CN1297881A - Preparation of aryl methyl ketone - Google Patents
Preparation of aryl methyl ketone Download PDFInfo
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- CN1297881A CN1297881A CN 99125283 CN99125283A CN1297881A CN 1297881 A CN1297881 A CN 1297881A CN 99125283 CN99125283 CN 99125283 CN 99125283 A CN99125283 A CN 99125283A CN 1297881 A CN1297881 A CN 1297881A
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Abstract
The preparation of aryl ethyl ketone includes the contact of one kind of ethyl arene with one kind of catalyst and one kind of oxygen containing atmosphere in the reaction conditions of 50-200 deg.c temperature and normal to 5 MPa pressure. The said catalyst is one or several metal complex with specific general expression and has a concentration of 10 to the minus -sixth - 10 to the minus 1 mole/L molarity in the catalyst system.
Description
The invention relates to and a kind ofly contain the method for C=O based compound, the method for more specifically saying so and being equipped with aryl methyl ketone with the molecular oxygen oxidation legal system about a kind of with oxidation style preparation.
The method of synthesizing aryl ethyl ketone has many reports, and wherein the simplest methyl phenyl ketone of structure is that the research report is maximum, also is the turnout maximum.With the synthetic methyl phenyl ketone of molecular oxygen oxidation ethylbenzene is the method that generally adopts, and oxidizing reaction is carried out in acetum, makes catalyzer with Cobaltous diacetate or cobalt naphthenate compounds, and bromide is made promotor, molecular oxygen or air oxidant.One of shortcoming of this method is that acetic acid corrodibility is stronger, and the conversion unit corrosion resistance nature is had relatively high expectations, and equipment needs to make with special rolling-mill section.Two of shortcoming is, because the existence of a large amount of acetate solvates makes that the reactor effective rate of utilization is low.Three of shortcoming is that solvent acetic acid need separate and reclaim.
Yasutaka Ishii (Journal of Molecular Catalysis A:Chemical 117, pp 123-137,1997) method that a kind of alkylbenzene oxidation prepares methyl phenyl ketone is disclosed, this method is catalyzer with the acetylacetone cobalt, and N-hydroxyphthalimide (N-hydroxyphthalimide) is made promotor, with molecular oxygen as oxidant, obtain higher methyl phenyl ketone yield, but this method is carried out in acetum equally, still has the shortcoming stronger to equipment corrosion.In addition, in this method, the consumption of promotor N-hydroxyphthalimide is big (10%) very, makes the price of catalyst system very expensive.
People such as Lei (Chinese Chemical Letters Vol.3, No.4, pp267-268,1992) disclose a kind of method for oxidation of alkylbenzene, this method need not any solvent, adopts 2, the complex compound of 2 '-dipyridyl and ruthenium is made catalyzer, molecular oxygen or air oxidant 100 ℃ of temperature, carry out under pressure 1 normal atmosphere.When adopting this method oxidation ethylbenzene, conversion of ethylbenzene is the highest to have only 43.8%, and the selectivity of methyl phenyl ketone has only 74%.
People such as Lei (Chinese Chemical Letters Vol.4, No.1, pp21-22,1993) disclose a kind of method for oxidation of alkylbenzene, this method also need not any solvent, adopt 2, the complex compound of the complex compound of 2 '-dipyridyl and iron or 1,10 phenanthroline and iron is made catalyzer, molecular oxygen as oxidant, 110 ℃ of temperature, carry out under pressure 1 normal atmosphere.When adopting this method to use different catalyzer, 5 milliliters of ethylbenzene consumptions, 2 milligrams of catalyst levelss, under the condition in 3.5 hours reaction times, conversion of ethylbenzene has only 11.42-34.58%, and the selectivity of methyl phenyl ketone has only 66.20-89.83%.
When disclosed method prepared methyl phenyl ketone in above-mentioned two pieces of documents according to people such as Lei, the selectivity of speed of response and methyl phenyl ketone can not be taken into account simultaneously.In other words, when speed of response was slow, the selectivity of methyl phenyl ketone was higher, and when speed of response was very fast, the selectivity of methyl phenyl ketone descended significantly.With ChineseChemical Letters Vol.4, No.1, pp21-22, best result is an example in 1993, when conversion of ethylbenzene is 25.3% (speed of response have only 686 moles/mole catalyzer hour), the selectivity of methyl phenyl ketone can be up to 89.8%, and when conversion of ethylbenzene is increased to 34.58% (speed of response be 1010 moles/mole catalyzer hour), the selectivity of methyl phenyl ketone drops to 67.22%.
In the prior art, for the oxidation that has substituent ethylbenzene and other ethylaromatics on the phenyl ring, as the oxidation of halo ethylbenzene, methyl-ethyl benzene, methoxyl group ethylbenzene, nitro ethylbenzene, ethyl naphthalene etc., generally all adopt superoxide to make oxygenant, do not see direct report with molecular oxygen as oxidant.
The purpose of this invention is to provide a kind of new, in the presence of no any solvent, make the ethylaromatics oxidation with molecular oxygen, the method for selective production of aryl base ethyl ketone.
It is 50-200 ℃ that method provided by the invention is included in temperature of reaction, and pressure is under the condition of normal pressure to 5 MPa, and a kind of ethylaromatics is contacted with a kind of catalyzer and a kind of oxygenous atmosphere, and the concentration of described catalyzer in reaction system is 10
-6-10
-1Mol, described catalyzer is selected from one or more in the metal complex with following general formula:
Wherein, a kind of in the M representative element periodictable in logical formula I, (II) and/or (III) in I B family metal, V B family metal, VI B family metal, VII B family metal and the VIII family metal, X and Y can be the same or different, represent a kind of in hydrogen atom, hydroxyl, alkyl, alkoxyl group, cycloalkyl, halogen atom, the nitro, Z representation hydroxy or hydrogen atom, R
1Represent a kind of in phenyl, naphthyl, quinolyl, the cycloalkyl, R
2Represent a kind of in phenyl, pyridyl, naphthyl, the quinolyl.
According to method provided by the invention, the R in the described catalyzer general formula
1Represent a kind of in phenyl, naphthyl, quinolyl, the cycloalkyl, preferably represent phenyl.
R in the described catalyzer general formula
2Represent a kind of in phenyl, naphthyl, quinolyl, the pyridyl, preferably represent phenyl or pyridyl.
X and Y in the described catalyzer general formula can be the same or different, and represent a kind of in hydrogen atom, hydroxyl, alkyl, alkoxyl group, cycloalkyl, halogen atom, the nitro, and under the preferable case, X is identical with Y, represents hydrogen atom.
When X is identical with Y, represent hydrogen atom, R
1And R
2All represent phenyl, during the Z representation hydroxy, the part of the complex compound that logical formula I is represented is N-hydroxy-n-phenylbenzamaide, represents with BPHA, and the logical represented complex compound of formula I is the complex compound of N-hydroxy-n-phenylbenzamaide and M, with M (BPHA)
2Expression.
When X is identical with Y, represent hydrogen atom, R
1Represent phenyl, R
2Represent pyridyl, the Z representation hydroxy, and carbonyl be positioned at the pyridine nitrogen atom between position or during contraposition, the part of the complex compound that logical formula I is represented is N-hydroxy-n-phenyl-3-pyridine carboxamide or N-hydroxy-n-phenyl-4-pyridine carboxamide, represent with m-PPHA or p-PPHA, the logical represented complex compound of formula I is the complex compound of N-hydroxy-n-phenyl-3-pyridine carboxamide or N-hydroxy-n-phenyl-4-pyridine carboxamide and M, with M (m-PPHA)
2Or M (p-PPHA)
2Expression.
According to method provided by the invention, the position of X on pyridine ring in logical formula II and (III) can be the position that may exist arbitrarily, as contraposition, ortho position or the position at nitrogen-atoms.
When X is identical with Y, all represent hydrogen atom, R
1Represent phenyl, during the Z representation hydroxy, the part of the complex compound that logical formula II is represented is N-hydroxy-n-phenyl-2-pyridine carboxamide, represents with o-PPHA, the logical represented complex compound of formula II is the complex compound of N-hydroxy-n-phenyl-2-pyridine carboxamide and M, with M (o-PPHA)
2Expression.
When X is identical with Y, all represent hydrogen atom, R
1When representing phenyl, the part of the complex compound that logical formula III is represented is N-phenyl-2-pyridine carboxamide, represents with HPPA, and the logical represented complex compound of formula III is the complex compound of N-phenyl-2-pyridine carboxamide and M, with M (HPPA)
2Expression.
The more preferred catalyzer of method provided by the invention is M (BPHA)
2, M (p-PPHA)
2, M (m-PPHA)
2, M (o-PPHA)
2And M (HPPA)
2In one or more.
According to method provided by the invention, described catalyzer general formula and M (BPHA)
2, M (p-PPHA)
2, M (m-PPHA)
2, M (o-PPHA)
2And M (HPPA)
2In M representative element periodictable in a kind of in I B family metal, V B family metal, VI B family metal, VII B family metal and the VIII family metal, preferred represent a kind of in iron, cobalt, nickel, copper, manganese, molybdenum, chromium, ruthenium, rhenium, the vanadium, more preferably represent a kind of in cobalt, nickel, copper and the manganese.
Method catalyst system therefor provided by the invention can prepare by the following method:
(1) preparation method of the represented complex compound catalyst of logical formula I comprises that the complex compound part is dissolved in the alcohol, and being made into concentration is 10
-3-1 mol is preferably the solution of 0.05-0.5 mol, at 20-75 ℃, under preferred 40-60 ℃ the temperature, under agitation adds the aqueous solution of metal ion M, react preferably 0.6-2 hour 0.2-5 hour.The concentration of the solution of metal ion M is 10
-2-1 mol is preferably the 0.1-0.4 mol, and it is 1-5 that the add-on of metal ions M makes the mol ratio of part and metal ions M, is preferably 2-3.Filter the precipitation that generates, to there not being acid ion, drying obtains the complex compound shown in logical formula I with the deionized water wash solid product.
Described alcohol can be selected from C
1-C
5Fatty alcohol, as the various isomer of methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, amylalcohol various isomer, wherein, preferred alcohol is ethanol or n-propyl alcohol, more preferred alcohol is ethanol.
The aqueous solution of described metal ion M is selected from the aqueous solution of the soluble salt of metal ions M, as chloride soln, nitrate solution, the sulfate liquor of metal ions M.
Described exsiccant temperature can be a room temperature to 150 ℃, is preferably 80-120 ℃.
Wherein, the preparation method of described part can be that example illustrates with BPHA, p-PPHA and m-PPHA.
The preparation method of BPHA comprises, at concentration of sodium carbonate is the 0.1-3 mol, be preferably in the anhydrous tetrahydrofuran solution of 0.5-1 mol, add the Benzoyl chloride and the N-hydroxyanilines that account for the heavy % of total solution weight 5-20, the mol ratio of Benzoyl chloride and N-hydroxyanilines is 1-3, at-20 to 20 ℃, be preferably-10 to 0 ℃ and reacted 1-5 hour preferred 2-3 hour down.With concentration is the 0.1-5 mol, and the sodium bicarbonate aqueous solution that is preferably the 0.3-0.6 mol washs to pH=8, at 80-150 ℃, is preferably under 100-120 ℃ the temperature dryly, obtains solid BPHA.
Wherein, the N-hydroxyanilines can adopt the preparation of following method: in the weight ratio of oil of mirbane and ammonium chloride is to add zinc powder in the oil of mirbane of 5-15 and the aqueous solution of ammonium chloride (it is that 1 mol is advisable that the consumption of water makes the concentration of oil of mirbane in the mixing solutions) to make reductive agent (it is 1-4 that the add-on of zinc powder makes the weight ratio of zinc powder and oil of mirbane, be preferably 1.4-2), at 30-100 ℃, be preferably under 50-70 ℃ the temperature reaction 3-6 hour, be preferably 4-5 hour, filter out the zinc oxide of generation, and being washed with distilled water to fewly twice, the consumption that at every turn washs distilled water is equivalent to or more than the weight of the zinc oxide that generates.In filtrate, add sodium-chlor to saturated, separate out the N-hydroxyanilines, filter, be used for the preparation of part after the drying.
The preparation method of m-PPHA and p-PPHA comprises, at concentration of sodium carbonate is the 0.1-3 mol, be preferably in the anhydrous tetrahydrofuran solution of 0.5-1 mol, add the 3-pyridine formyl chloride or 4-pyridine formyl chloride and the N-hydroxyanilines that account for the heavy % of total solution weight 5-20, the mol ratio of 3-pyridine formyl chloride or 4-pyridine formyl chloride and N-hydroxyanilines is 0.5-2, is preferably 0.8-1.2.At-20 to 30 ℃, be preferably-10 to 10 ℃ and reacted 1-6 hour preferred 2-4 hour down.With concentration is the 0.1-5 mol, and the sodium bicarbonate aqueous solution that is preferably the 0.3-0.6 mol washs to pH=8, at 80-150 ℃, be preferably under 100-120 ℃ the temperature dry, the solid m-PPHA or the p-PPHA that obtain.
Wherein, 3-pyridine formyl chloride or 4-pyridine formyl chloride can be used 3-pyridine carboxylic acid or 4-pyridine carboxylic acid and SOCl
2Reaction is 1-5 hour under reflux temperature, preferred 2-3 hour, uses the excessive SOCl of benzene flush away again
2And prepare.Wherein, 3-pyridine carboxylic acid or 4-pyridine carboxylic acid and SOCl
2Mol ratio be 0.1-0.8, be preferably 0.2-0.5.
Can to select N-hydroxyanilines, N-hydroxyl naphthylamines, N-hydroxyquinoline amine, the N-hydroxyl Cycloalkyl amine of the Benzoyl chloride, naphthoyl chloride, quinoline formyl chlorine, pyridine formyl chloride of hydroxyl accordingly, alkyl, alkoxyl group, halogen, nitro, substituted radical and hydroxyl, alkyl, alkoxyl group, halogen, nitro substituent group for use be raw material to used part in other logical formula I, prepares with method same as described above.
(2) preparation method of the represented complex compound catalyst of logical formula II comprises, the complex compound part is dissolved in the alcohol, being made into concentration is the 0.02-2 mol, be preferably the solution of 0.05-1 mol, at 10-80 ℃, be preferably 40-70 ℃, under agitation add the alcoholic solution of metal ion M, reacted preferred 0.5-3 hour 0.2-5 hour.The concentration of the solution of metal ion M is the 0.05-2 mol, is preferably the 0.1-1 mol, and it is 1-4 that the add-on of metal ions M makes the mol ratio of part and metal ions M, is preferably 2-3.Filter the precipitation that generates, the alcoholic solution that is at least 95 heavy % with concentration washs solid product to there not being acid ion, and drying obtains the complex compound shown in logical formula II.
Described alcohol can be selected from C
1-C
5Fatty alcohol, as the various isomer of methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, amylalcohol various isomer.Wherein, preferred alcohol is ethanol or n-propyl alcohol, and more preferred alcohol is ethanol.
The alcoholic solution of described metal ion M is selected from the alcoholic solution of the salt that dissolves in alcohol of metal ions M, as metal ions M muriate alcoholic solution, nitrate alcoholic solution, vitriol alcoholic solution.
Described exsiccant temperature can be a room temperature to 150 ℃, is preferably 100-120 ℃.
Wherein, the preparation method of described part can be that example illustrates with o-PPHA.
The preparation method of o-PPHA comprises, at concentration of sodium carbonate is the 0.1-3 mol, be preferably and add 2-pyridine formyl chloride and the N-hydroxyanilines that accounts for total solution weight 5-10% in the anhydrous tetrahydrofuran solution of 0.5-1 mol, the mol ratio of 2-pyridine formyl chloride and N-hydroxyanilines is 0.5-2, is preferably 0.8-1.2.At-20-30 ℃, reaction is 1-6 hour under preferred-10-10 ℃ the temperature, preferred 2-4 hour.With concentration is the 0.1-5 mol, and the sodium bicarbonate aqueous solution that is preferably the 0.3-0.6 mol washs to pH=8, at 80-150 ℃, be preferably under 100-120 ℃ the temperature dry, the solid o-PPHA that obtains.
Wherein, 2-pyridine formyl chloride can be used 2-pyridine carboxylic acid and SOCl
2(mol ratio is 0.02-0.5, preferred 0.05-0.1) reacted 1-5 hour under reflux temperature, preferred 2-3 hour, washed excessive SOCl off with benzene again
2And prepare.
The 2-pyridine formyl chloride that used part can be selected hydroxyl on the pyridine ring, alkyl, alkoxyl group, halogen, nitro substituent group for use in other logical formula II is a raw material with N-hydroxyanilines, N-hydroxyl naphthylamines, N-hydroxyquinoline amine, the N-hydroxyl Cycloalkyl amine of hydroxyl, alkyl, alkoxyl group, halogen, nitro substituent group, prepares with method same as described above.
(3) preparation method of the represented complex compound catalyst of logical formula III comprises, the complex compound part is dissolved in the alcohol, being made into concentration is the 0.05-2 mol, be preferably the solution of 0.1-1 mol, at 10-80 ℃, preferred 40-60 ℃, under agitation add the salt of metal ions M and the mixed aqueous solution of ammoniacal liquor, reacted preferred 1-2 hour 0.5-4 hour.In the salt of metal ions M and the mixed aqueous solution of ammoniacal liquor, the concentration of metal ions M is the 0.02-2 mol, is preferably the 0.05-1 mol.It is 1-5 that the add-on of metal ions M makes the mol ratio of part and metal ions M, is preferably 2-3.The concentration of ammonia is the 0.1-5 mol, is preferably the 0.5-2 mol.Filter the precipitation that generates, to there not being acid ion, drying obtains the complex compound shown in logical formula III with the deionized water wash solid product.
Described alcohol can be selected from C
1-C
5Fatty alcohol, as the various isomer of methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, amylalcohol various isomer.Wherein, preferred alcohol is ethanol or n-propyl alcohol, and more preferred alcohol is ethanol.
The salt of described metal ions M and the mixed aqueous solution of ammoniacal liquor are selected from the soluble salt of metal ions M, as the mixing solutions of metal ions M muriate, nitrate, vitriol and ammoniacal liquor.
Described exsiccant temperature can be a room temperature to 150 ℃, is preferably 100-120 ℃.
Wherein, the preparation method of described part can be that example illustrates with HPPA.
The preparation method of HPPA comprises, 2-pyridine formyl chloride, aniline and tetrahydrofuran (THF) are mixed, and the mol ratio that is made into 2-pyridine formyl chloride and aniline is 0.5-2, the solution of preferred 0.8-1.2.2-pyridine formyl chloride and aniline account for the heavy % of 5-10 of solution total amount in the solution.At 30-70 ℃, reaction is 1-6 hour under preferred 40-60 ℃ the temperature, preferred 2-4 hour, the cooling back is 7-8 with the sodium bicarbonate neutralization reaction product to pH, and filtration is with distilled water wash solid product at least twice, the consumption of each distilled water is at least 2 times of the solid product that obtains, drying.
The 2-pyridine formyl chloride that used part can be selected hydroxyl on the pyridine ring, alkyl, alkoxyl group, halogen, nitro substituent group for use in other logical formula III is a raw material with aniline, naphthylamines, quinolyl amine, the Cycloalkyl amine of hydroxyl, alkyl, alkoxyl group, halogen, nitro substituent group, prepares with method same as described above.
According to method provided by the invention, the concentration of described catalyzer in reaction system is 10
-6-10
-1Mol is preferably 10
-5-10
-2Mol.
Described temperature of reaction is 50-200 ℃, is preferably 100-150 ℃.
The oxygen pressure of described reaction is normal pressure to 5 MPa, is preferably normal pressure to 3 MPa, more preferably normal pressure-1.5 MPa.
Reaction times decides on catalyst concentration, temperature of reaction and reaction pressure, and temperature of reaction is high more, and speed of response is fast more, and therefore, the temperature of reaction high more institute palpus reaction times is short more.Reaction pressure is high more, and speed of response is fast more, and therefore, the reaction pressure high more institute palpus reaction times is short more.The high more speed of response of catalyst concn is fast more, and therefore, the catalyst concn high more institute palpus reaction times is short more.In general, the reaction times is 1-20 hour, preferred 2-12 hour.
Described oxygenous atmosphere can be pure oxygen, also can be to contain oxygen not influence the atmosphere of the gas of reaction with other, and oxygen content is at least 20 body % in the described oxygenous atmosphere.The described atmosphere that does not influence the gas of reaction comprises rare gas element, nitrogen, carbonic acid gas of periodic table of elements zero group etc.Preferred oxygenous atmosphere is oxygen, oxygen-rich air or air.
According to method provided by the invention, described ethylaromatics refers to have on the aromatic ring aromatic hydrocarbons of ethyl.For example, comprise ethylbenzene, ethyl naphthalene with or without other substituted radicals.Preferred ethylaromatics is selected from one or more in the ethyl naphthalene that has halogen, methyl, methoxyl group or nitro on halo ethylbenzene, methyl-ethyl benzene, methoxyl group ethylbenzene, nitro ethylbenzene, ethyl naphthalene and the naphthalene nucleus.They generate methyl phenyl ketone, halo acetophenone, methyl acetophenone, methoxyacetophenone, nitro-acetophenone, acetonaphthone respectively after oxidation.More preferred ethylaromatics is selected from ethylbenzene, halo ethylbenzene, methyl-ethyl benzene or methoxyl group ethylbenzene.
According to method provided by the invention, after reaction finished, catalyzer can adopt the distillatory method, separates with reaction system easily, and isolated catalyzer can recycle.
With existing, do not use the method for solvent to compare, method provided by the invention has the transformation efficiency of higher ethylaromatics, the selectivity of higher aryl methyl ketone.For example adopt method provided by the invention, when preparing methyl phenyl ketone by ethylbenzene, under the high conversion of conversion of ethylbenzene up to 35.1-64.0 mole %, the selectivity of methyl phenyl ketone still can be up to 81.4-92.5%.
More beat allly be, adopt method provided by the invention, under very high speed of response, still keep the selectivity of very high methyl phenyl ketone.For example, adopt method provided by the invention, up in the 2309 moles/mole catalyzer hour, the selectivity of methyl phenyl ketone still can be up to 81.4% in speed of response.This is
Prior art is incomparable.
The following examples will the present invention will be further described, but do not limit the present invention in any form.
Example 1
The preparation of catalyst system therefor of the present invention.
(1) with 20 mmole 2-pyridine carboxylic acids (chemical pure, Sigma company product) and 20 milliliters of SOCl
2(chemical pure, Chongqing chemical reagent work product) (2-pyridine carboxylic acid and SOCl
2Mol ratio be 0.077) add in the three-necked bottle, back flow reaction 2 hours is washed excessive SOCl off with benzene
2, obtain 2-pyridine formyl chloride.
(2) with 18 mmole 2-pyridine formyl chlorides and 20 mmole aniline (chemical pure, Chongqing chemical reagent work product) joins in 40 milliliters of anhydrous tetrahydro furans, reaction is 2 hours under 50 ℃ temperature, it is 7 that the cooling back is neutralized to pH with sodium bicarbonate, filter, use distilled water wash solid product three times, each washing 20 ml distilled waters, drying obtains HPPA.
(3) 1.1 mmole complex compound part HPPA are dissolved in 15 milliliters of ethanol, be made into the solution that concentration is 0.07 mol, at 45 ℃, under agitation adding 5 milliliters of cobalt chloride concentrations is that 0.1 mol, ammonia concentration are the mixed aqueous solution of 1 mol, reacts 1 hour, and the mol ratio of HPPA and cobalt is 2.2, filter the precipitation that generates, to there not being acid ion, 100 ℃ dry down, obtains complex compound catalyst Co (HPPA) with the deionized water wash solid product
2
Example 2-4
The preparation of catalyst system therefor of the present invention.
Prepare catalyzer by example 1 described method, different is, the consumption of part HPPA is 1.2 mmoles, use nickelous chloride respectively, manganous chloride and copper sulfate replace cobalt chloride, nickelous chloride, the concentration of manganous chloride and copper-bath is 0.1 mol, nickelous chloride, manganous chloride and copper-bath consumption be 5 milliliters, consumption of ethanol is 20 milliliters, ammonia concentration is 1 mol in the mixed aqueous solution, temperature of reaction is 50 ℃, reaction times was respectively 2 hours, 2 hours and 3 hours, HPPA and nickel, manganese and copper mol ratio be 2.4, obtain complex compound catalyst Ni (HPPA)
2, Mn (HPPA)
2And Cu (HPPA)
2
Example 5
The preparation of catalyst system therefor of the present invention.
(1) (volumetric molar concentration of mixed solution oil of mirbane is 1 mol at the mixed solution of 10 gram oil of mirbane, 1.2 gram ammonium chlorides and water, the weight ratio of oil of mirbane and ammonium chloride is 8.3) the middle 15 gram zinc powders (weight ratio of zinc powder and oil of mirbane is 1.5) that add, reaction is 4 hours under 70 ℃ temperature, make nitrobenzene reduction, filter out the zinc oxide of generation, with distilled water wash twice, the consumption of each distilled water is 20 milliliters.In filtrate, add sodium-chlor to saturated, separate out the N-hydroxyanilines, filter, obtain the N-hydroxyanilines after the drying.
(2) in the anhydrous tetrahydrofuran solution of the yellow soda ash that 30 milliliters of concentration of sodium carbonate are 1 mol, add Benzoyl chloride and the N-hydroxyanilines (mol ratio of Benzoyl chloride and N-hydroxyanilines is 1.2) that accounts for total solution weight 10 heavy %, reacted 3 hours down at-5 ℃.With concentration is that the sodium bicarbonate aqueous solution of 0.5 mol washs to pH=8, and 100 ℃ of dryings obtain complex compound part BPHA.
(3) 1.2 mmole complex compound part BPHA are dissolved in 15 milliliters of ethanol, are made into the solution that concentration is 0.08 mol, under 50 ℃ of stirrings, add concentration and be 6 milliliters of the cobalt chloride solutions of 0.1 mol, reacted 2 hours.The mol ratio of BPHA and cobalt is 2.0.Filter the precipitation that generates, to there not being acid ion, 110 ℃ of dryings obtain complex compound catalyst Co (BPHA) with the deionized water wash solid product
2
Example 6
The preparation of catalyst system therefor of the present invention.
(1) method by (1) in the example 1 prepares 2-pyridine formyl chloride.
(2) be in the anhydrous tetrahydrofuran solution of 0.6 mol at concentration of sodium carbonate, add the 2-pyridine formyl chloride and the N-hydroxyanilines that account for total solution weight 8%, the consumption of 2-pyridine formyl chloride is 20 mmoles, and the consumption of N-hydroxyanilines is 23 mmoles.Reaction is 2.5 hours under-5 ℃ temperature, filters, and with saturated sodium bicarbonate aqueous solution washing solid product twice, 20 milliliters of each consumptions are washed with distilled water to neutrality again, and 100 ℃ of dryings obtain complex compound part o-PPHA.
(3) 1.1 mmole complex compound part o-PPHA are dissolved in 15 milliliters of ethanol, be made into the solution that concentration is 0.08 mol, adding 5 ml concns under 50 ℃ of stirrings is the ethanolic soln of the cobalt chloride of 0.1 mol, reacts 2 hours, and the mol ratio of o-PPHA and cobalt is 2.2.Filter the precipitation that generates, the ethanolic soln washing solid product that with concentration is 95 heavy % is not to there being acid ion, and 110 ℃ dry down, obtains complex compound catalyst Co (o-PPHA)
2
Example 7
This example illustrates method provided by the invention.
At volume is the CATALYST Co (HPPA) that add 100 milliliters in ethylbenzene and example 1 preparation in 250 milliliters the reactor
2, CATALYST Co (HPPA)
2Concentration be 4 * 10
-4Mol.Charge into oxygen in the reactor, make oxygen pressure maintain 0.1 MPa all the time.Reaction is 6 hours under 130 ℃ of stirrings, forms with the gas chromatographic analysis product.The result is 40.5 moles of % for conversion of ethylbenzene, and the selectivity that generates methyl phenyl ketone is 92.5%, and speed of response is 1379 moles/mole catalyzer hour.
Wherein, mole number * 100% of the mole number/material ethylbenzene of the ethylbenzene of conversion of ethylbenzene=transformed; Molar content * 100% of the ethylbenzene of the molar content of the methyl phenyl ketone of the selectivity=generation of methyl phenyl ketone/transformed; Speed of response is the mole number of the ethylbenzene that per hour transforms of every mol catalyst.
Example 8
This example illustrates method provided by the invention.
At volume is the CATALYST Co (BPHA) that add 100 milliliters in ethylbenzene and example 5 preparations in 250 milliliters the reactor
2, CATALYST Co (BPHA)
2Concentration be 2 * 10
-4Mol.Charge into oxygen in the reactor, make oxygen pressure maintain 0.8 MPa all the time.Reaction is 8 hours under 140 ℃ of stirrings, forms with the gas chromatographic analysis product.The result is 39.8 moles of % for conversion of ethylbenzene, and the selectivity that generates methyl phenyl ketone is 87.3%, and speed of response is 2032 moles/mole catalyzer hour.
Example 9
This example illustrates method provided by the invention.
Method by example 8 prepares methyl phenyl ketone, different just CATALYST Co (BPHA)
2Concentration be 4 * 10
-4Mol, temperature of reaction are 130 ℃, and the reaction times is 6 hours.The result is 43.0 moles of % for conversion of ethylbenzene, and the selectivity that generates methyl phenyl ketone is 82.0%, and speed of response is 1463 moles/mole catalyzer hour.
Example 10
This example illustrates method provided by the invention.
At volume is the CATALYST Co (HPPA) that add 20 milliliters in ethylbenzene and example 1 preparation in 100 milliliters the reactor
2, CATALYST Co (HPPA)
2Concentration be 1 * 10
-3Mol.Charge into oxygen in the reactor, make oxygen pressure to 0.6 MPa.Reaction is 6 hours under 140 ℃ of stirrings, forms with the gas chromatographic analysis product.The result is, conversion of ethylbenzene is 50.5 moles of %, and the selectivity that generates methyl phenyl ketone is 90.9%, and speed of response is 1822 moles/mole catalyzer hour.
Example 11
This example illustrates method provided by the invention.
At volume is the CATALYST Co (o-PPHA) that add 20 milliliters in ethylbenzene and example 6 preparations in 100 milliliters the reactor
2, CATALYST Co (o-PPHA)
2Concentration be 1 * 10
-3Mol.Charge into oxygen in the reactor, make oxygen pressure to 0.8 MPa.Reaction is 6 hours under 130 ℃ of stirrings, forms with the gas chromatographic analysis product.The result is, conversion of ethylbenzene is 64.0 moles of %, and the selectivity that generates methyl phenyl ketone is 81.4%, and speed of response is 2309 moles/mole catalyzer hour.
Example 12
This example illustrates method provided by the invention.
At volume is the catalyst n i (HPPA) that add 20 milliliters in ethylbenzene and example 2 preparations in 100 milliliters the reactor
2, catalyst n i (HPPA)
2Concentration be 4 * 10
-4Mol.Charge into oxygen in the reactor, make oxygen pressure to 1.0 MPa.Reaction is 8 hours under 130 ℃ of stirrings, forms with the gas chromatographic analysis product.The result is, conversion of ethylbenzene is 35.8 moles of %, and the selectivity that generates methyl phenyl ketone is 85.3%, and speed of response is 968 moles/mole catalyzer hour.
Example 13
This example illustrates method provided by the invention.
Method by example 12 prepares methyl phenyl ketone, and different just catalyzer are the catalyzer Mn (HPPA) of example 3 preparations
2, catalyzer Mn (HPPA)
2Concentration be 4 * 10
-4Mol.The result is 35.1 moles of % for conversion of ethylbenzene, and the selectivity that generates methyl phenyl ketone is 88.2%, and speed of response is 949 moles/mole catalyzer hour.
Example 14
This example illustrates method provided by the invention.
At volume is the CATALYST Co (BPHA) that add 10 milliliters in adjacent bromine ethylbenzene and example 5 preparations in 100 milliliters the reactor
2, CATALYST Co (BPHA)
2Concentration be 3 * 10
-3Mol.Charge into oxygen in the reactor, make oxygen pressure maintain 0.8 MPa all the time.Reaction is 8 hours under 140 ℃ of stirrings, forms with the gas chromatographic analysis product.The result is, adjacent bromine conversion of ethylbenzene is 35.9 moles of %, and the selectivity that generates adjacent bromoacetophenone is 70.4%, and speed of response is 80.8 moles/mole catalyzer hour.
Wherein, mole number * 100% of the adjacent bromine ethylbenzene of the mole number of the adjacent bromine ethylbenzene of adjacent bromine conversion of ethylbenzene=transformed/raw material; Molar content * 100% of the adjacent bromine ethylbenzene of the molar content of the adjacent bromoacetophenone of the selectivity=generation of adjacent bromoacetophenone/transformed; Speed of response is the mole number of the adjacent bromine ethylbenzene that per hour transforms of every mol catalyst.
Example 15
This example illustrates method provided by the invention.
At volume is the CATALYST Co (BPHA) that add in 100 milliliters the reactor 10 milliliters of methyl-ethyl benzenes and example 5 preparations
2, CATALYST Co (BPHA)
2Concentration be 1.5 * 10
-3Mol.Charge into oxygen in the reactor, make oxygen pressure maintain 1.0 MPas all the time.Reaction is 6 hours under 140 ℃ of stirrings, forms with the gas chromatographic analysis product.The result is, is 58.7 moles of % to the methyl-ethyl benzene transformation efficiency, and the selectivity that generates p-methyl aceto phenone is 76.7%, and speed of response is 529 moles/mole catalyzer hour.
Wherein, mole number * 100% of the mole number/raw material methyl-ethyl benzene of the methyl-ethyl benzene of methyl-ethyl benzene transformation efficiency=transformed; Molar content * 100% of the methyl-ethyl benzene of the molar content of the methyl acetophenone of the selectivity=generation of methyl acetophenone/transformed; Speed of response is the mole number of the methyl-ethyl benzene that per hour transforms of every mol catalyst.
Example 16
This example illustrates method provided by the invention.
At volume is the Catalysts Cu (HPPA) that add in 100 milliliters the reactor 10 milliliters in methoxyl group ethylbenzene and example 4 preparations
2, Catalysts Cu (HPPA)
2Concentration be 1.5 * 10
-3Mol.Charge into oxygen in the reactor, make oxygen pressure maintain 1.0 MPas all the time.Reaction is 8 hours under 140 ℃ of stirrings, forms with the gas chromatographic analysis product.The result is, is 42.0 moles of % to the methoxyl group conversion of ethylbenzene, and the selectivity that generates p-methoxy-acetophenone is 75.2%, and speed of response is 284 moles/mole catalyzer hour.
Wherein, to methoxyl group conversion of ethylbenzene=transformed to the mole number/raw material of methoxyl group ethylbenzene mole number * 100% to methoxyl group ethylbenzene; Molar content to methoxyl group ethylbenzene * 100% of the molar content of the p-methoxy-acetophenone of the selectivity=generation of p-methoxy-acetophenone/transformed; Speed of response is the mole number to methoxyl group ethylbenzene that every mol catalyst per hour transforms.
Example 17
This example illustrates method provided by the invention.
Method by example 8 prepares methyl phenyl ketone, different just replaces oxygen as oxygenant with air, and air is sent into by the airway that inserts in the solution, and air flow quantity is 50 ml/min, unreacted air is emitted from the reactor reflux exchanger, and the reaction times is 10 hours.The result is, conversion of ethylbenzene is 31 moles of %, and the selectivity that generates methyl phenyl ketone is 89.1%, and speed of response is 1266 moles/mole catalyzer hour.
Claims (12)
1. the preparation method of an aryl methyl ketone, it is characterized in that it is 50-200 ℃ that this method is included in temperature of reaction, pressure is under the condition of normal pressure to 5 MPa, a kind of ethylaromatics is contacted with a kind of catalyzer and a kind of oxygenous atmosphere, and the concentration of described catalyzer in reaction system is 10
-6-10
-1Mol, described catalyzer is selected from one or more in the metal complex with following general formula:
Wherein, a kind of in the M representative element periodictable in logical formula I, (II) and/or (III) in I B family metal, V B family metal, VI B family metal, VII B family metal and the V III family metal, X and Y can be the same or different, represent a kind of in hydrogen atom, hydroxyl, alkyl, alkoxyl group, cycloalkyl, halogen atom, the nitro, Z representation hydroxy or hydrogen atom, R
1Represent a kind of in phenyl, pyridyl, naphthyl, quinolyl, the cycloalkyl, R
2Represent a kind of in phenyl, pyridyl, naphthyl, the quinolyl.
2. method according to claim 1 is characterized in that, the R in the described catalyzer general formula
1Represent phenyl.
3. method according to claim 1 is characterized in that, the R in the described catalyzer general formula
2Represent phenyl or pyridyl.
4. method according to claim 1 is characterized in that, the X in the described catalyzer general formula is identical with Y, all represents hydrogen atom.
5. method according to claim 1 is characterized in that, described catalyzer refers to that general formula is M (BPHA)
2, M (p-PPHA)
2, M (m-PPHA)
2, M (o-PPHA)
2And M (HPPA)
2Complex compound in one or more, wherein, BPHA, m-PPHA, p-PPHA, o-PPHA and HPPA refer to N-hydroxy-n-phenylbenzamaide, N-hydroxy-n-phenyl-3-pyridine carboxamide, N-hydroxy-n-phenyl-4-pyridine carboxamide, N-hydroxy-n-phenyl-2-pyridine carboxamide and N-phenyl-2-pyridine carboxamide respectively.
6. method according to claim 1 or 5 is characterized in that, M represents a kind of in iron, cobalt, nickel, copper, manganese, molybdenum, chromium, ruthenium, rhenium, the vanadium.
7. method according to claim 6 is characterized in that, M represents a kind of in cobalt, nickel, copper, the manganese.
8. method according to claim 1 is characterized in that, the concentration of described catalyzer in reaction system is 10
-5-10
-2Mol.
9. method according to claim 1 is characterized in that, described temperature of reaction is 100-150 ℃, and described reaction pressure is normal pressure-1.5 MPa, and the reaction times is 2-12 hour.
10. method according to claim 1 is characterized in that, described oxygenous atmosphere is oxygen, oxygen-rich air or air.
11. method according to claim 1, it is characterized in that described ethylaromatics is selected from one or more in the ethyl naphthalene that has halogen, methyl, methoxyl group or nitro on halo ethylbenzene, methyl-ethyl benzene, methoxyl group ethylbenzene, nitro ethylbenzene, ethylbenzene, ethyl naphthalene and the naphthalene nucleus.
12. method according to claim 11 is characterized in that, described ethylaromatics is selected from ethylbenzene, methyl-ethyl benzene, halo ethylbenzene or methoxyl group ethylbenzene.
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| CNB991252837A CN1136180C (en) | 1999-12-01 | 1999-12-01 | Preparation of aryl methyl ketone |
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|---|---|---|---|
| CNB991252837A CN1136180C (en) | 1999-12-01 | 1999-12-01 | Preparation of aryl methyl ketone |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503518A (en) * | 2017-02-28 | 2018-09-07 | 湖南师范大学 | A kind of preparation and its application of compound sepiolite base catalyst |
| CN111196754A (en) * | 2020-01-17 | 2020-05-26 | 上海应用技术大学 | Method for preparing aromatic aldehyde ketone by catalytic oxidation of aromatic hydrocarbon side chain by nickel compound |
| CN112782108A (en) * | 2020-12-31 | 2021-05-11 | 金华市强盛生物科技有限公司 | Enzyme method creatinine detection kit and detection method for resisting calcium dobesilate interference |
-
1999
- 1999-12-01 CN CNB991252837A patent/CN1136180C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503518A (en) * | 2017-02-28 | 2018-09-07 | 湖南师范大学 | A kind of preparation and its application of compound sepiolite base catalyst |
| CN111196754A (en) * | 2020-01-17 | 2020-05-26 | 上海应用技术大学 | Method for preparing aromatic aldehyde ketone by catalytic oxidation of aromatic hydrocarbon side chain by nickel compound |
| CN111196754B (en) * | 2020-01-17 | 2022-08-23 | 上海应用技术大学 | Method for preparing aromatic aldehyde ketone by catalytic oxidation of aromatic hydrocarbon side chain by nickel compound |
| CN112782108A (en) * | 2020-12-31 | 2021-05-11 | 金华市强盛生物科技有限公司 | Enzyme method creatinine detection kit and detection method for resisting calcium dobesilate interference |
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