CN105566169B - A kind of method that nitrone is prepared by secondary amine - Google Patents
A kind of method that nitrone is prepared by secondary amine Download PDFInfo
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Abstract
The present invention relates to a kind of method that nitrone is prepared by secondary amine, 2 mmol secondary amine is added in reactor, the mL of water 4~5, the mmol of TBAB 0.02~0.03 is sequentially added, catalyst WO is added3‑x 0.02~0.08 mmol and 30%~50% hydrogenperoxide steam generator 3~6 mmol, stirs 2~6 h at 25~60 DEG C；Or 2 mmol secondary amine is added in reactor, the mL of polar solvent 3~5 is added, catalyst WO is added3‑x 0.02~0.08 mmol and 30%~50% hydrogenperoxide steam generator 3~6 mmol, stirs 2~6 h at 25~60 DEG C；Reacted mixed solution is diluted to 15~20 mL, extracted, concentration, column chromatography for separation collects product.Catalyst of the present invention is the WO that there is oxygen vacancies3‑xNanometer sheet, catalytic oxidation activity is high, extensively, reaction condition is simple, and reaction temperature is low for raw material sources of the present invention, nitrone high income, water makes whole reactions steps pollution-free as reaction dissolvent, environmental protection, into cheap, not only there is important industrial application value, and with important environment and social effect.
Description
Technical field
The invention belongs to chemosynthesis technical field, and in particular to a kind of method that nitrone is prepared by secondary amine.
Background technology
Nitrone is the organic intermediate that a class has important application, can be used for the synthesis of medicine and natural products.Prepare
The simple and easy method of nitrone is that secondary amine oxidation is obtained into corresponding nitrone, and the most frequently used oxidant is hydrogen peroxide, the most frequently used catalysis
Agent is such as：Such as sodium tungstate (Na2WO4)（Shun-Ichi Murahashi, Hitoshi Mitsui, Tatsuki Shiota,
Tomoyasu Tsuda, and Shoji Watanabe, J. Org. Chem. 1990,55,1736-1744.）, but use
Sodium tungstate makees catalyst, and not only its catalytic efficiency is not high, it is necessary to add large excess of hydrogen peroxide, and selectivity is also poor.More
Many catalyst system and catalyzings are found, such as the oxide CH of rare metal rhenium3ReO3（Sanny Vermaa, Subodh Kumara,
Efrat Shawatb, Gilbert Daniel Nessimb, Suman L. Jain, Journal of Molecular
Catalysis A: Chemical 402 (2015) 46–52）Or graphene oxide-loaded metal rhenium oxide
（Praveen K. Khatri, Shivani Choudhary, Raghuvir Singh, Suman L. Jain and Om
P. Khatri, Dalton Trans., 2014,43,8054-8061）.Some have metallic compound to be catalyzed this
Reaction such as organic Titanium complex（Massimiliano Forcato, Miriam Mba, William A. Nugent,
And Giulia Licini, Eur. J. Org. Chem. 2010,740-748）With organic metal platinum complex（Marco
Colladon, Alessandro Scarso and Giorgio Strukul, Green Chem., 2008,10,793-
798）.Except some metal salts, metal oxide and organo-metallic compound, some organocatalysis systems can also be used
To prepare nitrone compound, such as aminated compounds containing polyhydroxy can be catalyzed such reaction（Massimiliano
Forcato, William A. Nugentb and Giulia Licini, Tetrahedron Letters 44 (2003)
49–52）, Tritox and hydrogen peroxide collective effect can be for preparing nitrone（Fatemeh Nikbakht, Akbar
Heydari, Tetrahedron Letters 55 (2014) 2513-2516）.Above-mentioned technical proposal comes with some shortcomings,
Expensive rare metal such as rhenium, platinum etc. are used the need for having；And some method for preparing catalyst complex industrializations are difficult, such as
The complex of some organic metal titaniums or platinum；And the system of nitrone is prepared by organic compound and hydrogen peroxide collective effect, then need
Substantial amounts of organic compound is added, the atom of Atom economy is not met while also also resulting in certain pressure to environment.
Chinese patent CN1058702C discloses a kind of new method for preparing nitrone, especially proposes to prepare the substitution warps of N- mono-
The method of base amine, including oxidant and it is at least one be selected from carbon dioxide, the compound of carbonic acid nitrogen salt and carbonate is deposited
The step of the lower formation nitrone with secondary amine.But, the patent requires liquid CO to reaction2, severe reaction conditions are only suitable for specific
Secondary amine oxidation, application is narrow.
The content of the invention
To overcome drawbacks described above, it is an object of the invention to provide a kind of method that nitrone is prepared by secondary amine, raw material sources
Extensively, reaction condition is simple, nitrone high income.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of method that nitrone is prepared by secondary amine, secondary amine is in catalyst WO3-xWith nitre is generated in the presence of hydrogenperoxide steam generator
Ketone, its reaction expression is as follows：
,
Or,
Wherein, R1For hydrogen, aryl, alkyl or heterocycle containing 1-6 carbon atom, R2For aryl, containing 1-6 carbon atom
Alkyl or heterocycle, R3For the alkyl containing 2-6 carbon atom, R4For hydrogen, methyl, ethyl or halogen, n=0,1,2,3,4, B
Ring is simple hydrogen, the phenyl ring or substituted pyridine ring of substitution.
According to the above-mentioned method that nitrone is prepared by secondary amine, described catalyst WO3-xIt is the WO that there is oxygen vacancies3-xNanometer
Piece, its preparation method comprises the following steps：
A. 1~3 mmol Disodium tungstate (Na2WO4) dihydrate is dissolved in 10~25 mL water, stirs 5~20 min, be made into
Even transparent solution；
B. the mL of ethanol 5~13 is added into step a solution, 5~20 min are stirred；
C. the mL of the concentrated sulfuric acid 15~25 is added into step b solution, 5~20 min are stirred；
D. 0.1~0.6 g PEG20000 is added into step c solution, 5~20 min are stirred；
E. the reacted mixed solutions of step d are transferred in round-bottomed flask, 120~160 DEG C of 3~5 h of stirring are cooled to
Room temperature；
F. added in the mixture after step e is cooled down in 300~500 mL distilled water, collect sediment, spend successively
Ionized water and absolute ethyl alcohol washing, vacuum drying obtain the WO that there is oxygen vacancies3-xNanometer sheet.
According to the above-mentioned method that nitrone is prepared by secondary amine, described secondary amine is N- tert-butyl benzyl amines, 2- methyl-benzyl uncles
Butylamine, 3- methyl-benzyls tert-butylamine, 4- methyl-benzyls tert-butylamine, 2- luorobenzyls tert-butylamine, 3- luorobenzyls tert-butylamine, 4- luorobenzyls
Tert-butylamine, 2- nitrobenzyls tert-butylamine, 3- nitrobenzyls tert-butylamine, 4- nitrobenzyls tert-butylamine, diethylamine, di-n-propylamine, two fourths
Amine, diisopropylamine, dibenzyl amine, nafoxidine, tetrahydroquinoline, tetrahydroisoquinoline, morpholine or piperidines.
According to the above-mentioned method that nitrone is prepared by secondary amine, the hydrogen peroxide that described hydrogenperoxide steam generator is 30~50%
Solution.
According to the above-mentioned method that nitrone is prepared by secondary amine, including following reactions steps：
（1）2 mmol secondary amine is added in reactor, sequentially add the mL of water 4~5, TBAB 0.02~
0.03 mmol, adds catalyst WO3-x 0.02~0.08 mmol and 30%~50% hydrogenperoxide steam generator 3~6 mmol, 25
2~6 h are stirred at~60 DEG C, mixed solution is obtained；
（2）By step（1）Reacted mixed solution is diluted to 15~20 mL, and organic solvent extraction, concentration removing is molten
Agent, column chromatography for separation collects product.
According to the above-mentioned method that nitrone is prepared by secondary amine, including following reactions steps：
（1）2 mmol secondary amine is added in reactor, the mL of polar solvent 3~5 is added, catalyst WO is added3-x
0.02~0.08 mmol and 30%~50% hydrogenperoxide steam generator 3~6 mmol, stirs 2~6 h at 25~60 DEG C, is mixed
Close solution；
（2）By step（1）Reacted mixed solution is diluted to 15~20 mL, and organic solvent extraction, concentration removing is molten
Agent, column chromatography for separation collects product.
According to the above-mentioned method that nitrone is prepared by secondary amine, step（1）Described polar solvent be methanol, ethanol, acetonitrile,
Acetic acid or N, N-METHYLFORMAMIDE.
According to the above-mentioned method that nitrone is prepared by secondary amine, step（2）Described organic solvent be ethyl acetate, ether,
Methyl tertiary butyl ether(MTBE), dichloromethane or chloroform.
According to the above-mentioned method that nitrone is prepared by secondary amine, step（2）Described column chromatography for separation condition is 200~300
Purpose silicagel column, eluant, eluent is petroleum ether and ethyl acetate, and both volume ratios are 10:1~2:1.
The positive beneficial effect of the present invention：
1. there is the tungsten oxide WO of oxygen vacancies in the present invention3-xNanometer sheet is in acid condition using tungstic acid hydrate sodium as raw material
Appropriate additive is added in certain solvent, is directly synthesized with solvent heat or the step of direct-fired method one, the present invention
There is the tungsten oxide WO of oxygen vacancies3-xNanometer sheet, preparation method is extremely simple, and production cost is low, it is easy to operate, in microcosmic knot
Have that oxygen vacancies, pattern are homogeneous, size is small, specific surface area is big on structure, with high catalytic oxidation activity.
2. raw material sources of the present invention are extensively, reaction condition is simple, and reaction temperature is low, nitrone high income, and water reacts
Solvent makes whole reactions steps pollution-free, environmental protection, into cheap, not only with important industrial application value, and tool
There are important environment and social effect.
Embodiment
With reference to some embodiments, the present invention is further described.
Embodiment 1
A kind of method that nitrone is prepared by N- tert-butyl benzyl amines, its reaction expression formula is as follows：
Comprise the following steps：
（1）2 mmol N- tert-butyl benzyl amines are added in 25 mL round-bottomed flasks, the mL of acetonitrile 3 is added, catalysis is added
Agent WO3-x0.02 mmol, 30% hydrogenperoxide steam generator 5 mmol, 25 DEG C of 3 h of stirring, obtains mixed solution；
（2）By step（1）Obtained mixed solution, which adds water, to be released to 20 mL, and dichloromethane extraction, concentration removes solvent, post
Chromatography, the silicagel column of 200~300 mesh, eluant, eluent is petroleum ether and ethyl acetate, and both volume ratios are 2:1, obtain white
Color solid, yield 96%.1H NMR (400 MHz; CDCl3, δ): 8.39-8.21 (2 H, m), 7.57 (1 H, s),
7.40 (3 H, m), 1.61 (9 H, s)。
Described catalyst WO3-xIt is the WO that there is oxygen vacancies3-xNanometer sheet, its preparation method comprises the following steps：
A. 1 mmol Disodium tungstate (Na2WO4) dihydrate is dissolved in 10 mL water, stirs 5 min, be made into the molten of homogeneous transparent
Liquid；
B. the mL of ethanol 5 is added into step a solution, 5 min are stirred；
C. the mL of the concentrated sulfuric acid 15 is added into step b solution, 5 min are stirred；
D. 0.1 g PEG20000 is added into step c solution, 5 min are stirred；
E. the reacted mixed solutions of step d are transferred in 100 mL round-bottomed flasks, 140 DEG C of 3 h of stirring are cooled to room
Temperature；
F. added in the mixture after step e is cooled down in 500 mL distilled water, collect sediment, deionization is used successively
Water and absolute ethyl alcohol washing, vacuum drying obtain the WO that there is oxygen vacancies3-xNanometer sheet.
Embodiment 2
A kind of method for preparing nitrone by 3- methyl-benzyl tert-butylamines, its reaction expression formula is as follows：
Comprise the following steps：
（1）2 mmol 3- methyl-benzyl tert-butylamines are added in 25 mL round-bottomed flasks, the mL of methanol 4.0 is added, plus
Enter catalyst WO3-x 0.04 mmol, 40% hydrogenperoxide steam generator 4 mmol, 25 DEG C of 2 h of stirring；
（2）Above-mentioned weak solution is added water and released to 16 mL, ethyl acetate extraction, concentration removes solvent, column chromatography for separation, 200
The silicagel column of~300 mesh, eluant, eluent is petroleum ether and ethyl acetate, and both volume ratios are 5:1, obtain white solid, yield
97%。1H NMR (400 MHz; CDCl3,δ): 8.33 (1 H, s), 7.91 (1 H, d, J= 7.8 Hz), 7.52
(1 H, s), 7.31 (1 H, t, J 7.7), 7.22 (1 H, d, J= 7.6 Hz), 2.38 (3 H, s), 1.62
(9 H, s)。
Described catalyst WO3-xIt is the WO that there is oxygen vacancies3-xNanometer sheet, its preparation method comprises the following steps：
A. 2 mmol Disodium tungstate (Na2WO4) dihydrate is dissolved in 21 mL water, stirs 10 min, be made into the molten of homogeneous transparent
Liquid；
B. the mL of ethanol 8 is added into step a solution, 10 min are stirred；
C. the mL of the concentrated sulfuric acid 16 is added into step b solution, 13 min are stirred；
D. 0.5 g PEG20000 is added into step c solution, 20 min are stirred；
E. the reacted mixed solutions of step d are transferred in round-bottomed flask, 120 DEG C of 5 h of stirring are cooled to room temperature；
F. added in the mixture after step e is cooled down in 400 mL distilled water, collect sediment, deionization is used successively
Water and absolute ethyl alcohol washing, vacuum drying obtain the WO that there is oxygen vacancies3-xNanometer sheet.
Embodiment 3
A kind of method that nitrone is prepared by nafoxidine, its reaction expression formula is as follows：
Comprise the following steps：
（1）2 mmol nafoxidine is added in 25 mL round-bottomed flasks, the mL of acetonitrile 5.0 is added, catalyst is added
WO3-x 0.06 mmol, 30% hydrogenperoxide steam generator 3 mmol, 30 DEG C of 2 h of stirring；
（2）Above-mentioned weak solution is added water and released to 15 mL, ethyl acetate extraction, concentration removes solvent, column chromatography for separation, 200
The silicagel column of~300 mesh, eluant, eluent is petroleum ether and ethyl acetate, and both volume ratios are 2:1, obtain white solid, yield
62%。1H NMR (400 MHz; CDCl3,δ): 6.88-6.92 (m, 1 H), 3.93-4.05 (m, 2 H), 2.72-
2.80 (m, 2 H), 2.20-2.34 (m, 2H),。
Described catalyst WO3-xIt is the WO that there is oxygen vacancies3-xNanometer sheet, its preparation method comprises the following steps：
A. 2 mmol Disodium tungstate (Na2WO4) dihydrate is dissolved in 23 mL water, stirs 10 min, be made into the molten of homogeneous transparent
Liquid；
B. the mL of ethanol 10 is added into step a solution, 10 min are stirred；
C. the mL of the concentrated sulfuric acid 16 is added into step b solution, 13 min are stirred；
D. 0.5 g PEG20000 is added into step c solution, 20 min are stirred；
E. the reacted mixed solutions of step d are transferred in round-bottomed flask, 130 DEG C of 4 h of stirring are cooled to room temperature；
F. added in the mixture after step e is cooled down in 300 mL distilled water, collect sediment, deionization is used successively
Water and absolute ethyl alcohol washing, vacuum drying obtain the WO that there is oxygen vacancies3-xNanometer sheet.
Embodiment 4
A kind of method that nitrone is prepared by tert-butyl benzyl amine, its reaction expression formula is as follows：
Comprise the following steps：
（1）2 mmol tert-butyl benzyl amine is added in 25 mL round-bottomed flasks, the mL of water 4 is added, tetrabutyl bromine is added
Change the mmol of ammonium 0.02, add catalyst WO3-x 0.02 mmol, 30% hydrogenperoxide steam generator 5 mmol, 25 DEG C of 5 h of stirring,
Obtain mixed solution；
（2）By step（1）Obtained mixed solution, which adds water, to be released to 15 mL, and ether extraction, concentration removes solvent, column chromatography
Separation, the silica gel of 200~300 mesh, eluant, eluent is petroleum ether and ethyl acetate, and both volume ratios are 2:1, obtain white solid
Body, yield 84%.1H NMR (400 MHz; CDCl3, δ): 8.39-8.21 (2 H, m), 7.57 (1 H, s),
7.40 (3 H, m), 1.61 (9 H, s)。
Described catalyst WO3-xIt is the WO that there is oxygen vacancies3-xNanometer sheet, its preparation method comprises the following steps：
A. 1 mmol Disodium tungstate (Na2WO4) dihydrate is dissolved in 10 mL water, stirs 5 min, be made into the molten of homogeneous transparent
Liquid；
B. the mL of ethanol 5 is added into step a solution, 5 min are stirred；
C. the mL of the concentrated sulfuric acid 15 is added into step b solution, 5 min are stirred；
D. 0.1 g PEG20000 is added into step c solution, 5 min are stirred；
E. the reacted mixed solutions of step d are transferred in 100 mL round-bottomed flasks, 140 DEG C of 3 h of stirring are cooled to room
Temperature；
F. added in the mixture after step e is cooled down in 500 mL distilled water, collect sediment, deionization is used successively
Water and absolute ethyl alcohol washing, vacuum drying obtain the WO that there is oxygen vacancies3-xNanometer sheet.
Embodiment 5
A kind of method for preparing nitrone by 2- methyl-benzyl tert-butylamines, its reaction expression formula is as follows：
Comprise the following steps：
（1）2 mmol 2- methyl-benzyl tert-butylamines are added in 25 mL round-bottomed flasks, the mL of water 4.6 is added, added
The mmol of TBAB 0.025, adds catalyst WO3-x0.06 mmol, 30% hydrogenperoxide steam generator 4.5 mmol, 30
DEG C stirring 4 h, obtain mixed solution；
（2）By step（1）Obtained mixed solution, which adds water, to be released to 20 mL, and ethyl acetate extraction, concentration removes solvent, post
Chromatography, the silicagel column of 200~300 mesh, eluant, eluent is petroleum ether and ethyl acetate, and both volume ratios are 2:1, obtain white
Color solid, yield 83%.1H NMR (400 MHz; CDCl3, δ): 9.17 (1 H, dd, J= 5.5, 3.9), 7.74
(1 H, s), 7.30-7.25 (2 H, m), 7.23 – 7.17 (1 H, m), 2.39 (3 H, s), 1.62 (9 H,
s)。
Described catalyst WO3-xIt is the WO that there is oxygen vacancies3-xNanometer sheet, its preparation method comprises the following steps：
A. 2 mmol Disodium tungstate (Na2WO4) dihydrate is dissolved in 20 mL water, stirs 10 min, be made into the molten of homogeneous transparent
Liquid；
B. the mL of ethanol 10 is added into step a solution, 10 min are stirred；
C. the mL of the concentrated sulfuric acid 20 is added into step b solution, 10 min are stirred；
D. 0.3 g PEG20000 is added into step c solution, 10 min are stirred；
E. the reacted mixed solutions of step d are transferred in 100 mL round-bottomed flasks, 160 DEG C of 4 h of stirring are cooled to room
Temperature；
F. added in the mixture after step e is cooled down in 400 mL distilled water, collect sediment, deionization is used successively
Water and absolute ethyl alcohol washing, vacuum drying obtain the WO that there is oxygen vacancies3-xNanometer sheet.
Embodiment 6
A kind of method for preparing nitrone by 3- methyl-benzyl tert-butylamines, its reaction expression formula is as follows：
Comprise the following steps：
（1）2 mmol 3- methyl-benzyl tert-butylamines are added in 25 mL round-bottomed flasks, the mL of water 4.2 is added, added
The mmol of TBAB 0.03, adds catalyst WO3-x 0.04 mmol, 50% hydrogenperoxide steam generator 4 mmol, 60 DEG C
Stir 2 h；
（2）Above-mentioned weak solution is added water and released to 16 mL, ethyl acetate extraction, concentration removes solvent, column chromatography for separation, 200
The silicagel column of~300 mesh, eluant, eluent is petroleum ether and ethyl acetate, and both volume ratios are 2:1, obtain white solid, yield
82%。1H NMR (400 MHz; CDCl3,δ): 8.33 (1 H, s), 7.91 (1 H, d, J= 7.8 Hz), 7.52
(1 H, s), 7.31 (1 H, t, J 7.7), 7.22 (1 H, d, J= 7.6 Hz), 2.38 (3 H, s), 1.62
(9 H, s)。
Described catalyst WO3-xIt is the WO that there is oxygen vacancies3-xNanometer sheet, its preparation method comprises the following steps：
A. 2 mmol Disodium tungstate (Na2WO4) dihydrate is dissolved in 21 mL water, stirs 10 min, be made into the molten of homogeneous transparent
Liquid；
B. the mL of ethanol 8 is added into step a solution, 10 min are stirred；
C. the mL of the concentrated sulfuric acid 16 is added into step b solution, 13 min are stirred；
D. 0.5 g PEG20000 is added into step c solution, 20 min are stirred；
E. the reacted mixed solutions of step d are transferred in round-bottomed flask, 120 DEG C of 5 h of stirring are cooled to room temperature；
F. added in the mixture after step e is cooled down in 300 mL distilled water, collect sediment, deionization is used successively
Water and absolute ethyl alcohol washing, vacuum drying obtain the WO that there is oxygen vacancies3-xNanometer sheet.
Embodiment 7
A kind of method for preparing nitrone by 4- methyl-benzyl tert-butylamines, its reaction expression formula is as follows：
Comprise the following steps：
（1）2 mmol 4- methyl-benzyl tert-butylamines are added in 25 mL round-bottomed flasks, the mL of water 5 is added, four are added
The mmol of butylammonium bromide 0.024, adds catalyst WO3-x0.08 mmol, 30% mmol of hydrogenperoxide steam generator 6,50 DEG C are stirred
Mix 3 h；
（2）Above-mentioned weak solution is added water and released to 20 mL, ethyl acetate extraction, concentration removes solvent, column chromatography for separation, 200
The silicagel column of~300 mesh, eluant, eluent is petroleum ether and ethyl acetate, and both volume ratios are 2:1, obtain white solid, yield
87%。1H NMR (400 MHz; CDCl3, δ): 8.19 (2 H, d, J = 8.3 Hz), 7.51 (1 H, s),
7.23 (2 H, d, J = 8.2 Hz), 2.38 (3 H, s), 1.61 (9 H, s)。
Described catalyst WO3-xIt is the WO that there is oxygen vacancies3-xNanometer sheet, its preparation method comprises the following steps：
A. 3 mmol Disodium tungstate (Na2WO4) dihydrate is dissolved in 25 mL water, stirs 20 min, be made into the molten of homogeneous transparent
Liquid；
B. the mL of ethanol 13 is added into step a solution, 20 min are stirred；
C. the mL of the concentrated sulfuric acid 25 is added into step b solution, 20 min are stirred；
D. 0.4 g PEG20000 is added into step c solution, 15 min are stirred；
E. the reacted mixed solutions of step d are transferred in round-bottomed flask, 150 DEG C of 5 h of stirring are cooled to room temperature；
F. added in the mixture after step e is cooled down in 500 mL distilled water, collect sediment, deionization is used successively
Water and absolute ethyl alcohol washing, vacuum drying obtain the WO that there is oxygen vacancies3-xNanometer sheet.
Embodiment 8
A kind of method that nitrone is prepared by piperidines, its reaction expression formula is as follows：
Comprise the following steps：
（1）2 mmol piperidines is added in 25 mL round-bottomed flasks, the mL of water 4 is added, TBAB is added
0.02 mmol, adds catalyst WO3-x0.08 mmol, 30% hydrogenperoxide steam generator 4 mmol, 25 DEG C of 6 h of stirring；
（2）Above-mentioned weak solution is added water and released to 18 mL, ethyl acetate extraction, concentration removes solvent, column chromatography for separation, 200
The silicagel column of~300 mesh, eluant, eluent is petroleum ether and ethyl acetate, and both volume ratios are 2:1, obtain white solid, yield
64%。1H NMR (400 MHz; CDCl3, δ): 7.28 (1 H,s), 3.78 (2H, m), 2.45 (2H, m),
1.97 (2H,m)1.66-1.81(2 H,m)。
Described catalyst WO3-xIt is the WO that there is oxygen vacancies3-xNanometer sheet, its preparation method comprises the following steps：
A. 3 mmol Disodium tungstate (Na2WO4) dihydrate is dissolved in 25 mL water, stirs 15 min, be made into the molten of homogeneous transparent
Liquid；
B. the mL of ethanol 10 is added into step a solution, 20 min are stirred；
C. the mL of the concentrated sulfuric acid 20 is added into step b solution, 15 min are stirred；
D. 0.6 g PEG20000 is added into step c solution, 20 min are stirred；
E. the reacted mixed solutions of step d are transferred in round-bottomed flask, 150 DEG C of 5 h of stirring are cooled to room temperature；
F. added in the mixture after step e is cooled down in 400 mL distilled water, collect sediment, deionization is used successively
Water and absolute ethyl alcohol washing, vacuum drying obtain the WO that there is oxygen vacancies3-xNanometer sheet.
Claims (7)
1. a kind of method that nitrone is prepared by secondary amine, it is characterised in that secondary amine is in catalyst WO3-xWith the work of hydrogenperoxide steam generator
With lower generation nitrone, its reaction expression is as follows：
Or
Wherein, R1For hydrogen, aryl, alkyl or heterocycle containing 1-6 carbon atom, R2Alkyl for aryl, containing 1-6 carbon atom
Or heterocycle, R3For the alkyl containing 2-6 carbon atom, R4For hydrogen, methyl, ethyl or halogen, n=0,1,2,3,4, B ring is simple
Hydrogen, substitution phenyl ring or substituted pyridine ring；
Described secondary amine is N- tert-butyl benzyl amines, 2- methyl-benzyls tert-butylamine, 3- methyl-benzyls tert-butylamine, the tertiary fourth of 4- methyl-benzyls
Amine, 2- luorobenzyls tert-butylamine, 3- luorobenzyls tert-butylamine, 4- luorobenzyls tert-butylamine, 2- nitrobenzyls tert-butylamine, 3- nitrobenzyl uncles
Butylamine, 4- nitrobenzyls tert-butylamine, diethylamine, di-n-propylamine, dibutyl amine, diisopropylamine, dibenzyl amine, nafoxidine, tetrahydrochysene quinoline
Quinoline, tetrahydroisoquinoline, morpholine or piperidines；
Described catalyst WO3-xIt is the WO that there is oxygen vacancies3-xNanometer sheet, its preparation method comprises the following steps：
A. 1~3mmol Disodium tungstate (Na2WO4) dihydrate is dissolved in 10~25mL water, stirs 5~20min, be made into homogeneous transparent
Solution；
B. 5~13mL of ethanol is added into step a solution, 5~20min is stirred；
C. 15~25mL of the concentrated sulfuric acid is added into step b solution, 5~20min is stirred；
D. 0.1~0.6g PEG20000 is added into step c solution, 5~20min is stirred；
E. the reacted mixed solutions of step d are transferred in round-bottomed flask, 120~160 DEG C of 3~5h of stirring are cooled to room temperature；
F. added in the mixture after step e is cooled down in 300~500mL distilled water, collect sediment, deionized water is used successively
With absolute ethyl alcohol washing, vacuum drying obtains the WO that there is oxygen vacancies3-xNanometer sheet.
2. the method according to claim 1 that nitrone is prepared by secondary amine, it is characterised in that described hydrogenperoxide steam generator is
30~50% hydrogenperoxide steam generator.
3. the method according to claim 1 that nitrone is prepared by secondary amine, it is characterised in that including following reactions steps：
(1) 2mmol secondary amine is added in reactor, sequentially add 4~5mL of water, TBAB 0.02~
0.03mmol, adds catalyst WO3-x0.02~0.08mmol and 30%~50% hydrogenperoxide steam generator 3~6mmol, 25~
2~6h is stirred at 60 DEG C, mixed solution is obtained；
(2) step (1) reacted mixed solution is diluted to 15~20mL, organic solvent extraction, concentration removes solvent, post layer
Analysis separation, collects product.
4. the method according to claim 1 that nitrone is prepared by secondary amine, it is characterised in that including following reactions steps：
(1) 2mmol secondary amine is added in reactor, adds 3~5mL of polar solvent, add catalyst WO3-x0.02~
0.08mmol and 30%~50% hydrogenperoxide steam generator 3~6mmol, stirs 2~6h at 25~60 DEG C, obtains mixed solution；
(2) step (1) reacted mixed solution is diluted to 15~20mL, organic solvent extraction, concentration removes solvent, post layer
Analysis separation, collects product.
5. the method according to claim 4 that nitrone is prepared by secondary amine, it is characterised in that the polarity described in step (1) is molten
Agent is methanol, ethanol, acetonitrile, acetic acid or N, N-METHYLFORMAMIDE.
6. the method that nitrone is prepared by secondary amine according to claim 3 or 4, it is characterised in that having described in step (2)
Machine solvent is ethyl acetate, ether, methyl tertiary butyl ether(MTBE), dichloromethane or chloroform.
7. the method that nitrone is prepared by secondary amine according to claim 3 or 4, it is characterised in that the post described in step (2)
Chromatography condition is the silicagel column of 200~300 mesh, and eluant, eluent is petroleum ether and ethyl acetate, and both volume ratios are 10:1
~2:1.
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