ABSTRACT
A family of (alkylsilyl)pyrene-1-carboxamides exhibits similar mechanofluorochromic responses upon grinding. However, their spontaneous fluorescence recovery processes are distinct despite their similarity in chemical structures and crystal packings. Fluorescence spectroscopy, crystallography, and nanomechanical tests revealed that the chromic direction is dominated by the packing motif, while the fluorescence recovery is driven by the intermolecular interactions and the reversibility of deformation.
ABSTRACT
In this paper, we describe the lithiation of N-benzylpyrene-1-carboxamide with RLi-TMEDA. We found that the reaction outcome strongly depends on the electrophile used in the quenching step. The electrophile can be introduced at either the benzylic position or at the C-2 position in the pyrene nucleus. Furthermore, when H+ was used as the quencher, the product of the intramolecular carbolithiation of the pyrene K-region was formed. Dehydrogenation of the obtained compound with DDQ allowed the synthesis of a novel nitrogen polycyclic compound with an aza-benzo[c,d]pyrene (azaolympicene) skeleton. Attempts to extend the reaction scope to the amides substituted in the phenyl ring 8a and 8b gave an unexpected result. The reaction of both compounds with BuLi gave 1-valerylpyrene (9) in good yield. Photophysical properties, including absorption spectra, emission spectra and quantum yields of the emission of selected products, were studied and discussed.
Subject(s)
Amides , PyrenesABSTRACT
The reaction of 2-aryl-3-hydroxyisoindolin-1-ones with the s-BuLi·TMEDA system in THF at -78 °C, affording a series of diastereomeric 3-aminoindan-1-ones via a novel rearrangement of the isoindolinone scaffold, is reported. It is proposed that α-elimination of LiOH from the transient N,O-dilithiated hemiaminal carbenoids leads to the formation of singlet carbenes followed by their trapping via an intramolecular C-H insertion. An alternative explanation based on an intramolecular Mannich reaction seem much less probable. A mechanistic-type study that combines spectroscopic data of the products and calculation results, with a special focus on the diverse lithiated intermediates that are most likely to engage in the title process (particularly those with internal Li bonds), is presented. The MP2 approach, including the NPA and QTAIM data, provided insight into structures and properties of all these species. Two reaction routes A and B appeared to be possible for the postulated carbene mechanism. An unusual metamorphosis of the CCN atom triad, from a near sp 1-azaallene-type in more stable noncarbene Li enolates to a roughly sp2 type in their carbene keto tautomers, is recognized in one of these pathways (route B). Dominant forms of resonance structures for the aforementioned tautomeric systems that have seven-membered quasi rings stabilized by Li+ ions bridging the N and carbonyl O atoms are indicated. Large computational difficulties arising from a huge impact of internal Li+ complexation on conformational preferences and electronic properties of carbonyl group-bearing lithium derivatives are also discussed. The new γ-keto carbene species under study belong to a subclass of acyclic aminoarylcarbenes.
ABSTRACT
Sterically hindered N,2,7-tri- tert-butylpyrene-1-carboxamide treated with n-BuLi, i-BuLi, s-BuLi, and n-HexLi in THF in the presence of TMEDA and air afforded trans- N,2,7-tri- tert-butylpyrene-10-alkyl-9-hydroxy-9,10-dihydropyrene-1-carboxamides in 63-74% yield. Trifluoroacetic acid promoted dehydration of these compounds gave 10-alkyl derivatives of the starting amide in 79-89% yield. The minor products of this reaction were deamidated compounds, 4-alkyl-2,7-di- tert-butylpyrenes.
