CN103920530B - The preparation method of 2-hydroxyl-5-alkylacetophenone oxime and used catalyst - Google Patents
The preparation method of 2-hydroxyl-5-alkylacetophenone oxime and used catalyst Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of 2-hydroxyl-5-alkylacetophenone oxime, 1), acetylation comprise:: add in reactor alkylphenol and acetic acid, and add PVTS molecular sieve catalyst, carry out stirring reaction in 105 ~ 115 DEG C, in course of reaction, the water of generation is steamed; When anhydrous steaming, be warming up to 150 ~ 200 DEG C and react, by still temperature drop to 60 ~ 70 DEG C after having reacted; 2), oximate: regulating step 1) pH value of reactant liquor of gained is 7 ~ 8; Add in still mass concentration be 30% hydrogen peroxide and mass concentration be the mixed liquor of the ammoniacal liquor of 30%, add rear insulation and continue reaction 0.5 hour; After reaction terminates, by still temperature drop to 20 ~ 25 DEG C, by reacting liquid filtering, filter cake is recrystallized in ethanol, obtains 2-hydroxyl-5-alkylacetophenone oxime.The present invention also also discloses the preparation method of above-mentioned PVTS molecular sieve catalyst.
Description
Technical field
The present invention relates to the preparation method of 2-hydroxyl-5-alkylacetophenone oxime and used catalyst.
Background technology
2-hydroxyl-5-alkylacetophenone oxime is a class chemical intermediate, can be used for synthesis or the allotment of organic extractant.Usually complete through acetylation and oximate two steps by preparing 2-hydroxyl-5-alkylacetophenone oxime to alkylphenol.The method commonly used alkylphenol acetylation is that phenol esterification+Fries resets (US5300689) or Friedel-Crafts acyl group (TetrahedronLetters, 27 (27), 3183-6,1986), all there is following problem in these two kinds of methods: yield is low, accessory substance is many, post processing is loaded down with trivial details, the three wastes are more; The method that oximation reaction is conventional is azanol reaction method (MonatsheftefuerChemie, 137 (3), 301-305,2006) and ammonia oxidation (EuropeanJournalofInorganicChemistry, 2013 (10-11), 1659-1663,2013), wherein the hydroxylamine assay three wastes are more, and ammonia oxidation is a kind of comparatively clean method.Because above two-step reaction needs different catalyst, at present not by the report being prepared by alkylphenol to 2-hydroxyl-5-alkylacetophenone oxime one pot process.
In above-mentioned prior art, in acetylation step, used catalyst is lewis acid, and usual amounts need with reactant equimolar amounts; In oximate step, used catalyst is HTS.
Suppose, all use lewis acid as catalyst in acetylation step and oximate step or all use HTS as catalyst, 2-hydroxyl-5-alkylacetophenone oxime cannot be prepared.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of one pot reaction method and its bifunctional catalyst used by preparing 2-hydroxyl-5-alkylacetophenone oxime to alkylphenol.
In order to solve the problems of the technologies described above, the invention provides the preparation method of a kind of PVTS molecular sieve catalyst (that is, difunctional PVTS molecular sieve catalyst), it is characterized in that comprising the following steps:
1., tetraethyl orthosilicate and triethyl phosphate mole are added in reactor according to 1:0.2, also distilled water is added in reactor, and be preferably 4 with dilute sulfuric acid adjust ph to 3 ~ 5(), be warming up to 45 ~ 55 DEG C and stir 1 hour (being preferably 50 DEG C to stir 1 hour);
Generally speaking: the tetraethyl orthosilicate of every 1mol and, the triethyl phosphate adapted 400 ~ 600ml(of 0.2mol is such as 500ml) distilled water, described dilute sulfuric acid refers to that mass concentration is the sulfuric acid of 25%;
2., under strong mixing, keep still temperature 55 ~ 65 DEG C (being preferably 60 DEG C), to the still liquid of step 1. gained prior to 30 ~ 60 minutes in slowly add the dilute hydrochloric acid solution of the titanium trichloride of mass concentration 20%, the sodium metavanadate aqueous solution of mass concentration 10% and mass concentration 15% ammonia spirit continuously, obtain reaction system; Described titanium trichloride and step 1. in the mol ratio of tetraethyl orthosilicate be 0.5:1; Described sodium metavanadate and step 1. in the mol ratio of tetraethyl orthosilicate be 0.2:1, the consumption of described mass concentration 15% ammonia spirit is the pH value 6 ~ 7 controlling reaction system;
Then continue to add mass concentration 15% ammonia spirit until adjust ph is 8 ~ 9 in reaction system; Insulation (55 ~ 65 DEG C, be preferably 60 DEG C) reaction 1 hour;
Remarks illustrate: watery hydrochloric acid to be mass concentration be 5% hydrochloric acid;
3., under strong mixing, keep still temperature 55 ~ 65 DEG C (being preferably 60 DEG C), in the still liquid of step 2. gained, slowly add the TBAH aqueous solution that mass concentration is 10% in 30 ~ 60 minutes, then adjust ph is 12 ~ 13, insulation (55 ~ 65 DEG C, be preferably 60 DEG C) 2 hours;
Described tetrabutylammonium hydroxide ammonia and step 1. in the mol ratio of tetraethyl orthosilicate be 0.3:1;
4., the still liquid of step 3. gained is added in Hydrothermal Synthesis still, in 150 ~ 170 DEG C of crystallization 190 ~ 210 hours (being preferably 160 DEG C of crystallization 200 hours), filter, gained filter cake is carried out wash, dry, then 200 ~ 300 DEG C of roastings 4.5 ~ 5.5 hours (being preferably 5 hours), PVTS molecular sieve catalyst is obtained.
Improvement as the preparation method of PVTS molecular sieve catalyst of the present invention: described step 4. in, wash and be: spend deionized water filter cake, can't detect chlorion in eluate till.
Remarks illustrate: described step 4. in drying be in 60 ~ 80 DEG C of dryings 1.5 ~ 2.5 hours.
Further improvement as the preparation method of PVTS molecular sieve catalyst of the present invention: described step 3. in, utilize mass concentration be 30% ammoniacal liquor adjust ph be 12 ~ 13.
The present invention also provides the preparation method of the 2-hydroxyl-5-alkylacetophenone oxime utilizing any one PVTS molecular sieve catalyst above-mentioned to carry out simultaneously, using shown in formula II to alkylphenol as raw material, carry out following steps successively:
1), acetylation:
Add in reactor alkylphenol and acetic acid, and add PVTS molecular sieve catalyst (namely, difunctional PVTS molecular sieve catalyst), in 30 ~ 120 minutes, just temperature slowly rises to 105 ~ 115 DEG C (being preferably 110 DEG C) and carries out stirring reaction, is steamed by the water of generation in course of reaction; When anhydrous steaming, still temperature is slowly risen to 150 ~ 200 DEG C (being preferably 150 ~ 170 DEG C) in 30 ~ 60 minutes to react, reaction time is 2 ~ 5 hours (being preferably 2 ~ 4 hours)), acetic acid is steamed in this process, after having reacted, (that is, the reaction time reaches rear) is by still temperature drop to 60 ~ 70 DEG C;
The described mol ratio to alkylphenol and acetic acid is that 1:1 ~ 2.5(is preferably 1:1.5 ~ 2.1); The consumption of described PVTS molecular sieve catalyst is be preferably 5% to 4 ~ 6%(of alkylphenol quality);
Remarks illustrate: the acetic acid steamed refers to not reaction and the acetic acid that can steam (can not steam because there being Van der Waals interaction force between a small amount of residual acetic acid meeting and reactant);
Above-mentioned 150 ~ 200 DEG C time, acetic acid does not react.
2), oximate:
Regulating step 1) pH value of reactant liquor of gained is 7 ~ 8; Keep temperature 60 ~ 70 DEG C, slowly added continuously in still in 30 ~ 60 minutes mass concentration be 30% hydrogen peroxide and mass concentration be the mixed liquor of the ammoniacal liquor of 30%, add rear insulation (60 ~ 70 DEG C) continuation reaction 0.5 hour;
Described hydrogen peroxide: ammonia: to the mol ratio (better mol ratio is 1.1:1.1 ~ 1.5:1) of alkylphenol=1.1:1 ~ 2:1;
After reaction terminates, by still temperature drop to 20 ~ 25 DEG C, by reacting liquid filtering, filter cake is recrystallized in ethanol, obtains the 2-hydroxyl-5-alkylacetophenone oxime shown in formula I;
In formula I, R is methyl, ethyl, nonyl or the tert-butyl group.
Remarks illustrate: during above-mentioned recrystallization when product dissolves completely, filter, obtain PVTS molecular sieve catalyst, thus realize the recovery of PVTS molecular sieve catalyst.
Generally speaking, every 0.2mol to alkylphenol as raw material time, the ethanol of adapted 50 ~ 150ml in above-mentioned recrystallization process.
Improvement as the preparation method of 2-hydroxyl-5-alkylacetophenone oxime of the present invention:
When described alkyl is methyl, the 2-hydroxyl-5-alkylacetophenone oxime shown in formula I is 2-hydroxy-5-methyl benzoylformaldoxime oxime;
When described alkyl is ethyl, the 2-hydroxyl-5-alkylacetophenone oxime shown in formula I is 2-hydroxyl-5-ethylo benzene acetophenone oxime;
When described alkyl is nonyl, the 2-hydroxyl-5-alkylacetophenone oxime shown in formula I is 2-hydroxyl-5-nonylacetophenone oxime;
When described alkyl is the tert-butyl group, the 2-hydroxyl-5-alkylacetophenone oxime shown in formula I is 2-hydroxyl-5-tert-butyl benzene acetophenone oxime.
Further improvement as the preparation method of 2-hydroxyl-5-alkylacetophenone oxime of the present invention: described step 2) in, utilize mass concentration be 30% ammoniacal liquor regulating step 1) pH value of reactant liquor of gained is 7 ~ 8.
In the present invention, stirring is 500 ~ 1000rpm; Strong mixing is 2000 ~ 3000rpm.
Inventive point of the present invention is mainly: in the preparation method of 2-hydroxyl-5-alkylacetophenone oxime, employ bifunctional catalyst (namely, PVTS molecular sieve catalyst), prior art there is no the report with this bifunctional catalyst, also there is no the one pot process of product involved in the present invention (2-hydroxyl-5-alkylacetophenone oxime).
In sum, the present invention by shown in formula II to alkylphenol through acetylation, oximate two-step reaction; The hydroxyl of 2-shown in production I-5-alkylacetophenone oxime.Preparation process adopts one kettle way to react.
The preparation method of the one pot reaction and bifunctional catalyst thereof by preparing 2-hydroxyl-5-alkylacetophenone oxime to alkylphenol of the present invention, course of reaction is simple to operate, and yield is higher, and reaction of atomic economy is higher, and the three wastes are less.
Advantage of the present invention is that one kettle way is simple to operate, and catalyst easily reclaims, and reaction of atomic economy is high, energy-saving and cost-reducing.
Detailed description of the invention
The preparation method of embodiment 1, PVTS molecular sieve catalyst (that is, difunctional PVTS molecular sieve catalyst), carries out following steps successively:
1., by the tetraethyl orthosilicate of 1mol and and the triethyl phosphate of 0.2mol and the distilled water of 500ml add in reactor, and by dilute sulfuric acid (mass concentration is the sulfuric acid of 25%) adjust ph to 4, be warming up to 50 DEG C and stir 1 hour.
2., under strong mixing, keep still temperature 60 DEG C, first simultaneously (adding complete in 60 minutes) 3 kinds of solution below are slowly added continuously: the dilute hydrochloric acid solution of mass concentration 20% titanium trichloride is (containing titanium trichloride 0.5mol in the still liquid of step 1. gained, watery hydrochloric acid to be mass concentration be 5% hydrochloric acid), the sodium metavanadate aqueous solution (containing sodium metavanadate 0.2mol) of mass concentration 10%, mass concentration 15% ammonia spirit, obtain reaction system; The consumption of described mass concentration 15% ammonia spirit is the pH value controlling reaction system is 6;
Then continue to add mass concentration 15% ammonia spirit until adjust ph is 8 in reaction system; Insulation (60 DEG C) reaction 1 hour.
3., under strong mixing, keep still temperature 60 DEG C, the TBAH aqueous solution (containing TBAH 0.3mol) that (adding complete in 60 minutes) mass concentration is 10% is slowly added in the still liquid of step 2. gained, add rear utilize mass concentration be 30% ammoniacal liquor adjust ph be 13, insulation (60 DEG C) 2 hours;
4., by the still liquid of step 3. gained add Hydrothermal Synthesis still, in 160 DEG C of crystallization 200 hours, filter, gained filter cake is carried out wash, dry, then 200 ~ 300 DEG C of roastings 5 hours, obtain PVTS molecular sieve catalyst.
Above-mentioned washing is specially: spend deionized water filter cake, can't detect chlorion in eluate till.
Above-mentioned drying is specially: 70 DEG C of dryings 2 hours.
The preparation method of embodiment 2,2-hydroxy-5-methyl benzoylformaldoxime oxime, carries out following steps successively:
1), acetylation:
P-methyl phenol 0.2mol(21.6g is added in reactor) and acetic acid 0.4mol(24g), add the PVTS molecular sieve catalyst (consumption is 5% of p-methyl phenol quality) of embodiment 1 gained, slowly (namely, 60 minutes) temperature is risen to 110 DEG C carry out stirring reaction, in course of reaction, the water of generation is steamed, when anhydrous steaming, slowly still temperature rise to 160 DEG C is reacted by (40 minutes), steam acetic acid in this process, the reaction time is 3 hours, by still temperature drop to 65 DEG C after having reacted.
Remarks illustrate: the acetic acid steamed refers to not reaction and the acetic acid that can steam (can not steam because there being Van der Waals interaction force between a small amount of residual acetic acid meeting and reactant);
160 DEG C time, acetic acid does not react.
2), oximate:
The ammoniacal liquor that mass concentration is 30% is slowly added, until regulate still liquid pH value to be 8 in the reactant liquor of step 1) gained.Keep temperature 65 DEG C, in still, slowly add (adding complete in about 45 minutes) mass concentration is continuously that the mixed liquor of the hydrogen peroxide of 30% and the ammoniacal liquor of 30% is (containing the hydrogen peroxide of 0.22mol, the ammoniacal liquor of 0.24mol, that is, be 1.1:1.2:1 with the mol ratio of p-methyl phenol); Add rear insulation (65 DEG C) and continue reaction 0.5 hour.
After reaction terminates, by still temperature drop to 20 ~ 25 DEG C, by reacting liquid filtering, filter cake carries out being recrystallized (when dissolving completely when product during recrystallization in ethanol (about 50 ~ 150ml), filter, obtain PVTS molecular sieve catalyst), obtaining 2-hydroxy-5-methyl benzoylformaldoxime oxime 28g(purity is 99%), yield is 85%.
Embodiment 3 ~ embodiment 5,
Change the kind to alkylphenol (mole is constant) in embodiment 2, acetic acid addition (being called for short M1), the temperature (being called for short T1) steaming the reaction after water and reaction time (be called for short t), oximation reaction temperature (being called for short T2), dioxygen water-ammonia-to the mol ratio of alkylphenol (being called for short R), the yield obtaining corresponding 2-hydroxyl-5-alkylacetophenone oxime is Y.Detailed data is in table 1.
Table 1
Remarks illustrate:
Embodiment 3 products therefrom is: 2-hydroxyl-5-ethylo benzene acetophenone oxime;
Embodiment 4 products therefrom is: 2-hydroxyl-5-nonylacetophenone oxime;
Embodiment 5 products therefrom is: 2-hydroxyl-5-tert-butyl benzene acetophenone oxime.
Comparative example 1-1, makes the mole of triethyl phosphate into 0.1mol by 0.2mol, and all the other are with embodiment 1.
Comparative example 1-2, makes titanium trichloride mole into 0.2mol by 0.5mol, and all the other are with embodiment 1.
Comparative example 1-3, makes sodium metavanadate mole into 0.5mol by 0.2mol, and all the other are with embodiment 1.
Comparative example 1-4, makes TBAH mole into 0.1mol by 0.3mol, and all the other are with embodiment 1.
By catalyst used in the catalyst alternate embodiment 2 of above-mentioned comparative example 1-1 ~ comparative example 1-4 gained, all the other are with embodiment 2.Acquired results is described in table 2 below.
Table 2
| Used catalyst | Product yield, Y, % |
| Comparative example 1-1 prepares and obtains | 78 |
| Comparative example 1-2 prepares and obtains | 70 |
| Comparative example 1-3 prepares and obtains | 65 |
| Comparative example 1-4 prepares and obtains | 72 |
Finally, it is also to be noted that what enumerate above is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (6)
- The preparation method of 1.PVTS molecular sieve catalyst, is characterized in that comprising the following steps:1., tetraethyl orthosilicate and triethyl phosphate are added in reactor according to the mol ratio of 1:0.2, in reactor, also add distilled water, and with dilute sulfuric acid adjust ph to 3 ~ 5, be warming up to 45 ~ 55 DEG C and stir 1 hour;2., under strong mixing, keep still temperature 55 ~ 65 DEG C, to the still liquid of step 1. gained prior to 30 ~ 60 minutes in slowly add the dilute hydrochloric acid solution of the titanium trichloride of mass concentration 20%, the sodium metavanadate aqueous solution of mass concentration 10% and mass concentration 15% ammonia spirit continuously, obtain reaction system; Described titanium trichloride and step 1. in the mol ratio of tetraethyl orthosilicate be 0.5:1; Described sodium metavanadate and step 1. in the mol ratio of tetraethyl orthosilicate be 0.2:1, the consumption of described mass concentration 15% ammonia spirit is the pH value 6 ~ 7 controlling reaction system;Then continue to add mass concentration 15% ammonia spirit until adjust ph is 8 ~ 9 in reaction system; Insulation reaction 1 hour;3., under strong mixing, keep still temperature 55 ~ 65 DEG C, in the still liquid of step 2. gained, slowly add the TBAH aqueous solution that mass concentration is 10% in 30 ~ 60 minutes, then adjust ph is 12 ~ 13, is incubated 2 hours;Described tetrabutylammonium hydroxide ammonia and step 1. in the mol ratio of tetraethyl orthosilicate be 0.3:1;4., the still liquid of step 3. gained is added in Hydrothermal Synthesis still, in 150 ~ 170 DEG C of crystallization 190 ~ 210 hours, filters, gained filter cake is carried out wash, dry, then 200 ~ 300 DEG C of roastings 4.5 ~ 5.5 hours, obtain PVTS molecular sieve catalyst.
- 2. the preparation method of PVTS molecular sieve catalyst according to claim 1, is characterized in that: described step 4. in, wash and be: spend deionized water filter cake, can't detect chlorion in eluate till.
- 3. the preparation method of PVTS molecular sieve catalyst according to claim 1 and 2, is characterized in that: described step 3. in, utilize mass concentration be 30% ammoniacal liquor adjust ph be 12 ~ 13.
- 4. utilize the preparation method of the 2-hydroxyl-5-alkylacetophenone oxime that prepared by claim 1 ~ 3 either method and the PVTS molecular sieve catalyst that obtains carries out, it is characterized in that: using shown in formula II to alkylphenol as raw material, carry out following steps successively:1), acetylation:Add alkylphenol and acetic acid in reactor, and add PVTS molecular sieve catalyst, in 30 ~ 120 minutes, temperature is slowly risen to 105 ~ 115 DEG C carry out stirring reaction, in course of reaction, the water of generation is steamed; When anhydrous steaming, in 30 ~ 60 minutes, still temperature is slowly risen to 150 ~ 200 DEG C and react, the reaction time is 2 ~ 5 hours, steams acetic acid in this process, by still temperature drop to 60 ~ 70 DEG C after having reacted;The described mol ratio to alkylphenol and acetic acid is 1:1 ~ 2.5; The consumption of described PVTS molecular sieve catalyst is to alkylphenol quality 4 ~ 6%;2), oximate:Regulating step 1) pH value of reactant liquor of gained is 7 ~ 8; Keep temperature 60 ~ 70 DEG C, slowly added continuously in still in 30 ~ 60 minutes mass concentration be 30% hydrogen peroxide and mass concentration be the mixed liquor of the ammoniacal liquor of 30%, add rear insulation continuation reaction 0.5 hour;Described hydrogen peroxide: ammoniacal liquor: to the mol ratio of alkylphenol=1.1:1 ~ 2:1;After reaction terminates, by still temperature drop to 20 ~ 25 DEG C, by reacting liquid filtering, filter cake is recrystallized in ethanol, obtains the 2-hydroxyl-5-alkylacetophenone oxime shown in formula I;In formula I, R is methyl, ethyl, nonyl or the tert-butyl group.
- 5. the preparation method of 2-hydroxyl-5-alkylacetophenone oxime according to claim 4, is characterized in that:When described alkyl is methyl, the 2-hydroxyl-5-alkylacetophenone oxime shown in formula I is 2-hydroxy-5-methyl benzoylformaldoxime oxime;When described alkyl is ethyl, the 2-hydroxyl-5-alkylacetophenone oxime shown in formula I is 2-hydroxyl-5-ethylo benzene acetophenone oxime;When described alkyl is nonyl, the 2-hydroxyl-5-alkylacetophenone oxime shown in formula I is 2-hydroxyl-5-nonylacetophenone oxime;When described alkyl is the tert-butyl group, the 2-hydroxyl-5-alkylacetophenone oxime shown in formula I is 2-hydroxyl-5-tert-butyl benzene acetophenone oxime.
- 6. the preparation method of 2-hydroxyl-5-alkylacetophenone oxime according to claim 5, is characterized in that: described step 2) in, utilize mass concentration be 30% ammoniacal liquor regulating step 1) pH value of reactant liquor of gained is 7 ~ 8.
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| EP0745587A1 (en) * | 1995-06-02 | 1996-12-04 | Basf Aktiengesellschaft | Process for the preparation of amine oxides |
| US5859265A (en) * | 1994-07-20 | 1999-01-12 | Basf Aktiengesellschaft | Oxidation catalyst, its preparation and oxidation using the oxidation catalyst |
| CN102206149A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Method for preparing corresponding diacid by catalytic oxidization of naphthene |
| CN102205974A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Method for preparing titanium silicon molecular sieve |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5859265A (en) * | 1994-07-20 | 1999-01-12 | Basf Aktiengesellschaft | Oxidation catalyst, its preparation and oxidation using the oxidation catalyst |
| EP0745587A1 (en) * | 1995-06-02 | 1996-12-04 | Basf Aktiengesellschaft | Process for the preparation of amine oxides |
| CN102206149A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Method for preparing corresponding diacid by catalytic oxidization of naphthene |
| CN102205974A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Method for preparing titanium silicon molecular sieve |
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