CN108299206B - Purification method of 1-nitroso-2-naphthol - Google Patents
Purification method of 1-nitroso-2-naphthol Download PDFInfo
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- CN108299206B CN108299206B CN201810256244.4A CN201810256244A CN108299206B CN 108299206 B CN108299206 B CN 108299206B CN 201810256244 A CN201810256244 A CN 201810256244A CN 108299206 B CN108299206 B CN 108299206B
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- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
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Abstract
A method for purifying 1-nitroso-2-naphthol comprises the following steps: firstly, mixing 1-nitroso-2-naphthol (crude product) with a structural formula shown as a compound (II) with an addition reagent and a solvent-1, and stirring at room temperature until the reaction is finished to obtain an addition product; and secondly, mixing the addition product with a solvent-2, and adding alkali at room temperature under the stirring condition to obtain the 1-nitroso-2-naphthol (refined product) with the structural formula shown as the compound (II).
Description
Technical Field
The invention relates to a purification method of an organic compound, in particular to a purification method of 1-nitroso-2-naphthol.
Background
6-nitro-1, 2-diazoxy-4-naphthalenesulfonic acid (V),
the nitro compound, 6-nitro compound for short, is an acid dye intermediate and is widely used in the synthesis process of mordant black T, acid black 172, acid black 194 and the like. At present, 2-naphthol with a structural formula shown as a compound (I) is used as a main starting material, and nitrosation reaction is carried out to obtain 1-nitroso-2-naphthol with a structural formula shown as a compound (II); carrying out addition-reduction-transposition reaction on 1-nitroso-2-naphthol shown in the structural formula of a compound (II) to obtain 1-nitroso-2-naphthol-4-sulfonic acid shown in the structural formula of a compound (III); carrying out diazotization reaction on 1-nitroso-2-naphthol-4-sulfonic acid with a structural formula shown as a compound (III) to obtain 1, 2-diazoxynaphthalene-4-sulfonic acid with a structural formula shown as a compound (IV); the 1, 2-diazoxynaphthalene-4-sulfonic acid with the structural formula shown as the compound (IV) is synthesized into the compound with the structural formula shown as the compound (IV) through nitration reaction6-nitro-1, 2-diazoxy-4-naphthalenesulfonic acid represented by the formula (V).
Expressed by the equation:
wherein, in the industrial production process of synthesizing 1-nitroso-2-naphthol from 2-naphthol through nitrosation reaction, 3-5% of 2-naphthol (the reaction is not completed, the expected purpose can not be effectively achieved by prolonging the reaction time and increasing the reaction temperature, even an unexpected byproduct can be generated) and a plurality of unknown impurities always exist in the system after the nitration reaction is finished, so that the purity of the 1-nitroso-2-naphthol can only reach 93-95%. The purity of the 1-nitroso-2-naphthol can directly influence the quality of downstream products, and even the quality of the final product 6-nitro-1, 2-diazoxy-4-naphthalene sulfonic acid can not meet the market demand, so that the improvement of the quality of the 1-nitroso-2-naphthol is particularly important.
The ketone carbonyl or aldehyde carbonyl in the molecular structure of the organic compound can react with sodium bisulfite (or similar substances) in a neutral or weakly acidic system to obtain an addition product, and the obtained addition product can return to the structure of the ketone carbonyl or aldehyde carbonyl through the reaction with alkali, so that the organic compound can be purified by utilizing the reversible carbonyl addition reaction.
Expressed by the equation:
wherein R is1、R2Can be one of hydrogen, alkyl and aryl, R1、R2May be the same or different.
Experiments have shown that nitroso groups have to some extent a chemical property similar to that of a ketone carbonyl or aldehyde carbonyl group, i.e. they can also undergo a reversible addition reaction with sodium bisulfite (or the like).
Disclosure of Invention
The invention discloses a purification method of an organic compound with a nitroso in a molecular structure, which specifically comprises the steps of carrying out addition reaction on a 1-nitroso-2-naphthol crude product and sodium bisulfite (or an analogue) to obtain an addition product, and reacting the obtained addition product with alkali to obtain a 1-nitroso-2-naphthol refined product with the purity of more than 99%.
The invention relates to a purification method of 1-nitroso-2-naphthol, which comprises the following steps:
firstly, mixing 1-nitroso-2-naphthol (crude product) with a structural formula shown as a compound (II) with an addition reagent and a solvent-1, and stirring at room temperature until the reaction is finished to obtain an addition product;
and secondly, mixing the addition product with a solvent-2, and adding alkali at room temperature under the stirring condition to obtain the 1-nitroso-2-naphthol (refined product) with the structural formula shown as the compound (II).
Further, the addition reagent is one of sodium sulfite, sodium metabisulfite, sodium bisulfite and sodium hydrosulfite, and the molar ratio of the addition reagent to the 1-nitroso-2-naphthol (crude product) with the structural formula shown as the compound (II) is 0.5-1.0.
Further, the addition reagent is sodium bisulfite.
Further, the solvent-1 is one of methanol, acetone, acetonitrile, DMF and DMSO, and the mass ratio of the solvent-1 to 1-nitroso-2-naphthol (crude product) with the structural formula shown as the compound (II) is 3-5: 1.
Further, the solvent-1 is methanol.
Further, drying the addition product, and then using the addition product for the second step reaction; or directly used for the second reaction without drying the addition product.
Further, the alkali is one of alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate and alkaline earth metal carbonate, and the molar ratio of the alkali to the addition product is 0.5-1.1.
Further, the solvent-2 is one of acetone, acetonitrile, DMF and DMSO, and the mass ratio of the solvent-2 to the addition product is 3-5: 1.
Still further, the solvent-2 is DMSO.
The method has the advantages of high product yield, capability of obtaining the 1-nitroso-2-naphthol refined product with the purity of more than 99 percent at one time, convenient operation and easy industrialization.
Detailed Description
The following examples further illustrate some of the features of the present invention, but the invention is not limited in its content and scope by the following examples.
Example 1
173 g of 1-nitroso-2-naphthol with 93.3 percent of HPLC normalization content and 519 g of methanol are mixed, 88.6 g of sodium metabisulfite is added under the condition of room temperature, and the mixture is stirred until the 1-nitroso-2-naphthol is completely reacted, so that 265 g of an addition product with 99.0 percent of HPLC normalization content is obtained, and the nuclear magnetic hydrogen spectrum data of the addition product compound are as follows: 1HNMR (500MHz, DMSO-d)6)：8.10(d,1H)，8.05(d,1H)，7.67(t,1H),7.64(t,1H)，7.45(t,1H)，7.37(d,1H)，5.35(br,1H)，1.92～2.05(br,2H)。
265 g of the addition product having HPLC normalized content of 99.0% was mixed with 1325 g of methanol and 133 g of 30% aqueous sodium hydroxide solution to obtain 156.1 g of a refined 1-nitroso-2-naphthol having HPLC normalized content of 99.2% in a yield of 99.24% (based on the active ingredient in the crude 1-nitroso-2-naphthol).
Example 2
173 g of 1-nitroso-2-naphthol with 93.3 percent of HPLC normalization content and 519 g of DMF are mixed, 117.5 g of sodium sulfite is added under the condition of room temperature, and the mixture is stirred until the 1-nitroso-2-naphthol completely reacts to obtain 255 g of addition product with 98.7 percent of HPLC normalization content;
255 g of the addition product having an HPLC normalized content of 98.7% obtained by the above-mentioned process was mixed with 765 g of acetonitrile and 64.4 g of potassium carbonate to obtain 157.1 g of a 1-nitroso-2-naphthol fine product having an HPLC normalized content of 99.2% at a yield of 99.16% (based on the active ingredient in the 1-nitroso-2-naphthol crude product).
Example 3
173 g of 1-nitroso-2-naphthol with 93.3 percent of HPLC normalization content and 519 g of methanol are mixed, 97 g of sodium bisulfite is added under the condition of room temperature, and the mixture is stirred until the 1-nitroso-2-naphthol completely reacts to obtain 253 g of addition product with 99.6 percent of HPLC normalization content;
253 g of the adduct having an HPLC normalized content of 99.6% was mixed with 765 g of DMSO and 33.7 g of calcium hydroxide to give 158.7 g of a refined 1-nitroso-2-naphthol having an HPLC normalized content of 99.7% in a yield of 99.83% (based on the active ingredient in the crude 1-nitroso-2-naphthol).
Example 4
173 g of 1-nitroso-2-naphthol with 93.3 percent of HPLC normalization content and 519 g of acetonitrile are mixed, 97 g of sodium hydrosulfite is added under the condition of room temperature, and the mixture is stirred until the 1-nitroso-2-naphthol completely reacts to obtain 253 g of addition product with 99.5 percent of HPLC normalization content;
253 g of the addition product having an HPLC normalized content of 99.5% was mixed with 765 g of DMSO and 33.7 g of calcium hydroxide to give 158.3 g of a 1-nitroso-2-naphthol crude product having an HPLC normalized content of 99.6% in a yield of 99.59% (based on the active ingredient in the 1-nitroso-2-naphthol crude product).
Comparative example 1
173 g of 1-nitroso-2-naphthol with 93.3 percent of HPLC normalization content and 519 g of water are mixed, 88.6 g of sodium metabisulfite is added under the condition of room temperature, and the mixture is stirred until the 1-nitroso-2-naphthol completely reacts to obtain a solid-liquid two-phase mixture;
the solid-liquid two-phase mixture obtained by the above process was mixed with 133 g of a 30% aqueous solution of sodium hydroxide to obtain 153.3 g of 1-nitroso-2-naphthol having an HPLC normalized content of 95.2% in a yield of 90.42% (based on the active ingredient in the crude product of 1-nitroso-2-naphthol).
Comparison with the results of example 1 shows that, after the completion of the addition reaction, the addition product was separated from the obtained solid-liquid two-phase mixture, and then the separated addition product was mixed with a base, whereby a purified 1-nitroso-2-naphthol product having a higher purity was obtained at one time.
Comparative example 2
173 g of 1-nitroso-2-naphthol with 93.3 percent of HPLC normalization content and 519 g of water are mixed, 97 g of sodium bisulfite is added under the condition of room temperature, and the mixture is stirred until the 1-nitroso-2-naphthol completely reacts to obtain 251 g of addition product with 96.6 percent of HPLC normalization content;
251 g of the addition product having HPLC normalized content of 96.6% obtained by the above-mentioned process was mixed with 753 g of acetone and 116.7 g of 30% aqueous sodium hydroxide solution to obtain 148.1 g of a refined 1-nitroso-2-naphthol product having HPLC normalized content of 98.9% at a yield of 90.75% (based on the active ingredient in the crude 1-nitroso-2-naphthol product).
In comparison with the results of examples 1 to 4, the organic solvent is used as the reaction solvent, and the refined 1-nitroso-2-naphthol product with good yield and purity can be obtained more easily than the water.
The results of example 3 show that the highest yield of the refined 1-nitroso-2-naphthol product is obtained when methanol is used as solvent-1 and DMSO is used as solvent-2.
Claims (3)
1. A method for purifying 1-nitroso-2-naphthol is characterized by comprising the following steps:
firstly, mixing a 1-nitroso-2-naphthol crude product with a structural formula shown as a compound (II) with an addition reagent and a solvent-1, and stirring at room temperature until the reaction is finished to obtain an addition product;
secondly, mixing the addition product with a solvent-2, and adding alkali at room temperature under the stirring condition to obtain a 1-nitroso-2-naphthol refined product with the structural formula shown as a compound (II);
the addition reagent is sodium bisulfite, and the molar ratio of the addition reagent to the 1-nitroso-2-naphthol crude product with the structural formula shown as the compound (II) is 0.5-1.0;
the solvent-1 is methanol, and the mass ratio of the solvent-1 to a 1-nitroso-2-naphthol crude product with a structural formula shown as a compound (II) is 3-5: 1;
the solvent-2 is DMSO, and the mass ratio of the solvent-2 to the addition product is 3-5: 1.
2. The method for purifying 1-nitroso-2-naphthol according to claim 1, wherein the addition product is dried and then used in the second reaction step; or directly used for the second reaction without drying the addition product.
3. The method for purifying 1-nitroso-2-naphthol according to claim 1, wherein the base is one of alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate and alkaline earth metal carbonate, and the molar ratio of the base to the addition product is 0.5 to 1.1.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101092380A (en) * | 2007-07-11 | 2007-12-26 | 重庆大学 | Method for preparing 1,2,4 acid through synthesis in homogeneous phase between water and alcohol solvent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101092380A (en) * | 2007-07-11 | 2007-12-26 | 重庆大学 | Method for preparing 1,2,4 acid through synthesis in homogeneous phase between water and alcohol solvent |
Non-Patent Citations (2)
| Title |
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| 6-硝合成工艺改进的研究;许秀丽;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20090615(第06期);第B016-17页 * |
| Reactivity of sulfur dioxide-anion radical toward reducible substrates;Dierk Knittel;《Monatshefte fuer Chemie》;19861231;第117卷(第3期);359-367 * |
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