CN103288655A - Method for preparing high-purity naphthalene ethylenediamine oxalate - Google Patents
Method for preparing high-purity naphthalene ethylenediamine oxalate Download PDFInfo
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- CN103288655A CN103288655A CN201310194812XA CN201310194812A CN103288655A CN 103288655 A CN103288655 A CN 103288655A CN 201310194812X A CN201310194812X A CN 201310194812XA CN 201310194812 A CN201310194812 A CN 201310194812A CN 103288655 A CN103288655 A CN 103288655A
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- naphthodiamide
- oxalic acid
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to a method for preparing high-purity naphthalene ethylenediamine oxalate. The concrete preparation method comprises the steps of: mixing naphthalene bromide with ethanediamine, refluxing for 6-10 hours at the temperature of 110-130 DEG C; then cooling to 70-80 DEG C; adding a copper catalyst into reactant to reflux for 6-10 hours and naturally cool; distilling at reduced pressure and recovering excessive ethanediamine; extracting by an organic solvent, filtering, distilling at reduced pressure and recovering a solvent; distilling at reduced pressure to obtain a product naphthalene ethanediamine; adding the naphthalene ethanediamine to oxalate solution, cooling to 0-5 DEG C, filtering the crystal, and recrystallizing the obtained crystal by ethanol to obtain the high-purity naphthalene ethylenediamine oxalate. The preparation method disclosed by the invention is simple and feasible; the generated oxalic acid naphthalene ethylenediamine is high in purity, and suitable for environment protection monitoring; various reagents also can be recovered in the reaction process, so that the residual reagent can be repeatedly used; the cost is saved.
Description
Technical field
The present invention relates to the preparation purification techniques field of organic compound, especially a kind of preparation method of high-purity oxalic acid naphthodiamide.
Background technology
The oxalic acid naphthodiamide is a kind of important environmental protection tests reagent, the oxynitride, aniline, methyl that is used for the monitoring air and waste gas is to carelessly, 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 solubility property, sensitivity, blank value and circulation ratio that general producer produces the oxalic acid naphthodiamide are all very poor, thereby have influenced the monitoring tolerance range, can not satisfy the requirement of environment monitoring.
By retrieval, do not find patent documentation related to the present invention as yet.
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 oxalic acid naphthodiamide of environment monitoring work reagent needs is provided.
The present invention realizes that the technical scheme of purpose is:
A kind of preparation method of high-purity oxalic acid naphthodiamide, step is as follows:
⑴ naphthalene bromide mixes with quadrol, and the 6～10h that refluxes under 110～130 ℃ of temperature is cooled to 70～80 ℃, gets reactant;
The ratio of weight and number of described naphthalene bromide and quadrol is 65～70:155～165;
⑵ add copper containing catalyst in step ⑴ reactant, the 6～10h that refluxes, cooling;
The ratio of weight and number of copper containing catalyst and step ⑴ reactant is 1～1.25:220～235;
⑶ underpressure distillation is also reclaimed excessive quadrol;
⑷ organic solvent extraction reactant filters, and underpressure distillation is also reclaimed solvent, gets reactant;
⑸ with the reactant underpressure distillation, and the cut of 170～175 ℃/5mmHg is naphthodiamide;
⑹ add naphthodiamide in the oxalic acid solution, and temperature is cooled to 0～5 ℃, filtering for crystallizing;
⑺ gained crystal with ethyl alcohol recrystallization after, namely obtain the high-purity oxalic acid naphthodiamide.
And copper containing catalyst is the mixture of copper powder and cupric oxide powder among the described step ⑵, and the weight ratio of copper and cupric oxide is 100:5～30.
And the underpressure distillation condition among the described step ⑶ is 85～90 ℃/50mm_Hg.
And organic solvent is benzene or dehydrated alcohol among the described step ⑷.
And the underpressure distillation condition among the described step ⑷ is 47～52 ℃/50mmHg.
And the mass percentage concentration of described step ⑹ mesoxalic acid solution is 20%～30%, oxalic acid solution: the weight ratio of naphthodiamide is 1.61～2.42:1.
Advantage of the present invention and positively effect are:
1, 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 oxalic acid, namely generate the high-purity oxalic acid naphthodiamide.This method is simple, and the oxalic acid naphthodiamide of generation is purity 〉=99.5% not only, is applicable to environment monitoring, and can also reclaim all ingredients in the reaction process, and remaining reagent can be reused, and saves cost.
2, bromine and the 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 to the nucleophilie nucleus ability of naphthalene bromide, thereby the reaction of naphthalene bromide and quadrol can be carried out smoothly.
3, naphthalene bromide, quadrol, copper catalyst and some byproducts of reaction among the present invention, if directly carry out next step reaction, in final product oxalic acid naphthodiamide, can contain above-mentioned impurity, this impurity can make the product purity of production 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.
Embodiment
The invention will be further described below by specific embodiment, and following examples are descriptive, is not determinate, can not limit protection scope of the present invention with this.
Employed reagent among the present invention if no special instructions, is commercially available conventional reagent; Employed method among the present invention if no special instructions, is the ordinary method of using in the art.
Embodiment 1
A kind of preparation method of high-purity oxalic acid naphthodiamide, concrete steps are:
⑴ add the quadrols of 69 gram naphthalene bromides and 160 grams in the reactor that the mechanical stirring cooling and reflux device is housed, heated mixt to 110 ℃, keep this temperature backflow 10h after, be cooled to 70 ℃;
With copper powder and cupric oxide powder after mix for 100:5, in 1.25 kg catalyst mixtures adding reactor, backflow 10h, naturally cooling;
⑶ excessive quadrol is reclaimed in underpressure distillation under the condition of 85～90 ℃/50mm_Hg;
⑷ filter with 5 times of benzene extractive reaction things to the reactant volume, and benzene is reclaimed in underpressure distillation under the condition of 47～52 ℃/50mmHg;
⑸ underpressure distillation, the cut of 170～175 ℃/5mmHg of collection namely gets naphthodiamide;
⑹ add mass concentration with naphthodiamide is that the weight ratio of the two is 1:2.42 in 20% the reagent oxalic acid solution, and temperature is cooled to 0 ℃, filtering for crystallizing;
⑺ obtain the high-purity oxalic acid naphthodiamide with the gained crystal after with ethyl alcohol recrystallization.
Embodiment 2
A kind of preparation method of high-purity oxalic acid naphthodiamide, concrete steps are:
⑴ add the quadrol of 414 kilograms of naphthalene bromides and 960 kilograms in the reactor that the mechanical stirring cooling and reflux device is housed, heated mixt to 130 ℃ keeps this temperature backflow 6h, and temperature is cooled to 80 ℃ then;
With copper powder and cupric oxide powder after mix for 100:30, in 6 kg catalyst mixtures adding reactor, backflow 6h, naturally cooling;
⑶ excessive quadrol is reclaimed in underpressure distillation under the condition of 85～90 ℃/50mm_Hg;
⑷ filter with 3 times of dehydrated alcohol extractive reaction things to the reactant volume, and ethanol is reclaimed in underpressure distillation under the condition of 47～52 ℃/50mmHg;
⑸ underpressure distillation, the cut of 170～175 ℃/5mmHg of collection namely gets naphthodiamide;
⑹ add mass concentration with naphthodiamide is that the weight ratio of the two is 1:1.93 in 25% the reagent oxalic acid solution, and temperature is cooled to 5 ℃, filtering for crystallizing;
⑺ obtain the high-purity oxalic acid naphthodiamide with the gained crystal after with ethyl alcohol recrystallization.
Embodiment 3
A kind of preparation method of high-purity oxalic acid naphthodiamide, concrete steps are:
⑴ add the quadrol of 207 kilograms of naphthalene bromides and 480 kilograms in the reactor that the mechanical stirring cooling and reflux device is housed, heated mixt to 120 ℃ keeps this temperature backflow 8h, and temperature is cooled to 75 ℃ then;
With copper powder and cupric oxide powder after mix for 100:20, in 3.3 kg catalyst mixtures adding reactor, backflow 8h, naturally cooling;
⑶ excessive quadrol is reclaimed in underpressure distillation under the condition of 85～90 ℃/50mm_Hg;
⑷ filter with 4 times of benzene extractive reaction things to the reactant volume, and benzene is reclaimed in underpressure distillation under the condition of 47～52 ℃/50mmHg;
⑸ underpressure distillation, the cut of 170～175 ℃/5mmHg of collection namely gets naphthodiamide;
⑹ add mass concentration with naphthodiamide is that the weight ratio of the two is 1:1.61 in 30% the reagent oxalic acid solution, and temperature is cooled to 4 ℃, filtering for crystallizing;
⑺ obtain the high-purity oxalic acid naphthodiamide with the gained crystal after with ethyl alcohol recrystallization.
Claims (6)
1. the preparation method of a high-purity oxalic acid naphthodiamide, it is characterized in that: step is as follows:
⑴ naphthalene bromide mixes with quadrol, and the 6～10h that refluxes under 110～130 ℃ of temperature is cooled to 70～80 ℃, gets reactant;
The ratio of weight and number of described naphthalene bromide and quadrol is 65～70:155～165;
⑵ add copper containing catalyst in step ⑴ reactant, the 6～10h that refluxes, cooling;
The ratio of weight and number of copper containing catalyst and step ⑴ reactant is 1～1.25:220～235;
⑶ underpressure distillation is also reclaimed excessive quadrol;
⑷ organic solvent extraction reactant filters, and underpressure distillation is also reclaimed solvent, gets reactant;
⑸ with the reactant underpressure distillation, and the cut of 170～175 ℃/5mmHg is naphthodiamide;
⑹ add naphthodiamide in the oxalic acid solution, and temperature is cooled to 0～5 ℃, filtering for crystallizing;
⑺ gained crystal with ethyl alcohol recrystallization after, namely obtain the high-purity oxalic acid naphthodiamide.
2. the preparation method of high-purity oxalic acid naphthodiamide according to claim 1, it is characterized in that: copper containing catalyst is the mixture of copper powder and cupric oxide powder among the described step ⑵, the weight ratio of copper and cupric oxide is 100:5～30.
3. the preparation method of high-purity oxalic acid naphthodiamide according to claim 1, it is characterized in that: the underpressure distillation condition among the described step ⑶ is 85～90 ℃/50mm_Hg.
4. the preparation method of a kind of high-purity oxalic acid naphthodiamide according to claim 1, it is characterized in that: organic solvent is benzene or dehydrated alcohol among the described step ⑷.
5. the preparation method of high-purity oxalic acid naphthodiamide according to claim 1, it is characterized in that: the underpressure distillation condition among the described step ⑷ is 47～52 ℃/50mmHg.
6. according to the preparation method of each described a kind of high-purity oxalic acid naphthodiamide of claim 1 to 5, it is characterized in that: the mass percentage concentration of described step ⑹ mesoxalic acid solution is 20%～30%, oxalic acid solution: the weight ratio of naphthodiamide is 1.61～2.42:1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117645546A (en) * | 2024-01-29 | 2024-03-05 | 天津市科密欧化学试剂有限公司 | Preparation method of naphthalene ethylenediamine |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117645546A (en) * | 2024-01-29 | 2024-03-05 | 天津市科密欧化学试剂有限公司 | Preparation method of naphthalene ethylenediamine |
| CN117645546B (en) * | 2024-01-29 | 2024-05-03 | 天津市科密欧化学试剂有限公司 | Preparation method of naphthalene ethylenediamine |
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