Nonnitrogenous compounds

One of the few nonnitrogenous compounds to show spasmolytic activity is a rather simple chromone. Acylation of the phenolic ketone, 31, with the half ester-half acid chloride from oxalic... 

The discovery of a potent and selective K-opioid receptor agonist compound, salvinorin A (54), a hallucinogenic neoclerodane diterpenoid from Salvia divinorum Epling and Jativa, has created particular interest in recent years, since it is the first nonnitrogenous compound found to demonstrate this type of activity. 

Colchicum ritchii from southern Jordan afforded, on extraction of the bulbs and removal of the alkaloids, three nonnitrogenous compounds named colchicone (7), 3-demethylcolchicone (8), and comigerone (9) (12). Because of their close chemical relationship with colchicinoids they are discussed here and are listed in Table I. The structures of these ketones were elucidated mainly on the basis of H-NMR and MS analysis, as well... 

In addition to neutral compounds the bark of this plant yielded Ar-methyl-a-( — )-canadine, (+ )-laurifoline, chelerythrine, and two bases (C20H15O5N HC1, mp 245° and C15H1103N, mp 216°). A number of nonnitrogenous compounds were also isolated as well as two amides 169 (C16H1703N mp 149-151°), which proved to be tembamide (172), and 170 (C18H1903N mp 175-176°), which appears to be new (173). 

Salvinorin A was found to be the major psychoactive compound of this plant, with significantly higher potency than even the closely related salvinorin Although initial attempts to discover its molecular target were unsuccessful, it was later found to be a potent and selective tt-opioid receptor agonist it is this agonist activity on the tt-opioid receptor that is most probably the reason for salvinorin A s psychoactive effects. Salvinorin A is the first nonnitrogenous compound to be detected with this activity. 

Aldol reactions, usually followed by dehydration, of /3-dicarbonyl compounds with the aldehyde forms of substituted nonnitrogenous monosaccharides are also known. 2,3-0-Isopropylidene-D-glyceraldehyde condenses with ethyl acetoacetate in the presence of piperidine, giving the 1,3-dideoxy-3-(ethoxycarbonyl)-5,C-0-isopropyIidenehexulose (54), presumably as a mixture of diastereoisomers, and 1,3,4-trideoxy-3-(ethoxy-carbonyl)-5,6-0-isopropylidene-D-gfi /cero-hex-3-enulose (55). Reaction of... 

On comparing the reactions of 2-amino-2-deoxyaldoses and 1-amino-l-deoxyketoses with 8-dicarbonyl compounds, which yield pyrroles (Scheme A, X = NH, A -alkyl, or A -aryl), with the reactions of the nonnitrogenous aldoses and ketoses with the same compounds, which yield furan derivatives (Scheme A, X = 0), it may be noted that the changes of bonds are the same. It seems reasonable, therefore, to assume that both processes proceed through the same, or at least similar, mechanisms. From the experimental point of view, the main differences between these two reactions concern rates and catalysts. Aldoses and ketoses react very slowly in the absence of such acidic catalysts as zinc chloride and ferric chloride. The reactions of the amino sugars are much faster and are usually performed under neutral or slightly basic conditions. 

Cornforth and coworkers and Gottschalk have expressed the view that the reaction of 2-amino-2-deoxy-n-glucose with pyruvic acid (and with 2,4-pentanedione) begins with the formation of a Schiff base [such as (85)], followed by an intramolecular aldol reaction to compounds (86). This interpretation cannot be extended to the reactions of nonnitrogenous sugars, and can only be applied in a modified way to the iV-alkylamino and M-arylamino sugars. Such compounds as (87) or (88) could be the... 

Amino-2-deoxyaldohexoses, 1-amino-l-deoxyketohexoses, and their V-alkyl and JV-aryl derivatives react with /3-dicarbonyl compounds, giving substituted (tetrahydroxybutyl)pyrroles. It is, most probably, a general reaction of 2-amino-2-deoxyaldoses and 1-amino-l-deoxyketoses which parallels the formation of (polyhydroxyalkyl)furans from nonnitrogenous monosaccharides. In the reactions with amino sugars in alkaline media, simpler pyrrole compounds lacking the tetrahydroxybutyl chain are also obtained. 

In connection with Scheme 1, the nonnitrogen-containing moiety of daphniteijsmanine (18) may be formed in vivo, as seen in Scheme 4. The direct precursor of 18 must take the stereochemistry as depicted in 25, because compound 22 has been recovered on acid treatment. 

Cationic The only cationic surfactant found in any quantity in the environment is ditallow dimethylammonium chloride, which is mainly the quaternary ammonium salt distearyldimethylammonium chloride. The organic chemistry and characterization of cationic surfactants has been reported and reviewed [149-153]. The different types of cationic surfactants are fatty acid amides, amidoamine, imidazohne, petroleum feed stock derived surfactants, nitrile-derived surfactants, aromatic and cychc surfactants, nonnitrogen containing compounds, polymeric cationic surfactants and amine oxides [152-157]. 

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