CN103204805A - Key intermediates of AB-type PBZ monomer, and preparation method thereof - Google Patents
Key intermediates of AB-type PBZ monomer, and preparation method thereof Download PDFInfo
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Abstract
The invention discloses key intermediates of an AB-type PBZ monomer, and a preparation method thereof. The key intermediates of the AB-type PBZ monomer are a compound (I) and a compound (IV), wherein in the formula (I) or (IV), Y is N, Z is NH, R is H; or Y is CH, Z is NH, R is OH; or Y is C-CH3, Z is O, R is H. The compound (IV) can be prepared from the compound (I) and used as a skeleton compound for preparing the AB-type PBZ monomer as shown in a formula (VIII); and the AB-type PBZ monomer can be prepared into PBZ fiber through homopolycondensation, thereby preventing problems of difficultly controlled equivalent proportion, complex polymerization technology, relatively long polymerization time and acidic gas generated in preparation of the PBZ through mixed polycondensation.
Description
(1) technical field
The intermediate that the application relates to the new monomer of AB type PBZ with and preparation method thereof.
(2) background technology
High-performance fiber (High Performance Fibers) is since the research and development sixties in 20th century and popularization, and its appearance makes traditional textile industry produce dramatic change.High-performance fiber has characteristics such as high strength, high-modulus, high temperature resistant, corrosion-resistant and radiation hardness, mainly develop based on the demand of Aeronautics and Astronautics and ocean and aspects such as war, field and safety, now be widely used in aspects such as new high-tech industry, aerospace and military affairs, it mainly comprises PPTA, PBI, PBO, M5(PIPD) etc. fiber.
Polybenzimidazole (PBI) is the linear polymer that has the imidazolyl heterocycle structure on a kind of main chain, there is fragrant heterocycle structure on its molecular structure, so PBI has characteristics such as mechanical property excellence, resistance to chemical attack, high temperature resistant, non-flame properties, it is having important use aspect high-performance fiber, high temperature resistant filtration fabrics, ion exchange resin material and the chemical resistant material.
PBI mainly contains four classes, and its molecular structure of chemistry is as follows.
The primary structure of PBI and kind
People such as Herward Vogel utilized melt phase polycondensation with 3 in 1996,3', 4,4'-tetramino biphenyl and diphenylisophthalate, 1, compounds such as 2,4,5-tetramino benzene and diphenylisophthalate at high temperature carry out polycondensation, generated a series of fragrant polybenzimidazole resins, reaction formula is as follows:
Synthesizing of aromatic series polybenzimidazole
But the very big and intermolecular strong hydrogen bond action of molecule chain rigidity causes their solvability very poor in the PBI structure of fragrant, composite adhered poor performance, and be difficult to process spinning, limited its range of application greatly.
Pbo fiber---polyparaphenylene Ben Bing Er oxazole (poly(p-phenylene-2 is one of the most representative polymkeric substance in the polybenzoxazole fibrid 6-benzobisoxazole), with its outstanding physicochemical property by various countries researchist extensive concern.Pbo fiber intensity reaches 5.8GPa, modulus 180GPa, limiting oxygen index(LOI) (LOI) is 68, and heat resisting temperature reaches 600 ℃, and maximum operation (service) temperature and decomposition temperature are respectively 350 ℃ and 650 ℃, and in combustion processes, heat release rate is low, and it is considerably less to produce toxic gases such as carbon monoxide and prussic acid, and these characteristics are superior to present organic and inorganic fibre far away, its molecular structure have cis and trans two kinds as follows, research based on cis at present.
The structural formula of PBO
Pbo fiber is by AA type monomer 4, and 6-diamino resorcin hydrochlorate (DAR2HCl) and BB type monomers terephthalic acid (TPA) are containing P
2O
5The PPA solvent in mix polycondensation and make (formula as follows) behind the PBO liquid crystal solution, obtain AS type spun by dry-jet wet-spinning again, make finally by the technology of high-temperature heat treatment more than 600 ℃.
Synthetic all employing of above-mentioned several high-performance fibers mixed polycondensating process, and there are many deficiencies in this technology, emits, needs two kinds of monomers of control etc. when more high excessively than reaction, polymerization temperature if any sour gas.Adopt the technology of preparing of the equal polycondensation of AB type monomer to address the above problem.This project team makes the new monomer of AB type that can be used for preparing PBO: 4-(5-Amide-6-hydroxy-2--benzoxazolyls) phenylformic acid (ABA) through the years of researches exploitation, and reaction scheme is as follows:
With reference to the preparation technology of ABA, the present invention proposes key intermediate and the preparation thereof of the new monomer of AB type PBZ, and this key intermediate of successful Application prepares the framework compound of the new monomer of AB type PBZ.
(3) summary of the invention
First purpose of the present invention provides a kind of new compound (I), and it can be used for preparing AB type PBZ(PBZ and represents PBO, PBI etc.) monomer.
Second purpose of the present invention provides the preparation method of compound (I).
The 3rd purpose of the present invention provides compound (I) as the application of the key intermediate of the new monomer of AB type PBZ, thereby provides a kind of by its compound that makes (IV), and it is the framework compound of preparation AB type PBZ monomer.
The 4th purpose of the present invention provides the preparation method of compound (IV).
Below technical scheme of the present invention is done and specified.
The invention provides a kind of compound, its structure is suc as formula shown in (I):
In the formula (I), Y is N or CH, and Z is NH; Perhaps Y is C-CH
3, Z is O.
The invention provides the preparation method of described compound (I), it can prepare by the following method:
In formula (I), Y is CH, and when Z was NH, the preparation method of described compound (I) comprised the steps:
Compound shown in the formula (II) (Y is CH in the formula (II), and Z is NH), water are joined in the reaction vessel, be heated to backflow, begin to drip sodium polysulfide solution, described sodium polysulfide solution is by Na
2S9H
2O, S and H
2O obtains according to mass ratio 1:0.2 ~ 0.5:2.5 ~ 4 preparations, and the add-on of described sodium polysulfide solution satisfies the Na that wherein contains
2S9H
2The mol ratio of O and compound (II) is 1.05 ~ 1.3:1, and 0.5 ~ 1.5h dropwises, back flow reaction 1.5 ~ 3h again, filtered while hot, after the cooling of gained filtrate more after filtration, dry compound (I);
In formula (I), Y is C-CH
3, when Z was O, the preparation method of described compound (I) comprised the steps:
(1) add 90 ~ 98% the vitriol oil in reaction vessel, be cooled to below 10 ℃, (Y is C-CH in the formula (III) to add compound (III) again
3, Z is O), treat that compound (III) is all after the dissolving, slowly the vitriol oil of dropping 98% and the mixed solution of 65% nitric acid react 20 ~ 60min down at 8 ~ 35 ℃ then, and reaction is slowly poured into solution in the frozen water after finishing, suction filtration, (Y is C-CH in the formula (II) to get compound (II) after the filter cake oven dry
3, Z is O);
(2) in reaction vessel, add the methyl alcohol of compound (II), volume fraction 80 ~ 95% or the Pd/C of aqueous ethanolic solution and charge capacity 8 ~ 10wt.%, solution is heated to backflow, the dropping massfraction is hydrazine hydrate-ethanolic soln of 10 ~ 20%, dropwise in the 1h, dropwise the back at 68 ~ 78 ℃ of reaction 2 ~ 5h, stop heating, cool the temperature to 45 ~ 55 ℃ and suction filtration, stir the also slow dripping hydrochloric acid of filtrate and separate out unreacted compound (II) completely, filter again, distillation filtrate, residual solution gets compound (I) with salt acid treating, activated carbon decolorizing again.
As preferably, in the described step (1), compound (III) and HNO
3Mol ratio be 1:2.1 ~ 2.3; Compound (II) is 1:2.2 ~ 2.83 with the mol ratio of hydrazine hydrate in the described step (2), and compound (II) is 1:0.083 ~ 0.25 with the mass ratio of Pd/C.
Y is N in formula (I), and when Z was NH, the preparation method of described compound (I) comprised the steps:
In reaction vessel, add compound (II) (Y is N in the formula (II), and Z is NH) and water, be heated to backflow, begin to drip sodium polysulfide solution after adding hydrazine hydrate, dropwise in 15 ~ 50min, 1.5 ~ 3h is reacted in the back under reflux temperature, filtered while hot, filtration cakes torrefaction get compound (I); Described compound (II) is 1:0.67 ~ 2 with the molar ratio of hydrazine hydrate, and described sodium polysulfide solution is by Na
2S9H
2O, S, water are formulated according to mass ratio 1:0.25 ~ 0.5:3.5 ~ 6, and the add-on of described sodium polysulfide solution satisfies the Na that wherein contains
2S9H
2The mass ratio of O and compound (II) is 1.1 ~ 1.5:1.
Compound of the present invention (I) can be used for preparing compound (IV), thus the new monomer of preparation AB type PBZ.
The invention provides a kind of compound, its structure is shown in formula IV:
In the formula IV, Y is N, and Z is NH, and R is H; Or Y is CH, and Z is NH, and R is OH; Or Y is C-CH
3, Z is O, R is H.
The present invention also provides the preparation method of compound (IV):
Y is CH in formula (IV), and Z is NH, and when R was OH, the preparation method of described compound (IV) comprised the steps:
(a) compound shown in the formula (II) (Y is CH in the formula (II), and Z is NH), water are joined in the reaction vessel, be heated to backflow, beginning to drip the described sodium polysulfide solution of sodium polysulfide solution is by Na
2S9H
2O, S and H
2O obtains according to mass ratio 1:0.2 ~ 0.5:2.5 ~ 4 preparations, and the add-on of described sodium polysulfide solution satisfies the Na that wherein contains
2S9H
2The mol ratio of O and compound (II) is 1.05 ~ 1.3:1, and 0.5 ~ 1.5h dropwises, back flow reaction 1.5 ~ 3h again, filtered while hot, after the cooling of gained filtrate more after filtration, dry compound (I) (Y is CH in the formula (I), and Z is NH);
(b) compound shown in the adding formula (V) (R is OH in the formula V) and quality are the sulfur oxychloride of 30 ~ 40 times of compound (V) quality in reaction vessel, heated and stirred back flow reaction 2 ~ 4h steams unreacted sulfur oxychloride and gets the compound shown in the formula VI (R is OH in the formula (VI));
(c) add the compound shown in diethylene glycol dimethyl ether and the formula (I) in reaction vessel, drip the diethylene glycol dimethyl ether solution of compound (VI) under the condition of ice bath, 30 ~ 60min dropwises, and dropwises the back and feeds N
2And heating, at 110 ~ 130 ℃ of reaction 2 ~ 5h, add polyphosphoric acid (PPA) again and continue reaction 3 ~ 6h, filtered while hot, filtrate cooling back is with refiltering after ammoniacal liquor, the hot wash, and drying gets compound (IV); Described compound (VI) is 1.05 ~ 1.35:1 with the mol ratio of compound (I), and the mass ratio of PPA and compound (I) is 3 ~ 6:1;
Y is C-CH in formula (IV)
3, Z is O, when R was H, the preparation method of described compound (IV) comprised the steps:
(A) add 90 ~ 98% the vitriol oil in reaction vessel, be cooled to below 10 ℃, (Y is C-CH in the formula (III) to add formula III again
3Z is O) shown in compound, after treating that compound (III) all dissolves, the vitriol oil of slow dropping 98% and the mixed solution of 65% nitric acid, react 20 ~ 60min down at 8 ~ 35 ℃ then, reaction is slowly poured solution in the frozen water after finishing, suction filtration, and (formula (II) Y is C-CH to get compound (II) after the filter cake oven dry
3, Z is O);
(B) in reaction vessel, add compound (II), the Pd/C of the methyl alcohol of volume fraction 80 ~ 95% or aqueous ethanolic solution and charge capacity 8 ~ 10%, solution is heated to backflow, the dropping massfraction is hydrazine hydrate-ethanolic soln of 10 ~ 20%, dropwise in the 1h, dropwise the back at 68 ~ 78 ℃ of reaction 2 ~ 5h, stop heating, cool the temperature to 45 ~ 55 ℃ and suction filtration, stir the also slow dripping hydrochloric acid of filtrate and separate out unreacted compound (II) completely, filter again, distillation filtrate, residual solution is used the salt acid treating again, activated carbon decolorizing gets compound (I), and (Y is C-CH in the formula (I)
3, Z is O);
(C) compound shown in the adding formula (V) (R is H in the formula V) and quality are the sulfur oxychloride of 23 ~ 40 times of compound (V) quality in reaction vessel, heated and stirred back flow reaction 1 ~ 2.5h steams unreacted sulfur oxychloride and gets compound shown in the formula VI (R is H in the formula (VI));
(D) in reaction vessel, add compound (I), heat temperature raising to 70 ~ 85 ℃, drip massfraction then and be the 4-methyl-2 pentanone solution of 4 ~ 8% compound (VI), 3 ~ 30min dropwises back back flow reaction 2 ~ 4h, obtain yellow solid after the cooling, separation and purification gets formula (VII), and (Y is C-CH in the formula (VII)
3, Z is O) shown in compound;
(E) in reaction vessel, add the diethylene glycol dimethyl ether that compound (VII) and quality are 14 ~ 17 times of compound (VII) quality, be heated to 150 ~ 161 ℃, adding quality again is the polyphosphoric acid (PPA) of 4 ~ 6 times of compound (VII) quality, be warming up to back flow reaction 2.5 ~ 3h, being cooled to room temperature pours in the frozen water again, suction filtration gets the compound shown in the formula (IV) behind the filter cake washing and drying; As preferably, in the described step (A), compound (III) and HNO
3Mol ratio be 1:2.1 ~ 2.3; Compound (II) is 1:2.2 ~ 2.83 with the mol ratio of hydrazine hydrate in the described step (B), and compound (II) is 1:0.083 ~ 0.25 with the mass ratio of Pd/C.
Y is N in formula (IV), and Z is NH, and when R was H, the preparation method of described compound (IV) comprised the steps:
(i) (Y is N in the formula (II) to add compound (II) in reaction vessel, Z is NH) and water, be heated to backflow, begin to drip sodium polysulfide solution after adding hydrazine hydrate, dropwise in 15 ~ 50min, 1.5 ~ 3h is reacted, filtered while hot in the back under reflux temperature, filtration cakes torrefaction gets compound (I) (Y is N in the formula (I), and Z is NH); Described compound (II) is 1:0.67 ~ 2 with the molar ratio of hydrazine hydrate, and described sodium polysulfide solution is by Na
2S9H2O, S, water are formulated according to mass ratio 1:0.25 ~ 0.5:3.5 ~ 6, and the add-on of described sodium polysulfide solution satisfies the Na that wherein contains
2S9H
2The mass ratio of O and compound (II) is 1.1 ~ 1.5:1;
(ii) in reaction vessel, add the compound shown in diethylene glycol dimethyl ether and the formula (V) (R is H in the formula V), heating makes compound (V) dissolving, when waiting to be warming up to 55 ~ 65 ℃, dripping thionyl chloride, dropwise afterreaction 0.5 ~ 1 h in 5 ~ 20 min, take out sour gas in the dereaction container with vacuum pump, add compound (I) again, be heated to 140 ~ 150 ℃ and react 0.5 ~ 1.5h, add polyphosphoric acid (PPA) again, be warming up to 160 ~ 170 ℃, reaction 2 ~ 4h, stopped reaction, be cooled to room temperature and filter, a layer oily liquid thing taken off in the filtrate layering, add methyl alcohol, be heated with stirring to backflow, in the time of 35 ~ 45 ℃, filter, obtain filtrate behind the filtration cakes torrefaction, adding water has yellow solid to separate out, and filtration drying obtains compound (IV).
Compound of the present invention (IV) can obtain the new monomer of AB type PBZ shown in the formula (VIII) through nitroreduction and hydrolysis of ester group, and the new monomer of this AB type PBZ can obtain high-performance fiber through equal polycondensation, for example PBO, PBI etc.,
Particularly, in the gained compound (IV), Y is CH, Z is NH, and R is OH, and namely its structure is suc as formula shown in (IV-1) time, can be used as the framework compound of the monomer of AB type PBI, can make the AB type PBI monomer shown in the formula (VIII-1) by hydrolysis, reducing process, and directly make the PBI of hydroxyl modification by equal polycondensation
In the compound (IV), when Y is N, Z is NH, R is H, be its structure suc as formula shown in (IV-2) time, can make the AB type PBI monomer shown in the formula (VIII-2) by hydrolysis, reducing process as the framework compound of the monomer of AB type PBI, and directly make a kind of new high-performance fiber PBI by equal polycondensation
In the compound (IV), when Y is C-CH
3, Z is O, R is H, be its structure suc as formula shown in (IV-3) time, can make the AB type PBO monomer shown in the formula (VIII-3) by hydrolysis, reducing process as the framework compound of the monomer of AB type PBO, and the direct PBO that makes the methyl modification by equal polycondensation
Compared with prior art, beneficial effect of the present invention is:
1. the compound (I) and the compound (IV) that synthesize of the present invention, can be used as intermediate for the preparation of the new monomer of AB type PBZ, and directly prepare PBZ by the equal polycondensation of the new monomer of AB type, the grade of having avoided mixed polycondensation to prepare existing among the PBZ is when controlling than difficulty, the polymerization technique complexity, polymerization time is longer, and problems such as sour gas generation are arranged.
2. compound (IV-1) makes the PBI of hydroxyl modification as framework compound via AB type PBI monomer (VIII-1), by the introducing of oh group, improves compressive property and the compoiste adhering performance of PBI.The new PB I fiber that compound (IV-2) makes via AB type PBZ monomer (VIII-2) as framework compound, two Sauerstoffatoms comparing with pbo fiber in the oxazole ring are replaced by two-NH group, contain pyridine ring simultaneously, these groups are easily at the strong hydrogen bond of intermolecular formation, thereby constitute the stronger two-way hydrogen bond network structure of reactive force, finally strengthen the performance of polymer fiber, can be used as a kind of new high-performance fiber developing direction.Compound (IV-3) makes the PBO of methyl modification as framework compound via AB type PBO monomer (VIII-3), has introduced methyl group in molecular chain, by removing H
2Form covalent linkage between molecular chain, thereby improve the anti-compression properties of pbo fiber.
3. the preparation method of compound of the present invention (I), selected reductive agent has higher selectivity, can selectivity must reduce a nitro.
(4) description of drawings
Fig. 1 is the infrared spectrum of 1,2,4-triamino-5-oil of mirbane (TANB).
Fig. 2 is the infrared spectrum of 2-methyl-4,6 dinitroresorcinol (2-MDNR).
Fig. 3 is the infrared spectrum of 2-methyl-4-amino-6-nitro-resorcinol hydrochloride (2-MANRHCl).
Fig. 4 is the nuclear-magnetism of 2,3,6-triamino-5-nitropyridine (TANP)
13The C-NMR spectrogram.
Fig. 5 is the infrared spectrum of 5-nitro-6-hydroxyl 7-methyl-2-(to the methoxycarbonyl phenyl) benzoxazole (7-MMNB).
Fig. 6 is the mass spectrogram of 4-(5-amino-6-nitro-4-N-pyridine-imidazole)-methyl benzoate (H-HE).
(5) embodiment
With specific embodiment technical scheme of the present invention is described further below, but protection scope of the present invention is not limited thereto:
Embodiment 11, the preparation of 2,4-triamino-5-oil of mirbane (TANB)
Get 9.00 g 1,3-diamino-4,6-dinitrobenzene (DADNB) (0.0454 mol) adds 60 g water in reaction vessel, be heated to backflow, and solid is not molten entirely, begins to drip sodium polysulfide solution (the 12.0 g Na that configured
2S9H
2O+3.0 g S+40 mL H
2O), dropwise in 45 min, back flow reaction 2.0 h, filtered while hot, filter cake 250mL hot wash treats that the filtrate cooling has red tabular crystal to separate out, filtration drying gets product TANB 2.85 g, purity 99.23%, yield 37.32%.Filter cake (DADNB) drying gets 4.50 g, purity 98.74%.The infrared spectrum of TANB is seen Fig. 1.
The preparation of comparative example 1 ~ 2 TANB
Adopt embodiment 1 identical operations and feed ratio to prepare TANB, different is to select for use different reductive agents to replace sodium polysulphide to experimentize, and the results are shown in Table 1:
Table 1:
| Comparative example | Reductive agent | Purity/% | Yield/% |
| 1 | Iron powder | 5.08 | 91.5 |
| 2 | Vat powder | 26.78 | 80.2 |
(1) vitriol oil of adding 20 mL 98% in reaction vessel is cooled to below 10 ℃; Add 1.0 g (0.081mol) 2-methylresorcinols (2-MR), until whole dissolvings, solution colour is light yellow transparent liquid; Slowly drip the vitriol oil of 2.5 mL 98% and the mixed solution of 1.28 mL, 65% nitric acid, the control temperature is at 6-8 ℃, and solution colour gradually becomes dark brown; After dropwising, react 30 min down at 6-8 ℃; Reaction is slowly poured solution in the 200 mL frozen water after finishing, and has a large amount of solids to separate out; Solution is carried out suction filtration, debris distilled water flushing 1 time; Filtration cakes torrefaction is obtained grey coffee-like powder 2-methyl-4,6 dinitroresorcinol (2-MDNR) 1.6 g, and purity is 98.99%, and yield is 92.08%.The 2-MDNR infrared spectrum is seen Fig. 2.
(2) in reaction vessel, add 3.0g (0.014mol) 2-MDNR, 30 mL, 95% ethanol, 0.48 g 10%Pd/C is heated to backflow with solution, drip the mixed solution of 1.98 g (0.0396mol) hydrazine hydrate and 15 mL, 95% ethanol, the control dropping time is in 1 h; Dropwise afterreaction 2 h, stop heating, cool the temperature to 50 ℃, suction filtration, get burgundy filtrate, HCl refrigeration 30min with filtrate and 3mL36.5%, dripping hydrochloric acid slowly in whipping process has the intact 2-MDNR of unreacted and separates out in the solution, filtrate is carried out underpressure distillation earlier, steam to surplus 5 mL filtrates, make with extra care with dilute hydrochloric acid, activated carbon decolorizing, filtrate being spin-dried for obtains blush product 2-methyl-4-amino-6 nitro-resorcinol hydrochloride (2-MANRHCl) 1.15 g, purity is 98.91%, and yield is 34.93%.The infrared spectrum of 2-MANRHCl is seen Fig. 3.
The preparation of embodiment 3 ~ 8 2-MDNR
Adopting and embodiment 2(1) identical operations prepares 2-MDNR, gets different parameters by parameter area of the present invention and experimentizes, and the results are shown in Table 2:
Table 2:
| Embodiment | n(2-MR):n(HNO 3) | Solvent | Temperature/℃ | Purity/% | Yield/% |
| 3 | 1:2.1 | 98%H 2SO 4 | 8 | 94.17 | 87.60 |
| 4 | 1:2.3 | 98%H 2SO 4 | 8 | 98.99 | 92.08 |
| 5 | 1:2.3 | 90%H 2SO 4 | 8 | 76.54 | 71.20 |
| 6 | 1:2.3 | 98%H 2SO 4 | 15 | 86.33 | 75.29 |
| 7 | 1:2.3 | 98%H 2SO 4 | 25 | 88.03 | 76.95 |
| 8 | 1:2.3 | 98%H 2SO 4 | 35 | 95.23 | 71.81 |
| Comparative example 3 | 1:2.6 | 98%H 2SO 4 | 8 | 64.70 | 41.38 |
| Comparative example 4 | 1:3.0 | 98%H 2SO 4 | 8 | 44.19 | 25.69 |
| Comparative example 5 | 1:2.3 | 85%H 2SO 4 | 8 | 64.03 | 52.12 |
| Comparative example 6 | 1:2.3 | 80%H 2SO 4 | 8 | 54.72 | 47.72 |
The preparation of embodiment 9 ~ 13 2-MANRHCl
Adopting and embodiment 2(2) identical operations prepares 2-MANRHCl, gets different parameters by parameter area of the present invention and experimentizes, and the results are shown in Table 4:
Table 4:
The preparation of comparative example 7 ~ 14 2-MANRHCl
Adopting and embodiment 2(2) identical operations prepares 2-MANRHCl, gets different parameters by parameter area of the present invention and experimentizes, and the results are shown in Table 5:
Table 5:
Embodiment 14 2, the preparation of 3,6-triamino-5-nitropyridine (TANP)
In reaction vessel, add 3g (0.015mol) 2,6-amino-3,5-di nitryl pyridine (DADNP) and 20ml water heated and stirred, solid is not molten entirely, the turbid liquid of yellowly, to refluxing, add 0.5g(0.01mol) begin to drip the sodium polysulfide solution for preparing in advance behind the hydrazine hydrate (by 4.0g Na
2The orange clear solution that S9H2O, 1.1g S, 15ml water heating for dissolving obtain), dropwises in the 30min, then reaction 2.0 h under reflux temperature, filtered while hot obtains red filter cake, with hot wash repeatedly, drying obtains filter cake TANP 1.50g, purity 99.2%, yield 58.4%.The nuclear-magnetism of TANP
13The C-NMR spectrogram is seen Fig. 4.
The preparation of embodiment 15 ~ 18 TANP
Adopt with embodiment 14 identical operations to prepare TANP, get different parameters by parameter area of the present invention and experimentize, the results are shown in Table 6:
Table 6:
| Embodiment | N (hydrazine hydrate): n (DADNP) | Reaction times/h | Purity/% | Yield/% |
| 15 | 1.33:1 | 2 | 99.1 | 55.7 |
| 16 | 2:1 | 2 | 98.1 | 53.1 |
| 17 | 0.67:1 | 1.5 | 96.8 | 53.0 |
| 18 | 0.67:1 | 3 | 97.4 | 60.0 |
| Comparative example 15 | 0 | 2 | 59.2 | 54.0 |
| Comparative example 16 | 0.33:1 | 2 | 65.1 | 60.8 |
| Comparative example 17 | 0.67:1 | 1 | 49.0 | 39.2 |
The preparation of embodiment 19 4-(5-amino-6-nitrobenzimidazole base)-2 hydroxybenzoic acid methyl esters (MANIHB)
In reaction vessel, add 1.30 g(0.0067mol) 2-hydroxyl terephthalic acid monomethyl ester (2-MHT), add 30 mL sulfur oxychloride heated and stirred again, after waiting to clarify, after reacting about 3.0 h again, steam unreacted sulfur oxychloride, leave standstill cool off product 3-hydroxyl-4-methoxycarbonyl Benzoyl chloride (3,4-HMBC).Measure 15 mL diethylene glycol dimethyl ethers and pour flask low-grade fever dissolving 3 into, 4-HMBC, the constant voltage drop-burette of pouring into to be cooled, in bottle, add 1.00 g TANB and 30mL diethylene glycol dimethyl ether, adopt the ice bath titration that 3,4-HMBC is added four-hole boiling flask, drip 45 min, remove ice bath after dripping off and slowly rise to stirring at room for a moment, more logical N
2Heating, temperature of reaction is controlled at 110 ~ 130 ℃ of about 3.5 h, and add 5.0 g 80%PPA and continued again to react 4 hours, filtered while hot, filtrate ammonia water by cooling, hot wash refilter drying and get product MANIHB 1.20 g, yield 61.47%.
The preparation of embodiment 20 5-nitro-6-hydroxyl 7-methyl-2-(to the methoxycarbonyl phenyl) benzoxazole (7-MMNB)
(1) in reaction vessel, adds 0.94 g (0.005mol) terephthalic acid monomethyl ester (MTA), 15 mL sulfur oxychlorides, heated and stirred is to refluxing, be yellow turbid solution, produce with a large amount of hydrogen chloride gas, stirring becomes settled solution until suspension, sulfur oxychloride is removed in distillation, obtains the beige solid after the cooling, add 5 mL 4-methyl-2 pentanones (MIBK) dissolvings after, pour in the constant pressure funnel, add 2-MANRHCl 1.05g(4.76 mmol in the reaction flask), heat temperature raising to 80 ℃ drips acyl chlorides 30 min, be warming up to 115 ℃ after dripping off, behind isothermal reaction 3 h, be pale brown look turbid solution, cooling obtains yellow solid, suction filtration, filtrate is carried out vacuum rotary steam, obtains yellow solid, twice yellow solid washing 3 times, refining with DMF again, refrigeration filter yellow solid 0.5 g, purity 93.29%, yield is 28.32%.
(2) in reaction vessel, add 0.2 g and go on foot product, add 3 mL diethylene glycol dimethyl ether solvents, the oil bath heating, magnetic agitation is warming up to 150 ℃, adds 1 g PPA, finishes to be warming up to back flow reaction 3 h, solution is brown, is cooled to room temperature then, and reaction solution is poured in the frozen water, there is pale brown look solid to separate out, suction filtration, filter cake water are given a baby a bath on the third day after its birth inferior, dry product 7-MMNB 0.18 g that gets, purity is 94.94%, and yield is 96.63%.The infrared spectrum of 7-MMNB is seen Fig. 5.
The preparation of embodiment 21 4-(5-amino-6-nitro-4-N-pyridine-imidazole)-methyl benzoate (H-HE)
In reaction vessel, drop into the 26.5g diethylene glycol dimethyl ether, 2g(0.011mol) terephthalic acid monomethyl ester (MTA), 2 DMF, heated and stirred makes its dissolving, when waiting to be warming up to 60 ℃, drips 1.85gSOCl
2(dripping off in 5min), reaction 0.5h produces SO
2With HCl gas, take out the sour gas that produces in the four-hole boiling flask with vacuum pump, add 2.3g(0.014mol) 2,3,6-triamino-5-nitropyridine (TANP) heats up, the control temperature is at 140 ~ 150 ℃, and the reaction solution color raises with temperature and deepens, and is deepened brown by yellow.Reaction adds 6.31g polyphosphoric acid (PPA) behind the 1h, stirs to make it continue reaction, is black on the four-hole boiling flask wall, is warming up to 160 ℃, and back flow reaction stops to heat after react about 3h, and it is slowly lowered the temperature.Cooled and filtered, the filtrate layering, separatory takes off a layer oily liquid thing, add 50mL methyl alcohol, stirring heating refluxes, and filters in the time of 40 ℃, obtains filtrate behind the filtration cakes torrefaction and adds water, have yellow solid to separate out, filtration drying obtains yellow solid H-HE 0.79g, HPLC purity 80.06%, yield 11.5%.The mass spectrogram of H-HE is seen Fig. 6.
Claims (10)
1. compound, its structure is suc as formula shown in (I):
In the formula (I), Y is N or CH, and Z is NH; Perhaps Y is C-CH
3, Z is O.
2. the preparation method of a compound as claimed in claim 1 is characterized in that: when Y is CH, when Z was NH, described preparation method comprised the steps:
Compound, water shown in the formula (II) are joined in the reaction vessel, be heated to backflow, beginning to drip the described sodium polysulfide solution of sodium polysulfide solution is by Na
2S9H
2O, S and H
2O obtains according to mass ratio 1:0.2 ~ 0.5:2.5 ~ 4 preparations, and the add-on of described sodium polysulfide solution satisfies the Na that wherein contains
2S9H
2The mol ratio of O and compound (II) is 1.05 ~ 1.3:1, and 0.5 ~ 1.5h dropwises, back flow reaction 1.5 ~ 3h again, filtered while hot, after the cooling of gained filtrate more after filtration, dry compound (I);
In formula (I) or the formula (II), Y is CH, and Z is NH.
3. the preparation method of a compound as claimed in claim 1 is characterized in that: when Y is C-CH
3, when Z was O, described preparation method comprised the steps:
(1) in reaction vessel, adds 90 ~ 98% the vitriol oil, be cooled to below 10 ℃, add compound (III) again, after treating that compound (III) all dissolves, slowly the vitriol oil of dropping 98% and the mixed solution of 65% nitric acid react 20 ~ 60min down at 8 ~ 35 ℃ then, and reaction is slowly poured into solution in the frozen water after finishing, suction filtration gets compound (II) after the filter cake oven dry;
(2) in reaction vessel, add the methyl alcohol of compound (II), volume fraction 80 ~ 95% or the Pd/C of aqueous ethanolic solution and charge capacity 8 ~ 10%, solution is heated to backflow, the dropping massfraction is hydrazine hydrate-ethanolic soln of 10 ~ 20%, dropwise in the 1h, dropwise the back at 68 ~ 78 ℃ of reaction 2 ~ 5h, stop heating, cool the temperature to 45 ~ 55 ℃ and suction filtration, stir the also slow dripping hydrochloric acid of filtrate and separate out unreacted compound (II) completely, filter again, distillation filtrate, residual solution gets compound (I) with salt acid treating, activated carbon decolorizing again;
In formula (I) or formula (II) or the formula III, Y is C-CH
3, Z is O.
4. compounds process for production thereof as claimed in claim 3 is characterized in that: in the described step (1), and compound (III) and HNO
3Mol ratio be 1:2.1 ~ 2.3; Compound (II) is 1:2.2 ~ 2.83 with the mol ratio of hydrazine hydrate in the described step (2), and compound (II) is 1:0.083 ~ 0.25 with the mass ratio of Pd/C.
5. the preparation method of a compound as claimed in claim 1 is characterized in that: when Y is N, when Z was NH, described preparation method comprised the steps:
Add compound (II) and water in reaction vessel, be heated to backflow, begin to drip sodium polysulfide solution behind the adding hydrazine hydrate, dropwise in 15 ~ 50min, 1.5 ~ 3h is reacted in the back under reflux temperature, filtered while hot, and filtration cakes torrefaction gets compound (I); Described compound (II) is 1:0.67 ~ 2 with the molar ratio of hydrazine hydrate, and described sodium polysulfide solution is by Na
2S9H
2O, S, water are formulated according to mass ratio 1:0.25 ~ 0.5:3.5 ~ 6, and the add-on of described sodium polysulfide solution satisfies the Na that wherein contains
2S9H
2The mass ratio of O and compound (II) is 1.1 ~ 1.5:1;
In formula (I) or the formula (II), Y is N, and Z is NH.
6. compound, its structure is shown in formula IV:
In the formula IV, Y is N, and Z is NH, and R is H; Or Y is CH, and Z is NH, and R is OH; Or Y is C-CH
3, Z is O, R is H.
7. the preparation method of a compound as claimed in claim 6 is characterized in that: when Y is CH, Z is NH, and when R was OH, described preparation method comprised the steps:
(a) compound, the water shown in the formula (II) is joined in the reaction vessel, be heated to backflow, begin to drip sodium polysulfide solution, described sodium polysulfide solution is by Na
2S9H
2O, S and H
2O obtains according to mass ratio 1:0.2 ~ 0.5:2.5 ~ 4 preparations, and the add-on of described sodium polysulfide solution satisfies the Na that wherein contains
2S9H
2The mol ratio of O and compound (II) is 1.05 ~ 1.3:1, and 0.5 ~ 1.5h dropwises, back flow reaction 1.5 ~ 3h again, filtered while hot, after the cooling of gained filtrate more after filtration, dry compound (I);
(b) compound shown in the adding formula (V) and quality are the sulfur oxychloride of 30 ~ 40 times of compound (V) quality in reaction vessel, and heated and stirred back flow reaction 2 ~ 4h steams unreacted sulfur oxychloride and gets the compound shown in the formula VI;
(c) add diethylene glycol dimethyl ether and compound (I) in reaction vessel, drip the diethylene glycol dimethyl ether solution of compound (VI) under the condition of ice bath, 30 ~ 60min dropwises, and dropwises the back and feeds N
2And heating, at 110 ~ 130 ℃ of reaction 2 ~ 5h, add polyphosphoric acid again and continue reaction 3 ~ 6h, filtered while hot, filtrate cooling back refilters with ammoniacal liquor, hot wash, and drying gets compound (IV); Described compound (VI) is 1.05 ~ 1.35:1 with the mol ratio of compound (I), and the mass ratio of polyphosphoric acid and compound (I) is 3 ~ 6:1;
In formula (II), formula (I) or formula (V) or the formula VI, Y is CH, and Z is NH, and R is OH.
8. the preparation method of a compound as claimed in claim 6 is characterized in that: when Y is C-CH
3, Z is O, when R was H, described preparation method comprised the steps:
(A) in reaction vessel, add 90 ~ 98% the vitriol oil, be cooled to below 10 ℃, add compound (III) again, after treating that compound (III) all dissolves, slowly the vitriol oil of dropping 98% and the mixed solution of 65% nitric acid react 20 ~ 60min down at 8 ~ 35 ℃ then, and reaction is slowly poured into solution in the frozen water after finishing, suction filtration gets compound (II) after the filter cake oven dry;
(B) in reaction vessel, add the methyl alcohol of compound (II), volume fraction 80 ~ 95% or the Pd/C of aqueous ethanolic solution and charge capacity 8 ~ 10%, solution is heated to backflow, the dropping massfraction is hydrazine hydrate-ethanolic soln of 10 ~ 20%, dropwise in the 1h, dropwise the back at 68 ~ 78 ℃ of reaction 2 ~ 5h, stop heating, cool the temperature to 45 ~ 55 ℃ and suction filtration, stir the also slow dripping hydrochloric acid of filtrate and separate out unreacted compound (II) completely, filter again, distillation filtrate, residual solution gets compound (I) with salt acid treating, activated carbon decolorizing again;
(C) compound shown in the adding formula (V) and quality are the sulfur oxychloride of 23 ~ 40 times of compound (V) quality in reaction vessel, and heated and stirred back flow reaction 1 ~ 2.5h steams unreacted sulfur oxychloride and gets compound shown in the formula VI;
(D) formula (VI) compound is configured to the 4-methyl-2 pentanone solution that massfraction is 4 ~ 8% compound (VI), in reaction vessel, add compound (I), heat temperature raising to 70 ~ 85 ℃, drip the 4-methyl-2 pentanone solution of compound (VI), 3 ~ 30min dropwises back back flow reaction 2 ~ 4h, obtain yellow solid after the cooling, separation and purification gets the compound shown in the formula (VII);
(E) in reaction vessel, add the diethylene glycol dimethyl ether that compound (VII) and quality are 14 ~ 17 times of compound (VII) quality, be heated to 150 ~ 161 ℃, adding quality again is the polyphosphoric acid of 4 ~ 6 times of compound (VII) quality, be warming up to back flow reaction 2.5 ~ 3h, being cooled to room temperature pours in the frozen water again, suction filtration gets compound (IV) behind the filter cake washing and drying;
In formula (I), (II), (III), (IV), (V), (VI) or (VII), Y is C-CH
3, Z is O, R is H.
9. compounds process for production thereof as claimed in claim 8 is characterized in that: in the described step (A), and compound (III) and HNO
3Mol ratio be 1:2.1 ~ 2.3; Compound (II) is 1:2.2 ~ 2.83 with the mol ratio of hydrazine hydrate in the described step (B), and compound (II) is 1:0.083 ~ 0.25 with the mass ratio of Pd/C.
10. the preparation method of a compound as claimed in claim 6 (IV) is characterized in that: when Y is N, Z is NH, and when R was H, described preparation method comprised the steps:
(i) add compound (II) and water in reaction vessel, be heated to backflow, begin to drip sodium polysulfide solution behind the adding hydrazine hydrate, dropwise in 15 ~ 50min, 1.5 ~ 3h is reacted in the back under reflux temperature, filtered while hot, and filtration cakes torrefaction gets compound (I); Described compound (II) is 1:0.67 ~ 2 with the molar ratio of hydrazine hydrate, and described sodium polysulfide solution is by Na
2S9H
2O, S, water are formulated according to mass ratio 1:0.25 ~ 0.5:3.5 ~ 6, and the add-on of described sodium polysulfide solution satisfies the Na that wherein contains
2S9H
2The mass ratio of O and compound (II) is 1.1 ~ 1.5:1;
(ii) in reaction vessel, add diethylene glycol dimethyl ether and compound (V), heating makes compound (V) dissolving, when waiting to be warming up to 55 ~ 65 ℃, dripping thionyl chloride, 5 ~ 20 min dropwise afterreaction 0.5 ~ 1 h, take out sour gas in the dereaction container with vacuum pump, add compound (I) again, be heated to 140 ~ 150 ℃ and react 0.5 ~ 1.5h, add polyphosphoric acid again, be warming up to 160 ~ 170 ℃, reaction 2 ~ 4h, stopped reaction, be cooled to room temperature and filter, a layer oily liquid thing taken off in the filtrate layering, add methyl alcohol, be heated with stirring to backflow, in the time of 35 ~ 45 ℃, filter, obtain filtrate behind the filtration cakes torrefaction, adding water has yellow solid to separate out, and filtration drying obtains compound (IV);
In formula (I), (II), (IV) or the formula (V), Y is N, and Z is NH, and R is H.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980133A (en) * | 2014-05-23 | 2014-08-13 | 郑州大学 | Method for preparing 2-methyl-4,6-diaminoresorcinol hydrochloride |
| CN104119534A (en) * | 2014-07-10 | 2014-10-29 | 金宁人 | Polyhydroxy p-phenylene benzo bisoxazole polymer and preparation and application thereof |
| CN106684414A (en) * | 2016-11-23 | 2017-05-17 | 长春工业大学 | Organic-inorganic composite type high-temperature proton exchange membrane used for fuel cell and preparation method for proton exchange membrane |
| CN110396052A (en) * | 2019-07-11 | 2019-11-01 | 浙江工业大学 | The synthetic method of 5- amino -2,4- dihydroxy-benzoic acid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1106716A1 (en) * | 1999-12-06 | 2001-06-13 | Toyo Boseki Kabushiki Kaisha | Polybenzazole and fiber thereof |
| CN1644578A (en) * | 2004-12-18 | 2005-07-27 | 浙江工业大学 | AB type poly(p-phenyl) benzdioxan monomer and its preparation and use |
| CN101289419A (en) * | 2008-06-06 | 2008-10-22 | 哈尔滨工业大学 | Process for preparing 2,3,5,6-tetraminopyridine hydrochloride |
| US20080269455A1 (en) * | 2005-09-13 | 2008-10-30 | Toyo Boseki Kabushiki Kaisha | Process for Production of Polybenzazole Polymer and the Polymer |
| CN102532546A (en) * | 2011-11-11 | 2012-07-04 | 浙江工业大学 | Preparation and application of hydroxyl modified poly-p-phenylene benzo imidazolinyl resin |
-
2012
- 2012-12-21 CN CN2012105628817A patent/CN103204805A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1106716A1 (en) * | 1999-12-06 | 2001-06-13 | Toyo Boseki Kabushiki Kaisha | Polybenzazole and fiber thereof |
| CN1644578A (en) * | 2004-12-18 | 2005-07-27 | 浙江工业大学 | AB type poly(p-phenyl) benzdioxan monomer and its preparation and use |
| US20080269455A1 (en) * | 2005-09-13 | 2008-10-30 | Toyo Boseki Kabushiki Kaisha | Process for Production of Polybenzazole Polymer and the Polymer |
| CN101289419A (en) * | 2008-06-06 | 2008-10-22 | 哈尔滨工业大学 | Process for preparing 2,3,5,6-tetraminopyridine hydrochloride |
| CN102532546A (en) * | 2011-11-11 | 2012-07-04 | 浙江工业大学 | Preparation and application of hydroxyl modified poly-p-phenylene benzo imidazolinyl resin |
Non-Patent Citations (2)
| Title |
|---|
| BOYER, J. H.和BURIKS, R. S.: "2,4,5-Triaminonitrobenzene", 《ORGANIC SYNTHESES,》, vol. 40, 31 December 1960 (1960-12-31), pages 96 * |
| BOYER, J. H.和BURIKS, R. S.: "2,4,5-Triaminonitrobenzene", 《ORGANIC SYNTHESES》, vol. 40, 31 December 1960 (1960-12-31), pages 96 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980133A (en) * | 2014-05-23 | 2014-08-13 | 郑州大学 | Method for preparing 2-methyl-4,6-diaminoresorcinol hydrochloride |
| CN103980133B (en) * | 2014-05-23 | 2016-06-08 | 郑州大学 | A kind of method preparing 2-methyl-4,6-diaminoresorcinol dihydrochloride |
| CN104119534A (en) * | 2014-07-10 | 2014-10-29 | 金宁人 | Polyhydroxy p-phenylene benzo bisoxazole polymer and preparation and application thereof |
| CN106684414A (en) * | 2016-11-23 | 2017-05-17 | 长春工业大学 | Organic-inorganic composite type high-temperature proton exchange membrane used for fuel cell and preparation method for proton exchange membrane |
| CN106684414B (en) * | 2016-11-23 | 2019-05-10 | 长春工业大学 | Fuel cell organic-inorganic compoiste high temperature proton exchange film and preparation method thereof |
| CN110396052A (en) * | 2019-07-11 | 2019-11-01 | 浙江工业大学 | The synthetic method of 5- amino -2,4- dihydroxy-benzoic acid |
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