CN108658715A - A method of preparing N- formylated aminated compounds - Google Patents

A method of preparing N- formylated aminated compounds Download PDF

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CN108658715A
CN108658715A CN201810369675.1A CN201810369675A CN108658715A CN 108658715 A CN108658715 A CN 108658715A CN 201810369675 A CN201810369675 A CN 201810369675A CN 108658715 A CN108658715 A CN 108658715A
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oxide
activated carbon
metal
cobalt
copper
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CN108658715B (en
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石峰
代兴超
袁航空
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
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Abstract

The invention discloses a kind of methods preparing N formylated aminated compounds; this method is with amine compounds and 1; 3 dihydroxyacetone (DHA)s are as reaction raw materials; in the presence of composite catalyst and oxidant; in reaction medium; under 0 100 DEG C of reaction temperature, react 2 48 hours in the reactor, to obtain the N formylateds aminated compounds.The method of the present invention is simple, reaction condition is mild, method through the invention, can low cost and obtain target product in high yield, the catalyst used has high catalytic activity, and is easy to detach and reuse from reaction system, and the method for the present invention whole process is environmental-friendly, reaction raw materials are easy to be transformed from biological diesel oil byproduct glycerine, promote the utilization of glycerine.

Description

A method of preparing N- formylated aminated compounds
Technical field
The present invention relates to a kind of methods preparing N- formylated aminated compounds.Specifically C3H6O3 is carbonyl The method realized amination and prepare N- formylated aminated compounds is reacted by the selectively fracture of C-C keys and with amine compounds in source.
Background technology
N- formylateds aminated compounds has been widely used in chemical and drug production field tool.Such as formamide can For use as organic synthesis raw material, paper treating agent, the softening agent of fiber industry, the softening agent of animal glue is also used as measuring The analytical reagent of amino acid content in rice；Formamide is also excellent organic solvent simultaneously, can be used for detaching chlorosilane, carries Pure grease etc.；In addition, formamide has active reactivity, a variety of reactions can occur, other than three hydrogen participate in reaction, also It can be dewatered, de- CO, introduce amino, acyl group and the reactions such as cyclization occur.By taking ring closure reaction as an example, formamide and malonic acid Diethylester cyclization can obtain the intermediate 4,6- dihydroxy-pyrimidines of adenine phosphate；It can be resisted with ortho-aminobenzoic acid cyclization The intermediate quinazolone-4 of arrhythmia drug Pyrozoline.It is well known that it is synthesis N- formylated amine that amine is reacted with formylation reagent The main method of class compound.Common formylation reagent has trichloroacetaldehyde, formic acid esters, ammonium formate and formic acid etc..Due to majority Formylation reagent has the shortcomings that expensive reagents, by-product are more, and so far, formic acid is widely used formylation reagent.But It is there is very strong corrosivity to instrument and equipment due to formic acid, and a large amount of solvents are needed in reaction process, the reaction time is longer, because This people is dedicated to the more clean reaction route of development.
Glycerine is the Main By product of biodiesel, how highly efficient, clear with the continuous development of Biodiesel Clean has become an important field of research now using biological diesel oil byproduct glycerin.For the purpose of industrial applications, There is tight demand by the preparation method of the high added value compound of raw material of glycerine to developing.And by microbial activity enzyme and Direct Catalytic Oxidation, the 1,3-Dihydroxyacetone for converting glycerine cheap and easy to get to high added value are in glycerine trans-utilization One important channel.As a kind of important Chemical Manufacture raw material, 1,3-Dihydroxyacetone fine chemistry industry, food, pharmacy and Cosmetic industry has a wide range of applications.
Invention content
The purpose of the present invention is to provide a kind of methods preparing N- formylated aminated compounds.
The method of the invention is under conditions of more mild, using aminated compounds and 1,3-Dihydroxyacetone as raw material, It is catalyzed by using composite catalyst and synthesizes N- formylated aminated compounds.
A method of preparing N- formylated aminated compounds, it is characterised in that with aminated compounds and 1,3- dihydroxy third Ketone is as reaction raw materials, in the presence of composite catalyst and oxidant, in reaction medium, under 0-100 DEG C of reaction temperature Reaction 2-48 hours, to obtain the N- formylateds aminated compounds；The composite catalyst is by following metal At least two oxide composition or by oxide and at least another kind metal list selected from least one of following metal Matter is formed or is formed by being selected from least one of following metal metal simple-substance and activated carbon：Aluminium, bismuth, zinc, tin, gold, silver, Copper, nickel, palladium, platinum, iridium, rhodium, cobalt, iron, ruthenium, osmium, manganese, rhenium, chromium, molybdenum, tungsten, vanadium, titanium, zirconium, lanthanum, yttrium, cerium, magnesium, calcium and barium；It is described Oxidant be the peroxide that general formula is R-O-O-R ', wherein R and R ' independently selected from H, the alkyl of C1 C 5 or metal from Son.
The aminated compounds is selected from：、、、、、、、、、Or, wherein R1And R2It is each independently selected from C1-18Alkyl, the integer that m is 1 to 6, and the integer that n is 1 to 12；Or it is selected from：、、、、、、、、 Or, wherein R1And R2It is each independently selected from hydrogen, C1-18Alkyl, methoxyl group, phenyl, phenoxy group, fluorine, chlorine, bromine or iodine, And the integer that n is 0 to 12.
The molar ratio of the aminated compounds and C3H6O3 is 1:1~10:1.
The mass ratio of the composite catalyst, oxidant and aminated compounds is 1:5:5~1:50:50.
The composite catalyst is made of at least two oxide in following metal or by being selected from following gold The oxide of at least one of category and at least another metal simple-substance form or by being selected from least one of following metal Metal simple-substance and activated carbon composition：Aluminium, zinc, silver, copper, palladium, platinum, rhodium, cobalt, iron, ruthenium, manganese, zirconium and cerium.
The reaction medium is water, toluene, dimethylbenzene, trimethylbenzene, dioxane, tetrahydrofuran, acetonitrile, normal octane and chlorine At least one of imitate.
The preparation method of the composite catalyst is：To selected from aluminium, bismuth, zinc, tin, gold, silver, copper, nickel, palladium, platinum, iridium, rhodium, At least one of cobalt, iron, ruthenium, osmium, manganese, rhenium, chromium, molybdenum, tungsten, vanadium, titanium, zirconium, lanthanum, yttrium, cerium, magnesium, calcium and barium metal it is solvable Property salt acetone soln in be added selected from aluminium, bismuth, zinc, tin, gold, silver, copper, nickel, palladium, platinum, iridium, rhodium, cobalt, iron, ruthenium, osmium, manganese, At least one of rhenium, chromium, molybdenum, tungsten, vanadium, titanium, zirconium, lanthanum, yttrium, cerium, magnesium, calcium and barium oxide or selected from big mesoporous activated carbon, At least one of transition mesoporous activated carbon and microporous activated carbon activated carbon are born by simple processing with obtaining solid as carrier Loading；It roasts the solid supported object to obtain the composite catalyst.
The solid supported object is in room temperature to carrying out 2-48 hours at 100 DEG C；The temperature of the roasting is 200-1000 DEG C And the time is 2-10 hours.
The soluble-salt is the nitrate or chloride of the metal, and the carrier be selected from aluminium, bismuth, zinc, tin, Gold, silver, copper, nickel, palladium, platinum, iridium, rhodium, cobalt, iron, ruthenium, osmium, manganese, rhenium, chromium, molybdenum, tungsten, vanadium, titanium, zirconium, lanthanum, yttrium, cerium, magnesium, calcium and At least one of ba oxide oxide or in big mesoporous activated carbon, transition mesoporous activated carbon and microporous activated carbon at least It is a kind of.
The composite catalyst obtained by be selected from alundum (Al2O3), zinc oxide, silver, copper oxide, cuprous oxide, copper, palladium, Platinum, rhodium, ruthenium, cobalt, cobalt sesquioxide, cobaltosic oxide, cobalt protoxide, di-iron trioxide, zirconium dioxide, ceria and three oxygen Change at least two oxides in two ceriums or in which at least one oxide and at least one metal simple-substance composition or at least one Kind metal simple-substance and activated carbon composition.
Compared with the prior art, the method that the present invention prepares N- formylated aminated compounds use 1,3-Dihydroxyacetone for Carbonyl source is economical, cheap and environmental-friendly；Catalyst preparation used in the method for the present invention is simple, high catalytic efficiency；The present invention Method prepares that reaction condition is mild, and catalyst is non-corrosive and is easily isolated and reuses.
Specific implementation mode
In the method provided by the invention for preparing N- formylated aminated compounds, the method is with amine compounds and 1,3- Dihydroxyacetone (DHA) is as reaction raw materials, in the presence of composite catalyst and oxidant, in reaction medium, at 0-100 DEG C Under reaction temperature, catalysis reaction 2-48 hours in the reactor, to obtain the N- formylateds aminated compounds.
In the present invention, term " N- formylateds aminated compounds " refers to N- formylateds secondary amine or N- formylateds-N, N- bis- Replace tertiary amine.
In the present invention, term " composite catalyst " refers to by two or more metal oxides or at least one metal Catalyst or at least one metal simple-substance and activated carbon that oxide and at least another metal simple-substance are combined it is compound and At catalyst.Preferably, used composite catalyst be made of at least two oxide in following metal or Person by selected from least one of following metal oxide and at least another metal simple-substance form or by being selected from following gold At least one of category metal simple-substance and activated carbon composition：Aluminium, bismuth, zinc, tin, gold, silver, copper, nickel, palladium, platinum, iridium, rhodium, cobalt, iron, Ruthenium, osmium, manganese, rhenium, chromium, molybdenum, tungsten, vanadium, titanium, zirconium, lanthanum, yttrium, cerium, magnesium, calcium and barium.Especially preferred composite catalyst by be selected from In lower metal at least two oxide composition or by selected from least one of following metal oxide and at least separately It a kind of metal simple-substance composition or is formed by being selected from least one of following metal metal simple-substance and activated carbon：Aluminium, zinc, silver, Copper, palladium, platinum, rhodium, cobalt, iron, ruthenium, manganese, zirconium and cerium.
In the present invention, used composite catalyst is preferably prepared by the following method：To selected from aluminium, bismuth, zinc, tin, Gold, silver, copper, nickel, palladium, platinum, iridium, rhodium, cobalt, iron, ruthenium, osmium, manganese, rhenium, chromium, molybdenum, tungsten, vanadium, titanium, zirconium, lanthanum, yttrium, cerium, magnesium, calcium and In the acetone soln of the soluble-salt of at least one of barium metal, be added selected from aluminium, bismuth, zinc, tin, gold, silver, copper, nickel, palladium, At least one of platinum, iridium, rhodium, cobalt, iron, ruthenium, osmium, manganese, rhenium, chromium, molybdenum, tungsten, vanadium, titanium, zirconium, lanthanum, yttrium, cerium, magnesium, calcium and barium oxygen Compound is selected from least one of big mesoporous activated carbon, transition mesoporous activated carbon and microporous activated carbon activated carbon as carrier process Simple processing is to obtain solid supported object；The solid supported object is roasted, to obtain the composite catalyst.
For example, in a specific embodiment, the method for preparing composite catalyst includes the following steps：Nitre will be selected from Sour aluminium, zinc nitrate, silver nitrate, copper nitrate, cobalt nitrate, ferric nitrate, chlorine palladium acid, potassium chloropalladate, chloroplatinic acid, radium chloride, ruthenic chloride, The aqueous solution of any one or two kinds in zirconium chloride, copper chloride, zirconium nitrate, cerous nitrate, ammonium ceric nitrate and cerium chloride is added and makees For the alundum (Al2O3) of carrier, magnesia, zinc oxide, zirconium oxide, di-iron trioxide, nickel sesquioxide, copper oxide, cobalt oxide or Person's activated carbon carries out dipping and simple processing, then the solid supported object obtained is obtained to described compound urge by roasting Agent.
Preferably, the dipping carries out 2-48 hours at room temperature；The temperature of the roasting is 200-800 DEG C and time It is 2-12 hours.
Preferably, pass through the obtained composite catalyst of the above method：By being selected from alundum (Al2O3), zinc oxide, silver, oxidation Copper, cuprous oxide, copper, palladium, platinum, rhodium, ruthenium, cobalt, cobalt sesquioxide, cobaltosic oxide, cobalt protoxide, di-iron trioxide, four oxygen Change three-iron, zirconium dioxide, ceria and at least two oxides in cerium sesquioxide or in which at least one oxide With at least one metal simple-substance composition or at least one metal simple-substance and activated carbon composition.
In the present invention, it is preferred to the 1,3-Dihydroxyacetone as carbonyl source and the reaction raw materials amine compounds Molar ratio is 1:1~1:10.The C3H6O3 and amine being used in the present invention can directly be bought acquisition by market.
In the present invention, it is preferred to which the amine compounds as reaction raw materials are the amine having following structure：、、、、、、、、、Or, wherein R1And R2It is each independently selected from C1-18Alkyl, m be 1 to 6 integer, and n be 1 to 12 it is whole Number；Or it is selected from：、、、、、、、、Or, wherein R1And R2It is each independently selected from hydrogen, C1-18Alkane Base, methoxyl group, phenyl, phenoxy group, fluorine, chlorine, bromine or iodine, and the integer that n is 0 to 12；
In the present invention, the reaction medium used is preferably water, toluene, dimethylbenzene, trimethylbenzene, dioxane, tetrahydrofuran, second At least one of nitrile, normal octane and chloroform.
In the present invention, used reaction vessel, which can be known in the art, can seal to keep certain in it Common pressure pipe in the container of pressure, such as chemical reaction, is commonly equipped with heating or cooling device, such as this field is normal Water-bath, oil bath or ice bath etc., and ventilation or emptying auxiliary facility, such as gas cylinder and pressure gauge etc., these are for ability Field technique personnel are known.
The preparation of composite catalyst
Embodiment 1
It weighs commercially available copper chloride dihydrate 2.2mg (0.013 mmol) to be added in 4 mL acetone, in 50 mL round-bottomed flask room temperatures Under the conditions of magnetic agitation.After dissolving completely, under stiring plus such as 400mg γ-Al2O3As carrier, then under room temperature after 24 h of continuous stirring obtain solid powder.450 DEG C of Muffle furnace roasts 4 hours, obtains the catalyst as grey powder, passes through XRD, XPS, TEM and EXAFS are analyzed（Collection of illustrative plates is not shown）, show that the catalyst is Cu/Al2O3Compound is denoted as catalyst A.
Embodiment 2
It weighs commercially available 3.1 mg of nitrate trihydrate copper (0.013 mmol) to be added in 4 mL acetone, in 50 mL round-bottomed flasks rooms Magnetic agitation under the conditions of temperature.After dissolving completely, under stiring plus such as 400mg γ-Al2O3As carrier, then under room temperature after 24 h of continuous stirring obtain solid powder.450 DEG C of Muffle furnace roasts 4 hours, obtains the catalyst as grey powder, passes through XRD, XPS, TEM and EXAFS are analyzed（Collection of illustrative plates is not shown）, show that the catalyst is Cu/Al2O3Compound is denoted as catalyst B.
Embodiment 3
Operation is with embodiment 1, only with 400mg Fe2O3Instead of γ-Al2O3, obtain catalyst Cu/Fe2O3, it is denoted as catalyst C.
Embodiment 4
Operation is with embodiment 1, only with 400mg Co2O3Instead of γ-Al2O3, obtain catalyst Cu/Co2O3, it is denoted as catalyst D.
Embodiment 5
Operation only replaces γ-Al with embodiment 1 with 400mg NiO2O3, obtain catalyst Cu/Ni2O3, it is denoted as catalyst E.
Embodiment 6
Operation only replaces γ-Al with embodiment 1 with 400mg ZnO2O3, catalyst Cu/ZnO is obtained, catalyst F is denoted as.
Embodiment 7
Operation only replaces γ-Al with embodiment 1 with 400mg MgO2O3, catalyst Cu/MgO is obtained, catalyst G is denoted as.
Embodiment 8
Operation only replaces γ-Al with embodiment 1 with 400mg activated carbons2O3, catalyst Cu/C is obtained, catalyst H is denoted as.
Embodiment 9
Operation only replaces copper chloride with 0.013 mmol zinc nitrates, obtains catalyst Z n/Al with embodiment 12O3, it is denoted as and urges Agent I.
Embodiment 10
Operation only replaces copper chloride with 0.014 mmol ferric nitrates, obtains catalyst and be denoted as Fe/Al with embodiment 12O3, note For catalyst J.
Embodiment 11
Operation only replaces copper nitrate with 0.006 mmol cerous nitrates, obtains catalyst Ce/ZrO with embodiment 12, it is denoted as catalysis Agent K.
Embodiment 12
Operation only replaces copper nitrate with the sour aqueous solutions of potassium of 0.008 mmol chlordenes palladium (IV), obtains catalyst with embodiment 1 Pd/Al2O3, it is denoted as catalyst L.
Embodiment 13
Operation only replaces copper nitrate with 0.008 mmol ruthenium trichloride aqueous solutions, obtains catalyst Ru/ with embodiment 1 Al2O3, it is denoted as catalyst M.
The preparation of N- formylated aminated compounds
Embodiment 14
25 mg of catalyst A prepared in embodiment 1 are weighed, is added in reaction tubes of 38 mL with magnetic agitation, then adds Enter 465 mg（5 mmol）Aniline, 90 mg (1 mmol) 1,3-Dihydroxyacetone, 0.5 mL（6 mmol）35% hydrogen peroxide With 5 mL chloroforms.Later, 50 DEG C are heated to using electric furnace and is kept for 12 hours.Then reaction tube is cold by water cooling But room temperature is arrived, centrifuge is used（Anting Scientific Instrument Factory, Shanghai）It is centrifuged 5 minutes with 8000 revs/min, separation is with mixed from reaction Close recycling catalyst A in liquid.As a comparison with N- formylated aniline standardized product, using 6890/5973 GC-MS gas phase matter of HP Spectrometer and Agilent 7890A（30m × 0.25mm × 0.33 μm capillary column, hydrogen flame ionization detector）It is qualitative fixed to carry out Amount is analyzed, and for example industrial rectification process obtains target product N- formylated aniline, yield knot by methods known in the art Fruit see the table below 1.
Embodiment 15-26
Operation only replaces catalyst A with catalyst B, C, D, E, F, G, H, I, J, K, L and M, obtains respectively with embodiment 14 As a result it see the table below 1.
Embodiment 27-34
Operation is with embodiment 14, only with water, toluene, dimethylbenzene, trimethylbenzene, dioxane, tetrahydrofuran, acetonitrile and normal octane Respectively instead of chloroform, obtained result see the table below 1.
Table 1
It is in table 1 the result shows that, by the present invention in that using amine compounds as reaction raw materials, using 1,3-Dihydroxyacetone as carbonyl Change reagent, hydrogen peroxide reacts in the presence of prepared composite catalyst in reaction medium as oxidant, makes The N- formylated aminated compounds as target product was obtained, yield is up to 90% or more.Moreover, the institute prepared by the present invention There is composite catalyst to all have higher catalytic activity in above-mentioned reaction.In addition, the result in table 1 is also shown that the present invention's Reaction can be achieved in differential responses medium.
The recycling of catalyst
Embodiment 35
The catalyst A recycled in embodiment 14 is carried out to use centrifuge（Anting Scientific Instrument Factory, Shanghai）With 8000 revs/min Centrifugation detaches after five minutes, is washed and is centrifuged at room temperature with chloroform, repeats 3 times.Use the catalyst for thus recycling acquisition A repeats the process of embodiment 14 again.As a comparison with N- formylated aniline standardized product, 6890/5973 GC-MS of HP are used Gaseous mass analyzer and Agilent 7890A（30m × 0.25mm × 0.33 μm capillary column, hydrogen flame ionization detector）It carries out The yield of qualitative and quantitative analysis, the N- formylated aniline of acquisition is 90%.
In addition, operation is same as above, after being recycled to the catalyst A after above-mentioned reuse, recycled again using this Catalyst A again repeat embodiment 14 process.As a comparison with N- formylated aniline standardized product, HP 6890/ is used 5973 GC-MS gaseous mass analyzers and Agilent 7890A（30m × 0.25mm × 0.33 μm capillary column, the inspection of hydrogen flame ion Survey device）Qualitative and quantitative analysis is carried out, the yield of the N- formylated aniline of acquisition is 85%.
As can be seen from the above results, the composite catalyst that prepared by the present invention can reuse, and reuse In, still have with it is initially use when comparable catalytic activity.
In addition, other catalyst B, C, D, E, F, G, H, I, J, K, L and M to above-mentioned preparation have also carried out reuse It investigates, obtained result is similar with catalyst A, i.e., these catalyst still have and initially use phase when repeatedly using When catalytic activity.
The use of differential responses raw material
Embodiment 36-73
Operation is with embodiment 14, and in reaction tubes of 38 mL with magnetic agitation, using 25 mg of catalyst A, reaction medium is Water 2-5 mL are separately added into 5 mmol of reaction raw materials amine, 1 mmol of 1,3-Dihydroxyacetone, 35% hydrogen peroxide, 6 mmol, so Afterwards in 25-50oC is reacted.Reaction time, temperature and target product are respectively displayed in the following table 2-4.Stop reaction simultaneously After being cooled to room temperature, 6890/5973 GC-MS gaseous mass analyzers of HP and Agilent 7890A are used（30m×0.25mm× 0.33 μm of capillary column, hydrogen flame ionization detector）Quantitative analysis carried out to reaction mixture, and passes through conventional separation and pure Such as rectifying of change means obtains target product, and the yield of target product see the table below 2-4.
Table 2
Table 3
Table 4
It is in table 2-4 the result shows that, method through the invention, using different amine compounds as reaction raw materials, with 1,3- Dihydroxyacetone (DHA) is as carbonylation agent, in the presence of prepared composite catalyst and oxidant, by anti-in reaction medium Corresponding target product N- formylated aminated compounds should can be made, yield is even as high as 99% or more.
In addition, the present invention is also existed respectively using other catalyst B, C, D, E, F, G, H, I, J, K, L and M of above-mentioned preparation It different amine compounds reaction raw materials, temperature, pressure and is reacted under the time, equally also obtains corresponding target product N- first Acylated aminated compounds, obtained result（It is unlisted）It is similar with above-mentioned catalyst A.
The present invention uses 1,3-Dihydroxyacetone as formylated source, can be using different amine compounds as substrate, letter It is single easily to prepare target product N- formylated aminated compounds, it is whole process economy, cheap and environmental-friendly；It is used to urge Agent can simply and inexpensively be made, and have high catalytic activity；Reaction condition is more mild, and catalyst is non-corrosive and is easy to It detaches and can reuse, the bright prospects with industrialized production.
It should be pointed out that the professional technician for making the art, without departing from the principle of the present invention, energy Enough realize various modifications to these embodiments, and these modifications also should be regarded as within the scope of the present invention.

Claims (10)

1. a kind of method preparing N- formylated aminated compounds, it is characterised in that with aminated compounds and 1,3-Dihydroxyacetone It is anti-under 0-100 DEG C of reaction temperature in reaction medium in the presence of composite catalyst and oxidant as reaction raw materials It answers 2-48 hours, to obtain the N- formylateds aminated compounds；The composite catalyst by following metal extremely Few two kinds of oxide composition or by oxide and at least another kind metal simple-substance selected from least one of following metal It forms or is formed by being selected from least one of following metal metal simple-substance and activated carbon：Aluminium, bismuth, zinc, tin, gold, silver, copper, Nickel, palladium, platinum, iridium, rhodium, cobalt, iron, ruthenium, osmium, manganese, rhenium, chromium, molybdenum, tungsten, vanadium, titanium, zirconium, lanthanum, yttrium, cerium, magnesium, calcium and barium；The oxygen Agent is the alkyl or metal ion of the peroxide that general formula is R-O-O-R ', wherein R and R ' independently selected from H, C1 C 5.
2. the method as described in claim 1, it is characterised in that the aminated compounds is selected from：、、、、、、、、、Or, Middle R1And R2It is each independently selected from C1-18Alkyl, the integer that m is 1 to 6, and the integer that n is 1 to 12；Or it is selected from：、、、、、、、、Or, wherein R1And R2It is each independently selected from hydrogen, C1-18Alkyl, methoxyl group, Phenyl, phenoxy group, fluorine, chlorine, bromine or iodine, and the integer that n is 0 to 12.
3. the method as described in claim 1, it is characterised in that the molar ratio of the aminated compounds and 1,3-Dihydroxyacetone It is 1:1~10:1.
4. the method as described in claim 1, it is characterised in that the composite catalyst, oxidant and aminated compounds quality Than being 1:5:5~1:50:50.
5. the method as described in claim 1, it is characterised in that the composite catalyst is by least two in following metal Kind oxide composition or by oxide and at least another kind metal simple-substance group selected from least one of following metal At or by being selected from least one of following metal metal simple-substance and activated carbon forms：Aluminium, zinc, silver, copper, palladium, platinum, rhodium, Cobalt, iron, ruthenium, manganese, zirconium and cerium.
6. the method as described in claim 1, it is characterised in that the reaction medium is water, toluene, dimethylbenzene, trimethylbenzene, two At least one of six ring of oxygen, tetrahydrofuran, acetonitrile, normal octane and chloroform.
7. the method as described in claim 1, it is characterised in that the preparation method of the composite catalyst is：To selected from aluminium, bismuth, Zinc, tin, gold, silver, copper, nickel, palladium, platinum, iridium, rhodium, cobalt, iron, ruthenium, osmium, manganese, rhenium, chromium, molybdenum, tungsten, vanadium, titanium, zirconium, lanthanum, yttrium, cerium, In the acetone soln of the soluble-salt of at least one of magnesium, calcium and barium metal be added selected from aluminium, bismuth, zinc, tin, gold, silver, copper, In nickel, palladium, platinum, iridium, rhodium, cobalt, iron, ruthenium, osmium, manganese, rhenium, chromium, molybdenum, tungsten, vanadium, titanium, zirconium, lanthanum, yttrium, cerium, magnesium, calcium and barium at least A kind of oxide or selected from least one of big mesoporous activated carbon, transition mesoporous activated carbon and microporous activated carbon activated carbon as carrying Body is by simple processing to obtain solid supported object；It roasts the solid supported object to obtain the composite catalyzing Agent.
8. the method for claim 7, it is characterised in that the solid supported object is small to progress 2-48 at 100 DEG C in room temperature When；The temperature of the roasting is 200-1000 DEG C and the time is 2-10 hours.
9. the method for claim 7, it is characterised in that the soluble-salt is the nitrate or chloride of the metal, And the carrier be selected from aluminium, bismuth, zinc, tin, gold, silver, copper, nickel, palladium, platinum, iridium, rhodium, cobalt, iron, ruthenium, osmium, manganese, rhenium, chromium, At least one of molybdenum, tungsten, vanadium, titanium, zirconium, lanthanum, yttrium, cerium, magnesium, calcium and ba oxide oxide or selected from big mesoporous activated carbon, At least one of transition mesoporous activated carbon and microporous activated carbon.
10. method as claimed in claim 5, it is characterised in that the composite catalyst by be selected from alundum (Al2O3), zinc oxide, Silver, copper oxide, cuprous oxide, copper, palladium, platinum, rhodium, ruthenium, cobalt, cobalt sesquioxide, cobaltosic oxide, cobalt protoxide, three oxidations two At least two oxides in iron, zirconium dioxide, ceria and cerium sesquioxide or in which at least one oxide and extremely A kind of few metal simple-substance composition or at least one metal simple-substance and activated carbon composition.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111471208A (en) * 2020-06-04 2020-07-31 周玉 Preparation process of flame-retardant polyurethane building insulation board

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107056567A (en) * 2017-06-06 2017-08-18 温州大学 A kind of new method of synthesis N substitute amide derivatives
CN107892670A (en) * 2017-11-27 2018-04-10 湘潭大学 A kind of method of cobalt catalysis formylation reaction synthesis carboxamides derivatives

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107056567A (en) * 2017-06-06 2017-08-18 温州大学 A kind of new method of synthesis N substitute amide derivatives
CN107892670A (en) * 2017-11-27 2018-04-10 湘潭大学 A kind of method of cobalt catalysis formylation reaction synthesis carboxamides derivatives

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
ANTONELLA GERVASINI等: "Dependence of Copper Species on the Nature of the Support for Dispersed CuO Catalysts", 《J. PHYS. CHEM. B》 *
CONGHUI TANG AND NING JIAO: "Copper-Catalyzed Aerobic Oxidative C-C Bond Cleavage for C-N Bond Formation: From Ketones to Amides", 《ANGEW. CHEM.》 *
JILEI XU等: "Selective oxidation of glycerol to formic acid catalyzed by Ru(OH)4/r-GO in the presence of FeCl3", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 *
P. M. SCHOSSELER等: "Uptake of Cu2+ by the calcium carbonates vaterite and calcite as studied by continuous wave (CW) and pulse electron paramagnetic resonance", 《GEOCHIMICA ET COSMOCHIMICA ACTA》 *
ZHENCHEN TANG等: "Transformation of Cellulose and its Derived Carbohydrates into Formic and Lactic Acids Catalyzed by Vanadyl Cations", 《CHEMSUSCHEM》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111471208A (en) * 2020-06-04 2020-07-31 周玉 Preparation process of flame-retardant polyurethane building insulation board
CN111471208B (en) * 2020-06-04 2021-09-17 有新绿建(山东)智能科技有限公司 Preparation process of flame-retardant polyurethane building insulation board

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