CN100369889C - Process for synthesizing salicylamide - Google Patents
Process for synthesizing salicylamide Download PDFInfo
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- CN100369889C CN100369889C CNB2006100483002A CN200610048300A CN100369889C CN 100369889 C CN100369889 C CN 100369889C CN B2006100483002 A CNB2006100483002 A CN B2006100483002A CN 200610048300 A CN200610048300 A CN 200610048300A CN 100369889 C CN100369889 C CN 100369889C
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- salicylamide
- urea
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Abstract
The invention discloses a synthesizing method of salicylamide, which comprises the following steps: adding solid alkaline catalyst in the compound of aquacare and phenol with molar rate at 1-100:1; setting the molar rate of catalyst and aquacare at 0.001-10:1; reacting under 0.1-3.5Mpa at 140-220 deg.c for 1-24h.
Description
Technical field
The invention belongs to a kind of method of synthesis salicylamide.
Background technology
Salicylic amide (salicylamide, structural formula is 2-(HO) C6H4CONH2) formal name used at school is 2-hydroxybenzamide (2-Hydroxylbenzamide), it is a kind of very important organic synthesis intermediate, be that synthetic its many important derivatives are (as the snail killing agent Niphesamide, analgesia ends medicine of a warm nature o-ethoxybenzamide etc.) raw material, be widely used in medicine, spices, dyestuff, numerous areas such as rubber ingredients.Salicylic amide is not only an important fine-chemical intermediate, and is a kind of being widely accepted and a large amount of antipyretic and analgesic that uses, and is used for fever and headache, neurodynia, and arthrodynia and reactivity rheumatism etc. have better curative effect.
At present, the method for synthesis salicylamide mainly contains Whitfield's ointment ammoniation process and wintergreen oil ammoniation process.The former is to be raw material with the Whitfield's ointment, adds ammoniacal liquor in suitable condition amination, and volume was big when this method was refining, and yield is low, and finished product usually is with pink color and luster, product purification process complexity.The present industrial wintergreen oil ammoniation process that mainly is to use, this method mainly is that wintergreen oil and ammoniacal liquor are mixed in the encloses container, stirs 3 hours prior to 20 ℃, in the time of 30 ℃, stirred 5 hours again, pH value=4 are regulated in cooling then, and crystallization promptly gets the thick product of salicylic amide.Because the higher raw material wintergreen oil of use cost makes that this method cost is too high, uneconomical.In a word, no matter the Whitfield's ointment ammoniation process still is the wintergreen oil ammoniation process, and its starting raw material is phenol, and its technical process is long, and equipment has high input, and the energy consumption height is a kind of very uneconomic synthetic method.
Goal of the invention
It is raw material with urea and phenol that the present invention aims to provide one, and technology is simple and direct, economical, green, the method for synthesis salicylamide efficiently.
Technological line
The object of the present invention is achieved like this: with urea and phenol is raw material, in stainless steel cauldron, react synthesis salicylamide under existing with solid base catalyst, and employing novel reactor, in reaction process, feed high pure nitrogen, keep constant voltage simultaneously, the control flow velocity, in time remove the by product ammonia that reaction process produces, thereby obtain the salicylic amide of high yield.Synthetic method of the present invention comprises the steps:
In urea and phenol mixture, add solid base catalyst, wherein the mol ratio of phenol and urea is 1-100: 1, the mol ratio of catalyzer and urea is 0.001-10: 1, in temperature of reaction is 140-220 ℃, reaction pressure is to react under the condition of 0.1-3.5MPa, and the reaction times is 1h-24h.
Aforesaid catalyzer is one or more in alkalimetal oxide, alkaline earth metal oxide or the transition metal oxide, and described alkalimetal oxide is K, Na oxide compound.Described alkaline earth metal oxide Ca, Mg oxide compound.Described transition metal oxide is the oxide compound of Zn, La.Used oxide catalyst is by coprecipitation method or its corresponding salt or alkali thermolysis and make.
Catalyzer also may be the oxide compound that impregnated in one or more the above-mentioned metals on certain carrier.Wherein carrier comprises various gacs, molecular sieve, aluminum oxide, silicon oxide etc.The present invention compared with prior art has following advantage:
1, reaction raw materials is cheap and easy to get, and the reaction product selectivity is higher, and by product is few; Owing to react by two kinds of direct one-step synthesis of raw material, technology is simple simultaneously, and energy consumption is low, so the building-up process economy is very obvious.
2, reaction process is simple, and than being easier to operation, the catalyst performance good reproducibility helps industrialization.
3, realize having meticulous catalytic process to replace the organic catalysis process efficiently to synthesize medicine intermediate, wherein use heterogeneous solid base catalyst, make that post catalyst reaction is easy to separate, help the product separation purifying.
Embodiment
Can illustrate in greater detail the present invention by following embodiment.
Embodiment 1 catalyzer is CaO, and (catalyzer is by CaCO
3Roasting makes)
Catalyst levels 0.3g, urea 15g, phenol 94g, 200 ℃ of temperature of reaction, the pressure in the reaction pressure 1.6MPa reactor is greater than 1.6MPa, and reacted ammonia reclaims after condensation, and the reaction times is 3h.Gained is the result the following is: conversion rate of urea 87.68%, the yield of salicylic amide are 85.72%
Embodiment 2 catalyzer are commercial ZnO
Catalyst levels 1.5g, urea 3g, phenol 235g, 150 ℃ of temperature of reaction, the pressure in the reaction pressure 0.5MPa reactor is greater than 0.5MPa, and reacted ammonia reclaims after condensation, and the reaction times is 4.5h.Gained is the result the following is: conversion rate of urea 88.35%, the yield of salicylic amide are 85.22%
Embodiment 3 catalyzer are that (catalyzer is by Zn (OH) for ZnO
2Roasting is obtained)
Catalyst levels 18g, urea 3.6g, phenol 94g, 220 ℃ of temperature of reaction, the pressure in the reaction pressure 3.0MPa reactor is greater than 3.0MPa, and reacted ammonia reclaims after condensation, and the reaction times is 2h.Gained is the result the following is: conversion rate of urea 87.45%, the yield of salicylic amide are 84.42%
Embodiment 4 catalyzer are ZnO (catalyzer is obtained by the zinc subcarbonate roasting)
Catalyst levels 4g, urea 12g, phenol 20g, 205 ℃ of temperature of reaction, the pressure in the reaction pressure 1.6MPa reactor is greater than 1.6MPa, and reacted ammonia reclaims after condensation, and the reaction times is 10h.Gained is the result the following is: conversion rate of urea 88.85%, the yield of salicylic amide are 85.73%
Embodiment 5 catalyzer are that (catalyzer is by Mg (OH) for MgO
2Roasting is obtained)
Catalyst levels 1.2g, urea 12g, phenol 94g, 180 ℃ of temperature of reaction, the pressure in the reaction pressure 2.0MPa reactor is greater than 2.0MPa, and reacted ammonia reclaims after condensation, and the reaction times is 4h.Gained is the result the following is: conversion rate of urea 87.65%, the yield of salicylic amide are 84.12%
Embodiment 6 catalyzer are that (catalyzer is by Pb (AcO) for PbO
2Roasting is obtained)
Catalyst levels 15g, urea 12g, phenol 94g, 190 ℃ of temperature of reaction, the pressure in the reaction pressure 1.6MPa reactor is greater than 1.6MPa, and reacted ammonia reclaims after condensation, and the reaction times is 8h.Gained is the result the following is: conversion rate of urea 89.33%, the yield of salicylic amide are 85.98%
Embodiment 7 catalyzer are that (catalyzer is by MgCaO for MgO
3Roasting is obtained)
Catalyst levels 1.2g, urea 12g, phenol 94g, 200 ℃ of temperature of reaction, the pressure in the reaction pressure 2.5MPa reactor is greater than 2.5MPa, and reacted ammonia reclaims after condensation, and the reaction times is 18h.Gained is the result the following is: conversion rate of urea 88.15%, the yield of salicylic amide are 85.33%
Embodiment 8 catalyzer are La
2O
3(catalyzer is by La
2(NO3)
3Roasting is obtained)
Catalyst levels 2.0g, urea 12g, phenol 94g, 220 ℃ of temperature of reaction, the pressure in the reaction pressure 2.0MPa reactor is greater than 2.0MPa, and reacted ammonia reclaims after condensation, and the reaction times is 1h.Gained is the result the following is: conversion rate of urea 86.83%, the yield of salicylic amide are 83.79%
Embodiment 9 catalyzer are ZnO/Al
2O
3(catalyzer is obtained by pickling process, and the content of ZnO is 15Wt%)
Catalyst levels 3.0g, urea 12g, phenol 94g, 200 ℃ of temperature of reaction, the pressure in the reaction pressure 2.0MPa reactor is greater than 2.0MPa, and reacted ammonia reclaims after condensation, and the reaction times is 1h.Gained is the result the following is: conversion rate of urea 86.03%, the yield of salicylic amide are 83.99%
Embodiment 10 catalyzer are composite catalyst
The ca nitrate soln of configuration 15% is placed in 60 ℃ of water-baths, and the sodium carbonate solution of adding 35% carries out co-precipitation, stir in the coprecipitation process fully, and to keep pH value be 9.0, and the gained precipitation, is dried down and at 350 ℃ of following roasting 2h in 110 ℃ to neutral through deionized water wash.Be reflected in the autoclave of 80ml and carry out, with the heating of electric heating heating jacket, catalyst levels is 1.5g, urea 6.08g, phenol 47.10g, 150 ℃ of temperature of reaction.Reaction pressure 2.1MPa, the pressure in the reactor are greater than 2.1MPa, and the ammonia that reaction generates reclaims reaction times 3.5h after condensation.The gained result is as follows: conversion rate of urea 87.55%, the yield of salicylic amide are 84.36%
Embodiment 11 catalyzer are composite catalyst
The nitrocalcite of configuration 20% and 40% zinc nitrate mixed solution, be placed in 60 ℃ of water-baths, slowly the ammoniacal liquor of adding 18% carries out co-precipitation, stir in the coprecipitation process fully, and maintenance pH value is 10.0, gained precipitation through deionized water wash to neutral, in 110 ℃ of oven dry and at 400 ℃ of following roasting 3h down.Be reflected in the autoclave of 80ml and carry out, with the heating of electric heating heating jacket, catalyst levels is 20g, urea 6.08g, phenol 47.10g, 200 ℃ of temperature of reaction.Reaction pressure 3.0MPa, the pressure in the reactor are greater than 3.0MPa, and reaction generates 165 ℃ of gas and reclaim reaction times 6h after condensation.The gained result is as follows: conversion rate of urea 88.81%, the yield of salicylic amide are 84.63%
Embodiment 12 catalyzer are composite catalyst
The nitrocalcite of configuration 25% and 25% zinc nitrate mixed solution, be placed in 60 ℃ of water-baths, slowly the ammoniacal liquor of adding 18% carries out co-precipitation, stir in the coprecipitation process fully, and maintenance pH value is 10.0, gained precipitation through deionized water wash to neutral, in 110 ℃ of oven dry and at 400 ℃ of following roasting 3h down.Be reflected in the autoclave of 80ml and carry out, with the heating of electric heating heating jacket, catalyst levels is 1.2g, urea 6.08g, phenol 47.10g, 190 ℃ of temperature of reaction.Reaction pressure 3.2MPa, the pressure in the reactor are greater than 3.2MPa, and the ammonia that reaction generates reclaims reaction times 2h after condensation.The gained result is as follows: conversion rate of urea 88.34%, the yield of salicylic amide are 84.57%.
Claims (7)
1. the method for a synthesis salicylamide is characterized in that comprising the steps:
In urea and phenol mixture, add solid base catalyst, wherein the mol ratio of phenol and urea is 1-100: 1, the mol ratio of catalyzer and urea is 0.001-10: 1, in temperature of reaction is 140-220 ℃, reaction pressure is to react under the condition of 0.1-3.5MPa, and the reaction times is 1h-24h.
2. the method for a kind of synthesis salicylamide as claimed in claim 1 is characterized in that described catalyzer is one or more in alkalimetal oxide, alkaline earth metal oxide or the transition metal oxide.
3. the method for a kind of synthesis salicylamide as claimed in claim 2 is characterized in that described alkalimetal oxide is the oxide compound of K or Na.
4. the method for a kind of synthesis salicylamide as claimed in claim 2 is characterized in that described alkaline earth metal oxide is Ca, Mg oxide compound.
5. the method for a kind of synthesis salicylamide as claimed in claim 2 is characterized in that described transition metal oxide is the oxide compound of Zn or La.
6. the method for a kind of synthesis salicylamide as claimed in claim 1 is characterized in that described catalyzer is one or more alkalimetal oxides, alkaline earth metal oxide or the transition metal oxide that impregnated on the carrier.
7. the method for a kind of synthesis salicylamide as claimed in claim 6 is characterized in that described carrier is gac, molecular sieve, aluminum oxide or silicon oxide.
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| CNB2006100483002A CN100369889C (en) | 2006-09-15 | 2006-09-15 | Process for synthesizing salicylamide |
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| CNB2006100483002A CN100369889C (en) | 2006-09-15 | 2006-09-15 | Process for synthesizing salicylamide |
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| CN100369889C true CN100369889C (en) | 2008-02-20 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891645A (en) * | 2010-07-27 | 2010-11-24 | 陕西科技大学 | Method for preparing salicylamide |
| CN105646269B (en) * | 2015-12-31 | 2017-11-21 | 镇江高鹏药业有限公司 | A kind of synthetic method of salicylamide |
| CN105944731B (en) * | 2016-05-27 | 2018-04-24 | 枣庄学院 | A kind of composite oxide catalysts of urea and phenol synthesis salicylamide and preparation method and application |
| CN110833845B (en) * | 2019-10-31 | 2022-08-16 | 润泰化学（泰兴）有限公司 | Preparation method of solid base catalyst, solid base catalyst and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050196418A1 (en) * | 2004-03-04 | 2005-09-08 | Yu Ruey J. | Bioavailability and improved delivery of alkaline pharmaceutical drugs |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20050196418A1 (en) * | 2004-03-04 | 2005-09-08 | Yu Ruey J. | Bioavailability and improved delivery of alkaline pharmaceutical drugs |
Non-Patent Citations (2)
| Title |
|---|
| 苯并噁唑酮合成方法综述. 罗贞礼.湖南化工，第3期. 1994 * |
| 邻乙氧基苯酰胺的合成. 迟文寿.辽宁化工，第2期. 1982 * |
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Assignee: Zhuhai Changxian Chemical Technology Co., Ltd. Assignor: Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences Contract record no.: 2010440001563 Denomination of invention: Process for synthesizing salicylamide Granted publication date: 20080220 License type: Exclusive License Open date: 20070307 Record date: 20101229 |
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Granted publication date: 20080220 Termination date: 20170915 |