CN104177265A - 4,6-diamino-resorcinol hydrochloride synthesis method - Google Patents
4,6-diamino-resorcinol hydrochloride synthesis method Download PDFInfo
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- CN104177265A CN104177265A CN201410353121.4A CN201410353121A CN104177265A CN 104177265 A CN104177265 A CN 104177265A CN 201410353121 A CN201410353121 A CN 201410353121A CN 104177265 A CN104177265 A CN 104177265A
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Abstract
The invention discloses a 4,6-diamino-resorcinol hydrochloride synthesis method which comprises the following steps: (1) slowly adding resorcinol into fuming sulfuric acid until the both are subjected to sulfonation reaction to obtain 2,4,6-trisulforesorcinol, nitrifying the product to obtain 2-sulfo-4,6-dinitroresorcinol, and adding water to perform hydrolysis reaction; and (2) performing nitroreduction on the product 4,6-dinitroresorcinol in the presence of a hydrazine hydrate/noble metal catalyst reduction system, and then dropwisely adding excessive concentrated hydrochloric acid to generate DAR hydrochloride crystal precipitate. The method reduces the consumption of the noble metal catalyst on the basis of the prior art; the purity of the prepared DAR hydrochloride can be up to 99.6%, and the total yield can be up to 64%; the hydrazine hydrate is cheap and accessible; the reaction byproducts are nitrogen gas and water, thus reducing environmental pollution; and meanwhile, the reaction conditions are mild, no high-pressure equipment is required, and the equipment investment is low, thus lowering the DAR synthesis cost on the whole.
Description
Technical field
The present invention relates to a kind of preparation method of aromatic diamine salt, be specifically related to a kind of method of synthetic 4,6-diaminoresorcinol hydrochloride.
Background technology
Polyparaphenylene's benzo-dioxazole (PBO) fiber is the best product of over-all properties in current fragrant heterocycle fiber, and 4,6-diamino resorcin (DAR) is the important monomer of preparation PBO polymkeric substance, and can its purity and quality have determined polymerization obtain the high performance PBO of high molecular.
The study on the synthesis of DAR starts from early 1980s, through the research and development of nearly 30 years, numerous synthetic routes are developed, but these synthetic routes all have its deficiency, or raw material is difficult to obtain or pollutes large or productive rate is low or product purity is low or with high costs, complex synthetic route etc. is not suitable for suitability for industrialized production.
Chinese patent (application number 00117956.X) proposes the method for the synthetic DAR of a kind of three sulfonation methods: taking Resorcinol as starting raw material, obtain 2 through excessive sulfuric acid sulfonation, 4,6-tri-sulfo group Resorcinols, then use nitrated 4,6 sulfo groups of nitrosonitric acid to obtain 2-sulfo group-4,6-dinitroresorcinol, this intermediate product removes 2 sulfo groups through hydrolysis, and the nitro that finally reduces makes DAR.It is high that the method has reaction preference, product purity advantages of higher, still need to use the noble metal catalyst of a large amount of costlinesses but finally reduce the step of nitro, in reaction under high pressure vessel, reduce, reaction conditions is harsher, and DAR preparation cost is high, be that PBO price is high, the major cause that is difficult to promote the use of.
Summary of the invention
In the process of the synthetic DAR of existing three sulfonation methods, owing to adopting a large amount of expensive noble metal catalysts, simultaneous reactions will carry out in reaction under high pressure vessel, and severe reaction conditions makes DAR cost high.In order to overcome above-mentioned defect, the object of the present invention is to provide a kind of synthetic 4, the novel method of 6-diamino resorcin hydrochlorate, the method on the basis of three sulfonation methods taking hydrazine hydrate and noble metal catalyst as reductive agent, do like this usage quantity that has reduced noble metal catalyst, hydrazine hydrate is cheap and easy to get, prepared DAR hydrochloride purity can be higher than 99%, total recovery can reach 70%, and byproduct of reaction is nitrogen G&W, and environmental pollution is low, simultaneous reactions mild condition, do not need high-tension apparatus, facility investment is little, thereby can reduce on the whole the synthetic cost of DAR.
Object of the present invention is achieved through the following technical solutions:
A method for synthetic 4,6-diaminoresorcinol hydrochloride, comprises the following steps:
(1) Resorcinol slowly being added in oleum, there is sulfonation reaction and obtains 2,4 in both, 6-tri-sulfo group Resorcinols, use concentrated nitric acid nitrated 2,4,6-tri-sulfo group Resorcinols obtain 2-sulfo group-4, and 6-dinitroresorcinol adds water to regulate H in reaction system
2sO
4massfraction to 40～70%, rear generation hydrolysis reaction, makes 2-sulfo group-4,6-dinitroresorcinol removes 2 sulfo groups and obtains 4,6-dinitroresorcinol;
(2) 4,6-dinitroresorcinol is dissolved in organic solvent, in hydrazine hydrate/noble metal catalyst reduction system, carries out nitroreduction, after reduction reaction finishes, in system, splash into excessive concentrated hydrochloric acid, generate DAR hydrochloride crystal settling;
The concentration of described oleum is preferably 20～40% (with the SO that dissociates
3mass content meter); In step (1), free SO in oleum
3be greater than 3:1 with the mol ratio of Resorcinol, preferably 3:1～5:1, sulfonation reaction is carried out 1～3h, preferably 90～120 DEG C of temperature of reaction;
In step (1), the concentration of concentrated nitric acid preferably 65%, HNO in concentrated nitric acid
3be less than or equal to 2:1 with the mol ratio of Resorcinol, preferably 2:1; The temperature of nitration reaction is 10～20 DEG C, reaction 2h;
In step (1), the reaction times of hydrolysis reaction is 5～15h, preferably 90～110 DEG C of temperature of reaction;
Organic solvent described in step (2) is more than one in methyl alcohol, ethanol, ethylene glycol, tetrahydrofuran (THF), DMF (dimethyl formamide), DMSO (dimethyl sulfoxide (DMSO)) or acetonitrile;
Hydrazine hydrate/noble metal catalyst reduction system described in step (2) is made up of hydrazine hydrate and noble metal catalyst; Wherein, the mol ratio of hydrazine hydrate and 4,6-dinitroresorcinol is 2:1～12:1, preferably 5:1; The add-on of noble metal catalyst accounts for 0.5～2.5% of 4,6-dinitroresorcinol weight fraction, and preferably 2%; Reduction reaction time 5～15h, preferably 50～70 DEG C of temperature of reaction;
Described noble metal catalyst is Raney's nickel, Pd/C or Pt/C, preferably Raney's nickel.
The present invention's sulfonated reagent used is oleum, and wherein effectively sulphonating agent is the SO of free state
3it is highly purified 2,4 that this step sulfonation reaction requires to generate, 6-tri-sulfo group Resorcinols, the by product of minute quantity all can affect follow-up phase final product 4, the purity of 6-diamino resorcin, and the concentration of sulfonated reagent and sulfonation temperature can affect final sulfonated products, for guaranteeing 2 of Resorcinol, 4,6 all there is sulfonation replacement, select 20～40% oleum, free SO in oleum
3need be greater than 3:1 with the mol ratio of Resorcinol.But excessive oleum can make reaction end form spent acid too much, intractability is large, as long as thereby the consumption of oleum can ensure the free SO that it is contained
3with the mol ratio of Resorcinol be 3:1～5:1.
Because sulfonation is strong exothermal reaction, reaction process should slowly add Resorcinol in oleum in batches, at 90～120 DEG C, reacts 1～3h.After sulfonation reaction finishes, splash into nitrating agent to reaction system, by controlling the add-on of nitrating agent, make intermediate product 2,4, there are 4,6 nitrated in position and replace in 6-tri-sulfo group Resorcinols, obtains 2 sulfo group-4,6-dinitroresorcinol.
Nitrating agent used in the present invention is the concentrated nitric acid of 65% concentration, HNO
3should be slightly less than or equal 2:1 with the mol ratio of Resorcinol.Because nitration reaction is strong exothermal reaction, for avoiding reaction too acutely to blast, in concentrated nitric acid dropping process, should take measures as ice-water bath, reaction system to be lowered the temperature, make system temperature remain on 10～20 DEG C, concentrated nitric acid dropwises, and keeps reaction 2h.
Nitration reaction is complete, slowly adds appropriate water, and the sulfuric acid concentration of regulation system is massfraction w (H
2sO
4) make them in 40～70% scopes, temperature of reaction remains on 90～110 DEG C, reaction 5～15h, and hydrolysis reaction is sloughed 2 sulfo groups, 4 of generation, 6-dinitroresorcinol is with yellow crystals Precipitation.
By 4 of hydrolysis reaction gained, 6-dinitroresorcinol is dissolved in organic solvent, optional organic solvent has the solubilized 4 such as methyl alcohol, ethanol, ethylene glycol, tetrahydrofuran (THF), DMF, DMSO, acetonitrile, the organic solvent of 6-dinitroresorcinol, or the mixed solvent of these organic solvents.
In solution, add hydrazine hydrate/noble metal catalyst to carry out nitro-reduction reaction, preferably 80% hydrazine hydrate, hydrazine hydrate and 4, the mol ratio of 6-dinitroresorcinol is 2:1～12:1, preferably 5:1, optional noble metal catalyst has Raney's nickel, Pd/C, Pt/C, catalyzer add-on accounts for 4, 0.5～2.5% of 6-dinitroresorcinol weight fraction, preferably 2%, the temperature of reduction reaction is 50～70 DEG C, if temperature of reaction is too high when hydrazine hydrate reduction nitroxyl, hydrazine hydrate decomposes too fast, the hydrogen proton producing has little time to make nitroxyl fully to reduce and is just combined into hydrogen effusion, for the temperature that obtains higher conversion reduction reaction is controlled at 50～70 DEG C, reaction times 5～15h, obtain 4, 6-diamino resorcin, add excessive concentrated hydrochloric acid, make it generate 4, 6-diamino resorcin hydrochlorate crystal settling.
The present invention has following advantage and effect with respect to prior art:
1, due to current 4, the synthetic method ubiquity of 6-diamino resorcin (DAR) pollutes large, raw material costliness, the problem that preparation cost is high, make its polymkeric substance polyparaphenylene benzene two oxazoles (PBO) and corresponding pbo fiber preparation cost high, be difficult to apply.Pollute greatly in order to solve traditional DAR synthetic route, the problem that preparation cost is high, the invention provides one eco-friendly, the synthetic method that preparation cost is lower, and this synthesis method is polluted low, and DAR yield and the purity of synthesized are high.
2, in the process of the synthetic DAR of existing three sulfonation methods, the reduction step of nitro adopts noble metal catalyst to complete by shortening in reaction under high pressure vessel, and reaction conditions is had relatively high expectations, and makes DAR cost high.In order to overcome above-mentioned defect, the invention provides a kind of synthetic 4, the novel method of 6-diamino resorcin hydrochlorate, the method on the basis of three sulfonation methods taking hydrazine hydrate and a small amount of noble metal catalyst as reductive agent, do like this usage quantity that has reduced noble metal catalyst, prepared DAR hydrochloride purity 99.6%, total recovery can reach 64%, hydrazine hydrate is cheap and easy to get, and byproduct of reaction is nitrogen G&W, and environmental pollution is low, simultaneous reactions mild condition, do not need high-tension apparatus, facility investment is little, thereby can reduce on the whole the synthetic cost of DAR.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
The present invention uses HPLC to analyze product purity, calculates by peak area, obtains product purity.
HPLC analysis condition is as follows:
(1) 2,4,6-, tri-sulfo group Resorcinols
Column temperature: 30 DEG C
Moving phase: acetonitrile/water/tetrabutylammonium=1 :/2/0.01
Detect wavelength: 254nm
Flow velocity: 1.0ml/min
(2) 4,6-diaminoresorcinol (DAR)
Column temperature: 30 DEG C
Moving phase: methyl alcohol/0.1mol/L aqueous solution of sodium bisulfite=7/13
Detect wavelength: 300nm
Flow velocity: 1.0ml/min
Embodiment 1
A method for synthetic 4,6-diaminoresorcinol hydrochloride, comprises the following steps:
(1) add 20% oleum 60g (to contain the free SO of 0.15mol at reaction flask
3), slowly add Resorcinol 5.5g (0.05mol), stirring reaction 3h at 90 DEG C, TLC follow the tracks of reaction between raw material point disappearance.Sampling, is used HLPC to analyze, and 2,4,6-, tri-sulfo group Resorcinol purity are 90.5%.Reaction mass is cooled to 10 DEG C, under ice-water bath, drips 9.7g65% concentrated nitric acid and (contain 0.1molHNO
3), keep system temperature at 10～20 DEG C, dropwise and continue reaction 2h, it is yellow that solution is, and slowly adds 70g deionized water in reaction system, obtains orange-yellow solution, H in solution
2sO
4massfraction be 40.0%, keep stirring reaction 5h at 90 DEG C of temperature, have a large amount of yellow crystals to generate, filter, filter cake recrystallization in methyl alcohol obtains light yellow crystal 4,6-dinitroresorcinol weighs heavy 6.5g, yield 65% after dry.
(2) 6g (0.03mol) is synthesized by above-mentioned steps 4,6-dinitroresorcinol is placed in 250ml reaction flask, add 60ml methyl alcohol, add 0.12g Raney's nickel, the hydrazine hydrate of 2.4g (0.06mol) 80% is slowly added drop-wise in flask, dropwises back flow reaction 5h at 50 DEG C.Remove by filter catalyzer, in filtrate, splash into excessive concentrated hydrochloric acid (until regeneration 4 not, 6-diamino resorcin hydrochlorate crystal settling, it is excessive to be), generate 4,6-diaminoresorcinol hydrochloride crystal settling, filter, filter cake is recrystallization in methyl alcohol, and is dried to obtain off-white color crystal 4.1g at normal temperatures, yield 64%.Product does liquid-phase chromatographic analysis, and peak and 4,6-diaminoresorcinol hydrochloride standard specimen peak coincide, purity 90.5%.
Embodiment 2
A method for synthetic 4,6-diaminoresorcinol hydrochloride, comprises the following steps:
(1) add 30% oleum 45g (to contain the free SO of 0.169mol at reaction flask
3), slowly add Resorcinol 5.5g (0.05mol), stirring reaction 2h at 110 DEG C, TLC follow the tracks of reaction between raw material point disappear, solution presents Vandyke brown, sampling is used HPLC analysis, product 2,4,6-tri-sulfo group Resorcinol purity are 99.6%.Reaction mass is cooled to 10 DEG C, under ice-water bath, drips 9.7g65% concentrated nitric acid and (contain 0.1molHNO
3), keep system temperature at 10～20 DEG C, dropwise and continue reaction 2h, it is yellow that solution is, and slowly adds 25g deionized water in reaction system, obtains orange-yellow solution, in solution, the massfraction of sulfuric acid is 50%, keep stirring reaction 10h at 100 DEG C of temperature, have a large amount of yellow crystals to generate, filter, filter cake recrystallization in methyl alcohol obtains light yellow crystal 4,6-dinitroresorcinol, dry rear heavy 7.8g, the yield 78% of weighing.
(2) 6g (0.03mol) is synthesized by above-mentioned steps 4,6-dinitroresorcinol is placed in 250ml reaction flask, add 60ml tetrahydrofuran (THF), add 0.12g Raney's nickel, the hydrazine hydrate of 6g (0.15mol) 80% is added drop-wise in flask, dropwises back flow reaction 10h at 60 DEG C.Remove by filter catalyzer, in filtrate, splash into excessive concentrated hydrochloric acid (until regeneration 4 not, 6-diamino resorcin hydrochlorate crystal settling, it is excessive to be), generate 4,6-diaminoresorcinol hydrochloride crystal settling, filter, filter cake is recrystallization in methyl alcohol, and is dried to obtain white crystal 5.25g at normal temperatures, yield 82%.Product does liquid-phase chromatographic analysis, and peak and 4,6-diaminoresorcinol hydrochloride standard specimen peak coincide, purity 99.5%.
Embodiment 3
A method for synthetic 4,6-diaminoresorcinol hydrochloride, comprises the following steps:
(1) add 40% oleum 50g (to contain the free SO of 0.25mol at reaction flask
3), slowly add Resorcinol 5.5g (0.05mol), stirring reaction 1h at 120 DEG C, TLC follow the tracks of reaction between raw material point disappearance.Sampling, is used HPLC to analyze, product 2,4, and 6-tri-sulfo group Resorcinol purity are 99.7%.Reaction mass is cooled to 10 DEG C, under ice-water bath, drips 9.7g65% concentrated nitric acid and (contain 0.1mol HNO
3), keep system temperature at 10～20 DEG C, dropwise and continue reaction 2h, it is yellow that solution is, and slowly adds 7.5g deionized water in reaction system, obtains orange-yellow solution, in solution, the massfraction of sulfuric acid is 70%, keep stirring reaction 15h at 110 DEG C of temperature, have a large amount of yellow crystals to generate, filter, filter cake recrystallization in methyl alcohol obtains light yellow crystal 4,6 ?dinitroresorcinol, weigh heavy 7.0g, yield 70% after dry.
(2) 6g (0.03mol) is synthesized by above-mentioned steps 4,6-dinitroresorcinol is placed in 250ml reaction flask, add 60ml tetrahydrofuran (THF), add 0.12g Raney's nickel, the hydrazine hydrate of 14.4g (0.36mol) 80% is added drop-wise in flask, dropwises back flow reaction 15h at 70 DEG C.Remove by filter catalyzer, in filtrate, splash into excessive concentrated hydrochloric acid (until regeneration 4 not, 6-diamino resorcin hydrochlorate crystal settling, it is excessive to be), generate 4,6 ?diamino resorcin hydrochlorate crystal settling, filter, filter cake is recrystallization in methyl alcohol, and is dried to obtain white crystal 4.6g at normal temperatures, yield 72%.Product does liquid-phase chromatographic analysis, and peak and 4,6-diaminoresorcinol hydrochloride standard specimen peak coincide, purity 99.6%.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (7)
1. a method for synthetic 4,6-diaminoresorcinol hydrochloride, is characterized in that comprising the following steps:
(1) Resorcinol slowly being added in oleum, there is sulfonation reaction and obtains 2,4 in both, 6-tri-sulfo group Resorcinols, use concentrated nitric acid nitrated 2,4,6-tri-sulfo group Resorcinols obtain 2-sulfo group-4, and 6-dinitroresorcinol adds water to regulate H in reaction system
2sO
4massfraction to 40～70%, rear generation hydrolysis reaction, 2-sulfo group-4,6-dinitroresorcinol removes 2 sulfo groups and obtains 4,6-dinitroresorcinol;
(2) 4,6-dinitroresorcinol is dissolved in organic solvent, in hydrazine hydrate/noble metal catalyst reduction system, carries out nitroreduction, after reduction reaction finishes, in system, splash into excessive concentrated hydrochloric acid, generate DAR hydrochloride crystal settling;
In step (1), the concentration of described oleum is 20～40% (with the SO that dissociates
3mass content meter), free SO in oleum
3with the mol ratio of Resorcinol be 3:1～5:1, the temperature of sulfonation reaction is 90～120 DEG C;
In step (1), HNO in concentrated nitric acid
3be less than or equal to 2:1 with the mol ratio of Resorcinol, the temperature of nitration reaction is 10～20 DEG C;
Hydrazine hydrate/noble metal catalyst reduction system described in step (2) is made up of hydrazine hydrate and noble metal catalyst; Wherein, the mol ratio of hydrazine hydrate and 4,6-dinitroresorcinol is 2:1～12:1, and the add-on of noble metal catalyst accounts for 0.5～2.5% of 4,6-dinitroresorcinol weight fraction, and reduction reaction temperature is 50～70 DEG C.
2. the method for synthetic 4,6-diaminoresorcinol hydrochloride according to claim 1, is characterized in that: in step (1), the concentration of concentrated nitric acid is 65%, HNO in concentrated nitric acid
3with the mol ratio of Resorcinol be 2:1.
3. the method for synthetic 4,6-diaminoresorcinol hydrochloride according to claim 1, is characterized in that: in step (1), the reaction times of hydrolysis reaction is 5～15h, and temperature of reaction is 90～110 DEG C.
4. according to claim 1 synthetic 4, the method of 6-diamino resorcin hydrochlorate, is characterized in that: the organic solvent described in step (2) is more than one in methyl alcohol, ethanol, ethylene glycol, tetrahydrofuran (THF), DMF, DMSO or acetonitrile.
5. the method for synthetic 4,6-diaminoresorcinol hydrochloride according to claim 1, is characterized in that: the mol ratio of hydrazine hydrate and 4,6-dinitroresorcinol is 5:1.
6. the method for synthetic 4,6-diaminoresorcinol hydrochloride according to claim 1, is characterized in that: the add-on of noble metal catalyst accounts for 2% of 4,6-dinitroresorcinol weight fraction.
7. the method for synthetic 4,6-diaminoresorcinol hydrochloride according to claim 1, is characterized in that: described noble metal catalyst is Raney's nickel, Pd/C or Pt/C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543006A (en) * | 2016-10-31 | 2017-03-29 | 华东理工大学 | The synthesis technique of 4,6 dinitroresorcinols |
| CN115784943A (en) * | 2021-09-09 | 2023-03-14 | 中石化南京化工研究院有限公司 | Method for improving preparation selectivity of 2-sulfonic-4, 6-dinitroresorcinol |
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| US5371281A (en) * | 1992-08-07 | 1994-12-06 | Hoechst Ag | Process for preparing alkali metal 3-sulfobenzoates |
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| CN106543006A (en) * | 2016-10-31 | 2017-03-29 | 华东理工大学 | The synthesis technique of 4,6 dinitroresorcinols |
| CN115784943A (en) * | 2021-09-09 | 2023-03-14 | 中石化南京化工研究院有限公司 | Method for improving preparation selectivity of 2-sulfonic-4, 6-dinitroresorcinol |
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Application publication date: 20141203 |