CN101613304A - A kind of method for preparing anilines diazosalt solid powder - Google Patents
A kind of method for preparing anilines diazosalt solid powder Download PDFInfo
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- CN101613304A CN101613304A CN200910069952A CN200910069952A CN101613304A CN 101613304 A CN101613304 A CN 101613304A CN 200910069952 A CN200910069952 A CN 200910069952A CN 200910069952 A CN200910069952 A CN 200910069952A CN 101613304 A CN101613304 A CN 101613304A
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- amino benzenes
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Abstract
The invention provides a kind of method for preparing anilines diazosalt solid powder, this method comprises the steps: (1) diazotization: slowly add exsiccant NaNO in anhydrous slufuric acid
2, adding amino benzenes compounds then, cooling after reaction is finished is diluted in the mixture of ice and water, gets amino benzenes compounds diazonium salt aqueous sulfuric acid.(2) crystallization is separated out: add anionic organic compounds in amino benzenes compounds diazonium salt aqueous sulfuric acid, stirred crystallization is separated out, and gets amino benzenes compounds diazonium salt filter cake after the filtration.(3) drying: with amino benzenes compounds diazonium salt filtration cakes torrefaction, getting powdery amino benzenes compounds diazonium salt is anilines diazosalt solid powder.
Description
Technical field
The invention belongs to the intermediate preparation field of synthetic dyestuff, particularly relate to the preparation method of anilines diazosalt solid powder, this diazonium salt is mainly used in synthetic azoic dyestuff.
Background technology
When synthesizing azoic dyestuff, often run into amino benzenes compounds diazotization problem, as C.I. reactive black 52.Amino benzenes compounds diazotization, in the vitriol oil of being everlasting, carry out, thereby after making coupled reaction, produce a large amount of vitriol, these vitriol can make colorant dissolubility descend, also can influence the dye uptake of dyestuff dsred protein fiber and look soundness and it is reduced, so if the most of sulfuric acid in the amino benzenes compounds diazonium salt can be removed, then highly beneficial to synthetic dyestuff.The amino benzenes compounds diazonium salt is soluble in water, even in the presence of a large amount of sulfuric acid, also is difficult to and water sepn, and after this diazonium salt dehydration drying, because active performance is strong, easily causes and decompose and blast, and bring danger or cause quality product to descend to production process.For solving above-mentioned two difficult problems, the invention provides a kind of new method for preparing the amino benzenes compounds diazonium salt, this method can solve the problems of the technologies described above.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of method for preparing anilines diazosalt solid powder, this method comprises that with amino benzenes compounds diazotization the crystallization of amino benzenes compounds diazonium salt is separated out and amino benzenes compounds diazonium salt drying.
Particularly, aforesaid method comprises the steps:
(1) diazotization: in anhydrous slufuric acid, slowly add exsiccant NaNO
2, adding amino benzenes compounds then, cooling after reaction is finished is diluted in the mixture of ice and water, gets amino benzenes compounds diazonium salt aqueous sulfuric acid.
(2) crystallization is separated out: add anionic organic compounds in amino benzenes compounds diazonium salt aqueous sulfuric acid, stirred crystallization is separated out, and gets amino benzenes compounds diazonium salt filter cake after the filtration.
(3) drying: with amino benzenes compounds diazonium salt filtration cakes torrefaction, getting powdery amino benzenes compounds diazonium salt is anilines diazosalt solid powder.
Wherein amino benzenes compounds is meant that a hydrogen atom is replaced by amino on the phenyl ring, the compound that the hydrogen of other positions is replaced by any other substituting groups on the phenyl ring.Preferably, the substituting group on the phenyl ring is selected from alkyl, alkoxyl group, halogen, the nitro one or more in the amino benzenes compounds.
Preferably, amino benzenes compounds is selected from the compound of following structure:
Wherein to be selected from halogen, carbonatoms be that alkyl or the carbonatoms of 1-3 is the alkoxyl group of 1-3 to R, and the m+n sum is the integer of 0-4.
In the aforesaid method, anionic organic compounds can combine with diazonium salt and form throw out, so anionic organic compounds herein has no particular limits, just can as long as can form precipitation with diazonium salt.
Preferably, anionic organic compounds is R-(SO
3H)
n, R is an alkyl or aryl, is preferably aryl, n is the integer of 1-3.
Preferably, anionic organic compounds be selected from as shown in the formula in (I), formula (II) and formula (III) compound one or more, perhaps be selected from as shown in the formula in the metal-salt of (I), formula (II) and formula (III) compound one or more:
N is the integer of 1-3 in the formula (I), and n is the integer of 1-3 in the formula (II), and m+n equals the integer of 1-3 in the formula (III).
In the aforesaid method, amino benzenes compounds is selected from 2,4-dinitraniline, 6-bromo-2, a kind of in 4-dinitraniline, p-Nitroaniline, m-nitraniline, o-Nitraniline, ORTHO ANISIDINE, m-anisidine, P-nethoxyaniline and the aniline, be preferably 2,4-dinitraniline and 6-bromo-2, a kind of in the 4-dinitraniline.
In the aforesaid method, diazotation step is:
In anhydrous slufuric acid, adding anhydrous Na NO below 30 ℃
2, add amino benzenes compounds again, in 35-45 ℃ of diazotization reaction 6-9 hour,, be diluted to then in the frozen water the reaction solution cooling, get amino benzenes compounds diazonium salt aqueous sulfuric acid.
Preferably, diazotation step is:
In anhydrous slufuric acid, adding anhydrous Na NO below 30 ℃
2, in 60-80 ℃ of reaction 2-4 hour, add amino benzenes compounds again, in 35-45 ℃ of diazotization reaction 6-9 hour, reaction solution is cooled to below 40 ℃, be diluted to then in the frozen water, get amino benzenes compounds diazonium salt aqueous sulfuric acid.
In the aforesaid method, crystallization is separated out step and is:
In amino benzenes compounds diazonium salt aqueous sulfuric acid, add Phenylsulfonic acid, stir and separate out more than 2 hours, get amino benzenes compounds diazonium salt filter cake after the filtration.
In the aforesaid method, drying step is:
At 85 ℃ of following dry benzene aminated compounds diazonium salt filter cakes, get anilines diazosalt solid powder.
In the aforesaid method, formula (I), formula (II) and formula (III) compound or its metal-salt can be bought from the market and obtain, and are chemical field raw materials commonly used.
The method for preparing the amino benzenes compounds diazonium salt of the present invention has following effect:
The present invention is in the process of preparation amino benzenes compounds diazonium salt, add anionic organic compounds, the amino benzenes compounds diazonium salt is precipitated from aqueous sulfuric acid separates out, after filtering, reach and remove a large amount of vitriolic purposes, a large amount of sulfuric acid are discharged with filtrate, and filter cake drying more promptly gets solid powder.This anilines diazosalt solid powder can be used as intermediate and sells, and also can continue synthetic dyestuff.The anilines diazosalt solid powder good stability that obtains with the present invention, dry as safe as a house below 85 ℃, can not produce decomposing phenomenon, more there is not explosion hazard, the free sulfuric acid that carries does not influence coupled reaction below 12%, has both solved coupling and has produced a large amount of inorganic salt problems, solve diazonium salt again and decomposed the quality product decline problem that causes, also avoided the explosion hazard in synthetic and the use.
Embodiment
Below by embodiment technical scheme of the present invention is further explained and illustrated, but be not any limitation of the invention.
Embodiment 1:
(1) diazotization: get the anhydrous slufuric acid of 135.3g, slowly add exsiccant NaNO in 25 ℃ of temperature
211.2g, in 80 ℃ of reactions 2 hours.Be cooled to below 40 ℃, add 2 of content 98% in 40 ℃ then, 4-dinitraniline 28g reacted 6 hours, was cooled to 10 ℃, was diluted in the mixture of ice and water, and controlled temperature≤0 ℃ obtains 2,4-dinitraniline diazonium salt aqueous sulfuric acid.
(2) crystallization is separated out: 2, in the 4-dinitraniline diazonium salt aqueous sulfuric acid, add the 50g Phenylsulfonic acid, stir and separate out more than 2 hours, get 2 after the filtration, and 4-dinitraniline diazonium salt filter cake, to be dried.
(3) drying: with 2,4-dinitraniline diazonium salt filter cake carries out drying in about 80 ℃, gets powdery 2, and 4-dinitraniline diazonium salt is 2,4-dinitraniline diazosalt solid pulvis.
Embodiment 2:
(1) diazotization: get 98% sulfuric acid 93 .7g, cooling is descended and 41.6g contains SO
320% oleum mixes, and makes the anhydrous slufuric acid of 135.3g.In this anhydrous slufuric acid, ℃ slowly add exsiccant NaNO in temperature≤30
211.2g, in 60 ℃ of reactions 3 hours.Be cooled to below 40 ℃, in 45 ℃ of 6-bromo-2 that add content 98%, 4-dinitraniline 32g react 8 hours, was cooled to below 15 ℃ then, was diluted in the mixture of ice and water, and controlled temperature≤0 ℃ must 6-bromo-2,4-dinitraniline diazonium salt aqueous sulfuric acid.
(2) crystallization is separated out: at 6-bromo-2, in the 4-dinitraniline diazonium salt aqueous sulfuric acid, add 1 of 35g, 5-naphthalene disulfonic acid and 15g sodium laurylsulfonate stir and separate out more than 2 hours, get 6-bromo-2 after the filtration, and 4-dinitraniline diazonium salt filter cake is to be dried.
(3) drying: with 6-bromo-2,4-dinitraniline diazonium salt filter cake carries out drying in 80 ℃, powdery 6-bromo-2,4-dinitraniline diazonium salt is a 6-bromo-2,4-dinitraniline diazosalt solid pulvis.
Embodiment 3:
(1) diazotization: get 98% sulfuric acid 93 .7g, cooling is descended and 41.6g contains SO
320% oleum mixes, and makes the anhydrous slufuric acid of 135.3g.In this anhydrous slufuric acid, ℃ slowly add exsiccant NaNO in temperature≤30
211.2g, in 70 ℃ of reactions 2 hours.Be cooled to below 40 ℃, in 35 ℃ of aniline 20g that add content 98%, react 8 hours then, be cooled to below 15 ℃, be diluted in the mixture of ice and water, controlled temperature≤0 ℃ must the diazonium salt of aniline aqueous sulfuric acid.
(2) crystallization is separated out: in the diazonium salt of aniline aqueous sulfuric acid, add 40g anthraquinone-2, the 5-disulfonic acid stirs and separates out more than 2 hours.Filter 2,4-dinitraniline diazonium salt filter cake, to be dried.
(3) drying: in carrying out drying below 80 ℃, getting the powdery diazonium salt of aniline is the diazonium salt of aniline solid powder with the diazonium salt of aniline filter cake.
The preparation method of anilines diazosalt solid powder of the present invention is described by specific embodiment.Those skilled in the art can use for reference links such as content appropriate change raw material of the present invention, processing condition and realize corresponding other purpose, its relevant change does not all break away from content of the present invention, all similar replacements and change will become apparent to those skilled in the art that and all be regarded as comprising within the scope of the present invention.
Claims (10)
1, a kind of method for preparing anilines diazosalt solid powder, this method comprises the steps:
(1) diazotization: in anhydrous slufuric acid, slowly add exsiccant NaNO
2, adding amino benzenes compounds then, cooling after reaction is finished is diluted in the mixture of ice and water, gets amino benzenes compounds diazonium salt aqueous sulfuric acid;
(2) crystallization is separated out: add anionic organic compounds in amino benzenes compounds diazonium salt aqueous sulfuric acid, stirred crystallization is separated out, and gets amino benzenes compounds diazonium salt filter cake after the filtration;
(3) drying: with amino benzenes compounds diazonium salt filtration cakes torrefaction, getting powdery amino benzenes compounds diazonium salt is anilines diazosalt solid powder;
Wherein amino benzenes compounds is meant that a hydrogen atom is replaced by amino on the phenyl ring, the compound that the hydrogen of other positions is replaced by any other substituting groups on the phenyl ring.
2, compound according to claim 1, wherein the substituting group on the phenyl ring is selected from alkyl, alkoxyl group, halogen, the nitro one or more in the amino benzenes compounds.
3, according to each described method of claim 1-2, wherein amino benzenes compounds is selected from the compound of following structure:
Wherein to be selected from halogen, carbonatoms be that alkyl or the carbonatoms of 1-3 is the alkoxyl group of 1-3 to R, and the m+n sum is the integer of 0-4.
4, according to each described method of claim 1-3, wherein anionic organic compounds is R-(SO
3H)
n, R is an alkyl or aryl, is preferably aryl, n is the integer of 1-3.
5, according to each described method of claim 1-4, wherein anionic organic compounds be selected from as shown in the formula in (I), formula (II) and formula (III) compound one or more, perhaps be selected from as shown in the formula in the metal-salt of (I), formula (II) and formula (III) compound one or more:
N is the integer of 1-3 in the formula (I), and n is the integer of 1-3 in the formula (II), and m+n equals the integer of 1-3 in the formula (III).
6, according to each described method of claim 1-5, wherein amino benzenes compounds is selected from 2,4-dinitraniline, 6-bromo-2, a kind of in 4-dinitraniline, p-Nitroaniline, m-nitraniline, o-Nitraniline, ORTHO ANISIDINE, m-anisidine, P-nethoxyaniline and the aniline, be preferably 2,4-dinitraniline and 6-bromo-2, a kind of in the 4-dinitraniline.
7, according to each method of claim 1-6, wherein diazotation step is:
In anhydrous slufuric acid, adding anhydrous Na NO below 30 ℃
2, add amino benzenes compounds again, in 35-45 ℃ of diazotization reaction 6-9 hour,, be diluted to then in the frozen water the reaction solution cooling, get amino benzenes compounds diazonium salt aqueous sulfuric acid.
8, according to each method of claim 1-7, wherein diazotation step is:
In anhydrous slufuric acid, adding anhydrous Na NO below 30 ℃
2, in 60-80 ℃ of reaction 2-4 hour, add amino benzenes compounds again, in 35-45 ℃ of diazotization reaction 6-9 hour, reaction solution is cooled to below 40 ℃, be diluted to then in the frozen water, get amino benzenes compounds diazonium salt aqueous sulfuric acid.
9, according to each method of claim 1-8, wherein crystallization is separated out step and is:
In amino benzenes compounds diazonium salt aqueous sulfuric acid, add Phenylsulfonic acid, stir and separate out more than 2 hours, get amino benzenes compounds diazonium salt filter cake after the filtration.
10, according to each method of claim 1-8, wherein drying step is:
At 85 ℃ of following dry benzene aminated compounds diazonium salt filter cakes, get anilines diazosalt solid powder.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724224A (en) * | 2013-12-19 | 2014-04-16 | 中国平煤神马集团开封兴化精细化工有限公司 | Diazo reaction technology in saccharin production |
| CN107082748A (en) * | 2017-06-23 | 2017-08-22 | 上海安诺其集团股份有限公司 | A kind of preparation method of diazol |
| CN109096145A (en) * | 2018-07-13 | 2018-12-28 | 南京卡邦科技有限公司 | A kind of method that multi-substituent aniline prepares diazonium salt |
-
2009
- 2009-07-30 CN CN200910069952A patent/CN101613304A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724224A (en) * | 2013-12-19 | 2014-04-16 | 中国平煤神马集团开封兴化精细化工有限公司 | Diazo reaction technology in saccharin production |
| CN107082748A (en) * | 2017-06-23 | 2017-08-22 | 上海安诺其集团股份有限公司 | A kind of preparation method of diazol |
| CN109096145A (en) * | 2018-07-13 | 2018-12-28 | 南京卡邦科技有限公司 | A kind of method that multi-substituent aniline prepares diazonium salt |
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Application publication date: 20091230 |