CN103265451A - Method for preparing hydrazone compound - Google Patents
Method for preparing hydrazone compound Download PDFInfo
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- CN103265451A CN103265451A CN2013101933745A CN201310193374A CN103265451A CN 103265451 A CN103265451 A CN 103265451A CN 2013101933745 A CN2013101933745 A CN 2013101933745A CN 201310193374 A CN201310193374 A CN 201310193374A CN 103265451 A CN103265451 A CN 103265451A
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- hydrochloride
- aqueous solution
- aldehyde compound
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Abstract
The invention discloses a method for preparing a hydrazone compound. The method is characterized in that an aldehyde compound is used to continuously chemically react with p-chlorophenylhydrazine hydrochloride under the protection of N2, and the reaction formula is shown as follows: p-ClC6H4N2H3-HCl+RCOCHO->p-ClC6H4NHNCH-COR+HCl+H2O, wherein R is any one of hydrogen, alkyl or hydroxyl. The method for preparing the hydrazone compound has the beneficial effects that the prepared hydrazone compound excludes polychlorinated biphenyl, the aldehyde compound is adopted and reacts with p-chlorophenylhydrazine hydrochloride, the reaction condition is controlled, and the process is optimized, therefore, the p-chlorophenylhydrazine hydrochloride can be reacted completely, polychlorinated biphenyl cannot be produced by the p-chlorophenylhydrazine hydrochloride, and production of dihydrazone impurities in the reaction can be avoided. The excessive aldehyde compound can be recycled, so that economy and environmental protection are realized.
Description
Technical field
The invention belongs to the synthetic field of organic chemical industry, be specifically related to a kind of method for preparing hydrazone compounds.
Background technology
Polychlorobiphenyl, the another name chlorodiphenyl, English name: Polychorinated biphenyls, be called for short PCBs.China is divided into trichloro biphenyl (PCB3), tetrachloro biphenyl (PCB4), pentachlorodiphenyl (PCB5), chlordene biphenyl (PCB6) etc. by the number that is replaced by chlorine on the biphenyl (no matter its position of substitution) with PCB traditionally.Polychlorobiphenyl belongs to strong carcinogen, is accumulated in fatty tissue easily, causes the disease of brain, skin and internal organ, and affect the nerves, reproduction and immunity.
P-hydrochloride is usually used in the intermediate of organic synthesis, with p-hydrochloride in oven dry with deposit in the process and will inevitably produce polychlorobiphenyl, though the content of polychlorobiphenyl is very low sometimes, has only 100ppm, but because polychlorobiphenyl is strong carcinogens, being zero tolerance in pharmacy, agricultural chemicals and food service industry, therefore even littler amount also is not allow, is to be necessary very much with unreacted p-hydrochloride removal completely therefore.
Hydrazone compounds is the organic chemistry intermediate, can form a series of nitrogen-containing heterocycle compounds; Be the important intermediate of medicine, agricultural chemicals, also do not disclose the method that can effectively prepare hydrazone compounds at present at home.
Summary of the invention
The objective of the invention is for a kind of method for preparing hydrazone compounds is provided.
For realizing purpose of the present invention, the technical scheme of employing is as follows:
A kind of method for preparing hydrazone compounds is characterized in that, at N
2Protection under, react with p-hydrochloride with aldehyde compound, reaction formula is as follows:
p-ClC
6H
4N
2H
3-HCl+RCOCHO→p-ClC
6H
4NHNCH-COR+HCl+H
2O
Wherein R is any one in hydrogen, alkyl or the hydroxyl,
Preparation process is as follows:
1), p-hydrochloride is dissolved in deionized water, under the protection of rare gas element, removes polychlorobiphenyl, obtain not having the p-hydrochloride aqueous solution of polychlorobiphenyl;
2), get aldehyde compound and mix with deionized water, obtaining concentration is the aldehyde compound aqueous solution of 0.5～1mol/L;
3), the p-hydrochloride aqueous solution that described step 1) is obtained and described step 2) the aldehyde compound aqueous solution that obtains of preparation joins in the reactor simultaneously, temperature of reaction in the control reactor is 20～30 ℃, ph value of reaction is PH3～6, the adding speed of the control p-hydrochloride aqueous solution is 0.1～0.2mol/min, the adding speed of the control aldehyde compound aqueous solution is 0.15～0.25mol/min, in the reaction process, keep whipped state, and the control stirring velocity is 80～100 commentaries on classics/min;
4), reacted material is carried out centrifugal, obtain solid crude product and mother liquor;
5), with the solid crude product aqueous solutions of organic solvent heating for dissolving that described step 4) obtains, carry out crystallization, centrifugal then, collect and to obtain final product.
Further, the mother liquor that obtains in the described step 4) is continued preparation aldehyde compound solution and also be used for reaction again.
Further, described alkyl is any one in methyl, ethyl, propyl group or the butyl.
Further, the mol ratio of the aldehyde compound aqueous solution and p-hydrochloride is 1.1:1～2:1 in the described reaction formula
Among the present invention, the physico-chemical property of various materials is as follows:
Aldehyde compound, soluble in water, be slightly acidic, chemical property is active, can carry out addition or condensation reaction with ammonia, acid amides, aldehyde, carboxylic compound.
In order to guarantee that p-hydrochloride reacts completely, the molar weight of the material of the aldehyde compound aqueous solution is higher than the molar weight of p-hydrochloride material,
Will remove the multi-joint chlorobenzene that wherein contains before p-hydrochloride reaction, doing like this is not have polychlorobiphenyl in order to allow in the hydrazone compounds that obtains after the reaction, and guarantees the p-hydrochloride reaction effect.Concrete removal step is: p-hydrochloride is dissolved in the deionized water, because the molecular polarity of p-hydrochloride compound is big, and the molecular polarity of multi-joint chlorobenzene compound is little, their solubleness in organic solvent is different, therefore polychlorobiphenyl can be isolated with solvent-extracted method, the p-hydrochloride aqueous solution of polychlorobiphenyl can be obtained not having.
The beneficial effect that the present invention has:
By the adding aldehyde compound aqueous solution and p-hydrochloride reactant aqueous solution, and the control reaction conditions, the p-hydrochloride total overall reaction can be fallen, and generate hydrazone compounds, and then can not produce multi-joint chlorobenzene again because of p-hydrochloride.
The unreacted aldehyde compound aqueous solution completely can be recycled, not only economy but also environmental protection.
The hydrazone compounds that the present invention obtains except the functional group (-NH-NCH-) of containing hydrazone, also have the carbonyl functional group (-COR), can generate the organic compound of more structures, lay a solid foundation for developing new compound.
Embodiment
Be further described below in conjunction with the present invention of embodiment, but protection scope of the present invention not only is confined to embodiment.
A kind of method for preparing hydrazone compounds is characterized in that, at N
2Protection under, react with p-hydrochloride with the aldehyde compound aqueous solution, reaction formula is as follows:
p-ClC
6H
4N
2H
3-HCl+RCOCHO→p-ClC
6H
4NHNCH-COR+HCl+H
2O
Wherein R is any one in hydrogen, alkyl or the hydroxyl,
Embodiment 1: get the R base and be hydrogen, namely aldehyde compound is oxalic dialdehyde, and chemical formula is C
2O
2H
2
1), p-hydrochloride is water-soluble, under the protection of rare gas element, polychlorobiphenyl is removed in extraction, obtains not having the p-hydrochloride aqueous solution of polychlorobiphenyl;
2), get oxalic dialdehyde and mix with deionized water, obtain the glyoxal water solution that concentration is 0.5mol/L;
3), with above-mentioned steps 1) the p-hydrochloride aqueous solution and the above-mentioned steps 2 that obtain) glyoxal water solution that obtains of preparation joins in the reactor simultaneously, temperature of reaction in the control reactor is 25 ℃, ph value of reaction is PH5～6, the adding speed of the control p-hydrochloride aqueous solution is 0.1mol/min, the adding speed of control glyoxal water solution is 0.15mol/min, in the reaction process, keep whipped state, and the control stirring velocity is 80 commentaries on classics/min.According to the add-on of glyoxal water solution and the p-hydrochloride aqueous solution in the concentration control reactor of glyoxal water solution and the p-hydrochloride aqueous solution, oxalic dialdehyde is 1.1:1 with the mol ratio of p-hydrochloride in the assurance reaction formula.
4), with above-mentioned steps 3) in reacted material carry out centrifugally, obtain solid crude product and mother liquor; Mother liquor can be used for the preparation of glyoxal solution again, continues on in the reaction.
5), solid crude product that described step 4) is obtained is with organic solvent and water heating for dissolving, carries out crystallization, centrifugal collection obtains final product.The chemical formula of final product is p-ClC
6H
4NHNCHCHO, i.e. hydrazone aldehyde.
Embodiment 2: get R base for hydroxyl (-OH), namely aldehyde compound is oxoethanoic acid, chemical formula is CHOCO
2H.
1), p-hydrochloride is water-soluble, under the protection of rare gas element, remove polychlorobiphenyl, obtain not having the p-hydrochloride aqueous solution of polychlorobiphenyl;
2), get oxoethanoic acid and mix with deionized water, obtain the aqueous glyoxylic acid that concentration is 0.5mol/L;
3), with above-mentioned steps 1) the p-hydrochloride aqueous solution and the above-mentioned steps 2 that obtain) aqueous glyoxylic acid that obtains of preparation joins in the reactor simultaneously, temperature of reaction in the control reactor is 23～26 ℃, ph value of reaction is PH5～6, the adding speed of the control p-hydrochloride aqueous solution is 0.15mol/min, the adding speed of control aqueous glyoxylic acid is 0.2mol/min, in the reaction process, keep whipped state, and the control stirring velocity is 90 commentaries on classics/min.According to the add-on of aqueous glyoxylic acid and the p-hydrochloride aqueous solution in the concentration control reactor of aqueous glyoxylic acid and the p-hydrochloride aqueous solution, the mol ratio of oxoethanoic acid and p-hydrochloride is 1.5:1 in the assurance reaction formula.
4), with above-mentioned steps 3) in reacted material carry out centrifugally, obtain solid crude product and mother liquor; Mother liquor can be used for the preparation glyoxylic acid solution again, and continues on in the reaction.
5), solid crude product that described step 4) is obtained is with organic solvent and water heating for dissolving, carries out crystallization, filter to collect to obtain final product.The chemical formula of final product is p-ClC
6H
4NHNCHCOOH, i.e. hydrazonic acid.
Embodiment 3: get the R base and be alkyl (-CH
3), namely aldehyde compound is pyruvic aldehyde, chemical formula be CH
3COCHO.
1), p-hydrochloride is water-soluble, under the protection of rare gas element, remove polychlorobiphenyl, obtain not having the p-hydrochloride aqueous solution of polychlorobiphenyl;
2), get pyruvic aldehyde and mix with deionized water, obtaining concentration is the pyruvic aldehyde aqueous solution of 1mol/L;
3), with above-mentioned steps 1) the p-hydrochloride aqueous solution and the above-mentioned steps 2 that obtain) the pyruvic aldehyde aqueous solution that obtains of preparation joins in the reactor simultaneously, temperature of reaction in the control reactor is 26～30 ℃, ph value of reaction is PH5～6, the adding speed of the control p-hydrochloride aqueous solution is 0.2mol/min, the adding speed of the control pyruvic aldehyde aqueous solution is 0.25mol/min, in the reaction process, keep whipped state, and the control stirring velocity is 100 commentaries on classics/min.According to the add-on of the pyruvic aldehyde aqueous solution and the p-hydrochloride aqueous solution in the concentration control reactor of the pyruvic aldehyde aqueous solution and the p-hydrochloride aqueous solution, the mol ratio of pyruvic aldehyde and p-hydrochloride is 2:1 in the assurance reaction formula.
4), with above-mentioned steps 3) in reacted material carry out centrifugally, obtain solid crude product and mother liquor; Mother liquor can be used for preparation pyruvic aldehyde solution again, and is used for reaction again.
5), solid crude product that described step 4) is obtained is with organic solvent and water heating for dissolving, carry out crystallization and filter to collect and obtain final product.The chemical formula of final product is p-ClC
6H
4NHNCHCOCH
3, i.e. hydrazone ketone.
It should be noted that at last: above embodiment is only in order to illustrate the present invention and unrestricted technical scheme described in the invention; Therefore, although this specification sheets has been described in detail with reference to above-mentioned the present invention of each embodiment,, those of ordinary skill in the art should be appreciated that still and can make amendment or be equal to replacement the present invention; And all do not break away from technical scheme and the improvement thereof of the spirit and scope of the present invention, and it all should be encompassed in the claim scope of the present invention.
Claims (4)
1. a method for preparing hydrazone compounds is characterized in that, at N
2Protection under, react with p-hydrochloride with aldehyde compound, reaction formula is as follows:
p-ClC
6H
4N
2H
3-HCl+RCOCHO→p-ClC
6H
4NHNCH-COR+HCl+H
2O
Wherein R is any one in hydrogen, alkyl or the hydroxyl,
Preparation process is as follows:
1), p-hydrochloride is dissolved in deionized water, under the protection of rare gas element, extraction process is removed polychlorobiphenyl, obtains not having the p-hydrochloride aqueous solution of polychlorobiphenyl;
2), take by weighing aldehyde compound and mix with deionized water, obtaining concentration is the aldehyde compound aqueous solution of 0.5～1mol/L;
3), the p-hydrochloride aqueous solution that described step 1) is obtained and described step 2) the aldehyde compound aqueous solution that obtains of preparation joins in the reactor simultaneously, temperature of reaction in the control reactor is 20～30 ℃, ph value of reaction is PH3～6, the adding speed of the control p-hydrochloride aqueous solution is 0.1～0.2mol/min, the adding speed of the control aldehyde compound aqueous solution is 0.15～0.25mol/min, in the reaction process, keep whipped state, and the control stirring velocity is 80～100 commentaries on classics/min;
4), reacted material is carried out centrifugal, obtain solid crude product and mother liquor;
5), solid crude product that described step 4) is obtained is with organic solvent and water heating for dissolving, crystallisation by cooling obtains final product.
2. the method for preparing hydrazone compounds according to claim 1 is characterized in that, the mother liquor that obtains in the described step 4) is continued preparation aldehyde compound solution and is used for reaction again.
3. the method for preparing hydrazone compounds according to claim 1 is characterized in that, described alkyl is any one in methyl, ethyl, propyl group or the butyl.
4. the method for preparing hydrazone compounds according to claim 1 is characterized in that, the mol ratio of aldehyde compound and p-hydrochloride is 1.1:1～2:1 in the described reaction formula.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310193374.5A CN103265451B (en) | 2013-05-22 | 2013-05-22 | Method for preparing hydrazone compound |
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|---|---|---|---|
| CN201310193374.5A CN103265451B (en) | 2013-05-22 | 2013-05-22 | Method for preparing hydrazone compound |
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| CN103265451A true CN103265451A (en) | 2013-08-28 |
| CN103265451B CN103265451B (en) | 2015-04-01 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005306805A (en) * | 2004-04-23 | 2005-11-04 | Sumitomo Chemical Co Ltd | Pyrazoline compound and its application to plant disease injury control |
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2013
- 2013-05-22 CN CN201310193374.5A patent/CN103265451B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005306805A (en) * | 2004-04-23 | 2005-11-04 | Sumitomo Chemical Co Ltd | Pyrazoline compound and its application to plant disease injury control |
Non-Patent Citations (2)
| Title |
|---|
| 刑其毅等: "《基础有机化学（第二版）》", 30 November 1993, article "和含氮亲核实际的加成", pages: 457 * |
| 程春生 等: "杀雄嗪酸的合成及其生物活性的研究", 《农药》, vol. 43, no. 7, 31 July 2004 (2004-07-31), pages 315 - 317 * |
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Granted publication date: 20150401 Termination date: 20170522 |