Thienothiophene-based organic light-emitting diode: synthesis, photophysical properties and application

• Recep Isci and
• Turan Ozturk

Beilstein J. Org. Chem. 2023, 19, 1849–1857, doi:10.3762/bjoc.19.137

• polyphosphoric acid (PPA) in refluxing chlorobenzene to give 3 (TT) in 86% yield. The brominated TT 4 was obtained through selective monobromination of compound 3 using NBS at −10 °C in DMF in 88% yield. The boronated triphenylamine 6 was constructed in a one-pot two-step reaction in 77% yield, by lithiation of

• nitrogen flow. Materials 3-Bromothiophene (97%, Across), 2-bromo-4′-methoxyacetophenone (97% Merck), N-bromosuccinimide (Sigma-Aldrich), polyphosphoric acid (PPA, 115% H3PO4 basis, Sigma-Aldrich), n-butyllithium (2.5 M in hexanes, Sigma-Aldrich), sodium sulfate (Merck), 4-bromotriphenylamine (Sigma-Aldrich

Strategies in the synthesis of dibenzo[b,f]heteropines

• David I. H. Maier,
• Barend C. B. Bezuidenhoudt and
• Charlene Marais

Beilstein J. Org. Chem. 2023, 19, 700–718, doi:10.3762/bjoc.19.51

• [36] via the polyphosphoric acid (PPA) catalysed cyclisation of 2,2'-diaminobibenzyl (20) at elevated temperatures (Scheme 3) [37][38]. 1.3 Catalytic dehydrogenation An early synthesis of 5H-dibenzo[b,f]azepine (1a) involved the gas phase dehydrogenation of 10,11-dihydro-5H-dibenzo[b,f]azepine (2a) to

• good yield (80%) by heating 23 in polyphosphoric acid (Scheme 5). Independently, in an effort to synthesise phenothiazine isosteres, Craig et al. [39] prepared 1a via a Wagner–Meerwein rearrangement of 23 with P2O5 (Scheme 5) the following year. The method was used to successfully synthesise

•  8). 2.4 Ring expansion of N-arylindoles (41) The polyphosphoric acid (PPA)-catalysed rearrangement of N-arylindoles 41 was first reported by Tokmakov and Grandberg [48]. The reaction provided moderate yields with a simple 2 step linear sequence from indole 39. The reaction requires heating at

Introducing a new 7-ring fused diindenone-dithieno[3,2-b:2',3'-d]thiophene unit as a promising component for organic semiconductor materials

• Valentin H. K. Fell,
• Joseph Cameron,
• Alexander L. Kanibolotsky,
• Eman J. Hussien and
• Peter J. Skabara

Beilstein J. Org. Chem. 2022, 18, 944–955, doi:10.3762/bjoc.18.94

• using polyphosphoric acid [16] and sulfuric acid failed [42], therefore we tried Friedel–Crafts acylation. For that, 27 was hydrolysed to the corresponding diacid 28 with lithium hydroxide [15]. In a manner similar to [24], firstly, a ‘cold’ Friedel–Crafts acylation in dichloromethane was attempted, in

• , 21.5 h, 79% [35]. Ring closure of key intermediate 27 to achieve 29: a) Methyl 5-bromo-2-iodobenzoate, Aliquat 336®, Pd(PPh3)4, K2CO3, THF/H2O, 70 °C, 40 h, 28% [40][41]; b) polyphosphoric acid [16], 100 °C, 4.5 h, then 130 °C, overnight, 0%; c) sulfuric acid, 115 °C, 6 h, 0% [42]; d) LiOH, THF, H2O

CF₃-substituted carbocations: underexploited intermediates with great potential in modern synthetic chemistry

• Anthony J. Fernandes,
• Armen Panossian,
• Bastien Michelet,
• Agnès Martin-Mingot,
• Frédéric R. Leroux and
• Sébastien Thibaudeau

Beilstein J. Org. Chem. 2021, 17, 343–378, doi:10.3762/bjoc.17.32

• alcohols was shown by Cohen and Kaluszyner [55][56] and by Streitwieser et al. [57]. The cyclodehydration of 9c occurs in polyphosphoric acid to afford fluorene 37 (Scheme 8) [57]. A mechanistic proposal invoking the initial generation of the α-(trifluoromethyl)carbenium ion 10c↔10c’ was mentioned by the

Synthesis of imidazo[1,5-a]pyridines via cyclocondensation of 2-(aminomethyl)pyridines with electrophilically activated nitroalkanes

• Dmitrii A. Aksenov,
• Nikolai A. Arutiunov,
• Vladimir V. Maliuga,
• Alexander V. Aksenov and
• Michael Rubin

Beilstein J. Org. Chem. 2020, 16, 2903–2910, doi:10.3762/bjoc.16.239

• , USA 10.3762/bjoc.16.239 Abstract Imidazo[1,5-a]pyridines were efficiently prepared via the cyclization of 2-picolylamines with nitroalkanes electrophilically activated in the presence of phosphorous acid in polyphosphoric acid (PPA) medium. Keywords: cyclization; heterocycles; imidazo[1,5-a

• ]pyridines; nitroalkanes; polyphosphoric acid; Introduction It is hard to overstate the importance of imidazo[1,5-a]pyridines in modern organic and medicinal chemistry. Several natural alkaloids possessing this core were isolated from marine sponges, for example, cribrostatin 6 (Figure 1) [1][2][3]. The

• heating in polyphosphoric acid, the nitroalkanes 1 convert into the phosphorylated nitronates 2, which exhibit strong electrophilic properties. This allowed for the employment of these species in reactions wherein electron-rich arenes serve as carbon-based nucleophilies [38][39][40]. It was also

Synthesis of 6,13-difluoropentacene

• Matthias W. Tripp and
• Ulrich Koert

Beilstein J. Org. Chem. 2020, 16, 2136–2140, doi:10.3762/bjoc.16.181

• –Crafts acylation is then performed in polyphosphoric acid at 140 °C, giving anthraquinone 11 in 53% yield over two steps. Reduction of 11 to the anthracene 9 proceeded smoothly using zinc powder in 1,4-dioxane and aqueous ammonia under copper catalysis [15]. To achieve good yields, it was crucial to

• corresponding pentacenequinone by chloride. This side reaction could be avoided using polyphosphoric acid as Friedel–Crafts reagent. The pentacenequinone showed very low solubility, which complicated a chromatographic isolation. However, the crude 1H NMR showed sufficiently clean conversion, hence the

Microwave-assisted synthesis of 2-substituted 4,5,6,7-tetrahydro-1,3-thiazepines from 4-aminobutanol

• María C. Mollo,
• Natalia B. Kilimciler,
• Juan A. Bisceglia and
• Liliana R. Orelli

Beilstein J. Org. Chem. 2020, 16, 32–38, doi:10.3762/bjoc.16.5

• Mitsunobu conditions led exclusively to the pyrrolidine derivative (76%) [32]. Therefore, the few literature examples reported until now are either complicated by side reactions or involve long reaction times and/or modest yields. Polyphosphoric acid (PPA) esters PPE (ethyl polyphosphate) and PPSE

The LANCA three-component reaction to highly substituted β-ketoenamides – versatile intermediates for the synthesis of functionalized pyridine, pyrimidine, oxazole and quinoxaline derivatives

• Tilman Lechel,
• Roopender Kumar,
• Mrinal K. Bera,
• Reinhold Zimmer and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2019, 15, 655–678, doi:10.3762/bjoc.15.61

• polyphosphoric acid to undergo a Fischer indole reaction to 5-indolyl-substituted oxazole OX20. To demonstrate the versatility of the route to new oxazole derivatives, typical palladium-catalyzed processes are compiled in Scheme 27. First, the acetyl moiety was converted into a vinyl or an ethynyl substituent

• -substituted oxazole derivatives OX. Hydrogenolyses of benzyloxy-substituted β-ketoenamides KE52 and KE54 to 1,2-diketone DK14 and to diastereomeric α-hydroxy-β-amino ketones 9. Conversions of 2,4-dicyclopropyl-substituted oxazole OX7 into oxazole derivatives OX18–20 (PPA = polyphosphoric acid). Syntheses of

Synthesis of dihydroquinazolines from 2-aminobenzylamine: N³-aryl derivatives with electron-withdrawing groups

• Nadia Gruber,
• Jimena E. Díaz and
• Liliana R. Orelli

Beilstein J. Org. Chem. 2018, 14, 2510–2519, doi:10.3762/bjoc.14.227

• -aryl-2-iminoazacycloalkanes [84] and 2-oxazolines or their higher homologues [85], using polyphosphoric acid esters PPE (ethyl polyphosphate) [86] and PPSE (trimethylsilyl polyphosphate) [87] under microwave irradiation. PPE and PPSE are aprotic irreversible dehydrating agents of the Lewis acid-type

One hundred years of benzotropone chemistry

• Arif Dastan,
• Haydar Kilic and
• Nurullah Saracoglu

Beilstein J. Org. Chem. 2018, 14, 1120–1180, doi:10.3762/bjoc.14.98

5-Aminopyrazole as precursor in design and synthesis of fused pyrazoloazines

• Ranjana Aggarwal and
• Suresh Kumar

Beilstein J. Org. Chem. 2018, 14, 203–242, doi:10.3762/bjoc.14.15

Reagent-controlled regiodivergent intermolecular cyclization of 2-aminobenzothiazoles with β-ketoesters and β-ketoamides

• Irwan Iskandar Roslan,
• Kian-Hong Ng,
• Gaik-Khuan Chuah and
• Stephan Jaenicke

Beilstein J. Org. Chem. 2017, 13, 2739–2750, doi:10.3762/bjoc.13.270

• ]. Polyphosphoric acid has also been used to access 5a by coupling 2-aminobenzothiazole with β-ketoesters [79][91][92]. We have previously shown that bismuth salts can catalyze the intermolecular cyclization of 2-aminopyridines and β-ketoesters to pyrido[1,2-a]pyrimidin-4-ones [6]. Using Bi(OTf)3 in 1.5 mmol 2

Solvent-free copper-catalyzed click chemistry for the synthesis of N-heterocyclic hybrids based on quinoline and 1,2,3-triazole

• Martina Tireli,
• Silvija Maračić,
• Stipe Lukin,
• Marina Juribašić Kulcsár,
• Dijana Žilić,
• Mario Cetina,
• Ivan Halasz,
• Silvana Raić-Malić and
• Krunoslav Užarević

Beilstein J. Org. Chem. 2017, 13, 2352–2363, doi:10.3762/bjoc.13.232

• -aminobiphenyl (1) with ethyl 4,4,4-trifluoro-3-oxobutanoate in polyphosphoric acid (PPA) followed by the cyclization of the Schiff base intermediate afforded the 2-(trifluoromethyl)-6-phenylquinolone 3 (Scheme 1). O-Alkynylquinoline derivative 4 required for the click synthesis of target triazoles was obtained

A novel approach to oxoisoaporphine alkaloids via regioselective metalation of alkoxy isoquinolines

• Benedikt C. Melzer and
• Franz Bracher

Beilstein J. Org. Chem. 2017, 13, 1564–1571, doi:10.3762/bjoc.13.156

• using polyphosphoric acid (Scheme 1). In the course of this cyclization, the methoxy group at C-6 is typically hydrolized to the phenol, subsequent O-methylation gives the 6-methoxy derivatives menisporphine (2) and dauriporphine (3). Recently, Zhang et al. [20] described an alternative approach

• valuable intermediates for the further conversion to the target oxoisoaporphines, and in previous protocols [7][17] the esters were typically converted into the corresponding carboxylic acids, and then cyclized using polyphosphoric acid. Previously we found that esters can directly be subjected to this

• type of intramolecular Friedel–Crafts-type acylations, and trifluoromethanesulfonic acid [25] is superior to polyphosphoric acid [26][27] for the synthesis of polycyclic ketones. Unfortunately, direct cyclization of esters 10a–c using this reagent failed completely, despite numerous variations of the

Syntheses of 3,4- and 1,4-dihydroquinazolines from 2-aminobenzylamine

• Jimena E. Díaz,
• Silvia Ranieri,
• Nadia Gruber and
• Liliana R. Orelli

Beilstein J. Org. Chem. 2017, 13, 1470–1477, doi:10.3762/bjoc.13.145

• reported the MW-assisted synthesis of 1,4,5,6-tetrahydropyrimidines and their homologues by cyclodehydration reactions promoted by polyphosphoric acid (PPA) esters PPE and PPSE [58][59][60]. This strategy was successfully applied to the synthesis of 1-aryl-2-imino-1-azacycloalkanes [61], 2-oxazolines, 5,6

Synthesis of 1-indanones with a broad range of biological activity

• Marika Turek,
• Dorota Szczęsna,
• Marek Koprowski and
• Piotr Bałczewski

Beilstein J. Org. Chem. 2017, 13, 451–494, doi:10.3762/bjoc.13.48

• -iodoaryl)propanonitriles 193 leading to the formation of the nitrile 195 as a byproduct (Scheme 55). Cyclization of 3-phenylnaphtalene-2-carbonitrile (199) in the presence of polyphosphoric acid gave 1-indanone 200 in 76% yield. The nitrile 199 was obtained from benzaldehyde 196 as a result of sequencial

Microwave-assisted cyclizations promoted by polyphosphoric acid esters: a general method for 1-aryl-2-iminoazacycloalkanes

• Jimena E. Díaz,
• María C. Mollo and
• Liliana R. Orelli

Beilstein J. Org. Chem. 2016, 12, 2026–2031, doi:10.3762/bjoc.12.190

• -2-iminoazacycloalkanes is presented, by microwave-assisted ring closure of ω-arylaminonitriles promoted by polyphosphoric acid (PPA) esters. 1-Aryl-2-iminopyrrolidines were easily prepared from the acyclic precursors employing a chloroformic solution of ethyl polyphosphate (PPE). The use of

• of conventional heating [17]. In previous work, we reported the microwave-assisted synthesis of 5 to 8 membered cyclic amidines by cyclodehydration of N-aryl-N´-acyl-1,n-alkanediamines (n = 2–5) promoted by polyphosphoric acid (PPA) esters PPE and PPSE (Scheme 1, reaction 1) [41][42][43]. In this

Practical synthetic strategies towards lipophilic 6-iodotetrahydroquinolines and -dihydroquinolines

• David R. Chisholm,
• Garr-Layy Zhou,
• Ehmke Pohl,
• Roy Valentine and
• Andrew Whiting

Beilstein J. Org. Chem. 2016, 12, 1851–1862, doi:10.3762/bjoc.12.174

• in Scheme 1, which requires cyclisation from the alkylated N-allylaniline 4. The use of polyphosphoric acid (PPA) in cyclisation reactions is well known in the literature, and has been used to form a large variety of ring structures [15]. Iodination of 3 could then be realised by utilising the rich

Pyridinoacridine alkaloids of marine origin: NMR and MS spectral data, synthesis, biosynthesis and biological activity

• Louis P. Sandjo,
• Victor Kuete and
• Maique W. Biavatti

Beilstein J. Org. Chem. 2015, 11, 1667–1699, doi:10.3762/bjoc.11.183

• -nitrobenzoyl)acetate to give a β-keto amide. The resulting amide was subjected to a Knorr cyclization in the presence of polyphosphoric acid to afford a quinolinone, which was further reduced to a quinoline in two steps. The Sandmeyer reaction permitted the replacement of the amide function with a carboxylic

• Japp–Klingemann reaction was used to transform the diazonium salt in the presence of ethyl 2-methyl-3-oxobutyrate into the respective hydrazone. The indole was formed from the treatment of the hydrazone with polyphosphoric acid. The last heterocyclic ring was formed by an intramolecular reaction of the

Selected synthetic strategies to cyclophanes

• Sambasivarao Kotha,
• Mukesh E. Shirbhate and
• Gopalkrushna T. Waghule

Beilstein J. Org. Chem. 2015, 11, 1274–1331, doi:10.3762/bjoc.11.142

Atherton–Todd reaction: mechanism, scope and applications

• Stéphanie S. Le Corre,
• Mathieu Berchel,
• Hélène Couthon-Gourvès,
• Jean-Pierre Haelters and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2014, 10, 1166–1196, doi:10.3762/bjoc.10.117

• solid phase by forming a thermal barrier between the solid phase and the gaseous phase. This charring process results from the formation of polyphosphoric acid derivatives. Interestingly, the association of phosphorus and nitrogen-based flame retardants proved to be efficient probably due to synergic

An overview of the synthetic routes to the best selling drugs containing 6-membered heterocycles

• Marcus Baumann and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2013, 9, 2265–2319, doi:10.3762/bjoc.9.265

• substituted Grignard reagent 1.26. A Friedel–Crafts type acylation promoted by either triflic acid or polyphosphoric acid (PPA) furnishes the tricyclic structure 1.28 which upon N-demethylation affords clarinex (1.22). One of the top-selling classes of pharmaceuticals containing the pyridine ring are the

Amyloid-β probes: Review of structure–activity and brain-kinetics relationships

• Todd J. Eckroat,
• Abdelrahman S. Mayhoub and
• Sylvie Garneau-Tsodikova

Beilstein J. Org. Chem. 2013, 9, 1012–1044, doi:10.3762/bjoc.9.116

• chain at position 5 of the benzoxazole core in place of the [125I] of 94 at position 6 to reduce lipophilicity, was prepared by polyphosphoric acid catalyzed condensation of 2-amino-4-methoxyphenol (106) and 4-monomethylaminobenzoic acid (107) to give the benzoxazole core, which was O-demethylated to

• (98) were prepared and studied for Aβ imaging [73][74][75]. The simple two-step synthesis of 97 used polyphosphoric acid trimethylsilyl ester (PPSE) catalyzed condensation of 4-fluoro-2-aminophenol (112) with a cinnamic acid 113 to give the benzoxazole core followed by conversion to the primary amine

An efficient access to the synthesis of novel 12-phenylbenzo[6,7]oxepino[3,4-b]quinolin-13(6H)-one derivatives

• Wentao Gao,
• Guihai Lin,
• Yang Li,
• Xiyue Tao,
• Rui Liu and
• Lianjie Sun

Beilstein J. Org. Chem. 2012, 8, 1849–1857, doi:10.3762/bjoc.8.213

• , is described, involving the intramolecular Friedel–Crafts acylation reaction of 2-(phenoxymethyl)-4-phenylquinoline-3-carboxylic acid derivatives 3a–l aided by the treatment with PPA (polyphosphoric acid) or Eaton’s reagent. The required starting compound (2) was obtained by Friedländer reaction of 2

• commonly available cyclization agents screened for the intramolecular Friedel–Crafts acylation reaction (e.g., AlCl3, H2SO4, p-TsOH, TiCl4, P2O5), the use of inexpensive and readily available polyphosphoric acid (PPA), requiring no additional solvent, was found to be very suitable for such a reaction in

An overview of the key routes to the best selling 5-membered ring heterocyclic pharmaceuticals

• Marcus Baumann,
• Ian R. Baxendale,
• Steven V. Ley and
• Nikzad Nikbin

Beilstein J. Org. Chem. 2011, 7, 442–495, doi:10.3762/bjoc.7.57

• . Subsequent treatment of the substituted intermediate with trifluoroacetic anhydride furnished the corresponding bis-hydrazide 278 which underwent cyclisation at elevated temperatures in the presence of polyphosphoric acid. Finally, the partial hydrogenation of triazolopyrazine derivative 279 with palladium