Chirality of the trisubstituted nitrogen center - XRD, dynamic NMR, and DFT investigation of 1,2-dihydrobenzo[e][1,2,4]triazine derivatives

被引：4

作者：

Kaszynski, Piotr ^{[1
,2
,3
]}

Klys, Arkadiusz ^{[2
]}

Domagala, Slawomir ^{[4
]}

Wozniak, Krzysztof ^{[4
]}

机构：

[1] Polish Acad Sci, Ctr Mol & Macromol Studies, Sienkiewicza 112, PL-90363 Lodz, Poland

[2] Univ Lodz, Dept Chem, Tamka 12, PL-91403 Lodz, Poland

[3] Middle Tennessee State Univ, Dept Chem, Murfreesboro, TN 37132 USA

[4] Univ Warsaw, Dept Chem, Pasteura 5, PL-02089 Warsaw, Poland

来源：

TETRAHEDRON | 2017年 / 73卷 / 27-28期

关键词：

Chirality; Dynamic NMR; Heterocyclic chemistry; Single crystal XRD; DFT calculations; CONFORMATIONAL RATE-PROCESSES; ASYMMETRIC NITROGEN; CONFIGURATIONAL STABILITY; MOLECULAR-STRUCTURE; HINDERED INVERSION; GEMINAL SYSTEMS; N BOND; HYDRAZINES; RESOLUTION; BARRIERS;

D O I：

10.1016/j.tet.2017.05.032

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Molecular structures of two 1-aryl-2-benzyloxycarbonyl-1,2-dihydrobenzo[e][1,2,4]triazines 1 were established by single crystal XRD and compared to those of 4-benzyloxycarbonyl (2) and 4-benzyl (4) analogues. The structures revealed a highly pyramidalized asymmetric N(1) center stabilized by steric interactions in 1, but not in 2 and 3. Activation parameters for enantiomer interconversion were obtained by DNMR methods in C6D5Cl: Delta H-double dagger = 18.1(1) kcal mol(-1), Delta S-double dagger= -0.6(1) cal mol(-1) K-1 for Ar = Ph (1a) and Delta H-double dagger = 18.6(4) kcal mol(-1), Delta S-double dagger = 5.2(6) cal mol(-1) K-1 for Ar = 2-anisyl (1b). DFT computational investigation of the origin of the interconversion barrier on model compounds revealed steric destabilization of the inversion TS. (C) 2017 Elsevier Ltd. All rights reserved.

引用

页码：3823 / 3830

页数：8

共 50 条

[1] Utilization of cleavage of the [1]benzofuro[2,3-e][1,2,4]triazine ring for the synthesis of oxygen, nitrogen and sulfur derivatives of [1,2,4]triazine [1]
Styskala, J
Slouka, J
Wiedermannová, I
Bednár, P
JOURNAL OF HETEROCYCLIC CHEMISTRY, 2003, 40 (05) : 805 - 811
[2] Access to 1,4-Dihydrobenzo[e][1,2,4]triazin-4-yl Derivatives
Constantinides, Christos P.
Obijalska, Emilia
Kaszynski, Piotr
ORGANIC LETTERS, 2016, 18 (05) : 916 - 919
[3] Synthesis and anticancer evaluation of novel acenaphtho [1,2-e]1,2,4- triazine derivatives
Sedeh, Somayeh Adibi
Mohammadi, Mohammad Kazem
Fereidoonnezhad, Masood
Javid, Ali
EURASIAN CHEMICAL COMMUNICATIONS, 2019, 1 (05): : 451 - 458
[4] A DFT investigation of structure and spectroscopic properties of pyrazolo[4,3-e][1,2,4] triazine natural products
Galasso, V.
CHEMICAL PHYSICS LETTERS, 2009, 472 (4-6) : 237 - 242
[5] Dipyrido[1,2-b:3′,4′-e][1,2,4]triazine Scaffolds from Pentafluoropyridine
Ranjbar-Karimi, Reza
Darehkordi, Ali
Bahadornia, Fahimeh
Poorfreidoni, Alireza
JOURNAL OF HETEROCYCLIC CHEMISTRY, 2018, 55 (11) : 2516 - 2521
[6] Magnetostructural Investigation of Orthogonal 1-Aryl-3-Phenyl-1,4-Dihydrobenzo[e][1,2,4]triazin-4-yl Derivatives
Gardias, Anita
Kaszynski, Piotr
Obijalska, Emilia
Trzybinski, Damian
Domagala, Slawomir
Wozniak, Krzysztof
Szczytko, Jacek
CHEMISTRY-A EUROPEAN JOURNAL, 2018, 24 (06) : 1317 - 1329
[7] SYNTHESIS, CHARACTERIZATION AND ANTIMICROBIAL EVALUATION OF SOME NOVEL FUSED PYRIMIDO[1,2-b][1,2,4]TRIAZINE, TRIAZINO[2,3-a]QUINAZOLINE AND IMIDAZO[1,2-b][1,2,4]TRIAZINE DERIVATIVES
Mohamed, Khaled S.
El-Sayed, Elsherbiny H.
HETEROCYCLES, 2018, 96 (11) : 1897 - 1909
[8] Synthesis, Chemical Reactivity and Fungicidal Activity of Pyrido[1,2-b][1,2,4]triazine Derivatives
Ibrahim, Magdy A.
Abdel-Rahman, Reda M.
Abdel-Halim, Ali M.
Ibrahim, Salah S.
Allimony, Hassan A.
JOURNAL OF THE BRAZILIAN CHEMICAL SOCIETY, 2009, 20 (07) : 1275 - 1286
[9] Reaction of 3-hydrazinoacenaphtheno[1,2-e][1,2,4]triazine with functionalized carbonyl compounds
Hamid, HA
Shoukry, M
ElAshry, ESH
HETEROCYCLIC COMMUNICATIONS, 1997, 3 (01) : 79 - 89
[10] NITRILES IN HETEROCYCLIC SYNTHESIS - SYNTHESIS OF PYRAZOLO[1,5-A]PYRIMIDINE, PYRAZOLO[1,5-C][1,2,4]TRIAZINE AND PYRAZOLO[4,3-E][1,2,4]TRIAZINE DERIVATIVES
ELAGAMEY, AGA
MOHAMED, F
ELTAWEEL, AA
JOURNAL FUR PRAKTISCHE CHEMIE, 1991, 333 (02): : 333 - 338

← 1 2 3 4 5 →