CN101407455A - Preparation method of 4, 4' -stilbene dicarboxylic acid - Google Patents
Preparation method of 4, 4' -stilbene dicarboxylic acid Download PDFInfo
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- CN101407455A CN101407455A CNA2008101802678A CN200810180267A CN101407455A CN 101407455 A CN101407455 A CN 101407455A CN A2008101802678 A CNA2008101802678 A CN A2008101802678A CN 200810180267 A CN200810180267 A CN 200810180267A CN 101407455 A CN101407455 A CN 101407455A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- SBBQDUFLZGOASY-OWOJBTEDSA-N 4-[(e)-2-(4-carboxyphenyl)ethenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1\C=C\C1=CC=C(C(O)=O)C=C1 SBBQDUFLZGOASY-OWOJBTEDSA-N 0.000 title claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000000047 product Substances 0.000 claims abstract description 13
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- OONPLQJHBJXVBP-UHFFFAOYSA-N 3-(2-phenylethenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=CC=2C=CC=CC=2)=C1C(O)=O OONPLQJHBJXVBP-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 7
- 229940073608 benzyl chloride Drugs 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 4
- XUHFBOUSHUEAQZ-UHFFFAOYSA-N bromobenzyl cyanide Chemical compound N#CC(Br)C1=CC=CC=C1 XUHFBOUSHUEAQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical group C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 3
- 229940117389 dichlorobenzene Drugs 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 5
- -1 p-cyanobenzyl halide Chemical class 0.000 abstract description 3
- 239000002912 waste gas Substances 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- VCZNNAKNUVJVGX-UHFFFAOYSA-N 4-methylbenzonitrile Chemical compound CC1=CC=C(C#N)C=C1 VCZNNAKNUVJVGX-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提出了一种4，4′－二苯乙烯二羧酸的制备工艺。它是以对氰基卤苄为起始原料，先经固体碱催化进行交联反应生成中间体4，4′－二苯乙烯二甲氰，然后在水溶剂体系中进行碱解反应得到最终产品。本发明具有反应条件温和、反应收率高和产物纯度高，生产过程不产生废水废气，污染小的特点。The present invention provides a preparation process of 4,4'-stilbene dicarboxylic acid. It uses p-cyanobenzyl halide as a starting material, firstly undergoes a cross-linking reaction catalyzed by a solid base to generate an intermediate 4,4'-stilbene dimethyl cyanide, and then undergoes an alkaline hydrolysis reaction in an aqueous solvent system to obtain a final product. The present invention has the characteristics of mild reaction conditions, high reaction yield and high product purity, and does not generate wastewater or waste gas during the production process, and has low pollution.
Description
Technical field
The present invention relates to the preparation method of synthetic plastics whitening agent and intermediate polymer, relate in particular to a kind of 4,4 '-preparation method of stilbenedicarboxylicacid acid.
Background technology
4,4 '-stilbenedicarboxylicacid acid is the intermediate of synthetic plastics whitening agent and polymkeric substance.Its structural formula is
4,4 '-synthetic method of stilbenedicarboxylicacid acid mainly is: be raw material with the paratolunitrile, with the coupled generation of sulphur, this method separation purifying technique is loaded down with trivial details; Or with the paratolunitrile chlorination, deriving is aldehyde and ester again, adopts the coupled generation of the uncommon reaction of ladder Wei, and this method separation and purification is easy but route is long.
In U.S. Pat 2677703, disclose by the excessive paratolunitrile of heating stoichiometry and sulphur with prepare 4 ', 4-dibenzyl dicarboxylic acid and 4,4 '-mixture of stilbenedicarboxylicacid acid.This production 4,4 '-shortcoming of stilbenedicarboxylicacid acid method has: (i) need 250～290 ℃ high temperature, (ii) contain raw material toluic acid and two kinds of products in the product mixtures, be difficult to separate, (iii) yield is low, for example the highest ability 40% (iv) need prevent the hydrogen sulfide escape that produces with the washing methods of costliness.
Now traditional production technique is, under alkaline matter pyridine condition, with sulphur oxidation methyl phenylformic acid, after saltout through twice, obtain product behind the acid out.The main drawback of this traditional processing technology is: it can produce a large amount of toxic gas hydrogen sulfide in production process, can produce a large amount of contaminated wastewater environment in treating process, and a large amount of sodium sulphite is arranged in the waste water.
In addition, toluylene benzoxazole white dyes precursor 4 is disclosed in U.S. Pat 4519953,4 '-preparation method of toluylene diformazan cyanogen,, be catalyzer with alkali metal hydroxide powder such as sodium hydroxide, promptly at polar aprotic solvent such as N to be raw material to cyano group benzyl chloride or adjacent cyano group benzyl chloride, dimerization reaction obtains 4 in the dinethylformamide, 4 '-toluylene diformazan cyanogen and 2,2 '-toluylene diformazan cyanogen, yield is about 80%.
Summary of the invention
The purpose of this invention is to provide a kind of reaction conditions gentleness, yield height, product purity height, production process do not produce waste water and gas, pollute little by 4,4 '-novel synthesis of stilbenedicarboxylicacid acid.
Technical scheme of the present invention comprises the steps:
(1) raw material under the dissolved state, adds alkaline matter to cyano group halogen benzyl in solvent, reaction generation intermediate 4,4 '-toluylene diformazan cyanogen; Wherein, raw material is to the cyano group benzyl chloride, to cyano-benzyl bromide, a kind of in the cyano-iodine benzyl to cyano group halogen benzyl, solvent is benzene,toluene,xylene, chlorobenzene, dichlorobenzene, ethyl acetate, N, dinethylformamide, N, a kind of in N-N,N-DIMETHYLACETAMIDE, the acetone, alkaline matter is NaOH, KOH, Na
2CO
3, K
2CO
3, a kind of in the pyridine, 1～70 ℃ of temperature of reaction, reaction times 1～14h, alkaline matter consumption are 1～5 times of raw materials quality, solvent load is 0.8～10 times of raw materials quality;
(2) to the intermediate 4,4 of step (1) '-add aqueous solvent, alkaline matter and auxiliary agent in the toluylene diformazan cyanogen, reaction generates 4,4 '-stilbenedicarboxylicacid acid; Wherein, alkaline matter is NaOH, KOH, Na
2CO
3, K
2CO
3, a kind of in the pyridine, auxiliary agent is a kind of in tetramethyl ammonium chloride, 4 bromide, Tetrabutyl amonium bromide, the benzyltriethylammoinium chloride, 70～190 ℃ of temperature of reaction, reaction times 7～28h, the alkaline matter consumption of every mole of intermediate is 1～9mol, the consumption of water is 2～10 times of intermediate quality, and auxiliary dosage is 0.02～2 times of intermediate quality.
More specifically, step (1) can be carried out in the four-necked bottle that thermometer, reflux condensing tube, agitator are housed, and reaction generally is controlled under 1～70 ℃, normal pressure carries out 1～14h, and reaction process is led to nitrogen protection.Preferred 1～50 ℃ of temperature of reaction, most preferably 1～30 ℃; Preferred 1～10h of reaction times, most preferably 1～7h.Utilizable solvent comprises benzene,toluene,xylene, chlorobenzene, dichlorobenzene, ethyl acetate, N, dinethylformamide, N,N-dimethylacetamide and acetone, ethyl acetate, N, dinethylformamide, chlorobenzene, dimethylbenzene.The consumption of solvent is generally 0.8～10 times of raw materials quality, is preferably 1～5 times.The example of operable alkaline matter comprises NaOH, KOH, Na
2CO
3, K
2CO
3And pyridine, preferred NaOH, KOH, Na
2CO
3The consumption of alkaline matter is generally 1～5 times of raw materials quality, is preferably 1～3 times.
Step (2) comprises add aqueous solvent, alkaline matter and auxiliary agent in the intermediate of step (1), reaction generates 4,4 '-stilbenedicarboxylicacid acid.Generally be under 70～190 ℃ of temperature, to carry out 7～28h.Preferred 90～180 ℃ of temperature of reaction, most preferably 110～160 ℃; Preferred 10～20h of reaction times, most preferably 12～16h.The example of operable alkaline matter comprises NaOH, KOH, Na
2CO
3, K
2CO
3And pyridine.The consumption of alkaline matter is generally every mole of intermediate with 1～9mol alkaline matter, is preferably 2～7mol.The consumption of aqueous solvent is generally 2～10 times of intermediate quality, and preferred 2～7 times, most preferably 2～5 times.Auxiliary agent can be selected from tetramethyl ammonium chloride, 4 bromide, Tetrabutyl amonium bromide and benzyltriethylammoinium chloride.The consumption of auxiliary agent is generally 0.02～2 of intermediate quality, and is preferred 0.03～1, and most preferably 0.03～0.8.
The inventive method can further include step (3), promptly after the reaction of step (2) finishes, and heat filtering, the filtrate cooling adds acid, and to be adjusted to the pH value be 2～7, cold filtration, the mother liquor drying obtains product.
The example of operable acid comprises hydrochloric acid, sulfuric acid, methylsulphonic acid, Phenylsulfonic acid, tosic acid and Witco 1298 Soft Acid, preferred hydrochloric acid, sulfuric acid; The pH value is advisable with 2～7, and is preferred 3～6, and most preferably 4～6.
Filter with the dry common process that adopts and get final product.
Preparation method's provided by the invention superiority shows: reaction conditions gentleness, yield height, product purity height, production process does not produce waste water and gas, pollutes little.
Embodiment
Further explain the present invention in the mode of embodiment below, but the present invention is not limited to these embodiment.
Intermediate 4,4 '-preparation of toluylene diformazan cyanogen
Embodiment 1
In the four-necked bottle of the 500mL that thermometer, reflux condensing tube, agitator are housed, add cyano group benzyl chloride 100g (0.66mol), toluene 120mL, logical nitrogen protection, whipping temp controls to 24 ℃, divides 6 batches to add Na in 30min
2CO
380 (0.75mol) react 8h then under this temperature.Cooling after reaction finishes is filtered, is washed, and obtains intermediate 58.3g, yield 76.81%.
Embodiment 2
In the four-necked bottle of the 500mL that thermometer, reflux condensing tube, agitator are housed; adding is to cyano-benzyl bromide 129g (0.66mol), ethyl acetate 90mL; logical nitrogen protection; whipping temp controls to 16 ℃; in 30min, divide 6 batches and add NaOH65 (1.63mol), under this temperature, react 8h then.Washing is filtered in cooling after reaction finishes, and obtains intermediate 61.5g, yield 81.02%.
Embodiment 3
In the four-necked bottle of the 500mL that thermometer, reflux condensing tube, agitator are housed; adding is to cyano group benzyl chloride 100g (0.66mol), N; dinethylformamide 140mL; logical nitrogen protection; whipping temp controls to 2 ℃; in 30min, divide 6 batches and add KOH125 (2.23mol), under this temperature, react 5.5h then.Washing is filtered in cooling after reaction finishes, and obtains intermediate 61g, yield 80.36%.
Embodiment 4
In the four-necked bottle of the 500mL that thermometer, reflux condensing tube, agitator are housed; adding is led to nitrogen protection to cyano-iodine benzyl 160g (0.66mol), dimethylbenzene 90mL, and whipping temp controls to 58 ℃; in 30min, divide 6 batches and add KOH125 (2.23mol), under this temperature, react 6h then.Washing is filtered in cooling after reaction finishes, and obtains intermediate 62.5g, yield 82.34%.
Embodiment 5
In the four-necked bottle of the 500mL that thermometer, reflux condensing tube, agitator are housed; adding is led to nitrogen protection to cyano group benzyl chloride 100g (0.66mol), acetone 170mL, and whipping temp controls to 20 ℃; in 30min, divide 5 batches and add KOH 130g (2.32mol), under this temperature, react 9h then.Washing is filtered in cooling after reaction finishes, and obtains intermediate 39g, yield 51.38%.
Embodiment 6
In the four-necked bottle of the 500mL that thermometer, reflux condensing tube, agitator are housed; adding is to cyano-benzyl bromide 129g (0.66mol), dimethylbenzene 160mL; logical nitrogen protection; whipping temp controls to 10 ℃; in 30min, drip adding pyridine 180g (2.28mol), under this temperature, react 7h then.Washing is filtered in cooling after reaction finishes, and obtains intermediate 59g, yield 77.73%.
Product 4,4 '-preparation of stilbenedicarboxylicacid acid
Embodiment 7
In the 250mL reactor, adding intermediate 4,4 '-toluylene diformazan cyanogen 36g (0.16mol), water 150mL, whipping temp controls to 130 ℃, add NaOH30g (0.75mol), benzyltriethylammoinium chloride 3g (0.01mol) reacts 15h then under this temperature.Heat filtering after reaction finishes, the filtrate cooling adds hydrochloric acid, and transferring to the pH value is 6, cold filtration, drying obtains product 34g, yield 81.15%.
Embodiment 8
In the 250mL reactor, adding intermediate 4,4 '-toluylene diformazan cyanogen 36g (0.16mol), water 100mL, whipping temp controls to 190 ℃, adds Na
2CO
380g (0.75mol), 4 bromide 5g (0.02mol) reacts 13h then under this temperature.Heat filtering after reaction finishes, the filtrate cooling adds sulfuric acid, and transferring to the pH value is 5, cold filtration, drying obtains product 33g, yield 78.80%.
Embodiment 9
In the 250mL reactor, adding intermediate 4,4 '-toluylene diformazan cyanogen 36g (0.16mol), water 100mL, whipping temp controls to 160 ℃, adds KOH41g (0.73mol), and tetramethyl ammonium chloride 3g (0.03mol) reacts 28h then under this temperature.Heat filtering after reaction finishes, the filtrate cooling adds tosic acid, and transferring to the pH value is 7, cold filtration, drying obtains product 32.5g, yield 77.56%.
Embodiment 10
In the 250mL reactor, adding intermediate 4,4 '-toluylene diformazan cyanogen 36g (0.16mol), water 100mL, whipping temp controls to 90 ℃, adds pyridine 80g (1.1mol), and Tetrabutyl amonium bromide 7g (0.02mol) reacts 12h then under this temperature.Heat filtering after reaction finishes, filtrate cooling methylate sulfonic acid, transferring to the pH value is 4, cold filtration, drying obtains product 35g, yield 83.53%.
Claims (5)
1, a kind of preparation 4,4 '-method of stilbenedicarboxylicacid acid, this method comprises following each step:
(1) raw material under the dissolved state, adds alkaline matter to cyano group halogen benzyl in solvent, reaction generation intermediate 4,4 '-toluylene diformazan cyanogen; Wherein, raw material is to the cyano group benzyl chloride, to cyano-benzyl bromide, a kind of in the cyano-iodine benzyl to cyano group halogen benzyl, solvent is benzene,toluene,xylene, chlorobenzene, dichlorobenzene, ethyl acetate, N, dinethylformamide, N, a kind of in N-N,N-DIMETHYLACETAMIDE, the acetone, alkaline matter is NaOH, KOH, Na
2CO
3, K
2CO
3, a kind of in the pyridine, 1～70 ℃ of temperature of reaction, reaction times 1～14h, alkaline matter consumption are 1～5 times of raw materials quality, solvent load is 0.8～10 times of raw materials quality;
(2) to the intermediate 4,4 of step (1) '-add aqueous solvent, alkaline matter and auxiliary agent in the toluylene diformazan cyanogen, reaction generates 4,4 '-stilbenedicarboxylicacid acid; Wherein, alkaline matter is NaOH, KOH, Na
2CO
3, K
2CO
3, a kind of in the pyridine, auxiliary agent is a kind of in tetramethyl ammonium chloride, 4 bromide, Tetrabutyl amonium bromide, the benzyltriethylammoinium chloride, 70～190 ℃ of temperature of reaction, reaction times 7～28h, the alkaline matter consumption of every mole of intermediate is 1～9mol, the consumption of water is 2～10 times of intermediate quality, and auxiliary dosage is 0.02～2 times of intermediate quality.
2, according to the method for claim 1, it is characterized in that, the condition of carrying out of step (1) is 1～30 ℃ of a temperature of reaction, reaction times 1～7h, the alkaline matter consumption is 1～3 times of raw materials quality, and solvent load is 1～5 times of raw materials quality, and solvent is ethyl acetate, N, a kind of in dinethylformamide, chlorobenzene, the dimethylbenzene, alkaline matter is NaOH, KOH, Na
2CO
3In a kind of.
3, according to the method for claim 1, it is characterized in that, the condition of carrying out of step (2) is 110～160 ℃ of temperature of reaction, reaction times 12～16h, the alkaline matter consumption of every mole of intermediate is 2～7mol, the consumption of water is 2～5 times of intermediate quality, and auxiliary dosage is 0.03～0.8 times of intermediate quality.
4, according to each method of claim 1～3, it is characterized in that, after the reaction that further comprises step (2) finishes, heat filtering, the filtrate cooling adds acid and is adjusted to pH 2～7, cold filtration, the mother liquor drying obtains product; Described acid is a kind of in hydrochloric acid, sulfuric acid, methylsulphonic acid, Phenylsulfonic acid, tosic acid, the Witco 1298 Soft Acid.
According to the method for claim 4, it is characterized in that 5, described acid is hydrochloric acid or sulfuric acid, being adjusted to the pH value is 4～6.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101802678A CN101407455A (en) | 2008-12-03 | 2008-12-03 | Preparation method of 4, 4' -stilbene dicarboxylic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101802678A CN101407455A (en) | 2008-12-03 | 2008-12-03 | Preparation method of 4, 4' -stilbene dicarboxylic acid |
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|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093149A (en) * | 2010-12-08 | 2011-06-15 | 天津理工大学 | Method for preparing carboxylic acid compound by promoting rapid hydrolysis of cyan |
| CN118271732A (en) * | 2024-05-08 | 2024-07-02 | 天津大学 | Polyethylene breakdown field intensity increasing method based on nanoparticle grafted voltage stabilizer |
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2008
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Cited By (3)
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| CN102093149A (en) * | 2010-12-08 | 2011-06-15 | 天津理工大学 | Method for preparing carboxylic acid compound by promoting rapid hydrolysis of cyan |
| CN118271732A (en) * | 2024-05-08 | 2024-07-02 | 天津大学 | Polyethylene breakdown field intensity increasing method based on nanoparticle grafted voltage stabilizer |
| CN118271732B (en) * | 2024-05-08 | 2024-10-25 | 天津大学 | Polyethylene breakdown field intensity increasing method based on nanoparticle grafted voltage stabilizer |
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