CN101397257A - Method for preparing high-purity hydrochloride naphthodiamide - Google Patents
Method for preparing high-purity hydrochloride naphthodiamide Download PDFInfo
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- CN101397257A CN101397257A CNA200710061278XA CN200710061278A CN101397257A CN 101397257 A CN101397257 A CN 101397257A CN A200710061278X A CNA200710061278X A CN A200710061278XA CN 200710061278 A CN200710061278 A CN 200710061278A CN 101397257 A CN101397257 A CN 101397257A
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- naphthodiamide
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- hydrochloride naphthodiamide
- quadrol
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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Abstract
The invention relates to a preparation method of high-purity naphthyl ethylenediamine hydrochloride. The method uses bromonaphthalene and ethylenediamine for carrying out the alkylation reaction under the action of a copper-copper oxide catalyst, thereby generating naphthyl ethylenediamine; and the reaction products are purified by using benzene, ethanol and other organic solvents, and the products after the purification are dissolved in hydrochloric acid, thereby generating the high-purity naphthyl ethylenediamine hydrochloride. The method is simple and easy, the generated naphthyl ethylenediamine hydrochloride not only has high purity, but also is applicable to the environmental monitoring; furthermore, the various reagents can be recycled during the reaction process, and the residual reagents can be reused, thereby saving the cost.
Description
Technical field
The present invention relates to the preparation purification techniques field of organic compound, especially a kind of preparation method who satisfies the high-purity hydrochloride naphthodiamide of environment monitoring requirement.
Background technology
Hydrochloride naphthodiamide (N-(1-naphthyl) ethylenedimine dihydrochloride) is a kind of important environmental protection tests reagent, be used for monitoring oxynitride, aniline, the parathion-methyl of air and waste gas, and the nitrate radical in the precipitation, nitrite anions, can also monitor nitrate nitrogen, nitrite nitrogen in water and the waste water, and phenyl amines and nitrobenzene compounds.But it is relatively poor that general producer produces the hydrochloride naphthodiamide quality product, mostly contains impurity, causes solubility property, sensitivity, blank value and the circulation ratio of hydrochloride naphthodiamide all very poor, thereby influenced the monitoring tolerance range, can not satisfy the requirement of environment monitoring.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation method who satisfies the high-purity hydrochloride naphthodiamide of environment monitoring reality of work needs is provided.
The technical solution used in the present invention is:
A kind of preparation method of high-purity hydrochloride naphthodiamide the steps include:
(1). naphthalene bromide mixes with quadrol, refluxes 6～10 hours under 110～130 ℃ of temperature, is cooled to 70～80 ℃ then;
(2). in above-mentioned reactant, add copper containing catalyst, refluxed naturally cooling 6～10 hours;
(3). underpressure distillation is also reclaimed excessive quadrol;
(4). use the organic solvent extraction reactant, filter, underpressure distillation is also reclaimed solvent;
(5). underpressure distillation obtains the product naphthodiamide;
(6). naphthodiamide is added in the hydrochloric acid soln, and temperature is cooled to 0～5 ℃, filtering for crystallizing;
(7). the gained crystal with ethyl alcohol recrystallization after, promptly obtain the high-purity hydrochloride naphthodiamide finished product.
And the ratio of weight and number of described naphthalene bromide and quadrol is 69:160.
And described copper containing catalyst is the mixture of copper powder and cupric oxide powder, and the weight ratio of copper and cupric oxide is 100:5～30.
And described organic solvent is benzene or dehydrated alcohol.
And the concentration of described hydrochloric acid soln is 4～8M.
Advantage of the present invention and positively effect are:
1. bromine and torpescence on the aromatic halides naphthalene bromide molecule used in the present invention, general being difficult for reacts with amine, therefore, significant variation hour can not take place in quadrol and naphthalene bromide mixing post-heating boiling number yet, after having only the copper containing catalyst of adding, the alkalescence of quadrol could be strengthened, make it become big, thereby the reaction of naphthalene bromide and quadrol can be carried out smoothly the nucleophilie nucleus ability of naphthalene bromide.
2. contain unreacted naphthalene bromide, quadrol, copper catalyst and some byproducts of reaction in the naphthodiamide that naphthalene bromide and quadrol generate among the present invention under the katalysis of copper containing catalyst, if directly carry out next step reaction, in the final product hydrochloride naphthodiamide, can contain above-mentioned impurity, this impurity can make the product purity of generation not high, can influence the environment monitoring result and may produce bigger error.Therefore, the present invention make extraction agent with benzene naphthodiamide is dissolved in the benzole soln, and benzene-insoluble impurity can be removed after the first step generates naphthodiamide, and organic solvents such as same ethanol also can be used as extraction agent.
3. the present invention carries out alkylated reaction with naphthalene bromide and quadrol under the effect of copper-copper oxide catalyst, generates naphthodiamide, purified after, be dissolved in again in the hydrochloric acid, promptly generate highly purified hydrochloride naphthodiamide.Present method is simple, and the hydrochloride naphthodiamide of generation is the purity height not only, is applicable to environment monitoring, and can also reclaim all ingredients in the reaction process, and remaining reagent can be reused, and has saved cost.
Embodiment
Below in conjunction with embodiment, the present invention is further described, and following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
The reaction formula of present method is:
Embodiment 1:
The preparation of high-purity hydrochloride naphthodiamide:
(1). in the reactor that the mechanical stirring cooling and reflux device is housed, add the quadrols of 69 gram naphthalene bromides and 160 grams, heated mixt to 110 ℃ keeps this temperature to reflux 10 hours, and temperature is cooled to 70 ℃ then;
(2). with copper powder and cupric oxide powder be by weight mix at 100: 5 after, the mixture of getting catalytic amount adds in the reactor, refluxes naturally cooling 10 hours;
(3). excessive quadrol is reclaimed in underpressure distillation;
(4). with benzene extractive reaction thing, filter, benzene is reclaimed in underpressure distillation;
(5). underpressure distillation obtains the product naphthodiamide;
(6). naphthodiamide is added in the reagent hydrochloric acid solution that concentration is 4M, and temperature is cooled to 0 ℃, filtering for crystallizing;
(7). the gained crystal is obtained high-purity hydrochloride naphthodiamide after with ethyl alcohol recrystallization.
Embodiment 2:
The preparation of high-purity hydrochloride naphthodiamide:
(1). in the reactor that the mechanical stirring cooling and reflux device is housed, add the quadrol of 414 kilograms of naphthalene bromides and 960 kilograms, heated mixt to 130 ℃ keeps this temperature to reflux 6 hours, and temperature is cooled to 80 ℃ then;
(2). copper powder and cupric oxide powder after mix for 100:30, are got in the mixture adding reactor of catalytic amount, refluxed naturally cooling 6 hours;
(3). excessive quadrol is reclaimed in underpressure distillation;
(4). use the alcohol extraction reactant, filter, ethanol is reclaimed in underpressure distillation;
(5). underpressure distillation obtains the product naphthodiamide;
(6). naphthodiamide is added in the reagent hydrochloric acid solution that concentration is 8M, with ice-cooled to 5 ℃, filtering for crystallizing;
(7). the gained crystal is obtained high-purity hydrochloride naphthodiamide after with ethyl alcohol recrystallization.
Embodiment 3:
The preparation of high-purity hydrochloride naphthodiamide:
(1). in the reactor that the mechanical stirring cooling and reflux device is housed, add the quadrol of 207 kilograms of naphthalene bromides and 480 kilograms, heated mixt to 120 ℃ keeps this temperature to reflux 8 hours, and temperature is cooled to 75 ℃ then;
(2). copper powder and cupric oxide powder after mix for 100:20, are got in the mixture adding reactor of catalytic amount, refluxed naturally cooling 8 hours;
(3). excessive quadrol is reclaimed in underpressure distillation;
(4). with benzene extractive reaction thing, filter, benzene is reclaimed in underpressure distillation;
(5). underpressure distillation obtains the product naphthodiamide;
(6). naphthodiamide is added in the reagent hydrochloric acid solution that concentration is 6M, with ice-cooled to 4 ℃, filtering for crystallizing;
(7). the gained crystal is obtained high-purity hydrochloride naphthodiamide after with ethyl alcohol recrystallization.
Claims (5)
1. the preparation method of a high-purity hydrochloride naphthodiamide is characterized in that:
The step of its preparation method is:
(1). naphthalene bromide mixes with quadrol, refluxes 6～10 hours under 110～130 ℃ of temperature, is cooled to 70～80 ℃ then;
(2). in above-mentioned reactant, add copper containing catalyst, refluxed naturally cooling 6～10 hours;
(3). underpressure distillation is also reclaimed excessive quadrol;
(4). use the organic solvent extraction reactant, filter, underpressure distillation is also reclaimed solvent;
(5). underpressure distillation obtains the product naphthodiamide;
(6). naphthodiamide is added in the hydrochloric acid soln, and temperature is cooled to 0～5 ℃, filtering for crystallizing;
(7). the gained crystal with ethyl alcohol recrystallization after, promptly obtain the high-purity hydrochloride naphthodiamide finished product.
2. the preparation method of high-purity hydrochloride naphthodiamide according to claim 1, it is characterized in that: the ratio of weight and number of described naphthalene bromide and quadrol is 69:160.
3. the preparation method of high-purity hydrochloride naphthodiamide according to claim 1, it is characterized in that: described copper containing catalyst is the mixture of copper powder and cupric oxide powder, the weight ratio of copper and cupric oxide is 100:5～30.
4. the preparation method of high-purity hydrochloride naphthodiamide according to claim 1, it is characterized in that: described organic solvent is benzene or dehydrated alcohol.
5. the preparation method of high-purity hydrochloride naphthodiamide according to claim 1, it is characterized in that: the concentration of described hydrochloric acid soln is 4～8M.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200710061278XA CN101397257A (en) | 2007-09-28 | 2007-09-28 | Method for preparing high-purity hydrochloride naphthodiamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200710061278XA CN101397257A (en) | 2007-09-28 | 2007-09-28 | Method for preparing high-purity hydrochloride naphthodiamide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101397257A true CN101397257A (en) | 2009-04-01 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA200710061278XA Pending CN101397257A (en) | 2007-09-28 | 2007-09-28 | Method for preparing high-purity hydrochloride naphthodiamide |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173996A (en) * | 2011-03-14 | 2011-09-07 | 天津市化学试剂研究所 | Preparation method of naphthyl ethylene diamine hydrochloride |
| CN102531924A (en) * | 2010-12-27 | 2012-07-04 | 中国科学院化学研究所 | N-(1-naphthyl) ethylenediamine dinitrate and preparation method and application thereof |
-
2007
- 2007-09-28 CN CNA200710061278XA patent/CN101397257A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531924A (en) * | 2010-12-27 | 2012-07-04 | 中国科学院化学研究所 | N-(1-naphthyl) ethylenediamine dinitrate and preparation method and application thereof |
| CN102531924B (en) * | 2010-12-27 | 2013-12-11 | 中国科学院化学研究所 | N-(1-naphthyl) ethylenediamine dinitrate and preparation method and application thereof |
| CN102173996A (en) * | 2011-03-14 | 2011-09-07 | 天津市化学试剂研究所 | Preparation method of naphthyl ethylene diamine hydrochloride |
| CN102173996B (en) * | 2011-03-14 | 2013-09-25 | 天津市化学试剂研究所 | Preparation method of naphthyl ethylene diamine hydrochloride |
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Open date: 20090401 |