CN101024602A - Method for making alcohol to generate aerobe oxidation with transistion metal catalyst using stable nitroxyl free radical under moderate condition - Google Patents
Method for making alcohol to generate aerobe oxidation with transistion metal catalyst using stable nitroxyl free radical under moderate condition Download PDFInfo
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Abstract
The invention relates to a method to oxidize alcohol. It uses primary alcohol or secondary alcohol to take reaction with oxygen containing gas under the existing of the catalyst agent compound of stable nitryl free radical derivative, nitrate resource, bromide resource to gain aldehyde or ketone.
Description
Technical field
The present invention relates in the presence of low pressure and stable nitroxyl radical, make primary alconol and secondary alcohol not have the method that the transition metal aerobic oxidation is corresponding aldehyde and ketone.
Background technology
Alcohol is oxidized to corresponding aldehyde, ketone or acid and has represented the most important functional group of class conversion reaction in the organic synthesis to a certain extent, and many method (Sheldon have been reported in the document, R.A., Kochi, J.K.Metal Catalysed Oxidations of Organic Compounds; Academic Press; New York, 1981; Hudlicky, M.Oxidations in Organic Chemistry; American Chemical Society:Washington D.C.1990).
But, seldom there are description elective oxidation of primary alcohols or secondary alcohol to become the method for corresponding aldehyde and ketone, great majority in them all are to use stoichiometric terminal oxygenant (terminal oxidant) usually, chromic oxide (Holum for example, J.R.J.Org.Chem.1961,26,4814-4816), dichromate (Lee, D.G; Spitzer, U.A J.Org.Chem.1970,35,3589-3590), manganese oxide (Highet, R.J.; Wildmax, W.C.J.Am.Chem.Soc.1955,77,4399-4401) and osmium or ruthenium as first-selected oxygenant (Murahashi, S.-I; Naota, T.J.Synth.Org.Chem.Jpn.1988,46,930-942).
Anelli and his colleague have reported the convenient method (J.Org.Chem., 1987,52,2559) of the pure and mild secondary alcohol of a kind of oxidation of primary.According to this method, oxidizing reaction is at the CH of pH 8.5-9.5
2CL
2Carry out in the aqueous buffer solution, use 2,2,6,6-tetramethyl piperidine-1-oxygen base (TEMPO) is as catalyzer, and KBr is a promotor.In this system, final oxygenant is NaOCl.Using clorox or any other hypohalite is each mol of alcohol generation oxidation in the reaction as the main drawback of oxidant stoichiometry, just has 1 mole of halide salt and generates.And, frequently use hypohalite to cause undesirable halogenated by-products to generate, therefore force oxidation products to be further purified.Also can in other document, find (Synthesis, 1996,1153-1174 based on a large amount of summaries based on the method for the oxidizing reaction of TEMPO; Topics in Catalysis 2004,27,49-66; Acc.Chem.Res.2002,35,774-781).
U.S.5,821,374 disclose at TEMPO catalyzed oxidation primary alconol to become in the reaction of aldehyde, use compound that N-chlorine such as N-chloro-4-toluol sulfonamide sodium salt for example replaces as oxygenant.The main drawback of this method is to use a large amount of solvent and toxic as the N-chlorine substituted aromatics of oxygenant.
In recent years, improve not only have selectivity but also eco-friendly be that oxygenant and transition metal salt are that people have made many effort aspect the catalyst system of promotor with air or oxygen as the method for oxidation of main oxygenant with based on stable nitroxyl radical.The most generally the promotor of Shi Yonging has (NH
4)
2Ce (NO
3)
6(Kim, S.S.; Jung, H.C.Synthesis 2003,14,2135-2137), CuBr
2-2,2 '-two pyridine complex (Gamez, P; Arends, I.W.C.E..; Reedijk, J.; Sheldon, R.A.Chem.Commun.2003,19,2414-2415), RuCl
2(PPh
3)
3(Inokuchi, T.; Nakagawa, K.; Torii, S.Tetrahedron Letters1995,36,3223-3226 and Dijksman, A.; Marino-Gonzalez, A.; Payeras, A.M.; Arends, I.W.C.E.; Sheldon, R.A.J.Am.Chem.Soc.2001,123,6826-6833), Mn (NO
3)
2-Co (NO
3)
2And Mn (NO
3)
2-Cu (NO
3)
2(Cecchetto, A.; Fontana, F.; Minisci, F.; Recupero, F.Tetrahedron Letters 2001,42,6651-6653), and the CuCl[bmim in ionic liquid] [PF
6] (Imtiaz, A.A; Gree, R.Organic Letters 2002,4,1507-1509).
Yet from the angle of economy and environmental protection, the above-mentioned method for oxidation of mentioning has a main drawback.They need mass expensive and/or deleterious transition metal complex, and, there are some also to need to use for example halide reagent such as methylene dichloride, make these methods be not suitable for plant-scale production.Recently, people such as Hu disclose with method (Liu, the R. based on catalyst system aerobic oxidation primary alconol and the secondary alcohol of TEMPO that do not use any transition metal as promotor; Liang, X.; Dong, C.; Hu, X.J.Am.Chem.Soc.2004,126,4112-4113).In the method, the author uses TEMPO (1mol%), and the mixture of SODIUMNITRATE (4-8mol%) and bromine (4mol%) is as the active catalytic system.Oxidizing reaction is carried out under temperature 80-100 ℃ and air pressure 4 crust.But this method only is applicable to reactive alcohols.If the use phenylcarbinol reacts Quantitative yield after 1-2 hour.If use inactive Fatty Alcohol(C12-C14 and C12-C18) (for example 1-octanol) or cycloalcohol (for example hexalin), air pressure need rise to 9 crust, and 3-4 hour reaction times of process just can reach conversion fully.Disadvantageously, this new method for oxidation also relies on methylene dichloride as solvent, and this is the major obstacle of this method in industrial application.And, as the simple substance bromine of promotor because its high-vapor-pressure, toxicity and serious corrodibility are difficult to operation on technical scale when using in the Standard Steel device.Other shortcoming of this method also has the concentration of substrate in employed solvent very low and detect the generation brominated by products.
Summary of the invention
Therefore one of purpose of the present invention provide a kind of under the condition of gentleness catalyzed oxidation alcohol become the method for corresponding aldehyde and ketone, this method uses oxygen-containing gas as " cleaning " oxygenant and environmental friendliness and easy-operating catalyst system, and selectivity is good, speed of reaction is fast, productive rate is high.
Another object of the present invention provides a kind of any transition-metal catalyst, the promotor of danger or method of halogenated solvent do not used, and can overcome the shortcoming of mentioning in above-mentioned oxidizing reaction.
Further purpose of the present invention provides and a kind ofly can be converted into plant-scale method for oxidation simply, safely.
Reach this purpose and other purpose by first embodiment of the present invention.This scheme comprises a kind of method that makes pure oxidation, comprising: in the presence of catalyst composition, with primary alconol or secondary alcohol and oxygen-containing gas reaction, obtain aldehydes or ketones thus, wherein catalyst composition comprises:
(i) stable nitroxyl radical derivative,
(ii) sources of nitrate,
(iii) bromide source, and
(iiii) carboxylic acid.
Description of drawings
Fig. 1 has shown the reaction times of oxidation 1-hexanol in liquid phase and the dependence of oxygen depletion (example I-IV).
Fig. 2 has shown the reaction times of oxidation 1-hexanol in liquid phase and the dependence of oxygen depletion (embodiment XV-XVI).
Embodiment
The present inventor is surprisingly found out that, even do not have any transition-metal catalyst or any halogenated solvent, under the reaction conditions of low pressure and gentleness, in the presence of oxygen-containing gas, by using stable nitroxyl radical, sources of nitrate, bromide source and carboxylic acid as catalytic activation system also oxidation alcohol optionally.Described method has been represented a kind of effective catalysed oxidation processes of high flow rate, and scale operation that can be simple, safe also is converted into technical scale.
In content of the present invention, " stable nitroxyl radical " is meant at room temperature, stores stable basically nitroxyl radical of at least 1 week under oxygen exists.Preferably, " stable nitroxyl radical " nitroxyl radical on the arbitrary α of nitrogen-atoms adjacent-C atom, not replaced by hydrogen.And " stable nitroxyl radical " preferably after storing for 1 week in the presence of 25 ℃ of oxygen, compared with the content of primary nitroxyl radical, and at least also remaining has 90% nitroxyl radical.
The present invention relates to does not have the method that transition metal-catalyzed oxidation alcohol becomes corresponding aldehydes or ketones.In one embodiment, method of the present invention comprises that be 0.1-10 crust with oxygen-containing gas, a kind of stable nitroxyl radical or its derivative, sources of nitrate, bromide source and carboxylic acid with general formula (II) structure with general formula (I) structure at oxygen partial pressure with alcohol, reacts under temperature 0-100 ℃ the condition.Oxygen partial pressure is included in all values and the subvalue in this numerical range, especially comprises 0.5,1,1.5,2,2.5,3,3.5,4,4.5,5,5.5,6,6.5,7,7.5,8,8.5,9 and 9.5 crust.This temperature comprises all value and subvalues in this scope, especially comprises 5,10,15,20,25,30,35,40,45,50,55,60,65,70,75,80,85,90 and 95 ℃.
In formula (I) with (II), R
1, R
2, R
3, R
4, R
5And R
6Represent (C simultaneously or separately
1-C
10)-alkyl, (C
1-C
10)-thiazolinyl, (C
1-C
10)-alkoxyl group, (C
6-C
18)-aryl, (C
7-C
19)-aralkyl, (C
6-C
18)-aryl-(C
1-C
8)-alkyl or (C
3-C
18)-heteroaryl;
R
5And R
6Can pass through (a C
1-C
4)-alkyl chain combines, and it can be saturated or unsaturated, and is unsubstituted or by R
1, C
1-C
8-amido, halogen, oxygen, hydroxyl, amino, alkylamino, dialkyl amido, the one or more replacements in virtue amino, ammonia diaryl base, alkyl carboxyl, aryl carboxyl, alkyl-carbonyl-amino or the aryl-amino-carbonyl.In formula (II), Y
-Group is a negatively charged ion.
Formula (I) or compound (II) can be used alone, but also also mix together.
Method of the present invention can be used for primary alconol and secondary alcohol.According to their reactive behavior, primary alconol gets faster than secondary alcohol oxidation.In the presence of the identical secondary alcohol of molecular formula, primary alcohol functions can be by the selectivity oxidation.Yet the alcohol that uses in the inventive method preferably has primary alcohol functions.
The term that uses among the present invention " alcohol " comprises the organic compound with uncle or secondary hydroxyl.Term used herein " lower alcohol " is meant the alcohol with 1-10 carbon atom, and term used herein " higher alcohols " is meant the alcohol with 11 or more carbon atoms.The example of alcohol comprises for example methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, 2-methyl-1-butene alcohol, 3-methyl isophthalic acid-butanols, neopentyl alcohol, hexanol, 2-methyl-1-pentene alcohol, new hexanol, enanthol, octanol, 2-ethyl-1-hexanol, nonyl alcohol, decyl alcohol, lauryl alcohol, dodecanol, eicosanol.The example of unsubstituted alcohol comprises vinyl carbinol, crotyl alcohol, propargyl alcohol.The example of aromatic alcohol comprises phenylcarbinol, phenylethyl alcohol, phenylpropyl alcohol etc.Described alcohol can be the mixture of a kind of alcohol or alcohol.
Stable nitroxyl radical can be to have general formula (I) structure or it has the derivative of general formula (II) structure, wherein R
1, R
2, R
3, R
4, R
5And R
6Represent (C simultaneously or separately
1-C
10)-alkyl, (C
1-C
10)-thiazolinyl, (C
1-C
10)-alkoxyl group, (C
6-C
18)-aryl, (C
7-C
19)-aralkyl, (C
6-C
18)-aryl-(C
1-C
8)-alkyl or (C
3-C
18)-heteroaryl; R
5And R
6Can pass through (a C
1-C
4)-alkyl chain combines, and it can be saturated or unsaturated, and is unsubstituted or by R
1, C
1-C
8-amido, halogen, oxygen, hydroxyl, amino, alkylamino, dialkyl amido, the one or more replacements in virtue amino, ammonia diaryl base, alkyl carboxyl, aryl carboxyl, alkyl-carbonyl-amino or the aryl-amino-carbonyl.In formula (II), Y
-Group is a negatively charged ion.
Stable nitroxyl radical or their oxygen ammonium (oxoammonium) derivative example comprise 2,2,6,6-tetramethyl-piperazine is fixed-1-oxygen base (TEMPO) and 4-substitutive derivative thereof 4-methoxyl group-2,2 for example, and 6,6-tetramethyl piperidine-1-oxygen base (4-MeO-TEMPO), 4-oxo-2,2,6,6-tetramethyl piperidine-1-oxygen base (the 4-oxo-TEMPO), 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen base (the 4-hydroxyl-TEMPO), 4-benzophenone oxygen base-2,2,6,6-tetramethyl piperidine-1-oxygen base (BnO-TEMPO), 4-acetylaminohydroxyphenylarsonic acid 2,2,6,6-tetramethyl piperidine-1-oxygen base, 4-acetylaminohydroxyphenylarsonic acid 2,2,6,6-tetramethyl piperidine-1-oxygen base (AA-TEMPO), 4-amino-2,2,6,6-tetramethyl piperidine-1-oxygen base, N, N-dimethylamino-2,2,6,6-tetramethyl piperidine-1-oxygen base (NNDMA-TEMPO), 3,6-dihydro-2,2,6,6-tetramethyl--1 (2H)-pyridine-oxygen base (DH-TEMPO), and two (2,2,6,6-tetramethyl piperidine-1-oxygen-4-yl) sebacate.Described stable nitroxyl radical can use separately also can mix use.
Formula (I) or (II) tetramethyl piperidine of structure-N-oxygen base or its mixture also can be bigger macromole substituting group, oligomeric or or even paradigmatic structure.An example of low poly structure is as follows:
Also can use stable nitroxyl radical or its oxygen ammonium derivative of " heterogeneous " form.This shows that nitroxyl radical or its oxygen ammonium derivative are to load on, for example on the solid carrier.Described solid carrier can be an inorganic carrier, aluminum oxide for example, silicon-dioxide, titanium oxide; Or zirconium white; Or polymkeric substance; Matrix material; Or carbon material.
Stable nitroxyl radical has no particular limits with respect to the ratio of pure substrate.Consider economy and ecological factor, preferably this ratio is low as much as possible.Based on the amount of described alcohol, can use the stable nitroxyl radical derivative of about 0.001-10mol%.Preferably, with respect to the amount of substrate alcohol, the catalytic amount of nitroxyl radical is 0.01-2mol%, most preferably 0.5-1mol%.The amount of stable nitroxyl radical is included in all values and the subvalue in this numerical range, especially comprises 0.005,0.01,0.05,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2,2.5,3,3.5,4,4.5,5,5.5,6,6.5,7,7.5,8,8.5,9, and 9.5mol%.
Described sources of nitrate can be nitric acid, ammonium nitrate, alkyl ammonium nitrate or any alkali metal or alkaline earth metal nitrate, preferred magnesium nitrate.Advantages such as magnesium nitrate has water soluble, and is nontoxic, inexpensive, as to be easy to get.Sources of nitrate can be used separately, also can mix use.Because sources of nitrate is present in the reaction as promotor among the present invention, so only need catalytic amount to get final product.Preferably, with respect to the amount of substrate alcohol, the amount of sources of nitrate can be 0.01-10mol%, more preferably 0.1-2mol%, most preferably 0.5-1mol%.The anionic amount of nitric acid is included in all values and the subvalue in this numerical range, especially comprises 0,0.5,0.1,0.5,1,1.5,2,2.5,3,3.5,4,4.5,5,5.5,6,6.5,7,7.5,8,8.5,9 and 9.5mol%.
Bromide source can be the material that any N-bromine replaces, for example N-bromine succinimide, the adjacent dicarboximide of N-bromobenzene, Tetrabutyl amonium bromide or inorganic salt NH for example
4Br or any other alkali metal bromide or alkaline earth metal bromide, preferred N-bromine succinimide.Bromide source can be used alone, but also also mix together.N-bromine succinimide have be easy to get, advantage such as non-corrosiveness, nontoxic and easy processing.Because bromide source is present in the reaction as promotor among the present invention, so only need catalytic amount to get final product.Preferably, with respect to the amount of substrate alcohol, the amount of bromide source can be 0.01-10mol%, more preferably 0.1-2mol%, most preferably 0.5-1mol%.The amount of bromide source is included in all values and the subvalue in this numerical range, especially comprises 0,0.5,0.1,0.5,1,1.5,2,2.5,3,3.5,4,4.5,5,5.5,6,6.5,7,7.5,8,8.5,9 and 9.5mol%.
Carboxylic acid can be that acetate, propionic acid or any other can form the carboxylic acid of homogeneous reaction mixture.Preferably, this organic acid is an acetate.Carboxylic acid can use separately, also can be several mixing use or share with other solvent.Can use added solvent to come the suspension reaction thing in the method for the present invention, also can.With respect to the volume of the substrate alcohol that uses, can use the solvent to about 70 volume % greater than 0 volume %.The amount of solvent is included in all values and the subvalue in this numerical range, especially comprises 5,10,15,20,25,30,35,40,45,50,55,60 and 65 volume %.
If desired, preferred solvent is acetonitrile, tetrahydrofuran (THF), ethyl acetate, acetone, diethyl ether, methyl tertiary butyl ether etc., or the mixture of these solvents.Preferably, with respect to the amount of substrate alcohol, the amount of carboxylic acid is 0.1-200mol%, most preferably 10-50mol%.The amount of carboxylic acid is included in all values and the subvalue in this numerical range, especially comprises 0.5,1,5,10,20,40,60,80,100,120,140,160 and 180mol%.
For optimizing space-time yield, the inventive method is not preferably used added solvent.Preferably, carboxylic acid is both as additive, also as making reaction mixture keep the homogeneous solvent.But because economic cause, the usage quantity of carboxylic acid should be low as far as possible.
As oxygen-containing gas, can use purity oxygen, any mixture of oxygen and rare gas element or more preferably air.Oxygen partial pressure can be selected according to pure substrate, but there is no particular limitation.Yet along with the raising of oxygen partial pressure, speed of reaction can significantly improve.Oxygen partial pressure maintains the scope of 0.1-10 crust usually, preferred 0.2-5 crust, most preferably 0.5-1 crust.
Temperature of reaction in the inventive method is decided according to the reactive behavior of pure substrate, usually between 0 ℃-100 ℃, and preferred 20 ℃-80 ℃, most preferably 40 ℃-60 ℃.Temperature of reaction is included in all values and the subvalue in this scope, especially comprises 10,20,30,40,50,60,70,80 and 90 ℃.
Technology of the present invention can be intermittently, semi-batch or carry out continuously.And, do not limit concrete type of reactor or device.Therefore, can use agitator tank reactor, tubular reactor, cascade reaction, the combination of microreactor or any described reactor.
Oxidation products can be handled by any known method, for example, is separated and distills organic phase by adding water.According to demand, also can use other any chemical process to purity.
Can implement method of the present invention by different modes.For example, with the sources of nitrate of aequum (Mg (NO for example
3)
26H
2O), bromide source (for example N-bromine succinimide (NBS)) in stable nitroxyl radical (for example TEMPO or AA-TEMPO) and carboxylic acid (for example acetate) reaction flask of packing into, is linked on the multitube volume meter then.Stir catalyst solution and dissolve fully, with twice of oxygen or air purging up to solid ingredient.Stirred preferred 5 minutes 30 seconds-10 minutes.To target temperature, use oxygen or air that flask is forced into desirable value mixture heating up.Be initiation reaction, the alcohol of aequum is injected reaction flask with gastight syringe by the partition shifting coupling.Continuous monitoring oxygen-consumption, record in time.After reaction was finished, product solution was analyzed by GC or GC/MS, used decane to make interior mark.
Alcohol also can inject with the form of carboxylic acid solution.Oxygen-containing gas also can add after other all reactive components mix again.All components except stable nitroxyl radical derivative can also be mixed, introduce stable nitroxyl radical derivative then and begin reaction.Have multiple modes of operation, good stability is the remarkable advantage of present method.
After the reaction, available currently known methods is handled product.A kind of advantageous method is at first to add water or saturated salt solution is separated to reaction product, uses suitable solvent extraction water then.The suitable solvent that uses in the extraction step is selected from methylene dichloride, ethyl acetate, butylacetate, di-tert-butyl ether, methyl tertiary butyl ether; Or saturated hydrocarbon solvent, for example pentane or hexane.Wish the aldehydes or ketones obtain can from the organic phase that merges, use ordinary methods such as distillation, fractionation, crystallization to reclaim or the aldehyde of gained can by with sodium metabisulfite (Na
2S
2O
5) reaction be further purified.
Conclusion is to obtain a kind of method of effective and eco-friendly aerobic oxidation alcohol by improvement.According to this new technology, molecular oxygen or air can be used as the terminal oxygenant.Catalyst system is made up of stable nitroxyl radical, nitrate, bromide source and carboxylic acid.Even in the scope of high initial determining alcohol, also can obtain high speed of reaction and high aldehyde selectivity, these are that most known catalytic compositions are inaccessiable.Another advantage of the inventive method is that primary hydroxyl can be by the selectivity oxidation under the situation that secondary alcohol exists.It is not need to use in chlorinated solvent and the product aldehyde without any halogenated by-products that present method also has additional advantage.
The present invention roughly describes so far, unless special explanation is arranged, helps further to understand the present invention below by the specific embodiment explanation, and it only is to be used for explaining the present invention, rather than limitation of the present invention.
Embodiment
Example I
Example I-IV describes some TEMPO derivatives selectively oxidation 1-hexanols that the catalyst composition among the present invention uses activity to hexanal.Example I-IV is used for illustrating the relatively low situation of concentration at initial action solution substrate alcohol.Fig. 1 has shown the diagram signal of oxidizing reaction.
With 0.0913g4-MeO-TEMPO (0.48mmol), 0.124gMg (NO
3)
26H
2O (0.48mmol) and .0086 g N-bromine succinimide (0.048mmol) are dissolved in the Glacial acetic acid of 10mL, gained solution are joined in the reaction flask of 75mL.Sealed flask, and it is connected with gas release capacity unit.Catalyst solution is heated to 46 ℃ with oxygen blow at least three times under stirring then.After temperature reaches target value, drip 2mL1-hexanol (16mmol) with gastight syringe.With oxygen the pressure of flask is risen to 1 crust (15psi) then, stirring velocity is set to 1200rpm, and oxidizing reaction is along with the consumption of oxygen is carried out, continuous monitoring oxygen-consumption, record in time.After reaction was finished, aliquots containig was analyzed with GC, adopted decane to make interior mark.From the curve 1 calculating oxygen consumption rate of Fig. 1 is 0.263mmol O
2/ min, it is 99.4% that the GC of reaction soln analyzes the transformation efficiency that shows alcohol, is 93.1% to the selectivity of hexanal.
Example II
Example II is described as the curve 2 among activity-Fig. 1 of the TEMPO derivative of catalyst composition composition.
With 0.0766gTEMPO (0.48mmol), 0.124gMg (NO
3)
26H
2O (0.48mmol) and 0.013g N-bromine succinimide (0.072mmol) are dissolved in the Glacial acetic acid of 10mL, gained solution are joined in the reaction flask of 75mL.Sealed flask, and it is connected with gas release capacity unit.Catalyst solution is heated to 46 ℃ with oxygen blow at least three times under stirring then.After temperature reaches target value, drip 2mL1-hexanol (16mmol) with gastight syringe.With oxygen the pressure of flask is risen to 1 crust (15psi) then, stirring velocity is set to 1200rpm, and oxidizing reaction is along with the consumption of oxygen is carried out, continuous monitoring oxygen-consumption, record in time.The oxygen consumption rate of record is 0.332mmol O
2/ min reacts after 6 minutes GC and analyzes and show that the transformation efficiency of initial alcohol is 96.0%, is 96.2% to the selectivity of hexanal---Fig. 1 curve 2.
EXAMPLE III
Example II is described activity---Fig. 1 curve 3 as the 4-hydroxyl-TEMPO derivative of the composition of catalyst composition.
With 0.169g4-hydroxyl-TEMPO (0.96mmol), 0.311 gMg (NO
3)
26H
2O (1.2mmol) and 0.0086 g N-bromine succinimide (0.048mmol) are dissolved in the Glacial acetic acid of 10mL, gained solution are joined in the reaction flask of 75mL.Sealed flask, and it is connected with gas release capacity unit.Catalyst solution is heated to 46 ℃ with oxygen blow at least three times under stirring then.After temperature reaches target value, drip 2mL1-hexanol (16mmol) with gastight syringe.With oxygen the pressure of flask is risen to 1 crust (15psi) then, stirring velocity is set to 1200rpm, and oxidizing reaction is along with the consumption of oxygen is carried out, continuous monitoring oxygen-consumption, record in time.The oxygen consumption rate of record is 0.467mmol O
2/ min reacts after 45 minutes GC and analyzes and show that the transformation efficiency of initial alcohol is 98.0%, is 93.8% to the selection life of hexanal---Fig. 1 curve 3.
EXAMPLE IV
EXAMPLE IV is described activity---Fig. 1 curve 4 as 4-acetylaminohydroxyphenylarsonic acid TEMPO (AA-TEMPO) derivative of the composition of catalyst composition.
With 0.1394g AA-T ' EMPO (0.64mmol), 0.311 g Mg (NO
3)
26H
2O (1.2mmol) and 0.0086 g N-bromine succinimide (0.048mmol) are dissolved in the Glacial acetic acid of 10mL, gained solution are joined in the reaction flask of 75mL.Sealed flask, and it is connected with gas release capacity unit.Catalyst solution is heated to 46 ℃ with oxygen blow at least three times under stirring then.After temperature reaches target value, drip 2mL 1-hexanol (16mmol) with gastight syringe.With oxygen the pressure of flask is risen to 1 crust (15psi) then, stirring velocity is set to 1200rpm, and oxidizing reaction is along with the consumption of oxygen is carried out, continuous monitoring oxygen-consumption, record in time.The oxygen consumption rate of record is 0.768mmol O
2/ min reacts after 20 minutes GC and analyzes and show that the transformation efficiency of initial alcohol is 100.0%, is 94.78% to the selectivity of hexanal---Fig. 1 curve 4.
EXAMPLE V-XI is described in the initial action solution of high substrate determining alcohol, the application of the selective oxidation of different alcohol of the present invention.
EXAMPLE V
With 0.1045g AA-TEMPO (0.48mmol), 0.124 gMg (NO
3)
26H
2O (0.48mmol) and 0.098 g N-bromine succinimide (0.55mmol) are dissolved in the Glacial acetic acid of 4mL, and gained solution is joined in the reaction flask.Sealed flask, and it is connected with gas release capacity unit.Catalyst solution is heated to 46 ℃ with oxygen blow at least three times under stirring then.After temperature reaches target value, drip the 1-hexanol (64mmol) of aequum with gastight syringe.With oxygen the pressure of flask is risen to 1 crust (15psi) then, stirring velocity is set to 1200rpm.The oxygen consumption rate of record is 0.211mmol O
2/ min reacts after 280 minutes GC and analyzes and show that the transformation efficiency of initial alcohol is 98%, is 94% to the selectivity of hexanal.
Example VI
Example VI is described the oxidation of 2-hexanol.
With 0.1045 gAA-TEMPO (0.48mmol), 0.124 gMg (NO
3)
26H
2O (0.48mmol) and 0.098 g N-bromine succinimide (0.55mmol) are dissolved in the Glacial acetic acid of 4mL, and gained solution is joined in the reaction flask.The amount of 2-hexanol, temperature, pressure and stir speed (S.S.) are identical with EXAMPLE V.The oxygen consumption rate of record is 0.024mmol O
2/ min reacts after 600 minutes GC and analyzes and show that the transformation efficiency of initial alcohol is 34%, is 96% to the selectivity of hexanal.
Example VII A
Present embodiment is described the oxidation of 1-enanthol.
With 0.1045 gAA-TEMPO (0.48mmol), 0.124 gMg (NO
3)
26H
2O (0.48mmol) and 0.098 g N-bromine succinimide (0.55mmol) are dissolved in the Glacial acetic acid of 4mL, and gained solution is joined in the reaction flask.The amount of 1-enanthol, temperature, pressure and stir speed (S.S.) are identical with EXAMPLE V.The oxygen consumption rate of record is 0.181mmol O
2/ min reacts after 400 minutes GC and analyzes and show that the transformation efficiency of initial alcohol is 100%, is 99% to the selectivity of enanthaldehyde.
Example VII A I
Present embodiment is described the oxidation of 1-octanol.
With 0.1045 gAA-TEMPO (0.48mmol), 0.124 gMg (NO
3)
26H
2O (0.48mmol) and 0.098 g N-bromine succinimide (0.55mmol) are dissolved in the Glacial acetic acid of 4mL, and gained solution is joined in the reaction flask.The amount of 1-octanol, temperature, pressure and stir speed (S.S.) are identical with EXAMPLE V.The oxygen consumption rate of record is 0.168mmol O
2/ min reacts after 400 minutes GC and analyzes and show that the transformation efficiency of initial alcohol is 100%, is 99% to the selectivity of octanal.
Example I X
Present embodiment is described the oxidation of 1-dodecanol.
With 0.1045 gAA-TEMPO (0.48mmol), 0.124 g Mg (NO
3)
26H
2O (0.48mmol) and 0.098 g N-bromine succinimide (0.55mmol) are dissolved in the Glacial acetic acid of 4mL, and gained solution is joined in the reaction flask.The amount of 1-dodecanol, temperature, pressure and stir speed (S.S.) are identical with EXAMPLE V.The oxygen consumption rate of record is 0.122mmol O
2/ min reacts after 400 minutes GC and analyzes and show that the transformation efficiency of initial alcohol is 93%, is 89% to the selectivity of dodecanal.
Embodiment X
Present embodiment is described the oxidation of phenylcarbinol.
With 0.1045 gAA-TEMPO (0.48mmol), 0.124 gMg (NO
3)
26H
2O (0.48mmol) and 0.098 g N-bromine succinimide (0.55mmol) are dissolved in the Glacial acetic acid of 4mL, and gained solution is joined in the reaction flask.The amount of phenylcarbinol, temperature, pressure and stir speed (S.S.) are identical with EXAMPLE V.The oxygen consumption rate of record is 0.631mmol O
2/ min reacts after 60 minutes GC and analyzes and show that the transformation efficiency of initial alcohol is 100%, is 93% to the selectivity of phenyl aldehyde.
Embodiment XI
Present embodiment is described the oxidation of 1-phenylethyl alcohol.
With 0.1045 g AA-TEMPO (0.48mmol), 0.124 g Mg (NO
3)
26H
2O (0.48mmol) and 0.098 g N-bromine succinimide (0.55mmol) are dissolved in the Glacial acetic acid of 4mL, and gained solution is joined in the reaction flask.The amount of 1-phenylethyl alcohol, temperature, pressure and stir speed (S.S.) are identical with EXAMPLE V.The oxygen consumption rate of record is 0.248mmol O
2/ min reacts after 240 minutes GC and analyzes and show that the transformation efficiency of initial alcohol is 89%, is 100% to the selectivity of phenyl aldehyde.
Following examples XII-XVI has described the different preparation modes of catalyst composition, the introducing mode of 1-hexanol substrate and to the exposure of oxygen.
Implement XII
Present embodiment is similar to EXAMPLE V, and just catalyst composition heats O in argon gas
2After injection 1-hexanol, introduce.
With 0.1045 gAA-TEMPO (0.48mmol), 0.124 gMg (NO
3)
26H
2O (0.48mmol) and 0.098 g N-bromine succinimide (0.55mmol) are dissolved in the Glacial acetic acid of 4mL, and gained solution is joined in the reaction flask.Sealed flask, and be connected with gas release capacity unit.Catalyst solution is heated to 46 ℃ with argon purge at least three times under stirring then.After temperature reaches target value, replace argon gas with oxygen, balance dripped the 1-hexanol (64mmol) of 8mL after two minutes with gastight syringe.The oxygen consumption rate of record is 0.221mmol O
2/ min reacts 200 minutes afterreaction solution GC and analyzes and show that the transformation efficiency of initial alcohol is 95.6%, is 93.7% to the selectivity of hexanal.
Embodiment XIII
Present embodiment is similar to EXAMPLE V, and just magnesium nitrate, N-bromine succinimide, part acetic acid and 1-hexanol heat in argon gas, pressurizes with oxygen behind the acetum of injection AA-TEMPO.
With 0.124 gMg (NO
3)
26H
2O (0.48mmol) and 0.098 g N-bromine succinimide (0.55mmol) and 8mL 1-hexanol (64mmol) are dissolved in the Glacial acetic acid of 3mL, and gained solution is joined in the reaction flask.This solution argon purge is heated to 46 ℃ then.After temperature reaches target value, in reactor, add 0.1045 gAA-TEMPO (0.48mmol) that is dissolved in the 1mL acetic acid, behind the balance 2min, substitute argon gas, and the pressure of flask is risen to 1 crust (15psi) with oxygen.The oxygen consumption rate of record is 0.242mmol O
2/ min, the GC that reacts 200 minutes afterreaction solution analyzes and shows that the transformation efficiency of initial alcohol is 97.5%, is 92.6% to the selectivity of hexanal.
Embodiment XIV
Present embodiment is similar to EXAMPLE V, and just magnesium nitrate, N-bromine succinimide, part acetic acid and 1-hexanol heat in argon gas, behind the injection AA-TEMPO solution, substitutes argon gas with oxygen.
With 0.124 gMg (NO
3)
26H-H
2O (0.48mmol) and 0.098 g N-bromine succinimide (0.55mmol) and 8mL 1-hexanol (64mmol) are dissolved in the Glacial acetic acid of 3mL, and gained solution is joined in the reaction flask.This solution argon purge is heated to 46 ℃ then.After temperature reaches target value, substitute argon gas with oxygen, then in reactor, add 0.1045 gAA-TEMPO (0.48mmol) with the 1mL acetate dissolution.The oxygen consumption rate of record is 0.256mmol O
2/ min, the GC that reacts 200 minutes afterreaction solution analyzes and shows that the transformation efficiency of initial alcohol is 96.4%, is 92.6% to the selectivity of hexanal.
Following embodiment XV-XVII is identical with EXAMPLE V, just uses N
2-O
2Air pressure rose to 5.17 crust (75psi) when mixed gas replaced oxygen.
Embodiment XV
N in the present embodiment
2/ O
2Than being 30: 45.
With 0.1045gAA-TEMPO (0.48mmol), 0.124 gMg (NO
3)
26H
2O (0.48mmol) and 0.098 g N-bromine succinimide (0.55mmol) are dissolved in the Glacial acetic acid of 4mL, and gained solution is joined in the reaction flask.Sealed flask, and be connected with gas release capacity unit.Catalyst solution is heated to 48 ℃ with oxygen blow at least three times under stirring then.After temperature reaches target value, with 1-hexanol (64mmol) the injection reaction vessel of gastight syringe with aequum.Use N then
2The pressure of flask is risen to 2.07 crust (30psi), is connected with the oxygen releasing device then and rises to 5.17 until pressure and cling to (75psi).The oxygen consumption rate of record is 0.260mmol O
2/ min, the GC that reacts 140 minutes afterreaction solution analyzes and shows that the transformation efficiency of initial alcohol is 95.3%, is 95.2% to the selectivity of hexanal.The oxygen-consumption curve of present embodiment is shown in Fig. 2 curve 1.
Embodiment XVI
N in the present embodiment
2/ O
2Than being 60: 15.
With 0.1045gAA-TEMPO (0.48mmol), 0.124 gMg (NO
3)
26H
2O (0.48mmol) and 0.098 g N-bromine succinimide (0.55mmol) are dissolved in the Glacial acetic acid of 4mL, and gained solution is joined in the reaction flask.Sealed flask, and be connected with gas release capacity unit.Catalyst solution is heated to 48 ℃ with oxygen blow at least three times under stirring then.After temperature reaches target value, with 1-hexanol (64mmol) the injection reaction vessel of gastight syringe with aequum.Use N then
2The pressure of flask is risen to 4.14 crust (60psi), is connected with the oxygen releasing device then and rises to 5.17 until pressure and cling to (75psi).The oxygen consumption rate of record is 0.170mmol O
2/ min, the GC that reacts 240 minutes afterreaction solution analyzes and shows that the transformation efficiency of initial alcohol is 96.7%, is 93.7% to the selectivity of hexanal.The oxygen-consumption curve of present embodiment is shown in Fig. 2 curve 2.
Following embodiment XVII-XVIII is identical with EXAMPLE V, and just reacting weight is 800mmol, N
2-O
2Gas mixture is 13.79 crust (200psi) and 6.9 crust (100psi).Oxidizing reaction is carried out in the Parr autoclave.
Embodiment XVII
With 1.31 gAA-TEMPO (6.0mmol), 1.55gMg (NO
3)
26H
2O (6.0mmol) and 1.23 g N-bromine succinimides (6.9mmol) are dissolved in the Glacial acetic acid of 50mL, and gained solution is joined in the stainless steel high-pressure reactor.Seal this reactor, and be connected with the gas release unit.Catalyst solution is heated to 46 ℃ with oxygen blow at least three times under stirring then.After temperature reaches target value, 100mL1-hexanol (800mmol) is injected reaction vessel with gastight syringe.At first use N then
2The pressure of flask is risen to 11.03 crust (160psi), is connected with the oxygen releasing device then and rises to 13.79 until pressure and cling to (200psi).The oxygen consumption rate of record is 2.72mmol O
2/ min, the GC that reacts 200 minutes afterreaction solution analyzes and shows that the transformation efficiency of initial alcohol is 98.0%, is 93.1% to the selectivity of hexanal.
Embodiment XVIII
With 1.31 gAA-TEMPO (6.0mmol), 1.55 gMg (NO
3)
26H
2O (6.0mmol) and 1.23 g N-bromine succinimides (6.9mmol) are dissolved in the Glacial acetic acid of 50mL, and gained solution is joined in the stainless steel high-pressure reactor.Seal this reactor, and be connected with gas release capacity unit.Catalyst solution is heated to 46 ℃ with oxygen blow at least three times under stirring then.After temperature reaches target value, 100mL1-hexanol (800mmol) is injected reaction vessel with gastight syringe.At first use N then
2The pressure of flask is risen to 5.52 crust (80 psi), is connected with the oxygen releasing device then and rises to 6.9 until pressure and cling to (100 pis).The oxygen consumption rate of record is 2.05mmol O
2/ min, the GC that reacts 300 minutes afterreaction solution analyzes and shows that the transformation efficiency of initial alcohol is 94.9%, is 94.4% to the selectivity of hexanal.
All the above-mentioned patents mentioned and public publication are introduced herein as a reference.
Various modifications and variations of the present invention all may be from the enlightenment of above-mentioned technology.Therefore the present invention is construed as in the protection domain of claim with other embodiment outside describing herein.
Claims (30)
1 ,-and the method for kind of oxidation alcohol, comprising:
In the presence of catalyst composition, with primary alconol or secondary alcohol and oxygen-containing gas reaction, obtain aldehydes or ketones thus, wherein this catalyst composition comprises:
(i) stable nitroxyl radical derivative,
(ii) sources of nitrate,
(iii) bromide source, and
(iiiii) carboxylic acid.
2, method as claimed in claim 1, wherein said stable nitroxyl radical derivative is represented by formula (I) or formula (II):
Wherein, R
1, R
2, R
3, R
4, R
5And R
6Represent (C simultaneously or separately
1-C
10)-alkyl, (C
1-C
10)-thiazolinyl, (C
1-C
10)-alkoxyl group, (C
6-C
18)-aryl, (C
7-C
19)-aralkyl, (C
6-C
18)-aryl-(C
1-C
8)-alkyl or (C
3-C
18)-heteroaryl;
R
5And R
6Can pass through (a C
1-C
4)-alkyl chain is combined in-rises, and it can be saturated or unsaturated, and is unsubstituted or by R
1, C
1-C
8-amido, halogen, oxygen, hydroxyl, amino, alkylamino, dialkyl amido, in virtue amino, ammonia diaryl base, alkyl carboxyl, aryl carboxyl, alkyl-carbonyl-amino or the aryl-amino-carbonyl-individual or a plurality of replacements, and
Y
-Be negatively charged ion.
3, the process of claim 1 wherein that described alcohol is selected from methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, 2-methyl-1-butene alcohol, 3-methyl isophthalic acid-butanols, neopentyl alcohol, hexanol, 2-methyl-1-pentene alcohol, new hexanol, enanthol, octanol, 2-ethyl-1-hexanol, nonyl alcohol, decyl alcohol, lauryl alcohol, dodecanol, eicosanol, unsaturated alcohol, aromatic alcohol and composition thereof.
4, the process of claim 1 wherein that described stable nitroxyl radical is selected from 2,2,6,6-tetramethyl piperidine-1-oxygen base, 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen base, 4-methoxyl group-2,2,6,6-tetramethyl piperidine-1-oxygen base, 4-oxo-2,2,6,6-tetramethyl piperidine-1-oxygen base, N, N-dimethylamino-2,2,6,6-tetramethyl piperidine-1-oxygen base, 4-amino-2,2,6,6-tetramethyl piperidine-1-oxygen base, 4-acetylaminohydroxyphenylarsonic acid 2,2,6,6-tetramethyl piperidine-1-oxygen base, 4-acetylaminohydroxyphenylarsonic acid 2,2,6,6-tetramethyl piperidine-1-oxygen base, 4-benzoyloxy-2,2,6,6-tetramethyl piperidine-1-oxygen base, 3,6-dihydro-2,2,6,6-tetramethyl--1 (2H)-pyridine-oxygen base, two (2,2,6,6-tetramethyl piperidine-1-oxygen-4-yl) sebacate and composition thereof.
5, the process of claim 1 wherein amount based on described alcohol, have the stable nitroxyl radical derivative of about 0.001-10mol%.
6, wherein based on the amount of described alcohol, there is the stable nitroxyl radical derivative of about 0.01-2mol% in the method for claim 5.
7, the process of claim 1 wherein that sources of nitrate is selected from base metal nitrate, alkine earth metal nitrate, ammonium nitrate, alkyl ammonium nitrate, nitric acid and composition thereof.
8, the process of claim 1 wherein that sources of nitrate is a magnesium nitrate.
9, the process of claim 1 wherein that the amount of sources of nitrate is about 0.01-10mol% based on the amount of described alcohol.
10, the process of claim 1 wherein that the amount of sources of nitrate is about 0.1-2mol% based on the amount of described alcohol.
11, the process of claim 1 wherein that bromide source is selected from N-bromine succinimide, the adjacent dicarboximide of N-bromobenzene, Tetrabutyl amonium bromide, NH
4Br, alkali metal bromide, alkaline earth metal bromide and composition thereof.
12, the process of claim 1 wherein that bromide source is a N-bromine succinimide.
13, the process of claim 1 wherein amount based on described alcohol, have the bromide source of about 0.01-10mol%.
14, the process of claim 1 wherein amount based on described alcohol, have the bromide source of about 0.1-2mol%.
15, the process of claim 1 wherein that oxygen-containing gas is selected from i) purity oxygen, ii) air, the iii) mixture and iv) their mixture of oxygen and rare gas element.
16, the process of claim 1 wherein that carboxylic acid is carboxylic acid of acetate, propionic acid, formation homogeneous reaction mixture and composition thereof.
17, the process of claim 1 wherein that described carboxylic acid is an acetate.
18, the process of claim 1 wherein this method in alcoholic solution at least-kind of solvent in the presence of the reaction, described solvent is selected from acetonitrile, tetrahydrofuran (THF), ethyl acetate, acetone, diethyl ether, methyl tertiary butyl ether and composition thereof.
19, wherein based on the volume of described alcohol, there is the described solvent to about 70 volume % greater than 0 volume % in the method for claim 18.
20, the process of claim 1 wherein that described oxidizing reaction carries out in the presence of solvent-free.
21, the process of claim 1 wherein that temperature of reaction is 0-100 ℃.
22, the method for claim 21, wherein temperature of reaction is 20-80 ℃.
23, the process of claim 1 wherein that oxygen partial pressure is the 0.1-10 crust.
24, the process of claim 1 wherein that oxygen partial pressure is the 0.2-5 crust.
25, the method for claim 1, advance-go on foot to comprise use be selected from distillation, fractionation, crystallization, with sodium metabisulfite reaction and the method for purification that is used in combination these methods described aldehydes or ketones of purifying.
26, the process of claim 1 wherein that this method carries out in the presence of no transition metal.
27, the process of claim 1 wherein that described stable nitroxyl radical derivative is by the representative of formula (I) or formula (II):
Wherein, R
1, R
2, R
3, R
4, R
5And R
6Represent (C simultaneously or separately
1-C
10)-alkyl, (C
1-C
10)-thiazolinyl, (C
1-C
10)-alkoxyl group, (C
6-C
18)-aryl, (C
7-C
19)-aralkyl, (C
6-C
18)-aryl-(C
1-C
8)-alkyl or (C
3-C
18)-heteroaryl;
R
5And R
6Can pass through (a C
1-C
4)-alkyl chain combines, and it can be saturated or unsaturated, and is unsubstituted or by R
1, C
1-C
8-amido, halogen, oxygen, hydroxyl, amino, alkylamino, dialkyl amido, in virtue amino, ammonia diaryl base, alkyl carboxyl, aryl carboxyl, alkyl-carbonyl-amino or the aryl-amino-carbonyl-individual or a plurality of replacements;
Y
-Be negatively charged ion; And
The stable nitroxyl radical derivative of wherein at least a described formula (I) or formula (II) or its mixture are the substituting group of macromole, low poly structure or paradigmatic structure.
28, the process of claim 1 wherein that described stable nitroxyl radical derivative is by the representative of formula (I) or formula (II):
Wherein, R
1, R
2, R
3, R
4, R
5And R
6Represent (C simultaneously or separately
1-C
10)-alkyl, (C
1-C
10)-thiazolinyl, (C
1-C
10)-alkoxyl group, (C
6-C
18)-aryl, (C
7-C
19)-aralkyl, (C
6-C
18)-aryl-(C
1-C
8)-alkyl or (C
3-C
18)-heteroaryl;
R
5And R
6Can pass through (a C
1-C
4)-alkyl chain combines, and it can be saturated or unsaturated, and is unsubstituted or by R
1, C
1-C
8-amido, halogen, oxygen, hydroxyl, amino, alkylamino, dialkyl amido, in virtue amino, ammonia diaryl base, alkyl carboxyl, aryl carboxyl, alkyl-carbonyl-amino or the aryl-amino-carbonyl-individual or a plurality of replacements;
Y
-Be negatively charged ion; And
Stable nitroxyl radical derivative or its mixture of wherein at least a formula (I) or formula (II) are present on the solid carrier.
29, the process of claim 1 wherein described alcohol be selected from vinyl carbinol, crotyl alcohol, propargyl alcohol with and composition thereof.
30, the process of claim 1 wherein that described alcohol is selected from phenylcarbinol, phenylethyl alcohol, phenylpropyl alcohol and composition thereof.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565361B (en) * | 2008-04-25 | 2012-05-23 | 中国科学院大连化学物理研究所 | Method for preparing carbonyl compound by oxygen catalysis and alcohol oxidation |
| CN101565344B (en) * | 2008-04-25 | 2013-04-03 | 中国科学院大连化学物理研究所 | Method for preparing aldehyde or alkone by oxygen catalysis and alcohol oxidation under mild condition |
| JP2015502972A (en) * | 2011-12-22 | 2015-01-29 | ロケット・フルーレ | Improved method for selectively oxidizing 5-hydroxymethylfuraldehyde |
-
2006
- 2006-02-17 CN CN 200610073906 patent/CN101024602A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565361B (en) * | 2008-04-25 | 2012-05-23 | 中国科学院大连化学物理研究所 | Method for preparing carbonyl compound by oxygen catalysis and alcohol oxidation |
| CN101565344B (en) * | 2008-04-25 | 2013-04-03 | 中国科学院大连化学物理研究所 | Method for preparing aldehyde or alkone by oxygen catalysis and alcohol oxidation under mild condition |
| JP2015502972A (en) * | 2011-12-22 | 2015-01-29 | ロケット・フルーレ | Improved method for selectively oxidizing 5-hydroxymethylfuraldehyde |
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