CN102675077A - 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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- CN102675077A CN102675077A CN2012101365352A CN201210136535A CN102675077A CN 102675077 A CN102675077 A CN 102675077A CN 2012101365352 A CN2012101365352 A CN 2012101365352A CN 201210136535 A CN201210136535 A CN 201210136535A CN 102675077 A CN102675077 A CN 102675077A
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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 30-100DEG 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 Verospirone 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, be dissolved in cold alcohol and water hardly for carbon and dithiocarbonic anhydride.At present, domestic production 2,3,5,6-tetrachlorobenzoquinone is the Resorcinol chlorination.Because Resorcinol price height and market value are 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 use 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 influences the ordinary production of downstream producer.Seek alternative materials and produce 2,3,5,6-tetrachlorobenzoquinone is an industry problem demanding prompt solution.
Summary of the invention:
It is a kind of 2,3 that the technical problem that the present invention will solve provides, and two kinds of preparing methods of 5,6-tetrachlorobenzoquinone substitute Resorcinol with PARA AMINOPHENOL, have advantages such as raw materials cost is low, auxiliary material is easy to get, reacted solvent is reusable.
The present invention realizes through following technical scheme:
Method one: 2,3,5, two kinds of preparing methods of 6-tetrachlorobenzoquinone may further comprise the steps:
(1) under agitation condition, PARA AMINOPHENOL is dissolved in the organic solvent, PARA AMINOPHENOL is 1mmol:3-20ml with the organic solvent ratio, feeds chlorine then; Under 30-100 ℃, react, detect in the material PARA AMINOPHENOL less than 0.5%, 2,3; 5,6-tetrachloro p-aminophenyl quinone stopped logical chlorine greater than 95% o'clock, and the 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 PARA 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 title product finishes greater than reaction in 95% o'clock, 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, and hydrolysis in temperature is 80-250 ℃ detects diazonium thing in the material less than 0.5%; Title product finishes greater than reaction in 95% o'clock, and material is cooled to below 30 ℃, carries out solid-liquid separation; It is 5 that solid is washed with water to pH value, and oven dry obtains high-load 2,3; 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 acetate, 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; PARA AMINOPHENOL is dissolved in the organic acid soln, adds vitriol then, in 0-50 ℃, drop into the diazonium agent in batches; Carry out diazotization reaction; PARA AMINOPHENOL in the detection material is less than 0.5%, and title product finishes greater than reaction in 95% o'clock, obtains PARA AMINOPHENOL diazonium thing;
The mol ratio of PARA 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, feed chlorine and carry out chlorination reaction, detect PARA AMINOPHENOL diazonium thing in the material less than 0.5%, title product finishes greater than reaction in 95% o'clock; Material is cooled to below 30 ℃, carries 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 PARA AMINOPHENOL and chlorine is 1:4.5-7;
(6) it is in 5-30% 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; Hydrolysis in temperature is 80-100 ℃, the chlorophenosic acid diazonium salt in the detection material are less than 0.5%, and title product finishes greater than reaction in 95% o'clock, and 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 high-load 2,3; 5,6-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 an acetic acid soln, 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:
Method one is to adopt HPLC to detect with the detection described in the method two, and promptly HPLC detects.
Embodiment:
Method one embodiment 1
2,3, two kinds of preparing methods of 5,6-tetrachlorobenzoquinone may further comprise the steps:
(1) under agitation condition, PARA AMINOPHENOL is dissolved in the chlorobenzene, PARA AMINOPHENOL is 1mmol:5ml with the chlorobenzene ratio, feeds chlorine then; Under 50 ℃, react, adopt HPLC to detect PARA AMINOPHENOL less than 0.5%, title product was greater than 95% o'clock; Reaction finishes to stop logical chlorine, and the chlorine in the material is caught up with to the greatest extent with air or nitrogen, obtains 2; 3,5,6-tetrachloro p-aminophenyl quinone;
The mol ratio of PARA 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 title product finishes greater than reaction in 95% o'clock, 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, to be hydrolysis in 100 ℃ in temperature that the diazonium thing that step (2) is obtained joins concentration, adopts HPLC to detect the diazonium thing less than 0.5%, and title product was greater than 95% o'clock; 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, and oven dry obtains high-load 2,3; 5,6-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 preparing methods of 5,6-tetrachlorobenzoquinone may further comprise the steps:
(1) under agitation condition, PARA AMINOPHENOL is dissolved into (can mix by arbitrary proportion, present embodiment by volume 1:1 mixes) in chlorobenzene and the ethyl acetate mixture, PARA AMINOPHENOL is 1mmol:10 ml with the chlorobenzene ratio; Feed chlorine then, 60 ℃ of reactions down, adopt HPLC to detect PARA AMINOPHENOL less than 0.5%, title product was greater than 95% o'clock; Reaction finishes to stop logical chlorine, and the chlorine in the material is caught up with to the greatest extent with air or nitrogen, obtains 2; 3,5,6-tetrachloro p-aminophenyl quinone;
The mol ratio of PARA 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 title product finishes greater than reaction in 95% o'clock, 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 by arbitrary proportion, 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, adopts HPLC to detect in the material diazonium thing less than 0.5%; Title product judges that greater than 95% o'clock reaction finishes, and is cooled to below 30 ℃, carries out solid-liquid separation; It is 5 that solid is washed with water to pH value, and oven dry obtains high-load 2,3; 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 preparing methods of 5,6-tetrachlorobenzoquinone may further comprise the steps:
(1) under agitation condition, PARA AMINOPHENOL is dissolved into (can mix by arbitrary proportion, present embodiment by volume 1:1 mixes) in chlorobenzene and the ethyl acetate mixture, PARA AMINOPHENOL is 1mmol:15ml with the chlorobenzene ratio; Feed chlorine then, 70 ℃ of reactions down, adopt HPLC to detect PARA AMINOPHENOL less than 0.5%, title product was greater than 95% o'clock; Reaction finishes to stop logical chlorine, and the chlorine in the material is caught up with to the greatest extent with air or nitrogen, obtains 2; 3,5,6-tetrachloro p-aminophenyl quinone;
The mol ratio of PARA 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 title product finishes greater than reaction in 95% o'clock, 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 by arbitrary proportion, 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, adopts HPLC to detect in the material diazonium thing less than 0.5%; Title product judges that greater than 95% o'clock reaction finishes, and is cooled to below 30 ℃, carries out solid-liquid separation; It is 5 that solid is washed with water to pH value, and oven dry obtains high-load 2,3; 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 preparing methods of 5,6-tetrachlorobenzoquinone may further comprise the steps:
(4) under agitation condition, PARA AMINOPHENOL is dissolved into (strength of solution is 60%) in the acetic acid soln solution, add ferrous sulfate then; In 20 ℃, drop into nitric acid (strength of solution is 55%) in batches; Carry out diazotization reaction, PARA AMINOPHENOL is less than 0.5% in the employing HPLC detection material, and title product was greater than 95% o'clock; Judge that reaction finishes, and obtains PARA AMINOPHENOL diazonium thing;
The mol ratio of PARA 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, feed chlorine and carry out chlorination reaction, adopt HPLC to detect that PARA AMINOPHENOL diazonium thing is less than 0.5% in the material, title product was greater than 95% o'clock; Judge that reaction finishes, material cooled to below 30 ℃ that carry 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 PARA AMINOPHENOL and chlorine is 1:5;
(6) it is in 15% the hydrochloric acid, to be hydrolysis in 80 ℃ in temperature that the chlorophenosic acid diazonium salt and the part 2,3 that step (5) are obtained, 5,6-tetrachlorobenzoquinone join strength of solution; Adopt HPLC to detect in the material 2,3,5,6-chlorophenosic acid diazonium salt is less than 0.5%, and title product was greater than 95% o'clock; Judge that reaction finishes, material is cooled to below 30 ℃ that carry out solid-liquid separation, it is 5 that solid is washed with water to pH value, oven dry obtains high-load 2; 3,5,6-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 preparing methods of 5,6-tetrachlorobenzoquinone may further comprise the steps:
(4) under agitation condition, PARA AMINOPHENOL is dissolved into (strength of solution is 40%) in the acetic acid soln solution, add ferrous sulfate, copper sulfate, sodium sulfate mixture (can arbitrary proportion) then; In 25 ℃, drop into Sodium Nitrite in batches; Carry out diazotization reaction, PARA AMINOPHENOL is less than 0.5% in the employing HPLC detection material, and title product was greater than 95% o'clock; Judge that reaction finishes, and obtains PARA AMINOPHENOL diazonium thing;
The mol ratio of PARA 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, feed chlorine and carry out chlorination reaction, adopt HPLC to detect that PARA AMINOPHENOL diazonium thing is less than 0.5% in the material, title product was greater than 95% o'clock; Reaction cools to material below 30 ℃ after finishing, and carries out solid-liquid separation, and 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 PARA AMINOPHENOL and chlorine is 1:6;
(6) it is in 20% the hydrochloric acid, to be hydrolysis in 90 ℃ in temperature that the chlorophenosic acid diazonium salt and the part 2,3 that step (5) are obtained, 5,6-tetrachlorobenzoquinone join strength of solution; Adopt HPLC to detect in the material 2,3,5,6-chlorophenosic acid diazonium salt is less than 0.5%, and title product was greater than 95% o'clock; Judge that reaction finishes, material is cooled to below 30 ℃ that carry out solid-liquid separation, it is 5 that solid is washed with water to pH value, oven dry obtains high-load 2; 3,5,6-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 preparing methods of 5,6-tetrachlorobenzoquinone may further comprise the steps:
(4) under agitation condition, PARA AMINOPHENOL is dissolved into (strength of solution is 70%) in the acetic acid soln solution, add vitriolate of tartar then; In 35 ℃, drop into nitric acid (strength of solution is 70%) in batches; Carry out diazotization reaction, PARA AMINOPHENOL was less than 0.5% o'clock in the employing HPLC detection material, and title product is greater than 95%; Judge that reaction finishes, and obtains PARA AMINOPHENOL diazonium thing;
The mol ratio of PARA 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, feed chlorine and carry out chlorination reaction, adopt HPLC to detect that PARA AMINOPHENOL diazonium thing is less than 0.5% in the material, title product was greater than 95% o'clock; Reaction cools to material below 30 ℃ after finishing, and carries out solid-liquid separation, and 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 PARA AMINOPHENOL and chlorine is 1:7;
(6) it is in 20% the hydrochloric acid, to be hydrolysis in 95 ℃ in temperature that the chlorophenosic acid diazonium salt and the part 2,3 that step (5) are obtained, 5,6-tetrachlorobenzoquinone join strength of solution; Adopt HPLC to detect in the material 2,3,5,6-chlorophenosic acid diazonium salt is less than 0.5%, and title product was greater than 95% o'clock; Judge that reaction finishes, material is cooled to below 30 ℃ that carry out solid-liquid separation, it is 5 that solid is washed with water to pH value, oven dry obtains high-load 2; 3,5,6-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, two kinds of preparing methods of 6-tetrachlorobenzoquinone is characterized in that may further comprise the steps:
(1) under agitation condition, PARA AMINOPHENOL is dissolved in the organic solvent, PARA AMINOPHENOL is 1mmol:3-20ml with the organic solvent ratio; Feed chlorine then, under 30-100 ℃, react, detect in the material PARA AMINOPHENOL less than stopping logical chlorine at 0.5% o'clock; 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 PARA 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 reaction in 0.5% o'clock, 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 ℃, and the diazonium thing that detects in the material finishes less than reaction in 0.5% o'clock; 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 high-load 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, two kinds of preparing methods of 5,6-tetrachlorobenzoquinone is characterized in that: the organic solvent described in the step (1) is a kind of in acetate, chlorobenzene, ethyl acetate or the methyl acetate, or two kinds or two or more mixture.
3. as claimed in claim 12,3, two kinds of preparing methods 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, two kinds of preparing methods 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, two kinds of preparing methods of 5,6-tetrachlorobenzoquinone is characterized in that: said detection is to adopt HPLC to detect, and promptly HPLC detects.
6.2,3,5, two kinds of preparing methods of 6-tetrachlorobenzoquinone is characterized in that may further comprise the steps:
(4) under agitation condition, PARA AMINOPHENOL is dissolved in the organic acid soln, add vitriol then; In 0-50 ℃, drop into the diazonium agent in batches; Carry out diazotization reaction, the PARA AMINOPHENOL that detects in the material finishes less than reaction in 0.5% o'clock, obtains PARA AMINOPHENOL diazonium thing;
The mol ratio of PARA 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, feed chlorine and carry out chlorination reaction, the PARA AMINOPHENOL diazonium thing that detects in the material finishes less than reaction in 0.5% o'clock, and 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 PARA AMINOPHENOL and chlorine is 1:4.5-7;
(6) it is in 5-30% 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; Hydrolysis in temperature is 80-100 ℃, the chlorophenosic acid diazonium salt that detects in the material finishes less than reaction in 0.5% o'clock, and 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 high-load 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, two kinds of preparing methods of 5,6-tetrachlorobenzoquinone is characterized in that: the organic acid soln described in the step (4) is an acetic acid soln, and strength of solution is 30-90%.
8. as claimed in claim 62; 3; 5; Two kinds of preparing methods of 6-tetrachlorobenzoquinone is characterized in 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.
9. as claimed in claim 62,3, two kinds of preparing methods 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, two kinds of preparing methods of 5,6-tetrachlorobenzoquinone is characterized in that: said detection is to adopt HPLC to detect, and promptly HPLC detects.
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| CN106866399A (en) * | 2017-03-03 | 2017-06-20 | 南通书创药业科技有限公司 | Tetrachloroquinone and preparation method thereof |
| CN107653273A (en) * | 2017-04-28 | 2018-02-02 | 青岛科技大学 | A kind of method of the benzoquinones of 5 alkylamino of double 2,3 dimethyl of enzyme one pot process 1,4 |
| CN112694393A (en) * | 2020-12-25 | 2021-04-23 | 浙江神洲药业有限公司 | Preparation method of regenerated chloranil |
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| CN106966882A (en) * | 2017-03-28 | 2017-07-21 | 许克宇 | A kind of preparation method of tetrachloroquinone |
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| CN1105976A (en) * | 1993-10-25 | 1995-08-02 | 赫彻斯特股份公司 | Preparation of tetrachlor-1,4-benzochinon |
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2012
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0469353A (en) * | 1990-07-09 | 1992-03-04 | Honsyu Kagaku Kogyo Kk | Production of tetrachloro-1,4-benzoquinone |
| JPH069353A (en) * | 1992-03-10 | 1994-01-18 | Goldwell Ag | Hair bleach composition and preparation thereof |
| CN1105976A (en) * | 1993-10-25 | 1995-08-02 | 赫彻斯特股份公司 | Preparation of tetrachlor-1,4-benzochinon |
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| 朱旭容等: "四氯苯醌的合成", 《南京化工大学学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866399A (en) * | 2017-03-03 | 2017-06-20 | 南通书创药业科技有限公司 | Tetrachloroquinone and preparation method thereof |
| CN107653273A (en) * | 2017-04-28 | 2018-02-02 | 青岛科技大学 | A kind of method of the benzoquinones of 5 alkylamino of double 2,3 dimethyl of enzyme one pot process 1,4 |
| 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 |
| CN112694393A (en) * | 2020-12-25 | 2021-04-23 | 浙江神洲药业有限公司 | Preparation method of regenerated chloranil |
| 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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