CN107721864B - Preparation method of thermosensitive material N, N-di-N-amyl m-aminophenol - Google Patents
Preparation method of thermosensitive material N, N-di-N-amyl m-aminophenol Download PDFInfo
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- CN107721864B CN107721864B CN201711130750.0A CN201711130750A CN107721864B CN 107721864 B CN107721864 B CN 107721864B CN 201711130750 A CN201711130750 A CN 201711130750A CN 107721864 B CN107721864 B CN 107721864B
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- 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
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Abstract
The invention provides a preparation method of a thermosensitive material N, N-di-N-amyl m-aminophenol, which comprises the steps of feeding, heating and dripping alkali liquor. The purity of the product prepared by the method is greatly improved, n-pentane chloride is used as a raw material, the selectivity is greatly improved, the generation of trisubstituents is avoided, side reactions are few, byproducts are few, the purity of a crude product is improved to more than 98 percent (the purity of a material layer obtained after layering) from 91 to 93 percent originally, and the purity of the product after distillation reaches more than 99.5 percent; the product prepared by the invention has the yield of 96-97 percent calculated by m-aminophenol; the invention adopts water as the solvent to replace the organic solvent in the prior art, greatly reduces the difficulty of post-treatment without influencing the reaction condition, and is more in line with the process route of green production; the invention has cheap raw materials and saves the raw material cost of 7500 yuan to 8500 yuan per ton.
Description
Technical Field
The invention relates to a preparation method of a new thermosensitive material N, N-di-N-amyl m-aminophenol, belonging to the technical field of chemical synthesis.
Background
N, N-di-N-amyl meta-aminophenol is an important intermediate for synthesizing the thermal dye black 305. In the traditional synthetic route of the product, m-aminophenol and bromo-N-pentane (iodo-N-pentane) react in the presence of an organic solvent to obtain N, N-di-N-amyl m-aminophenol.
The prior art has the following defects:
the raw materials are expensive; the side product is excessive in trisubstituent; the yield is low, and the product purity is not high; resulting in high cost of the whole product and unfavorable for industrial production.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a new thermosensitive material N, N-di-N-amyl m-aminophenol, which takes chloro-N-pentane and m-aminophenol as raw materials under the action of a catalyst copper iodide; and (2) dropwise adding an alkali liquor aqueous solution into water serving as a solvent, and after the reaction is finished, carrying out layering and organic layer distillation to obtain the N, N-di-N-amyl m-aminophenol.
The invention aims to:
(1) the purity of the product is improved, the purity of the crude product reaches more than 98 percent, and the content of the refined product reaches more than 99.5 percent.
(2) The yield is improved.
The synthesis route of the patent is as follows:
in order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a thermosensitive material N, N-di-N-amyl m-aminophenol comprises the following steps:
(1) feeding material
Putting m-aminophenol, chloro-n-pentane, catalyst copper iodide and solvent water into a high-pressure kettle;
the mass ratio of m-aminophenol to chloro-n-pentane is 1: 1.95-2.05;
the mass ratio of the m-aminophenol to the copper iodide is 1: 0.05-0.08;
the mass ratio of the m-aminophenol to the water is 1: 0.25-1.
(2) Temperature rise
Heating to 105-110 deg.c and maintaining for 1.5-2.5 hr.
(3) Dropping alkali liquor
Dropwise adding the prepared alkali liquor aqueous solution into a reactor to react with the materials, wherein the time is maintained at 5.5-7.5h, the temperature is controlled at 105-110 ℃, and the pressure is maintained at 0.2-0.5 MPa;
the molar ratio of the m-aminophenol to the alkali is 1: 1.09-1.18; the base is a protic base;
the alkali is one of sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydroxide or strong potassium oxide;
the base is preferably sodium carbonate;
the mass ratio of the m-aminophenol to the aqueous lye solution is preferably 1: 5-5.08.
(4) Distillation
After the reaction is finished, materials are layered (the upper layer is a material layer, and the lower layer is a water layer), and the materials are distilled under negative pressure to obtain the N, N-di-N-amyl m-aminophenol.
Due to the adoption of the technical scheme, the invention achieves the technical effects that:
(1) the purity of the product prepared by the method is greatly improved. The method adopts the chloro-n-pentane as a raw material, so that the selectivity is greatly improved, the generation of trisubstituents is avoided, the side reaction is less, the by-products are less, the purity of a crude product is improved to more than 98 percent (the purity of a material layer obtained after layering) from 91 to 93 percent, and the purity of the product after distillation reaches more than 99.5 percent.
(2) The yield of the product prepared by the invention is between 96 and 97 percent based on m-aminophenol.
(3) The invention adopts water as the solvent to replace the organic solvent in the prior art, greatly reduces the difficulty of post-treatment without influencing the reaction condition, and is more in line with the process route of green production.
(4) The invention has cheap raw materials and saves the raw material cost of 7500 yuan to 8500 yuan per ton.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
EXAMPLE 1 preparation of N, N-di-N-pentylm-aminophenol as a thermosensitive material
The method comprises the following steps:
(1) feeding material
M-aminophenol (100 g), n-pentane chloride (195 g), and copper iodide (5 g) as a catalyst, 25g of water were charged into a 1000ml autoclave.
(2) Temperature rise
The temperature is raised to 105 ℃, and then the temperature is kept for 1.5 h.
(3) Dropping alkali liquor
Adding the prepared aqueous solution of alkali liquor (100g/400g) into a reactor through a dropping pump to react with the materials, maintaining the time at 5.5h, controlling the temperature at 105 ℃ and the pressure at 0.2-0.38 MPa;
the base is sodium carbonate;
the alkali liquor contains 20% of sodium carbonate.
(4) Distillation
After the reaction, the materials were layered (upper layer is material layer, lower layer is water layer). Carrying out negative pressure distillation on the material to obtain N, N-di-N-amyl m-aminophenol (220.2 g), wherein the yield is 96.37 percent calculated by the m-aminophenol; the purity is 99.58%.
EXAMPLE 2 preparation of N, N-di-N-pentylm-aminophenol as a thermosensitive Material
The method comprises the following steps:
(1) feeding material
M-aminophenol (100 g), n-pentane chloride (200 g), copper iodide (6 g) as a catalyst, and 50g of water were placed in a 1000ml autoclave.
(2) Temperature rise
The temperature is raised to 107.5 ℃, and then the temperature is kept for 2.5 h.
(3) Dropping alkali liquor
Adding the prepared aqueous alkali solution (102g/400g) into a reactor through a dropping pump to react with the materials for 6.5 hours. The temperature was controlled at 107.5 ℃. The pressure is maintained between 0.2 and 0.42 MPa;
the base is sodium carbonate;
the alkali liquor contains 20.3 percent of sodium carbonate.
(4) Distillation
After the reaction, the materials were layered (upper layer is material layer, lower layer is water layer). The material was distilled under reduced pressure to give N, N-di-N-pentylm-aminophenol (219.8 g). The yield is 96.19 percent calculated by m-aminophenol; the purity is 99.63%.
EXAMPLE 3 preparation of N, N-di-N-pentylm-aminophenol as a thermosensitive Material
The method comprises the following steps:
(1) feeding material
M-aminophenol (100 g), n-pentane chloride (205 g), copper iodide (8 g) as a catalyst, and 100g of water were placed in a 1000ml autoclave.
(2) Temperature rise
The temperature is raised to 110 ℃, and then the temperature is kept for 2.5 h.
(3) Dropping alkali liquor
Adding the prepared aqueous solution of alkali liquor (108g/400g) into a reactor through a dropping pump to react with the materials, maintaining the time at 7.5h, controlling the temperature at 110 ℃ and the pressure at 0.2-0.48 MPa;
the base is sodium carbonate;
the alkali liquor contains 21.3 percent of sodium carbonate.
(4) Distillation
After the reaction, the materials were layered (upper layer is material layer, lower layer is water layer). The material was distilled under reduced pressure to give N, N-di-N-pentylm-aminophenol (221.1 g). The yield is 96.76 percent calculated by m-aminophenol; the purity is 99.54%.
Unless otherwise stated, the percentages used in the present invention are percentages by weight, and the proportions described in the present invention are proportions by mass.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. A preparation method of a thermosensitive material N, N-di-N-amyl m-aminophenol is characterized by comprising the following steps: the preparation method comprises the steps of feeding, heating and dropping alkali liquor;
the mass ratio of m-aminophenol to chloro-n-pentane in the feeding is 1: 1.95-2.05;
the catalyst is copper iodide; the mass ratio of the m-aminophenol to the copper iodide is 1: 0.05-0.08;
the solvent of the feeding is water, and the mass ratio of the m-aminophenol to the water is 1: 0.25-1;
heating to a reaction temperature of 105-110 ℃, and then preserving heat for 1.5-2.5 h;
the dropping alkali liquor is an aqueous solution of the dropping alkali liquor, the dropping time is maintained at 5.5-7.5h, the temperature is controlled at 105-;
the molar ratio of the m-aminophenol to the alkali is 1: 1.09-1.18; the base is a protic base.
2. The method for preparing a thermosensitive material, N-di-N-pentylm-aminophenol, according to claim 1, wherein: the proton alkali is one of sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydroxide or potassium hydroxide.
3. The method for preparing a thermosensitive material, N-di-N-pentylm-aminophenol, according to claim 1, wherein: the proton alkali is sodium carbonate; the mass ratio of the m-aminophenol to the aqueous solution of the alkali liquor is 1: 5-5.08.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883132A (en) * | 2017-01-18 | 2017-06-23 | 中山大学 | With N, the substitution hydrazides of N bis- is the copper catalysis C N coupling methods of part to one kind |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883132A (en) * | 2017-01-18 | 2017-06-23 | 中山大学 | With N, the substitution hydrazides of N bis- is the copper catalysis C N coupling methods of part to one kind |
Non-Patent Citations (2)
| Title |
|---|
| Chemotherapeutic Dyes. I. 5-Aralkylamino-9-alkylaminobenzo[a] phenoxazines1;Moses L. Crossley等;《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》;19520205;第74卷;第577页左栏第4-6段 * |
| Moses L. Crossley等.Chemotherapeutic Dyes. I. 5-Aralkylamino-9-alkylaminobenzo[a] phenoxazines1.《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》.1952,第74卷 * |
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