CN104607182A - Preparation of nano-palladium catalyst as well as application of nano-palladium catalyst to synthesis of vanillin compounds - Google Patents
Preparation of nano-palladium catalyst as well as application of nano-palladium catalyst to synthesis of vanillin compounds Download PDFInfo
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- CN104607182A CN104607182A CN201510021029.2A CN201510021029A CN104607182A CN 104607182 A CN104607182 A CN 104607182A CN 201510021029 A CN201510021029 A CN 201510021029A CN 104607182 A CN104607182 A CN 104607182A
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Abstract
The invention discloses preparation of a nano-palladium catalyst as well as an application of the nano-palladium catalyst to synthesis of vanillin compounds and relates to the technical field of organic synthesis. The active ingredient of the nano-palladium catalyst is zero-valence-state single-substance palladium nanoparticles which are obtained by loading high-valence-state palladium salt on a carrier and then reducing the palladium salt to the active ingredient; then vanillyl alcohol compounds are oxidized into the vanillin compounds by the aid of air under actions of the nano-palladium catalyst and an alkali under normal temperature and normal pressure conditions. The prepared nano-palladium catalyst has the characteristics of good selectivity and high yield, is easy to separate after participating in reactions, recyclable and environment-friendly and has a certain industrial application value.
Description
Technical field:
The present invention relates to technical field of organic synthesis, be specifically related to a kind of preparation of nano Pd catalyst and the application in the synthesis of vanillic aldehyde compounds thereof.
Background technology:
Vanillic aldehyde has charming vanilla fragrance, and molecular formula is C
8h
8o
3, systematic naming method is Vanillin.As spices, vanillic aldehyde consumption is very big, in spices market, the world today, occupy first place, is also one of most important synthetic perfume simultaneously, is described as " king of spices ".
Vanillic aldehyde has purposes very widely: in the food products markets such as carbonated drink, ice cream, cheese, seasoning matter, sweets, dish, dessert and roasted seeds and nuts, be used as perfume material, flavoring product and fixastive; In wine brewing and cigarette field, be used as aromatizing agent and help pastil; Perfuming deodorant tune is used as in the conventional cosmetics such as perfume, shampoo, washing powder and washing cream and skin makeup product scope; Anti-hardening agent is used as in rubber, plastic products and other Related product; In addition, vanillic aldehyde can also be used as the plating brightener of the metal such as nickel, cadmium, and meanwhile, in cultivation industry, vanillic aldehyde can be used as Feed flavours; Research shows, vanillic aldehyde is harmless to have no side effect, and therefore, the application of vanillic aldehyde has been deep into the every field of people's life.
Originate respectively for main three kinds of vanillic aldehyde: extracted form natural plant, fermentable and chemical synthesis.Wherein, the ratio that chemical synthesis is shared in vanillic aldehyde is produced is maximum.Main synthetic method has laricin method, eugenol method, lignin method, guaiacol method, safrole method, parahydroxyben-zaldehyde method.The Nitrosation Process of current domestic main employing guaiacol produces vanillic aldehyde, this method process route is longer, corollary equipment is many, three waste discharge is serious, and reaction efficiency is low, and the accessory substance obtained is many, very large inconvenience is brought to the separation and purification in later stage, this method is faced with huge environmental protection pressure, is not inconsistent with environmentally friendly production theory, will certainly replace by other eco-friendly process routes.
Summary of the invention:
Technical problem to be solved by this invention is the preparation of the nano Pd catalyst providing a kind of yield high and environmentally friendly and the application in the synthesis of vanillic aldehyde compounds thereof.
Technical problem to be solved by this invention adopts following technical scheme to realize:
A kind of nano Pd catalyst, active component is the simple substance Pd nano particle of zero-valent state, restores active components obtain by being loaded to by the palladium salt of high-valence state after on carrier.
Described palladium salt is selected from the one in palladium bichloride, chlorine palladium acid sodium, palladium, palladium trifluoroacetate; One or more in carriers selected from silica, aluminium oxide, magnesia, titanium oxide, active carbon, imvite, kaolin, preferred active carbon, magnesia and aluminium oxide.
The load capacity of described active component on carrier is 0.5mmol/g.
Described nano Pd catalyst is prepared by immersion reduction method, and concrete steps are as follows:
(1) in inert environments, first palladium salt is made into maceration extract, then by carrier bubble in this maceration extract, fully stir and make catalyst cupport complete, subsequently after filtration, obtain catalyst precursor after vacuum drying;
(2) by gained catalyst precursor in atmosphere of hydrogen in 250 DEG C of reduction treatment 24h, obtain target nano Pd catalyst.
Described hydrogen flowing quantity is 50-60mL/min, and pressure is 0.1-0.2MPa.
Described carrier needs to carry out pretreatment before use, comprises acid treatment and alkali treatment, and described acid is selected from the one in hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and oxalic acid, preferred nitric acid; Described alkali is selected from the one in potassium hydroxide, NaOH, ammoniacal liquor, triethylamine, sodium acid carbonate and potassium phosphate, preferred potassium hydroxide.
The application of described nano Pd catalyst in the synthesis of vanillic aldehyde compounds, under normal temperature and pressure, first vanillic alcohol compounds is fully dissolved in organic solvent, add nano Pd catalyst and alkali again, fully react with air, reaction terminates rear Filtration of catalyst, is extracted with ethyl acetate after washed reaction liquid, organic phase decompression distillation, obtains vanillic aldehyde compounds finally by column chromatography.
The structural formula of described vanillic alcohol compounds is
Wherein, R is selected from the straight or branched alkane of carbon to four carbon.
Described organic solvent is selected from the one in benzene, toluene, methyl alcohol, ethanol, acetonitrile, Isosorbide-5-Nitrae-dioxane, oxolane, 1,2-dichloroethanes, preferred toluene; Described alkali is selected from the one in sodium carbonate, sodium acid carbonate, potassium phosphate, potash, saleratus, potassium acetate, sodium acetate, preferred potash.
Described nano Pd catalyst consumption is with the 2-10% of the gauge of supported palladium for vanillic alcohol compounds mole, and alkali consumption is 1-1.5 times of vanillic alcohol compounds mole.
The invention has the beneficial effects as follows:
(1) nanocatalyst of working load type of the present invention, is easy to after reaction be separated, can recycles;
(2) nano Pd catalyst of the present invention has selective good, feature that productive rate is high;
(3) the present invention is environmentally friendly, has certain industrial application value.
Detailed description of the invention:
The technological means realized to make the present invention, creation characteristic, reaching object and effect is easy to understand, below in conjunction with specific embodiment, setting forth the present invention further.
One, the preparation of nano Pd catalyst
Under argon atmosphere, the palladium salt of 1g nanoscale magnesium carrier and 0.5mmol is added in 50ml deionized water and is made into maceration extract, then at 5 DEG C, fully stir 12h, obtain brown MgO-Supported palladium salt catalyst, by solid filtering, vacuum drying; Then in atmosphere of hydrogen, take above-mentioned catalyst 1g, sodium borohydride 1.5g joins the ethanolic solution of 30ml drying, fully 5h is stirred at 5 DEG C, obtain the zero valent palladium catalyst of the MgO-Supported of black, solid filtering is also washed 3 times repeatedly with deionized water and acetone, and vacuum drying obtains final catalyst.
Two, the synthesis of vanillic aldehyde compounds
Example is synthesized with vanillic aldehyde:
Embodiment 1
In the there-necked flask of 50ml, add vanillic alcohol (1.54g, 10mmol), nano Pd catalyst (0.7g, 10%), potash (1.66g, 12mmol) and toluene 30ml, under magnetic agitation, at 80 DEG C, react 3h.Reaction terminates rear cooling reactant liquor, adds isopyknic deionized water after filtering recovering catalyst, is separated organic phase, aqueous phase is extracted with ethyl acetate three times, each 5min, merges organic phase, decompression is spin-dried for, and be separated required product 1.4g with column chromatography, yield is 90%.
Embodiment 2
In the there-necked flask of 50ml, add vanillic alcohol (1.54g, 10mmol), nano Pd catalyst (0.4g, 6%), potash (1.66g, 12mmol) and toluene 30ml, under magnetic agitation, at 80 DEG C, react 3h.Reaction terminates rear cooling reactant liquor, adds isopyknic deionized water after filtering recovering catalyst, is separated organic phase, aqueous phase is extracted with ethyl acetate three times, each 5min, merges organic phase, decompression is spin-dried for, and be separated required product 1.43g with column chromatography, yield is 93%.
Embodiment 3
In the there-necked flask of 50ml, add vanillic alcohol (1.54g, 10mmol), nano Pd catalyst (0.35g, 5%), potash (1.66g, 12mmol) and toluene 30ml, under magnetic agitation, at 80 DEG C, react 3h.Reaction terminates rear cooling reactant liquor, adds isopyknic deionized water after filtering recovering catalyst, is separated organic phase, aqueous phase is extracted with ethyl acetate three times, each 5min, merges organic phase, decompression is spin-dried for, and be separated required product 1.44g with column chromatography, yield is 95%.
Embodiment 4
In the there-necked flask of 50ml, add vanillic alcohol (1.54g, 10mmol), nano Pd catalyst (0.25g, 3%), potash (1.66g, 12mmol) and toluene 30ml, under magnetic agitation, at 80 DEG C, react 3h.Reaction terminates rear cooling reactant liquor, adds isopyknic deionized water after filtering recovering catalyst, is separated organic phase, aqueous phase is extracted with ethyl acetate three times, each 5min, merges organic phase, decompression is spin-dried for, and be separated required product 1.08g with column chromatography, yield is 70%.
Embodiment 5
In the there-necked flask of 50ml, add vanillic alcohol (1.54g, 10mmol), nano Pd catalyst (0.35g, 5%), potash (1.66g, 12mmol) and toluene 30ml, under magnetic agitation, react 12h at normal temperatures.Reaction terminates rear cooling reactant liquor, adds isopyknic deionized water after filtering recovering catalyst, is separated organic phase, aqueous phase is extracted with ethyl acetate three times, each 5min, merges organic phase, decompression is spin-dried for, and be separated required product 1.44g with column chromatography, yield is 95%.
Embodiment 6
In the there-necked flask of 50ml, add vanillic alcohol (1.54g, 10mmol), nano Pd catalyst (0.35g, 5%), sodium acid carbonate (1g, 12mmol) and toluene 30ml, under magnetic agitation, react 12h at normal temperatures.Reaction terminates rear cooling reactant liquor, adds isopyknic deionized water after filtering recovering catalyst, is separated organic phase, aqueous phase is extracted with ethyl acetate three times, each 5min, merges organic phase, decompression is spin-dried for, and be separated required product 1.12g with column chromatography, yield is 73%.
Embodiment 7
In the there-necked flask of 50ml, add vanillic alcohol (1.54g, 10mmol), nano Pd catalyst (0.35g, 5%), potash (1.66g, 12mmol) and ethanol 30ml, under magnetic agitation, react 12h at normal temperatures.Reaction terminates rear cooling reactant liquor, adds isopyknic deionized water after filtering recovering catalyst, is separated organic phase, aqueous phase is extracted with ethyl acetate three times, each 5min, merges organic phase, decompression is spin-dried for, and be separated required product 0.92g with column chromatography, yield is 61%.
Table 1 differential responses condition is on the impact of productive rate
As can be seen from Table 1, the vanillic aldehyde productive rate that the present invention obtains is very high, and condition as mild as a dove, and production process is polluted few, and post processing is simple.
More than show and describe general principle of the present invention and principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and description just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (11)
1. a nano Pd catalyst, is characterized in that: active component is the simple substance Pd nano particle of zero-valent state, restores active components obtain by being loaded to by the palladium salt of high-valence state after on carrier.
2. nano Pd catalyst according to claim 1, is characterized in that: described palladium salt is selected from the one in palladium bichloride, chlorine palladium acid sodium, palladium, palladium trifluoroacetate; One or more in carriers selected from silica, aluminium oxide, magnesia, titanium oxide, active carbon, imvite, kaolin, preferred active carbon, magnesia and aluminium oxide.
3. nano Pd catalyst according to claim 1, is characterized in that: the load capacity of described active component on carrier is 0.5mmol/g.
4. the preparation method of nano Pd catalyst according to claim 1, is characterized in that, described nano Pd catalyst is prepared by immersion reduction method, and concrete steps are as follows:
(1) in inert environments, first palladium salt is made into maceration extract, then by carrier bubble in this maceration extract, fully stir and make catalyst cupport complete, subsequently after filtration, obtain catalyst precursor after vacuum drying;
(2) by gained catalyst precursor in atmosphere of hydrogen in 250 DEG C of reduction treatment 24h, obtain target nano Pd catalyst.
5. the preparation method of nano Pd catalyst according to claim 4, is characterized in that: described hydrogen flowing quantity is 50-60mL/min, and pressure is 0.1-0.2MPa.
6. the preparation method of nano Pd catalyst according to claim 4, it is characterized in that: described carrier needs to carry out pretreatment before use, comprise acid treatment and alkali treatment, described acid is selected from the one in hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and oxalic acid, preferred nitric acid; Described alkali is selected from the one in potassium hydroxide, NaOH, ammoniacal liquor, triethylamine, sodium acid carbonate and potassium phosphate, preferred potassium hydroxide.
7. the application of nano Pd catalyst in the synthesis of vanillic aldehyde compounds as claimed in claim 1.
8. the application of nano Pd catalyst in the synthesis of vanillic aldehyde compounds according to claim 7, it is characterized in that: under normal temperature and pressure, first vanillic alcohol compounds is fully dissolved in organic solvent, add nano Pd catalyst and alkali again, fully react with air, reaction terminates rear Filtration of catalyst, is extracted with ethyl acetate after washed reaction liquid, organic phase decompression distillation, obtains vanillic aldehyde compounds finally by column chromatography.
9. the application of nano Pd catalyst in the synthesis of vanillic aldehyde compounds according to claim 8, is characterized in that: the structural formula of described vanillic alcohol compounds is
Wherein, R is selected from the straight or branched alkane of carbon to four carbon.
10. the application of nano Pd catalyst in the synthesis of vanillic aldehyde compounds according to claim 8, it is characterized in that: described organic solvent is selected from benzene, toluene, methyl alcohol, ethanol, acetonitrile, 1, one in 4-dioxane, oxolane, 1,2-dichloroethanes, preferred toluene; Described alkali is selected from the one in sodium carbonate, sodium acid carbonate, potassium phosphate, potash, saleratus, potassium acetate, sodium acetate, preferred potash.
11. application of nano Pd catalyst in the synthesis of vanillic aldehyde compounds according to claim 8, it is characterized in that: described nano Pd catalyst consumption is with the 2-10% of the gauge of supported palladium for vanillic alcohol compounds mole, and alkali consumption is 1-1.5 times of vanillic alcohol compounds mole.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397138A (en) * | 2016-08-22 | 2017-02-15 | 滕州市天水生物科技有限公司 | New technique for production of vanillin alcohol |
| CN106944041A (en) * | 2017-02-24 | 2017-07-14 | 安徽师范大学 | Nanotube-palladium composite material and preparation method thereof |
| CN108187670A (en) * | 2017-12-27 | 2018-06-22 | 赣南师范大学 | Hydroxyl activity charcoal loaded palladium catalyst and preparation method thereof |
| CN112409146A (en) * | 2020-12-08 | 2021-02-26 | 南通亚香食品科技有限公司 | Continuous preparation process of vanillin |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397138A (en) * | 2016-08-22 | 2017-02-15 | 滕州市天水生物科技有限公司 | New technique for production of vanillin alcohol |
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| CN106944041A (en) * | 2017-02-24 | 2017-07-14 | 安徽师范大学 | Nanotube-palladium composite material and preparation method thereof |
| CN108187670A (en) * | 2017-12-27 | 2018-06-22 | 赣南师范大学 | Hydroxyl activity charcoal loaded palladium catalyst and preparation method thereof |
| CN108187670B (en) * | 2017-12-27 | 2020-10-30 | 赣南师范大学 | Palladium catalyst loaded with hydroxyl activated carbon and preparation method thereof |
| CN112409146A (en) * | 2020-12-08 | 2021-02-26 | 南通亚香食品科技有限公司 | Continuous preparation process of vanillin |
| CN112409146B (en) * | 2020-12-08 | 2023-07-07 | 南通亚香食品科技有限公司 | Continuous preparation process of vanillin |
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Application publication date: 20150513 |