CN1450050A - Process for preparing 4,6-diamino resorcinol hydrochloride - Google Patents
Process for preparing 4,6-diamino resorcinol hydrochloride Download PDFInfo
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- CN1450050A CN1450050A CN 03116760 CN03116760A CN1450050A CN 1450050 A CN1450050 A CN 1450050A CN 03116760 CN03116760 CN 03116760 CN 03116760 A CN03116760 A CN 03116760A CN 1450050 A CN1450050 A CN 1450050A
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- benzene
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- dinitrobenzene
- dihydroxy
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Abstract
The present invention discloses a preparation method of 4,6-diaminoresorcinol hydrochloride, including catalytioc hydrogenation step of 4,6-dinitro-2-chloro-1,3-dihydroxybenzene by using hydrogen in the organic solvent and in the presence of rare metal catalyst at normal pressure or middle pressure and normal temp. or under the condition of heating. Said catalyst is formed from carrier which is stable for organic solvent and rare metal loaded on the carrier, and the rare metal content is 0.1-10 wt% of total weight of said carrier. Said invention not only can continuously make multiple hydrogenation, and activity of said catalyst is not reduced, at the same time, but also can obtain high-yield and high-quality 4,6-diaminoresorbinol hydrochloride.
Description
Technical field
The present invention relates to a kind ofly 4, the preparation method of 6-diamino resorcin hydrochlorate, this method be by 4,6-dinitrobenzene-2-chloro-1, and the 3-dihydroxy-benzene makes 4, the 6-diamino resorcin hydrochlorate through catalytic hydrogenation.
Background technology
4, the 6-diamino resorcin hydrochlorate is that the important structure unit of multiple polymer (particularly polybenzoxazole) is (referring to people's such as Wolf " Macromolecules " 1981,14:915).
Its structural formula is as follows:
US5399768 and US5371281 and US925358 have narrated by 4,6-dinitrobenzene-2-chloro-1, the 3-dihydroxy-benzene is through catalytic hydrogenation preparation 4, the method of 6-diamino resorcin, a significant disadvantages of described method is 4,6-dinitrobenzene-2-chloro-1, the 3-dihydroxy-benzene carries out heterogeneous catalyzed hydration with batch hydrogenation on the Pd/C catalyzer, the recirculation of expensive rare metal catalyst economy is used.Simultaneously, because 4,6-diamino resorcin stable low in the aqueous solution occurred 4 in the process of product and Pd/C catalyst separating, the oxidation of 6-diamino resorcin, and catalyzer is difficult to separation.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of new 4, the preparation method of 6-diamino resorcin hydrochlorate, occur 4 in recirculation use and product and the Pd/C catalyst separating process economically to overcome rare metal catalyzer that prior art exists, the oxidation of 6-diamino resorcin and catalyzer are difficult to isolating shortcoming.
Method of the present invention comprises the steps:
With 4,6-dinitrobenzene-2-chloro-1, the 3-dihydroxy-benzene carries out catalytic hydrogenation with hydrogen under normal pressure or middle pressure and normal temperature or heating in organic solvent with in the presence of the rare metal catalyzer, can obtain saidly 4, the 6-diamino resorcin hydrochlorate is by 4,6-dinitrobenzene-2-chloro-1, the 3-dihydroxy-benzene is a benchmark, 4, and 6-diamino resorcin hydrochlorate mole yield can reach more than 98%.
The catalyzer of being addressed is by the stable carrier of described organic solvent is constituted with the rare metal that is carried on this carrier;
The rare metal of being addressed comprises one or more in palladium, platinum, gold, ruthenium or the rhodium, preferred palladium or platinum, and its amount is the 0.1-10wt% of total catalyst weight;
The carrier of being addressed is a carrier well known in the art, comprises gac, silicon-dioxide, aluminum oxide or molecular sieve.
Preferred hydrogenation catalyst is the gac that contains palladium 4～6wt%.
Said catalyzer can adopt dipping method well known in the art to be prepared.
Catalyst consumption must be enough to make raw material change into 4 in the presence of hydroborating reagent the 6-diamino resorcin.Generally speaking, in every mole of dinitrobenzene chlorination dihydroxy-benzene with about 0.002 to about 2 moles catalyzer.In entire reaction course, every mole of dinitrobenzene chlorination dihydroxy-benzene catalyst consumption is the best with 0.02 mole to about 1 mole, preferably 0.02 to 0.2 mole.
The organic solvent of being addressed is with 4, and the organic solvent that the 6-diamino resorcin hydrochlorate dissolves each other is to guarantee that catalyst separating is convenient and to recycle.Preferred organic comprises one or more in alcohol, ether, ester, aromatic hydrocarbons, alkane aromatic hydrocarbons or the organic acid, preferably comprises C
1～C
3Unit alcohol, tetrahydrofuran (THF), benzene,toluene,xylene, ethyl acetate, Glacial acetic acid or propionic acid; Most preferably methyl alcohol or ethanol, especially methyl alcohol, because 4,6-diamino resorcin hydrochlorate solubleness in METHANOL MEDIUM is big, turn into making 4 owing to methanol solvent again, the 6-diamino resorcin hydrochlorate can't crystalline deposit, can separate with solid catalyst by simple filtering, and isolating catalyzer can be repeatedly used.
Follow-up 4, the condensing crystal of 6-diamino resorcin hydrochlorate can be realized by steaming methyl alcohol.
Organic solvent and 4,6-dinitrobenzene-2-chloro-1, the weight ratio of 3-dihydroxy-benzene is:
Organic solvent: 4,6-dinitrobenzene-2-chloro-1,3-dihydroxy-benzene=1～100: 1 (mol), preferred 5～25: 1.
In the reaction medium 4,6-dinitrobenzene-2-chloro-1, the suitable concentration of 3-dihydroxy-benzene must satisfy can reclaim this requirement of product effectively.For example, suitable concentration range is about 0.25～2mol/L, and being about good, the most desirable concentration with 0.5mol/L～1mol/L is 0.75 mole/L.
Reaction pressure is 1-10Mpa, preferred 1.5-3.0Mpa, especially 1.7-2.5Mpa, and temperature is 20-150 ℃, is preferably 20-100 ℃, especially 30-70 ℃.
Reaction also can add the suitable hydrogen material of releasing, as hydrazine, hydrazine hydrate, formic acid, ammonium formiate, the acid of second ammonium and composition thereof, to improve the concentration of hydrogen in the reaction solution.
By above-mentioned disclosed technical scheme as seen, adopt method of the present invention, not only can once connect and once carry out repeatedly hydrogenation and catalyst activity does not reduce, and obtaining 4 of high productive rate and high quality in economic especially mode, the 6-diamino resorcin hydrochlorate is by 4,6-dinitrobenzene-2-chloro-1, the 3-dihydroxy-benzene is a benchmark, 4, and 6-diamino resorcin hydrochlorate mole yield can reach more than 98%.Therefore proposed by the invention 4,6-diamino resorcin hydrochlorate method is a kind of highly effective 4, and the preparation method of 6-diamino resorcin hydrochlorate has bigger suitability for industrialized production prospect.
Embodiment
Embodiment 1
In the reactor of 200ml, add 15g 4,6-dinitrobenzene-2-chloro-1, the Pt/C of 3-dihydroxy-benzene, 60ml ethanol, 4g formic acid, 1.5g 5%.With N
2Import in this sealed reactor displaced air three times, use H again
2Replace three times.35 ℃ of temperature of reaction, pressure are 1.0Mpa.After reaction finished, reaction material liquid was cooled to room temperature.By a riser tube that filter is housed, use N
2Reaction solution is pressed into 100ml contains 4g SnCl
22H
2In the 3N dilute hydrochloric acid solution of O, the Pt/C catalyzer is stayed reactor.Ethanol is removed in underpressure distillation, adds the chemical pure concentrated hydrochloric acid of 50ml in distillate, and diamino resorcin hydrochlorate is precipitated out from flaxen solution.Filtration obtains white filter cake, and promptly 4,6-diamino resorcin hydrochlorate white crystal, its dry weight is 9.2g (by 4,6-dinitrobenzene-2-chloro-1,3-dihydroxy-benzene are benchmark, 4,6-diamino resorcin hydrochlorate mole yield is 70%).
Embodiment 2
In the reactor of 200ml, add 15g 4,6-dinitrobenzene-2-chloro-1, the Pd/C of 3-dihydroxy-benzene, 70ml propyl alcohol, 4g ammonium acetate, 2.0g 3%.With N
2Import in this sealed reactor displaced air three times, use H again
2Replace three times.H
2Pressure reaches 3Mpa, and temperature reaches 90 ℃.After reaction finished, reaction material liquid was cooled to room temperature.By a riser tube that filter is housed, use N
2Reaction solution is pressed into 100ml contains 4g SnCl
22H
2In the 3N dilute hydrochloric acid solution of O, the Pd/C catalyzer is stayed reactor.Propyl alcohol is removed in underpressure distillation, adds 50ml chemical pure concentrated hydrochloric acid in distillate, and diamino resorcin hydrochlorate is precipitated out from flaxen solution.Filtration obtains white filter cake, i.e. diamino resorcin hydrochlorate white crystal, and its dry weight is 13.2g (by 4,6-dinitrobenzene-2-chloro-1,3-dihydroxy-benzene are benchmark, and diamino resorcin hydrochlorate mole yield is 98.3%).
Embodiment 3
In the reactor of 200ml, add 15g 4,6-dinitrobenzene-2-chloro-1, the Pt/C of 3-dihydroxy-benzene, 50ml benzene, 4g hydrazine hydrate, 1.5g 5%.With N
2Import in this sealed reactor displaced air three times, use H again
2Replace three times.H
2Pressure reaches 0.5Mpa, and temperature reaches 50 ℃.After reaction finished, reaction material liquid was cooled to room temperature.By a riser tube that filter is housed, use N
2Reaction solution is pressed into 100ml contains 4gSnCl
22H
2In the 3N dilute hydrochloric acid solution of O, the Pt/C catalyzer is stayed reactor.Benzene is removed in underpressure distillation, adds 50ml chemical pure concentrated hydrochloric acid in distillate, and diamino resorcin hydrochlorate is precipitated out from flaxen solution.Filtration obtains white filter cake, i.e. diamino resorcin hydrochlorate white crystal, and its dry weight is 6.6g (by 4,6-dinitrobenzene-2-chloro-1,3-dihydroxy-benzene are benchmark, and diamino resorcin hydrochlorate mole yield is 49.1%).
Embodiment 4
In the reactor of 200ml, add 15g 4,6-dinitrobenzene-2-chloro-1, the Ru/C of 3-dihydroxy-benzene, 75ml toluene, 4g hydrazine hydrate, 1.5g 5%.With N
2Import in this sealed reactor displaced air three times, use H again
2Replace three times.H
2Pressure reaches 3Mpa, and temperature is a room temperature.After reaction finished, reaction material liquid was cooled to room temperature.By a riser tube that filter is housed, use N
2Reaction solution is pressed into 100ml contains 4g SnCl
22H
2In the 3N dilute hydrochloric acid solution of O, the Pd/C catalyzer is stayed reactor.Toluene is removed in underpressure distillation, adds 50ml chemical pure concentrated hydrochloric acid in distillate, and diamino resorcin hydrochlorate is precipitated out from flaxen solution.Filtration obtains white filter cake, i.e. diamino resorcin hydrochlorate white crystal, and its dry weight is 13.1g (by 4,6-dinitrobenzene-2-chloro-1,3-dihydroxy-benzene are benchmark, and diamino resorcin hydrochlorate mole yield is 97.8%).
Embodiment 5
In the reactor of 200ml, add 20g 4,6-dinitrobenzene-2-chloro-1, the Pd/C of 3-dihydroxy-benzene, 75ml methyl alcohol, 2g formic acid, 1.5g 5%.With N
2Import in this sealed reactor displaced air three times, use H again
2Replace three times.H
2Press to be 20Mpa, temperature is 20 ℃, and after reaction finished, reaction material liquid was cooled to room temperature.By a riser tube that filter is housed, use N
2Reaction solution is pressed into 100ml contains 4gSnCl
22H
2In the 3N dilute hydrochloric acid solution of O, the Pd/C catalyzer is stayed reactor.Methyl alcohol is removed in underpressure distillation, adds the commercial concentrated hydrochloric acid of 50ml in distillate, and diamino resorcin hydrochlorate is precipitated out from flaxen solution.Filtration obtains white filter cake, i.e. diamino resorcin hydrochlorate white crystal, and its dry weight is 17.7g (by 4,6-dinitrobenzene-2-chloro-1,3-dihydroxy-benzene are benchmark, and diamino resorcin hydrochlorate mole yield is 98.5%).
Embodiment 6
In the reactor of 200ml, add 15g 4,6-dinitrobenzene-2-chloro-1, the Pd/C of 3-dihydroxy-benzene, 50ml ethyl acetate, 4g ammonium acetate, 1.5g 3%.With N
2Import in this sealed reactor displaced air three times, use H again
2Replace three times.H
2Pressure reaches 2.5Mpa, 30 ℃ of temperature.After reaction finished, reaction material liquid was cooled to room temperature.By a riser tube that filter is housed, use N
2Reaction solution is pressed into 100ml contains 4g SnCl
22H
2In the 3N dilute hydrochloric acid solution of O, the Pd/C catalyzer is stayed reactor.Ethyl acetate is removed in underpressure distillation, adds 50ml chemical pure concentrated hydrochloric acid in distillate, and diamino resorcin hydrochlorate is precipitated out from flaxen solution.Filtration obtains white filter cake, i.e. diamino resorcin hydrochlorate white crystal, and its dry weight is 13.2g (by 4,6-dinitrobenzene-2-chloro-1,3-dihydroxy-benzene are benchmark, and diamino resorcin hydrochlorate mole yield is 98.2%).
Embodiment 7
Mode similarly to Example 5 adopts and has used 15 times catalyzer, adds 15g 4,6-dinitrobenzene-2-chloro-1,3-dihydroxy-benzene, 75ml methyl alcohol, 4g ammonium acetate.With N
2Import in this sealed reactor displaced air three times, use H again
2Replace three times.H
2Pressure reaches 2.5Mpa, 30 ℃ of temperature.After reaction finished, reaction material liquid was cooled to room temperature.By a riser tube that filter is housed, use N
2Reaction solution is pressed into 100ml contains 4g SnCl
22H
2In the 3N dilute hydrochloric acid solution of O, the Pd/C catalyzer is stayed reactor.Methyl alcohol is removed in underpressure distillation, adds 50ml chemical pure concentrated hydrochloric acid in distillate, and diamino resorcin hydrochlorate is precipitated out from flaxen solution.Filtration obtains white filter cake, i.e. diamino resorcin hydrochlorate white crystal, and its dry weight is 13.2g (by 4,6-dinitrobenzene-2-chloro-1,3-dihydroxy-benzene are benchmark, and diamino resorcin hydrochlorate mole yield is 98.4%).
Claims (10)
1. one kind 4, the preparation method of 6-diamino resorcin hydrochlorate is characterized in that, this method comprises the steps:
With 4,6-dinitrobenzene-2-chloro-1,3-dihydroxy-benzene carry out catalytic hydrogenation with hydrogen in organic solvent with in the presence of the rare metal catalyzer;
The catalyzer of being addressed is by the stable carrier of described organic solvent is constituted with the rare metal that is carried on this carrier;
The rare metal of being addressed comprises one or more in palladium, platinum, gold, ruthenium or the rhodium;
The organic solvent of being addressed is with 4, the organic solvent that the 6-diamino resorcin hydrochlorate dissolves each other.
2. method according to claim 1 is characterized in that, rare metal is palladium or platinum, and its amount is the 0.1-10wt% of total catalyst weight.
3. method according to claim 1 is characterized in that carrier comprises gac, silicon-dioxide, aluminum oxide or molecular sieve.
4. method according to claim 3 is characterized in that, catalyzer is the gac that contains palladium 4～6wt%.
5. method according to claim 1 is characterized in that, organic solvent comprises one or more in alcohol, ester, ether, aromatic hydrocarbons, alkane aromatic hydrocarbons or the organic acid.
6. method according to claim 5 is characterized in that organic solvent comprises C
1～C
3Unit alcohol, tetrahydrofuran (THF), benzene,toluene,xylene, Glacial acetic acid or propionic acid.
7. according to each described method of claim 1～6, it is characterized in that every mole of dinitrobenzene chlorination dihydroxy-benzene catalyst consumption is 0.02 mole to about 1 mole, preferably 0.02 to 0.2 mole.
8. method according to claim 7 is characterized in that, reaction pressure is 1-10Mpa, and temperature is 20-150 ℃.
9. method according to claim 8 is characterized in that, reaction pressure is 1.5-3Mpa, and temperature is 20-100 ℃, adds during reaction and releases the hydrogen material.
10. want 9 described methods according to right, it is characterized in that, organic solvent and 4,6-dinitrobenzene-2-chloro-1, the weight ratio of 3-dihydroxy-benzene is:
Organic solvent: 4,6-dinitrobenzene-2-chloro-1,3-dihydroxy-benzene=1～100: 1 (mol), preferred 5～25: 1;
In the reaction medium 4,6-dinitrobenzene-2-chloro-1, the concentration range of 3-dihydroxy-benzene is 0.25～2mol/L, is that good, the most desirable concentration is 0.75 mole/L with 0.5mol/L～1mol/L.
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| CN 03116760 CN1450050A (en) | 2003-05-06 | 2003-05-06 | Process for preparing 4,6-diamino resorcinol hydrochloride |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215472B (en) * | 2008-01-15 | 2010-06-02 | 东华大学 | Fluorine-containing hetero-aromatic ring liquid crystal polymer and preparation method thereof |
| CN101962326A (en) * | 2010-08-20 | 2011-02-02 | 南化集团研究院 | Method for preparing 4,6-diamino resorcinol hydrochloride by continuous hydrogenation |
| CN104447314A (en) * | 2013-09-25 | 2015-03-25 | 中国石油化工股份有限公司 | Treatment method for acetic acid-containing waste liquid |
| CN105461575A (en) * | 2015-12-31 | 2016-04-06 | 江苏尚莱特医药化工材料有限公司 | Preparation method of 4,6-diamidoresorcinol or salts thereof |
-
2003
- 2003-05-06 CN CN 03116760 patent/CN1450050A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215472B (en) * | 2008-01-15 | 2010-06-02 | 东华大学 | Fluorine-containing hetero-aromatic ring liquid crystal polymer and preparation method thereof |
| CN101962326A (en) * | 2010-08-20 | 2011-02-02 | 南化集团研究院 | Method for preparing 4,6-diamino resorcinol hydrochloride by continuous hydrogenation |
| CN104447314A (en) * | 2013-09-25 | 2015-03-25 | 中国石油化工股份有限公司 | Treatment method for acetic acid-containing waste liquid |
| CN105461575A (en) * | 2015-12-31 | 2016-04-06 | 江苏尚莱特医药化工材料有限公司 | Preparation method of 4,6-diamidoresorcinol or salts thereof |
| CN105461575B (en) * | 2015-12-31 | 2018-07-03 | 江苏尚莱特医药化工材料有限公司 | The preparation method of 4,6- diamino resorcins or its salt |
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