CN101085741B - Method for synthesizing 3,4-diaminophenol - Google Patents
Method for synthesizing 3,4-diaminophenol Download PDFInfo
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- CN101085741B CN101085741B CN 200710023873 CN200710023873A CN101085741B CN 101085741 B CN101085741 B CN 101085741B CN 200710023873 CN200710023873 CN 200710023873 CN 200710023873 A CN200710023873 A CN 200710023873A CN 101085741 B CN101085741 B CN 101085741B
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- OVOZYARDXPHRDL-UHFFFAOYSA-N 3,4-diaminophenol Chemical compound NC1=CC=C(O)C=C1N OVOZYARDXPHRDL-UHFFFAOYSA-N 0.000 title claims abstract description 5
- 238000000034 method Methods 0.000 title claims abstract description 4
- 230000002194 synthesizing effect Effects 0.000 title abstract 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- IQXUIDYRTHQTET-UHFFFAOYSA-N 4-amino-3-nitrophenol Chemical compound NC1=CC=C(O)C=C1[N+]([O-])=O IQXUIDYRTHQTET-UHFFFAOYSA-N 0.000 claims abstract description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000006396 nitration reaction Methods 0.000 claims abstract description 4
- 238000006722 reduction reaction Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- 238000010189 synthetic method Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- YTICOPNSVXMERO-UHFFFAOYSA-N ethyl n-(2-phenylacetyl)carbamate Chemical class CCOC(=O)NC(=O)CC1=CC=CC=C1 YTICOPNSVXMERO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003495 polar organic solvent Substances 0.000 claims description 4
- 239000006104 solid solution Substances 0.000 claims description 4
- 238000005917 acylation reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- -1 carbethoxy benzamido Chemical group 0.000 abstract description 2
- HSCNPJOXRGUVFK-UHFFFAOYSA-N (4-acetamido-3-nitrophenyl) acetate Chemical compound CC(=O)NC1=CC=C(OC(C)=O)C=C1[N+]([O-])=O HSCNPJOXRGUVFK-UHFFFAOYSA-N 0.000 abstract 1
- JJXKDLJAHRXDIX-UHFFFAOYSA-N 1-(diethylamino)-3-[(2,3-dimethoxy-6-nitroacridin-9-yl)amino]propan-2-ol;dihydrochloride Chemical compound Cl.Cl.COC1=C(OC)C=C2C(NCC(O)CN(CC)CC)=C(C=CC(=C3)[N+]([O-])=O)C3=NC2=C1 JJXKDLJAHRXDIX-UHFFFAOYSA-N 0.000 abstract 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract 1
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000000802 nitrating effect Effects 0.000 abstract 1
- 235000011118 potassium hydroxide Nutrition 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000009835 boiling Methods 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000003851 azoles Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000000507 anthelmentic effect Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000242711 Fasciola hepatica Species 0.000 description 1
- 241000243974 Haemonchus contortus Species 0.000 description 1
- 241001137878 Moniezia Species 0.000 description 1
- 241000244206 Nematoda Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- ZVIDWFUBDDXAJA-UHFFFAOYSA-N [2-(methoxycarbonylamino)-3h-benzimidazol-5-yl] 4-fluorobenzenesulfonate Chemical compound C1=C2NC(NC(=O)OC)=NC2=CC=C1OS(=O)(=O)C1=CC=C(F)C=C1 ZVIDWFUBDDXAJA-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- REEJOFMTJPOBAY-UHFFFAOYSA-N benzene;1h-pyrrole Chemical class C=1C=CNC=1.C1=CC=CC=C1 REEJOFMTJPOBAY-UHFFFAOYSA-N 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 208000006275 fascioliasis Diseases 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229950001484 luxabendazole Drugs 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- PNPIRSNMYIHTPS-UHFFFAOYSA-N nitroso nitrate Chemical class [O-][N+](=O)ON=O PNPIRSNMYIHTPS-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Abstract
The invention relates to a method for synthesizing 3, 4- diaminophenol, comprising acylating reaction, nitration, hydrolysis and reduction. It comprises following steps: taking aminophenol as raw material, acylating with acetic anhydride taking acetate as disslovant, synthesizing carbethoxy benzamido; nitrating with nitrate, synthesizing 3- nitro- 4- acetaminophenol acetate; hydrolyzing with carbethoxy or potassium hydrate and getting 4- amino- 3- nitrophenol; reducing with entozon and getting final product. The invention is characterized by temperate reaction condition, easy operation, high productivity and suitability for industrial production.
Description
Technical field
The present invention relates to 3, the synthetic method of 4-diaminophenol belongs to the field of chemical synthesis.
Background technology
The benzene azoles (Luxabendazole) of rattling away in Shandong is the beastly dual-purpose broad-spectrum de-worming medicine of a kind of efficient, safe people, and be the medicine of anthelminthic effect the best in the benzimidazoles medicine, effective to liver fluke, dicrocoelid, moniezia, haemonchus contortus, the garden shape nematode equal altitudes of sheep.Not only anthelminthic effect is good for it, applied range, and also toxicity is little, and safe in utilization.At present, less to the rattle away R and D of azoles of Shandong benzene both at home and abroad, benzene the rattle away production of azoles in domestic Shandong can not be satisfied the demand in market far away.
3, the 4-diaminophenol is into the rattle away important intermediate of azoles of Shandong benzene.Concrete structure is as shown below:
3, the synthetic problems such as hydrolysis is incomplete, aftertreatment is difficult, cost height that exist of 4-diaminophenol, at present domestic also do not have 3, the relevant report of the synthetic method of 4-diaminophenol and patent application.
Summary of the invention
The purpose of this invention is to provide a kind of suitable suitability for industrialized production, and production cost is low, efficient is high 3,4-diaminophenol synthetic method.Of the present invention 3, the synthetic method of 4-diaminophenol may further comprise the steps:
(1) acylation reaction: in anhydrous acetic acid, reflux is reacted, and obtains the acetic acid solution to the ethoxycarbonyl phenyl-acetamides with raw material p-aminophenol and diacetyl oxide mixed dissolution;
(2) nitration reaction: drip salpeter solution in step (1) gained solution, stir and react, the gained reaction solution obtains 3-nitro-4-acetaminophenol ethyl ester solid through crystallization, filtration;
(3) hydrolysis reaction: add sodium hydroxide or potassium hydroxide solution in the solid that step (2) obtains, stir and react, the gained reaction solution obtains 4-amino-3-nitro phenol solid through crystallization, filtration;
(4) reduction reaction: to the pH value is to add iron powder or zinc powder in 1～2 the acidic solution, with its mixing and be heated to 50 ℃～100 ℃, and in the gained mixture, add step (3) gained solid solution, reflux is reacted, obtain 3,4-diaminophenol, described step (3) gained solid solution are that step (3) gained 4-amino-3-nitro phenol solid is dissolved in the solution that obtains behind the polar organic solvent.
The mol ratio of raw material p-aminophenol and diacetyl oxide is 1: 2～1: 3 in the step (1), and the temperature that reflux is reacted is 120 ℃～130 ℃, and the reaction times is 3～8 hours.
The temperature of controlled step (1) gained solution is at 20 ℃～30 ℃ in the step (2), and the adding massfraction is 70%～95% salpeter solution, stirs to react after 1～4 hour to obtain described reaction solution, and the gained reaction solution is cooled to 0 ℃～10 ℃ crystallizatioies.
Stir in the step (2) and react that can to add massfraction after 1～4 hour again be 60%～70% salpeter solution, stirring reaction obtains described reaction solution after 1～3 hour once more.
The concentration of sodium hydroxide described in the step (3) or potassium hydroxide solution is 1 mol～3 mol.The temperature that stirring is reacted is 40 ℃～80 ℃, and the reaction times is 3～5 hours.
PH value with the gained reaction solution in the step (3) is adjusted in 3～5, and it is cooled to 10 ℃～20 ℃ crystallizatioies.
Iron powder or zinc powder and step (3) gained 4-amino-3-nitro phenol solid mol ratio are 3: 1～5: 1 in the step (4).Wherein the reflux temperature of reacting is 80 ℃～100 ℃, and the reaction times is 4～10 hours.
Acidic solution described in the step (4) is hydrochloric acid or sulphuric acid soln, and described polar organic solvent is an ethanol.
Of the present invention 3, the synthetic method novelty of 4-diaminophenol, problems such as the hydrolysis that exists in the prior art is incomplete, aftertreatment is difficult, cost height have been solved, raw material has adopted cheap and facile p-aminophenol and diacetyl oxide, synthesis condition gentleness, easy to operate, and product yield is higher, is fit to suitability for industrialized production.Of the present invention 3, the synthetic method of 4-diaminophenol has been filled up the blank in domestic this field, has certain economic and is worth and practical value.
Embodiment
Embodiment
Step (1) acylation reaction:
Get 21 gram p-aminophenol, 50 milliliters of anhydrous acetic acid acid anhydrides and 16 milliliters of Glacial acetic acid insert 250 milliliters and four-hole boiling flask that have thermometer and whipping appts in mix, solution in the four-hole boiling flask is heated to 128 ℃, heating reflux reaction 4 hours obtains the acetic acid solution to the ethoxycarbonyl phenyl-acetamides.
Step (2) nitration reaction:
The acetic acid solution to the ethoxycarbonyl phenyl-acetamides that step (1) reaction is obtained is cooled to 25 ℃, the temperature of the described four-hole boiling flask of controlled step (1) is under the situation about 25 ℃, drip 30 milliliters of nitrosonitric acids, behind the stirring reaction 1.5 hours, drip 20 milliliter of 66% nitric acid again, control reaction temperature is at 20 ℃, behind the stirring reaction 1.5 hours, again the gained reaction solution is poured in a large amount of frozen water, have yellow crystals to separate out immediately, be neutral with pure water washing yellow crystals 2～3 times to washings, last suction filtration also makes yellow solid with the filter cake oven dry, be 3-nitro-4-acetaminophenol ethyl ester solid 34.6 grams, this step yield is 75.5%.The fusing point of gained yellow solid is at 144 ℃～146 ℃, and the measurement result of IR spectrum is as follows: IR spectrum (the KBr cm that films
-1) 1678 (C=C), 3142,3350 (NH
2), 1759 (C=O), 1135.3 (C-O-C).1342(-NO
2)，846(C-N)。
Step (3) hydrolysis reaction:
Get the 3-nitro-4-acetaminophenol ethyl ester solid of 5.4 gram step (2) gained and 30 milliliter of 3 mol NaOH solution and insert 150 milliliters and have temperature and take into account in the four-hole boiling flask of whipping appts, solution in the four-hole boiling flask is heated to 60 ℃ and keep stirring under this temperature and reacted 4 hours.After reaction finishes, reaction solution being cooled to 5 ℃, is the pH value 3～4 of 50% hydrochloric acid soln conditioned reaction liquid again with massfraction, separate out red crystals, last suction filtration also makes the red-brown solid with the filter cake oven dry, i.e. 4-amino-3-nitro phenol solid 2.7 grams, and this step yield is 77.1%.Gained red-brown solid fusing point is at 149 ℃～150 ℃, and the measurement result of IR spectrum is as follows: IR spectrum (the KBr cm that films
-1) 3340 (NH
2), 3210,1205 (OH), 1518 (NO
2), 1322,1340 (C-N).
Step (4) reduction reaction:
Have temperature to 250 milliliters and take into account the hydrochloric acid soln that adds 11.2 gram iron powders and 50 milliliter of 0.1 mol in the four-hole boiling flask of whipping appts successively, stir and made its thorough mixing and heated and boiled 10 minutes.Other gets 7.7 gram step (3) gained 4-amino-3-nitro phenol solids and is dissolved in 80 milliliters of dehydrated alcohols, move into constant pressure funnel, at rotating speed is under 600 rev/mins brute force stirs, after slowly being added drop-wise to the ethanolic soln of 4-amino-3-nitro phenol in the four-hole boiling flask, this four-hole boiling flask is heated to 90 ℃, vlil is reacted in the bottle, react after 6 hours, elimination iron powder while hot, the concentrated solvent after-filtration, obtain product 4.5 grams 3 after the vacuum-drying, 4-diaminophenol solid, this step yield is 72.6%.
Whole 3, the yield of the building-up process of 4-diaminophenol is: 42.3%.
Claims (10)
1. one kind 3, the synthetic method of 4-diaminophenol is characterized in that, this method may further comprise the steps:
(1) acylation reaction: in anhydrous acetic acid, reflux is reacted, and obtains the acetic acid solution to the ethoxycarbonyl phenyl-acetamides with raw material p-aminophenol and diacetyl oxide mixed dissolution;
(2) nitration reaction: drip salpeter solution in step (1) gained solution, stir and react, the gained reaction solution obtains 3-nitro-4-acetaminophenol ethyl ester solid through crystallization, filtration;
(3) hydrolysis reaction: add sodium hydroxide or potassium hydroxide solution in the solid that step (2) obtains, stir and react, the gained reaction solution obtains 4-amino-3-nitro phenol solid through crystallization, filtration;
(4) reduction reaction: to the pH value is to add iron powder or zinc powder in 1～2 the acidic solution, with its mixing and be heated to 50 ℃～100 ℃, and in the gained mixture, add step (3) gained solid solution, reflux is reacted, obtain 3,4-diaminophenol, described step (3) gained solid solution are meant that step (3) gained 4-amino-3-nitro phenol solid is dissolved in the solution that obtains behind the polar organic solvent.
2. according to claim 1 a kind of 3, the synthetic method of 4-diaminophenol, it is characterized in that: the mol ratio of raw material p-aminophenol and diacetyl oxide is 1: 2～1: 3 in the step (1), and the temperature that reflux is reacted is 120 ℃～130 ℃, and the reaction times is 3～8 hours.
3. according to claim 1 a kind of 3, the synthetic method of 4-diaminophenol, it is characterized in that: the temperature of controlled step (1) gained solution is at 20 ℃～30 ℃ in the step (2), the adding massfraction is 70%～95% salpeter solution, stirring is reacted after 1～4 hour and is obtained described reaction solution, and the gained reaction solution is cooled to 0 ℃～10 ℃ crystallizatioies.
4. according to claim 1 a kind of 3, the synthetic method of 4-diaminophenol, it is characterized in that: the temperature of controlled step (1) gained solution is at 20 ℃～30 ℃ in the step (2), the adding massfraction is 70%～95% salpeter solution, stirring reacts that to add massfraction after 1～4 hour again be 60%～70% salpeter solution, stirring reaction obtains described reaction solution after 1～3 hour once more, and the gained reaction solution is cooled to 0 ℃～10 ℃ crystallizatioies.
5. according to claim 1 a kind of 3, the synthetic method of 4-diaminophenol is characterized in that: the concentration of sodium hydroxide described in the step (3) or potassium hydroxide solution is 1 mol～3 mol.
6. according to claim 1 a kind of 3, the synthetic method of 4-diaminophenol is characterized in that: stirring the temperature of reacting in the step (3) is 40 ℃～80 ℃, and the reaction times is 3～5 hours.
7. according to claim 1 a kind of 3, the synthetic method of 4-diaminophenol is characterized in that: the pH value with the gained reaction solution in the step (3) is adjusted in 3～5, and it is cooled to 10 ℃～20 ℃ crystallizatioies.
8. according to claim 1 a kind of 3, the synthetic method of 4-diaminophenol is characterized in that: iron powder or zinc powder and step (3) gained 4-amino-3-nitro phenol solid mol ratio are 3: 1～5: 1 in the step (4).
9. according to claim 1 a kind of 3, the synthetic method of 4-diaminophenol is characterized in that: the acidic solution described in the step (4) is hydrochloric acid or sulphuric acid soln, and described polar organic solvent is an ethanol.
10. according to claim 1 a kind of 3, the synthetic method of 4-diaminophenol is characterized in that: the temperature that reflux is reacted in the step (4) is 80 ℃～100 ℃, and the reaction times is 4～10 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200710023873 CN101085741B (en) | 2007-06-22 | 2007-06-22 | Method for synthesizing 3,4-diaminophenol |
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|---|---|---|---|
| CN 200710023873 CN101085741B (en) | 2007-06-22 | 2007-06-22 | Method for synthesizing 3,4-diaminophenol |
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| CN101538211B (en) * | 2009-01-15 | 2012-10-10 | 台州市经纬化工有限公司 | Method for preparing m-aminophenol by catalytic hydrolysis of m-phenylenediamine |
| CN102249963A (en) * | 2011-05-18 | 2011-11-23 | 长沙理工大学 | Method for synthesizing 4-methyl-2-amino thiophenol |
| CN106699578B (en) * | 2015-11-13 | 2019-07-02 | 江苏先声药业有限公司 | A kind of synthetic method of important pharmaceutical-chemical intermediate 4- amino -3- chlorophenol |
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| CN1462737A (en) * | 2003-06-18 | 2003-12-24 | 江苏扬子江药业集团有限公司 | Method for preparing 4-chlorine-3-nitroanisole |
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| CN1462737A (en) * | 2003-06-18 | 2003-12-24 | 江苏扬子江药业集团有限公司 | Method for preparing 4-chlorine-3-nitroanisole |
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Address after: 215400 No. 1, Jian Xiong Road, science and Education Town, Taicang, Suzhou, Jiangsu Patentee after: SUZHOU CHIEN-SHIUNG INSTITUTE OF TECHNOLOGY Address before: 215011, 1, Xueyuan Road, Taicang, Jiangsu, the southern suburbs of Jiangsu Province Patentee before: CHIEN-SHIUNG INSTITUTE OF TECHNOLOGY |