Derivatives from P-Nitro Alcohols

Potential precursors to stereoselective INOC and ISOC reactions (e.g., 195 and 196, respectively) have been prepared via stereoselective conjugate additions of several allylic alcohols (e.g., 194,X = 0) and an allylic thiol (e.g., 194,X = S) to a chiral (E)-nitro alkene (e. g., 193) that was derived from (P)-2,3-isopropylidene... 

Ono, N., Kamimura, A. and Kaji, A. (1984) A new synthesis of aUyhc alcohols or their derivatives via reductive elimination from y-(phenylthio)-P-nitro alcohols with fributyltin hydride. Tetrahedron Letters, 25, 5319-5322. 

In like manner lodal (VI), on condensation with 6-nitro-3 4-methylene-dioxyphthalide (IV) yields nitro-a -adlumine (I R = NOj . O. CHa. O. at C and C replaced by 20Me), which crystallises from chloroform-methyl alcohol in orange, rectangular plates, m.p. 180-1° dec.), and on reduction yields the corresponding amino-derivative, bundles of minute needles, m.p. 218-9°. 

Pentryl, or 2,4,6-trinitrophenyInitraminoethyI nitrate, is another explosive which is derived from ethylene. It is a nitric ester, an aromatic nitro compound, and a nitroamine. The substance was described in 1925 by Moran54 who prepared it by the action of mixed acid on 2,4-dinitrophenylethanolamine (large orange-yellow crystals from alcohol, m.p. 92°) procured by the interaction of dinitrochlorobenzene with ethanolamine. von Herz later prepared pentryl by the nitration of 0-hydroxyethylaniline, a material which is more commonly called phenylethanolamine and is now available commercially in this country, and was granted... 

The X component of the substrate may be derived not only from amino acids but also from alcohols, ammonia, mercaptans, aniline, and p-nitro-phenol. A benzoyl or carbobenzoxy group has generally been employed as the R substituent of the synthetic substrate. Examination of the peptides produced by cleavage of various proteins has confirmed the rather indiscriminate specificity of this group of enzymes. 

Trinitroaniline, orange-red crystals from alcohol, m.p. 186 1 has but little interest as an explosive for the reason that other more powerful and more valuable explosives may be prepared from the same raw materials. It may be prepared by nitrating aniline in glacial acetic acid solution or by the use of mixed nitric-sulfuric acid in which no large excess of sulfuric acid is present. The presence of nitrous acid must be avoided, as this attacks the amino group, replaces it by hydroxyl, and results in the formation of picric acid. The nitration of aniline in the presence of a large amount of concentrated sulfuric acid yields m-nitroaniline and later the nitro compounds which are derived from it. 

The nitro compound is also an ester which can be derived from an alcohol and an acid derivative. In this case, it would be best to synthesize the ester from the acid chloride, p-chlorobenzoyl chloride, and the amino alcohol in the presence of base. The base will prevent protonation of the amino group by the subsequently formed HCl. The nitro group can be given its proper para orientation by directly nitrating toluene. Subsequent oxidation of the methyl group and treatment with thionyl chloride will yield the acid chloride. The alcohol portion of the ester can be derived from the reaction of diethylamine with ethylene oxide. Thus, the synthetic scheme would be... 

Various i-prolinamides, derived from chiral p-amino alcohols, are active hifunctional catalysts for nitro-Michael additions of ketones to p-nitrostyr-enes. In particular, catalyst 25e exhibits the highest catalytic performance working in polar aprotic solvents. 

Treatment of ll,ll-dichloro-l,6-methano[10]annulene with Bu"Li in an ether solvent yields C22H hydrocarbons of labile and complex nature/ Trapping experiments support the intermediacy of compounds ( )6) and (607) formed by the sequence of rearrangements (605)- (606)- (607). Reaction of cyclo-octa-2,4,6-trien-l-one with the anion of methyl 4-(dimethylphosphinyl)but-2-enoate gave (608) and (609) the predominant isomer (609) resulted from base-catalysed isomerization of (608) under the conditions of reaction. Low-temperature oxygenation of the enolate anion derived from the mixture of (608) and (609), followed by reduction with triethyl phosphite, gave a 1 1 mixture of 8-methoxycarbonylbicyclo[5,3,l]undeca-l,3,5,9-tetraen-8-exo-ol and -1,3,5,8-tetraen-lO-exo-ol. Pyrolysis of the p-nitro-benzoate esters of these alcohols effected their conversion into methyl 1,5-methano-[10]annulenecarboxylate (610). 

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