CN103980133B - A kind of method preparing 2-methyl-4,6-diaminoresorcinol dihydrochloride - Google Patents
A kind of method preparing 2-methyl-4,6-diaminoresorcinol dihydrochloride Download PDFInfo
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Abstract
The invention discloses a kind of method preparing 2-methyl-4,6-diaminoresorcinol dihydrochloride compound, belong to organic chemical synthesis field. The method is with 2-methylresorcinol for raw material, through nitrated prepared 2-methyl-4,6-dinitroresorcinol, then using oxolane as solvent, zinc powder is as reducing agent, ferrous salt is as promoter, at a reflux temperature, by 2-methyl-4,6-dinitroresorcinol is reduced into 2-methyl-4,6-diamino resorcin, adds concentrated hydrochloric acid and obtains 2-methyl-4,6-diaminoresorcinol dihydrochloride. The method is avoided using severe toxicity methylchloroformate and explosive diazol, 2-methyl-4, the reduction of 6-dinitroresorcinol adopts metal (zinc) reducing process, compare with precious metal catalyst hydrogenation method, there is cost low, easily operate, and owing to the addition of ferrous salt promoter, shortening the response time of metallic reducing, it is easier to industrialized production, product yield reaches more than 65%.
Description
Technical field
The present invention relates to a kind of method preparing 2-methyl-4,6-diaminoresorcinol dihydrochloride, belong to organic chemical synthesis field.
Background technology
4,6-diamino resorcin dihydrochloride is the important monomer of synthesized high-performance polyphenylene benzodiazole (PBO) material, although the fiber obtained through fiber spinning from crystalline state has high intensity, high-modulus and the advantage such as high temperature resistant, but its compressive resistance is relatively low, limits its application. Polymer1997, the 38, the 621st page describes respectively with 2-methylterephthalic acid and 2,5-dimethyl terephthalic acid is as the monomer of polymerization, molecular backbone introduces pending methyl group crosslinking points, after high-temperature process, between strand, generates crosslinking chemical bond, improve the compressive resistance of pbo fiber. JP2005-332470, JP2005-332471, JP2006-219772, JP2006-219773, JP2006-219774 and JP2007-211362 describe with 2-alkyl-4,6-diamino resorcin dihydrochloride is as polymerization single polymerization monomer, crosslinking chemical bond is generated between strand after high-temperature process, pbo fiber compressive strength is the 200% of uncrosslinked pbo fiber, but it is silent on the synthetic method of 2-alkyl-4,6-diaminoresorcinol dihydrochloride.
The preparation method that USP5021580 describes 2-methyl-4,6-diaminoresorcinol dihydrochloride, is divided into 4 steps:
First step 2-methylresorcinol and methylchloroformate reaction, be changed into carbonic ester by phenolic hydroxyl group;Second step concentrated sulphuric acid and concentrated nitric acid nitration mixture carry out nitrated; 3rd step is in acid alcohol/aqueous solution, it is hydrolyzed, obtain 2-methyl-4,6-dinitroresorcinol, the 4th step palladium/carbon catalytic hydrogenation method is by 2-methyl-4, and 6-dinitroresorcinol is reduced into 2-methyl-4,6-diamino resorcin, and form 2-methyl-4,6-diaminoresorcinol dihydrochloride with hydrochloric acid, do not provide the yield of each step reaction. To use the methylchloroformate of severe toxicity in the present invention as stated above, and step is many, is unfavorable for industrialized production.
WO95/23130 describes 4 footwork synthesis 2-methyl-4,6-diamino resorcin dihydrochloride: first step aniline generates diazol, second step diazol and 2-methyl-4,6-dinitroresorcinol reacts generation 4,6-bis-(phenylazo)-2-resorcinol in the basic conditions, and the 3rd step passes through palladium/carbon catalytic hydrogenating reduction, generate 2-methyl-4,6-diamino resorcin, the 4th step and hydrochloric acid form 2-methyl-4,6-diaminoresorcinol dihydrochloride. To use explosive diazol in this invention, be unfavorable for industrialized production equally.
Summary of the invention
It is an object of the invention to provide a kind of new method preparing 2-methyl-4,6-diaminoresorcinol dihydrochloride compound, meet industrial production demand.
For realizing the object of the invention, the preparation method of 2-methyl of the present invention-4,6-diaminoresorcinol dihydrochloride compound comprises the steps:
1, with 2-methylresorcinol for raw material, add mass percent 65% concentrated nitric acid and dehydrated alcohol, be warming up to backflow, carry out nitration reaction, obtain 2-methyl-4,6-dinitroresorcinol;
2, using oxolane as solvent, zinc powder is as reducing agent, and ferrous salt is as promoter, at a reflux temperature, in 2-methyl-4 of step (1) gained, 6-dinitroresorcinol drips mass percent 35% concentrated hydrochloric acid and reacts, obtain 2-methyl-4,6-diaminoresorcinol; Add the concentrated hydrochloric acid dissolved with two hydrated stannous chlorides, form 2-methyl-4,6-diaminoresorcinol dihydrochloride, Precipitation.
2-methyl-4, the synthesis of 6-dinitroresorcinol can also adopt indirect digestion method: at 0 DEG C��60 DEG C temperature, first with mass percent 98% concentrated sulphuric acid, 2-methylresorcinol is carried out sulfonation, generate 2-methyl-4,6-disulfonic acid base resorcinol, then, at 10 DEG C��70 DEG C temperature, carry out nitrated with mass percent 65% concentrated nitric acid. The sulfonating reaction temperature of 2-methylresorcinol preferably 20 DEG C��40 DEG C, concentrated sulphuric acid consumption is 3 times to 10 times of 2-methylresorcinol quality, it is preferable that 5 times to 8 times. Nitration reaction temperature preferably 20 DEG C��40 DEG C, concentrated nitric acid and 2-methylresorcinol mol ratio are 4:1��8:1, it is preferable that 4:1��5:1.
During step (1) reaction, the mol ratio of 2-methylresorcinol and concentrated nitric acid is 1:4��1:10, it is preferable that 1:5��1:7.
Zinc powder and 2-methyl-4 during step (2) reaction, the mol ratio of 6-dinitroresorcinol is 6:1��20:1, it is preferable that 7:1��10:1. Described ferrous salt is ferrous chloride or ferrous sulfate, and consumption is 2-methyl-4, the 1%��10% of the amount of substance of 6-dinitroresorcinol, it is preferable that 2%��5%. Concentrated hydrochloric acid and 2-methyl-4,6-dinitroresorcinol mol ratio is 10:1��50:1, it is preferable that 20:1��30:1. First the present invention avoids and uses severe toxicity methylchloroformate and explosive diazol in USP5021580 and WO95/23130 document, secondly 2-methyl-4, the reduction of 6-dinitroresorcinol have employed metal (zinc) reducing process, compare with precious metal catalyst hydrogenation method, there is cost low, easily operate, and owing to the addition of ferrous salt promoter, shortening the response time of metallic reducing, it is easier to industrialized production, product yield reaches more than 65%.
Accompanying drawing explanation
Fig. 1 is 2-methyl-4, the FTIR spectrogram of 6-dinitroresorcinol.
Fig. 2 is 2-methyl-4, the 1HNMR spectrogram of 6-dinitroresorcinol.
Fig. 3 is 2-methyl-4, the DSC figure of 6-dinitroresorcinol.
Fig. 4 is the FTIR spectrogram of 2-methyl-4,6-diaminoresorcinol dihydrochloride.
Fig. 5 is the 1HNMR spectrogram of 2-methyl-4,6-diaminoresorcinol dihydrochloride.
Detailed description of the invention
Several embodiment preparation method to 2-methyl-4,6-diaminoresorcinol dihydrochloride is given below be described in further details.
Embodiment 1:2-methyl-4, the direct nitrification process synthesis of 6-dinitroresorcinol
In 250ml single port bottle, add 3.72g2-methylresorcinol (0.03mol), 50ml dehydrated alcohol and 12ml mass percent 65% concentrated nitric acid, it is warming up to back flow reaction 1 hour, after reaction terminates, decompression distills out about 50ml liquid, surplus solution system is down to room temperature, there is crystallization, it is filtrated to get brown-red solid, wash with cold water, it is dissolved in after drying in the sodium hydrate aqueous solution of 50ml1M, hydrochloric acid is dripped under stirring, acid system pH value is to 2��3, there is khaki Precipitation, filter, with cold water washing to neutral, obtain 2.91g khaki solid (yield 45.2%) after drying.
Embodiment 2:2-methyl-4, the indirect nitrification process synthesis of 6-dinitroresorcinol
In 250ml there-necked flask, add 3.72g2-methylresorcinol (0.03mol), under nitrogen protection, in ice-water bath, dropping 12ml mass percent 98% concentrated sulphuric acid, 25 DEG C of reaction 2h it are warming up to after dropwising, then in ice-water bath, drip 8ml mass percent 65% concentrated nitric acid, 30 DEG C of reaction 2h it are warming up to after dropwising, after reaction terminates, ice-water bath drips 30ml frozen water, system there is a large amount of reddish brown precipitation produce, filter, wash with cold water, it is dissolved in after drying in the sodium hydrate aqueous solution of 50ml1M, hydrochloric acid is dripped under stirring, acid system pH value is to 2��3, there is khaki Precipitation, filter, with cold water washing to neutral, obtain 3.42g khaki solid (yield 53.1%) after drying.
Embodiment 1 2-in-1 with example become 2-methyl-4,6-dinitroresorcinol detects through IR and 1HNMR, and for target product, it is as follows that IR and 1HNMR analyzes result:
IR(KBr, cm-1): 3441,3161,3092,2928,1638,1591,1566,1461,1440,1326,1303,1253,1223,1187,1099,947,812,755,685; 1HNMR(CDCl3,400MHz, �� (ppm)): 11.39 (s, 2H), 8.99 (s, 1H), 2.28 (s, 3H).
Embodiment 1 2-in-1 with example become 2-methyl-4,6-dinitroresorcinol through DSC test, its fusing point is 139.4 DEG C, 20 DEG C/min of heating rate.
The metal deoxidization synthesis of embodiment 3:2-methyl-4,6-diaminoresorcinol dihydrochloride
In 500ml single port bottle, add 3.30g2-methyl-4,6-dinitroresorcinol (0.015mol), 150ml oxolane (THF), 7.86g zinc powder and 0.05g ferrous chloride, it is warming up to backflow, the HCl solution of dropping 34ml, after dropwising, continue to be stirred at reflux reaction 1.5h, filtered while hot removes unreacted zinc powder, the lower dropping of stirring is dissolved with the mass percent 35% concentrated hydrochloric acid 50ml of 0.05g bis-hydrated stannous chloride, a large amount of white precipitate is had to generate, filter, and with absolute ethanol washing, vacuum drying obtains white solid 2.33g(yield 68.4%).
2-methyl-4,6-diaminoresorcinol the dihydrochloride of embodiment 3 synthesis detects through IR and 1HNMR, and for target product, it is as follows that IR and 1HNMR analyzes result:
IR(KBr, cm-1): 3374,3050,2925,2564,1623,1558,1527,1489,1331,1278,1180,1130,866; 1HNMR(DMSO-d6,400MHz, �� (ppm)): 9.84 (m, 8H), 7.34 (s, 1H), 2.16 (s, 3H).
2-methyl-4,6-diaminoresorcinol the dihydrochloride of embodiment 3 synthesis is tested through DSC, and its fusing point is 269.2 DEG C, is attended by decomposition, 20 DEG C/min of heating rate in melting process.
Claims (3)
- The preparation method of 1.2-methyl-4,6-diaminoresorcinol dihydrochloride compound, it is characterised in that comprise the steps:(1), with 2-methylresorcinol for raw material, add mass percent 65% concentrated nitric acid and dehydrated alcohol, be warming up to backflow, carry out nitration reaction, obtain 2-methyl-4,6-dinitroresorcinol; The mol ratio of 2-methylresorcinol and concentrated nitric acid is 1:4��1:10;(2), using oxolane as solvent, zinc powder is as reducing agent, ferrous salt is as promoter, at a reflux temperature, 2-methyl-4 in step (1) gained, 6-dinitroresorcinol drips mass percent 35% concentrated hydrochloric acid react, obtain 2-methyl-4,6-diaminoresorcinol; Add the concentrated hydrochloric acid dissolved with two hydrated stannous chlorides, form 2-methyl-4,6-diaminoresorcinol dihydrochloride, Precipitation; Zinc powder and 2-methyl-4, the mol ratio of 6-dinitroresorcinol is 6:1��20:1; Described ferrous salt is ferrous chloride or ferrous sulfate, and consumption is 2-methyl-4, the 1%��10% of the amount of substance of 6-dinitroresorcinol; Described concentrated hydrochloric acid and 2-methyl-4,6-dinitroresorcinol mol ratio is 10:1��50:1.
- 2. 2-methyl-4 as claimed in claim 1, the preparation method of 6-diamino resorcin dihydrochloride compound, it is characterized in that, 2-methyl-4, the synthesis of 6-dinitroresorcinol adopts indirect nitrification process: at 0 DEG C��60 DEG C temperature, first with mass percent 98% concentrated sulphuric acid, 2-methylresorcinol is carried out sulfonation, generate 2-methyl-4,6-disulfonic acid base resorcinol, then at 10 DEG C��70 DEG C temperature, carries out nitrated with mass percent 65% concentrated nitric acid.
- 3. 2-methyl-4 as claimed in claim 2, the preparation method of 6-diamino resorcin dihydrochloride compound, it is characterized in that, the sulfonating reaction temperature of 2-methylresorcinol selects 20 DEG C��40 DEG C, and concentrated sulphuric acid consumption is 3 times to 10 times of 2-methylresorcinol quality; Nitration reaction temperature selects 20 DEG C��40 DEG C, and concentrated nitric acid and 2-methylresorcinol mol ratio are 4:1��8:1.
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| CN104262171B (en) * | 2014-09-24 | 2016-08-24 | 哈尔滨工业大学 | A kind of preparation method of 1,4,5,8-tetramino naphthalene stannic chloride hydrochlorate |
| CN106554287A (en) * | 2015-09-29 | 2017-04-05 | 中国石油化工集团公司 | A kind of method that stannous chloride is quantitatively adding in 4,6- diaminourea hydrochlorides |
| CN105504270B (en) * | 2016-01-14 | 2018-06-08 | 郑州大学 | The preparation method of crosslinked polyphenylene Benzo-dioxazole film |
| CN114315526A (en) * | 2020-09-27 | 2022-04-12 | 中石化南京化工研究院有限公司 | Preparation method of resorcinol |
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| US5021580A (en) * | 1989-10-23 | 1991-06-04 | The Dow Chemical Company | Polybenzoxazoles having pendant methyl groups |
| WO1995023130A1 (en) * | 1994-02-24 | 1995-08-31 | The Dow Chemical Company | Preparation of 4,6-diaminoresorcinol through a bisazoarylresorcinol intermediate |
| CN101250118A (en) * | 2008-03-28 | 2008-08-27 | 河北建新化工股份有限公司 | Method for preparing 4,6-diaminoresorcinol hydrochloride |
| CN103204805A (en) * | 2012-12-21 | 2013-07-17 | 浙江工业大学 | Key intermediates of AB-type PBZ monomer, and preparation method thereof |
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Patent Citations (4)
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| US5021580A (en) * | 1989-10-23 | 1991-06-04 | The Dow Chemical Company | Polybenzoxazoles having pendant methyl groups |
| WO1995023130A1 (en) * | 1994-02-24 | 1995-08-31 | The Dow Chemical Company | Preparation of 4,6-diaminoresorcinol through a bisazoarylresorcinol intermediate |
| CN101250118A (en) * | 2008-03-28 | 2008-08-27 | 河北建新化工股份有限公司 | Method for preparing 4,6-diaminoresorcinol hydrochloride |
| CN103204805A (en) * | 2012-12-21 | 2013-07-17 | 浙江工业大学 | Key intermediates of AB-type PBZ monomer, and preparation method thereof |
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