CN101337909A - Method for preparing 2-hydrazinobenzoic acid hydrochloride - Google Patents
Method for preparing 2-hydrazinobenzoic acid hydrochloride Download PDFInfo
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- CN101337909A CN101337909A CNA200810021715XA CN200810021715A CN101337909A CN 101337909 A CN101337909 A CN 101337909A CN A200810021715X A CNA200810021715X A CN A200810021715XA CN 200810021715 A CN200810021715 A CN 200810021715A CN 101337909 A CN101337909 A CN 101337909A
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- Prior art keywords
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- phenylhydrazine hydrochloride
- carboxyl phenylhydrazine
- gained
- carboxyl
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- ZGNNOFKURIXXRF-UHFFFAOYSA-N 2-hydrazinylbenzoic acid;hydron;chloride Chemical compound Cl.NNC1=CC=CC=C1C(O)=O ZGNNOFKURIXXRF-UHFFFAOYSA-N 0.000 title claims description 24
- 238000000034 method Methods 0.000 title abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000006722 reduction reaction Methods 0.000 claims abstract description 15
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims abstract description 9
- 235000010262 sodium metabisulphite Nutrition 0.000 claims abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 230000002829 reductive effect Effects 0.000 claims description 9
- 238000006193 diazotization reaction Methods 0.000 claims description 7
- 235000010288 sodium nitrite Nutrition 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- LRGSPQUJOKBFOM-UHFFFAOYSA-L [Cl-].[N+](=[N-])=C1CC=CC=C1.[Cl-].C1(=CC=CC=C1)[N+]#N.C1(=CC=CC=C1)[N+]#N Chemical compound [Cl-].[N+](=[N-])=C1CC=CC=C1.[Cl-].C1(=CC=CC=C1)[N+]#N.C1(=CC=CC=C1)[N+]#N LRGSPQUJOKBFOM-UHFFFAOYSA-L 0.000 claims description 6
- ZPHQBFRCXUIIAZ-UHFFFAOYSA-N benzene;hydrochloride Chemical compound Cl.C1=CC=CC=C1 ZPHQBFRCXUIIAZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012954 diazonium Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 235000021463 dry cake Nutrition 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- CLRSZXHOSMKUIB-UHFFFAOYSA-M benzenediazonium chloride Chemical compound [Cl-].N#[N+]C1=CC=CC=C1 CLRSZXHOSMKUIB-UHFFFAOYSA-M 0.000 abstract description 3
- KFGVDCBVGNMCJC-UHFFFAOYSA-N 2-hydrazinylbenzoic acid Chemical compound NNC1=CC=CC=C1C(O)=O KFGVDCBVGNMCJC-UHFFFAOYSA-N 0.000 abstract 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 abstract 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 abstract 1
- -1 more particularly Chemical compound 0.000 abstract 1
- 229940001584 sodium metabisulfite Drugs 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- JOVOSQBPPZZESK-UHFFFAOYSA-N phenylhydrazine hydrochloride Chemical compound Cl.NNC1=CC=CC=C1 JOVOSQBPPZZESK-UHFFFAOYSA-N 0.000 description 3
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 241000233855 Orchidaceae Species 0.000 description 1
- UEJQQMLXZQUJHF-UHFFFAOYSA-L [K+].[I+].[I-].[I-] Chemical compound [K+].[I+].[I-].[I-] UEJQQMLXZQUJHF-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing 2-carboxyl phenyl hydrazine, which comprises the following steps: (1) 2-aminobenzoic acid is used as starting material, and benzene diazonium chloride is prepared through diazo reaction; (2) benzene diazonium chloride obtained from the step (1) is utilized to further prepare reduction products through the reduction reaction under the action of a reducing agent; (3) the reduction products obtained from the step (2) undergoes the hydrolysis reaction under the action of hydrochloric acid to generate 2-carboxyl phenyl hydrazine, more particularly, sodium metabisulfite is used as the reducing agent in the reduction reaction in the step (2), and the reaction is performed under the condition that the temperature is 15 to 25 DEG C and the pH value is 7 to 9. The method has higher yield, and can shorten the production period and reduce the manufacture cost at the same time.
Description
Technical field
The present invention relates to a kind of preparation method of hydrazinobenzene hydrochloride salt, particularly relate to a kind of preparation method of 2-carboxyl phenylhydrazine hydrochloride.
Background technology
2-carboxyl phenylhydrazine hydrochloride is a kind of important intermediate, is mainly used to produce be mainly used to produce indoles and pyrazolone derivative, also can be used to produce other Chemicals.The traditional preparation process technology of 2-carboxyl phenylhydrazine hydrochloride comprises that aniline diazotization and benzene diazonium chloride diazo benzene chloride reduce two step process, wherein mostly aniline diazotization is in hydrochloric acid medium, pH equals under 2 the condition, adds the Sodium Nitrite reaction under 0～5 ℃ low temperature, generates benzene diazonium chloride diazo benzene chloride.Benzene diazonium chloride diazo benzene chloride reduction general employing S-WAT and sodium bisulfite are reductive agent, the ammonium bisulfite of employing and ammonium hydroxide are also arranged as reductive agent, and the phenylhydrazine stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate feed liquid after the reduction enters the acid out still through pressure filter, obtaining hydrazinobenzene hydrochloride salt through the acid out operation.The synthetic method of the hydrazinobenzene hydrochloride salt that this is traditional, the reaction times reaches 3～4 hours, and yield is only between 63-72%, and in addition, when the reductive agent that uses during as S-WAT and sodium bisulfite, cost is higher, strengthens production cost; And when using ammonium bisulfite and ammonium hydroxide to make reductive agent,, be difficult for transportation and storage because they are liquid.In addition, will adopt reduction kettle, pressure filter and acid out still in this technology, equipment is many, and investment is big.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method with 2-carboxyl phenylhydrazine hydrochloride of higher yields, and it is with short production cycle, production cost is low.
For solving above technical problem, the present invention adopts following technical scheme:
A kind of preparation method of 2-carboxyl phenylhydrazine hydrochloride comprises the steps:
(1), be starting raw material with the 2-benzaminic acid, make benzene diazonium chloride diazo benzene chloride through diazotization reaction;
(2), by (1) gained benzene diazonium chloride diazo benzene chloride further under the effect of reductive agent, take place reduction react reduzate;
(3), issue unboiled water by step (2) gained reduzate in the effect of hydrochloric acid and separate reaction and generate described 2-carboxyl phenylhydrazine hydrochloride,
Particularly, in the step (2), reduction reaction is reductive agent with the Sodium Pyrosulfite, and at 15～25 ℃, pH carries out under 7～9 the condition.
As preferred scheme, in the step (1), the concrete steps of described diazotization reaction are: add the 2-benzaminic acid in reactor, stir and add hydrochloric acid down, after treating that the 2-benzaminic acid is dissolved fully, be cooled to below 0 ℃, slowly add sodium nitrite in aqueous solution then, finish, control reactor in temperature of charge at 0～5 ℃, stirring reaction 20～30 minutes, filter the diazonium chloride benzole soln, wherein, the mol ratio of described 2-benzaminic acid, hydrochloric acid and Sodium Nitrite is 1: 2.5～3: 1～1.1.
In the step (2), the concrete steps of described reduction reaction are: Sodium Pyrosulfite is dissolved in the water, add sodium hydroxide then and regulate pH7～9, be cooled to 15～18 ℃, slowly add the diazonium chloride benzole soln by (1) gained, controlled temperature is at 15～25 ℃, and reaction obtained containing the solution of reduzate in 25～35 minutes, wherein, the mol ratio of described Sodium Pyrosulfite and 2-benzaminic acid is 0.95～1.
In the step (3), the concrete steps of described hydrolysis reaction are: the hydrochloric acid that adds 3～4 times of 2-benzaminic acid molar weights in by the solution that contains product of (2) gained, be warming up to 95～100 ℃, insulation reaction obtained containing the solution of described 2-carboxyl phenylhydrazine hydrochloride in 25～35 minutes.
, keep and dry cake promptly gets 2-carboxyl phenylhydrazine hydrochloride finished product further through activated carbon decolorizing, cooling, filtration by the solution that contains 2-carboxyl phenylhydrazine hydrochloride of step (4) gained.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
Adopt Sodium Pyrosulfite as reductive agent, shortened the reduction reaction time greatly, generally only needed half hour can reach reaction end, production cost is low, yield higher (greater than 73%), and the product purity height (greater than 98%) of taking the inventive method to make.
Embodiment
Below the specific embodiment of the present invention is described, but be not limited thereto example.
Preparation method according to the 2-carboxyl phenylhydrazine hydrochloride of present embodiment comprises the steps:
(1), diazotization reaction
Add water 200ml at the 800ml beaker, 2-benzaminic acid 27.4g, stir, add 10N hydrochloric acid 57.5g, fully stirred 30 minutes, after treating that the 2-benzaminic acid is dissolved fully, slowly solution is cooled to below 0 ℃, slowly adds sodium nitrite in aqueous solution (being made into) then, add by 15g Sodium Nitrite and 30ml water dissolution, temperature of charge is 5 ℃ in the beaker, and potassiumiodide iodine powder test paper is little orchid.The control temperature of charge continued stirring reaction 20 minutes at 0～5 ℃, and the solution 400～450ml that filters brownly is the diazonium chloride benzole soln.
(2), reduction reaction
Add water 200ml at the 1000ml beaker, stirring adds Sodium Pyrosulfite 64g, all dissolve back end hydrogenation sodium oxide 56.3g, this moment about 30～35 ℃ of temperature, pH is 7, on the rocksly is cooled to 15～18 ℃, diazonium chloride benzole soln above slowly adding, finish, 18～20 ℃ of controlled temperature, insulation reaction obtained containing the solution of reduzate in 30 minutes.
(3), hydrolysis reaction
In the solution that contains reduzate by (2) gained, add 10N hydrochloric acid 115g, be heated to 97～100 ℃, insulation reaction 30 minutes must contain the light brown solution of 2-carboxyl phenylhydrazine hydrochloride, in this solution, add gac 7g, reacted 5 minutes, and filtered, get flaxen solution, cooling yellow solution to 5～10 ℃, white mass is separated out, filter drain white filter cake 40g, dry to such an extent that 27.43g is a 2-carboxyl phenylhydrazine hydrochloride finished product.In 2-carboxyl phenylhydrazine hydrochloride, its molar yield is 73%, and it is 98.80% that high performance liquid chromatography detects its purity.
Claims (5)
1, a kind of preparation method of 2-carboxyl phenylhydrazine hydrochloride comprises the steps:
(1), be starting raw material with the 2-benzaminic acid, make benzene diazonium chloride diazo benzene chloride through diazotization reaction;
(2), by (1) gained benzene diazonium chloride diazo benzene chloride further under the effect of reductive agent, take place reduction react reduzate;
(3), issue unboiled water by step (2) gained reduzate in the effect of hydrochloric acid and separate reaction and generate described 2-carboxyl phenylhydrazine hydrochloride,
It is characterized in that: in the step (2), described reduction reaction is reductive agent with the Sodium Pyrosulfite, and at 15～25 ℃, pH carries out under 7～9 the condition.
2, the preparation method of a kind of 2-carboxyl phenylhydrazine hydrochloride according to claim 1, it is characterized in that: in the step (1), the concrete steps of described diazotization reaction are: add the 2-benzaminic acid in reactor, stir and add hydrochloric acid down, after treating that the 2-benzaminic acid is dissolved fully, be cooled to below 0 ℃, slowly add sodium nitrite in aqueous solution then, finish, control reactor in temperature of charge at 0～5 ℃, stirring reaction 20～30 minutes, filter the diazonium chloride benzole soln, wherein, described 2-benzaminic acid, the mol ratio of hydrochloric acid and Sodium Nitrite is 1: 2.5～3: 1～1.1.
3, the preparation method of a kind of 2-carboxyl phenylhydrazine hydrochloride according to claim 2, it is characterized in that: in the step (2), the concrete steps of described reduction reaction are: Sodium Pyrosulfite is dissolved in the water, add sodium hydroxide then and regulate pH 7～9, be cooled to 15～18 ℃, slowly add diazonium chloride benzole soln by (1) gained, controlled temperature is at 15～25 ℃, insulation reaction obtained containing the solution of reduzate in 25～35 minutes, wherein, the mol ratio of Sodium Pyrosulfite and 2-benzaminic acid is 0.95～1.
4, the preparation method of a kind of 2-carboxyl phenylhydrazine hydrochloride according to claim 3, it is characterized in that: in the step (3), the concrete steps of described hydrolysis reaction are: the hydrochloric acid that adds 3～4 times of 2-benzaminic acid molar weights in by the solution that contains product of (2) gained, be warming up to 95～100 ℃, insulation reaction obtained containing the solution of described 2-carboxyl phenylhydrazine hydrochloride in 25～35 minutes.
5, the preparation method of a kind of 2-carboxyl phenylhydrazine hydrochloride according to claim 4, it is characterized in that: through activated carbon decolorizing, cooling, filtration, keep and dry cake gets 2-carboxyl phenylhydrazine hydrochloride finished product by the solution that contains 2-carboxyl phenylhydrazine hydrochloride of step (4) gained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200810021715XA CN101337909A (en) | 2008-08-11 | 2008-08-11 | Method for preparing 2-hydrazinobenzoic acid hydrochloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200810021715XA CN101337909A (en) | 2008-08-11 | 2008-08-11 | Method for preparing 2-hydrazinobenzoic acid hydrochloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101337909A true CN101337909A (en) | 2009-01-07 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200810021715XA Pending CN101337909A (en) | 2008-08-11 | 2008-08-11 | Method for preparing 2-hydrazinobenzoic acid hydrochloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101337909A (en) |
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2008
- 2008-08-11 CN CNA200810021715XA patent/CN101337909A/en active Pending
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Open date: 20090107 |