodium cyanide-2-sulfonic acid is not less than 2.0:1.
Adopt method of the present invention, need not rectifying, low, the simple easy handling of energy consumption, the products production cost is low; Can directly apply mechanically through 8 times; Excessive sodium cyanide can be with directly the applying mechanically and recycle of mother liquor, thereby reduced the discharging of toxic substance; The product that is partly dissolved in the solvent can reclaim use, thereby has lowered the loss amount of product at solvent; The usage quantity of total solvent is 1/8 amount of traditional method, greatly reduces the consumption of solvent.
With respect to prior art, technique effect of the present invention is:
(1) new preparation process of the present invention at synthetic Isosorbide-5-Nitrae-diamino-2 take Isosorbide-5-Nitrae-diamino-anthraquinone-2-sulfonic acid as raw material, during 3-cyano group anthraquinone, only has one production process of cyaniding, and technical process is short, operates simplyr, has greatly shortened the production cycle;
(2) new preparation process of the present invention, during with the sodium cyanide cyaniding, with suitable oxygenant and alkali-binding agent, and in the mother liquid recycle process suitable reduction the consumption of sodium cyanide, can make like this consumption of sodium cyanide be controlled at suitable scope, and when having avoided single to use sodium cyanide, the trouble that the processing of excessive sodium cyanide brings and processing cost, thereby reduced production cost, reduced the aftertreatment work that is brought by sodium cyanide;
(3) new preparation process of the present invention, during as mixed solvent, reaction solution filters and obtains product after reaction finishes with dimethyl formamide and water, mother liquor can directly be applied mechanically, reduced the trouble of distillation, reduced energy consumption, dimethyl formamide can use by direct circulation, excessive sodium cyanide also can use by direct circulation, reduced the usage quantity of hypertoxic sodium cyanide, reduced the risk of single treatment, real realization the decrease of production cost;
(4) new preparation process of the present invention, when mother liquid recycle, its Isosorbide-5-Nitrae-diamino-2, the productive rate of 3-cyano group anthraquinone increases by two increases with the number of times of applying mechanically, its reason is owing to Isosorbide-5-Nitrae-diamino-2, the good dispersity of 3-cyano group anthraquinone in water, when filtering, Isosorbide-5-Nitrae-diamino-2 that a small amount of part is arranged, 3-cyano group anthraquinone has been stayed in the mother liquor, when the number of times with mother liquid recycle increases, Isosorbide-5-Nitrae-diamino-2, the amount that 3-cyano group anthraquinone is separated out can increase, 1,4-diamino-2, the output of 3-cyano group anthraquinone is the highest can to reach 120%, and the reason that far exceeds theoretical yield is because the result of product residue accumulation during mother liquid recycle;
(5) new preparation process of the present invention, when using dimethyl formamide and water as mixed solvent, mother liquor can't be realized overlapping the time spent again, can reclaim dimethyl formamide by the method for distillation;
(6) new preparation process of the present invention is compared with traditional technique, product Isosorbide-5-Nitrae-diamino-2 not only, and the content of 3-cyano group anthraquinone significantly improves, and has reached more than 98%, and average yield can reach more than 95%, has improved nearly about 20%.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited only to following embodiment.
Embodiment 1
In 500 milliliters of four-hole boiling flasks with airtight electric mixer, thermometer and dropping funnel, add 1,4-diamino-anthraquinone-2-sulfonic acid 39 grams (0.1225mol), sodium cyanide 19 grams (0.3878mol), oil of mirbane 22.6 grams (0.1837mol), then add N, dinethylformamide is that 60% the aqueous solution is made solvent (being that the quality percentage composition is 60% DMF), about 240g.Be warmed up to 70 ℃, keep reaction solution stable.In reaction solution, drip Glacial acetic acid (acetic acid) 0.0945mol, dropwise in the 1-1.5h.The control temperature is incubated 4 hours between 70-75 ℃, the liquid chromatogram measuring reaction is complete, stopped reaction.Filtered while hot after reaction finishes is kept recycled with primary filtrate, and filter cake is fully cleaned, dried with hot water, makes finished product Isosorbide-5-Nitrae-diamino-2,3-dicyan anthraquinone 31.8 grams, and the yield of product is 90%, the content of product is 99.4%.
The quality of the mother liquor that obtains is 278 grams, contains Isosorbide-5-Nitrae-diamino-2 in the mother liquor, and 3-dicyan anthraquinone 1.07%, the content of dimethyl formamide are 51.7%.(weightening finish be the product Isosorbide-5-Nitrae-diamino-2 of inorganic salt, by product dissolving aniline and dissolving, 3-dicyan anthraquinone).
Below be the mother liquid recycle embodiment:
Embodiment 2:
In 500 milliliters of four-hole boiling flasks with airtight electric mixer, thermometer and dropping funnel, add 1,4-diamino-anthraquinone-2-sulfonic acid (content is 52%) 75 grams (0.1225mol), sodium cyanide 15 grams (0.3061mol), oil of mirbane 16.95 restrains (0.1377mol), then adds the mother liquor of embodiment 1.Be warmed up to 70 ℃, keep reaction solution stable.Drip Glacial acetic acid in the reaction solution and in reaction solution, drip Glacial acetic acid 0.092mol, dropwise in the 1-1.5h.The control temperature is incubated 4 hours, liquid chromatogram measuring between 70-75 ℃.If be incubated 4 hours still less than reaction end, can take the circumstances into consideration to add the sodium cyanide solid, until Isosorbide-5-Nitrae-diamino-anthraquinone-2-sulfonic acid completely dissolve, filtered while hot after reaction finishes, primary filtrate is kept recycled, and filter cake is fully cleaned, is dried with hot water, makes finished product 1,4-diamino-2,3-dicyan anthraquinone 32.5 grams, the yield of product is 92%, the content of product is 99.4%.
The quality of the mother liquor that obtains is 290 grams, contains Isosorbide-5-Nitrae-diamino-2 in the mother liquor, and 3-dicyan anthraquinone 1.0%, the content of dimethyl formamide are 49.6%.(weightening finish be the product Isosorbide-5-Nitrae-diamino-2 of inorganic salt, by product dissolving aniline and dissolving, 3-dicyan anthraquinone).
Embodiment 3:
In 500 milliliters of four-hole boiling flasks with airtight electric mixer, thermometer and dropping funnel, add 1,4-diamino-anthraquinone-2-sulfonic acid (content is 52%) 75 grams (0.1225mol), sodium cyanide 15 grams (0.3061mol), oil of mirbane 12.18 restrains (0.0989mol), then adds the mother liquor of embodiment 2.Be warmed up to 70 ℃, keep reaction solution stable.Drip Glacial acetic acid in the reaction solution and in reaction solution, drip Glacial acetic acid 0.0944mol, dropwise in the 1-1.5h.The control temperature is incubated 4 hours, liquid chromatogram measuring between 70-75 ℃.If be incubated 4 hours still less than reaction end, can take the circumstances into consideration to add the sodium cyanide solid, until Isosorbide-5-Nitrae-diamino-anthraquinone-2-sulfonic acid completely dissolve, filtered while hot after reaction finishes, primary filtrate is kept recycled, and filter cake is fully cleaned, is dried with hot water, makes finished product 1,4-diamino-2,3-dicyan anthraquinone 32.5 grams, the yield of product is 92%, the content of product is 99.1%.
The quality of the mother liquor that obtains is 300 grams, contains Isosorbide-5-Nitrae-diamino-2 in the mother liquor, and 3-dicyan anthraquinone 1.18%, the content of dimethyl formamide are 48%.(weightening finish be the product Isosorbide-5-Nitrae-diamino-2 of inorganic salt, by product dissolving aniline and dissolving, 3-dicyan anthraquinone).
Embodiment 4:
In 500 milliliters of four-hole boiling flasks with airtight electric mixer, thermometer and dropping funnel, add 1,4-diamino-anthraquinone-2-sulfonic acid (content is 52%) 75 grams (0.1225mol), sodium cyanide 13 grams (0.2653mol), oil of mirbane 22.6 restrains (0.1837mol), then adds the mother liquor of embodiment 3.Be warmed up to 70 ℃, keep reaction solution stable.Drip Glacial acetic acid in the reaction solution and in reaction solution, drip Glacial acetic acid 0.0932mol, dropwise in the 1-1.5h.The control temperature is incubated 4 hours, liquid chromatogram measuring between 70-75 ℃.If be incubated 4 hours still less than reaction end, can take the circumstances into consideration to add the sodium cyanide solid, until Isosorbide-5-Nitrae-diamino-anthraquinone-2-sulfonic acid completely dissolve, filtered while hot after reaction finishes, primary filtrate is kept recycled, and filter cake is fully cleaned, is dried with hot water, makes finished product 1,4-diamino-2,3-dicyan anthraquinone 34.8 grams, the yield of product is 99%, the content of product is 98.6%.
The quality of the mother liquor that obtains is 310 grams, contains Isosorbide-5-Nitrae-diamino-2 in the mother liquor, and 3-dicyan anthraquinone 1.07%, the content of dimethyl formamide are 45%.(weightening finish be the product Isosorbide-5-Nitrae-diamino-2 of inorganic salt, by product dissolving aniline and dissolving, 3-dicyan anthraquinone).
Embodiment 5:
In 500 milliliters of four-hole boiling flasks with airtight electric mixer, thermometer and dropping funnel, add 1,4-diamino-anthraquinone-2-sulfonic acid (content is 52%) 75 grams (0.1225mol), sodium cyanide 12 grams (0.2449mol), oil of mirbane 22.16 restrains (0.180mol), then adds the mother liquor of embodiment 4.Be warmed up to 70 ℃, keep reaction solution stable.Drip Glacial acetic acid in the reaction solution and in reaction solution, drip Glacial acetic acid 0.092mol, dropwise in the 1-1.5h.The control temperature is incubated 4 hours, liquid chromatogram measuring between 70-75 ℃.If be incubated 4 hours still less than reaction end, can take the circumstances into consideration to add the sodium cyanide solid, until Isosorbide-5-Nitrae-diamino-anthraquinone-2-sulfonic acid completely dissolve, filtered while hot after reaction finishes, primary filtrate is kept recycled, and filter cake is fully cleaned, is dried with hot water, makes finished product 1,4-diamino-2,3-dicyan anthraquinone 36.4 grams, the yield of product is 103%, the content of product is 98%.
The quality of the mother liquor that obtains is 320 grams, contains Isosorbide-5-Nitrae-diamino-2 in the mother liquor, and 3-dicyan anthraquinone 1.07%, the content of dimethyl formamide are 44%.(weightening finish be the product Isosorbide-5-Nitrae-diamino-2 of inorganic salt, by product dissolving aniline and dissolving, 3-dicyan anthraquinone).
Embodiment 6:
In 500 milliliters of four-hole boiling flasks with airtight electric mixer, thermometer and dropping funnel, add 1,4-diamino-anthraquinone-2-sulfonic acid (content is 52%) 75 grams (0.1225mol), sodium cyanide 12 grams (0.2449mol), oil of mirbane 18.92 restrains (0.1537mol), then adds the mother liquor of embodiment 5.Be warmed up to 70 ℃, keep reaction solution stable.Drip Glacial acetic acid in the reaction solution and in reaction solution, drip Glacial acetic acid 0.0945mol, dropwise in the 1-1.5h.The control temperature is incubated 4 hours, liquid chromatogram measuring between 70-75 ℃.If be incubated 4 hours still less than reaction end, can take the circumstances into consideration to add the sodium cyanide solid, until Isosorbide-5-Nitrae-diamino-anthraquinone-2-sulfonic acid completely dissolve, filtered while hot after reaction finishes, primary filtrate is kept recycled, and filter cake is fully cleaned, is dried with hot water, makes finished product 1,4-diamino-2,3-dicyan anthraquinone 36.4 grams, the yield of product is 103%, the content of product is 97.5%.
The quality of the mother liquor that obtains is 320 grams, contains Isosorbide-5-Nitrae-diamino-2 in the mother liquor, and 3-dicyan anthraquinone 1.07%, the content of dimethyl formamide are 43%.(weightening finish be the product Isosorbide-5-Nitrae-diamino-2 of inorganic salt, by product dissolving aniline and dissolving, 3-dicyan anthraquinone).
Embodiment 7:
In 500 milliliters of four-hole boiling flasks with airtight electric mixer, thermometer and dropping funnel, add 1,4-diamino-anthraquinone-2-sulfonic acid (content is 52%) 75 grams (0.1225mol), sodium cyanide 12 grams (0.2449mol), oil of mirbane 11.3 restrains (0.0917mol), then adds the mother liquor of embodiment 6.Be warmed up to 70 ℃, keep reaction solution stable.Drip Glacial acetic acid in the reaction solution and in reaction solution, drip Glacial acetic acid 0.092mol, dropwise in the 1-1.5h.The control temperature is incubated 4 hours, liquid chromatogram measuring between 70-75 ℃.If be incubated 4 hours still less than reaction end, can take the circumstances into consideration to add the sodium cyanide solid, until Isosorbide-5-Nitrae-diamino-anthraquinone-2-sulfonic acid completely dissolve, filtered while hot after reaction finishes, primary filtrate is kept recycled, and filter cake is fully cleaned, is dried with hot water, makes finished product 1,4-diamino-2,3-dicyan anthraquinone 34.8 grams, the yield of product is 99%, the content of product is 96%.
The quality of the mother liquor that obtains is 335 grams, contains Isosorbide-5-Nitrae-diamino-2 in the mother liquor, and 3-dicyan anthraquinone 1.07%, the content of dimethyl formamide are 41.7%.(weightening finish be the product Isosorbide-5-Nitrae-diamino-2 of inorganic salt, by product dissolving aniline and dissolving, 3-dicyan anthraquinone)
Embodiment 8:
In 500 milliliters of four-hole boiling flasks with airtight electric mixer, thermometer and dropping funnel, add 1,4-diamino-anthraquinone-2-sulfonic acid (content is 52%) 75 grams (0.1225mol), sodium cyanide 12 grams (0.2449mol), oil of mirbane 17.09 restrains (0.1388mol), then adds the mother liquor of embodiment 7.Be warmed up to 70 ℃, keep reaction solution stable.Drip Glacial acetic acid in the reaction solution and in reaction solution, drip Glacial acetic acid 0.0945mol, dropwise in the 1-1.5h.The control temperature is incubated 4 hours, liquid chromatogram measuring between 70-75 ℃.If be incubated 4 hours still less than reaction end, can take the circumstances into consideration to add the sodium cyanide solid, until Isosorbide-5-Nitrae-diamino-anthraquinone-2-sulfonic acid completely dissolve, filtered while hot after reaction finishes, primary filtrate is kept recycled, and filter cake is fully cleaned, is dried with hot water, makes finished product 1,4-diamino-2,3-dicyan anthraquinone 34.8 grams, the yield of product is 99%, the content of product is 95%.
The quality of the mother liquor that obtains is 340 grams, contains Isosorbide-5-Nitrae-diamino-2 in the mother liquor, and 3-dicyan anthraquinone 1.07%, the content of dimethyl formamide are 41%.(weightening finish be the product Isosorbide-5-Nitrae-diamino-2 of inorganic salt, by product dissolving aniline and dissolving, 3-dicyan anthraquinone)
After Recycling Mother Solution is directly applied mechanically 8 times, Isosorbide-5-Nitrae-diamino-2, the content of 3-dicyan anthraquinone has been reduced to 95%, stops mother liquor and directly applies mechanically.Can with its mother liquor by the underpressure distillation evaporate to dryness, reclaim its DMF and water.
As mentioned above, can implement preferably the present invention.
Claims (7)
1. eco-friendly preparation Isosorbide-5-Nitrae-diamino-2, the novel method of 3-dicyan anthraquinone, it is characterized in that, take Isosorbide-5-Nitrae-diamino-2-sulfonic group anthraquinone as raw material, be mixed into solvent with dimethyl formamide and water, oil of mirbane is oxygenant, and acetic acid is used the sodium cyanide cyaniding for the bundle alkaline agent in reaction unit, clean after filtration,, dry, obtain Isosorbide-5-Nitrae-diamino-2, the 3-dicyan anthraquinone.
2. a kind of eco-friendly preparation 1 according to claim 1,4-diamino-2, the novel method of 3-dicyan anthraquinone, it is characterized in that, with the sodium cyanide cyaniding time, in the used mixed solvent, the solvent quality that dimethyl formamide accounts for is 40-80%, the mol ratio of the Isosorbide-5-Nitrae-diamino of sodium cyanide and drying-2-sulfonic group anthraquinone is 2.5-4:1; The mol ratio of the consumption of oil of mirbane and Isosorbide-5-Nitrae-diamino-2-sulfonic group anthraquinone is 0.7486-1.4996:1; The mol ratio of acetic acid consumption and Isosorbide-5-Nitrae-diamino-2-sulfonic group anthraquinone is 0.7306-0.7714:1; The cyaniding temperature is 70-75 ℃.
3. a kind of eco-friendly preparation Isosorbide-5-Nitrae-diamino-2 according to claim 2, the novel method of 3-dicyan anthraquinone, it is characterized in that, the mother liquor of described filtration directly causes the reaction unit recycled by return line without distillation, as the reaction solvent of the 2nd cyaniding.
4. a kind of eco-friendly preparation 1 according to claim 3,4-diamino-2, the novel method of 3-dicyan anthraquinone, it is characterized in that the mother liquor that filters behind described the 2nd cyanogenation directly causes the reaction unit recycled by return line without distillation, reaction solvent as the 3rd time, reacted mother liquor continues recycled, until the 5th recycled, as the reaction solvent of the 6th cyaniding.
5. a kind of eco-friendly preparation 1 according to claim 3,4-diamino-2, the novel method of 3-dicyan anthraquinone, it is characterized in that the mother liquor that filters behind described the 2nd cyanogenation directly causes the reaction unit recycled by return line without distillation, reaction solvent as the 3rd time, reacted mother liquor continues recycled, until the 7th recycled, as the reaction solvent of the 8th cyaniding.
6. according to claim 1 to 5 each described a kind of eco-friendly preparation Isosorbide-5-Nitrae-diamino-2, the novel method of 3-dicyan anthraquinone is characterized in that, described method prepares Isosorbide-5-Nitrae-diamino-2, and the purity of 3-dicyan anthraquinone is 95-99.9%.
7. according to claim 3 to 5 each described a kind of eco-friendly preparations 1,4-diamino-2, the novel method of 3-dicyan anthraquinone, it is characterized in that, described mother liquor adds the sodium cyanide of anhydrous solid powder when recycled, the mol ratio of the Isosorbide-5-Nitrae-diamino of maintenance sodium cyanide and drying-2-sulfonic group anthraquinone is 2.0.-2.5:1; The mol ratio of the consumption of oil of mirbane and Isosorbide-5-Nitrae-diamino-2-sulfonic group anthraquinone is 0.7486-1.4996:1; The mol ratio of acetic acid consumption and Isosorbide-5-Nitrae-diamino-2-sulfonic group anthraquinone is 0.7306-0.7714:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103271203A CN102993049A (en) | 2012-09-07 | 2012-09-07 | Environment-friendly method for preparing 1,4-diamido-2,3-dicyano anthraquinone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103271203A CN102993049A (en) | 2012-09-07 | 2012-09-07 | Environment-friendly method for preparing 1,4-diamido-2,3-dicyano anthraquinone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102993049A true CN102993049A (en) | 2013-03-27 |
Family
ID=47922232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012103271203A Pending CN102993049A (en) | 2012-09-07 | 2012-09-07 | Environment-friendly method for preparing 1,4-diamido-2,3-dicyano anthraquinone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102993049A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112500718A (en) * | 2020-09-21 | 2021-03-16 | 浙江恩盛染料化工有限公司 | Resource utilization method of C.I. disperse blue 60 condensation reclaimed material |
| CN116082219A (en) * | 2022-08-11 | 2023-05-09 | 山东大学 | Preparation method of disperse blue 60-based disperse dye |
| CN116082219B (en) * | 2022-08-11 | 2024-04-26 | 山东大学 | Preparation method of disperse blue 60-based disperse dye |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4294769A (en) * | 1979-08-07 | 1981-10-13 | Bayer Aktiengesellschaft | Process for the preparation of 1,4-diamino-2,3-dicyano-anthraquinones |
| JPS57176944A (en) * | 1981-04-23 | 1982-10-30 | Sumitomo Chem Co Ltd | Preparation of anthraquinone-type intermediate |
| CN1995012A (en) * | 2006-12-28 | 2007-07-11 | 江苏亚邦染料股份有限公司 | Process for preparing 1,4-diamino-2,3-dicyan anthraquinone |
-
2012
- 2012-09-07 CN CN2012103271203A patent/CN102993049A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4294769A (en) * | 1979-08-07 | 1981-10-13 | Bayer Aktiengesellschaft | Process for the preparation of 1,4-diamino-2,3-dicyano-anthraquinones |
| JPS57176944A (en) * | 1981-04-23 | 1982-10-30 | Sumitomo Chem Co Ltd | Preparation of anthraquinone-type intermediate |
| CN1995012A (en) * | 2006-12-28 | 2007-07-11 | 江苏亚邦染料股份有限公司 | Process for preparing 1,4-diamino-2,3-dicyan anthraquinone |
Non-Patent Citations (1)
| Title |
|---|
| 李少文: "双氰合成新工艺", 《安徽化工》, vol. 35, no. 1, 28 February 2009 (2009-02-28), pages 43 - 46 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112500718A (en) * | 2020-09-21 | 2021-03-16 | 浙江恩盛染料化工有限公司 | Resource utilization method of C.I. disperse blue 60 condensation reclaimed material |
| CN116082219A (en) * | 2022-08-11 | 2023-05-09 | 山东大学 | Preparation method of disperse blue 60-based disperse dye |
| CN116082219B (en) * | 2022-08-11 | 2024-04-26 | 山东大学 | Preparation method of disperse blue 60-based disperse dye |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105461572B (en) | A kind of cleaning procedure for being continuously synthesizing to the chloroaniline of 2,4 dinitro 6 | |
| CN100543012C (en) | Preparation 1,4-diamino-2, the method for 3-dicyan anthraquinone | |
| CN102504567A (en) | Environment-friendly production method for permanent violet RL | |
| CN110980782A (en) | Method for producing high-purity magnesium sulfate by using alkylation waste sulfuric acid and application thereof | |
| CN107640780A (en) | A kind of preparation method of high-purity hydrogen aluminum oxide | |
| CN103073459A (en) | Preparation method for laurinol polyoxyethylene ether (7) isooctyl sulfosuccinate mixed sodium diester | |
| CN101391759B (en) | Sulfamic acid production process | |
| CN105461571A (en) | Clean technology for continuously synthesizing 2,6-dichloro-p-nitroaniline | |
| CN105693560A (en) | Method for preparing energy-efficient H-acid | |
| CN101492399A (en) | Method for preparing methylpropene sodium sulfonate | |
| CN101343419B (en) | Process for preparing disperse red 60 | |
| CN101284949B (en) | New process for synthesizing reduced olive T dye | |
| CN103979577B (en) | A kind of coking desulfurization mixed salt extracts the method for sodium sulfocyanate | |
| CN102993049A (en) | Environment-friendly method for preparing 1,4-diamido-2,3-dicyano anthraquinone | |
| CN106349733B (en) | A kind of technique and its equipment for synthesizing disperse red FB | |
| CN105237417A (en) | Synthetic method for solvent violet 13 | |
| CN101838204B (en) | Novel process for controlling waste residue and recycling resources in 1-anthraquinone production | |
| CN102206431B (en) | Method for oxidizing brown vat dye | |
| CN104478747B (en) | A kind of method utilizing organic solvent to produce glycine | |
| CN105566171B (en) | A kind of device for preparing H acid | |
| CN103540167B (en) | A kind of method of comprehensive utilization of the refining waste residue of 1-amino anthraquinones | |
| CN212293389U (en) | Permanent purple refining system | |
| CN104610173B (en) | A kind of cycle production process of nigrosine | |
| CN105753744B (en) | A kind of H acid preparation facilities with energy-saving effect | |
| CN107868014A (en) | A kind of process for cleanly preparing of glycine in coproduction with ammonium chloride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20151202 |
|
| C20 | Patent right or utility model deemed to be abandoned or is abandoned |