CN101914028B - Method for preparing 2-amido-4,6-dichlorophenol - Google Patents
Method for preparing 2-amido-4,6-dichlorophenol Download PDFInfo
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- CN101914028B CN101914028B CN2010102532781A CN201010253278A CN101914028B CN 101914028 B CN101914028 B CN 101914028B CN 2010102532781 A CN2010102532781 A CN 2010102532781A CN 201010253278 A CN201010253278 A CN 201010253278A CN 101914028 B CN101914028 B CN 101914028B
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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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Abstract
The invention relates to a method for preparing 2-amido-4,6-dichlorophenol. The method comprises the following steps of: adding a Ni-B/SiO2 amorphous catalyst, 2,4-dichloro-6-nitrophenol and a polar solvent into an autoclave in turn; replacing air by using nitrogen and hydrogen in turn; introducing H2 until the pressure is between 0.5 and 1.0Mpa; heating the autoclave in a water bath to 333-353K;starting stirring, adjusting the stirring rotating speed more than or equal to 500r/min, continuously reacting for 10min when the pressure does not change; and extracting solution in the autoclave, filtering out the catalyst, and drying the product in vacuum after the filtrate is decompressed and distilled. The method for preparing the 2-amido-4,6-dichlorophenol by adopting the Ni-B/SiO2 amorphous catalyst requires small hydrogen pressure and less equipment investment, and the solvent and the catalyst can be recycled, so that the continuously pollution-free production for preparing the 2-amido-4,6-dichlorophenol is realized.
Description
Technical field
The present invention relates to 2-amino-4, the preparation method of 6-chlorophenesic acid belongs to chemical industry and chemical field of medicaments.
Background of invention
2-amino-4, the 6-chlorophenesic acid (2-amino-4 6-dichlorophenol) also claims " 2,4-, two chloro-6-amino-phenols ", and its structural formula is:
2-amino-4,6-chlorophenesic acid are a kind of important fine-chemical intermediates, are widely used in production and the organic synthesis of fine chemicals such as dyestuff.United States Patent (USP) 3349090 in 1967 reports that it is the essential raw material of synthetic treatment pig, cattle and sheep schistosomicide medicine OXYCLOZANIDE BPV; United States Patent (USP) 244196 report 2-amino-4 in 1987, the 6-chlorophenesic acid is as the intermediate of synthetic cyano-containing first and (mensuration magnesium ion); Its important intermediate as synthetic profibr(in)olysin amides inhibitor of report in the United States Patent (USP)s 20050124667 in 2005.
The 2-of report preparation both at home and abroad amino-4,6-chlorophenesic acid method has eight kinds:
Above-mentioned preparation method have respectively separately characteristics and the problem of existence.Such as, though the mild condition that has, waste reaction solution is difficult to handle, environmental pollution is serious; The operation steps complexity that has, condition is loaded down with trivial details, and product is oxidation very easily; The used reductive agent that has is expensive, and environmental pollution is serious, such as hydrazine hydrate; The required hydrogen pressure that has is bigger, and is higher and exist selectivity relatively poor to equipment requirements, and dechlorination is serious and need precious metal to make the shortcoming of catalyzer; The desired raw material that has is rare.
In recent years, amorphous alloy has caused people's attention owing to the good catalytic performance that its particular structure has, and becomes the focus of catalytic field research.People such as Wang Minghui have reported a kind of Ni-B/SiO in " catalysis journal " Vol.22 (3) 2001
2Amorphous catalyst is used for the preparation of oil of mirbane; People such as Sun Yu have reported utilization Ni-B/SiO in " dyestuff and dyeing " Vol.42 (6) 2005
2Amorphous catalyst prepares Ortho-Chloro aniline and obtains effect preferably.But the preparation method of 2,4-, two chloro-6-nitrophenolss is not developed as yet.
Summary of the invention
According to above situation, the present invention adopts Ni-B/SiO
2Amorphous catalyst prepares 2-amino-4, and the 6-chlorophenesic acid provides a kind of easy and simple to handle, environmental pollution is little, target product purity is high method.
Preparation 2-amino-4 of the present invention, the chemical equation of 6-chlorophenesic acid is as follows:
2-amino-4 of the present invention, the preparation method of 6-chlorophenesic acid comprises the steps,
The hydrogenation reduction of 2,4-, two chloro-6-nitrophenolss: in autoclave, add Ni-B/SiO successively
2Amorphous catalyst, 2,4-two chloro-6-nitrophenolss, polar solvent are respectively replaced 3 times with nitrogen, hydrogen successively, to remove air, feed H at last
2To 0.5～1.0Mpa; Ni-B/SiO wherein
2The mass ratio of amorphous catalyst and 2,4-, two chloro-6-nitrophenolss is 1.0～1.175: 2.5～5; 2,4-, two chloro-6-nitrophenolss and polar solvent are 2.5～5: 75 (g/mL) with quality and volume ratio; With autoclave heating in water bath to 333～353K; Start stirring, regulate mixing speed 〉=500r/min, by observe and the record autoclave in pressure monitoring reaction process over time, when treating that pressure no longer changes, continue to stop behind the reaction 10min; Extract solution in the still out, filter out catalyzer (treating to apply mechanically next time), filtrate is behind the evaporated under reduced pressure solvent, with products obtained therefrom vacuum-drying; Wherein said polar solvent is methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, acetone, chlorobenzene or their any mixed solvent;
Ni-B/SiO of the present invention
2Amorphous catalyst, be made up of nickel, boron and silicon-dioxide: their mass ratio is 0.32～1.5: 0.14～0.39: 4～5.
Ni-B/SiO of the present invention
2Amorphous catalyst adopts the chemical reduction method preparation: being solvent with methyl alcohol, ethanol, water, is the reducing loaded nickel ion on silicon-dioxide of reductive agent with hydrazine hydrate and POTASSIUM BOROHYDRIDE, may further comprise the steps:
(1) silicon-dioxide is placed 70 ℃～80 ℃ baking oven activate;
(2) by nickel: the mass ratio of silicon-dioxide is that 0.32～1.5: 4～5 mass ratio has calculated required NiCl
2, silicon-dioxide quality, with the NiCl that calculates
2Be dissolved in the distilled water, and add the silicon-dioxide that step (1) activated, dipping spends the night.Extremely dry in the 343K stirring in water bath then, with the roasting under oven dry and 473K under the 373K respectively of gained material; Add methyl alcohol, ethanol, hydrazine hydrate, sodium hydroxide, distilled water and POTASSIUM BOROHYDRIDE successively in the there-necked flask under 60 ℃ of water-baths, wherein said methyl alcohol (mL): ethanol (mL): hydrazine hydrate (mL): sodium hydroxide (g): distilled water (mL): the ratio of POTASSIUM BOROHYDRIDE (g) is 25～35: 4～5: 4.6～11: 0.09～0.26: 0.7～2: 0.7～2; N (the NH of hydrazine hydrate wherein
2NH
2H
2O)/n (Ni
2+)=9, the wherein n (KBH of POTASSIUM BOROHYDRIDE
4)/n (Ni
2+)=1.25 are stirred to dissolving, and with good the pouring in the there-necked flask of roasting, stirring reaction is not emitted to there being bubble, obtains Ni-B/SiO
2Sample is used distilled water and ethanol repetitive scrubbing successively, is kept in the ethanol standby at last.
Superiority of the present invention is:
1.Ni-B/SiO
2The manufacture craft of amorphous alloy catalyst is simple, and raw material is easy to get, and is easy to recovery set usefulness, avoids adopting FeCl
3/ N
2H
4H
2O, SnCl
2Or Na
2S
2Environment is polluted and adopts PtO
2Cause cost too high with Pt, be unfavorable for the drawback of large-scale production.
2. prepare 2-amino-4 with hydrogen reducing, the 6-chlorophenesic acid, the required hydrogen pressure of reduction process is little, can reduce facility investment, and this technology in the process of 6-chlorophenesic acid, does not have the discharging of waste residue, waste gas, waste liquid at preparation 2-amino-4, be a kind of free of contamination process for cleanly preparing, be easy to realize large industrialized production.
3.2, the transformation efficiency of 4-two chloro-6-nitrophenolss is 100%, 2-amino-4, the selectivity of 6-chlorophenesic acid reaches 98%, reached medicinal requirement, can realize serialization, automatization, with other its scale effects of technology comparison production cost be reduced significantly, strengthen the competitive power of product on market.
Embodiment
Below example is further set forth preparation method of the present invention by experiment, but this should be interpreted as that the scope of theme of the present invention only limits to following embodiment.
Embodiment 1
Take by weighing 2.0g NiCl
2Be dissolved in the 6.5mL distilled water, in beaker, add 5g SiO
2(BET specific surface area=198m
2/ g), dipping spends the night, and the 343K stirring in water bath is to dry, 373K baking 6 hours, 473K roasting 4 hours is stand-by.Under the 333K water-bath, in there-necked flask, add methyl alcohol 32.5mL, ethanol 5mL, hydrazine hydrate 7.5mL, sodium hydroxide 1.0g, distilled water 1.0mL and POTASSIUM BOROHYDRIDE 1.0g successively, be stirred to dissolving, take by weighing a certain amount of catalyst precursor and pour in the there-necked flask, obtain Ni-B/SiO
2Sample is used distilled water and ethanol repetitive scrubbing successively, is kept in the ethanol standby at last.
Add catalyzer weight in wet base 2.35g, 2 in the 500ml autoclave successively, 4-two chloro-6-nitrophenols 7.5g and 150mL ethanol are respectively replaced 3 times with nitrogen, hydrogen successively, removing air, and, feed H
2To 0.5MPa.Start stirring, stirring velocity 800r/min slowly is heated to 333K with autoclave.By observe and the record autoclave in pressure monitoring reaction process over time, when treating that pressure no longer changes, continue to stop behind the reaction 10min.Extract solution in the still out, filter out catalyzer (treating to apply mechanically next time), filtrate is behind the evaporated under reduced pressure solvent, with products obtained therefrom vacuum-drying.The transformation efficiency that detects 2,4-, two chloro-6-nitrophenolss through HPLC is 100%, 2-amino-4, and the selectivity of 6-chlorophenesic acid reaches 98%.
Embodiment 2
The Preparation of Catalyst operating process is with example 1.SiO
2(BET specific surface area=198m
2/ g) be 5.0g, NiCl
2Be 2.0g, methyl alcohol 32.5mL, ethanol 5mL, hydrazine hydrate 7.5mL, sodium hydroxide 0.17g, distilled water 1.25mL and POTASSIUM BOROHYDRIDE 1.25g.
Add catalyzer weight in wet base 2.2g, 2 in the 500mL autoclave successively, 4-two chloro-6-nitrophenols 7.5g and 150ml ethanol are respectively replaced 3 times with nitrogen, hydrogen successively, to remove air, feed H
2To 0.6MPa.Start stirring, stirring velocity 800r/min slowly is heated to 333K with autoclave.By observe and the record autoclave in pressure monitoring reaction process over time, when treating that pressure no longer changes, continue to stop behind the reaction 10min.Extract solution in the still out, filter out catalyzer (treating to apply mechanically next time), filtrate is behind the evaporated under reduced pressure solvent, with products obtained therefrom vacuum-drying.The transformation efficiency that detects 2,4-, two chloro-6-nitrophenolss through HPLC is 100%, 2-amino-4, and the selectivity of 6-chlorophenesic acid reaches 97.8%.
Embodiment 3
The Preparation of Catalyst operating process is with example 1.SiO
2(BET specific surface area=198m
2/ g) be 5.0g, NiCl
2Be 2.0g, 373K baking 6 hours, 573K roasting 4 hours, methyl alcohol 32.5mL, ethanol 5mL, hydrazine hydrate 7.5mL, sodium hydroxide 0.17g, distilled water 1.25mL and POTASSIUM BOROHYDRIDE 1.25g.
Add catalyzer weight in wet base 2.35g, 2 in the 500mL autoclave successively, 4-two chloro-6-nitrophenols 7.5g and 150mL propyl alcohol are respectively replaced 3 times with nitrogen, hydrogen successively, to remove air, feed H
2To 0.5MPa.Start stirring, stirring velocity 800r/min slowly is heated to 343K with autoclave.By observing and record autoclave internal pressure monitoring reaction process over time, when treating that pressure no longer changes, continue to stop behind the reaction 10min.Extract solution in the still out, filter out catalyzer (treating to apply mechanically next time), filtrate is behind the evaporated under reduced pressure solvent, with products obtained therefrom vacuum-drying.The transformation efficiency that detects 2,4-, two chloro-6-nitrophenolss through HPLC is 99.68%, 2-amino-4, and the selectivity of 6-chlorophenesic acid reaches 97.92%.
Embodiment 4
The Preparation of Catalyst operating process is with example 1.SiO
2(BET specific surface area=198m
2/ g) be 5.0g, NiCl
2Be 2.25g, methyl alcohol 32.5mL, ethanol 5mL, hydrazine hydrate 8.5mL, sodium hydroxide 0.2g, distilled water 1.4mL and POTASSIUM BOROHYDRIDE 1.4g.
Add catalyzer weight in wet base 2.15g, 2 in the 500mL autoclave successively, 4-two chloro-6-nitrophenols 7.5g and 150mL chlorobenzenes are respectively replaced 3 times with nitrogen, hydrogen successively, to remove air, feed H
2To 0.6MPa.Start stirring, stirring velocity 600r/min slowly is heated to 333K with autoclave.By observe and the record autoclave in pressure monitoring reaction process over time, by observe and the record autoclave in pressure monitoring reaction process over time, when treating that pressure no longer changes, continue to stop behind the reaction 10min.Extract solution in the still out, filter out catalyzer (treating to apply mechanically next time), filtrate is behind the evaporated under reduced pressure solvent, with products obtained therefrom vacuum-drying.The transformation efficiency that detects 2,4-, two chloro-6-nitrophenolss through HPLC is 99.96%, 2-amino-4, and the selectivity of 6-chlorophenesic acid reaches 98.02%.
Embodiment 5
The Preparation of Catalyst operating process is with example 1.SiO
2(BET specific surface area=198m
2/ g) be 5.0g, NiCl
2Be 2.50g, methyl alcohol 32.5mL, ethanol 5mL, hydrazine hydrate 9.0mL, sodium hydroxide 0.2g, distilled water 1.6mL and POTASSIUM BOROHYDRIDE 1.6g.
Add catalyzer weight in wet base 2.0g, 2 in the 500mL autoclave successively, 4-two chloro-6-nitrophenols 10g and 150mL chlorobenzenes are respectively replaced 3 times with nitrogen, hydrogen successively, to remove air, feed H
2To 0.6MPa.Start stirring, stirring velocity 800r/min slowly is heated to 343K with autoclave.By observe and the record autoclave in pressure monitoring reaction process over time, when treating that pressure no longer changes, continue to stop behind the reaction 10min.Extract solution in the still out, filter out catalyzer (treating to apply mechanically next time), filtrate is behind the evaporated under reduced pressure solvent, with products obtained therefrom vacuum-drying.Through HPLC detect 2, the transformation efficiency of 4-two chloro-6-nitrophenolss is 100%, 2-amino-4, the selectivity of 6-chlorophenesic acid reaches 98.15%.
Embodiment 6
The Preparation of Catalyst operating process is with example 1.SiO
2(BET specific surface area=198m
2/ g) be 5.0g, NiCl
2Be 2.25g, methyl alcohol 32.5mL, ethanol 5mL, hydrazine hydrate 8.5mL, sodium hydroxide 0.2g, distilled water 1.4mL and POTASSIUM BOROHYDRIDE 1.4g.
Add catalyzer weight in wet base 2.35g, 2 in the 500mL autoclave successively, 4-two chloro-6-nitrophenols 10g and 150mL chlorobenzenes are respectively replaced 3 times with nitrogen, hydrogen, successively to remove air.Start stirring, stirring velocity 600r/min slowly is heated to 353K with autoclave, feeds H
2To 0.8MPa.By observing and record autoclave internal pressure monitoring reaction process over time, when treating that pressure no longer changes, continue to stop behind the reaction 10min.Extract solution in the still out, filter out catalyzer (treating to apply mechanically next time), filtrate is behind the evaporated under reduced pressure solvent, with products obtained therefrom vacuum-drying.Through HPLC detect 2, the transformation efficiency of 4-two chloro-6-nitrophenolss is 99.83%, 2-amino-4, the selectivity of 6-chlorophenesic acid reaches 99.03%.
Claims (2)
1.2-amino-4, the preparation method of 6-chlorophenesic acid is characterized in that comprising the steps: adding successively Ni-B/SiO in autoclave
2Amorphous catalyst, 2,4-two chloro-6-nitrophenolss, polar solvent, successively with nitrogen, hydrogen exchange to remove air, feed H at last
2To 0.5～1.0Mpa; With autoclave heating in water bath to 333～353K; Start stirring, regulate mixing speed 〉=500r/min, when treating that pressure no longer changes, continue to stop behind the reaction 10min; Extract solution in the still out, filter out catalyzer, filtrate is behind the evaporated under reduced pressure solvent, with products obtained therefrom vacuum-drying;
Ni-B/SiO wherein
2The mass ratio of amorphous catalyst and 2,4-, two chloro-6-nitrophenolss is 1.0～1.175:2.5～5; 2,4-, two chloro-6-nitrophenolss and polar solvent are 2.5～5:75(g/mL) with quality and volume ratio;
Described Ni-B/SiO
2Amorphous catalyst adopts the chemical reduction method preparation: being solvent with methyl alcohol, ethanol, water, is the reducing loaded nickel ion on silicon-dioxide of reductive agent with hydrazine hydrate and POTASSIUM BOROHYDRIDE; Ni-B/SiO
2Amorphous catalyst, be made up of nickel, boron and silicon-dioxide: their mass ratio is 0.32～1.5:0.14～0.39:4～5; Its preparation may further comprise the steps:
(1) silicon-dioxide is placed 70 ℃～80 ℃ baking oven activate;
(2) by nickel: the mass ratio of silicon-dioxide is that the mass ratio of 0.32～1.5:4～5 has calculated required NiCl
2, silicon-dioxide quality, with the NiCl that calculates
2Be dissolved in the distilled water, and add the silicon-dioxide that step (1) activated, dipping spends the night; Extremely dry in the 343K stirring in water bath then, with the roasting under oven dry and 473K under the 373K respectively of gained material; Add methyl alcohol, ethanol, hydrazine hydrate, sodium hydroxide, distilled water and POTASSIUM BOROHYDRIDE successively in the there-necked flask under 60 ℃ of water-baths, wherein said methyl alcohol: ethanol: hydrazine hydrate: sodium hydroxide: distilled water: the ratio of POTASSIUM BOROHYDRIDE is 25～35:4～5:4.6～11:0.09～0.26:0.7～2:0.7～2; Be stirred to dissolving, with good the pouring in the there-necked flask of roasting, stirring reaction is not emitted to there being bubble, obtains Ni-B/SiO
2Sample is used distilled water and ethanol repetitive scrubbing successively, is kept in the ethanol standby at last; Wherein said hydrazine hydrate and NiCl
2Mol ratio be n (NH
2NH
2H
2O)/(Ni
2+)=9, wherein POTASSIUM BOROHYDRIDE and NiCl
2Mol ratio be n (KBH
4)/n (Ni
2+)=1.25.
2. 2-amino-4 according to claim 1, the preparation method of 6-chlorophenesic acid, wherein said polar solvent is methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, acetone, chlorobenzene or their any mixed solvent.
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| CN2010102532781A CN101914028B (en) | 2010-08-13 | 2010-08-13 | Method for preparing 2-amido-4,6-dichlorophenol |
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|---|---|---|---|
| CN2010102532781A CN101914028B (en) | 2010-08-13 | 2010-08-13 | Method for preparing 2-amido-4,6-dichlorophenol |
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|---|---|
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| CN101914028B true CN101914028B (en) | 2013-08-14 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0608896A1 (en) * | 1993-01-29 | 1994-08-03 | Sumitomo Chemical Company, Limited | Process for producing aromatic amide compounds useful as cyan coupler for color photographes |
| JP2005289835A (en) * | 2004-03-31 | 2005-10-20 | Konica Minolta Chemical Co Ltd | Method for producing 5-substituted-2-amidophenol |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06306024A (en) * | 1993-04-26 | 1994-11-01 | Nippon Synthetic Chem Ind Co Ltd:The | Production of 2-amino-3,6-dichlorophenol |
-
2010
- 2010-08-13 CN CN2010102532781A patent/CN101914028B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0608896A1 (en) * | 1993-01-29 | 1994-08-03 | Sumitomo Chemical Company, Limited | Process for producing aromatic amide compounds useful as cyan coupler for color photographes |
| JP2005289835A (en) * | 2004-03-31 | 2005-10-20 | Konica Minolta Chemical Co Ltd | Method for producing 5-substituted-2-amidophenol |
Non-Patent Citations (2)
| Title |
|---|
| Ni-B/SiO2非晶态催化剂应用于硝基苯液相加氢制苯胺;王明辉;《催化学报》;20010531;第22卷(第3期);287页第2段至288页第1段 * |
| Ni-B/SiO2非晶态合金催化加氢制备邻氯苯胺;孙昱;《染料与染色》;20051231;第42卷(第6期);32页第1段至第4段 * |
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Effective date of registration: 20151109 Address after: Daitou town of Liyang City Ferry Street 213311 Jiangsu city of Changzhou province 8-2 No. 7 Patentee after: Liyang Chang Technology Transfer Center Co., Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: Changzhou University |