CN107556201A - A kind of process for preparing m-aminophenol - Google Patents
A kind of process for preparing m-aminophenol Download PDFInfo
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- CN107556201A CN107556201A CN201710803486.6A CN201710803486A CN107556201A CN 107556201 A CN107556201 A CN 107556201A CN 201710803486 A CN201710803486 A CN 201710803486A CN 107556201 A CN107556201 A CN 107556201A
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- aminophenol
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- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229940018563 3-aminophenol Drugs 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 238000002360 preparation method Methods 0.000 claims abstract description 32
- 238000010792 warming Methods 0.000 claims abstract description 27
- OTGAHJPFNKQGAE-UHFFFAOYSA-N cresatin Chemical compound CC(=O)OC1=CC=CC(C)=C1 OTGAHJPFNKQGAE-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229960000862 cresatin Drugs 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005457 ice water Substances 0.000 claims abstract description 18
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000000605 extraction Methods 0.000 claims abstract description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 8
- FQCRIFDLUQGBHF-UHFFFAOYSA-N 3-oxo-3-phenoxypropanoic acid Chemical compound OC(=O)CC(=O)OC1=CC=CC=C1 FQCRIFDLUQGBHF-UHFFFAOYSA-N 0.000 claims abstract description 7
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 6
- 238000004809 thin layer chromatography Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 11
- FTGJLZQGQMUPQB-UHFFFAOYSA-N 2-acetyl-4-chlorobenzoic acid Chemical compound C(C)(=O)C1=C(C(=O)O)C=CC(=C1)Cl FTGJLZQGQMUPQB-UHFFFAOYSA-N 0.000 claims description 10
- GSWYUZQBLVUEPH-UHFFFAOYSA-N 3-(azaniumylmethyl)benzoate Chemical compound NCC1=CC=CC(C(O)=O)=C1 GSWYUZQBLVUEPH-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 10
- 229910001917 perchloryl Inorganic materials 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- 239000008247 solid mixture Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 5
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 5
- 229910017912 NH2OH Inorganic materials 0.000 claims description 5
- 229910006124 SOCl2 Inorganic materials 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 5
- 229940100630 metacresol Drugs 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000009413 insulation Methods 0.000 abstract description 2
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 abstract 2
- -1 Carboxyl acetic acid phenyl ester Chemical compound 0.000 abstract 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 abstract 1
- 229940049953 phenylacetate Drugs 0.000 abstract 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- VARLXUCWCIPCBT-UHFFFAOYSA-N benzene propanedioic acid Chemical compound C(CC(=O)O)(=O)O.C1=CC=CC=C1 VARLXUCWCIPCBT-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- RTZZCYNQPHTPPL-UHFFFAOYSA-N 3-nitrophenol Chemical compound OC1=CC=CC([N+]([O-])=O)=C1 RTZZCYNQPHTPPL-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of process for preparing m-aminophenol, belongs to technical field of chemical material preparation, and limited technical problem when solving to use phenylacetate as preparing raw material, the present invention has the advantages that simple to operate, product yield is high, reaction is easily controllable.Solution is：Carboxyl acetic acid phenyl ester between preparing after cresatin is prepared, m-aminophenol is prepared with carboxyl acetic acid phenyl ester between obtained：A, C is taken9H8O4Reagent is added in ethyl acetate solution to be stirred well to and is completely dissolved, and thionyl chloride is added dropwise in system under the conditions of ice-water bath and is incubated 1 ± 0.5 hour, is flowed back after being warming up to 60 DEG C；B, under the conditions of ice-water bath, triethylamine and hydroxylamine hydrochloride are added into system, insulation is warming up to room temperature after 2 hours；C, solvent is spin-dried on a rotary evaporator, then adds water and potassium carbonate, be warming up to 60~70 DEG C of hydrolysis；D, solution is extracted with ethyl acetate, and determines whether that extraction is complete using thin-layer chromatography, is finished product m-aminophenol after the completion of extraction.
Description
Technical field
The invention belongs to technical field of chemical material preparation, more particularly to a kind of process for preparing m-aminophenol.
Background technology
M-aminophenol is a kind of important fine chemical material and organic intermediate, in petro chemical industry, agricultural chemicals, doctor
The application in the fields such as medicine, dyestuff is very extensive.Up to the present, the technique that have developed a variety of synthesis m-aminophenols, mainly
There are nitrobenzene method, resorcinol ammonolysis process, metanitrophenol electrolysis, aniline hydroxylating method and m-phenylene diamine (MPD) Hydrochloric Acid Hydrolysis Method
Deng, but they are mostly respectively present that technique is backward, seriously polluted, cost is higher, yield and selectivity be not high and will to equipment
Ask the problem of higher.
The content of the invention
A kind of the defects of it is an object of the invention to overcome prior art, there is provided process for preparing m-aminophenol.
The present invention is achieved by the following technical programs.
A kind of process for preparing m-aminophenol, is carried out successively as follows：
Ith, the preparation of m-aminophenol reaction raw materials cresatin：
A, reaction equation is as follows：
C7H8O+CH3CClO→C9H10O2+HCl↑
B, preparation process is：
First, metacresol 21.6g is taken in 100ml conical flasks, and 15ml dichloromethane is then added into conical flask
As solvent；Secondly, under the conditions of 0~5 DEG C of ice-water bath, 15.7g chloroacetic chloride reagent dropwises are entered into body with constant pressure funnel
In system, fully react 30~60 minutes；Again, continue the low-temp reaction under the conditions of 0~5 DEG C of the ice-water bath to start to rise after 60 minutes
Temperature, system temperature are controlled at 60 ± 5 DEG C, are reacted 2~3 hours, and the tail gas for reacting generation is passed through in sodium hydrate aqueous solution and absorbed；
Finally, the solid mixture generated after being reacted in conical flask takes out, and is removed using Rotary Evaporators in solid mixture not
The methylene chloride to react, obtained cresatin are walked after remaining and used；
IIth, between m-aminophenol reaction raw materials carboxyl acetic acid phenyl ester preparation：
A, reaction equation is as follows：
C9H10O2+2KMnO4→C9H8O4+2MnO2+2KOH
B, preparation process is：
A, cresatin made from step I in 100ml triangular flasks, adds water 50ml and is sufficiently stirred, so before taking 7.5g
After add 5ml glacial acetic acid, system is warming up to 60~80 DEG C；
B, potassium permanganate 243g is weighed, is slowly repeatedly added in cresatin system on a small quantity, treats that potassium permanganate is complete
After portion adds, system temperature is maintained at 50~80 DEG C and reacted 8~10 hours；After purple all takes off in system, system liter
Temperature is reacted 2~3 hours to 90~110 DEG C, and it is 8 ± 0.2 that reaction determines system solution pH value after terminating, and the solution of generation is taken advantage of
Heat filtering, the filter cake that filter process uses after filtering are washed 3 times repeatedly with hot water, remain next use；
C, filtrate will be made in upper step b with salt acid for adjusting pH≤1, solution is kept without precipitating or have microprecipitation, Ran Houyong
Ethyl acetate is extracted, and the extractant in mixture is removed using Rotary Evaporators after extraction, that is, carboxyl acetic acid benzene between being made
Ester solid product, walk and use after remaining；
IIIth, the preparation of m-aminophenol
A, reaction equation is as follows：
C9H8O4+SOCl2→C9H7ClO3+SO2+HCl；
C9H7ClO3+NH2OH·HCl→C9H9NO4+2HCl；
B, preparation process is：
A, C is taken9H8O4Reagent 1.73g is added in 15ml ethyl acetate solutions to be stirred well to and is completely dissolved, in 0~5 DEG C of ice
1.78g thionyl chlorides are added dropwise in system under water bath condition, are incubated 1 ± 0.5 hour, are warming up to 60 DEG C, are flowed back 6~8 hours；
B, under the conditions of 0~5 DEG C of ice-water bath, 7.1g triethylamines and 0.96g hydroxylamine hydrochlorides are added into system, insulation 2 is small
When after be warming up to room temperature；
C, solvent is spin-dried on a rotary evaporator, then adds water 50ml, potassium carbonate 2.6g, be warming up to 60~70 DEG C of hydrolysis
2~3 hours；
D, solution is extracted with ethyl acetate 3~4 times, determines whether that extraction is complete using thin-layer chromatography, is developed the color in iodine cylinder,
It is finished product m-aminophenol after the completion of extraction.
The present invention has the advantages that compared with prior art.
A kind of process for preparing m-aminophenol provided by the invention, has that reaction condition is gentle, raw material is easy to get, grasped
Make the advantages that simple, product yield is high, reaction is easily controllable, be advantageous to industrialized production.
Embodiment
The present invention is elaborated with reference to embodiment：The present embodiment is carried out premised on technical solution of the present invention
Implement, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment one
A kind of process for preparing m-aminophenol in the present embodiment, is carried out successively as follows：
Ith, the preparation of m-aminophenol reaction raw materials cresatin：
A, reaction equation is as follows：
C7H8O+CH3CClO→C9H10O2+HCl↑
B, preparation process is：
First, metacresol 21.6g is taken in 100ml conical flasks, and 15ml dichloromethane is then added into conical flask
As solvent；Secondly, under the conditions of 1 DEG C of ice-water bath, 15.7g chloroacetic chloride reagent dropwises are entered into system with constant pressure funnel
In, fully reaction 30 minutes；Again, continue the low-temp reaction under the conditions of 1 DEG C of the ice-water bath to start to warm up after 60 minutes, system temperature
Degree control is reacted 2 hours at 55 DEG C, and the tail gas for reacting generation is passed through in sodium hydrate aqueous solution and absorbed；Finally, by conical flask
The solid mixture generated after middle reaction is taken out, and the solvent two not reacted in solid mixture is removed using Rotary Evaporators
Chloromethanes, obtained cresatin are walked after remaining and used；
IIth, between m-aminophenol reaction raw materials carboxyl acetic acid phenyl ester preparation：
A, reaction equation is as follows：
C9H10O2+2KMnO4→C9H8O4+2MnO2+2KOH
B, preparation process is：
A, cresatin made from step I in 100ml triangular flasks, adds water 50ml and is sufficiently stirred, so before taking 7.5g
After add 5ml glacial acetic acid, system is warming up to 60 DEG C；
B, potassium permanganate 243g is weighed, is slowly repeatedly added in cresatin system on a small quantity, treats that potassium permanganate is complete
After portion adds, system temperature is maintained at 50 DEG C and reacted 8 hours；After purple all takes off in system, system is warming up to 90 DEG C,
Reaction 2 hours, it is 7.8 that reaction determines system solution pH value after terminating, and the solution of generation is filtered while hot, filtered after filtering
The filter cake that journey uses is washed 3 times repeatedly with hot water, remains next use；
C, filtrate will be made in upper step b with salt acid for adjusting pH≤1, solution is kept without precipitating or have microprecipitation, Ran Houyong
Ethyl acetate is extracted, and the extractant in mixture is removed using Rotary Evaporators after extraction, that is, carboxyl acetic acid benzene between being made
Ester solid product, walk and use after remaining；
IIIth, the preparation of m-aminophenol
A, reaction equation is as follows：
C9H8O4+SOCl2→C9H7ClO3+SO2+HCl；
C9H7ClO3+NH2OH·HCl→C9H9NO4+2HCl；
B, preparation process is：
A, C is taken9H8O4Reagent 1.73g is added in 15ml ethyl acetate solutions to be stirred well to and is completely dissolved, in 1 DEG C of frozen water
1.78g thionyl chlorides are added dropwise in system under the conditions of bath, are incubated 0.5 hour, are warming up to 60 DEG C, are flowed back 6 hours；
B, under the conditions of 1 DEG C of ice-water bath, 7.1g triethylamines and 0.96g hydroxylamine hydrochlorides are added into system, after being incubated 2 hours
It is warming up to room temperature；
C, solvent is spin-dried on a rotary evaporator, then adds water 50ml, potassium carbonate 2.6g, it is small to be warming up to 60 DEG C of hydrolysis 2
When；
D, solution is extracted with ethyl acetate 3 times, determines whether that extraction is complete using thin-layer chromatography, develops the color, extract in iodine cylinder
I.e. finished product m-aminophenol after the completion of taking.
Embodiment two
A kind of process for preparing m-aminophenol, is carried out successively as follows：
Ith, the preparation of m-aminophenol reaction raw materials cresatin：
A, reaction equation is as follows：
C7H8O+CH3CClO→C9H10O2+HCl↑
B, preparation process is：
First, metacresol 21.6g is taken in 100ml conical flasks, and 15ml dichloromethane is then added into conical flask
As solvent；Secondly, under the conditions of 3 DEG C of ice-water bath, 15.7g chloroacetic chloride reagent dropwises are entered into system with constant pressure funnel
In, fully reaction 45 minutes；Again, continue the low-temp reaction under the conditions of 3 DEG C of the ice-water bath to start to warm up after 60 minutes, system temperature
Degree control is reacted 2.5 hours at 60 DEG C, and the tail gas for reacting generation is passed through in sodium hydrate aqueous solution and absorbed；Finally, triangle is burnt
The solid mixture generated after being reacted in bottle is taken out, and the solvent not reacted in solid mixture is removed using Rotary Evaporators
Dichloromethane, obtained cresatin are walked after remaining and used；
IIth, between m-aminophenol reaction raw materials carboxyl acetic acid phenyl ester preparation：
A, reaction equation is as follows：
C9H10O2+2KMnO4→C9H8O4+2MnO2+2KOH
B, preparation process is：
A, cresatin made from step I in 100ml triangular flasks, adds water 50ml and is sufficiently stirred, so before taking 7.5g
After add 5ml glacial acetic acid, system is warming up to 70 DEG C；
B, potassium permanganate 243g is weighed, is slowly repeatedly added in cresatin system on a small quantity, treats that potassium permanganate is complete
After portion adds, system temperature is maintained at 70 DEG C and reacted 9 hours；After purple all takes off in system, system is warming up to 100
DEG C, react 2.5 hours, it is 8 that reaction determines system solution pH value after terminating, and the solution of generation is filtered while hot, filtered after filtering
The filter cake that process uses is washed 3 times repeatedly with hot water, remains next use；
C, filtrate will be made in upper step b with salt acid for adjusting pH≤1, solution is kept without precipitating or have microprecipitation, Ran Houyong
Ethyl acetate is extracted, and the extractant in mixture is removed using Rotary Evaporators after extraction, that is, carboxyl acetic acid benzene between being made
Ester solid product, walk and use after remaining；
IIIth, the preparation of m-aminophenol
A, reaction equation is as follows：
C9H8O4+SOCl2→C9H7ClO3+SO2+HCl；
C9H7ClO3+NH2OH·HCl→C9H9NO4+2HCl；
B, preparation process is：
A, C is taken9H8O4Reagent 1.73g is added in 15ml ethyl acetate solutions to be stirred well to and is completely dissolved, in 3 DEG C of frozen water
1.78g thionyl chlorides are added dropwise in system under the conditions of bath, are incubated 1 hour, are warming up to 60 DEG C, are flowed back 6~8 hours；
B, under the conditions of 3 DEG C of ice-water baths, 7.1g triethylamines and 0.96g hydroxylamine hydrochlorides are added into system, after being incubated 2 hours
It is warming up to room temperature；
C, solvent is spin-dried on a rotary evaporator, then adds water 50ml, potassium carbonate 2.6g, be warming up to 65 DEG C of hydrolysis 2.5
Hour；
D, solution is extracted with ethyl acetate 3 times, determines whether that extraction is complete using thin-layer chromatography, develops the color, extract in iodine cylinder
I.e. finished product m-aminophenol after the completion of taking.
Embodiment three
A kind of process for preparing m-aminophenol, is carried out successively as follows：
Ith, the preparation of m-aminophenol reaction raw materials cresatin：
A, reaction equation is as follows：
C7H8O+CH3CClO→C9H10O2+HCl↑
B, preparation process is：
First, metacresol 21.6g is taken in 100ml conical flasks, and 15ml dichloromethane is then added into conical flask
As solvent；Secondly, under the conditions of 5 DEG C of ice-water bath, 15.7g chloroacetic chloride reagent dropwises are entered into system with constant pressure funnel
In, fully reaction 60 minutes；Again, continue the low-temp reaction under the conditions of 5 DEG C of the ice-water bath to start to warm up after 60 minutes, system temperature
Degree control is reacted 3 hours at 65 DEG C, and the tail gas for reacting generation is passed through in sodium hydrate aqueous solution and absorbed；Finally, by conical flask
The solid mixture generated after middle reaction is taken out, and the solvent two not reacted in solid mixture is removed using Rotary Evaporators
Chloromethanes, obtained cresatin are walked after remaining and used；
IIth, between m-aminophenol reaction raw materials carboxyl acetic acid phenyl ester preparation：
A, reaction equation is as follows：
C9H10O2+2KMnO4→C9H8O4+2MnO2+2KOH
B, preparation process is：
A, cresatin made from step I in 100ml triangular flasks, adds water 50ml and is sufficiently stirred, so before taking 7.5g
After add 5ml glacial acetic acid, system is warming up to 80 DEG C；
B, potassium permanganate 243g is weighed, is slowly repeatedly added in cresatin system on a small quantity, treats that potassium permanganate is complete
After portion adds, system temperature is maintained at 80 DEG C and reacted 10 hours；After purple all takes off in system, system is warming up to 110
DEG C, react 3 hours, it is 8.2 that reaction determines system solution pH value after terminating, and the solution of generation is filtered while hot, filtered after filtering
The filter cake that process uses is washed 3 times repeatedly with hot water, remains next use；
C, filtrate will be made in upper step b with salt acid for adjusting pH≤1, solution is kept without precipitating or have microprecipitation, Ran Houyong
Ethyl acetate is extracted, and the extractant in mixture is removed using Rotary Evaporators after extraction, that is, carboxyl acetic acid benzene between being made
Ester solid product, walk and use after remaining；
IIIth, the preparation of m-aminophenol
A, reaction equation is as follows：
C9H8O4+SOCl2→C9H7ClO3+SO2+HCl；
C9H7ClO3+NH2OH·HCl→C9H9NO4+2HCl；
B, preparation process is：
A, C is taken9H8O4Reagent 1.73g is added in 15ml ethyl acetate solutions to be stirred well to and is completely dissolved, in 5 DEG C of frozen water
1.78g thionyl chlorides are added dropwise in system under the conditions of bath, are incubated 1.5 hours, are warming up to 60 DEG C, are flowed back 8 hours；
B, under the conditions of 5 DEG C of ice-water baths, 7.1g triethylamines and 0.96g hydroxylamine hydrochlorides are added into system, after being incubated 2 hours
It is warming up to room temperature；
C, solvent is spin-dried on a rotary evaporator, then adds water 50ml, potassium carbonate 2.6g, it is small to be warming up to 70 DEG C of hydrolysis 3
When；
D, solution is extracted with ethyl acetate 4 times, determines whether that extraction is complete using thin-layer chromatography, develops the color, extract in iodine cylinder
I.e. finished product m-aminophenol after the completion of taking.
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any
Be familiar with those skilled in the art the invention discloses technical scope in, the change or replacement that can readily occur in should all be contained
Cover within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (1)
1. a kind of process for preparing m-aminophenol, it is characterised in that carry out successively as follows：
Ith, the preparation of m-aminophenol reaction raw materials cresatin：
A, reaction equation is as follows：
C7H8O+CH3CClO→C9H10O2+HCl↑
B, preparation process is：
First, metacresol 21.6g is taken in 100ml conical flasks, and 15ml dichloromethane conducts are then added into conical flask
Solvent；Secondly, under the conditions of 0~5 DEG C of ice-water bath, 15.7g chloroacetic chloride reagent dropwises are entered in system with constant pressure funnel,
Fully reaction 30~60 minutes；Again, continue the low-temp reaction under the conditions of 0~5 DEG C of the ice-water bath to start to warm up after 60 minutes, body
Be temperature control at 60 ± 5 DEG C, react 2~3 hours, the tail gas for reacting generation is passed through in sodium hydrate aqueous solution and absorbed；Finally,
The solid mixture generated after being reacted in conical flask takes out, and is removed in solid mixture and not occurred instead using Rotary Evaporators
The methylene chloride answered, obtained cresatin are walked after remaining and used；
IIth, between m-aminophenol reaction raw materials carboxyl acetic acid phenyl ester preparation：
A, reaction equation is as follows：
C9H10O2+2KMnO4→C9H8O4+2MnO2+2KOH
B, preparation process is：
A, cresatin made from step I in 100ml triangular flasks, adds water 50ml and is sufficiently stirred, Ran Houzai before taking 7.5g
5ml glacial acetic acid is added, system is warming up to 60~80 DEG C；
B, potassium permanganate 243g is weighed, is slowly repeatedly added in cresatin system on a small quantity, treats that potassium permanganate all adds
After entering, system temperature is maintained at 50~80 DEG C and reacted 8~10 hours；After purple all takes off in system, system is warming up to
90~110 DEG C, react 2~3 hours, reaction determines system solution pH value after terminating be 8 ± 0.2, by the solution of generation mistake while hot
Filter, the filter cake that filter process uses after filtering are washed 3 times repeatedly with hot water, remain next use；
C, filtrate will be made in upper step b to be kept without precipitating or having microprecipitation with salt acid for adjusting pH≤1, solution, then uses acetic acid
Ethyl ester is extracted, and the extractant in mixture is removed using Rotary Evaporators after extraction, that is, carboxyl acetic acid phenyl ester is consolidated between being made
Body product, walk and use after remaining；
IIIth, the preparation of m-aminophenol
A, reaction equation is as follows：
C9H8O4+SOCl2→C9H7ClO3+SO2+HCl；
C9H7ClO3+NH2OH·HCl→C9H9NO4+2HCl；
B, preparation process is：
A, C is taken9H8O4Reagent 1.73g is added in 15ml ethyl acetate solutions to be stirred well to and is completely dissolved, in 0~5 DEG C of ice-water bath
Under the conditions of 1.78g thionyl chlorides are added dropwise in system, be incubated 1 ± 0.5 hour, be warming up to 60 DEG C, flow back 6~8 hours；
B, under the conditions of 0~5 DEG C of ice-water bath, 7.1g triethylamines and 0.96g hydroxylamine hydrochlorides are added into system, after being incubated 2 hours
It is warming up to room temperature；
C, solvent is spin-dried on a rotary evaporator, then adds water 50ml, potassium carbonate 2.6g, be warming up to 60~70 DEG C of hydrolysis 2~3
Hour；
D, solution is extracted with ethyl acetate 3~4 times, determines whether that extraction is complete using thin-layer chromatography, develops the color, extract in iodine cylinder
After the completion of i.e. finished product m-aminophenol.
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