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Synthesis of Acridines Through Alkyne Addition to Diarylamines

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Synthesis of Acridines Through Alkyne Addition to Diarylamines molecules Article Synthesis of Acridines through Alkyne Addition to Diarylamines Kristen E. Berger, Grant M. McCormick, Joseph A. Jaye, Christina M. Rozeske and Eric H. Fort * Department of Chemistry, University of St. Thomas, 2115 Summit Avenue, St. Paul, MN 55115, USA; [email protected] (K.E.B.); [email protected] (G.M.M.); [email protected] (J.A.J.); [email protected] (C.M.R.) * Correspondence: [email protected]; Tel.: +1-651-962-5588 Academic Editor: Igor V. Alabugin Received: 15 October 2018; Accepted: 31 October 2018; Published: 3 November 2018 Abstract: A new synthesis of substituted acridines is achieved by palladium-catalyzed addition of terminal acetylenes between the aryl rings of bis(2-bromophenyl)amine. By including a diamine base and elevating the temperature, the reaction pathway favors the formation of acridine over a double Sonogashira reaction to form bis(tolan)amine. This method is demonstrated with several aryl-alkynes and alkyl-alkynes. Keywords: cyclization; acridine; one-pot; terminal-alkyne; polycycles 1. Introduction New approaches to the synthesis of aromatic molecules have proven repeatedly to yield more than just new structures. Advances in the understanding of pyrolysis have opened the door to fullerenes and carbon nanotubes and their rational synthesis [1–5]. Study of ring closures and the packing of small molecules have bolstered the reputation and uses of grapheme [6–8]. Our group has focused on the ring-closure mechanisms of aromatic molecules, including the changes induced when boron and nitrogen are introduced into the carbon framework [9,10]. In synthesizing new precursors for study, well-known cross-coupling pathways were diverted to produce a variety of polycyclic aromatic molecules, particularly 9-substituted acridines. This approach to acridine synthesis has not been observed previously, and it holds a great deal of potential for future synthetic and mechanistic insight. Acridines are characterized by the linear fusing of three aromatic 6-membered rings with a nitrogen atom included in the center ring [11]. Acridines were first isolated from coal tar by Graebe in 1870 [12]. The ability of acridine to bind DNA has made it a target for anticancer and antimicrobial uses, but it is most often found in organic dyes and staining agents for microscopy [13–15]. More recently, acridines have been investigated for their electronic properties and as photo-redox catalysts [16]. This work began upon the observation that the microwave reaction of phenylacetylene with bis(2-bromophenyl)amine (3) in the presence of a diamine solvent resulted in a significant yield of an unknown molecule. Isolation and characterization of this structure revealed that the reaction was producing 9-benzylacridine as the major product, as well as other aromatic products such as carbazole. Acridines are typically synthesized by electrophilic aromatic substitution of pendant carboxylic acid derivatives or by adding groups to the edges of smaller rings [17–23]. Both of these methods typically require further processing to aromatize the acridine ring following closure. Though some tandem processes have been shown previously, none incorporates alkynes in a manner similar to this work [24–27]. Two elegant C-H activation papers have been produced, both beginning with already-formed acridine [28,29]. Since alkynes are carbon-rich, they provide an especially attractive departure point into the aromatic chemistry [30]. The aryl-bromides in our system appeared to be providing an avenue for coupling and cyclization at the terminal carbon of the phenylacetylene, Molecules 2018, 23, 2867; doi:10.3390/molecules23112867 www.mdpi.com/journal/molecules Molecules 2018, 23, x 2 of 7 with already-formed acridine [28,29]. Since alkynes are carbon-rich, they provide an especially Molecules 2018, 23, 2867 2 of 7 attractive departure point into the aromatic chemistry [30]. The aryl-bromides in our system appeared to be providing an avenue for coupling and cyclization at the terminal carbon of the ratherphenylacetylene, than proceeding rather tothan a second proceeding cross-coupling to a second reaction cross-coupling with an additional reaction with alkyne. an Theadditional diaryl aminealkyne. route The isdiaryl a fast amine and versatile route is route a fast for and adding versatile complexity. route Thoughfor adding the reactioncomplexity. described Though below the wasreaction first described observed below in a microwave, was first observed it also proceeds in a micr withowave, traditional it also proceeds heating. with Several traditional methods heating. have previouslySeveral methods used microwave have previously chemistry used to producemicrowave acridines, chemistry but noto similarproduce pathway acridines, to benzylacridines but no similar canpathway be found to benzylacridine in the literature.s can The be workfound described in the literature. below explores The work the described reaction inbelow detail explores in order the to elucidatereaction in its detail versatility in order [31 to,32 elucidate]. its versatility [31,32]. 2. Results The precursor bis(2-bromophenyl)amine (3) was synthesized in 68% yield from 2-bromoaniline2-bromoaniline ((1)) and and bromoiodobenze bromoiodobenze (2) ( 2by) bya palladium-catalyzed a palladium-catalyzed cross cross coupling coupling reaction reaction in the presence in the presence of bis(2- ofdiphenylphosphino)phenyl)ether bis(2-diphenylphosphino)phenyl)ether (DPEPhos) (DPEPhos) (Figure 1) [33]. (Figure This1)[ system33]. allows This systemfor a nearly allows complete for a nearlyreaction complete between the reaction iodine between and the aniline the iodine grou andps, with the little aniline evidence groups, for with homocoupling little evidence between for homocouplinghalides or bromo-iodo between halidesmixtures or bromo-iodoin the products. mixtures The in dibromo the products. product The dibromo3 is converted product to3 isbis(tolan)amine converted to bis(tolan)amine (4a) in 63% yield (4a) inby 63% a double yield by Sonogashira a double Sonogashira cross-coupling cross-coupling reaction with reaction phenyl- with phenyl-acetyleneacetylene and using and diisopro using diisopropylaminepylamine as a solvent. as a solvent. Figure 1. Cross-coupling reactions to produce precursor 3 and bis(tolan)amine ((4a4a)[) [34,35].34,35]. In anan efforteffort toto increaseincrease yields,yields, diisopropylaminediisopropylamine waswas replacedreplaced withwith ethyleneethylene diaminediamine and thethe temperature was raised.raised. The results showed that thethe presence of the di-aryl amine and two bromine atoms makes 3 a multi-faceted molecule for synthesis. The amine group can be further functionalized by Buchwald-Hartwig-type reactions, the halides are excellent handles for cross couplings, and and inter- inter- and intra-molecular homocoupling reactions are possiblepossible as well [[34].34]. With With the diamine solvent, bis(tolan)amineMolecules 2018, 23, x was no longer the major product of thethe reaction.reaction. Instead, 9-benzylacridine (5a) 3 waswas of 7 present withwith smallsmall amountsamounts of of4a 4aand and carbazole carbazole ( 6()6) from from homocoupling homocoupling of of the the ortho-bromides ortho-bromides (Table (Table1). 1). Table 1. Production of 9-substituted acridines 5a–f. Table 1. Production of 9-substituted acridines 5a–f. The reaction was screened at varying temperatures with one equivalent of phenyl acetylene to optimize for acridine. Though 180 °C did not have the highest yield of acridine, it appeared that bis(tolan)amine 4a and carbazole 6 products were minimized. This vastly simplified purification by shutting down other mechanistic pathways. The equivalents of alkyne, solvents, and substituents were varied. Yields of the acridine increased with more alkyne, while the byproducts did not seem to become more abundant.Entry Ethylene Alkyne diamine (R) was Temp. replaced 4/5/6with (%) tetramethylethylene4 diamine Entry Alkyne (R) Temp. 4/5/6 (%) 4 (TMEDA) to determine if the hydrogen1 atoms of the amine◦ solvent were required, and the acridine 11 1 a a(Ph)(Ph) 120 120 °CC 7/14/3 7/14/3 1 ◦ yield remained comparable 21to the ethylenea (Ph) diamine. 140 Electron-richC trace/9/7 and -poor terminal alkynes, 2 a (Ph) 140 °C◦ trace/9/7 including alkyl substituted 3alkynes,1 alla (Ph)produced 160acridineC in3/29/13 varying amounts. A range of 9- 3 1 1 a (Ph) 160 °C◦ 3/29/13 substituted products were pr4oduced, includinga (Ph) benzyl 180 (5aC), 4-methylbenzyl trace/24/trace (5b), 4-methoxybenzyl 45 1 1 a a(Ph)(Ph) 180 200 °C◦C trace/24/trace trace/30/7 (5c), 4-fluorobenzyl (5d), heptyl2 (5e), and 4-phenylbutyl◦ (5f). Though electron-rich substituents 56 1 a a(Ph)(Ph) 200 180 °CC trace/30/7 trace/53/6 2,3 ◦ produced higher yields, it was2 possible ato obtain acridines with 4-fluorophenylacetylene, and even 67 a (Ph)(Ph) 180 180 °CC trace/53/6 0/51/9 2 ◦ alkynes with no conjugated aromatic82,3 b groups,(p-MeC 6suchH4) as 180octyneC and 5-phenyl-1-pentyne. 0/55/3 The major side- 7 2 a (Ph) 180 °C◦ 0/51/9 products remained carbazoles9 from cintramolecular(p-MeOC6H4) homocoupling 180 C trace/35/trace of the halides, as well as a variety 8 2 2 b (p-MeC6H4) 180 °C◦ 0/55/3 of products with the terminal10 alkyne addingd (p-FC6 toH 4the) amine 180 Cor alkyne 0/27/6 degradation products, though all 2 2 6 4 ◦ 911 c (p-MeOCe (CH2)5CHH3) 180180 °CC trace/35/trace 0/19/3 of these to a lesser extent than2 the2 formation of the acridine.◦ 1012 d f(p-FC(C3H66HPh)4) 180 180 °CC 0/27/6 0/10/3 2 11 e (CH2)5CH3 180 °C 0/19/3 1 1 eq. of alkyne; 2 2 eq. of alkyne; 3 tetramethylethylenediamine; 4 All reported values are isolated yields; 2 trace indicates observed in 112H-NMR andf not(C3 isolated.H6Ph) 180 °C 0/10/3 1.1 eq. of alkyne; 2 2 eq. of alkyne; 3 tetramethylethylenediamine; 4 All reported values are isolated yields; trace indicates observed in 1H-NMR and not isolated.
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