Efficient Bromination of Naphthalene Dianhydride and Microwave-Assisted Synthesis of Core-Brominated Naphthalene Diimides

Thompson, Annelise C.; Grimm, Haley; McKnight, Keenan J.; Reczek, Joseph J.

doi:10.1080/00397911.2015.1004096

Cited by 6 publications

(9 citation statements)

References 13 publications

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“…Monomeric NDI-2 ( Figure 3) was synthesized by a second, but harsher, microwave-assisted SNAr (step b), dissolving pure NDI-15 in neat N 1 ,N 1 -dimethylpropane-1,3-diamine (150 °C, 200 psi, 200 W, 3 min, sealed reaction vessels), thus obtaining the target compound in almost quantitative yield [29]. On the other hand, to obtain NDI-18 (Figure 4), one of the precursor units of dimeric NDI compounds, we used a previously reported synthetic procedure [30], which required quite harsh conditions to provide the target product in good yield. Starting from synthetic 2,6-dibromo-1,4,5,8naphtalenetetracarboxylic bisanhydride (Di-Br-NDA) [31], four equivalents of 6-aminohexanoic acid On the other hand, to obtain NDI-18 (Figure 4), one of the precursor units of dimeric NDI compounds, we used a previously reported synthetic procedure [30], which required quite harsh conditions to provide the target product in good yield.…”

Section: Synthesis Of the Functionalized Monomeric And Dimeric Naphthmentioning

confidence: 99%

“…On the other hand, to obtain NDI-18 (Figure 4), one of the precursor units of dimeric NDI compounds, we used a previously reported synthetic procedure [30], which required quite harsh conditions to provide the target product in good yield. Starting from synthetic 2,6-dibromo-1,4,5,8naphtalenetetracarboxylic bisanhydride (Di-Br-NDA) [31], four equivalents of 6-aminohexanoic acid On the other hand, to obtain NDI-18 (Figure 4), one of the precursor units of dimeric NDI compounds, we used a previously reported synthetic procedure [30], which required quite harsh conditions to provide the target product in good yield. Starting from synthetic 2,6-dibromo-1,4,5,8-naphtalenetetracarboxylic bisanhydride (Di-Br-NDA) [31], four equivalents of 6-aminohexanoic acid were added in acetic acid, and the reaction was performed at 120 • C for 20 min, under microwave assistance.The product did not require a purification step after the work-up reaction.…”

Section: Synthesis Of the Functionalized Monomeric And Dimeric Naphthmentioning

confidence: 99%

See 1 more Smart Citation

Trifunctionalized Naphthalene Diimides and Dimeric Analogues as G-Quadruplex-Targeting Anticancer Agents Selected by Affinity Chromatography

Platella

Pirota

Musumeci

et al. 2020

IJMS

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A focused library of newly designed monomeric and dimeric naphthalene diimides (NDIs) was analyzed in its ability to recognize specific G-quadruplex (G4) structures discriminating duplex DNA. The best G4 ligands—according to an affinity chromatography-based screening method named G4-CPG—were tested on human cancer and healthy cells, inducing DNA damage at telomeres, and in parallel, showing selective antiproliferative activity on HeLa cancer cells with IC50 values in the low nanomolar range. CD and fluorescence spectroscopy studies allowed detailed investigation of the interaction in solution with different G4 and duplex DNA models of the most promising NDI of the series, as determined by combining the biophysical and biological assays’ data.

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Section: Synthesis Of the Functionalized Monomeric And Dimeric Naphthmentioning

confidence: 99%

Section: Synthesis Of the Functionalized Monomeric And Dimeric Naphthmentioning

confidence: 99%

Trifunctionalized Naphthalene Diimides and Dimeric Analogues as G-Quadruplex-Targeting Anticancer Agents Selected by Affinity Chromatography

Platella

Pirota

Musumeci

et al. 2020

IJMS

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“…For the synthesis of the NTI building blocks, monothiophene-fused NDIs (2), the same synthetic chemistry as that of NDTI can be applied to the mono-brominated NDA 66 (Scheme 6, the upper route). 40 Very recently we successfully developed a reliable protocol to synthesize N,N¤-unsubstituted NTI (14) by following the procedure depicted in Scheme 5 (Scheme 6, the lower route).…”

Section: Synthesis Of Ndti and Nti Derivativesmentioning

confidence: 99%

Thiophene-Fused Naphthalene Diimides: New Building Blocks for Electron Deficient π-Functional Materials

Takimiya

Nakano

2017

Bulletin of the Chemical Society of Japan

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Development of novel π-conjugated building blocks that can be integrated into molecular or macromolecular systems is key to the evolution of new superior organic semiconductors utilized as the active materials in organic electronics devices such as organic field-effect transistors (OFETs), organic photovoltaics (OPVs), and organic thermoelectric (TE) devices. This review affords a brief overview of thiophene-fused naphthalene diimide (NDI), namely naphtho[2,3-b:6,7-b¤]dithiophene diimide (NDTI) and naphtho [2,3-b]thiophene diimide (NTI), recently developed as novel electron deficient building blocks for n-type and ambipolar organic semiconductors. These thiophene-fused NDI building blocks had not been known until 2013 owing to their synthetic difficulty; more precisely, the difficulty in attaching fused-thiophene ring(s) on the NDI core. We have successfully established a thiophene-annulation reaction on ethyne-substituted NDI derivatives, which allows us to elaborate various NDTI and NTI derivatives. The key features of these building blocks are low-lying energy levels of lowest unoccupied molecular orbitals (LUMO, 3.84.1 eV below the vacuum level) and easy functionalizability of the thiophene ¡-positions, which allows their derivatives and polymers to conjugate efficiently with additional π-and comonomer units. These features make the NDTI-and NTIderivatives and polymers promising n-type and ambipolar materials for OFETs and acceptors for OPVs. In fact, various useful materials have already been derived from the NDTI and NTI building blocks: air-stable n-type small molecules and polymers with high electron mobility (³0.8 cm 2 V ¹1 s ¹1), ambipolar oligomers and polymers with well-balanced hole and electron mobilities, doped n-type semiconductors affording bulk conductors applicable to n-type TE materials, and electron acceptor molecules and polymers for OPVs showing promising power conversion efficiencies of up to 9%. These impressive and diversified device performances testify the usefulness of thiophene-fused NDI building blocks in the development of new electron deficient π-functional materials.

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“…In this context, the common synthetic approach is to brominate naphthalenetetracarboxylic anhydride (NDA) with an electrophilic brominating agent in a strong acidic condition, followed by imidization with the desired amine . However, the bromination step often results in a mixture of mono‐, di‐, and other multi‐brominated products that are difficult to separate and thus directly used in the imidization step . Since after bromination the reactivity of NDA towards imidization is reduced, imidization reaction is thus carried out in acetic acid using large excess amount of corresponding amines, some of which are either expensive or difficult to access.…”

Section: Methodsmentioning

confidence: 99%

“…[3] However,t he bromination step often results in am ixture of mono-, di-, and other multi-brominated products that are difficult to separate and thus directly used in the imidization step. [13] Since after bromination the reactivity of NDA towards imidization is reduced, imidization reaction is thus carried out in acetic acid using large excessa mount of corresponding amines, [3] some of which are either expensive or difficult to access. Moreover,d uring the imidization reaction amines with strong nucleophilicity can also undergo nucleophilic reaction at the bromine sites on the NDI core, reducing the yields and adding furthert roubles to the purification step.…”

mentioning

confidence: 99%

Synthesis of Thiophene‐annulated Naphthalene Diimide‐based Small‐Molecular Acceptors via Two‐step C−H Activation

Matsidik

Takimiya

2019

Chemistry An Asian Journal

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Thiophene-annulated naphthalene diimide (NTI)-based molecules have recently emerged as an important class of n-type electronic materials. However,t heir synthesis has predominantly been achieved by Stille or Suzuki coupling reactions despite the presence of ap otential CÀHb ond in NTI. Additionally,t he synthesis of NTI or more generally mono-functionalizationo fn aphthalene diimide (NDI) starts with ac umbersome bromination that results in al ow yield, is unselective, and requires tedious purification. Weh erein thus addresst hese issues via a two-step CÀHa ctivation:arhodium-catalyzed direct CÀH iodinization is first presented for NDI, followed by establishing an efficient direct arylation protocol for NTI with high yield and robustness. Coupling of up to four NTI units on ab enzene or pyrene core is demonstrated along with other aryl bromide substrates. Allt he herein reported NTI-based small molecules showed n-type semiconductor behavior under air. 1,4,5,8-Naphthalenetetracarboxylic diimide is the smallest member in the class of rylene diimides. Due to its uniqueproperties, such as ease of structural modification,e lectron deficient and planars tructure, high electron mobility and unconventional morphological behavior,N DI has become one of the most versatile and widely studied skeletons. [1][2][3] NDI-derived materials thus play an important role in research fields ranging from supramolecular chemistry,e lectron transfer systems, to organic electronics. [4,5] In the course of NDI-based materials for organic electronics, p-extension of NDIc ore through ringfusion at its four a-positions or coupling through its 2,6-positions has been aw idely applied strategy to control opto/electronic properties. [1][2][3] Nevertheless, mono-functionalization of the NDI core has received lessa ttention due to synthetic difficulties resulting from as imilar reactivity of the a-positions on the NDI core, despitei ts potential to further extend the material scope of NDI-based opto/electronics tructures. [6,7] We recently reported am ono-thiophene-fused NDI, namely naphtho[2,3-b]thiophene diimide( NTI), [6] which was then applied to generatev ariousN TI-terminated p-conjugated architectures that showed excellent n-type performance in organic electronics, demonstrating its potential as av ersatile building block. [6,8] However,t he synthesis of these NTI-terminated structures has been achieved to date by conventional coupling techniques such as Stille or Suzuki cross-coupling reactions, [6,8] while ad irect arylation (DA) protocol has recently been reported fors ymmetric thiophene-annulated NDI. [9] Indeed, the CÀH bond at the a-position of thiophene on NTI holds ag reat potential to be used in DA, in which NTI can be directlyc oupled with halogenated substrates, making the bromination of NTI and prefuctionalization to generate reactive organometallic substrates that are necessary in other coupling reactions redundant. [10][11][12] Thus, developing an efficient CÀHa ctivation protocol fort he NTI unit not only reduces synthetic st...

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Efficient Bromination of Naphthalene Dianhydride and Microwave-Assisted Synthesis of Core-Brominated Naphthalene Diimides

Cited by 6 publications

References 13 publications

Trifunctionalized Naphthalene Diimides and Dimeric Analogues as G-Quadruplex-Targeting Anticancer Agents Selected by Affinity Chromatography

Trifunctionalized Naphthalene Diimides and Dimeric Analogues as G-Quadruplex-Targeting Anticancer Agents Selected by Affinity Chromatography

Thiophene-Fused Naphthalene Diimides: New Building Blocks for Electron Deficient π-Functional Materials

Synthesis of Thiophene‐annulated Naphthalene Diimide‐based Small‐Molecular Acceptors via Two‐step C−H Activation

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