New Methods of Preparative Organic Chemistry IV. Cyclization of Dialdehydes with Nitromethane

Abstract

Condensation of nitromethane with suitable diadehydes in alkaline medium provides a general method of cyclization, in which the methyl group of the nitromethane is incorporated into the ring. This method leads to 5‐, 6‐, and 7‐membered rings and is equally applicable to aliphatic, aromatic, and sugar dialdehydes. For example, glyoxal is converted into 1,4‐dideoxy‐1,4‐dinitro‐neo‐inositol, and glutaraldehyde into trans‐2‐nitrocyclohexane‐1,3‐diol, while the corresponding cyclization of xylo‐trihydroxyglutaraldehyde leads to deoxy‐nitroinositols having the scyllo, myo‐1, and muco‐3 configurations.‐In the case of aromatic dialdehydes, the cyclization is accompanied by elimination of water. Thus, phthalaldehyde, naphthalene‐2,3‐dicarboxaldehyde, and homophthalaldehyde yield, respectively, 2‐nitroindenol, 2‐nitrobenzindenol, and 2‐nitronaphthalene. ‐Application of the method to sugar dialdehydes (aldehydic diglycol derivatives of monosaccharides formed by periodate oxidation) constitutes an excellent synthesis of 3‐amino sugars, since 3‐deoxy‐3‐nitropyranoses are formed smoothly on cyclization, and the corresponding 3‐amino derivatives are obtained by hydrogenation. Thus, the reaction sequence: periodate oxidation → cyclization with nitromethane → hydrogenation, leads in the case of α‐and β‐D‐pentosides to 3‐amino‐3‐deoxy‐D‐and‐L‐pentosides, respectively, with ribo, xylo, and arabino configurations. α‐D‐hexosides give derivatives with gluco, manno, and galacto configurations. 3‐Amino‐3,6‐dideoxyglucosides of the D‐and L‐series are obtained from 6‐deoxy‐D‐or‐L‐hexosides, respectively, and 3‐aminohexosans with gulo, ido, and altro configurations are obtained from 1,6‐anhydro sugars. Cyclization of the dialdehydes obtained from sedoheptulose and methyl 4,6‐O‐ethylidene‐α‐D‐glucoside by periodate oxidation, leads to 3‐nitro and, after hydrogenation, to 3‐amino derivatives of 3‐deoxyheptopyranoses.

Synthesis, Structure, and Explosive Properties of a New Trinitrate Derivative of an Unexpected Condensation Product of Nitromethane with Glyoxal

“…Condensation of aliphatic monoaldehydes with aliphatic nitrocompounds (particularly with nitromethane) is well‐known and commonly applied in the organic synthesis as a convenient route to many useful products 3, 4. Since the 1950s an analogical condensation of nitrocompounds with aliphatic dialdehydes has been known 4–7. The preparation of dinitrodiols of R CH(NO 2 )CH(OH)(CH 2 ) n CH(OH)CH(NO 2 ) R type via condensation of nitroalkanes with dialdehydes in alkaline solution was reported 5.…”

Nitroaldol Reaction in Aqueous Media: An Important Improvement of the Henry Reaction

“…Carbon−carbon bond formation is the essence of organic synthesis; the Henry reaction, an aldol-type reaction, represents one of the classical C−C bond-forming processes, and its variants have been used extensively in many important syntheses. − …”

“…The classical nitroaldol reaction is performed, as routine procedure, in presence of a base (Scheme ) in an organic solvent. Since basic reagents are also catalysts for the aldol condensation and for the Cannizzaro reaction when aldehydes are used as carbonyl sources, it is necessary to adopt experimental conditions to suppress these competitive reactions. − ,, To obtain better yields of 2-nitro alcohols a careful control of the basicity of the reaction medium is necessary, and long reaction times are demanded. Furthermore, the β-nitroalkanols formed may undergo base-catalyzed elimination of water to give nitroalkenes that readily polymerize.…”

Nitro- and Amino-polysaccharide Formation from Dextran

“…1) Later this reaction was widely adopted for dialdehyde derived from aliphatic, aromatic compounds and nucleosides. [2][3][4][5][6][7] As examples of this reaction applied to polysaccharides cellulose 6 ) and starch 2 ) are enumerated. However, there is no clear conclusion about the constitution of the reaction products.…”