阅读说明：本技术 一种5-氨基-1-萘酚盐酸盐的制备方法 (Preparation method of 5-amino-1-naphthol hydrochloride ) 是由 李昌德 马思聪 王越 许锦凤 张秀岩 祁咏梅 于 2021-07-14 设计创作，主要内容包括：一种5-氨基-1-萘酚盐酸盐的制备方法,该方法包括以下步骤：(1)在高压反应釜中,加入1,5-二羟基萘；(2)加入水,水与1,5-二羟基萘之间的重量比为3:1～5:1；(3)加入亚硫酸氢钠,亚硫酸氢钠与1,5-二羟基萘之间的摩尔比为1:1～1.5:1；(4)加入浓度为25％的氨水,氨水与1,5-二羟基萘之间的摩尔比为1:1～1.5:1；(5)封闭高压釜,加热至80～100℃,在该温度下反应3～6小时；(6)降温至10～25℃,搅拌分散析出8～10小时,过滤,烘干,得到粗产品5-氨基-1-萘酚；(7)粗产品溶解于浓盐酸和甲醇中重结晶,得到5-氨基-1-萘酚盐酸盐。本发明工艺简单,适合工业化生产。(A preparation method of 5-amino-1-naphthol hydrochloride comprises the following steps: (1) adding 1, 5-dihydroxynaphthalene into a high-pressure reaction kettle; (2) adding water, wherein the weight ratio of the water to the 1, 5-dihydroxynaphthalene is 3: 1-5: 1; (3) adding sodium bisulfite, wherein the molar ratio of the sodium bisulfite to the 1, 5-dihydroxynaphthalene is 1: 1-1.5: 1; (4) adding 25% ammonia water, wherein the molar ratio of the ammonia water to the 1, 5-dihydroxynaphthalene is 1: 1-1.5: 1; (5) sealing the autoclave, heating to 80-100 ℃, and reacting for 3-6 hours at the temperature; (6) cooling to 10-25 ℃, stirring, dispersing and separating out for 8-10 hours, filtering, and drying to obtain a crude product 5-amino-1-naphthol; (7) the crude product is dissolved in concentrated hydrochloric acid and methanol for recrystallization to obtain 5-amino-1-naphthol hydrochloride. The invention has simple process and is suitable for industrial production.)

1. A preparation method of 5-amino-1-naphthol hydrochloride is characterized by comprising the following steps: the method comprises the following steps:

(1) adding 1, 5-dihydroxynaphthalene into a high-pressure reaction kettle;

(2) adding water, wherein the weight ratio of the water to the 1, 5-dihydroxynaphthalene is 2: 1-3: 1;

(3) adding sodium bisulfite, wherein the molar ratio of the sodium bisulfite to the 1, 5-dihydroxynaphthalene is 1: 1-1.5: 1;

(4) adding 25% ammonia water, wherein the molar ratio of the ammonia water to the 1, 5-dihydroxynaphthalene is 1: 1-2: 1;

(5) sealing the autoclave, heating to 80-100 ℃, and reacting for 3-6 hours at the temperature;

(6) cooling to 10-25 ℃, stirring, dispersing and separating out for 8-10 hours, filtering, and drying to obtain a crude product 5-amino-1-naphthol;

(7) the crude product is dissolved in concentrated hydrochloric acid and methanol for recrystallization to obtain 5-amino-1-naphthol hydrochloride.

2. The method of claim 1, wherein: the molar ratio of the hydrochloric acid to the 1, 5-dihydroxy naphthalene is 1: 1-1.2: 1.

3. The method of claim 1, wherein: the weight ratio of the methanol to the 1, 5-dihydroxy naphthalene is 3: 1-5: 1.

Technical Field

The invention relates to a dye intermediate, in particular to a preparation method of 5-amino-1-naphthol hydrochloride.

Background

The structural formula of the 5-amino-1-naphthol hydrochloride is as follows:

the synthesis method of amino-1-naphthol hydrochloride is not reported in documents, the common synthesis method of the compounds is that amino naphthalene sulfonic acid and sodium hydroxide are fused at high temperature of over 240 ℃ to generate amino naphthol, and then the amino naphthalene sulfonic acid and the sodium hydroxide react with hydrochloric acid to generate the amino naphthol hydrochloride, and the method has overhigh reaction temperature and serious pollution and is not beneficial to industrial production.

Disclosure of Invention

Aiming at the technical problems, the invention provides the preparation method of the 5-amino-1-naphthol hydrochloride, which has the advantages of high yield, high product purity, low reaction temperature, simple operation and suitability for industrial preparation.

The purpose of the invention is realized by the following technical scheme:

the invention relates to a preparation method of 5-amino-1-naphthol hydrochloride, which comprises the following steps:

(1) adding 1, 5-dihydroxynaphthalene into a high-pressure reaction kettle;

(2) adding water, wherein the weight ratio of the water to the 1, 5-dihydroxynaphthalene is 2: 1-3: 1;

(3) adding sodium bisulfite, wherein the molar ratio of the sodium bisulfite to the 1, 5-dihydroxynaphthalene is 1: 1-1.5: 1;

(4) adding 25% ammonia water, wherein the molar ratio of the ammonia water to the 1, 5-dihydroxynaphthalene is 1: 1-2: 1;

(5) sealing the autoclave, heating to 80-100 ℃, and reacting for 3-6 hours at the temperature;

(6) cooling to 10-25 ℃, stirring, dispersing and separating out for 8-10 hours, filtering, and drying to obtain a crude product 5-amino-1-naphthol;

(7) the crude product is dissolved in concentrated hydrochloric acid and methanol for recrystallization to obtain 5-amino-1-naphthol hydrochloride.

Furthermore, the molar ratio of the hydrochloric acid to the 1, 5-dihydroxynaphthalene is 1: 1-1.2: 1.

Further, the weight ratio of the methanol to the 1, 5-dihydroxy naphthalene is 3: 1-5: 1.

Compared with the prior art, the invention has the following advantages:

1. the method has the advantages of high yield, high product purity, low reaction temperature, simple operation and suitability for industrialization.

2. In the invention, the generation amount of the byproduct 1, 5-diaminonaphthalene is successfully controlled by adjusting the reaction temperature and the raw material ratio, a crude product containing a small amount of byproduct 1, 5-diaminonaphthalene is generated, and then the crude product reacts with hydrochloric acid in methanol to generate a mixture of 5-amino-1-naphthol hydrochloride and a small amount of 1, 5-diaminonaphthalene hydrochloride, and the mixture is recrystallized in methanol to finally obtain a 5-amino-1-naphtholate product with high purity.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.

The reaction formula of 5-amino-1-naphthol hydrochloride is as follows:

example 1: adding 100 g of 1, 5-dihydroxynaphthalene, 300 g of water, 65 g of sodium bisulfite, 131 g of 25% ammonia water into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, heating to 80 ℃, reacting for 6 hours at the temperature, cooling to 10-25 ℃, stirring, dispersing and separating out for 8-10 hours, filtering, and drying to obtain a crude product, namely 5-amino-1-naphthol. The crude product is dissolved in 75 g of concentrated hydrochloric acid and 350 g of methanol, and after all the crude product is dissolved, the crude product is cooled, separated out, filtered and dried to obtain a gray 5-amino-1-naphtholate hydrochloride product with the content of 99.0 percent and the yield of 76 percent.

Example 2:

adding 100 g of 1, 5-dihydroxynaphthalene, 300 g of water, 65 g of sodium bisulfite, 122.5 g of ammonia water with the concentration of 25%, sealing the autoclave, heating to 90 ℃, reacting for 5 hours at the temperature, cooling to 10-25 ℃, stirring, dispersing and separating out for 8-10 hours, filtering, and drying to obtain a crude product, namely 5-amino-1-naphthol. The crude product is dissolved in 80 g of concentrated hydrochloric acid and 300 g of methanol, and after all the crude product is dissolved, the crude product is cooled, separated out, filtered and dried to obtain a gray 5-amino-1-naphtholate hydrochloride product with the content of 99.2 percent and the yield of 78 percent.

Example 3

Adding 100 g of 1, 5-dihydroxynaphthalene, 300 g of water, 75 g of sodium bisulfite, 100 g of ammonia water with the concentration of 25%, sealing the autoclave, heating to 100 ℃, reacting for 4 hours at the temperature, cooling to 10-25 ℃, stirring, dispersing and separating out for 8-10 hours, filtering, and drying to obtain a crude product, namely 5-amino-1-naphthol. The crude product is dissolved in 74 g of concentrated hydrochloric acid and 300 g of methanol, and after all the crude product is dissolved, the crude product is cooled, separated out, filtered and dried to obtain a gray 5-amino-1-naphtholate hydrochloride product with the content of 99.3 percent and the yield of 80 percent.

Example 4

Adding 100 g of 1, 5-dihydroxynaphthalene, 300 g of water, 65 g of sodium bisulfite, 150 g of ammonia water with the concentration of 25%, sealing the autoclave, heating to 100 ℃, reacting for 4 hours at the temperature, cooling to 10-25 ℃, stirring, dispersing and separating out for 8-10 hours, filtering, and drying to obtain a crude product, namely 5-amino-1-naphthol. The crude product is dissolved in 80 g of concentrated hydrochloric acid and 400 g of methanol, and after all the crude product is dissolved, the crude product is cooled, separated out, filtered and dried to obtain a gray 5-amino-1-naphtholate hydrochloride product with the content of 99.5 percent and the yield of 79 percent.

Example 5

Adding 100 g of 1, 5-dihydroxynaphthalene, 280 g of water, 70 g of sodium bisulfite and 105 g of ammonia water into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, heating to 100 ℃, reacting at the temperature for 5 hours, cooling to 10-25 ℃, stirring, dispersing and separating out for 8-10 hours, filtering and drying to obtain a crude product, namely the 5-amino-1-naphthol. The crude product is dissolved in 85 g of concentrated hydrochloric acid and 450 g of methanol, and after all the crude product is dissolved, the crude product is cooled, separated out, filtered and dried to obtain a gray 5-amino-1-naphtholate hydrochloride product with the content of 99.6 percent and the yield of 78 percent.

Example 6

Adding 100 g of 1, 5-dihydroxynaphthalene into a high-pressure reaction kettle, adding 200 g of water, adding 97 g of sodium bisulfite, adding 90 g of ammonia water, sealing the high-pressure reaction kettle, heating to 100 ℃, reacting at the temperature for 5 hours, cooling to 10-25 ℃, stirring, dispersing and separating out for 8-10 hours, filtering, and drying to obtain a crude product, namely 5-amino-1-naphthol. The crude product was dissolved in 88 g of concentrated hydrochloric acid and 500 g of methanol, and after all dissolved, it was cooled to precipitate, filtered and dried to obtain a gray 5-amino-1-naphtholate hydrochloride product with a content of 99.7% and a yield of 77%.

Example 7

Adding 100 g of 1, 5-dihydroxynaphthalene into a high-pressure reaction kettle, adding 250 g of water, adding 90 g of sodium bisulfite and 90 g of ammonia water, sealing the high-pressure reaction kettle, heating to 100 ℃, reacting for 5 hours at the temperature, cooling to 10-25 ℃, stirring, dispersing and separating out for 8-10 hours, filtering, and drying to obtain a crude product, namely 5-amino-1-naphthol. The crude product was dissolved in 78 g of concentrated hydrochloric acid and 440 g of methanol, and after complete dissolution, it was cooled to precipitate, filtered and dried to give a gray 5-amino-1-naphtholate hydrochloride product with a content of 99.4% and a yield of 81%.

Example 8

Adding 100 g of 1, 5-dihydroxynaphthalene into a high-pressure reaction kettle, adding 250 g of water, adding 77 g of sodium bisulfite, adding 120 g of ammonia water, sealing the high-pressure reaction kettle, heating to 100 ℃, reacting at the temperature for 5 hours, cooling to 10-25 ℃, stirring, dispersing and separating out for 8-10 hours, filtering, and drying to obtain a crude product, namely 5-amino-1-naphthol. The crude product was dissolved in 76 g of concentrated hydrochloric acid and 340 g of methanol, and after all dissolved, it was cooled to precipitate, filtered and dried to obtain a gray 5-amino-1-naphtholate hydrochloride product with a content of 99.1% and a yield of 83%.

Example 9

Adding 100 g of 1, 5-dihydroxynaphthalene, 250 g of water, 65 g of sodium bisulfite and 88 g of ammonia water into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, heating to 100 ℃, reacting at the temperature for 5 hours, cooling to 10-25 ℃, stirring, dispersing and separating out for 8-10 hours, filtering and drying to obtain a crude product, namely 5-amino-1-naphthol. The crude product was dissolved in 75 g of concentrated hydrochloric acid and 300 g of methanol, and after all dissolved, it was cooled to precipitate, filtered and dried to obtain a gray 5-amino-1-naphtholate hydrochloride product with a content of 99.0% and a yield of 77%.

It should be understood that the detailed description of the present invention is only for illustrating the present invention and is not limited by the technical solutions described in the embodiments of the present invention, and those skilled in the art should understand that the present invention can be modified or substituted equally to achieve the same technical effects; as long as the use requirements are met, the method is within the protection scope of the invention.