Nitrocarbons. 4. Reaction of polynitrobenzenes with hydrogen halides. Formation of polynitrohalobenzenes

Abstract

Hexanitrobenzene and pentanitrobenzene in benzene solution react with hydrogen halides (HC1, HBr, HI, but not HF) at 25 °C to produce high yields of pentanitrohalobenzenes and 2,3,4,6-tetranitrohalobenzenes, respectively. Pentanitrofluorobenzene also reacts readily with HC1 to yield 3-chloro-2,4,5,6-tetranitrofluorobenzene, but the other pentanitrohalobenzenes are much less reactive. 1,2,3,5-and 1,2,4,5-tetranitrobenzenes react rapidly with concentrated hyrochloric or hydrobromic acids at reflux to form picryl halides and l-halo-2,4,5-trinitrobenzenes, respectively; pentanitrotoluene reacts very slowly under these conditions to form 3-halo-2,4,5,6-tetranitrotoluenes in lower yields. The scope and limitations of this regioselective reaction are defined, and comparison is made to related reactions. A mechanism is presented and discussed.Reactions between nitroaromatics and hydrogen halides(1) Part 3:

Synthesis and Energetic Properties of 4‐Diazo‐2,6‐dinitrophenol and 6‐Diazo‐3‐hydroxy‐2,4‐dinitrophenol

“…An overall synthetic protocol is displayed in Scheme . 4‐Fluoro‐3,5‐dinitroaniline ( 2 ) was synthesized as described by Nielsen et al15 Compound 3 was obtained by reaction of 2 with ammonia in ethanol. Any further attempts to synthesize a tri‐ or tetranitro derivative of 1,4‐diaminobenzene by various nitration conditions resulted in the formation of 4‐diazo‐2,6‐dinitrophenol ( 4 ).…”

Full-nitro-nitroamino cooperative action: Climbing the energy peak of benzenes with enhanced chemical stability

“…The full nitrification of benzene is extremely challenging, and the preparation of HNB requires extremely harsh reaction conditions, including the use of ultradry solvents and dangerous chemicals such as 90% H 2 O 2 or 30% SO 3 /H 2 SO 4 (21)(22)(23)(24)(25). However, because the acylation-activation-nitration method was used, the synthetic conditions for TNTNB were milder than those for HNB.…”

“…For instance, TNT (three nitro groups) is highly stable and is still widely used for national defense purposes (14)(15)(16). In contrast, HNB (six nitro groups) exhibits a higher energy than TNT but has poor chemical stability and decomposes rapidly in moist air, thereby limiting its practical application (21)(22)(23)(24)(25). With an increasing number of nitro groups, the number of hydrogen bond acceptors (-NO 2 ) increases, whereas the number of hydrogen bond donors (hydrogen atoms) of the benzene ring decreases, thus weakening the intramolecular hydrogen bonding interactions.…”

Synthesis and characterization of N‐methyl‐2,6‐dinitrodiphenylamine‐4‐diazonium salt and its diazoresin

“…The reaction mixture was heated carefully to reflux under stirring for 2 h and cooled to room temperature, then the 1,2‐dichloroethane layer was removed. The rest solution was poured into ice, and the precipitate was collected by filtration and washing with water to give II (43 g, yield 80%) as yellow‐orange powder crystals 15…”