CN105801435A - Preparing method of 2-amino-4-N-(beta-ethoxyl)aminoanisole sulfate - Google Patents
Preparing method of 2-amino-4-N-(beta-ethoxyl)aminoanisole sulfate Download PDFInfo
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- CN105801435A CN105801435A CN201610249523.9A CN201610249523A CN105801435A CN 105801435 A CN105801435 A CN 105801435A CN 201610249523 A CN201610249523 A CN 201610249523A CN 105801435 A CN105801435 A CN 105801435A
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- 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
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- 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
- C07C213/08—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 not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
Abstract
The invention relates to a preparing method of a chemical intermediate, in particular to a preparing method of 2-amino-4-N-(beta-ethoxyl)aminoanisole sulfate.The preparing method comprises the steps that concentrated nitric acid, concentrated sulfuric acid and p-anisidine are subjected to a digestion reaction, and after neutralization, chloroethyl chloroformate, glycol dimethyl ether, calcium carbonate and water are added for a reaction; alkali liquor and ethyl alcohol are dripped for a hydrolysis reaction, and after decoloring and filtering are carried out with active carbon, a methanol solution is added for refining of a pure intermediate; methanol and palladium carbon are added, a hydrogenation reaction is carried out, refining is carried out through vacuum distillation, active carbon and water, and the product is obtained.According to the preparing method of 2-amino-4-N-(beta-ethoxyl)aminoanisole sulfate, the production temperature is low, production pressure is small, few byproducts of the product are generated, and the impurity 2,4-diamnio-methoxybenzene can be controlled to be 100 ppm or lower so as to reduce damage of the product to the human body.
Description
Technical field
The present invention relates to the preparation method of a kind of chemical intermediate, especially relate to the preparation method of a kind of 2-amino-4-N-(beta-hydroxyethyl) aminobenzoic ether sulfate.
Background technology
2-amino-4-N-(beta-hydroxyethyl) aminobenzoic ether sulfate is a kind of developer, is mainly used in the developer of cosmetics coloring hairs it can also be used to the dyeing of Pilus Caprae seu Ovis, fur etc..At present in the preparation process of 2-amino-4-N-(beta-hydroxyethyl) aminobenzoic ether sulfate, impurity 2 in the product of production, the content of 4-methyl phenyl ethers anisole is 1000PPM, and 2,4-diamino anisoles are a kind of noxious substances, can be carcinogenic, harmful.
Summary of the invention
For above-mentioned technical problem, the present invention provides the preparation method of a kind of 2-amino-4-N-(beta-hydroxyethyl) aminobenzoic ether sulfate, to reduce impurity harmful in product.
Concrete technical scheme is:
The preparation method of 2-amino-4-N-(beta-hydroxyethyl) aminobenzoic ether sulfate, comprises the steps:
(1) add concentrated nitric acid in reactor, concentrated sulphuric acid, paraphenetidine stirring carry out digestion reaction, enter concentrated nitric acid, the mass concentration of concentrated sulphuric acid is 75 ~ 90%, and concentrated nitric acid, concentrated sulphuric acid, paraphenetidine weight ratio are 2.5～3.0:0.5～0.8:1；
(2) add in alkali liquor and after, add ethyl chloroformate, glycol dimethyl ether, calcium carbonate and water, control temperature 50～65 DEG C, after having added, insulation reaction 2～4h；Water, ethyl chloroformate, calcium carbonate, the weight ratio 3.5～4.5:0.8～1.3:0.3～0.5 of 3 glycol dimethyl ethers:
(3) dropping alkali liquor and ethanol are hydrolyzed reaction, and control temperature 60～80 DEG C, after being added dropwise to complete, insulation reaction 0.5～2h obtains intermedium crude product；
(4) intermedium crude product is after activated carbon decolorizing filters, and adds methanol solution and carries out refined intermedium sterling；
(5) intermedium sterling adds methanol and palladium charcoal, carry out hydrogenation reaction, after reaction completely, be filtered into product crude salt through salpeter solution and activated carbon decolorizing；Methanol, palladium charcoal, the weight ratio of intermedium sterling are 3～4:0.005～0.015:1, and reaction pressure is 0.5～0.7MPa, and temperature controls 30 ~ 35 DEG C, response time 1.5～3.5h, when reaction system no longer inhales hydrogen, when pressure no longer declines, in 30 DEG C, pressure 0.5MPa, it is incubated 1 hour；
(6) hydrogen exchange is complete, then inflated with nitrogen 1MPa, the stirring that heats up after replacement completion is to 50 DEG C, and product crude salt obtains product after decompression distillation, activated carbon and crystal's system.
The preparation method of 2-amino-4-N-(beta-hydroxyethyl) the aminobenzoic ether sulfate that the present invention provides, the temperature produced is low, pressure is little, and the by-product of product is less, impurity 2,4-diamino anisole can be controlled in below 100ppm and reduces product to the harm to human body.
Detailed description of the invention
Below in conjunction with specific embodiment, invention is described further.
Embodiment
1
The preparation method of 2-amino-4-N-(beta-hydroxyethyl) aminobenzoic ether sulfate, comprises the steps:
(1) add concentrated nitric acid in reactor, concentrated sulphuric acid, paraphenetidine stirring carry out digestion reaction, enter concentrated nitric acid, the mass concentration of concentrated sulphuric acid is 75 ~ 90%, and concentrated nitric acid, concentrated sulphuric acid, paraphenetidine weight ratio are 2.5:0.6:1；
(2) add in alkali liquor and after, add ethyl chloroformate, glycol dimethyl ether, calcium carbonate and water, control temperature 50～65 DEG C, after having added, insulation reaction 2～4h；Water, ethyl chloroformate, calcium carbonate, weight ratio 3.5:1.0:0.5 of 3 glycol dimethyl ethers:
(3) dropping alkali liquor and ethanol are hydrolyzed reaction, and control temperature 60～80 DEG C, after being added dropwise to complete, insulation reaction 0.5～2h obtains intermedium crude product；
(4) intermedium crude product is after activated carbon decolorizing filters, and adds methanol solution and carries out refined intermedium sterling；
(5) intermedium sterling adds methanol and palladium charcoal, carry out hydrogenation reaction, after reaction completely, be filtered into product crude salt through salpeter solution and activated carbon decolorizing；Methanol, palladium charcoal, the weight ratio of intermedium sterling are 4:0.005:1, and reaction pressure is 0.5～0.7MPa, and temperature controls 30 ~ 35 DEG C, response time 1.5～3.5h, when reaction system no longer inhales hydrogen, when pressure no longer declines, in 30 DEG C, pressure 0.5MPa, it is incubated 1 hour；
(6) hydrogen exchange is complete, then inflated with nitrogen 1MPa, the stirring that heats up after replacement completion is to 50 DEG C, and product crude salt obtains product after decompression distillation, activated carbon and crystal's system.
Embodiment
2
The preparation method of 2-amino-4-N-(beta-hydroxyethyl) aminobenzoic ether sulfate, comprises the steps:
(1) add concentrated nitric acid in reactor, concentrated sulphuric acid, paraphenetidine stirring carry out digestion reaction, enter concentrated nitric acid, the mass concentration of concentrated sulphuric acid is 75 ~ 90%, and concentrated nitric acid, concentrated sulphuric acid, paraphenetidine weight ratio are 3.0:0.8:1；
(2) add in alkali liquor and after, add ethyl chloroformate, glycol dimethyl ether, calcium carbonate and water, control temperature 50～65 DEG C, after having added, insulation reaction 2～4h；Water, ethyl chloroformate, calcium carbonate, weight ratio 4.5:0.8:0.3 of 3 glycol dimethyl ethers:
(3) dropping alkali liquor and ethanol are hydrolyzed reaction, and control temperature 60～80 DEG C, after being added dropwise to complete, insulation reaction 0.5～2h obtains intermedium crude product；
(4) intermedium crude product is after activated carbon decolorizing filters, and adds methanol solution and carries out refined intermedium sterling；
(5) intermedium sterling adds methanol and palladium charcoal, carry out hydrogenation reaction, after reaction completely, be filtered into product crude salt through salpeter solution and activated carbon decolorizing；Methanol, palladium charcoal, the weight ratio of intermedium sterling are 3.5:0.015:1, and reaction pressure is 0.5～0.7MPa, and temperature controls 30 ~ 35 DEG C, response time 1.5～3.5h, when reaction system no longer inhales hydrogen, when pressure no longer declines, in 30 DEG C, pressure 0.5MPa, it is incubated 1 hour；
(6) hydrogen exchange is complete, then inflated with nitrogen 1MPa, the stirring that heats up after replacement completion is to 50 DEG C, and product crude salt obtains product after decompression distillation, activated carbon and crystal's system.
Embodiment
3
The preparation method of 2-amino-4-N-(beta-hydroxyethyl) aminobenzoic ether sulfate, comprises the steps:
(1) add concentrated nitric acid in reactor, concentrated sulphuric acid, paraphenetidine stirring carry out digestion reaction, enter concentrated nitric acid, the mass concentration of concentrated sulphuric acid is 75 ~ 90%, and concentrated nitric acid, concentrated sulphuric acid, paraphenetidine weight ratio are 2.8:0.5:1；
(2) add in alkali liquor and after, add ethyl chloroformate, glycol dimethyl ether, calcium carbonate and water, control temperature 50～65 DEG C, after having added, insulation reaction 2～4h；Water, ethyl chloroformate, calcium carbonate, weight ratio 4:1.3:0.4 of 3 glycol dimethyl ethers:
(3) dropping alkali liquor and ethanol are hydrolyzed reaction, and control temperature 60～80 DEG C, after being added dropwise to complete, insulation reaction 0.5～2h obtains intermedium crude product；
(4) intermedium crude product is after activated carbon decolorizing filters, and adds methanol solution and carries out refined intermedium sterling；
(5) intermedium sterling adds methanol and palladium charcoal, carry out hydrogenation reaction, after reaction completely, be filtered into product crude salt through salpeter solution and activated carbon decolorizing；Methanol, palladium charcoal, the weight ratio of intermedium sterling are 4:0.01:1, and reaction pressure is 0.5～0.7MPa, and temperature controls 30 ~ 35 DEG C, response time 1.5～3.5h, when reaction system no longer inhales hydrogen, when pressure no longer declines, in 30 DEG C, pressure 0.5MPa, it is incubated 1 hour；
(6) hydrogen exchange is complete, then inflated with nitrogen 1MPa, the stirring that heats up after replacement completion is to 50 DEG C, and product crude salt obtains product after decompression distillation, activated carbon and crystal's system.
Claims (1)
1. the preparation method of 2-amino-4-N-(beta-hydroxyethyl) aminobenzoic ether sulfate, it is characterised in that comprise the steps:
(1) add concentrated nitric acid in reactor, concentrated sulphuric acid, paraphenetidine stirring carry out digestion reaction, enter concentrated nitric acid, the mass concentration of concentrated sulphuric acid is 75 ~ 90%, and concentrated nitric acid, concentrated sulphuric acid, paraphenetidine weight ratio are 2.5～3.0:0.5～0.8:1；
(2) add in alkali liquor and after, add ethyl chloroformate, glycol dimethyl ether, calcium carbonate and water, control temperature 50～65 DEG C, after having added, insulation reaction 2～4h；Water, ethyl chloroformate, calcium carbonate, the weight ratio 3.5～4.5:0.8～1.3:0.3～0.5 of 3 glycol dimethyl ethers:
(3) dropping alkali liquor and ethanol are hydrolyzed reaction, and control temperature 60～80 DEG C, after being added dropwise to complete, insulation reaction 0.5～2h obtains intermedium crude product；
(4) intermedium crude product is after activated carbon decolorizing filters, and adds methanol solution and carries out refined intermedium sterling；
(5) intermedium sterling adds methanol and palladium charcoal, carry out hydrogenation reaction, after reaction completely, be filtered into product crude salt through salpeter solution and activated carbon decolorizing；Methanol, palladium charcoal, the weight ratio of intermedium sterling are 3～4:0.005～0.015:1, and reaction pressure is 0.5～0.7MPa, and temperature controls 30 ~ 35 DEG C, response time 1.5～3.5h, when reaction system no longer inhales hydrogen, when pressure no longer declines, in 30 DEG C, pressure 0.5MPa, it is incubated 1 hour；
(6) hydrogen exchange is complete, then inflated with nitrogen 1MPa, the stirring that heats up after replacement completion is to 50 DEG C, and product crude salt obtains product after decompression distillation, activated carbon and crystal's system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610249523.9A CN105801435A (en) | 2016-04-21 | 2016-04-21 | Preparing method of 2-amino-4-N-(beta-ethoxyl)aminoanisole sulfate |
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| CN201610249523.9A CN105801435A (en) | 2016-04-21 | 2016-04-21 | Preparing method of 2-amino-4-N-(beta-ethoxyl)aminoanisole sulfate |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5508467A (en) * | 1993-09-03 | 1996-04-16 | Cassella Aktiengesellschaft | Process for the preparation of hydroxyalkylaminonitrobenzene derivatives |
| CN101589019A (en) * | 2006-04-20 | 2009-11-25 | 宝洁公司 | The novel method of preparation 4-hydroxyalkyl amino-2-Nitroanisole |
-
2016
- 2016-04-21 CN CN201610249523.9A patent/CN105801435A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5508467A (en) * | 1993-09-03 | 1996-04-16 | Cassella Aktiengesellschaft | Process for the preparation of hydroxyalkylaminonitrobenzene derivatives |
| CN101589019A (en) * | 2006-04-20 | 2009-11-25 | 宝洁公司 | The novel method of preparation 4-hydroxyalkyl amino-2-Nitroanisole |
Non-Patent Citations (1)
| Title |
|---|
| 金建平等: "新型染发显色剂2-氨基-4-(β-羟乙基氨基)苯甲醚的合成", 《染料工业》 * |
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