CN102675077B - Two preparation methods of 2, 3, 5 6-chloranil - Google Patents
Two preparation methods of 2, 3, 5 6-chloranil Download PDFInfo
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- CN102675077B CN102675077B CN 201210136535 CN201210136535A CN102675077B CN 102675077 B CN102675077 B CN 102675077B CN 201210136535 CN201210136535 CN 201210136535 CN 201210136535 A CN201210136535 A CN 201210136535A CN 102675077 B CN102675077 B CN 102675077B
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- Prior art keywords
- tetrachlorobenzoquinone
- diazonium
- aminophenol
- acid
- chlorine
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims abstract description 106
- 239000012954 diazonium Substances 0.000 claims abstract description 64
- 239000000463 material Substances 0.000 claims abstract description 62
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims abstract description 44
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000460 chlorine Substances 0.000 claims abstract description 33
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000006193 diazotization reaction Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 23
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 150000001989 diazonium salts Chemical class 0.000 claims description 20
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims description 18
- -1 2,3,5,6-tetrachloro p-aminophenyl quinone Chemical compound 0.000 claims description 16
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 16
- 238000013019 agitation Methods 0.000 claims description 15
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical group [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 150000007524 organic acids Chemical class 0.000 claims description 9
- 235000010288 sodium nitrite Nutrition 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 238000005660 chlorination reaction Methods 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 208000006558 Dental Calculus Diseases 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 235000010755 mineral Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229940095054 ammoniac Drugs 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 12
- 238000001816 cooling Methods 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003814 drug Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical group C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- 239000002170 aldosterone antagonist Substances 0.000 description 1
- 229940083712 aldosterone antagonist Drugs 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses two preparation methods of 2, 3, 5, 6-chloranil, wherein one method comprises the following steps of: (1) in case of stirring, dissolving p-aminophenol into organic solvent, introducing chlorine, reacting at the temperature of 30-100 DEG C, when the p-aminophenol is detected to be less than 0.5%, and the target product is detected to be more than 95%, stopping introducing the chlorine, and exhausting the chlorine in material; (2) cooling the material in the step (1) to 0-30 DEG C, and carrying out diazotization reaction to obtain diazonium; and (3) adding the diazonium obtained in the step (2) into 15-80% of inorganic acid solution, hydrolyzing at the temperature of 80-250 DEG C, cooling to be less than 30 DEG C after hydrolysis reaction, carrying out solid-liquid separation, washing the solid with water till the pH value is 5, and drying to obtain the high-content 2, 3, 5, 6-chloranil.
Description
Technical field:
The invention belongs to chemical field, be specifically related to 2,3, the preparation of 5,6-tetrachlorobenzoquinone.
Background technology:
2,3,5,6-tetrachlorobenzoquinone is the important intermediate of dyestuff, medicine industry, in medicine industry, can be used for the production of anti-malignant-tumor agent solaziquonum, the antisterone of aldosterone antagonist medicine.2,3,5,6-tetrachlorobenzoquinone is golden yellow lobate crystallization, 290 ℃ of fusing points.Be dissolved in ether, be slightly soluble in alcohol, be insoluble in chloroform, tetrachloro for carbon and dithiocarbonic anhydride, be dissolved in hardly cold alcohol and water.At present, domestic production 2,3,5,6-tetrachlorobenzoquinone is the Resorcinol chlorination process.Because the Resorcinol price is high and market value is very unstable in recent years, cause the production output of tetrachlorobenzoquinone restricted, the enterprise that makes that the Resorcinol price is high sometimes can't be with it as raw material production 2,3,5,6-tetrachlorobenzoquinone, otherwise must cause manufacturing enterprise's loss of capital, often therefore cause 2,3, the strained market supply of 5,6-tetrachlorobenzoquinone affects the normal production of downstream producer.Seek alternative materials and produce 2,3,5,6-tetrachlorobenzoquinone is industry problem demanding prompt solution.
Summary of the invention:
It is a kind of 2,3 that the technical problem to be solved in the present invention provides, and two kinds of preparation methods of 5,6-tetrachlorobenzoquinone substitute Resorcinol with p-aminophenol, have the advantages such as raw materials cost is low, auxiliary material is easy to get, reacted solvent is reusable.
The present invention is achieved through the following technical solutions:
Method one: 2,3,5, two kinds of preparation methods of 6-tetrachlorobenzoquinone may further comprise the steps:
(1) under agitation condition, p-aminophenol is dissolved in the organic solvent, p-aminophenol is 1mmol:3-20ml with the organic solvent ratio, then pass into chlorine, react under 30-100 ℃, p-aminophenol is less than 0.5% in the detection material, 2,3,5,6-tetrachloro p-aminophenyl quinone stops logical chlorine greater than 95% the time, chlorine in the material is caught up with to the greatest extent with air or nitrogen, obtained 2,3,5,6-tetrachloro p-aminophenyl quinone;
The mol ratio of p-aminophenol and chlorine is 1:4.5-7;
(2) under agitation condition, the material of step (1) is cooled to 0-30 ℃, drop into the diazonium agent in batches, detect in the material 2,3,5,6-tetrachloro p-aminophenyl quinone is less than 0.5%, and target product reaction greater than 95% time finishes, and material is cooled to carries out solid-liquid separation below 20 ℃ and obtain the diazonium thing;
2,3, the mol ratio of 5,6-tetrachloro p-aminophenyl quinone and diazonium agent is 1:1-1.25;
(3) it is in 15-80% the inorganic acid aqueous solution that the diazonium thing that step (2) is obtained joins concentration, hydrolysis in temperature is 80-250 ℃ detects diazonium thing in the material less than 0.5%, and target product reaction greater than 95% time finishes, material is cooled to below 30 ℃, carry out solid-liquid separation, it is 5 that solid is washed with water to pH value, and oven dry obtains 2 of high-content, 3,5,6-tetrachlorobenzoquinone, molar yield are 90-97%;
The diazonium thing with the ratio of mineral acid is: 1mmol:4-20ml.
The further improvement project of the present invention is, the organic solvent described in the step (1) is a kind of in acetic acid, chlorobenzene, ethyl acetate or the methyl acetate, or two kinds or two or more mixture.
The further improvement project of the present invention is step (2)
InDescribed diazonium agent is Sodium Nitrite or nitric acid, salpeter solution concentration 50-70%.
The further improvement project of the present invention is, the inorganic acid solution described in the step (3) is a kind of in sulphuric acid soln, hydrochloric acid soln or the phosphoric acid solution, or two kinds or three kinds of mixtures.
Reaction process:
(4) under agitation condition, p-aminophenol is dissolved in the organic acid soln, then add vitriol, in 0-50 ℃, drop into the diazonium agent in batches, carry out diazotization reaction, detect p-aminophenol in the material less than 0.5%, target product reaction greater than 95% time finishes, and obtains p-aminophenol diazonium thing;
The mol ratio of p-aminophenol and vitriol is 1:1-2, with the mol ratio of diazonium agent be 1:1-1.25, with organic acid than being 1mmol:2-20ml;
(5) in the material of step (4) under 80-100 ℃ of conditions, pass into chlorine and carry out chlorination reaction, detect p-aminophenol diazonium thing in the material less than 0.5%, target product finishes greater than 95% time reaction, and material is cooled to below 30 ℃, carries out solid-liquid separation, mother liquor reclaims the solvent of doing step (4), obtain 2,3,5,6-chlorophenosic acid diazonium salt and part 2,3,5,6-tetrachlorobenzoquinone;
The mol ratio of p-aminophenol and chlorine is 1:4.5-7;
(6) the chlorophenosic acid diazonium salt that step (5) is obtained and part 2,3,5, it is in 5-30% the hydrochloric acid that 6-tetrachlorobenzoquinone joins strength of solution, and hydrolysis in temperature is 80-100 ℃ detects chlorophenosic acid diazonium salt in the material less than 0.5%, target product finishes greater than 95% time reaction, and material is cooled to below 30 ℃, carries out solid-liquid separation, it is 5 that solid is washed with water to pH value, oven dry obtains 2,3,5 of high-content, 6-tetrachlorobenzoquinone, molar yield are 90-97%
Chlorophenosic acid diazonium salt and part 2,3,5,6-tetrachlorobenzoquinone is 1mmol:4-20ml with the ratio of hydrochloric acid.
The further improvement project of the present invention is, the organic acid soln described in the step (4) is acetic acid solution, and strength of solution is more than the 30-99%.
The further improvement project of the present invention is that the vitriol described in the step (4) is a kind of or two kinds or the two or more mixture in ferrous sulfate, copper sulfate, sodium sulfate, vitriolate of tartar, sulfate of ammoniac, sal epsom, Tai-Ace S 150 or the zinc sulfate.
The further improvement project of the present invention is step (5)
InDescribed diazonium agent is Sodium Nitrite or nitric acid, salpeter solution concentration 50-70%.
Reaction process:
Detection described in method one and the method two is to adopt HPLC to detect, and namely high performance liquid chromatography detects.
Embodiment:
Method one embodiment 1
2,3, two kinds of preparation methods of 5,6-tetrachlorobenzoquinone may further comprise the steps:
(1) under agitation condition, p-aminophenol is dissolved in the chlorobenzene, p-aminophenol is 1mmol:5ml with the chlorobenzene ratio, then pass into chlorine, react under 50 ℃, adopt HPLC to detect p-aminophenol less than 0.5%, target product is greater than 95% the time, reaction finishes to stop logical chlorine, chlorine in the material is caught up with to the greatest extent with air or nitrogen, obtained 2,3,5,6-tetrachloro p-aminophenyl quinone;
The mol ratio of p-aminophenol and chlorine is 1:5;
(2) under agitation condition, the material of step (1) is cooled to 10 ℃, drop into strength of solution in batches and be 60% nitric acid, carry out diazotization reaction, adopt HPLC to detect in the material 2,3,5,6-tetrachloro p-aminophenyl quinone is less than 0.5%, and target product reaction greater than 95% time finishes, and material is cooled to carries out solid-liquid separation below 20 ℃ and obtain the diazonium thing;
2,3, the mol ratio of 5,6-tetrachloro p-aminophenyl quinone and nitric acid is 1:1;
(3) it is in 30% the sulphuric acid soln that the diazonium thing that step (2) is obtained joins concentration, is hydrolysis in 100 ℃ in temperature, adopts HPLC to detect the diazonium thing less than 0.5%, target product is greater than 95% the time, judge that reaction finishes, be cooled to below 30 ℃, carry out solid-liquid separation, it is 5 that solid is washed with water to pH value, oven dry obtains 2,3,5 of high-content, 6-tetrachlorobenzoquinone, molar yield are 95%;
The diazonium thing with the ratio of mineral acid is: 1mmol:8 ml.
Method one embodiment 2
2,3, two kinds of preparation methods of 5,6-tetrachlorobenzoquinone may further comprise the steps:
(1) under agitation condition, p-aminophenol is dissolved into (can mix in any proportion, the present embodiment by volume 1:1 mixes) in chlorobenzene and the ethyl acetate mixture, p-aminophenol is 1mmol:10 ml with the chlorobenzene ratio, then passes into chlorine, 60 ℃ of lower reactions, adopt HPLC to detect p-aminophenol less than 0.5%, target product is greater than 95% the time, and reaction finishes to stop logical chlorine, and the chlorine in the material is caught up with to the greatest extent with air or nitrogen, obtain 2,3,5,6-tetrachloro p-aminophenyl quinone;
The mol ratio of p-aminophenol and chlorine is 1:6;
(2) under agitation condition, the material of step (1) is cooled to 15 ℃, drop into Sodium Nitrite in batches, carry out diazotization reaction, adopt HPLC to detect in the material 2,3,5,6-tetrachloro p-aminophenyl quinone is less than 0.5%, and target product reaction greater than 95% time finishes, and material is cooled to carries out solid-liquid separation below 20 ℃ and obtain the diazonium thing;
2,3, the mol ratio of 5,6-tetrachloro p-aminophenyl quinone and nitric acid is 1:1.1;
(3) it is (can mix in any proportion, the present embodiment by volume 1:1 mixes) in 40% the sulfuric acid and phosphoric acid solution that the diazonium thing that step (2) is obtained joins concentration, is hydrolysis in 150 ℃ in temperature, adopt HPLC to detect in the material diazonium thing less than 0.5%, target product judges that reaction finishes greater than 95% the time, be cooled to below 30 ℃, carry out solid-liquid separation, it is 5 that solid is washed with water to pH value, and oven dry obtains 2 of high-content, 3,5,6-tetrachlorobenzoquinone, molar yield are 96%;
The diazonium thing with the mixed solution ratio of sulfuric acid and phosphoric acid is: 1mmol:10 ml.
Method one embodiment 3
2,3, two kinds of preparation methods of 5,6-tetrachlorobenzoquinone may further comprise the steps:
(1) under agitation condition, p-aminophenol is dissolved into (can mix in any proportion, the present embodiment by volume 1:1 mixes) in chlorobenzene and the ethyl acetate mixture, p-aminophenol is 1mmol:15ml with the chlorobenzene ratio, then passes into chlorine, 70 ℃ of lower reactions, adopt HPLC to detect p-aminophenol less than 0.5%, target product is greater than 95% the time, and reaction finishes to stop logical chlorine, and the chlorine in the material is caught up with to the greatest extent with air or nitrogen, obtain 2,3,5,6-tetrachloro p-aminophenyl quinone;
The mol ratio of p-aminophenol and chlorine is 1:7;
(2) under agitation condition, the material of step (1) is cooled to 20 ℃, drop into strength of solution in batches and be 70% nitric acid, carry out diazotization reaction, adopt HPLC to detect in the material 2,3,5,6-tetrachloro p-aminophenyl quinone is less than 0.5%, and target product reaction greater than 95% time finishes, and material is cooled to carries out solid-liquid separation below 20 ℃ and obtain the diazonium thing;
2,3, the mol ratio of 5,6-tetrachloro p-aminophenyl quinone and nitric acid is 1:1.2;
(3) it is (can mix in any proportion, the present embodiment by volume 1:1 mixes) in 50% the sulfuric acid and phosphoric acid solution that the diazonium thing that step (2) is obtained joins concentration, is hydrolysis in 200 ℃ in temperature, adopt HPLC to detect in the material diazonium thing less than 0.5%, target product judges that reaction finishes greater than 95% the time, be cooled to below 30 ℃, carry out solid-liquid separation, it is 5 that solid is washed with water to pH value, and oven dry obtains 2 of high-content, 3,5,6-tetrachlorobenzoquinone, molar yield are 96%;
The diazonium thing with the mixed solution ratio of sulfuric acid and phosphoric acid is: 1mmol:15 ml.
Method two embodiment 4
2.1,2,3, two kinds of preparation methods of 5,6-tetrachlorobenzoquinone may further comprise the steps:
(4) under agitation condition, p-aminophenol is dissolved into (strength of solution is 60%) in the acetic acid solution solution, then add ferrous sulfate, in 20 ℃, drop into nitric acid (strength of solution is 55%) in batches, carry out diazotization reaction, adopt HPLC to detect in the material p-aminophenol less than 0.5%, target product is greater than 95% the time, judge that reaction finishes, and obtains p-aminophenol diazonium thing;
The mol ratio of p-aminophenol and ferrous sulfate is 1:1, with the mol ratio of nitric acid be 1:1.1, with organic acid than being 1mmol:10ml;
(5) in the material of step (4) under 80 ℃ of conditions, pass into chlorine and carry out chlorination reaction, adopt HPLC to detect in the material p-aminophenol diazonium thing less than 0.5%, target product judges that reaction finishes, and cools to material below 30 ℃ greater than 95% the time, carry out solid-liquid separation, mother liquor reclaims the solvent of doing step (4), obtains 2,3,5,6-chlorophenosic acid diazonium salt and part 2,3,5,6-tetrachlorobenzoquinone;
The mol ratio of p-aminophenol and chlorine is 1:5;
(6) it is in 15% the hydrochloric acid that the chlorophenosic acid diazonium salt and the part 2,3 that step (5) are obtained, 5,6-tetrachlorobenzoquinone join strength of solution, be hydrolysis in 80 ℃ in temperature, adopt HPLC to detect in the material 2,3,5,6-chlorophenosic acid diazonium salt is less than 0.5%, and target product is greater than 95% the time, judge that reaction finishes, material is cooled to below 30 ℃, carry out solid-liquid separation, it is 5 that solid is washed with water to pH value, and oven dry obtains 2,3 of high-content, 5,6-tetrachlorobenzoquinone, molar yield are 96%;
Chlorophenosic acid diazonium salt and part 2,3,5,6-tetrachlorobenzoquinone is 1mmol:10 ml with the ratio of hydrochloric acid.
Method two embodiment 5
2.1,2,3, two kinds of preparation methods of 5,6-tetrachlorobenzoquinone may further comprise the steps:
(4) under agitation condition, p-aminophenol is dissolved into (strength of solution is 40%) in the acetic acid solution solution, then add ferrous sulfate, copper sulfate, sodium sulfate mixture (can arbitrary proportion), in 25 ℃, drop into Sodium Nitrite in batches, carry out diazotization reaction, adopt HPLC to detect in the material p-aminophenol less than 0.5%, target product is greater than 95% the time, judge that reaction finishes, and obtains p-aminophenol diazonium thing;
The mol ratio of p-aminophenol and ferrous sulfate is 1:1.5, with the mol ratio of Sodium Nitrite be 1:1.15, with organic acid than being 1mmol:15ml;
(5) in the material of step (4) under 90 ℃ of conditions, pass into chlorine and carry out chlorination reaction, adopt HPLC to detect in the material p-aminophenol diazonium thing less than 0.5%, target product is greater than 95% the time, and reaction cools to material below 30 ℃ after finishing, carry out solid-liquid separation, mother liquor reclaims the solvent of doing step (4), obtains 2,3,5,6-chlorophenosic acid diazonium salt and part 2,3,5,6-tetrachlorobenzoquinone;
The mol ratio of p-aminophenol and chlorine is 1:6;
(6) it is in 20% the hydrochloric acid that the chlorophenosic acid diazonium salt and the part 2,3 that step (5) are obtained, 5,6-tetrachlorobenzoquinone join strength of solution, be hydrolysis in 90 ℃ in temperature, adopt HPLC to detect in the material 2,3,5,6-chlorophenosic acid diazonium salt is less than 0.5%, and target product is greater than 95% the time, judge that reaction finishes, material is cooled to below 30 ℃, carry out solid-liquid separation, it is 5 that solid is washed with water to pH value, and oven dry obtains 2,3 of high-content, 5,6-tetrachlorobenzoquinone, molar yield are 96%;
Chlorophenosic acid diazonium salt and part 2,3,5,6-tetrachlorobenzoquinone is 1mmol:15 ml with the ratio of hydrochloric acid.
Method two embodiment 6
2.1,2,3, two kinds of preparation methods of 5,6-tetrachlorobenzoquinone may further comprise the steps:
(4) under agitation condition, p-aminophenol is dissolved into (strength of solution is 70%) in the acetic acid solution solution, then add vitriolate of tartar, in 35 ℃, drop into nitric acid (strength of solution is 70%) in batches, carry out diazotization reaction, adopt HPLC to detect in the material p-aminophenol less than 0.5% the time, target product is greater than 95%, judge that reaction finishes, and obtains p-aminophenol diazonium thing;
The mol ratio of p-aminophenol and vitriolate of tartar is 1:1.8, with the mol ratio of nitric acid be 1:1.2, with organic acid than being 1mmol:18ml;
(5) in the material of step (4) under 95 ℃ of conditions, pass into chlorine and carry out chlorination reaction, adopt HPLC to detect in the material p-aminophenol diazonium thing less than 0.5%, target product is greater than 95% the time, and reaction cools to material below 30 ℃ after finishing, carry out solid-liquid separation, mother liquor reclaims the solvent of doing step (4), obtains 2,3,5,6-chlorophenosic acid diazonium salt and part 2,3,5,6-tetrachlorobenzoquinone;
The mol ratio of p-aminophenol and chlorine is 1:7;
(6) it is in 20% the hydrochloric acid that the chlorophenosic acid diazonium salt and the part 2,3 that step (5) are obtained, 5,6-tetrachlorobenzoquinone join strength of solution, be hydrolysis in 95 ℃ in temperature, adopt HPLC to detect in the material 2,3,5,6-chlorophenosic acid diazonium salt is less than 0.5%, and target product is greater than 95% the time, judge that reaction finishes, material is cooled to below 30 ℃, carry out solid-liquid separation, it is 5 that solid is washed with water to pH value, and oven dry obtains 2,3 of high-content, 5,6-tetrachlorobenzoquinone, molar yield are 96%;
Chlorophenosic acid diazonium salt and part 2,3,5,6-tetrachlorobenzoquinone is 1mmol:18 ml with the ratio of hydrochloric acid.
Claims (10)
1.2,3,5, the preparation method of 6-tetrachlorobenzoquinone is characterized in that may further comprise the steps:
(1) under agitation condition, p-aminophenol is dissolved in the organic solvent, p-aminophenol is 1mmol:3-20ml with the organic solvent ratio, then passes into chlorine, reacts under 30-100 ℃, detect in the material p-aminophenol and stop logical chlorine less than 0.5% the time, chlorine in the material is caught up with to the greatest extent with air or nitrogen, obtained 2,3,5,6-tetrachloro p-aminophenyl quinone;
The mol ratio of p-aminophenol and chlorine is 1:4.5-7;
(2) under agitation condition, the material of step (1) is cooled to 0-30 ℃, drop into the diazonium agent in batches, detect in the material 2,3,5,6-tetrachloro p-aminophenyl quinone finishes less than 0.5% time reaction, material is cooled to carries out solid-liquid separation below 20 ℃ and obtain the diazonium thing;
2,3, the mol ratio of 5,6-tetrachloro p-aminophenyl quinone and diazonium agent is 1:1-1.25;
(3) it is in 15-80% the inorganic acid aqueous solution that the diazonium thing that step (2) is obtained joins concentration, hydrolysis in temperature is 80-250 ℃, the diazonium thing reaction less than 0.5% time that detects in the material finishes, material is cooled to below 30 ℃, carries out solid-liquid separation, it is 5 that solid is washed with water to pH value, the oven dry obtain molar yield be 90-97% 2,3,5,6-tetrachlorobenzoquinone;
The diazonium thing with the ratio of mineral acid is: 1mmol:4-20ml.
2. as claimed in claim 12,3, the preparation method of 5,6-tetrachlorobenzoquinone is characterized in that: the organic solvent described in the step (1) is a kind of or two or more mixtures in acetic acid, chlorobenzene, ethyl acetate or the methyl acetate.
3. as claimed in claim 12,3, the preparation method of 5,6-tetrachlorobenzoquinone is characterized in that: step (2)
InDescribed diazonium agent is Sodium Nitrite or nitric acid, salpeter solution concentration 50-70%.
4. as claimed in claim 12,3, the preparation method of 5,6-tetrachlorobenzoquinone is characterized in that: the inorganic acid solution described in the step (3) is a kind of in sulphuric acid soln, hydrochloric acid soln or the phosphoric acid solution, or two kinds or three kinds of mixtures.
5. as claimed in claim 12,3, the preparation method of 5,6-tetrachlorobenzoquinone is characterized in that: described detection is to adopt high performance liquid chromatography to detect.
6.2,3,5, the preparation method of 6-tetrachlorobenzoquinone is characterized in that may further comprise the steps:
(4) under agitation condition, p-aminophenol is dissolved in the organic acid soln, then add vitriol, in 0-50 ℃, drop into the diazonium agent in batches, carry out diazotization reaction, the p-aminophenol reaction less than 0.5% time that detects in the material finishes, and obtains p-aminophenol diazonium thing;
The mol ratio of p-aminophenol and vitriol is 1:1-2, with the mol ratio of diazonium agent be 1:1-1.25, with organic acid than being 1mmol:2-20ml;
(5) in the material of step (4) under 80-100 ℃ of conditions, pass into chlorine and carry out chlorination reaction, the p-aminophenol diazonium thing reaction less than 0.5% time that detects in the material finishes, material is cooled to below 30 ℃, carry out solid-liquid separation, mother liquor reclaims the solvent of doing step (4), obtains 2,3,5,6-chlorophenosic acid diazonium salt and part 2,3,5,6-tetrachlorobenzoquinone;
The mol ratio of p-aminophenol and chlorine is 1:4.5-7;
(6) the chlorophenosic acid diazonium salt that step (5) is obtained and part 2,3,5, it is in 5-30% the hydrochloric acid that 6-tetrachlorobenzoquinone joins strength of solution, hydrolysis in temperature is 80-100 ℃, the chlorophenosic acid diazonium salt reaction less than 0.5% time that detects in the material finishes, and material is cooled to below 30 ℃, carry out solid-liquid separation, it is 5 that solid is washed with water to pH value, the oven dry obtain molar yield be 90-97% 2,3,5,6-tetrachlorobenzoquinone;
Chlorophenosic acid diazonium salt and part 2,3,5,6-tetrachlorobenzoquinone is 1mmol:4-20ml with the ratio of hydrochloric acid.
7. as claimed in claim 62,3, the preparation method of 5,6-tetrachlorobenzoquinone is characterized in that: the organic acid soln described in the step (4) is acetic acid solution, and strength of solution is 30-90%.
8. as claimed in claim 62,3, the preparation method of 5,6-tetrachlorobenzoquinone is characterized in that: the vitriol described in the step (4) is a kind of or two or more mixtures in ferrous sulfate, copper sulfate, sodium sulfate, vitriolate of tartar, sulfate of ammoniac, sal epsom, Tai-Ace S 150 or the zinc sulfate.
9. as claimed in claim 62,3, the preparation method of 5,6-tetrachlorobenzoquinone is characterized in that: step (5)
InDescribed diazonium agent is Sodium Nitrite or nitric acid, salpeter solution concentration 50-70%.
10. as claimed in claim 62,3, the preparation method of 5,6-tetrachlorobenzoquinone is characterized in that: described detection is to adopt high performance liquid chromatography to detect.
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| CN107653273B (en) * | 2017-04-28 | 2021-03-02 | 青岛科技大学 | Method for synthesizing 2, 3-dimethyl-5 alkylamino-1, 4-benzoquinone by double-enzyme one-pot method |
| CN112694393B (en) * | 2020-12-25 | 2022-06-17 | 浙江神洲药业有限公司 | Preparation method of regenerated chloranil |
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