Synthesis of 6-azabenzo[a]pyrene

Fukuhara, Kiyoshi; Miyata, Naoki; Kamiya, Shozo

doi:10.1016/s0040-4039(00)97459-8

Cited by 13 publications

(8 citation statements)

References 8 publications

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“…Our synthesis began with selective arylation of 11 via Suzuki–Miyaura cross-coupling to provide terphenyl 6 (Scheme ). Although the coupling of organometallic species with phenalenone ( 5 ) had been shown before, addition of 2 equiv of 5 was unprecedented . Additions of 5 to monometalated species generated sequentially only led to complex mixtures, so we deduced that dimetalation was essential.…”

Section: Resultsmentioning

confidence: 83%

A Concise Synthetic Strategy for Accessing Ambient Stable Bisphenalenyls toward Achieving Electroactive Open-Shell π-Conjugated Materials

2019

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Open-shell, π-conjugated molecules represent exciting next-generation materials due to their unique optoelectronic and magnetic properties and their potential to exploit unpaired spin densities to engineer exceptionally close π−π interactions. However, prior syntheses of ambient stable, openshell molecules required lengthy routes and displayed intermolecular spin−spin coupling with limited dimensionality. Here we report a general fragment-coupling strategy with phenalenone that enables the rapid construction of both biradicaloid (Ph 2 -s-IDPL, 1) and radical [10(OTf)] bisphenalenyls in ≤7 steps from commercial starting materials. Significantly, we have discovered an electronically stabilized π-radical cation [10(OTf)] that shows multiple intermolecular closer-than-vdW contacts (<3.4 Å) in its X-ray crystal structure. DFT simulations reveal that each of these close π−π interactions allows for intermolecular spin−spin coupling to occur and suggests that 10(OTf) achieves electrostatically enhanced intermolecular covalent-bonding interactions in two dimensions. Single crystal devices were fabricated from 10(OTf) and demonstrate average electrical conductivities of 1.31 × 10 −2 S/cm. Overall, these studies highlight the practical synthesis and device application of a new π-conjugated material, based on a design principle that promises to facilitate spin and charge transport.

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Section: Resultsmentioning

confidence: 83%

A Concise Synthetic Strategy for Accessing Ambient Stable Bisphenalenyls toward Achieving Electroactive Open-Shell π-Conjugated Materials

2019

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“…In the case of benzo[o]pyrene (BaP, 1) analogues, only a few studies were done on the toxicity of azabenzo[o]pyrenes (azaBaPs) themselves and none on the toxicity of the nitrated derivatives; this is in contrast to numerous reports on BaP carcinogenecis (7)(8)(9)(10). We have already reported the synthesis of 6-azaBaP (naphth-[2,1,8-mnojacridine, 2) and 6-azaBaP JV-oxide (3) having a nitrogen atom at the 6-position that is the highest electron density position in the BaP molecule (11). Recently, 2 was detected in airborne particulates from urban air.…”

Section: Introductionmentioning

confidence: 79%

“…The UV absorption spectra of nitrated azaBaPs (6-9) are illustrated in Figure 1. The similarity of the UV absorption spectra of 8 to that of 1-nitro-BaP (10) and the similarity of the spectra of 9 to that of 3-nitro-BaP (11) allowed tentative positional assignments of the nitro group to be made (12). Final assignments were made based on 1-D and 2-D (CO-SY) -NMR spectra (Table I).…”

Section: Resultsmentioning

confidence: 99%

1- and 3-Nitro-6-azabenzo[a]pyrenes and their N-oxides: highly mutagenic nitrated azaarenes

Fukuhara¹,

Hakura²,

Sera³

et al. 1992

Chem. Res. Toxicol.

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“…However, the direct synthesis of cyclic imines from the corresponding nitroketones by reductive cyclization would be more attractive. Such reductive cyclizations were reported using Ni (COD) 2 [11] or Zn in AcOH [12] and Pd/C [13] or PtO 2 [14] under hydrogen atmosphere. However these methods provided low yields or were restricted only to the highly conjugated aromatic system.…”

Section: Introductionmentioning

confidence: 85%

A New Convenient Method for the Synthesis of 2H‐1,4‐Benzoxazine Derivatives from Nitroketones via Intramolecular Reductive Cyclization.

et al. 2003

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Dedicated to Professor Herbert C. Brown on the occasion of his 90 th birthday.Potentially bioactive 2H-1,4-benzoxazine derivatives could be conveniently prepared in one step from the corresponding nitroketones using 10% palladium on carbon with triethylamine in the presence of hydrogen (Pd/C-TEA-H 2 ) system. Several other tertiary amines such as nicotine, pyridine, and quinoline also could be used, but TEA gave the best results.

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Synthesis of 6-azabenzo[a]pyrene

Cited by 13 publications

References 8 publications

A Concise Synthetic Strategy for Accessing Ambient Stable Bisphenalenyls toward Achieving Electroactive Open-Shell π-Conjugated Materials

A Concise Synthetic Strategy for Accessing Ambient Stable Bisphenalenyls toward Achieving Electroactive Open-Shell π-Conjugated Materials

1- and 3-Nitro-6-azabenzo[a]pyrenes and their N-oxides: highly mutagenic nitrated azaarenes

A New Convenient Method for the Synthesis of 2H‐1,4‐Benzoxazine Derivatives from Nitroketones via Intramolecular Reductive Cyclization.

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