CN1063170C - Process for preparing 2-naphthylhydrazine in one step - Google Patents
Process for preparing 2-naphthylhydrazine in one step Download PDFInfo
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- CN1063170C CN1063170C CN97106620A CN97106620A CN1063170C CN 1063170 C CN1063170 C CN 1063170C CN 97106620 A CN97106620 A CN 97106620A CN 97106620 A CN97106620 A CN 97106620A CN 1063170 C CN1063170 C CN 1063170C
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- naphthylhydrazine
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- hydrazine hydrate
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Abstract
The present invention discloses a method for preparing 2-naphthylhydrazine in one-step, and belongs to the organic synthetic field. In the method, 2-naphthol and hydrazine hydrate are used as raw materials, and the 2-naphthoylhydrazine is synthesized by the one-step reaction. The method simplifies the preparation process of the 2-naphthoylhydrazine, and avoids the cancerogenic 2-naphthylamine; the method has the advantages of mild reaction condition, simple operation, wide industrial application prospects.
Description
The invention belongs to the organic synthesis field, relate to a kind of preparation method of 2-naphthylhydrazine.
The 2-naphthylhydrazine is a kind of purposes organic synthesis intermediate very widely, is usually used in the preparation of chemical such as dyestuff, medicine and agricultural chemicals, also is the important source material of the synthetic whipping agent of preparation.Many scientific worker's development researches prepare the method for 2-naphthylhydrazine, more typically have following several:
(1) the 2-naphthylamines is reduced the method for preparing the 2-naphthylhydrazine after diazotization, this is a kind of classics and comparatively practical method, but because the 2-naphthylamines is a kind of strong carcinogens, applying of this method is restricted;
(2) document Hilger, H., et a1., Chem.Ber., 1909,35,1841 disclose a kind of method with 2-naphthene sulfonic acid and hydrazine sodium prepared in reaction 2-naphthylhydrazine, and this method productive rate is very high, but very harsh to the working condition requirement, is difficult to realize suitability for industrialized production;
(3) United States Patent (USP) (U.S.P.4,013,758) discloses a kind of method with N-halo-2-naphthylamines and ammonia or amido sodium prepared in reaction 2-naphthylhydrazine, this method raw material is difficult for obtaining, production technique is comparatively complicated, and production cost is higher, and practical application has certain difficulty.
Also have lot of documents to report the preparation method of other 2-naphthylhydrazine, but all more loaded down with trivial details and lack practicality, so branch of industry urgently wish the preparation method of a kind of new 2-naphthylhydrazine of scientific and technical personnel's development research, to satisfy industrial actual needs.
The objective of the invention is to overcome the above-mentioned defective of prior art, a kind of method that is prepared the 2-naphthylhydrazine by beta naphthal and hydrazine hydrate through single step reaction is provided, this reaction raw materials source is abundant, operational condition is simple and convenient, it is a kind of method for preparing the 2-naphthylhydrazine of economy, suitable laboratory prepares on a small quantity, also is fit to suitability for industrialized production.
Design of the present invention is such:
The said method for preparing the 2-naphthylhydrazine of the present invention is that mechanism with Bucherer reaction is foundation, and the Bucherer reaction is to be raw material with beta naphthal and ammonia, is catalyzer with the sodium bisulfite, and its product is the 2-naphthylamines.The present invention's imagination replaces ammonia with hydrazine hydrate, makes the reaction of beta naphthal and hydrazine hydrate under certain conditions, directly obtains the 2-naphthylhydrazine, and to avoid using the 2-naphthylamines with carinogenicity, its reaction formula is:
According to above-mentioned design, the contriver has related parameter to carry out a large amount of tests to each that reacts, and concrete technical scheme is as described below:
Raw material-beta naphthal that reaction is required and 85% hydrazine hydrate aqueous solution place reactor according to a certain ratio, heated and stirred reaction 8-30 hour, reaction times increases, raising to reaction yield is favourable, but, reaction times surpasses 24 hours, and the raising of productive rate is no longer very remarkable, and the general reaction times was controlled at about 20 hours; The consumption of hydrazine hydrate aqueous solution (85%) is 1-10 times (wt%) of beta naphthal, and hydrazine hydrate both had been a raw material in reaction, was again reaction solvent, the hydrazine hydrate consumption is too much, will increase post-processing difficulty, and uneconomical, the hydrazine hydrate consumption very little, the reaction solution thickness be difficult for to stir, cause feed liquid inhomogeneous, be unfavorable for therefore, generally being controlled at the carrying out that react about 2 times, unnecessary hydrazine hydrate solution can heavily steam recovery, reuses; Can add catalyzer-sodium bisulfite in reaction, also can not add catalyzer, the consumption of sodium bisulfite is generally the 0.8-1 of beta naphthal consumption doubly about (weight);
Reaction is poured reaction solution in the water into after finishing, and promptly has the 2-naphthylhydrazine to separate out, and filters, and washing can obtain finished product-2-naphthylhydrazine after the drying, and productive rate can reach 68%.Products therefrom can adopt the method for recrystallization to purify, and purity can reach more than 98%.
Further illustrate content of the present invention below in conjunction with embodiment.
Embodiment 1
In 100 milliliters of there-necked flasks that have stirring and reflux condensing tube, add 11 gram beta naphthals (industrial goods), 50 gram hydrazine hydrates (85%) and 8 gram sodium bisulfites, heating reflux reaction 20 hours, cooling then, filter, with deionized water rinsing to pH value constant substantially till, white solid 2-naphthylhydrazine 5.2 grams will can be got behind the filtration cakes torrefaction, productive rate is 43.1%, with the solution weight crystallization of ethanol/water=1/1, can get lenticular 2-naphthylhydrazine 5.2 grams, productive rate is 43.1%, with the solution weight crystallization of ethanol/water=1/1, can get lenticular 2-naphthylhydrazine 3.9 grams.
Embodiment 2
In 100 milliliters of there-necked flasks that have stirring and reflux condensing tube, add 20 gram beta naphthals (industrial goods), 20 gram hydrazine hydrates (85%), heating reflux reaction 8 hours, be cooled to 95 ℃ then, stir adding 50 ml deionized water down, promptly have the 2-naphthylhydrazine to separate out, filter, drying can get solid 2-naphthylhydrazine 11.5 grams, and productive rate is 52.4%.
Embodiment 3
In 100 milliliters of there-necked flasks that have stirring and reflux condensing tube, add 30 gram beta naphthals (analytical pure), 50 gram hydrazine hydrates (85%), heating reflux reaction 20 hours is poured reacting liquor while hot in 80 milliliters of frozen water into, promptly has a large amount of 2-naphthylhydrazines to separate out, filter, drying can get white solid 2-naphthylhydrazine 22.5 grams, and productive rate is 68.3%, with the solution weight crystallization of ethanol/water=1/1, can get lenticular 2-naphthylhydrazine 15.6 grams.
Embodiment 4
In 1000 milliliters of there-necked flasks that have stirring and reflux condensing tube, add 300 gram beta naphthals (industrial goods), 600 gram hydrazine hydrates (85%), heating reflux reaction 30 hours, reacting liquor while hot is poured in 600 milliliters of frozen water, promptly there are a large amount of 2-naphthylhydrazines to separate out, filter drying, can get white solid 2-naphthylhydrazine 22.5 grams, productive rate is 55.4%.
Embodiment 5
In 1 cubic metre the reactor that has stirring of anchor formula and reflux exchanger, add 200 kilograms of beta naphthals, 250 kilograms of hydrazine hydrates (85%), heating reflux reaction 18 hours is after reaction finishes, reaction solution is cooled to 80 ℃, under agitation slowly add 400 kilograms of frozen water, continue to stir 20 minutes, filter, washing, drying can get 121 kilograms of white solid 2-naphthylhydrazines, and productive rate is 55.1%.
Embodiment 6
In 100 milliliters of there-necked flasks that have stirring and reflux condensing tube, add 20 gram beta naphthals (industrial goods), 200 gram hydrazine hydrates (85%), heating reflux reaction 8 hours, be cooled to 95 ℃ then, stir adding 200 ml deionized water down, promptly have the 2-naphthylhydrazine to separate out, filter, drying can get solid 2-naphthylhydrazine 10.5 grams, and productive rate is 48.2%.
Claims (4)
1. the method for a preparing 2-naphthylhydrazine in one step is characterized in that being is raw material and synthetic with beta naphthal and hydrazine hydrate, and its reaction formula is:
The processing condition of reaction are: the consumption of hydrazine hydrate aqueous solution (85%) is the 1-10 doubly (weight) of beta naphthal, 8-30 hour heating reflux reaction time, reaction product after separating, get final product solid state target product-2-naphthylhydrazine.
2. according to the described method of claim 1., add catalyzer-sodium bisulfite when it is characterized in that reacting, add-on is 0.8-1 times (weight) of beta naphthal.
3. according to claim 1 or 2 described methods, the consumption that it is characterized in that hydrazine hydrate aqueous solution (85%) is 2 times (weight) of beta naphthal, and the reaction times is 20 hours.
4. according to the described method of claim 1, it is characterized in that the separation of reaction product is performed such: will react resulting solution cooling or pour in the water, after filtration, washing, drying can obtain solid state target product-2-naphthylhydrazine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106620A CN1063170C (en) | 1997-09-23 | 1997-09-23 | Process for preparing 2-naphthylhydrazine in one step |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106620A CN1063170C (en) | 1997-09-23 | 1997-09-23 | Process for preparing 2-naphthylhydrazine in one step |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1175571A CN1175571A (en) | 1998-03-11 |
| CN1063170C true CN1063170C (en) | 2001-03-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97106620A Expired - Fee Related CN1063170C (en) | 1997-09-23 | 1997-09-23 | Process for preparing 2-naphthylhydrazine in one step |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110305057A (en) * | 2019-04-27 | 2019-10-08 | 安徽秀朗新材料科技有限公司 | A kind of preparation method of bromo- 7H- benzo [c] carbazole of 10- |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995007888A1 (en) * | 1993-09-17 | 1995-03-23 | Societe D'etudes Et De Recherches Biologiques | Method for the preparation of high purity substituted benz[e]indoles and the alkaline salts thereof |
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- 1997-09-23 CN CN97106620A patent/CN1063170C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995007888A1 (en) * | 1993-09-17 | 1995-03-23 | Societe D'etudes Et De Recherches Biologiques | Method for the preparation of high purity substituted benz[e]indoles and the alkaline salts thereof |
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| CN1175571A (en) | 1998-03-11 |
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