Synthesis of novel 2,4,6,8,10-pentaaza[3.3.3]propellane derivatives

Lee

Bulletin Korean Chem Soc

et al. 2017

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The development of high energy materials (HEMs) with both high explosive performance and decreased sensitivity is a main theme of current research for energetic materials. Polynitroazoles are good building blocks for new energetic materials because of their stable chemical properties. Two new bis(dinitropyrazolyl)methanes as potential insensitive HEMs were prepared via either the coupling of dinitropyrazole or the nitration of bis(mononitropyrazolyl)methane. Their insensitive properties are also reported and compared to those of RDX (trinitrohexahydro‐s‐triazine) and HNIW (CL‐20, hexanitrohexaazaisowurtzitane).

Section: Introductionmentioning

confidence: 99%

Bis(dinitropyrazolyl)methanes as Stable High Energy Materials

Lee

Bulletin Korean Chem Soc

et al. 2017

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Applied Chemistry for Engineering

“…그러나 현재까지 실질적 으로 응용되고 있는 고에너지 물질은 강력한 폭발력을 가짐과 동시에 안정성도 가지고 있어야 하므로 그 종류가 한정되어 있다. 이에 최근에 는 밀도가 높고, 구조 대칭성이 있으며, 잠재에너지가 높아 폭발 성능의 개선이 기대되며, 구조적으로 안정한 다중고리 화합물인 adamantane, cubane, isowurtzitane, glycoluril 등을 기본 골격으로 한 고에너지 물질 인 trinitroadamantane (TNA), octanitrocubane (ONC), hexanitrohexaazai- † Corresponding Author: Seoul National University, Department of Chemical and Biological Engineering, 1 Gwanak-ro, Gwanak-gu, Seoul 151-742, Korea Tel: +82-2-880-8347 e-mail: ygkim@snu.ac.kr 4,6,8,10-pentanitro-3,7,9,11-tetraoxo-2,4,6,8,10-pentaaza[3.3.3]-propellane (PNTOPAP)을 구상하였고, 최근에 PNTOPAP의 주요 골격인 3,7,9,11-tetraoxo-2,4,6, 8,10-pentaaza[3.3.3]propellane (TOPAP) 2의 간편한 합성방법을 최초로 발표하였다( Figure 2) [3]. 이 결과를 바탕으로 본 연구에서는 분자 내 질소 에 치환기가 도입되지 않은 TOPAP 2의 구조에 간단한 N-니트로화 반응을 하여 고에너지 물질로의 전환이 쉬울 것이라 예상하였고 TOPAP 2의 니트 로화 반응에 대하여 처음으로 보고하려고 한다.…”

Section: )unclassified

“…1. 3,7,9,4,6,8,propellane (TOP AP) 2의 합성[3] Glycoluril diethyl ester의 합성은 보고된 문헌의 방법 [3,5] H NMR (acetone-d6) δ 9.86 (s, 2H) 4.38 (q, 4H, J = 7.1 Hz), 1.27 (t, 6H, J = 7.14 Hz); 13 C NMR (acetone-d6) δ 162. 6,147.4,76.0,66.1,14.1;Anal.…”

Section: )unclassified

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Nitration of 3,7,9,11-Tetraoxo-2,4,6,8,10-pentaaza[3.3.3]propellane

Shin¹,

Ha²,

Chung³

et al. 2014

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강력한 폭발 특성을 가지며 안정성이 높은 고에너지 물질을 개발하기 위하여 밀도가 높고 잠재에너지가 큰 다중고리 화합물을 이용한 고에너지 물질이 요구되고 있다. 하지만 분자 내 질소가 여러 개 치환된 다중고리 화합물의 경우 합 성의 어려움이 있어 많은 구조가 개발되지는 못하였다. 새로운 고에너지 물질 후보로 다중고리 화합물이며 분자 내 질소가 다섯개 치환된 pentanitropentaaza[3.3.3]propellane을 설계하였고, 이 중에 골격구조에 치환기가 도입되지 않은 3,7,9,11-tetraoxo-2,4,6,8,10-pentaaza[3.3.3]propellane (TOPAP) 2를 최근에 합성하였다. 본 연구에서는 TOPAP 2에 최초로 니트로화 반응을 진행하여 새로운 고에너지 물질을 합성하고자 하였다. 그 결과 NO2BF4와 무수 질산을 이용하여 지금 까지 보고되지 않은 2, 6-dinitro-3,7,9,11-tetraoxo-2,4,6,8,10-pentaaza[3.3.3]propellane 5C를 최대 82%의 수율로 처음 합성하 였다. 합성한 5C의 구조는 분광학적 분석결과를 이용하여 구조를 확인하였다.Until now, there has been much efforts for the development of polycyclic molecules as high energy materials because of their high density and potential energy. However, there were only a few reports on the development of highly N-substituted polycyclic compounds due to difficulties of the synthesis. We have designed pentaazapropellanes as new high energy materials and we have recently reported unsubstituted 3,7,9,11-tetraoxo-2, 4,6,8,10-pentaaza[3.3.3]propellane (TOPAP) 2 as a new skeleton for high energy materials. Herein, the nitration of TOPAP 2 was reported for the first time. Thus, 2,7,9,4,6,8,propellane (2,6-DNTOPAP) 5C, which is a new nitro derivative of TOPAP 2, was obtained up to 82% yield by the reaction of NO2BF4 and anhydrous HNO3. The structure of 5C was determined by spectroscopic analysis. ,4,6,8,10-pentanitro-3,7,9,11-tetraoxo-2,4,6,8,10-pentaaza[3.3.3]-propellane (PNTOPAP)을 구상하였고, 최근에 PNTOPAP의 주요 골격인 3,7,9,11-tetraoxo-2,4,6, 8,10-pentaaza[3.3.3]propellane (

“…11,12 Aza-propellanes can be used as synthons for natural products, [13][14][15] as ligands for transition-metal-mediated reactions and as building blocks for the cucurbiturils. 16 Although the strain present in propellane compounds may be the reason for their instability and makes their synthesis difficult, many derivatives of these compounds have been prepared. [17][18][19][20][21][22][23] Recently, multicomponent reactions (MCRs) have been used for the synthesis of heteropropellanes.…”

mentioning

confidence: 99%

Synthesis of Oxa-aza- and Bis-oxathiaaza[3.3.3]propellanes from Dicyanomethylene-1,3-indanedione and 2,5-Dithiobiureas

et al. 2015

An efficient route for the synthesis of oxa-aza-and bis-oxathiaaza[3.3.3]propellanes via reactions of symmetrical and unsymmetrical N 1 ,N 2-disubstituted hydrazine-1,2-dicarbothioamides (2,5dithiobiureas) with (1,3-dioxo-2,3-dihydro-1H-inden-2-ylidene)propanedinitrile in tetrahydrofuran is described. The rationale behind these conversions involving nucleophilic addition on the dicyanomethylene carbon atom is presented. The structures of these unusual products are confirmed by X-ray crystal structure analysis.