CN105214692A - Supported solid catalyst and preparation method thereof and application thereof - Google Patents

Supported solid catalyst and preparation method thereof and application thereof Download PDF

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CN105214692A
CN105214692A CN201510700254.9A CN201510700254A CN105214692A CN 105214692 A CN105214692 A CN 105214692A CN 201510700254 A CN201510700254 A CN 201510700254A CN 105214692 A CN105214692 A CN 105214692A
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solid catalyst
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supported solid
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CN105214692B (en
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杜治平
文武强
李亮
丁一刚
张巨寿
刘生鹏
邓伏礼
龙秉文
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HUBEI XUNDA PHARMACEUTICAL CO Ltd
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HUBEI XUNDA PHARMACEUTICAL CO Ltd
Wuhan Institute of Technology
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Abstract

The present invention relates to a kind of supported solid catalyst and preparation method thereof and application thereof.Described catalyst chemical formula is M xo y-SO 4 2-/ TiO 2-Al 2o 3-SiO 2, wherein, M is metal ion, x and y is valent state equilibrium number, and carrier is TiO 2-Al 2o 3-SiO 2.The employing step impregnation method preparation of described catalyst, loads to carrier TiO by the nitrate of metal ions M or hydrochloride and ammonium sulfate or ammonium persulfate successively 2-Al 2o 3-SiO 2on obtained.Catalyst of the present invention is particularly useful as catalyst in the technique of synthesis loxoprofen intermediate 2-(4 '-2-bromomethylphenyl) propionic ester, there is selective height, conversion ratio is high, reaction condition is gentle, and the separation of catalyst is simple, industrial wastewater is few, be conducive to the advantage of suitability for industrialized production.

Description

Supported solid catalyst and preparation method thereof and application thereof
Technical field
The present invention relates to chemical technology field, specifically a kind of loaded catalyst and preparation method thereof and application thereof.
Background technology
If the gastrointestinal side effect that traditional NSAIDs long-term taking may cause gastric ulcer, hemorrhage and perforation etc. serious, and to take NSAIDs be one of reason causing severe drug bad reaction maximum.The NSAIDs of the modified form that loxoprofen went on the market as the later stage eighties 20th century, curative effect maintains antipyretic, the analgesia of traditional NSAIDs, antiinflammatory action, and rapid-action, effect is strong.And loxoprofen is in security, because of the design feature of its phenoxy propionic acid pro-drug, significantly reduce the generation of gastrointestinal side effect.Therefore loxoprofen is by feat of good drug effect, anti-inflammatory pain-stopping effect, and indication is wide, and lower toxic and side effect, has prospect, even likely replace present paracetamol and the market of naproxen in Chinese market pole.
At present, representative on large-scale production loxoprofen technique only two kinds.One take toluene as initiation material, through step synthetic intermediates such as acidylate, ketal, rearrangements to the different benzenpropanoic acid of methyl, synthesizes end product further.Another kind be with after the different benzenpropanoic acid methanol esterification of bromomethyl with the condensation of 2-carbethoxyl group cyclopentanone, obtain the synthetic route of end product through hydrolysis.Wherein 2-(4 '-2-bromomethylphenyl) propionic ester is the intermediate of these synthetic methods, and it is synthesized through esterification by 2-(4 '-2-bromomethylphenyl) propionic acid and alcohol.In synthesis, the interpolation concentrated sulfuric acid or p-methyl benzenesulfonic acid make esterification catalyst usually, but the oxidisability due to the concentrated sulfuric acid easily causes the oxidation of raw material 2-(4 '-2-bromomethylphenyl) propionic acid, thus reducing the yield of ester, product colour is partially yellow simultaneously, just must can reach requirement through being repeatedly recrystallized; Although p-methyl benzenesulfonic acid avoids the problem of concentrated sulfuric acid strong oxidizing property, easily produce unmanageable p-methyl benzenesulfonic acid industrial wastewater.Therefore for these problems, the present invention have developed a kind of Novel solid-catalyst, can solve the problem preferably.
Summary of the invention
The object of the invention is to solve the problems of the technologies described above, a kind of supported solid catalyst for the synthesis of loxoprofen intermediate 2-(4 '-2-bromomethylphenyl) propionic ester is provided, this catalyst choice is high, conversion ratio is high, reaction condition is gentle, and the separation of catalyst is simple, industrial wastewater is few, is conducive to suitability for industrialized production.
Another object of the present invention is to provide that a kind of production technology is simple, the preparation method of the above-mentioned supported solid catalyst of good reliability.
The present invention also provides the application of a kind of above-mentioned supported solid catalyst in synthesis loxoprofen intermediate 2-(4 '-2-bromomethylphenyl) propionic ester technique.
Supported solid catalyst chemical formula of the present invention is M xo y-SO 4 2-/ TiO 2-Al 2o 3-SiO 2, wherein, M is metal ion, x and y is valent state equilibrium number, and carrier is TiO 2-Al 2o 3-SiO 2.
Described carrier TiO 2-Al 2o 3-SiO 2the mass percent of middle Ti, Al, Si is (0.5 ~ 0.9): (0.05 ~ 0.5): (0.05 ~ 0.5).
Described M xo ybe 0.001 ~ 0.3:1 with the mass ratio of carrier; SO 4 2-be 0.001 ~ 0.3:1 with the mass ratio of carrier.
Described M is one or both in metal ion Ni, Fe, Cu, Sb, V, Sn, Bi, Pb.
The preparation method of above-mentioned supported solid catalyst, adopts step impregnation method preparation: the first step, adopts infusion process at carrier TiO 2-Al 2o 3-SiO 2upper load contains nitrate or the hydrochloride of metal ions M, carries out roasting and obtain M after drying xo y/ TiO 2-Al 2o 3-SiO 2pressed powder; Second step, load ammonium sulfate or ammonium persulfate on the described pressed powder adopting infusion process to obtain in the first step, it is M that dry roasting obtains chemical formula xo y-SO 4 2-/ TiO 2-Al 2o 3-SiO 2supported solid catalyst, wherein, M is metal ion, x and y is valent state equilibrium number, and carrier is TiO 2-Al 2o 3-SiO 2.
In the described first step and second step, sintering temperature is 300 ~ 800 DEG C, preferably 400 ~ 700 DEG C, and the time is 0.5 ~ 6 hour, preferably 1 ~ 4 hour.
Described carrier TiO 2-Al 2o 3-SiO 2the mass percent of middle Ti, Al, Si is (0.5 ~ 0.9): (0.05 ~ 0.5): (0.05 ~ 0.5); Described M xo ybe 0.001 ~ 0.3:1 with the mass ratio of carrier; SO 4 2-be 0.001 ~ 0.3:1 with the mass ratio of carrier.
M is one or both in metal ion Ni, Fe, Cu, Sb, V, Sn, Bi, Pb.
The application of above-mentioned supported solid catalyst in the technique of synthesis loxoprofen intermediate 2-(4 '-2-bromomethylphenyl) propionic ester: the supported solid catalyst described in 2-(4 '-2-bromomethylphenyl) propionic acid and any one of claim 1-4 is reacted under the existence of methyl alcohol or ethanol, obtains 2-(4 '-2-bromomethylphenyl) propionic ester.
The mass ratio of described 2-(4 '-2-bromomethylphenyl) propionic acid and supported solid catalyst is 1:0.001 ~ 0.1, the mol ratio of 2-(4 '-2-bromomethylphenyl) propionic acid and methyl alcohol or ethanol is 1:1 ~ 50, described reaction temperature is 60 ~ 120 DEG C, 0.5 ~ 10 hour reaction time.
For catalyst Problems existing in existing synthesis loxoprofen intermediate 2-(4 '-2-bromomethylphenyl) propionic ester technique, inventor develops a kind of new supported solid catalyst, and it is with TiO 2-Al 2o 3-SiO 2as carrier, TiO 2-Al 2o 3the specific area larger than single oxide can be provided and more can supply the sour site of regulation and control, SiO 2add and contribute to stable TiO 2and Al 2o 3crystalline structure, improve service life of catalyst, there is significant technique effect.Further, step impregnation method is adopted when preparing supported solid catalyst, first by metal ions M load on carrier, there is provided sour point on the one hand, the sulfate ion of stable later stage load can be played on the other hand, therefore can either avoid the problem of concentrated sulfuric acid strong oxidizing property, the industrial wastewater problem that enough toluene sulfonic acides bring can be kept away again, both improve yield and the product quality of synthesis product, and also served environment amenable object, there is energy-saving and cost-reducing technique effect.In the present invention, one or both in metal ion preferred Ni, Fe, Cu, Sb, V, Sn, Bi, Pb of described M, are more preferably the one in Sb, V, Sn, Bi, Pb or two kinds.
Further, in the present invention, M xo ybe 0.001 ~ 0.3:1 with the mass ratio of carrier, be more preferably 0.001 ~ 0.1:1; Too much carrier surface can be covered, interference carrier and SO 4 2-effect, cross that I haven't seen you for ages does not have stable SO 4 2-effect; SO 4 2-be 0.001 ~ 0.3:1 with the mass ratio of carrier, be more preferably 0.001 ~ 0.15, too much can be difficult to form strong acid site, the activity of very few catalyst is not high.
In the technique of synthesis loxoprofen intermediate 2-(4 '-2-bromomethylphenyl) propionic ester, the mass ratio of described 2-(4 '-2-bromomethylphenyl) propionic acid and supported solid catalyst is 1:0.001 ~ 0.1, more be preferably 1:0.01 ~ 0.1, adopt catalyst of the present invention, catalytic reaction is effective, use amount is few, can effectively reduce costs.
Catalyst preparation process of the present invention is simple and reliable, when being used as catalyst use in synthesis loxoprofen intermediate 2-(4 '-2-bromomethylphenyl) propionic ester technique, reaction condition is gentle, industrial wastewater is few, and production cost is low, and the separation of catalyst simply can Reusability, be conducive to suitability for industrialized production, 2-(4 '-2-bromomethylphenyl) propionic ester obtained has selective height, Stability Analysis of Structures, the advantage that conversion ratio is high, has wide market application foreground.
Detailed description of the invention
Embodiment 1
Catalyst preparing: the Cu (NO taking 3.04g 3) 23H 2o, is dissolved in 20ml water, then adds 10g carrier TiO 2-Al 2o 3-SiO 2(TiO 2, Al 2o 3with SiO 2mass percent be 0.9:0.05:0.05), stir 3h, slowly heat up evaporating water, then by gained solid roasting 4h at 450 DEG C, obtains CuO/TiO 2-Al 2o 3-SiO 2pressed powder is for subsequent use.Get (the NH of 2.31g again 4) 2sO 4, be dissolved in suitable quantity of water, dipping CuO/TiO 2-Al 2o 3-SiO 2, dry, finally roasting 2h at 650 DEG C, obtains CuO-SO 4 2-/ TiO 2-Al 2o 3-SiO 2solid catalyst.
2-(4 '-2-bromomethylphenyl) propionic ester synthesis example: in the 50ml there-necked flask being equipped with condenser pipe, thermometer, adds the CuO-SO of 2.4g2-(4 '-2-bromomethylphenyl) propionic acid, 20ml methyl alcohol and 0.24g 4 2-/ TiO 2-Al 2o 3-SiO 2solid catalyst, reacts 8h at 65 DEG C, obtains 2-(4 '-2-bromomethylphenyl) methyl propionate, its yield 75.2%, selective 98.5%.
Embodiment 2
Except carrier TiO 2-Al 2o 3-SiO 2middle TiO 2, Al 2o 3with SiO 2mass percent be outside 0.5:0.25:0.25, other condition obtains 2-(4 '-2-bromomethylphenyl) methyl propionate with embodiment 1, its yield 60.3%, selective 96.3%.
Embodiment 3-6
Except catalyst, other condition is with embodiment 1.The results are shown in following table:
Embodiment number Catalyst Yield/% Selective/%
3 Bi 2O 3-SO 4 2-/TiO 2-Al 2O 3-SiO 2 75.4 99.1
4 V 2O 5-SO 4 2-/TiO 2-Al 2O 3-SiO 2 55.9 94.2
5 aSnO 2-PbO-SO 4 2-/TiO 2-Al 2O 3-SiO 2 89.5 99.0
6 b SnO 2-Bi 2O 3-SO 4 2-/TiO 2-Al 2O 3-SiO 2 80.9 99.3
The mol ratio of remarks: a:Sn and Pb is the mol ratio of 1:1.b:Sn and Bi is 1:1.
Embodiment 7
Catalyst preparation example: Catalysts Cu O-SO 4 2-/ TiO 2-Al 2o 3-SiO 2preparation in, except carrier TiO 2-Al 2o 3-SiO 2middle TiO 2, Al 2o 3with SiO 2mass percent be outside 0.5:0.45:0.05, other condition is with embodiment 1.
2-(4 '-2-bromomethylphenyl) propionic ester synthesis example: in the 50ml there-necked flask being equipped with circulation water knockout drum (loading the Anhydrous potassium carbonate of 5g in water knockout drum in advance), thermometer and 10ml dropping funel, add the CuO-SO of 2.4g2-(4 '-2-bromomethylphenyl) propionic acid, 20ml toluene and 0.024g respectively 4 2-/ TiO 2-Al 2o 3-SiO 2solid catalyst, then adds the methyl alcohol of 2ml at dropping funel.After temperature rises to 110 DEG C, methyl alcohol is slowly added drop-wise in reactant liquor, the yield 92.3% of circular response time 6h, the 2-obtained (4 '-2-bromomethylphenyl) methyl propionate, selective 98.8%.
Embodiment 8
Catalyst preparation example: the Pb (NO taking 0.15g 3) 2, be dissolved in 10ml water, then added 10g carrier TiO 2-Al 2o 3-SiO 2(TiO 2, Al 2o 3with SiO 2mass percent be 0.7:0.05:0.25), stir 7h, slowly heat up evaporating water, then by gained solid roasting 2h at 400 DEG C, obtains PbO/TiO 2-Al 2o 3-SiO 2pressed powder is for subsequent use.Get (the NH of 3.01g again 4) 2s 2o 8, be dissolved in suitable quantity of water, dipping PbO/TiO 2-Al 2o 3-SiO 2, dry, finally roasting 4h at 500 DEG C, obtains PbO-SO 4 2-/ TiO 2-Al 2o 3-SiO 2solid catalyst.
2-(4 '-2-bromomethylphenyl) propionic ester synthesis example: in the 50ml there-necked flask being equipped with condenser pipe, thermometer, adds the PbO-SO of 2.45g2-(4 '-2-bromomethylphenyl) propionic acid, 20ml methyl alcohol and 0.13g 4 2-/ TiO 2-Al 2o 3-SiO 2solid catalyst, reacts 2h at 65 DEG C, the yield 87.7% of 2-(4 '-2-bromomethylphenyl) methyl propionate obtained, selective 98.7%.
Embodiment 9
Except (NH 4) 2s 2o 8consumption change into outside 0.61g, other condition with embodiment 8, the yield 52.1% of 2-(4 '-2-bromomethylphenyl) methyl propionate obtained, selective 89.8%.
Embodiment 10
Except using FeCl 2replace the Pb (NO in embodiment 8 3) 2, dipping iron ion after sintering temperature change into outside 650 DEG C, other condition is with embodiment 4, and the catalyst of preparation is Fe 3o 4-SO 4 2-/ TiO 2-Al 2o 3-SiO 2, the yield 57.1% of 2-(4 '-2-bromomethylphenyl) methyl propionate obtained, selective 92.3%.
Embodiment 11
Except replacing methyl alcohol with absolute ethyl alcohol, reaction temperature is outside 70 DEG C, other condition with embodiment 8, the yield 77.3% of 2-(4 '-2-bromomethylphenyl) ethyl propionate obtained, selective 95.2%.
Embodiment 12
With SnO 2-PbO-SO 4 2-/ TiO 2-Al 2o 3-SiO 2for catalyst, ethanol is esterifying agent, other condition with embodiment 5, the yield 97.2% of 2-(4 '-2-bromomethylphenyl) ethyl propionate obtained, selective 99.4%.

Claims (10)

1. a supported solid catalyst, is characterized in that, its chemical formula is M xo y-SO 4 2-/ TiO 2-Al 2o 3-SiO 2, wherein, M is metal ion, x and y is valent state equilibrium number, and carrier is TiO 2-Al 2o 3-SiO 2.
2. supported solid catalyst as claimed in claim 1, is characterized in that, described carrier TiO 2-Al 2o 3-SiO 2the mass percent of middle Ti, Al, Si is (0.5 ~ 0.9): (0.05 ~ 0.5): (0.05 ~ 0.5).
3. supported solid catalyst as claimed in claim 1 or 2, is characterized in that, described M xo ybe 0.001 ~ 0.3:1 with the mass ratio of carrier; SO 4 2-be 0.001 ~ 0.3:1 with the mass ratio of carrier.
4. supported solid catalyst as claimed in claim 1, is characterized in that, M is one or both in metal ion Ni, Fe, Cu, Sb, V, Sn, Bi, Pb.
5. a preparation method for supported solid catalyst, is characterized in that, adopts step impregnation method preparation: the first step, adopts infusion process at carrier TiO 2-Al 2o 3-SiO 2upper load contains nitrate or the hydrochloride of metal ions M, carries out roasting and obtain M after drying xo y/ TiO 2-Al 2o 3-SiO 2pressed powder; Second step, load ammonium sulfate or ammonium persulfate on the described pressed powder adopting infusion process to obtain in the first step, it is M that dry roasting obtains chemical formula xo y-SO 4 2-/ TiO 2-Al 2o 3-SiO 2supported solid catalyst, wherein, M is metal ion, x and y is valent state equilibrium number, and carrier is TiO 2-Al 2o 3-SiO 2.
6. the preparation method of supported solid catalyst as claimed in claim 5, is characterized in that, in the described first step and second step, sintering temperature is 300 ~ 800 DEG C, and the time is 0.5 ~ 6 hour.
7. the preparation method of supported solid catalyst as claimed in claim 5, is characterized in that, described carrier TiO 2-Al 2o 3-SiO 2the mass percent of middle Ti, Al, Si is (0.5 ~ 0.9): (0.05 ~ 0.5): (0.05 ~ 0.5); Described M xo ybe 0.001 ~ 0.3:1 with the mass ratio of carrier; SO 4 2-be 0.001 ~ 0.3:1 with the mass ratio of carrier.
8. the preparation method of the supported solid catalyst as described in any one of claim 5-7, is characterized in that, M is one or both in metal ion Ni, Fe, Cu, Sb, V, Sn, Bi, Pb.
9. the application of the supported solid catalyst described in an any one of claim 1-4 in the technique of synthesis loxoprofen intermediate 2-(4 '-2-bromomethylphenyl) propionic ester, it is characterized in that, supported solid catalyst described in 2-(4 '-2-bromomethylphenyl) propionic acid and any one of claim 1-4 is reacted under the existence of methyl alcohol or ethanol, obtains 2-(4 '-2-bromomethylphenyl) propionic ester.
10. the application of supported solid catalyst as claimed in claim 9 in the technique of synthesis loxoprofen intermediate 2-(4 '-2-bromomethylphenyl) propionic ester, it is characterized in that, the mass ratio of described 2-(4 '-2-bromomethylphenyl) propionic acid and supported solid catalyst is 1:0.001 ~ 0.1, the mol ratio of 2-(4 '-2-bromomethylphenyl) propionic acid and methyl alcohol or ethanol is 1:1 ~ 50, described reaction temperature is 60 ~ 120 DEG C, 0.5 ~ 10 hour reaction time.
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