Methane, nitro syntheses with

D-glucuronic acid in, VIII, 251-275 Methane, nitro-, syntheses with, VI, 291-318 Methyl ethers. See Ethers, methyl. Molasses, cane, III, 113-128... 

The key intermediate in another total synthesis of secoquettamine (234), elaborated by Stevenson et al. (185), was 2-arylbenzofuran 241 prepared by a coupling reaction of the copper salt of 4-benzyloxyphenylacetylene with bromoisovanillin (Scheme 37). In the next step condensation with nitro-methane and reduction gave amine 242, which when N-methylated and debenzylated resulted in secoquettamine (234). 

The recent work of Fischer and collaborators on the reaction of nitro-methane with aldoses will make the synthesis of some hexitols much... 

The synthesis is of course very short.10 Three equivalents of methyl acrylate add to nitro-methane with catalytic (5%) DBU to give the adduct 37 and reduction leads to spontaneous cyclisation of one of the ester groups to give 35. The rest is as planned. 

Helferich reported that mercuric cyanide is sometimes superior to silver carbonate as base in the synthesis of glycosides and disaccharides. Thus the condensation of tetra-O-benzoylbromoglucose (1 equiv.) with benzyl alcohol (1 equiv.) in nitro-methane in the presence of mercuric cyanide (1 equiv.) gives tetra-O-benzoylbenzyl-/3-D-glucose in 90% yield. Zorbach used this general procedure, except that 1,2-dichloroethane was used as the solvent, in a successful synthesis of the cardiac-active... 

Benzylic Reactivity. 2,5-Dimethyl-3,4-dinitrothiophen has been condensed with aromatic aldehydes to give 3,4-dinitro-2,5-distyryl-thiophens. " An improved synthesis of 3-nitro-2-styryl-thiophens involves bromination of 3-methyl-2-nitrothiophen with A-bromosuccinimide, followed by a modified Wit-tig reaction. From 2,5-di(chloromethyl)thiophen, the phosphonate was prepared by the Arbusov reaction, which was used for the preparation of 2,5-distyryl-thiophens. Trichloromethyl(thienyl)carbinols have been converted into the corresponding fluoro-derivatives through the reaction with phenyl-tetrafluorophosphorane. The liquid-phase catalytic oxidation of phenyl-(2-thienyl)methane in acetic acid in the presence of cobalt(ll) acetate and sodium bromide has been investigated. ... 

Sasha pointed to one bottle filled with a mass of needle-like white crystals suspended in clear liquid. "What s that " he quizzed me. I peered at the label... C(N02)4. "Surely that s some kind of explosive " I answered. He looked pleased. "Tetra-nitro-methane. As a liquid it s not too bad -- the tri-nitro- is worse -- but once it gets cool enough to crystallize, I try not to touch the bottle again until spring." I got a brief glance at his latest project, a synthesis for DBT (N,N-dibutyl-tryptamine.) As both the dimethyl- and diethyl- tryptamines are so important, Sasha has decided to survey as many of the N,N-dialkyl-tryptamines as he can synthesize. So far, he is only up to the butyls. 

Nitroalkene Synthesis. Henry reaction of (phenylthio)nitro-methane with aldehydes fohowed by dehydration has been used to prepare (. -l-nitro-l-phenylthioalkenes. potassium 7eri-butoxide-catalyzed addition and dehydration via mesylation (eq 1), or direct condensation catalyzed by piperidinium acetate (eq 2), are the methods of choice. Henry reaction can be also carried out by reaction of the nitroalkene dianion with aldehydes. ... 

A new promising method for the synthesis of mixed biaryls consists in the reaction of the ethanolamine esters of diarylboronic acids with NBS in dichloro-methane/aqueous buffer at pH 9. In this way, 2- and 3-phenylthiophen, 2,2 -bi-thienyl, and 2-(2-thienyl)furan were obtained. The nitration of 2,3 -bithienyl has been studied. 2-Nitro-2 -amino-3,3 -bithienyl and 3-nitro-3 -amino-2,2 -bithienyl have been found to be stable. Carbonyl derivatives of 2-aryl-thiophens have been prepared, and reactivity constants for 2-aryl-thiophens determined. Some 2,5-bis(4 -n-alkyldiphenyl-4"-yl)thiophens, which are liquid crystals, have been prepared from the corresponding 1,4-diketones and P4S10. Various naphthyl-thiophens have been synthesized in order to study their anti-inflammatory and antibacterial properties. ... 

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