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Synthesis of Naphthalene-Based Push-Pull Molecules with a Heteroaromatic Electron Acceptor

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Synthesis of Naphthalene-Based Push-Pull Molecules with a Heteroaromatic Electron Acceptor molecules Article Synthesis of Naphthalene-Based Push-Pull Molecules with a Heteroaromatic Electron Acceptor David Šarlah 1,†, Amadej Juranoviˇc 1,†, Boris Kožar 1,†, Luka Rejc 1,†, Amalija Golobiˇc 1,† and Andrej Petriˇc 1,2,* 1 Faculty of Chemistry and Chemical Technology, University of Ljubljana, Veˇcnapot 113, 1000 Ljubljana, Slovenia; [email protected] (D.Š.); [email protected] (A.J.); [email protected] (B.K.); [email protected] (L.R.); [email protected] (A.G.) 2 EN-FIST Centre of Excellence, Trg Osvobodilne fronte 13, SI-1000 Ljubljana, Slovenia * Correspondence: [email protected]; Tel.: +386-1-479-8519 † These authors contributed equally to this work. Academic Editor: Wim Dehaen Received: 4 January 2016 ; Accepted: 22 February 2016 ; Published: 2 March 2016 Abstract: Naphthalene derivatives bearing electron-accepting and electron-donating groups at the 2,6-positions belong to the family of D-π-A push-pull dyes. It has been found that these compounds, e.g., 2-(1-(6-((2-(fluoro)ethyl)(methyl)amino)naphthalen-2-yl)ethylidene)malononitrile (FDDNP), show not only interesting optical properties, such as solvatochromism, but they have the potential to label protein aggregates of different compositions formed in the brain of patients suffering from neurodegenerative diseases like Alzheimer’s (AD). In continuation of our research we set our goal to find new FDDNP analogs, which would inherit optical and binding properties but hopefully show better specificity for tau protein aggregates, which are characteristic for neurodegeneration caused by repetitive mild trauma. In this work we report on the synthesis of new FDDNP analogs in which the acceptor group has been formally replaced with an aromatic five- or six-membered heterocycle. The heterocyclic moiety was annealed to the central naphthalene ring either by classical ring closure reactions or by modern transition metal-catalyzed coupling reactions. The chemical characterization, NMR spectra, and UV/vis properties of all new compounds are reported. Keywords: FDDNP analogs; push-pull dyes; heterocyclization; cross-coupling reactions; UV/vis spectroscopy 1. Introduction Molecules with a delocalized π-system end-capped with an electron donor (D) and an acceptor (A) group (D-π-A) are widely utilized in optoelectronic devices and other functional materials. Intense research was dedicated to determine the effects of the donor, acceptor, and the π-system parts of a push-pull chromophore on its properties [1]. The interaction between the donor and the acceptor (intramolecular charge transfer, ICT) is mediated by the π-system; it can be expressed by limiting resonance forms as exemplified for 2-(1-(6-((2-(fluoro)ethyl)(methyl)amino)naphthalen-2-yl)- ethylidene)malononitrile (FDDNP, Figure1). The extent of delocalization and consequently the corresponding HOMO-LUMO gap as well as optical properties are governed by several factors: (i) The donor group. The most efficient donor groups are those exhibiting positive resonance effect (+R). Of those, N,N-dialkylamino groups proved to be one of the most efficient and frequently utilized in D-π-A molecules. Molecules 2016, 21, 267; doi:10.3390/molecules21030267 www.mdpi.com/journal/molecules Molecules 2016, 21, 267 2 of 16 Molecules 2016, 21, 267 2 of 16 N N N N C C C C Molecules 2016, 21, 267 2 of 16 F F N N N N N N C C C C FDDNP FigureFigure 1. Limiting 1. Limiting resonance resonance forms forms showing electron electron delocalization delocalization in FDDNP. in FDDNP. F F The spatial arrangementN of the substituents at the donorN nitrogen atom was found to influence The spatial arrangement of the substituents at the donor nitrogen atom was found to influence the donor efficacy. In aziridineFDDNP and piperidine, the ring is puckered and the substituents around the the donornitrogen efficacy. are pushed In aziridine out of the and plane. piperidine, This pyrami thedal ring arrangement is puckered hinders and an the efficient substituents delocalization around the Figure 1. Limiting resonance forms showing electron delocalization in FDDNP. nitrogenof the are nitrogen pushed lone out electron of the plane. pair towards This pyramidal the A-group. arrangement In open-chain hinders dialkylamines, an efficient azetidine, delocalization or pyrrolidine the arrangement is planar, resulting in an efficient delocalization of the electron pair; this of the nitrogenThe spatial lone arrangement electron pair of towardsthe substituents the A-group. at the donor In open-chain nitrogen atom dialkylamines, was found to influence azetidine, or is reflected in absorption maxima at longer wavelengths and smaller chemical shifts of neighboring pyrrolidinethe donor the efficacy. arrangement In aziridine is planar, and piperidine, resulting the inan ring efficient is puckered delocalization and the substituents of the electron around pair; the this protons in NMR spectra [2]; is reflectednitrogen in are absorption pushed out maxima of the plane. at longer This pyrami wavelengthsdal arrangement and smaller hinders chemical an efficient shifts delocalization of neighboring protons(ii)of the inThe NMRnitrogen π-system. spectra lone As electron [ 2the]; π-link pair between towards the the A A- andgroup. D groups In open-chain in D-π-A dialmoleculeskylamines, usually azetidine, serves anor pyrrolidinearomatic/heteroaromatic the arrangement is ring planar, alone resulting or combined in an efficient with a conjugated delocalization alkene of the or electronalkyne structural pair; this (ii) Theis reflectedπelement.-system. in Itabsorption has As been the π shown,maxima-link betweenthat at longera conjugation the wave Alengths and with D an and groups alkene smaller instructural D-chemicalπ-A element molecules shifts ofleads neighboring usually to higher serves anprotons aromatic/heteroaromaticA–D in interactions NMR spectra than [2]; the ringacetylene alone one or [1,3]. combined with a conjugated alkene or alkyne structural element.(iii) The acceptor. It has been Groups shown, with that nega ative conjugation resonance with(–R) and/or an alkene inductive structural effects element (–I), such leads as cyano, to higher (ii) The π-system. As the π-link between the A and D groups in D-π-A molecules usually serves an nitro and carbonyl are the most efficient acceptors. As the A group, five or six-membered A–Daromatic/heteroaromatic interactions than the acetylene ring alone one or combined [1,3]. with a conjugated alkene or alkyne structural electron-deficient heterocycles, such as thiazole, benzo[d]thiazole, imidazole, pyrazine, pyridine (iii) The acceptor.element. It Groups has been with shown, negative that a conjugation resonance wi (–R)th an and/or alkeneinductive structural element effects (–I),leads such to higher as cyano, etc. bearing one or more electron-withdrawing substituents, can also be applied [1,4]. nitroA–D and interactions carbonyl arethan thethe acetylene most efficient one [1,3]. acceptors. As the A group, five or six-membered electron-deficient(iii) 2-(1-(6-(Dimethylamino)naphthalen-2-yl)ethylidenThe acceptor. Groups heterocycles, with nega suchtive as resonance thiazole, (–R) benzo[e)malononitrile and/ord]thiazole, inductive (DDNP) imidazole, effects was (–I), initially pyrazine,such developed as cyano, pyridine etc.as abearing nitrosolvent and onepolarity/viscosity carbonyl or more are electron-withdrawing the dependent most efficient fluorescent accept substituents, ors.D-π -AAs typethe canA dye, group, also which be five applied can or besix-membered [utilized1,4]. for tissueelectron-deficient staining in fluorescence heterocycles, microscopy such [5].as thiazole, We have benzo[ used itds]thiazole, analogue imidazole,FDDNP with pyrazine, different pyridine in vitro 2-(1-(6-(Dimethylamino)naphthalen-2-yl)ethylidene)malononitrileand inetc. vivo bearing techniques one or tomore detect electron-withdrawing changes in the centra substituents,l nervous cansystem also presentbe applied (DDNP) in the [1,4]. brain was of initiallythe developedpatients as suffering a solvent from polarity/viscosity a variety of neurodegenerat dependentive diseases fluorescent [6–8]. D- Inπ conjunction-A type dye, with which positron can be 2-(1-(6-(Dimethylamino)naphthalen-2-yl)ethylidene)malononitrile (DDNP) was initially developed emission tomography (PET), radiolabeled [18F]FDDNP was used as the molecular probe for the utilizedas a for solvent tissue polarity/viscosity staining in fluorescence dependent microscopy fluorescent D- [5].π-A We type have dye, used which its analogue can be utilized FDDNP for with diagnosis of the Alzheimer’s disease in living patients [9]. In recent years, a number of in vitro and differenttissuein staining vitro and in fluorescencein vivo techniques microscopy to detect[5]. We changes have used in it thes analogue central FDDNP nervous with system different present in vitro in the in vivo imaging techniques for the detection of protein deposits in the CNS has been developed in brainand of the in vivo patients techniques suffering to detect from changes a variety in of the neurodegenerative central nervous system diseases present [6– 8in]. Inthe conjunction brain of the with order to help diagnose the disease in early stages [10]. New compounds derived from fused aromatic positronpatients emission suffering tomography from a variety (PET), of neurodegenerat radiolabeled [18iveF]FDDNP diseases [6–8]. was usedIn conjunction as the molecular with positron probe for heterocycles like THK5105, T807, or T808 (Figure
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