CN101475515B - Method for preparing 5-amino-2-chloro-N-(2,4-xylyl)-benzene sulfonic amide in water phase - Google Patents
Method for preparing 5-amino-2-chloro-N-(2,4-xylyl)-benzene sulfonic amide in water phase Download PDFInfo
- Publication number
- CN101475515B CN101475515B CN2009100958081A CN200910095808A CN101475515B CN 101475515 B CN101475515 B CN 101475515B CN 2009100958081 A CN2009100958081 A CN 2009100958081A CN 200910095808 A CN200910095808 A CN 200910095808A CN 101475515 B CN101475515 B CN 101475515B
- Authority
- CN
- China
- Prior art keywords
- xylyl
- chloro
- benzsulfamide
- active ingredient
- amino
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 5-amino-2-chlorine-N-(2,4-xylyl)-benzsulfamide of which the structure is as shown in a formula (II) in a water phase, which comprises: performing catalytic hydrogenation reaction on 5-nitryl-2-chlorine-N-(2,4-xylyl)-benzsulfamide of which the structure is as shown in a formula (I) in a water solvent in a closed reactor under the action of a supported catalyst under the condition of stirring, and preparing target products, wherein the temperature of the catalytic hydrogenation reaction is between 30 and 150 DEG C, and the pressure in the closed reactor is between 0.1 and 4.0 MPa; a supporter of the supported catalyst is gamma-Al2O3; and active ingredients of the gamma-Al2O3 are one or complexes of more than two of Pa, Ru, Pt, Ni, Fe, Co, Sn, Ge, Al, Zn, Ce and Au in any proportion, or complexes of non-metal B or P and metals in any proportion. The method is performed in the water phase, and has the advantages of high conversion rate, high selectivity, mild reaction conditions, simple technique, clean production and no pollution.
Description
One, technical field
The present invention relates to a kind of method for preparing 5-amino-2-chloro-N-(2, the 4-xylyl)-benzsulfamide at aqueous phase.
Two, background technology
(2, the 4-xylyl)-benzsulfamide is important organic synthesis intermediate to 5-amino-2-chloro-N-, is widely used in high-visibility pigment, dyestuff, medicine, pesticide field.At present, nitro-(2, the 4-xylyl)-benzsulfamide is a raw material to 2-chloro-N-to main both at home and abroad employing 5-, in acidic medium, is reductive agent with the iron powder, carries out the reduction of nitro on the phenyl ring, and reaction formula is as follows:
This is a chemical reduction method, has contaminate environment and potential safety hazard, and throughput also is restricted simultaneously.People attempt to utilize the shortening means to accomplish this reduction reaction at present.
Scrutinize this reaction, this is a chloronitrobenzene compound hydrogenation reaction.The shortening of chloronitrobenzene compound is a very complicated process, is accompanied by various side reactions, and topmost side reaction is the C-Cl key hydrogenolysis of chloronitrobenzene compound, generates c h bond.Therefore, people concentrate on the selectivity that how to improve reaction to main research, prevent that dechlorination reaction from taking place, and promptly press down chlorine.At present, pressing down the chlorine means roughly has two kinds, and the one, in reaction, add the dechlorination suppressor factor; Another is that catalyst property is optimized.Professor Hirai like the U.S. waits to have reported with Pt/C to be catalyzer; Methyl alcohol is solvent; Alkyl monoamine, aliphatic cyclic amine and polyalkylenepolyamines etc. be suppressor factor to the chloronitrobenzene shortening, the result shows, when particularly a spot of polyalkylenepolyamines of the existence of amino-complex and alkylamine or aliphatic cyclic amine one work; Can suppress dechlorination effectively, the content of chloroaniline is greater than 98.9% in the product.The Lv Lianhai professor seminar of Dalian University of Technology has developed the nanometer Ru/C catalyzer of high dispersing; Under the situation of not adding any auxiliary agent, temperature is at 343～403K, reaction pressure 2～3MPa; Multiple chloronitrobenzene is carried out shortening, and its transformation efficiency and productive rate are 100%.The tight new shining seminar of Zhejiang Polytechnical University has developed the hydrogenation that amorphous alloy catalyst is used for chloronitrobenzene and has also obtained effect preferably.The influence of supported catalyst agent carrier to the shortening of chloronitrobenzene that also some scholar's research arranged prepared the selective hydrogenation that the Ru/SBA-15 catalyzer is used for chloronitrobenzene like the Komandur V.R.Chary.Chakra-vartula S.Srikanth of India.But make a general survey of every scholar's research work, almost completely concentrate on the research of chloronitrobenzene catalyst system therefor, when how to make nitro become amino, dechlorination reaction does not take place.Dechlorination reaction is also relevant with reaction conditionss such as solvents.The present invention develops the method that a kind of aqueous phase shortening prepares 5-amino-2-chloro-N-(2, the 4-xylyl)-benzsulfamide.Use catalytic hydrogenation method to prepare 5-amino-2-chloro-N-(2 at present; The 4-xylyl)-not the appearing in the newspapers of benzsulfamide; Preparing 5-amino-2-chloro-N-(2, the 4-xylyl)-benzsulfamide at the shortening of aqueous phase 5-nitro-2-chloro-N-(2, the 4-xylyl)-benzene sulfonyl has not just more had.We think that the catalytic performance of catalyzer is relevant with the environment that it plays a role, and are the functions of reactive system, so the performance of research catalyzer can not be left reaction environment, medium---the solvent that especially reacts.Before the present invention, all preparing methods need carry out in organic solvent, and the present invention has developed aqueous phase shortening 5-nitro-2-chlorine N-(2, the 4-xylyl)-benzsulfamide technology, to solve the pollution problem of this technology to environment.
Three, summary of the invention
The method that the problem that the present invention will solve provides a kind of high conversion, highly selective, reaction conditions is gentle, technology is simple, produce cleaning, free of contamination aqueous phase prepares 5-amino-2-chloro-N-(2, the 4-xylyl)-benzsulfamide.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of structure is suc as formula the 5-amino shown in (II)-2-chloro-N-(2; The 4-xylyl)-preparation method of benzsulfamide is following: in closed reactor; Structure suc as formula the 5-nitro shown in (I)-2-chloro-N-(2, the 4-xylyl)-benzsulfamide under the loaded catalyst effect, catalytic hydrogenation reaction under in water solvent, stirring; Make 5-amino-2-chloro-N-(2, the 4-xylyl)-benzsulfamide; Said catalytic hydrogenation reaction temperature is 30～150 ℃, and pressure is 0.1～4.0MPa in the closed reactor; Said loaded catalyst comprises carrier and is carried on the active ingredient on the carrier that described carrier is γ-Al
2O
3, described active ingredient is the compound of one or more arbitrary proportions among Pa, Ru, Pt, Ni, Fe, Co, Sn, Ge, Al, Zn, Ce, the Au, perhaps active ingredient is the composite of nonmetal B or P and said metal arbitrary proportion;
Loaded catalyst of the present invention is homemade, and concrete preparation method is the conventional load method for preparing catalyst:
When the active ingredient of described loaded catalyst was metal, its preparation method was following:
The nitrate salt or the hydrochloride of active ingredient are dissolved in the water, and to use the pH value of nitric acid regulator solution be about 2～3, then the spray solution of preparing at γ-Al
2O
3On the carrier, leave standstill 2～4h, every 30min stirs once.Dry 7～12h puts into retort furnace then in 110～150 ℃ baking oven, 160～450 ℃ of gradient increased temperature roastings (recommend roasting method following: 160 ℃, 2h; 200 ℃, 2h; 300 ℃, 2h; 400 ℃, 2h; 450 ℃, 2h).Behind the naturally cooling, catalyzer is put into airtight containers for future use.The quality consumption of the nitrate salt of described active ingredient or hydrochloride is counted γ-Al with active ingredient wherein
2O
3Carrier 1～5% of the quality that feeds intake.
When the active ingredient of described loaded catalyst is nonmetal B or P and said metal arbitrary proportion composite; Its preparation method is following: the nitrate salt or the hydrochloride of described metal are dissolved in the water; And to use the pH value of nitric acid regulator solution be about 2～3, cooling back adding KBH
4Solution or NaBH
4, perhaps sodium hydrogen phosphate or phosphoric acid hydrogen potassium solution fully stir, regulate pH value to 11～12 with alkali aqueous solution again and process prewired solution, then prewired spray solution at γ-Al
2O
3On the carrier, leave standstill 2～4h, filtration, washing obtain described loaded catalyst, and its feed ratio feeds intake according to the charge capacity of required loaded catalyst.
Further, the charge capacity of active ingredient is generally 1～5% in the loaded catalyst of the present invention, and preferred 1～3%.The consumption of described loaded catalyst is 0.1～5% of 5-nitro-2-chloro-N-(2, the 4-xylyl)-benzsulfamide quality, is preferably 1～3%.
Compound with two kinds of a kind of among the preferred Pt of the active ingredient of described loaded catalyst, Ni, Pa, the Ru.
It is 1: 10～100 that the present invention recommends the mass ratio that feeds intake of described 5-nitro-2-chloro-N-(2, the 4-xylyl)-benzsulfamide and water, be preferably 1: 10～and 70.
Reaction times of the present invention is generally at 0.5～5h, preferred 3～5h.
The reaction conditions of shortening of the present invention is preferably: temperature of reaction is preferably 40～90 ℃, and hydrogen pressure is preferably 0.1～2MPa in the closed reactor, and the reaction times is preferably 3～5h.
The concrete described preparation method of recommendation of the present invention carries out according to following steps: in reactor drum, add 5-nitro-2-chloro-N-(2, the 4-xylyl)-benzsulfamide, water, loaded catalyst, said 5-nitro-2-chloro-N-(2; The 4-xylyl)-and the mass ratio that feeds intake of benzsulfamide, loaded catalyst and water is 1: 0.1～5: 10～100, closed reactor is put into oil bath; With gas in the nitrogen replacement reactor drum at least three times, use in the hydrogen exchange reactor drum nitrogen again three times, fill hydrogen to 0.1～4MPa pressure then; Be heated to 30～150 ℃; Stirring issues answers 0.5～5h, makes described 5-amino-2-chloro-N-(2, the 4-xylyl)-benzsulfamide; Active ingredient is selected from the compound of one or more arbitrary proportions among Pa, Ru, Pt, Ni, Fe, Co, Sn, Ge, Al, Zn, Ce, the Au in the described loaded catalyst; Perhaps active ingredient is the composite of nonmetal B or P and said metal arbitrary proportion, and the charge capacity of said active ingredient is 1～5%.
Compared with prior art, the invention has the beneficial effects as follows:
1) in 5-nitro-2-chloro-N-(2, the 4-xylyl)-benzsulfamide shortening process, do not add any dechlorination suppressor factor, the transformation efficiency 100% of 5-nitro-2-chloro-N-(2, the 4-xylyl)-benzsulfamide, selectivity is more than 90%.
2) in the shortening process of 5-nitro-2-chloro-N-(2, the 4-xylyl)-benzsulfamide, all accomplish, do not need any organic appearance agent at aqueous phase; And preparation condition is 30～150 ℃, and pressure 0.1～4MPa, reaction conditions are relatively gentleer; Technology is simple, produces cleaning, and is pollution-free.
3) in the shortening process of 5-nitro-2-chloro-N-(2, the 4-xylyl)-benzsulfamide, the solvent of reaction is a water, makes to produce cleaning, and is pollution-free.
Four, specific embodiment
With specific embodiment technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto:
Embodiment 1
Get the 1.45g Palladous chloride and be dissolved in the water, and to use the pH value of 5% rare nitric acid regulator solution be about 2～3 that cryosel is bathed and is cooled to 0 ℃, under agitation dropwise adds the KBH of 0.5mol/L
4Do not have gas to solution and produce, process prewired solution after the NaOH solution adjusting pH value to 11 with 10mol/L, then the γ-Al of prewired spray solution at 30g
2O
3On the carrier, leave standstill 2h, filter, using deionized water to wash this catalyzer to washing lotion pH value is 7, uses 3 catalyzer of absolute ethanol washing then, obtains Pa-B/Al
2O
3Catalyzer.Be kept at catalyzer in the absolute ethyl alcohol subsequent use.This catalyst cupport total amount is 3%.
In the high pressure tank reactor of 50ml, add 5-nitro-2-chloro-N-(2, the 4-xylyl)-benzsulfamide of 3g, be dissolved in the 30ml water Pa-B/Al of 0.3g
2O
3Catalyzer, airtight high pressure tank reactor is placed on reactor drum in the oil bath fixing; Air in the logical nitrogen replacement reactor drum 3 times with the nitrogen in the hydrogen exchange reactor drum 3 times, leads to hydrogen 1MPa; Be heated to 75 ℃ to reactor drum; Reaction 3h, reaction finishes, and liquid chromatography is carried out in the sampling of cooling back and mass spectrometry is qualitative to product, quantitative analysis.The transformation efficiency 100% of 5-amido-2-chloro-N-(2, the 4-xylyl)-benzsulfamide, selectivity 100%.
Embodiment 2
0.378g hydrochloric acid palladium and 1.134g ruthenium chloride are dissolved in the water, and to use the pH value of nitric acid regulator solution be about 2～3, then the γ-Al of the spray solution of preparing at 30g
2O
3On the carrier, leave standstill 3h, every 30min stirs once.Dry 10h in 130 ℃ baking oven puts into retort furnace then, and 160～450 ℃ of gradient increased temperature roastings, roasting method is following: 160 ℃, and 2h; 200 ℃, 2h; 300 ℃, 2h; 400 ℃, 2h; 450 ℃, 2h.Behind the naturally cooling, catalyzer is put into airtight containers for future use.The quality consumption of described active ingredient is counted γ-Al with active ingredient wherein
2O
3Carrier 3% of the quality that feeds intake.
In the high pressure tank reactor of 50ml, add 5-nitro-2-chloro-N-(2, the 4-xylyl)-benzsulfamide of 3g, be dissolved in the 30ml water Pa-Ru/Al of 0.4g
2O
3Catalyzer, airtight high pressure tank reactor is placed on reactor drum in the oil bath fixing; Air in the logical nitrogen replacement reactor drum 3 times with the nitrogen in the hydrogen exchange reactor drum 3 times, leads to hydrogen 1.2MPa; Be heated to 95 ℃ to reactor drum; Reaction 3h, reaction finishes, and liquid chromatography is carried out in the sampling of cooling back and mass spectrometry is qualitative to product, quantitative analysis.The transformation efficiency 100% of 5-amido-2-chloro-N-(2, the 4-xylyl)-benzsulfamide, selectivity 100%.
Embodiment 3
Get the 1.987g nickelous chloride and be dissolved in the water, and to use the pH value of 5% rare nitric acid regulator solution be about 2～3, under agitation dropwise add the KBH of 0.5mol/L
4Do not have gas to solution and produce, regulate pH value to 12 with alkali aqueous solution again and process prewired solution, then the γ-Al of prewired spray solution at 30g
2O
3On the carrier, leave standstill 2h, cryosel is bathed and is cooled to 0 ℃, filters, and it is 7 that cakes with deionized water is washed this catalyzer to washing lotion pH value, uses the absolute ethanol washing filter cake then 3 times, obtains Ni-B/Al
2O
3Catalyzer.Be kept at catalyzer in the absolute ethyl alcohol subsequent use.This catalyst cupport is 3%.
In the high pressure tank reactor of 50ml, add 5-nitro-2-chloro-N-(2, the 4-xylyl)-benzsulfamide of 2.5g, be dissolved in the 30ml water Ni-B/Al of 0.3g
2O
3Catalyzer, airtight high pressure tank reactor is placed on reactor drum in the oil bath fixing; Air in the logical nitrogen replacement reactor drum 3 times with the nitrogen in the hydrogen exchange reactor drum 3 times, leads to hydrogen 1.5MPa; Be heated to 75 ℃ to reactor drum; Reaction 3h, reaction finishes, and liquid chromatography is carried out in the sampling of cooling back and mass spectrometry is qualitative to product, quantitative analysis.The transformation efficiency 100% of 5-amido-2-chloro-N-(2, the 4-xylyl)-benzsulfamide, selectivity 96%.
Embodiment 4
1.5g the hydrochloric acid palladium is dissolved in the water, and to use the pH value of nitric acid regulator solution be about 2～3, then the γ-Al of the spray solution of preparing at 30g
2O
3On the carrier, leave standstill 3h, every 30min stirs once.Dry 10h in 130 ℃ baking oven puts into retort furnace then, and 160～450 ℃ of gradient increased temperature roastings, roasting method is following: 160 ℃, and 2h; 200 ℃, 2h; 300 ℃, 2h; 400 ℃, 2h; 450 ℃, 2h.Behind the naturally cooling, catalyzer is put into airtight containers for future use.The quality consumption of described active ingredient is counted γ-Al with active ingredient wherein
2O
3Carrier 3% of the quality that feeds intake.
In the high pressure tank reactor of 50ml, add 5-nitro-2-chloro-N-(2, the 4-xylyl)-benzsulfamide of 2.5g, be dissolved in the 30ml water Pd/Al of 0.3g
2O
3Catalyzer, airtight high pressure tank reactor is placed on reactor drum in the oil bath fixing; Air in the logical nitrogen replacement reactor drum 3 times with the nitrogen in the hydrogen exchange reactor drum 3 times, leads to hydrogen 1.5MPa; Be heated to 75 ℃ to reactor drum; Reaction 3h, reaction finishes, and liquid chromatography is carried out in the sampling of cooling back and mass spectrometry is qualitative to product, quantitative analysis.The transformation efficiency 85% of 5-amido-2-chloro-N-(2, the 4-xylyl)-benzsulfamide, selectivity 92%.
Embodiment 5
0.7514g hydrochloric acid palladium and 1.6136g platinum chloride are dissolved in the water, and to use the pH value of nitric acid regulator solution be about 2～3, then the γ-Al of the spray solution of preparing at 30g
2O
3On the carrier, leave standstill 3h, every 30min stirs once.Dry 10h in 130 ℃ baking oven puts into retort furnace then, and 160～450 ℃ of gradient increased temperature roastings, roasting method is following: 160 ℃, and 2h; 200 ℃, 2h; 300 ℃, 2h; 400 ℃, 2h; 450 ℃, 2h.Behind the naturally cooling, catalyzer is put into airtight containers for future use.The quality consumption of described active ingredient is counted γ-Al with active ingredient wherein
2O
3Carrier 3% of the quality that feeds intake.
In the high pressure tank reactor of 50ml, add 5-nitro-2-chloro-N-(2, the 4-xylyl)-benzsulfamide of 4g, be dissolved in the 40ml water Pt-Pa/Al of 0.5g
2O
3Catalyzer, airtight high pressure tank reactor is placed on reactor drum in the oil bath fixing; Air in the logical nitrogen replacement reactor drum 3 times with the nitrogen in the hydrogen exchange reactor drum 3 times, leads to hydrogen 0.5MPa; Be heated to 80 ℃ to reactor drum; Reaction 3h, reaction finishes, and liquid chromatography is carried out in the sampling of cooling back and mass spectrometry is qualitative to product, quantitative analysis.The transformation efficiency 100% of 5-amido-2-chloro-N-(2, the 4-xylyl)-benzsulfamide, selectivity 98%.
Embodiment 6
1g hydrochloric acid nickel and 0.72g tin chloride are dissolved in the water, and to use the pH value of nitric acid regulator solution be about 2～3, then the γ-Al of the spray solution of preparing at 30g
2O
3On the carrier, leave standstill 3h, every 30min stirs once.Dry 10h in 130 ℃ baking oven puts into retort furnace then, and 160～450 ℃ of gradient increased temperature roastings, roasting method is following: 160 ℃, and 2h; 200 ℃, 2h; 300 ℃, 2h; 400 ℃, 2h; 450 ℃, 2h.Behind the naturally cooling, catalyzer is put into airtight containers for future use.The quality consumption of described active ingredient is counted γ-Al with active ingredient wherein
2O
3Carrier 3% of the quality that feeds intake
In the high pressure tank reactor of 50ml, add 5-nitro-2-chloro-N-(2, the 4-xylyl)-benzsulfamide of 3g, be dissolved in the 30ml water Ni-Sn/Al of 0.3g
2O
3Catalyzer, airtight high pressure tank reactor is placed on reactor drum in the oil bath fixing; Air in the logical nitrogen replacement reactor drum 3 times with the nitrogen in the hydrogen exchange reactor drum 3 times, leads to hydrogen 1.3MPa; Be heated to 80 ℃ to reactor drum; Reaction 3h, reaction finishes, and liquid chromatography is carried out in the sampling of cooling back and mass spectrometry is qualitative to product, quantitative analysis.The transformation efficiency 100% of 5-amido-2-chloro-N-(2, the 4-xylyl)-benzsulfamide, selectivity 90%.
Embodiment 7
NiCl with 5.65g
26H
2O and 5.0gNaH
2PO
4H
2O and 3.1gCH
3COONa is soluble in water, after the NaOH solution adjusting pH value to 11 with 10mol/L, is added to γ-Al
2O
3In, heat 70 ℃, do not produce to there being deposition, left standstill 5 hours, filter, filter cake is with the NH of 8mol/L
3H
2O, zero(ppm) water, absolute ethyl alcohol respectively wash three times, make Ni-P/Al at last
2O
3Catalyzer is kept in the absolute ethyl alcohol subsequent use.
In the high pressure tank reactor of 50ml, add 5-nitro-2-chloro-N-(2, the 4-xylyl)-benzsulfamide of 4g, be dissolved in the 40ml water Ni-P catalyzer/Al of 0.5g
2O
3Catalyzer, airtight high pressure tank reactor is placed on reactor drum in the oil bath fixing; Air in the logical nitrogen replacement reactor drum 3 times with the nitrogen in the hydrogen exchange reactor drum 3 times, leads to hydrogen 0.5MPa; Be heated to 80 ℃ to reactor drum; Reaction 3h, reaction finishes, and liquid chromatography is carried out in the sampling of cooling back and mass spectrometry is qualitative to product, quantitative analysis.The transformation efficiency 100% of 5-amido-2-chloro-N-(2, the 4-xylyl)-benzsulfamide, selectivity 97%.
Claims (8)
1. a structure is suc as formula the 5-amino shown in (II)-2-chloro-N-(2; The 4-xylyl)-and the preparation method of benzsulfamide, it is characterized in that described preparation method is following: in closed reactor, structure is suc as formula the 5-nitro shown in (I)-2-chloro-N-(2; The 4-xylyl)-benzsulfamide is under the loaded catalyst effect; Catalytic hydrogenation reaction under in water solvent, stirring makes 5-amino-2-chloro-N-(2, the 4-xylyl)-benzsulfamide; Said catalytic hydrogenation reaction temperature is 30～150 ℃, and pressure is 0.1～4.0MPa in the closed reactor; Said loaded catalyst comprises carrier and is carried on the active ingredient on the carrier that described carrier is γ-Al
2O
3, described active ingredient is the compound of one or more arbitrary proportions among metal Pa, Ru, Pt, Ni, Fe, Co, Sn, Ge, Al, Zn, Ce, the Au, perhaps active ingredient is the composite of nonmetal B or P and said metal arbitrary proportion; The total loading amount of active ingredient is 1～5% in the described loaded catalyst, and the consumption of described loaded catalyst is 0.1～5% of 5-nitro-2-chloro-N-(2, the 4-xylyl)-benzsulfamide quality; The mass ratio that feeds intake of described 5-nitro-2-chloro-N-(2, the 4-xylyl)-benzsulfamide and water is 1: 10～100;
2. the preparation method of 5-amino as claimed in claim 1-2-chloro-N-(2, the 4-xylyl)-benzsulfamide is characterized in that the described reaction times is 0.5～5h.
3. according to claim 1 or claim 2 5-amino-2-chloro-N-(2; The 4-xylyl)-preparation method of benzsulfamide; The active ingredient that it is characterized in that described loaded catalyst is a metal; Described loaded catalyst prepares according to following method: the nitrate salt or the hydrochloride of active ingredient are dissolved in the water, and to use the pH value of nitric acid regulator solution be 2～3, then the spray solution of preparing at γ-Al
2O
3On the carrier, leave standstill 2～4h,, put into retort furnace then,, promptly obtain described loaded catalyst behind the naturally cooling at 160～450 ℃ of gradient increased temperature roasting 10～16h at 110～150 ℃ of drying 7～12h; The quality consumption of the nitrate salt of described active ingredient or hydrochloride is counted γ-Al with active ingredient wherein
2O
3Carrier 1～5% of the quality that feeds intake.
4. according to claim 1 or claim 2 5-amino-2-chloro-N-(2; The 4-xylyl)-preparation method of benzsulfamide; It is characterized in that described active ingredient is the composite of nonmetal B or P and said metal arbitrary proportion; Described loaded catalyst prepares according to following method: the nitrate salt or the hydrochloride of described metal are dissolved in the water, and to use the pH value of nitric acid regulator solution be 2～3, cooling back adding KBH
4Solution or NaBH
4, perhaps sodium hydrogen phosphate or phosphoric acid hydrogen potassium solution fully stir, regulate pH value to 11～12 with alkali aqueous solution again and process prewired solution, then described prewired spray solution at γ-Al
2O
3On the carrier, leave standstill 2～4h, filtration, washing obtain described loaded catalyst.
5. according to claim 1 or claim 2 the preparation method of 5-amino-2-chloro-N-(2, the 4-xylyl)-benzsulfamide, the active ingredient that it is characterized in that described loaded catalyst are selected from compound with two kinds of a kind of among Pt, Ni, Pa, the Ru.
6. according to claim 1 or claim 2 5-amino-2-chloro-N-(2; The 4-xylyl)-preparation method of benzsulfamide; The reaction conditions that it is characterized in that described catalytic hydrogenation is: temperature of reaction is 40～90 ℃, and pressure is 0.1～2MPa in the closed reactor, and the reaction times is 3～5h.
7. according to claim 1 or claim 2 5-amino-2-chloro-N-(2; The 4-xylyl)-preparation method of benzsulfamide; The mass ratio that feeds intake that it is characterized in that described 5-nitro-2-chloro-N-(2, the 4-xylyl)-benzsulfamide, loaded catalyst and water is 1: 0.01～0.03: 10～70.
8. the preparation method of 5-amino as claimed in claim 1-2-chloro-N-(2, the 4-xylyl)-benzsulfamide is characterized in that described preparation method carries out according to following steps: in reactor drum, add 5-nitro-2-chloro-N-(2; The 4-xylyl)-and benzsulfamide, water, loaded catalyst, the mass ratio that feeds intake of said 5-nitro-2-chloro-N-(2, the 4-xylyl)-benzsulfamide, loaded catalyst and water is 1: 0.01～0.5: 10～100; Closed reactor is put into oil bath, with gas in the nitrogen replacement reactor drum; Use gas in the hydrogen exchange reactor drum again; Filling hydrogen to reactor pressure then is 0.1～4MPa, is heated to 30～150 ℃, stirs reaction 0.5～5h down; Make described 5-amino-2-chloro-N-(2, the 4-xylyl)-benzsulfamide; Active ingredient is selected from the compound of one or more arbitrary proportions among Pa, Ru, Pt, Ni, Fe, Co, Sn, Ge, Al, Zn, Ce, the Au in the described loaded catalyst, and the charge capacity of said active ingredient is 1～3%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100958081A CN101475515B (en) | 2009-01-24 | 2009-01-24 | Method for preparing 5-amino-2-chloro-N-(2,4-xylyl)-benzene sulfonic amide in water phase |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100958081A CN101475515B (en) | 2009-01-24 | 2009-01-24 | Method for preparing 5-amino-2-chloro-N-(2,4-xylyl)-benzene sulfonic amide in water phase |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101475515A CN101475515A (en) | 2009-07-08 |
| CN101475515B true CN101475515B (en) | 2012-07-11 |
Family
ID=40836304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100958081A Expired - Fee Related CN101475515B (en) | 2009-01-24 | 2009-01-24 | Method for preparing 5-amino-2-chloro-N-(2,4-xylyl)-benzene sulfonic amide in water phase |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101475515B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172523B (en) * | 2011-12-23 | 2015-09-30 | 南京理工大学 | The method of the selective N-primary amine that methylates |
| CN103145593A (en) * | 2013-03-26 | 2013-06-12 | 河北永泰柯瑞特化工有限公司 | Preparation method of 4,4'-diaminobenzenesulphonamide |
| CN108339551B (en) * | 2018-02-09 | 2021-05-28 | 扬州虹光生物科技有限公司 | Preparation method of novel antibacterial drug linezolid intermediate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4264529A (en) * | 1980-03-24 | 1981-04-28 | Mallinckrodt, Inc. | Method for preparing p-aminophenol |
| CN1724508A (en) * | 2005-07-06 | 2006-01-25 | 浙江工业大学 | A kind of 3, the production method of 4-dichlorphenamide bulk powder |
-
2009
- 2009-01-24 CN CN2009100958081A patent/CN101475515B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4264529A (en) * | 1980-03-24 | 1981-04-28 | Mallinckrodt, Inc. | Method for preparing p-aminophenol |
| CN1724508A (en) * | 2005-07-06 | 2006-01-25 | 浙江工业大学 | A kind of 3, the production method of 4-dichlorphenamide bulk powder |
Non-Patent Citations (1)
| Title |
|---|
| 罗雄军 等.非晶态Pd-B/Al2O3 催化剂用于邻氯硝基苯加氢合成邻氯苯胺的研究.《高校化学工程学报》.2006,第20卷(第3期),476-480. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101475515A (en) | 2009-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100554243C (en) | The method of a kind of (containing substituent) nitrophenols shortening preparation (containing substituent) amino-phenol | |
| CN102188975B (en) | Loaded nickel-base bi-component catalyst and application thereof | |
| CN101811973A (en) | Method for synthesizing halogen aromatic amines by high-selectivity liquid phase hydrogenation under the condition of no solvent | |
| CN109985628A (en) | Hydrotalcite composite transition metal catalyst faces the purposes in hydrogen ammonolysis reaction for aldehydes or ketone compounds | |
| CN101333169A (en) | Production method of o-chloroaniline | |
| CN102786424B (en) | Method for preparing 3-chloro-4-methylaniline through catalytic hydrogenation | |
| CN110551278B (en) | Supported catalyst and preparation method and application thereof | |
| CN104693038A (en) | Method and device for preparing propane diamine by taking propylene glycol and liquid ammonia as raw materials | |
| CN106807377A (en) | A kind of catalyst for synthesizing hexamethylene diamine | |
| CN104693037A (en) | A method of preparing 1,2-diaminopropane from isopropanolamine and liquid ammonia and a device thereof | |
| CN101475515B (en) | Method for preparing 5-amino-2-chloro-N-(2,4-xylyl)-benzene sulfonic amide in water phase | |
| CN102633647A (en) | Environment-friendly preparation method of tert-butylamine | |
| CN103977802A (en) | Nano needle-like nickel-coated graphite compound particle and preparation method and application thereof | |
| CN109745986A (en) | Hydrotalcite composite transition metal catalyst is for the purposes in cyclohexanol ammonolysis reaction | |
| CN107999089A (en) | Catalyst for producing diethyl toluene diamine and preparation method thereof, application | |
| CN106807395A (en) | A kind of catalyst for synthesizing hexamethylene diamine | |
| CN102179245A (en) | Palladium/active carbon catalyst and application thereof in synthesizing N,N'-dibenzylethylenediamine | |
| CN107952490A (en) | A kind of preparation method of silver-raney copper catalyst, catalyst prepared therefrom and application | |
| CN101565383A (en) | Method for synthesizing 3-amino-4-methacetin by catalytic hydrogenation | |
| CN110496645B (en) | Supported aminoalkyl ion liquid-metal catalyst and preparation and application thereof | |
| CN101880242B (en) | Method for preparing 3-amino-4-methoxyacetanilide by taking Raney nickel as catalyst | |
| CN102050746A (en) | Method for preparing o-chloroaniline | |
| CN101161339B (en) | Application of Chinese lacquer original nickel in the preparation of m-phenylene diamine with m-dinitrobenzene liquid phase hydrogenation | |
| CN102020568A (en) | Method for preparing 1,5-diaminonaphthalene and 1,8-diaminonaphthalene | |
| CN102631916A (en) | Mesoporous carbon catalyst with load palladium (Pd) and application of mesoporous carbon catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120711 Termination date: 20150124 |
|
| EXPY | Termination of patent right or utility model |