TY - JOUR
T1 - Synthesis of Nitro- and Acetyl Derivatives of 3,7,10-Trioxo-2,4,6,8,9,11-hexaaza[3.3.3]propellane
AU - Glukhacheva, Vera S.
AU - Il’yasov, Sergey G.
AU - Shestakova, Elena O.
AU - Zhukov, Egor E.
AU - Il’yasov, Dmitri S.
AU - Minakova, Anastasia A.
AU - Eltsov, Ilia V.
AU - Nefedov, Andrey A.
AU - Genaev, Alexander M.
N1 - Funding Information:
The work was performed under the auspices of the Ministry of Science and Higher Education of the Russian Federation (project No. 121061500029-7) using instruments provided by the Biysk Regional Center for Shared Use of Scientific Equipment of the SB RAS (IPCET SB RAS, Biysk).
Publisher Copyright:
© 2022 by the authors.
PY - 2022/12
Y1 - 2022/12
N2 - Here, we report the study results of the nitration of 3,7,10-trioxo-2,4,6,8,9,11-hexaaza[3.3.3]propellane (THAP) by different nitrating agents such as nitric acid, mixed nitric/sulfuric acids, nitric anhydride, and mixed concentrated nitric acid/acetic anhydride to furnish 3,7,10-trioxo-2-nitro-2,4,6,8,9,11-hexaaza[3.3.3]propellane and 3,7,10-trioxo-2,8-dinitro-2,4,6,8,9,11-hexaaza[3.3.3]propellane, whereas a lactam–lactim rearrangement was found to take place upon vigorous cooling to give 10-hydroxy-2,4,6,8,9,11-hexaazatricyclo[3.3.3.01,5]undec-9-ene-3,7-dione. The two competing reactions, lactam–lactim rearrangement, and nitration were found to take place. The acylation of 3,7,10-trioxo-2,4,6,8,9,11-hexaaza[3.3.3]propellane was examined and the formation conditions of 2,6-di- and 2,6,9-triacetyl-substituted and 3,7,10-trioxo-2,4,6,8,9,11-hexaacetyl-2,4,6,8,9,11-hexaaza[3.3.3]propellane were established. The acetyl derivatives were found to be instable in an acidic medium and to undergo deacylation. The obtained findings correlate well with the quantum-chemical calculations.
AB - Here, we report the study results of the nitration of 3,7,10-trioxo-2,4,6,8,9,11-hexaaza[3.3.3]propellane (THAP) by different nitrating agents such as nitric acid, mixed nitric/sulfuric acids, nitric anhydride, and mixed concentrated nitric acid/acetic anhydride to furnish 3,7,10-trioxo-2-nitro-2,4,6,8,9,11-hexaaza[3.3.3]propellane and 3,7,10-trioxo-2,8-dinitro-2,4,6,8,9,11-hexaaza[3.3.3]propellane, whereas a lactam–lactim rearrangement was found to take place upon vigorous cooling to give 10-hydroxy-2,4,6,8,9,11-hexaazatricyclo[3.3.3.01,5]undec-9-ene-3,7-dione. The two competing reactions, lactam–lactim rearrangement, and nitration were found to take place. The acylation of 3,7,10-trioxo-2,4,6,8,9,11-hexaaza[3.3.3]propellane was examined and the formation conditions of 2,6-di- and 2,6,9-triacetyl-substituted and 3,7,10-trioxo-2,4,6,8,9,11-hexaacetyl-2,4,6,8,9,11-hexaaza[3.3.3]propellane were established. The acetyl derivatives were found to be instable in an acidic medium and to undergo deacylation. The obtained findings correlate well with the quantum-chemical calculations.
KW - acetylation
KW - nitration
KW - propellane
KW - quantum-chemical predictions
UR - http://www.scopus.com/inward/record.url?scp=85143803186&partnerID=8YFLogxK
UR - https://www.mendeley.com/catalogue/ee6a2b9f-32d5-328d-a173-00cf93c9dff0/
U2 - 10.3390/ma15238320
DO - 10.3390/ma15238320
M3 - Article
C2 - 36499831
AN - SCOPUS:85143803186
VL - 15
JO - Materials
JF - Materials
SN - 1996-1944
IS - 23
M1 - 8320
ER -