CN101265189A - Process for preparing 4,6-dinitroresorcinol - Google Patents
Process for preparing 4,6-dinitroresorcinol Download PDFInfo
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- CN101265189A CN101265189A CNA2008100367373A CN200810036737A CN101265189A CN 101265189 A CN101265189 A CN 101265189A CN A2008100367373 A CNA2008100367373 A CN A2008100367373A CN 200810036737 A CN200810036737 A CN 200810036737A CN 101265189 A CN101265189 A CN 101265189A
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- dinitroresorcinol
- preparation
- reaction
- dinitrobenzene
- alkali aqueous
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Abstract
The invention relates to the technology field of high molecular synthetic material, in particular to a method of preparing 4, 6-dinitroresorcinol, and the method is also used for synthesizing 4, 6-bis-aminoresorcinol, etc. and polymer material. The method of preparing the 4, 6-dinitroresorcinol comprises 4, 6-dinitro-m-dichlorobenzene, polymer dihydric alcohol, fatty primary alcohol and liquid caustic. The method is characterized in that when the polymer dihydric alcohol which is used as a catalyst exists, the 4, 6-dinitro-m-dichlorobenzene and the fatty primary alcohol as well as the liquid caustic effect catalytic etherealization reaction under a normal temperature condition or a high temperature condition; generated 4, 6-dinitro-3-methoxyphenol reacts with sulphuric acid, phenolic ether is hydrolyzed to protect hydroxyl phenolic group to react, so that the 4, 6-dinitroresorcinol is prepared. Compared with prior art, the method has reasonable formulation and simple technology, and corresponds to the requirement of the industrial production; the produced products has no organic solvent, the viscosity of polymer is high, the hot melt is strong, and the blank is filled.
Description
[technical field]
The present invention relates to the high molecular synthetic material technical field, particularly relate to a kind of with 4, the preparation method of 6-dinitroresorcinol, be used for synthetic 4,6-diamino resorcin etc. and macromolecular material.
[background technology]
4, the 6-dinitroresorcinol is the starting raw material of polyparaphenylene's benzo-dioxazole synthetic materials, the principal feature of this synthetic materials, and good heat resistance, the intensity height is applied in heat-resisting strongthener and weaving, military supplies, space flight and aviation, industrial production, fields such as culture and sports.
USP4912246 etc. have narrated by Resorcinol through the chloro-formic ester alkanisation, mixed acid nitrification, operations such as catalytic hydrolysis, preparation 4, the method for 6-dinitroresorcinol, this method shortcoming is that reaction product purity is not high, need to separate, repeatedly purify, simultaneously through impurity, this method also needs with expensive starting raw material, and is unfavorable to reducing product cost.The USP4745232 report, by the direct nitration reaction preparation 4 of Resorcinol, the method for 6-dinitroresorcinol, shortcoming are that product purity is low, yield is not high, is difficult to suitability for industrialized production.
[summary of the invention]
The invention provides a kind of newly 4,6-dinitroresorcinol preparation method is a starting raw material with the Meta Dichlorobenzene, through catalyst etherifying, and the sulphuric acid hydrolysis method, there is complex process in the preparation target product, the shortcoming that cost is higher to solve in the art methods.
To achieve these goals; design a kind of 4; the preparation method of 6-dinitroresorcinol; comprise 4; 6-dinitrobenzene Meta Dichlorobenzene, macromolecule diol, primary aliphatic alcohols and caustic-alkali aqueous; it is characterized in that 4; 6-dinitrobenzene Meta Dichlorobenzene in the presence of the macromolecule diol catalyzer, with primary aliphatic alcohols, caustic-alkali aqueous solution; under normal temperature or the hot conditions; carry out 4 of catalyst etherifying reaction generation, 6-dinitrobenzene-3-methoxyphenol and sulfuric acid react, the reaction of phenolic ether hydrolysis Tuo Bao Hu Hydroxyalkyl phenolic group; preparation 4, the 6-dinitroresorcinol.
Described catalyzer is the binary aliphatic alcohol of low carbon chain, and with the alkylating agent that alkali aqueous solution and alcohols mix, molecular weight is at 200-2000.
Described alkylating agent is methyl alcohol or ethanol.
Described alkali aqueous solution is an aqueous sodium hydroxide solution, and concentration is at 10-50%.
The temperature of reaction of described etherification reaction is 60 ℃-95 ℃.
Described phenolic ether hydrolysis adopts 70-90% sulfuric acid to make hydrolytic reagent, is the reaction of Tuo Bao Hu Hydroxyalkyl phenolic group.
Described sulphuric acid hydrolysis reaction, temperature is 120-145 ℃.
The present invention compares with prior art, prescription is reasonable, and technology is simple, and its principal feature is to be starting raw material with the Meta Dichlorobenzene, through catalyst etherifying, the sulphuric acid hydrolysis method, the preparation target product meets the industrialization production requirement, the product of producing does not contain organic solvent, the polymer viscosity height, thermally melting is strong, fills a hole in the market.
[embodiment]
Preparation method of the present invention comprises the steps:
One, intermediate product 4,6-dinitrobenzene-3-methoxyphenol, and its structural formula is as follows:
4,6-dinitrobenzene Meta Dichlorobenzene and methyl alcohol particularly in the presence of sodium hydroxide, add an amount of macromolecule diol catalyzer in the presence of caustic alkali, under the ideal reaction conditions, and preparation 4,6-dinitrobenzene-3-methoxyphenol.Suitable reaction temperature is between 50 ℃-100 ℃.Catalyzer is a macromolecule diol, and the operating weight ratio is 4, the 1-4% of 6-dinitrobenzene Meta Dichlorobenzene.The consumption of methyl alcohol, part by weight are 4, and the 1-5 of 6-dinitrobenzene Meta Dichlorobenzene doubly.
Two, 4, the 6-dinitroresorcinol, its structural formula is as follows:
4,6-dinitrobenzene-3-methoxyphenol under certain conditions, with effect of sulfuric acid, phenolic ether decomposes, obtain required 4, the 6-dinitroresorcinol.Sulfuric acid concentration is 50-90%, and temperature of reaction 100-160 ℃, suitable reaction temperature is 135 degree, reaction times 6-10 hour.
Embodiment 1:4, the preparation of 6-dinitrobenzene-3-methoxyphenol
In four-hole boiling flask, add 4 of 380 grams, 6-dinitrobenzene Meta Dichlorobenzene, the methyl alcohol of 1600 grams, 15 gram catalyzer, the aqueous sodium hydroxide solution of 2523 grams 10% stirs and heating in water bath is warming up to 70 ℃, keeps this temperature 18 hours, reaction finishes, be cooled to room temperature, filter, filtrate is with 30% hydrochloric acid acid out, PH=1 promptly ends, stir half an hour, filter, filter cake with the little water washing once, filter is done, drying gets 322 grams 4,6-dinitrobenzene-3-methoxyphenol, HPLC purity check 〉=96% is 90% of theoretical yield.
Embodiment 2:4, the preparation of 6-dinitroresorcinol
The sulfuric acid that adds 1000 grams 80% in four-hole boiling flask slowly adds 214 grams 4,6-dimethoxy Meta-dinitrobenzene, stirring is warming up to 130 degree, keeps this temperature 8 hours, and reaction finishes, be cooled to room temperature, be diluted in the frozen water of 2500 grams, throw out is separated out, stir half an hour, filter, filter cake with a little cold water washing once, filter is done, and drying gets 4,6-dinitroresorcinol 166 grams, HPLC purity check 〉=98% is 80% of theoretical yield.
Embodiment 3:4, the preparation of 6-dinitrobenzene Meta Dichlorobenzene
In flask, add 240 grams, 100% sulfuric acid for preparing in advance, slowly drip 66 gram nitrosonitric acids then, note heating, keep cooling, keep below 50 ℃, be warming up to 95 ℃ after dripping, drip 295 gram Meta Dichlorobenzenes, temperature dropwises at 95-100 ℃, continue insulation three hours, reaction finishes, and is cooled to 75 ℃, is diluted in the 4000 gram frozen water, temperature is no more than 40 ℃, stirred 15 minutes, and filtered, filter cake washes with water, dry, get raw product, use recrystallizing methanol, get 400 grams 4,6 dinitrobenzene Meta Dichlorobenzenes, HPLC purity check 〉=93%.
Claims (7)
1. one kind 4, the preparation method of 6-dinitroresorcinol comprises 4; 6-dinitrobenzene Meta Dichlorobenzene, macromolecule diol, primary aliphatic alcohols and caustic-alkali aqueous is characterized in that 4, and 6-dinitrobenzene Meta Dichlorobenzene is in the presence of the macromolecule diol catalyzer; with primary aliphatic alcohols; caustic-alkali aqueous solution under normal temperature or the hot conditions, carries out 4 of catalyst etherifying reaction generation; 6-dinitrobenzene-3-methoxyphenol and sulfuric acid react; the reaction of phenolic ether hydrolysis Tuo Bao Hu Hydroxyalkyl phenolic group, preparation 4,6-dinitroresorcinol.
2. as claimed in claim 1 a kind of 4, the preparation method of 6-dinitroresorcinol is characterized in that described catalyzer is the binary aliphatic alcohol of low carbon chain, and with the alkylating agent that alkali aqueous solution and alcohols mix, molecular weight is at 200-2000.
3. as claimed in claim 1 or 2 a kind of 4, the preparation method of 6-dinitroresorcinol is characterized in that described alkylating agent is methyl alcohol or ethanol.
4. as claimed in claim 1 a kind of 4, the preparation method of 6-dinitroresorcinol is characterized in that described alkali aqueous solution is an aqueous sodium hydroxide solution, and solubility is at 10-50%.
5. as claimed in claim 1 a kind of 4, the preparation method of 6-dinitroresorcinol, the temperature of reaction that it is characterized in that described etherification reaction are 60 ℃-95 ℃.
6. as claimed in claim 1 a kind of 4, the preparation method of 6-dinitroresorcinol is characterized in that described phenolic ether hydrolysis adopts 70-90% sulfuric acid to make hydrolytic reagent, is the reaction of Tuo Bao Hu Hydroxyalkyl phenolic group.
7. as claimed in claim 1 a kind of 4, the preparation method of 6-dinitroresorcinol is characterized in that described sulphuric acid hydrolysis reaction, and temperature is 120-145 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNA2008100367373A CN101265189A (en) | 2008-04-28 | 2008-04-28 | Process for preparing 4,6-dinitroresorcinol |
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| CNA2008100367373A CN101265189A (en) | 2008-04-28 | 2008-04-28 | Process for preparing 4,6-dinitroresorcinol |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106748796A (en) * | 2016-12-29 | 2017-05-31 | 南京理工大学 | The method for preparing the dinitro benzene of 1,5 difluoro 2,4 |
| CN109912422A (en) * | 2019-03-29 | 2019-06-21 | 山东润博生物科技有限公司 | A kind of preparation method of 4,6- dinitroresorcinol |
-
2008
- 2008-04-28 CN CNA2008100367373A patent/CN101265189A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106748796A (en) * | 2016-12-29 | 2017-05-31 | 南京理工大学 | The method for preparing the dinitro benzene of 1,5 difluoro 2,4 |
| CN106748796B (en) * | 2016-12-29 | 2019-04-16 | 南京理工大学 | The method for preparing the fluoro- 2,4- dinitrobenzene of 1,5- bis- |
| CN109912422A (en) * | 2019-03-29 | 2019-06-21 | 山东润博生物科技有限公司 | A kind of preparation method of 4,6- dinitroresorcinol |
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Open date: 20080917 |