CN116854602A - Synthesis process of 2, 3-dichloro-4-aminophenol - Google Patents
Synthesis process of 2, 3-dichloro-4-aminophenol Download PDFInfo
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- CN116854602A CN116854602A CN202310718421.7A CN202310718421A CN116854602A CN 116854602 A CN116854602 A CN 116854602A CN 202310718421 A CN202310718421 A CN 202310718421A CN 116854602 A CN116854602 A CN 116854602A
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- 238000000034 method Methods 0.000 title claims abstract description 34
- OQHWFUQNSLMSBG-UHFFFAOYSA-N 4-amino-2,3-dichlorophenol Chemical compound NC1=CC=C(O)C(Cl)=C1Cl OQHWFUQNSLMSBG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 230000008569 process Effects 0.000 title claims abstract description 23
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 63
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 53
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 20
- JSTCPNFNKICNNO-UHFFFAOYSA-N 4-nitrosophenol Chemical compound OC1=CC=C(N=O)C=C1 JSTCPNFNKICNNO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000004434 industrial solvent Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims 3
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 5
- 239000007789 gas Substances 0.000 abstract description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 231100000783 metal toxicity Toxicity 0.000 abstract description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 7
- 238000006462 rearrangement reaction Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000009935 nitrosation Effects 0.000 description 3
- 238000007034 nitrosation reaction Methods 0.000 description 3
- 230000008707 rearrangement Effects 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 description 1
- UFNOUKDBUJZYDE-UHFFFAOYSA-N 2-(4-chlorophenyl)-3-cyclopropyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol Chemical compound C1=NC=NN1CC(O)(C=1C=CC(Cl)=CC=1)C(C)C1CC1 UFNOUKDBUJZYDE-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 239000005757 Cyproconazole Substances 0.000 description 1
- 238000012369 In process control Methods 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000010965 in-process control Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a synthesis process of 2, 3-dichloro-4-aminophenol, relates to the technical field of organic synthesis, and aims at the existing synthesis process of 2, 3-dichloro-4-aminophenol, the raw materials are expensive and not easy to obtain, and the synthesis process has no cost advantage in production; meanwhile, the heavy metal catalyst is used for high-pressure hydrogenation reaction, the equipment requirement is high, the heavy metal toxicity is high, the environment is not friendly, and the process is not easy to control, and the scheme is provided as follows, and the method comprises the following steps: s1: sequentially selecting Agilent1260 high performance liquid chromatograph, phenol, sodium nitrite, thionyl chloride, DMF and ethyl acetate for later use; s2: a500 ml reaction flask equipped with a stirrer, a condenser and a thermometer was charged with 37.6 g (0.4 mol) of phenol and 80.0 g (0.2 mol) of 10% aqueous alkali. The application has reasonable design, eliminates the strong corrosive hydrogen chloride gas, uses cheap thionyl chloride to replace, has more controllable production operation and low equipment requirement, and is more suitable for large-scale production.
Description
Technical Field
The application relates to the technical field of organic synthesis, in particular to a synthesis process of 2, 3-dichloro-4-aminophenol.
Background
The 2, 3-dichloro-4-aminophenol is an important chemical intermediate and has wide application in the fields of medicines, pesticides and photosensitive materials. The pesticide cyproconazole prepared by taking 2, 3-dichloro-4-aminophenol as an important synthetic raw material belongs to systemic and protective bactericides, has no teratogenicity and carcinogenicity, and is an ideal medicament for controlling crop and environmental-friendly harmful substances.
However, the existing synthesis processes of 2, 3-dichloro-4-aminophenol mainly comprise two processes, one is a nitration reduction method which takes 2, 3-dichlorophenol as a starting material, and the method has the advantages of high raw material price, low availability and no cost advantage in production; meanwhile, heavy metal catalysts are used for high-pressure hydrogenation reaction, so that the equipment requirement is high, the heavy metal toxicity is high, and the method is not friendly to the environment; the other is nitrosation rearrangement method, which uses phenol as initial raw material, generates p-nitrosophenol through nitrosation, and obtains 2, 3-dichloro-4-aminophenol through chloro rearrangement under the action of hydrogen chloride gas, the method uses hydrogen chloride gas, has high requirements on production equipment and is not easy to control in process; both the two methods for preparing 2, 3-dichloro-4-aminophenol have defects and are not beneficial to industrial production.
Disclosure of Invention
The application aims to solve the problems that the raw materials are expensive and not easy to obtain in the existing synthesis process of 2, 3-dichloro-4-aminophenol, and the method has no cost advantage in production; meanwhile, heavy metal catalysts are used for high-pressure hydrogenation reaction, so that the method has the defects of high equipment requirement, high heavy metal toxicity, environment friendliness and difficulty in process control, and the proposed synthesis process of the 2, 3-dichloro-4-aminophenol is provided.
In order to achieve the above purpose, the present application adopts the following technical scheme:
the synthesis process of 2, 3-dichloro-4-aminophenol comprises the following steps:
s1: sequentially selecting Agilent1260 high performance liquid chromatograph, phenol, sodium nitrite, thionyl chloride, DMF and ethyl acetate for later use;
s2: into a 500 ml reaction flask equipped with a stirrer, a condenser and a thermometer were charged 37.6 g (0.4 mol) of phenol and 80.0 g (0.2 mol) of 10% liquid alkali, and an aqueous solution of 27.6 g (0.4 mol) of sodium nitrite dissolved in 160 ml of water was added under stirring at room temperature;
s3: the reaction solution is cooled to the internal temperature of 0 to 5 ℃, 117.6 g (0.36 mol) of 30 percent sulfuric acid is slowly added dropwise, the internal temperature is controlled below 5 ℃, and the addition is completed in 2 hours;
s4: after the addition, stirring for 2 hours at the same temperature, carrying out suction filtration, washing a filter cake with 60 ml of ice water, and carrying out suction drying to obtain brown solid; drying the solid to constant weight at 50 ℃ by blowing to obtain 35.2 g of brown solid, wherein the weight yield is 93.5%, and the product content is 98.4%;
s5: in a 250 ml reaction bottle equipped with a stirrer, a condenser and a thermometer, adding 30 ml of DMF, cooling the reaction liquid to an internal temperature of-5 ℃, slowly and dropwise adding 57.1 g (0.48 mol) of thionyl chloride, controlling the internal temperature to be lower than 5 ℃, and finishing the addition for 2 hours;
s6: after the addition, stirring was completed for 1 hour, and 20 g (97.4%, 0.16 mol) of p-nitrosophenol solid was added in three portions, and half an hour; after the addition, stirring for 4 hours at the temperature of 0-5 ℃; ethyl acetate was added and stirred for 1 hour; filtering, washing with 20 ml of ethyl acetate to obtain a tan solid;
s7: dissolving the solid in 250 ml of water, adding active carbon, heating and refluxing for half an hour, and performing hot filtration to obtain pale yellow clear liquid; slowly neutralizing with liquid alkali until pH is 6.0 under cooling with ice water, and stirring for 1 hr; filtering, washing with 20 ml of water, pumping to obtain pale yellow solid, and vacuum drying at 80 ℃ to constant weight to obtain 2, 3-dichloro-4-aminophenol.
In a preferred embodiment, phenol, sodium nitrite and thionyl chloride in S1 are commercially available chemical pure reagents, and DMF and ethyl acetate are commercially available industrial grade solvents.
In a preferred embodiment, the ethyl acetate in S6 is used in an amount of 60 ml.
In a preferred embodiment, the activated carbon in S7 weighs 2.0 grams.
In the synthesis process of the 2, 3-dichloro-4-aminophenol, cheap and easily available phenol is used as a starting material, an intermediate p-nitrosophenol is generated under the action of sodium nitrite, and thionyl chloride is used as a chloro reagent to perform a chloro rearrangement reaction to obtain the 2, 3-dichloro-4-aminophenol. Experimental results show that when the molar feed ratio of thionyl chloride to p-nitrosophenol is 3.0:1.0 and the reaction temperature is controlled between 0 and 5 ℃, the yield of 2, 3-dichloro-4-aminophenol can reach 89.26 percent and the content is 98.21 percent;
the application has reasonable design, eliminates the strong corrosive hydrogen chloride gas, uses cheap thionyl chloride to replace, has more controllable production operation and low equipment requirement, and is more suitable for large-scale production.
Drawings
FIG. 1 is a schematic diagram of the synthetic route of the synthetic process of 2, 3-dichloro-4-aminophenol according to the present application;
FIG. 2 is a schematic diagram showing the effect of sulfoxide chloride consumption on the product in the synthesis process of 2, 3-dichloro-4-aminophenol according to the present application;
FIG. 3 is a schematic diagram showing the effect of reaction temperature on the product of the synthesis process of 2, 3-dichloro-4-aminophenol according to the present application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments.
Example 1
Referring to fig. 1 and 2, an embodiment provided in this scheme: the synthesis process of 2, 3-dichloro-4-aminophenol comprises the following steps:
s1: sequentially selecting Agilent1260 high performance liquid chromatograph, phenol, sodium nitrite, thionyl chloride, DMF and ethyl acetate for later use;
s2: into a 500 ml reaction flask equipped with a stirrer, a condenser and a thermometer were charged 37.6 g (0.4 mol) of phenol and 80.0 g (0.2 mol) of 10% liquid alkali, and an aqueous solution of 27.6 g (0.4 mol) of sodium nitrite dissolved in 160 ml of water was added under stirring at room temperature;
s3: the reaction solution is cooled to the internal temperature of 0 to 5 ℃, 117.6 g (0.36 mol) of 30 percent sulfuric acid is slowly added dropwise, the internal temperature is controlled below 5 ℃, and the addition is completed in 2 hours;
s4: after the addition, stirring for 2 hours at the same temperature, carrying out suction filtration, washing a filter cake with 60 ml of ice water, and carrying out suction drying to obtain brown solid; drying the solid to constant weight at 50 ℃ by blowing to obtain 35.2 g of brown solid, wherein the weight yield is 93.5%, and the product content is 98.4%;
s5: in a 250 ml reaction bottle equipped with a stirrer, a condenser and a thermometer, adding 30 ml of DMF, cooling the reaction liquid to an internal temperature of-5 ℃, slowly and dropwise adding 57.1 g (0.48 mol) of thionyl chloride, controlling the internal temperature to be lower than 5 ℃, and finishing the addition for 2 hours;
s6: after the addition, stirring was completed for 1 hour, and 20 g (97.4%, 0.16 mol) of p-nitrosophenol solid was added in three portions, and half an hour; after the addition, stirring for 4 hours at the temperature of 0-5 ℃; ethyl acetate was added and stirred for 1 hour; filtering, washing with 20 ml of ethyl acetate to obtain a tan solid;
s7: dissolving the solid in 250 ml of water, adding active carbon, heating and refluxing for half an hour, and performing hot filtration to obtain pale yellow clear liquid; slowly neutralizing with liquid alkali until pH is 6.0 under cooling with ice water, and stirring for 1 hr; filtering, washing with 20 ml of water, pumping to obtain pale yellow solid, and vacuum drying at 80 ℃ to constant weight to obtain 2, 3-dichloro-4-aminophenol.
In this example, phenol, sodium nitrite and thionyl chloride in S1 are commercially available chemical pure reagents, and DMF and ethyl acetate are commercially available industrial solvents.
In this example, the amount of ethyl acetate used in S6 was 60 ml.
In this example, the weight of the activated carbon in S7 was 2.0 g.
Under the conditions that the reaction temperature, the reaction time and the feeding amount of the nitrosophenol and the DMF of S5-S7 are unchanged, the influence of the consumption of thionyl chloride on the synthesis yield and the content of 2, 3-dichloro-4-aminophenol is examined, and the experimental result is shown in figure 2:
FIG. 2 shows that when the dosage of thionyl chloride is small, the chlorination and rearrangement reactions are incomplete, and the reaction conversion rate is low; with the increase of the dosage of the thionyl chloride, the yield and the content of the product are all in an ascending trend; when the molar feeding ratio of thionyl chloride to p-nitrosophenol is 3.0:1.0, the product yield reaches 89.26%; and when the feeding ratio of thionyl chloride to p-nitrosophenol is continuously increased to 4.0:1.0, the product yield and content are not obviously increased. From the aspects of production raw material cost, post-treatment cost, three-waste reduction and the like, the optimal molar charging ratio of thionyl chloride and p-nitrosophenol is determined to be 3.0:1.0.
Example two
Referring to fig. 1 and 3, an embodiment provided in this scheme: the synthesis process of 2, 3-dichloro-4-aminophenol comprises the following steps:
s1: sequentially selecting Agilent1260 high performance liquid chromatograph, phenol, sodium nitrite, thionyl chloride, DMF and ethyl acetate for later use;
s2: into a 500 ml reaction flask equipped with a stirrer, a condenser and a thermometer were charged 37.6 g (0.4 mol) of phenol and 80.0 g (0.2 mol) of 10% liquid alkali, and an aqueous solution of 27.6 g (0.4 mol) of sodium nitrite dissolved in 160 ml of water was added under stirring at room temperature;
s3: the reaction solution is cooled to the internal temperature of 0 to 5 ℃, 117.6 g (0.36 mol) of 30 percent sulfuric acid is slowly added dropwise, the internal temperature is controlled below 5 ℃, and the addition is completed in 2 hours;
s4: after the addition, stirring for 2 hours at the same temperature, carrying out suction filtration, washing a filter cake with 60 ml of ice water, and carrying out suction drying to obtain brown solid; drying the solid to constant weight at 50 ℃ by blowing to obtain 35.2 g of brown solid, wherein the weight yield is 93.5%, and the product content is 98.4%;
s5: in a 250 ml reaction bottle equipped with a stirrer, a condenser and a thermometer, adding 30 ml of DMF, cooling the reaction liquid to an internal temperature of-5 ℃, slowly and dropwise adding 57.1 g (0.48 mol) of thionyl chloride, controlling the internal temperature to be lower than 5 ℃, and finishing the addition for 2 hours;
s6: after the addition, stirring was completed for 1 hour, and 20 g (97.4%, 0.16 mol) of p-nitrosophenol solid was added in three portions, and half an hour; after the addition, stirring for 4 hours at the temperature of 0-5 ℃; ethyl acetate was added and stirred for 1 hour; filtering, washing with 20 ml of ethyl acetate to obtain a tan solid;
s7: dissolving the solid in 250 ml of water, adding active carbon, heating and refluxing for half an hour, and performing hot filtration to obtain pale yellow clear liquid; slowly neutralizing with liquid alkali until pH is 6.0 under cooling with ice water, and stirring for 1 hr; filtering, washing with 20 ml of water, pumping to obtain pale yellow solid, and vacuum drying at 80 ℃ to constant weight to obtain 2, 3-dichloro-4-aminophenol.
In this example, phenol, sodium nitrite and thionyl chloride in S1 are commercially available chemical pure reagents, and DMF and ethyl acetate are commercially available industrial solvents.
In this example, the amount of ethyl acetate used in S6 was 60 ml.
In this example, the weight of the activated carbon in S7 was 2.0 g.
Under the condition that the reaction time and the reactant feeding ratio of S5-S7 are unchanged, the influence of the reaction temperature on the synthesis yield and content of 2, 3-dichloro-4-aminophenol is examined, and the experimental result is shown in figure 3:
as can be seen from FIG. 3, when the reaction temperature is lower than 0deg.C, the reaction solution is viscous, the chlorination reaction speed is slow, the conversion rate of the raw material to nitrosophenol is low, resulting in unsatisfactory product yield and product content; when the reaction temperature is higher than 10 ℃, side reactions are increased except for chloro rearrangement reaction, the color of the reaction solution is deepened, and the yield and the content of the product are obviously reduced; when the reaction temperature is between 0 and 5 ℃, the raw materials can be completely reacted in a short time, the side reaction can be inhibited to a certain extent, and the ideal product yield and the product content can be considered. Therefore, the temperature of the chloro rearrangement reaction is controlled to 0 to 5 ℃.
According to the application, the preparation process of 2, 3-dichloro-4-aminophenol is improved, phenol which is low in cost and easy to obtain is used as a starting raw material, an intermediate p-nitrosophenol is generated under the action of sodium nitrite, thionyl chloride is used as a chloro reagent, and a chloro rearrangement reaction is carried out to obtain 2, 3-dichloro-4-aminophenol; when the molar feed ratio of thionyl chloride to p-nitrosophenol is 3.0:1.0 and the reaction temperature is controlled between 0 and 5 ℃, the yield of 2, 3-dichloro-4-aminophenol can reach 89.26 percent and the content is 98.21 percent. Compared with the prior nitrosation rearrangement method, the method eliminates the hydrogen chloride gas with strong corrosiveness, uses cheap thionyl chloride to replace, has more controllable production operation and low equipment requirement, and is more suitable for large-scale production.
In the description of the present application, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings are merely for convenience in describing the present application and simplifying the description, and do not indicate or imply that the apparatus or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present application.
The foregoing is only a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any person skilled in the art, who is within the scope of the present application, should make equivalent substitutions or modifications according to the technical scheme of the present application and the inventive concept thereof, and should be covered by the scope of the present application.
The preferred embodiments of the application disclosed above are intended only to assist in the explanation of the application. The preferred embodiments are not exhaustive or to limit the application to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the application and the practical application, to thereby enable others skilled in the art to best understand and utilize the application. The application is limited only by the claims and the full scope and equivalents thereof.
Claims (4)
- The synthesis process of 1.2,3-dichloro-4-aminophenol is characterized by comprising the following steps of:s1: sequentially selecting Agilent1260 high performance liquid chromatograph, phenol, sodium nitrite, thionyl chloride, DMF and ethyl acetate for later use;s2: into a 500 ml reaction flask equipped with a stirrer, a condenser and a thermometer were charged 37.6 g (0.4 mol) of phenol and 80.0 g (0.2 mol) of 10% liquid alkali, and an aqueous solution of 27.6 g (0.4 mol) of sodium nitrite dissolved in 160 ml of water was added under stirring at room temperature;s3: the reaction solution is cooled to the internal temperature of 0 to 5 ℃, 117.6 g (0.36 mol) of 30 percent sulfuric acid is slowly added dropwise, the internal temperature is controlled below 5 ℃, and the addition is completed in 2 hours;s4: after the addition, stirring for 2 hours at the same temperature, carrying out suction filtration, washing a filter cake with 60 ml of ice water, and carrying out suction drying to obtain brown solid; drying the solid to constant weight at 50 ℃ by blowing to obtain 35.2 g of brown solid, wherein the weight yield is 93.5%, and the product content is 98.4%;s5: in a 250 ml reaction bottle equipped with a stirrer, a condenser and a thermometer, adding 30 ml of DMF, cooling the reaction liquid to an internal temperature of-5 ℃, slowly and dropwise adding 57.1 g (0.48 mol) of thionyl chloride, controlling the internal temperature to be lower than 5 ℃, and finishing the addition for 2 hours;s6: after the addition, stirring was completed for 1 hour, and 20 g (97.4%, 0.16 mol) of p-nitrosophenol solid was added in three portions, and half an hour; after the addition, stirring for 4 hours at the temperature of 0-5 ℃; ethyl acetate was added and stirred for 1 hour; filtering, washing with 20 ml of ethyl acetate to obtain a tan solid;s7: dissolving the solid in 250 ml of water, adding active carbon, heating and refluxing for half an hour, and performing hot filtration to obtain pale yellow clear liquid; slowly neutralizing with liquid alkali until pH is 6.0 under cooling with ice water, and stirring for 1 hr; filtering, washing with 20 ml of water, pumping to obtain pale yellow solid, and vacuum drying at 80 ℃ to constant weight to obtain 2, 3-dichloro-4-aminophenol.
- 2. The process for synthesizing 2, 3-dichloro-4-aminophenol according to claim 1, characterized in that: in the S1, phenol, sodium nitrite and thionyl chloride are all commercial chemical pure reagents, and DMF and ethyl acetate are commercial industrial solvents.
- 3. The process for synthesizing 2, 3-dichloro-4-aminophenol according to claim 1, characterized in that: the ethyl acetate dosage in the S6 is 60 milliliters.
- 4. The process for synthesizing 2, 3-dichloro-4-aminophenol according to claim 1, characterized in that: the weight of the activated carbon in the S7 is 2.0 g.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310718421.7A CN116854602A (en) | 2023-06-15 | 2023-06-15 | Synthesis process of 2, 3-dichloro-4-aminophenol |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310718421.7A CN116854602A (en) | 2023-06-15 | 2023-06-15 | Synthesis process of 2, 3-dichloro-4-aminophenol |
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| CN202310718421.7A Pending CN116854602A (en) | 2023-06-15 | 2023-06-15 | Synthesis process of 2, 3-dichloro-4-aminophenol |
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