Oxidation of Amines to Aldehydes on Clay with Cu(II)-NO3/H2O2 under solvent-free microwave conditions
The reference for this article was found on Rhodium's (https://www.thevespiary.org/rhodium/Rhodium/chemistry/mw.clays.txt)
(https://www.thevespiary.org/rhodium/Rhodium/chemistry/mw.clays.txt) page:
Check out ref. 16 for the conversion of phenyl acetic acids to benzaldehydes or conversion of phenethylamine to phenylacetaldehyde
Already mentioned by Post 400186 (https://www.thevespiary.org/talk/index.php?topic=9528.msg40018600#msg40018600)
(Bubbleplate: "Some Research Starting Points", Methods Discourse):
General Oxidation Reaction-Claycop [Copper(II) nitrate/Clay]/H2O2: Tetrahedron Lett.,39, 1307 (1998)
Post 417460 (https://www.thevespiary.org/talk/index.php?topic=12241.msg41746000#msg41746000)
(Sunlight: "Oxydation of tryptamine", Novel Discourse):
Sunlight: Please post details of the procedure of oxydation of amines to ketones, it could be used to oxidize tryptamine into indol 3 acetaldehyde, then easily converted to DMT or other with NaBH4 reductive amination .
Here we go:
Tetrahedron Letters, 1998, 39, 1307-1308
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The experimental procedure involves a simple mixing of neat substances with claycop (0.46 g per mmol of the substrate) followed by the addition of 30% H2O2 (0.1 mL) in an open container. The mixture is placed in an alumina bath inside a microwave oven and is irridating for 15-90 sec in the solid state. Upon completion of the reaction, monitored on TLC (hexane:AcOEt, 10:1), the product is extracted into methylene chloride and solvent removed to afford pure products.
R1R2CHR3 --> R1R2C=O
Entry;R1;R2;R3;Mole Ratioa;Time (sec); Yield(%)
1;C6H5;H;COOH;1:0.8:1;60;83
2;C6H5;C6H5;COOH;1:0.8:1;90;82
3;C6H5;H;CN;1:1.6:2b;45;80
4;C6H5;H;NH2;1:0.8:1;30;76
5;C6H5;H;Br;1:0.8:1;30;75
6;p-NO2-C6H5;H;H;1:1.6:2;90;69
7;Triphenylphospine;;;1:0.8:1;15;85
8;Hydroquinone;;;1:0.8:1;30;71
a: copper(II) nitrate:hydrogen peroxide [0.46 gram of claycop contains 0.8 mmol of copper(II nitrate].
b: Using 0.8 mmol equivalents of the copper(II) nitrate results in the formation of phenylacetic acid.
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