CN101314571A - Catalysis synthesis method for nitrobenzene ether catalysis synthesis method for paranitroanisole - Google Patents
Catalysis synthesis method for nitrobenzene ether catalysis synthesis method for paranitroanisole Download PDFInfo
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- CN101314571A CN101314571A CNA2008101240666A CN200810124066A CN101314571A CN 101314571 A CN101314571 A CN 101314571A CN A2008101240666 A CNA2008101240666 A CN A2008101240666A CN 200810124066 A CN200810124066 A CN 200810124066A CN 101314571 A CN101314571 A CN 101314571A
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- nitromethoxybenzene
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Abstract
The invention relates to a method for synthesizing paranitroanisole. The raw materials used by the method are green chemicals dimethyl carbonate (DMC) and p-nitrophenol, and the catalyst is NaY molecular sieve, activated aluminum oxide or activated carbon which is impregnated by alkali metals or alkaline-earth metal compounds. Good conversion rate of the raw materials and good selectivity of target products can be obtained by using the method provided by the invention under the reaction conditions that: the temperature is between 90 and 200 DEG C, and the reaction time is between 1 and 5 hours; the mol ratio of the p-nitrophenol to the dimethyl carbonate of the raw materials is between 1 to 5 and 1 to 15, and the amount of the catalyst is 2 to 20 percent of the mass of the raw materials, wherein, the conversion rate of the p-nitrophenol can reach over 64 percent, and the selectivity of the paranitroanisole can reach 100 percent. The method takes the DMC as a methylated reagent to actually realize a green synthetic route, takes solid alkali as the catalyst, and is superior to the prior synthetic method of homogeneous catalysis or phase-transfer catalysis; and the catalyst is simple to separate and can be reused.
Description
Technical field
The present invention relates to the organic chemical industry field, the method for the synthetic p-Nitromethoxybenzene of particularly a kind of catalysis.
Background technology
P-Nitromethoxybenzene also claims p-nitroanisole, colourless or faint yellow rib shape crystal, density 1.2540g/cm
3, 54 ℃ of fusing points, 274 ℃ of boiling points are soluble in alcohol, ether and hot sherwood oil, are slightly soluble in cold sherwood oil, and are water insoluble, can be used as dyestuff intermediate and other organic synthesis raw materials, also can be used as the intermediate of medicine and agricultural chemicals, also can make inert solvent in organic synthesis.
At present, the oxyalkylated synthetic route of the many employings of the method for domestic production p-Nitromethoxybenzene, be raw material promptly with p-Nitrophenyl chloride, methyl alcohol and sodium hydroxide, under the pressure of 0.3MPa, carry out methoxylation, get p-Nitromethoxybenzene through underpressure distillation again, this method by product p-NP produces more, and transformation efficiency and yield are all low, waste liquid is many, and environmental pollution is serious.Be raw material with p-Nitrophenyl chloride, methyl alcohol and sodium hydroxide at present, make phase-transfer catalyst, the existing report of synthetic p-Nitromethoxybenzene under normal pressure with benzyltriethylammoinium chloride.This processing condition gentleness does not need pressure, and the reaction times is short, and transformation efficiency and yield are all high.Though but the polymer phase-transfer catalyst is respond well catalyzer, can reuse again, its synthetic trouble, cost is also higher, and alkali used in the building-up process is sodium hydroxide.Methylcarbonate is emerging in recent years a kind of green chemical, because its intramolecularly contains methyl, carbonyl, methoxyl group and methoxycarbonyl isoreactivity group, can substitute materials such as hypertoxic chemical such as methyl-sulfate, methyl chloride, phosgene and participate in organic synthesis.
Methylcarbonate (DMC) decomposes that the back produces has only methyl alcohol and carbonic acid gas, is a kind of real green chemical industry raw material.Because the synthetic technology of methylcarbonate is perfect gradually in recent years, industrial scale also enlarges gradually, this just provides possibility (Delledonne D for carrying out the methylcarbonate derived product, Rivetti F, Romano U.Developments in the production and application of dimethyl carbonate.Applied Catalysis A:General.2001,221 (1-2): 245-251; Ono Y.Catalysis in the production and reactions of dimethylcarbonate, an environmentally benign building block[J] .Applied Catalysis A:General.1997,155:133-166).
The present invention adopts p-NP and dimethyl carbonate to prepare p-Nitromethoxybenzene and compares with other some traditional preparation methods, have the raw material low toxicity, the reaction conditions gentleness, Preparation of Catalyst is simple, many advantages such as convenient separation have very high using value.
Summary of the invention
Technical problem solved by the invention provides the method for a kind of green, the synthetic p-Nitromethoxybenzene of efficient catalytic.
For solving the problems of the technologies described above, the concrete scheme that is adopted is as follows:
It is characterized in that by being the synthetic p-Nitromethoxybenzene of raw material with p-NP and methylcarbonate with catalyzer.
Catalyst system therefor is through basic metal or the impregnated NaY molecular sieve of alkaline earth metal compound, activated alumina or gac.
Used alkali metal compound is oxyhydroxide, carbonate or the acetate of potassium or sodium, and its consumption is the 5-30% of carrier quality.
Used alkaline earth metal compound is oxyhydroxide, carbonate or the acetate of magnesium or calcium, and its consumption is the 5-30% of carrier quality.
Used reaction conditions is: 90～200 ℃ of temperature, in 1～5 hour reaction times, feed molar proportioning p-NP: methylcarbonate 1: 5～1: 15, catalyst levels are the 2-20% of raw materials quality.
The present invention is better than traditional homogeneous catalysis or phase-transfer catalysis synthetic method, and catalyst separating is simple, and is reusable.With DMC is the greenization that methylating reagent has really been realized synthetic route.
Embodiment
Embodiment 1
With the impregnated gac of 20% potassium hydroxide is catalyzer, catalyst levels is 5% of a raw materials quality, feed molar proportioning p-NP: methylcarbonate is 1: 10,150 ℃ of temperature of reaction, reaction times is 4 hours, the p-NP transformation efficiency is 98.8%, and the p-Nitromethoxybenzene selectivity is 100%.
Embodiment 2
With the impregnated gac of 5% potassium hydroxide is catalyzer, catalyst levels is 5% of a raw materials quality, feed molar proportioning p-NP: methylcarbonate is 1: 10,150 ℃ of temperature of reaction, reaction times is 4 hours, the p-NP transformation efficiency is 7.1%, and the p-Nitromethoxybenzene selectivity is 100%.
Embodiment 3
With the impregnated gac in 30% potassium hydroxide place is catalyzer, catalyst levels is 5% of a raw materials quality, feed molar proportioning p-NP: methylcarbonate is 1: 10,150 ℃ of temperature of reaction, reaction times is 4 hours, the p-NP transformation efficiency is 83.2%, and the p-Nitromethoxybenzene selectivity is 96.4%.
Embodiment 4
With the impregnated gac in 20% sodium hydroxide place is catalyzer, catalyst levels is 5% of a raw materials quality, feed molar proportioning p-NP: methylcarbonate is 1: 10,150 ℃ of temperature of reaction, reaction times is 4 hours, the p-NP transformation efficiency is 41.3%, and the p-Nitromethoxybenzene selectivity is 100%.
Embodiment 5
With the impregnated gac in 20% lime acetate place is catalyzer, catalyst levels is 5% of a raw materials quality, feed molar proportioning p-NP: methylcarbonate is 1: 10,150 ℃ of temperature of reaction, reaction times is 4 hours, the p-NP transformation efficiency is 15.3%, and the p-Nitromethoxybenzene selectivity is 100%.
Embodiment 6
With the impregnated gac in 20% magnesiumcarbonate place is catalyzer, catalyst levels is 5% of a raw materials quality, feed molar proportioning p-NP: methylcarbonate is 1: 10,150 ℃ of temperature of reaction, reaction times is 4 hours, the p-NP transformation efficiency is 35.8%, and the p-Nitromethoxybenzene selectivity is 100%.
Embodiment 7
With the impregnated gac in 20% magnesium hydroxide place is catalyzer, catalyst levels is 5% of a raw materials quality, feed molar proportioning p-NP: methylcarbonate is 1: 10,150 ℃ of temperature of reaction, reaction times is 4 hours, the p-NP transformation efficiency is 38.9%, and the p-Nitromethoxybenzene selectivity is 100%.
Embodiment 8
With the impregnated gac in 20% sodium acetate place is catalyzer, catalyst levels is 5% of a raw materials quality, feed molar proportioning p-NP: methylcarbonate is 1: 10,150 ℃ of temperature of reaction, reaction times is 4 hours, the p-NP transformation efficiency is 64.7%, and the p-Nitromethoxybenzene selectivity is 100%.
Embodiment 9
With the impregnated gac in 20% potassium hydroxide place is catalyzer, catalyst levels is 2% of a raw materials quality, feed molar proportioning p-NP: methylcarbonate is 1: 10,150 ℃ of temperature of reaction, reaction times is 4 hours, the p-NP transformation efficiency is 3.7%, and the p-Nitromethoxybenzene selectivity is 54.2%.
Embodiment 10
With the impregnated gac in 20% potassium hydroxide place is catalyzer, catalyst levels is 20% of a raw materials quality, feed molar proportioning p-NP: methylcarbonate is 1: 10,150 ℃ of temperature of reaction, reaction times is 4 hours, the p-NP transformation efficiency is 100%, and the p-Nitromethoxybenzene selectivity is 93.1%.
Embodiment 11
With the impregnated gac in 20% potassium hydroxide place is catalyzer, catalyst levels is 5% of a raw materials quality, feed molar proportioning p-NP: methylcarbonate is 1: 5,150 ℃ of temperature of reaction, reaction times is 4 hours, the p-NP transformation efficiency is 90.6%, and the p-Nitromethoxybenzene selectivity is 97.0%.
Embodiment 12
With the impregnated gac in 20% potassium hydroxide place is catalyzer, catalyst levels is 5% of a raw materials quality, feed molar proportioning p-NP: methylcarbonate is 1: 15,150 ℃ of temperature of reaction, reaction times is 4 hours, the p-NP transformation efficiency is 93.2%, and the p-Nitromethoxybenzene selectivity is 99.4%.
Embodiment 13
With the impregnated gac in 20% potassium hydroxide place is catalyzer, catalyst levels is 5% of a raw materials quality, feed molar proportioning p-NP: methylcarbonate is 1: 10,90 ℃ of temperature of reaction, reaction times is 4 hours, the p-NP transformation efficiency is 12.9%, and the p-Nitromethoxybenzene selectivity is 100%.
Embodiment 14
With the impregnated gac in 20% potassium hydroxide place is catalyzer, catalyst levels is 5% of a raw materials quality, feed molar proportioning p-NP: methylcarbonate is 1: 10,200 ℃ of temperature of reaction, reaction times is 4 hours, the p-NP transformation efficiency is 88.0%, and the p-Nitromethoxybenzene selectivity is 96.5%.
Embodiment 15
With the impregnated gac in 20% potassium hydroxide place is catalyzer, catalyst levels is 5% of a raw materials quality, feed molar proportioning p-NP: methylcarbonate is 1: 10,150 ℃ of temperature of reaction, reaction times is 1 hour, the p-NP transformation efficiency is 56.9%, and the p-Nitromethoxybenzene selectivity is 100%.
Embodiment 16
With the impregnated gac in 20% potassium hydroxide place is catalyzer, catalyst levels is 5% of a raw materials quality, feed molar proportioning p-NP: methylcarbonate is 1: 10,150 ℃ of temperature of reaction, reaction times is 5 hours, the p-NP transformation efficiency is 92.1%, and the p-Nitromethoxybenzene selectivity is 98.6%.
Embodiment 17
With the impregnated activated alumina in 20% potassium hydroxide place is catalyzer, catalyst levels is 5% of a raw materials quality, feed molar proportioning p-NP: methylcarbonate is 1: 10,150 ℃ of temperature of reaction, reaction times is 4 hours, the p-NP transformation efficiency is 81.2%, and the p-Nitromethoxybenzene selectivity is 63.7%.
Embodiment 18
With the impregnated NaY molecular sieve in 20% potassium hydroxide place is catalyzer, catalyst levels is 5% of a raw materials quality, feed molar proportioning p-NP: methylcarbonate is 1: 10,150 ℃ of temperature of reaction, reaction times is 4 hours, the p-NP transformation efficiency is 41.6%, and the p-Nitromethoxybenzene selectivity is 21.5%.
Claims (3)
- The method of 1 one kinds of synthetic p-Nitromethoxybenzenes of catalysis, it is characterized in that by being the synthetic p-Nitromethoxybenzene of raw material with p-NP and methylcarbonate with catalyzer, catalyst system therefor is through basic metal or the impregnated NaY molecular sieve of alkaline earth metal compound, activated alumina or activated carbon, reaction conditions is: 90～200 ℃ of temperature, 1～5 hour reaction times, feed molar proportioning nitrophenols: methylcarbonate 1: 5～1: 15, catalyst levels are the 2-20% of raw materials quality.
- The method of the synthetic p-Nitromethoxybenzene of 2 a kind of catalysis as claimed in claim 1 is characterized in that used alkali metal compound is oxyhydroxide, carbonate or the acetate of potassium or sodium, and its consumption is the 5-30% of carrier quality.
- The method of the synthetic p-Nitromethoxybenzene of 3 a kind of catalysis as claimed in claim 1 is characterized in that used alkaline earth metal compound is oxyhydroxide, carbonate or the acetate of magnesium or calcium, and its consumption is the 5-30% of carrier quality.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980097A (en) * | 2014-05-21 | 2014-08-13 | 芜湖职业技术学院 | Method for synthesizing phenols by etherifying |
| CN104741139A (en) * | 2013-12-31 | 2015-07-01 | 西北大学 | Method for preparing alkali-earth metal carbonate-carbon aerogel composite catalyst |
| CN111646904A (en) * | 2020-05-28 | 2020-09-11 | 浙江闰土研究院有限公司 | Method for synthesizing p-nitroanisole |
| CN114736128A (en) * | 2022-03-10 | 2022-07-12 | 青岛科技大学 | Method for preparing o-aminophenyl ether |
-
2008
- 2008-06-12 CN CNA2008101240666A patent/CN101314571A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104741139A (en) * | 2013-12-31 | 2015-07-01 | 西北大学 | Method for preparing alkali-earth metal carbonate-carbon aerogel composite catalyst |
| CN103980097A (en) * | 2014-05-21 | 2014-08-13 | 芜湖职业技术学院 | Method for synthesizing phenols by etherifying |
| CN103980097B (en) * | 2014-05-21 | 2016-06-22 | 芜湖职业技术学院 | A kind of synthetic method of phenols etherificate |
| CN111646904A (en) * | 2020-05-28 | 2020-09-11 | 浙江闰土研究院有限公司 | Method for synthesizing p-nitroanisole |
| CN114736128A (en) * | 2022-03-10 | 2022-07-12 | 青岛科技大学 | Method for preparing o-aminophenyl ether |
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