CN101209998A - Method for synthesizing 5-amide-6-hydroxy-2-(4-carboxylphenyl)benzoxazole - Google Patents
Method for synthesizing 5-amide-6-hydroxy-2-(4-carboxylphenyl)benzoxazole Download PDFInfo
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Abstract
The invention relates to a synthesis method of 5-amido-6-oxhydryl-2-(4-carboxyl benzyl group) benzoxazole (ABA), which takes 5-nitryl-6-oxhydryl-2-(4-methoxycarbonyl phenyl) benzoxazole (NHAB) as raw material that is put into hydrosolvent for hydrolysis by alkaline substance at 60-100 DEG C and then one-spot method is directly used for preparing the ABA through in situ synthesis with the effect of reducer, wherein, the alkaline substance is carbonate of alkali metals. Mass ratio of feeding of the NHAB to the alkali substance is 1:0.8 to 2.25, and the reducer is sodium hydrosulfite (Na2S2O4) or hydrogen. When the Na2S2O4 is used as the reducer, the dosage is 2.0-3.0 time of the mass of the NHAB. The invention has concise technique, high yield and low requirement for equipment. The solvent used in the invention is water, which avoids induction of organ solvent, thereby reducing production cost without polluting the environment. The prepared ABA has high purity and better polycondensation effect, thereby showing good industrial prospect.
Description
(1) technical field
The present invention relates to a kind of 5-Amide-6-hydroxy-2--(to the synthetic method of carboxyl phenyl) benzoxazole (ABA).
(2) background technology
PBO is a cis polyparaphenylene Ben Bing Er oxazole, is that (it can make high-performance fiber---the Zylon that belongs to the organic-inorganic fiber by the high molecule liquid crystal spining technology to cis-poly for p-phenylene-2, abbreviation 6-benzobisoxaole).
Study so far, (Toyobo) house journal (spy opens 2000-38371) is spun by Japanese Japan, and warp (1) formula is by 4 under shear conditions, and 6-diamino resorcin hydrochlorate (DAR2HCl) and terephthalic acid (TPA) mixed polycondensation obtain the PBO resin:
Though the Zylon-HM type pbo fiber that makes has presented very excellent physics, chemistry and mechanical property, but its production unit requirement is very high, processing condition control is extremely harsh, except that Japanese Japan is spun, be general institute and be difficult to reach and realize, yet intensity that is reached and modulus also only are 29% and 43.9% of theoretical prediction value.Trace it to its cause, except that good spining technology, mainly be the easy oxygenolysis of DAR monomer, and emit due to the combined influences such as HCl and TPA inhomogeneous reaction during formula (1) polymerization, and DAR and waiting fully of TPA ought be particularly more remarkable than the influence at random that is difficult to accurate control in the reaction.On the other hand, the technical requirements of preparation high purity DAR2HCl is very strict, though adopt tri-chlorination benzene route synthetic DAR to realize the suitability for industrialized production of PBO, but Japan spins the result of the further research of patent (spy opens 2002-121282) of company and shows, the further raising that not exclusively affects the polymerization degree significantly of last dechlorination reaction, and the polymerization degree of PBO and molecular weight are the keys that directly influences fibrous mechanical property; Though DAR has adopted 2 molecule HCl to carry out salify protection, in transportation and polycondensation process, also be difficult to guarantee the high purity more than 99.8%.If the purity of monomer DAR2HCl reduces to 96% from 99.8%, the PBO polymerization degree of mixing the polycondensation Theoretical Calculation according to Flory two monomers (DAR and TPA) just reduces about 20 times.In fact improper for monomer DAR2HCl if storage and use has slightly, in three months purity reduce to 96% and the outward appearance blackening happen occasionally, so how guarantee monomeric high purity and realize waiting accurately when outstanding apparent more important than metering.For head it off and remove HCl, DAR2HCl is formed after the TPA salt technology of polycondensation more earlier though there is the Japan of employing to spin house journal (US20010014756, US5919890, EP1108709):
But because the ionic linkage character of DAR/TPA salt, actual oxidation is faster and be difficult to operation and store than DAR2HCl, moreover still be with DAR2HCl raw material and since process many single step reaction make price expensive more, do not solve the difficulty of DAR preparation and problem such as oxygenolysis very easily in essence.
ABA synthetic as far back as nineteen ninety had one piece of report (Polymer preprints, 1990,31 (2), 681-682), the operational path of employing as the formula (3),
And utilize prepared ABA monomer to prepare PBO, and wherein, be raw material with ABA, the Vanadium Pentoxide in FLAKES dewatering agent exists and N in polyphosphoric acid (PPA) solvent
2Protection is the preparation in 24.5 hours of the temperature programming self-condensation reaction between 90～200 ℃ polyparaphenylene's Ben Bing Er oxazole (PBO) resin down, as the formula (4), the limiting viscosity of PBO [η] be up to 12.5dl/g (30 ℃, MSA):
The reaction of formula (4) only produces 2 molecule H
2O, process does not have emitting and disturbing of obnoxious flavoures such as HCl and methyl alcohol.But contained the poly-impurity DMF of PBO resistance by formula (3) ABA of hydrogenation preparing in the DMF solvent, had a strong impact on the further raising of PBO molecular weight, be unfavorable for that ABA prepares the application of PBO.The reactions steps of formula (3) path of preparing ABA is many in addition, yield is low, price costlinesses such as dewatering agent trimethyl silane polyphosphate TSPP and hydrogenation catalyst Pd/C and consumption are big, (solvent 1 is orthodichlorobenzene and three-step reaction all carries out in organic solvent, solvent 2 is an ethylene glycol, and DMF etc.), organic contamination is big, simultaneously residual solvent DMF can have a strong impact on its polymerization process among the ABA, adds that its preparation cost is high and lacks practicality, is difficult to carry out industrialization.So far do not see other reports that ABA is synthetic and study yet.The state of the art of expensive now, highly difficult preparation PBO has seriously hindered preparation, expansion and the application of high-performance PBO material.
(3) summary of the invention
The purpose of this invention is to provide the 5-Amide-6-hydroxy-2-shown in a kind of formula (I)-(to the new synthetic method of carboxyl phenyl) benzoxazole (ABA), the ABA of preparation prepares in polycondensation and does not produce any obnoxious flavour and interference among the PBO, do not contain the poly-impurity of any PBO resistance simultaneously, and method is also more economical, reasonable, effective.
The technical solution used in the present invention is as follows:
A kind of 5-Amide-6-hydroxy-2--(to the synthetic method of carboxyl phenyl) benzoxazole (ABA), with 5-nitro-6-hydroxyl-2-(to the methoxycarbonyl phenyl) benzoxazole (NHAB) shown in the formula (II) is raw material, in water solvent under 60～100 ℃ through the alkaline matter hydrolysis, the direct synthetic described ABA of one kettle way original position under the effect of reductive agent again.Described alkaline matter is alkali-metal carbonate, and NHAB and the alkaline matter mass ratio that feeds intake is 1: 0.8～2.25; Described reductive agent is V-Brite B Na
2S
2O
4Or hydrogen: reductive agent is Na
2S
2O
4The time, consumption is 2.0～3.0 times of NHAB quality, when reductive agent is hydrogen, need under the Pd/C catalyst, carry out, and be 5% Pd/C catalyzer if use loading, then consumption is 0.05～0.1 times of NHAB quality.
Further, the consumption of described water is 30～80 times of NHAB quality, preferred 40～60 times.
Further, described alkaline matter is yellow soda ash or salt of wormwood, and consumption is preferably 0.8～1.6 times of NHAB quality.
Preferably, described alkaline matter is a salt of wormwood, and described reductive agent is Na
2S
2O
4, the synthetic method of described ABA is NHAB 60～100 ℃ of following hydrolysis in the aqueous solution of salt of wormwood, again at Na
2S
2O
4Effect under under-5～40 ℃ of conditions reduction generate described ABA, wherein NHAB: K
2CO
3: water: Na
2S
2O
4The mass ratio that feeds intake is: 1: 0.8～1.6: 40～60: 2.0～3.0.Reaction formula is as follows:
Comparatively concrete, NHAB is at K
2CO
3The aqueous solution under 60～100 ℃ of conditions hydrolysis reaction 30～80min clarify to solution, be cooled to then under-5～5 ℃ of vigorous stirring and add V-Brite B Na again
2S
2O
4, control reaction temperature-5～5 ℃ reaction 20～30min filters, and filter cake washing final vacuum is drying to obtain described ABA compound, is generally yellow crystal, NHAB: K
2CO
3: water: Na
2S
2O
4The mass ratio that feeds intake is 1: 0.8～1.6: 40～60: 2.6～2.75.
This method is finished reductive hydrolysis two-step reaction one kettle way, prepares the new monomer A BA of high purity AB type that does not contain the poly-impurity of resistance, has more advantages such as need not hydrogenation unit, simple to operate and product colour excellence.
If described alkaline matter is a salt of wormwood, described reductive agent is a hydrogen, and the loading of described Pd/C catalyzer is 4～6%, is preferably 5%, and then described method is that NHAB is at K
2CO
3The aqueous solution in 60～100 ℃ of following hydrolysis 30～80min clarify to solution, in this solution, add the Pd/C catalyzer then, temperature is that 30～60 ℃, hydrogen pressure are 0.2～0.4MPa reaction down, and reaction finishes promptly to get described ABA compound through aftertreatment, and the mass ratio that feeds intake is NHAB: K
2CO
3: water: 5%Pd/C is 1: 0.8～1.6: 40～60: 0.05～0.1.
Described aftertreatment is that reacting liquid filtering is removed Pd/C, uses NaHSO
3Saturated aqueous solution is transferred pH to 6.5～7.0, separates out precipitation, and filtration, washing and drying promptly get described ABA compound.Preferably, remove the Pd/C catalyzer after, can be with filtrate with after the activated carbon adsorption decolouring, re-adjustment pH value.
Described Pd/C catalyzer can directly be bought from the market and obtain.
When taking hydrogenating reduction, except using the Pd/C catalyzer, also can use Raney's nickel catalyst, identical when operating process is Pd/C with catalyzer, but the consumption of Raney's nickel catalyst is preferably 1.0～1.2 times of the NHAB quality.Described Raney's nickel catalyst is to be made by alumino nickel (mass ratio 1: 1) 60 ℃ of reactions in 20% NaOH solution.Also can adopt commercially available Raney's nickel catalyst.
The 5-Amide-6-hydroxy-2--(to carboxyl phenyl) benzoxazole (being called for short ABA), belong to the new monomer of acid AB type PBO, have the polycondensation group and wait fully when reaching 260 ℃ of special propertys such as (higher) than the new monomer M AB of ester formula AB type PBO than initial heat decomposition temperature in, the nitrogen.After simultaneously it stores 10 months in air, have the advantages that the constant and HPLC purity of outward appearance only is declined by less than 0.15% antioxidative stabilizer excellence.
One of method that is prepared described polyparaphenylene Ben Bing Er oxazole PBO resin by ABA is as follows:
In general glass reaction flask, add ABA, and quality be its 20 times of PPA solvents, it is ABA quality 6-8 times P that quality is arranged in the solvent
2O
5Need not to add any oxidation inhibitor, in 150 ℃ stir 2～3h after, polycondensation promptly begins to carry out lentamente, this moment, solution began to become thickness, when be warming up to 170～210 ℃ stir 5～7h after himself equal polycondensation finish substantially, add polymer fluid in the entry then, separate out the red-brown solid, filtration, washing and drying get polymer P BO resin.Its intrinsic viscosity η be 8～12dl/g (30 ℃, MSA).
The present invention compared with prior art, its beneficial effect is embodied in:
Technology of the present invention is terse, the yield height; Low normal pressure and temperature reduction is lower to the requirement of equipment; The solvent that hydrolysis and reduction are adopted is water, has avoided the introducing of other organic solvents, has reduced production cost, and is free from environmental pollution again; The ABA purity height that makes has not contained the poly-impurity of the resistance that influences polycondensation, than the better effects if by MAB that contains residual solvent DMF or ABA polycondensation.Be applied to PBO resin and fiber production advantage obviously, have a extensive future.Be the technology of reductive agent with the V-Brite B particularly, do not need hydrogenation unit, also need not expensive Pd/C catalyzer, greatly reduce production cost, good industrial prospect and advantage are arranged.
(4) embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1:5-Amide-6-hydroxy-2--(carboxyl phenyl) benzoxazole (ABA) is prepared
With 4.0g K
2CO
3Be dissolved in the water solvent of 150ml, get NHAB3.0g (purity 96.5%) and add in this dilute alkaline soln, stir and to be warming up to 80 ℃, hydrolysis reaction 50min and to clarify, under vigorous stirring, slowly add 8.0g Na when being cooled to 0 ℃ to solution
2S
2O
4, control 0-5 ℃ of reduction reaction 20min, filter yellow crystal, after the frozen water washing, vacuum-drying gets faint yellow crystallized product 2.12g, purity 98.9%, through FT-IR qualitatively,
13C-NMR,
1H-NMR attribution analysis and ultimate analysis thereof are defined as the new monomer of acid AB type PBO: i.e. 5-Amide-6-hydroxy-2--(to carboxyl phenyl) benzoxazole ABA monomer, yield 84.2%.
FT-IR(KBr，cm
-1)：3333.4，3269.7，3151.1，1676.8，1617.0，1579.4，1466.6，1409.7，1380.8，1294.0，1177.3，1129.1，1053.9，972.9，879.4，860.1，784.9，709.7。Ultimate analysis value: C, 62.03; H, 3.75; N, 10.45.Calculated value (C
14H
10N
2O
4): C, 62.22; H, 3.73; N, 10.37.
Embodiment 2～6:
Adopt the same operation of embodiment 1, get different parameters (differing temps, material purity and Na by parameter area of the present invention
2S
2O
4Consumption) react, the results are shown in Table 1:
Table 1 is by NHAB hydrolyzing N a
2S
2O
4Reduction " one kettle way " preparation ABA monomer
Embodiment 7: alkaline hydrolysis, hydrogenating reduction in-situ synthesis prepare ABA
With 4.5g K
2CO
3Be dissolved in the water solvent of 180ml, getting NHAB 3.00g (purity 94.4%) adds in this dilute alkaline soln, stirring is warming up to 60 ℃, hydrolysis reaction 60min to solution and clarifies, reaction solution is transferred in the autoclave, add 0.3g 5%Pd/C, vigorous stirring was reacted 3 o'clock under the hydrogen pressure of 30 ℃ and 0.3-0.4MPa, remove by filter catalyzer after, filtrate is cooled to room temperature and after the charcoal absorption decolouring, uses NaHSO
3Saturated aqueous solution transfers to pH 6.5～7.0 and separates out precipitation, filters, and vacuum-drying gets khaki color crystallized product 2.05g, purity 98.2%, yield 82.6%.FT-IR,
13C-NMR,
1H-NMR attribution analysis and embodiment 1 identical qualitative be the ABA monomer.
FT-IR(KBr，cm
-1)：3334.3，3269.7，3146.3，1675.8，1617.0，1579.4，1466.6，1409.7，1380.8，1294.0，1177.3，1129.1，1053.9，972.9，878.4，861.0，784.9，709.7。
Embodiment 8～13:
Adopt the same operation of embodiment 7, get different parameters (two kinds hydrogenation catalyst and proportioning, differing temps and different material purities) by parameter area of the present invention and react, wherein the loading of Pd/C catalyzer is 5%, the results are shown in Table 2:
Table 2 is by NHAB hydrolysis hydrogenating reduction " one kettle way " preparation ABA monomer
*Embodiment 12,13: employing RaneyNi is a catalyzer, and hydrogenation reduction process is embodiment 7 roughly the same, and hydrogenation time is 3h, product F T-IR (KBr, cm
-1): 3334.3,3272.6,3144.4,1676.8,1618.0,1582.3,1466.6,1410.7,1378.9,1293.0,1179.2,1128.2,1054.9,972.0,880.4,860.1,782.0,710.6.Identical with embodiment 7 qualitative be the ABA monomer.
Embodiment 14～15 is ABA preparation method's a Comparative Examples
Embodiment 14:NHAB hydrolysis, reduction stepwise reaction prepare ABA
The NHAB hydrolysis prepares NBA
With 2.4g K
2CO
3Be dissolved in the water solvent of 150ml, get NHAB 3.00g (purity 93.9%) and add in this dilute alkaline soln, stir and to be warming up to 100 ℃, hydrolysis reaction 60min and to clarify, be cooled to room temperature and after the charcoal absorption decolouring, use NaHSO to solution
3Saturated aqueous solution transfers to pH 6.5～7.0 and separates out precipitation, filters, and vacuum-drying gets khaki color crystallized product NBA 2.52g, purity 97.8%, yield 91.6%.
IR(KBr，cm
-1)：1692.2(s)，1643.1(s)，1620.9(s)，1546.6(s)，1443.5(s)，1316.2(s)，1284.4(s)，711.6(s)。
1H-NMR：7.46(s，1H)，8.16(s，2H)，8.26(s，1H)，8.39(s，2H)。
NBA reduction preparation ABA
With 1.44g K
2CO
3Be dissolved in the water solvent of 80ml, get NBA 1.8g (purity 97.8%) adding stirring and be warming up to 60 ℃ of solution clarifications, under vigorous stirring, slowly add 4.5g Na when being cooled to 0 ℃
2S
2O
4, control 0～5 ℃ of reduction reaction 20min, filter yellow crystal, after the frozen water washing, vacuum-drying gets faint yellow crystallized product ABA 1.29g, purity 99.1%, yield 84.4%.
Perhaps with 1.44g K
2CO
3Be dissolved in the water solvent of 80ml, get NBA 1.8g (purity 97.8%) adding stirring and be warming up to 60 ℃ of solution clarifications, be transferred in the autoclave, add 0.2g 5%Pd/C, the vigorous stirring reaction is 3 hours under the hydrogen pressure of 30 ℃ and 0.3-0.4MPa, after removing by filter catalyzer, after filtrate is cooled to room temperature, use NaHSO
3Saturated aqueous solution transfers to pH 6.5-7.0 and separates out precipitation, filters, and vacuum-drying gets khaki color crystallized product ABA monomer 1.26g, purity 98.9%, yield 78.7%.
Embodiment 15:
Get NHAB 2.0g (purity 94.8%, 0.00603mol) add in the 35ml ethylene glycol, be warming up to 75 ℃ after, drip the solution of 1.2g KOH in 16ml ethylene glycol, finish 75 ℃ of insulation 4h, pour into after the cooling in the mixture of 29ml methyl alcohol and 29ml water, transfer pH value of solution, leave standstill to acid, filter, the dry khaki color crystallized product NBA 1.75g that gets, purity is 94.0%, yield 90.8%.
Get 4g (0.0125mol) NBA, 0.3g5%Pd/C adds among the 150ml DMF, and 30 ℃ feed 0.25MPa H down
2Reaction 1.5h, cooled and filtered is removed spent catalyst, in filtrate, add 200ml water elutriation, wet cake after the filtration is repeatedly with after 100ml/ time the deionized water vigorous stirring washing making beating 3 times, vacuum-drying 8h below 60 ℃, ABA monomer 3.08g that must isabelline powder crystallization, yield 89.6%, purity 98.5%.Residual solvent DMF content 0.6%.
1H-NMR(DMSO)δ：6.95(s，1H)，7.04(s，1H)，8.09(s，2H)，8.16(s，2H)。
The equal polycondensation of embodiment 16:ABA prepares the PBO resin
The ABA (purity 98.99%) that in polymerization reactor, adds 0.8g embodiment 1 preparation, 19.48gPPA, the P of 9g
2O
5, feed nitrogen; Stirring is warming up to 120 ℃, reaction 3h, and color is orange; Be warming up to 160 ℃, reaction 3h, color becomes the tenne opalescence phenomenon that presents; Continue to be warmed up to 180 ℃, reaction 2h, color becomes breen; Be warming up to 200 ℃ at last, reaction 3h color is blackish green, and homopolymerization finishes.Cooling, and polymkeric substance is put into 100ml/ water be warming up to 60 ℃, agitator treating twice (in case of necessity polymkeric substance being shredded after scouring) and handle, 105 ℃ of dry 10h down, PBO polymkeric substance 0.76g, record limiting viscosity [η] and be 10.31dl/g (30 ℃, MSA).
IR (KBr, cm
-1) characteristic peak and ownership be: 1627 (1495 (s) heterocycle absorbs, 1410,1116,1056 (s) phenyl ring C-C skeleton peak, C-H on 873 (s), 851 (s)/703 (s) phenyl ring for s) oxazole C=N peak, 1581,1557 (s) phenyl ring C=C peak.Characteristic peak and ownership analysis meet the molecular structure of PBO fully.
Embodiment 17:DAR2HCl-TPA copolycondensation legal system is equipped with the PBO resin
In the self-control polymerization reactor, add DAR2HCl (9.39mmol) and the 15.32g polyphosphoric acid of 2g, feed N
2, remove hydrogenchloride in 90 ℃ of stirrings, measure no HCl gas with the pH test paper behind the 3h and emit.The terephthalic acid (9.32mmol), the 0.1gSnCl that add about 1.5g
2With the Vanadium Pentoxide in FLAKES of 5.42g, be warming up to 120 ℃, reaction 5h, color becomes green; Rise to 135 ℃, reaction 7h, color becomes yellow-green colour, khaki color by green; 150 ℃ are reacted 7h down, and color becomes golden yellow by khaki color, and opalescence is arranged, and becomes liquid crystal state; Be raised to 170 ℃, reaction 8h, color becomes green; Be raised to 190 ℃ at last, reaction 11h stops heating, and product is taken out in cooling, handle, 105 ℃ of dry down back 1.63g, yield is 81.5%, limiting viscosity be 7.03dl/g (30 ℃, MSA).IR (KBr, cm
-1) characteristic peak and ownership be: 1624.7 (s) oxazole C=N peaks, 1557.2 (s) phenyl ring C=C peak, 1495 (s) heterocycle absorbs, 1410,1116,1056 (s) phenyl ring C-C skeleton peak, 1277 (m) 1056 (the C-O peak of s) oxazole, C-H on 873,703 (s) phenyl ring.Identical with the infrared absorption of embodiment 16.
The equal polycondensation legal system of embodiment 18:MAB is equipped with the PBO resin
MAB (the containing DMF0.9%) monomer, the 19.08gPPA that in reactor, add 0.69g, the P of 5.2g
2O
5, feed nitrogen, be warming up to 100 ℃, reaction 2h, color becomes brown; 150 ℃, reaction 10h, color becomes black and becomes brownly again, and liquid crystal state appears in volume-diminished; Be raised to 170 ℃, reaction 5h, color is constant; Be raised to 190 ℃, reaction 2h; Be raised to 200 ℃, reaction 1.5h.Stop heating, product is taken out in cooling, handle, after 105 ℃ of following dryings the PBO resin, record limiting viscosity and be 4.14dl/g (30 ℃, MSA).
Embodiment 19: the equal polycondensation of ABA that contains residual DMF prepares PBO
ABA (the containing DMF0.6%) monomer, the 19.08gPPA that in reactor, add 0.80g, the P of 5.2g
2O
5, feed nitrogen, be warming up to 100 ℃, reaction 2h, color becomes brown; 150 ℃, reaction 10h, color becomes black and becomes brownly again, and liquid crystal state appears in volume-diminished; Be raised to 170 ℃, reaction 5h, color is constant; Be raised to 190 ℃, reaction 2h; Be raised to 200 ℃, reaction 1.5h.Stop heating, product is taken out in cooling, handle, after 105 ℃ of following dryings, record limiting viscosity and be 5.76dl/g (30 ℃, MSA).
Result's contrast of embodiment 16～19 preparation PBO resins sees Table 3:
Table 3 embodiment 16-19 prepares PBO result's contrast
A. polymerization-grade DAR2HCl monomer, its mixed polycondensation is seen formula (1); The intrinsic viscosity of b.PBO resin
Claims (10)
1. synthetic method suc as formula the 5-Amide-6-hydroxy-2-shown in (I)-(to carboxyl phenyl) benzoxazole (ABA), with 5-nitro-6-hydroxyl-2-(to the methoxycarbonyl phenyl) benzoxazole (NHAB) shown in the formula (II) is raw material, in water solvent under 60～100 ℃ through the alkaline matter hydrolysis, the direct synthetic described ABA of one kettle way original position under the effect of reductive agent again
Described alkaline matter is alkali-metal carbonate, and NHAB and the alkaline matter mass ratio that feeds intake is 1: 0.8～2.25; Described reductive agent is V-Brite B Na
2S
2O
4Or hydrogen, reductive agent is Na
2S
2O
4The time, consumption is 2.0～3.0 times of NHAB quality, when reductive agent is hydrogen, need carry out under the Pd/C catalyst, loading is that 5% Pd/C catalyst consumption is 0.05～0.1 times of NHAB quality.
2. the synthetic method of ABA as claimed in claim 1, the consumption that it is characterized in that described aqueous solvent is 30～80 times of NHAB quality.
3. the synthetic method of ABA as claimed in claim 1 is characterized in that described alkaline matter is yellow soda ash or salt of wormwood.
4. the synthetic method of ABA as claimed in claim 1, the amount that it is characterized in that described alkaline matter is 0.8～1.6 times of NHAB quality.
5. the synthetic method of ABA as claimed in claim 1 is characterized in that described alkaline matter is a salt of wormwood, and described reductive agent is Na
2S
2O
4
6. the synthetic method of ABA as claimed in claim 1 is characterized in that described method is NHAB 60～100 ℃ of following hydrolysis in the aqueous solution of salt of wormwood, again at Na
2S
2O
4Effect under under-5～40 ℃ of conditions reduction generate described ABA, wherein NHAB: K
2CO
3: water: Na
2S
2O
4The mass ratio that feeds intake is: 1: 0.8～1.6: 40～60: 2.0～3.0.
7. the synthetic method of ABA as claimed in claim 6 is characterized in that described method is that NHAB is at K
2CO
3The aqueous solution under 60～100 ℃ of conditions hydrolysis reaction 30～80min clarify to solution, be cooled to-5～5 ℃ then, add V-Brite B Na under the vigorous stirring again
2S
2O
4, control reaction temperature-5～5 ℃ reaction 20～30min filters, and filter cake washing after drying promptly gets described ABA compound, NHAB: K
2CO
3: water: Na
2S
2O
4The mass ratio that feeds intake is 1: 0.8～1.6: 40～60: 2.6～2.75.
8. the synthetic method of ABA as claimed in claim 1 is characterized in that described alkaline matter is a salt of wormwood, and described reductive agent is a hydrogen, and catalyzer is that loading is 5% Pd/C.
9. the synthetic method of ABA as claimed in claim 8 is characterized in that described method is that NHAB is at K
2CO
3The aqueous solution in 60～100 ℃ of following hydrolysis 30～80min clarify to solution, add the Pd/C catalyzer then, temperature is that 30～60 ℃, hydrogen pressure are 0.2～0.4MPa reaction down, reaction finishes promptly to get described ABA compound through aftertreatment, the mass ratio that feeds intake is NHAB: K
2CO
3: water: 5%Pd/C is 1: 0.8～1.6: 40～60: 0.05～0.1.
10. the synthetic method of ABA as claimed in claim 9 is characterized in that described aftertreatment is that reaction solution is removed Pd/C after filtration, and filtrate is used NaHSO
3Saturated aqueous solution is transferred pH to 6.5～7.0, separates out precipitation, and filtration, washing and drying promptly get described ABA compound.
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| CN102942533A (en) * | 2012-11-16 | 2013-02-27 | 盐城鼎龙化工有限公司 | Preparation method of 4-(5-amino-6-hydroxy-2-benzoxazolyl) benzoic acid (ABA) |
| CN102977045A (en) * | 2012-11-28 | 2013-03-20 | 浙江工业大学 | 4-(5-amino-6-hydroxybenzoxazole-2-yl)ammonium benzoate as well as preparation method and application thereof |
| WO2014075403A1 (en) * | 2012-11-16 | 2014-05-22 | 浙江工业大学 | 4-(5-amino-6-hydroxybenzoxazol-2-yl)ammonium benzoate and preparation method and use thereof |
| CN108003894A (en) * | 2016-11-02 | 2018-05-08 | 达兴材料股份有限公司 | Liquid crystal compound, liquid crystal composition and liquid crystal display device using the same |
| CN110437846A (en) * | 2019-08-30 | 2019-11-12 | 陕西师范大学 | Fluorine containing acetylene bond replaces benzoxazoles liquid-crystal compounds and preparation method thereof |
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| JP2001172238A (en) * | 1999-12-17 | 2001-06-26 | Toyobo Co Ltd | Aromatic diamine/aromatic dicarboxylic acid salt and method for producing the same |
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| CN102942533A (en) * | 2012-11-16 | 2013-02-27 | 盐城鼎龙化工有限公司 | Preparation method of 4-(5-amino-6-hydroxy-2-benzoxazolyl) benzoic acid (ABA) |
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| US9725424B2 (en) | 2012-11-16 | 2017-08-08 | Zhejiang University Of Technology | 4-(5-amino-6-hydroxybenzoxazol-2-yl) ammonium benzoate and preparation method and use thereof |
| CN102977045A (en) * | 2012-11-28 | 2013-03-20 | 浙江工业大学 | 4-(5-amino-6-hydroxybenzoxazole-2-yl)ammonium benzoate as well as preparation method and application thereof |
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| CN108003894B (en) * | 2016-11-02 | 2020-11-03 | 达兴材料股份有限公司 | Liquid crystal compound, liquid crystal composition and liquid crystal display device using the same |
| CN111087315A (en) * | 2018-10-24 | 2020-05-01 | 武汉武药科技有限公司 | Synthetic method of eltrombopag intermediate and synthetic method of eltrombopag |
| CN110437846A (en) * | 2019-08-30 | 2019-11-12 | 陕西师范大学 | Fluorine containing acetylene bond replaces benzoxazoles liquid-crystal compounds and preparation method thereof |
| CN110437846B (en) * | 2019-08-30 | 2022-02-25 | 陕西师范大学 | Fluorine substituted benzoxazole liquid crystal compound containing acetylene bond and preparation method thereof |
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