Alkylation of alkali metal salts of aliphatic polynitro compounds ? A general method for preparing different types of polynitro derivatives

Шевелев, С. А.; Erashko, V. I.; Fainzil'berg, A. A.

doi:10.1007/bf00920895

Cited by 2 publications

(3 citation statements)

References 10 publications

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“…24-27 Nitronic esters (with rare excep tion 28 ) are unstable and highly susceptible to decom position. [24][25][26] In its chemical properties, 2,4,6 trichloro 1,3,5 tri azine (cyanuric chloride (CC)) 17 is similar to acid chlo rides. The latter interact with polynitro compound salts to yield unstable mixed nitronic anhydrides.…”

Section: Resultsmentioning

confidence: 99%

“…[24][25][26] In N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sci ences, these works were initiated in 1953, for a long period of time being headed by S. S. Novikov. Trinitromethyl anion is ambident, so generally, its interaction with halogenated organic compounds (if occurs) may proceed giving two types of products, i.e., trinitromethyl deriva tives (C alkylation) and dinitromethanenitronic acid es ters (O alkylation).…”

Section: Resultsmentioning

confidence: 99%

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Trinitromethylation reactions of chloro-1,3,5-triazines

2009

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Reactions of chloro 1,3,5 triazines with trinitromethane salts were studied. Depending on conditions, trinitromethane salts used and special additives, six types of 2,4,6 trichloro 1,3,5 triazine trinitromethylation reactions were revealed, namely, bis trinitromethylation-nitro nyloxylation, bis trinitromethylation-amination, bis trinitromethylation-hydroxylation, tri nitromethylation-dialkoxylation, trinitromethylation-diaryloxylation, and trinitromethyl ation-alkoxylation-aryloxylation. The mechanisms of reactions are proposed.Polynitromethyl 1,3,5 triazines are of interest as ener getic materials as well as intermediates in synthesis of the latter 1 and bioactive compounds. 2,3 To date the known synthetic methods for polynitromethyl 1,3,5 triazines are based on the building of 1,3,5 triazine cycle from the moi eties carrying polynitromethyl group (through the cyclo trimerization of polynitro acetonitriles and imido esters 4-7 ) either on generation of trinitromethyl group in 1,3,5 tri azine derivatives (the nitration of methyl 1,3,5 triazines 8 and the destructive nitration of dicarboxymethyl deriva tives of 1,3,5 triazine 6,9 ). To synthesize bis and mono trinitromethyl 1,3,5 triazines with various substituents on the ring, the method has been proposed that is based on replacing trinitromethyl groups in trinitromethyl 1,3,5 triazines under the action of nucleophilic reagents. 10-15 As yet there are no literature data on the routes to tri nitromethyl 1,3,5 triazines involving nucleophilic re placement of chlorine atoms in chloro 1,3,5 triazines re acted with trinitromethane salts. In the comprehensive reviews on the chemistry of 1,3,5 triazines 16-19 and in the review papers on the synthesis of 1,3,5 triazine derivatives exploiting chloro 1,3,5 triazine reactions, 20-23 no men tion has been made of the chloro 1,3,5 triazine reactions with trinitromethane salts. This work attempts to general ize the results obtained while studying chloro 1,3,5 tri azine trinitromethylation with trinitromethane salts (the results mostly belong to 1980´s-90´s but could not be reported earlier). Results and DiscussionTrinitromethylation is a bimolecular nucleophilic sub stitution reaction that was studied in detail over a range of aliphatic halogenated compounds. 24-26 In N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sci ences, these works were initiated in 1953, for a long period of time being headed by S. S. Novikov. Trinitromethyl anion is ambident, so generally, its interaction with halogenated organic compounds (if occurs) may proceed giving two types of products, i.e., trinitromethyl deriva tives (C alkylation) and dinitromethanenitronic acid es ters (O alkylation). 24-27 Nitronic esters (with rare excep tion 28 ) are unstable and highly susceptible to decom position. 24-26In its chemical properties, 2,4,6 trichloro 1,3,5 tri azine (cyanuric chloride (CC)) 17 is similar to acid chlo rides. The latter interact with polynitro compound salts to yield unstable mixed nitronic anhydrides. 29,30 This is ex actly...

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Trinitromethylation reactions of chloro-1,3,5-triazines

2009

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“…The starting salts 1a-d, 16 as well as the authentic samples of products 2a,b, 17 3a-d, 18 4a,b, 19 and 5, 6 were synthesized according to known procedures. The reaction mixtures were analyzed by TLC (Silufol UV 254 plates) and 1 H, 13 C, and 14 N NMR spectroscopy on a Bruker AM 300 spectrometer with the working frequencies 300.13, 75.7, and 21.5 MHz, respectively (the reactions were carried out in an NMR tube in CD 3 CN).…”

Section: Methodsmentioning

confidence: 99%

Reaction of nitrosolic acid salts with dinitrogen tetraoxide

et al. 2009

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It is known that the reactions of salts of various α,α dinitromethyl compounds with N 2 O 4 in inert organic solvents afford the corresponding trinitromethyl deriva tives and/or nitrolic acids, furoxans, and nitriles. 1-13 The first step of this process is the nitrosation of the dinitro methyl anion leading to the α,α dinitro α nitrosomethyl intermediate, 2,5,6,8,12 which is transformed into this or another product depending on the reaction conditions. Literature data on the reaction of salts of α,α dinitroso methyl compounds (nitrosolic acid salts) with N 2 O 4 are missing, and only few reactions of nitrosolic acids are known.We found that the treatment of a suspension of alkylnitrosolic acid salt 1a,b with one equivalent of N 2 O 4 in acetonitrile or diethyl ether at -10 °С resulted in the smooth formation of the corresponding nitrolic acid 2a,b, which can be isolated in 80-85% yield (Scheme 1). Scheme 1 R = Me (a), Et (b). i. 1 equiv.; ii. > 2 equiv.

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Alkylation of alkali metal salts of aliphatic polynitro compounds ? A general method for preparing different types of polynitro derivatives

Cited by 2 publications

References 10 publications

Trinitromethylation reactions of chloro-1,3,5-triazines

Trinitromethylation reactions of chloro-1,3,5-triazines

Reaction of nitrosolic acid salts with dinitrogen tetraoxide

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