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Simple Procedures for the Preparation of 1,3,5-Substituted 2,4,6-Trimethoxy -.:. Michael Pittelkow

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Simple Procedures for the Preparation of 1,3,5-Substituted 2,4,6-Trimethoxy -.:. Michael Pittelkow LETTER ▌2437 Simpleletter Procedures for the Preparation of 1,3,5-Substituted 2,4,6-Trimethoxy- benzenes BjarnePreparation of 1,3,5-Substituted E. Nielsen, 2,4,6-Trimethoxybenzenes Henrik Gotfredsen, Brian Rasmussen, Christian G. Tortzen, Michael Pittelkow* Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 Copenhagen, Denmark Fax +4535320212; E-mail: [email protected] Received: 09.07.2013; Accepted after revision: 23.07.2013 Abstract: We describe straightforward protocols for the prepara- tion of a number of 1,3,5-substituted 2,4,6-trimethoxybenzenes. A two-step procedure for the preparation of a 1,3,5-tris-methylamino- 2,4,6-trimethoxybenzene and further synthetic elaboration of this key substrate to yield a triamide, a tricarbamate and three different triureas is described. We also present a computational (DFT) study that investigates the different possible conformations of the over- crowded benzene substrate and a single-crystal X-ray structure of one of the key intermediates. (From left to right) Michael Pittelkow was born in 1977 and raised Key words: supramolecular chemistry, tripodal receptors, ureas, in Brøndby Strand, near Copenhagen. At the University of Copenha- amides, overcrowded aromatics gen he received his PhD degree in 2006. During his studies he spent extended periods in Australia (CSIRO in Melbourne), The Nether- lands (The Technical University of Eindhoven) and England (the Uni- versity of Cambridge). He undertook postdoctoral studies in the UK The subtle interplay between rigidity and flexibility with Prof. J. K. M. Sanders (the University of Cambridge) before makes the design of receptors in supramolecular chemis- moving back to Denmark to start as an Assistant Professor at the De- try complex and sometimes unpredictable.1 Preorganiza- partment of Chemistry, University of Copenhagen in November tion has proven a reliable strategy in receptor design, but 2008. In 2013 he became Associate Professor at the same department. His research interests include organic synthesis, physical organic this is only truly effective if there is a good fit with the chemistry, dendrimers and supramolecular chemistry. binding partner. A particularly popular and simple scaf- Brian Rasmussen was born in 1980 in Denmark and initiated his fold that relies on preorganization is the 1,3,5-substituted chemistry studies at the University of Copenhagen in 2001. Under the 2,4,6-triethylbenzene scaffold.2 Receptors based on this guidance of Associate Professor Jørn B. Christensen, his Bachelor’s scaffold have the unique feature that the three ethyl sub- and Master’s project work concerned supramolecular chemistry at stituents predominantly orient themselves towards one dendrimer surfaces, and his PhD work was concentrated on dendrimer synthesis and the development of new organocatalytic dendrimers for side of the central benzene ring, while the three other sub- the Diels–Alder reaction. From 2010, he has been employed as a Post 3 stituents point towards the other side of the benzene ring. Doc at the University of Copenhagen under the guidance of Associate This feature has been used extensively in the preparation Professor Michael Pittelkow where he is mainly working with or- of receptors for a wide range of guest molecules.2 The ganoselenium chemistry, supramolecular chemistry, and dynamic central benzene ring can potentially engage in the molec- combinatorial chemistry. ular recognition events. This has inspired a renewed inter- Henrik Gotfredsen received his Bachelor’s degree at the University of Copenhagen under the guidance of Associate Professor Michael est in the preparation of tripodal structures with Pittelkow in 2013 where he worked with organoselenium chemistry alternative substitution patterns on the central benzene and dynamic combinatorial chemistry. Henrik is currently pursuing a ring. This opens up new opportunities for fine-tuning the Master’s degree in the same group. binding properties of these privileged receptor structures. Bjarne E. Nielsen received his Master’s degree at the University of Downloaded by: Koebenhavns Universitetsbibliotek. Copyrighted material. A strategy to improve the binding properties of the tripo- Copenhagen under the guidance of Associate Professor Michael Pit- telkow in 2013 where he worked with dynamic combinatorial chem- dal receptors is to modify the electronic properties of the istry for the recognition of carbohydrates. He is now pursuing a PhD benzene ring by changing the three ethyl substituents to degree in the same group working with the development of new near- three methoxy substituents.4 This subtle change in design infrared dyes. (three CH2 groups substituted for three oxygens) appears Christian G. Tortzen is a scientist at the Department of Chemistry at to provide less preorganized structures, presumably be- the University of Copenhagen with specialty in NMR spectroscopy cause three almost aligned O–Me dipoles in a completely and organic synthesis. Christian received his Master’s degree under the guidance of Prof. Jesper Wengel and Associate Prof Otto Dahl at alternating structure would not be favorable, and receptors the University of Copenhagen and has since worked in the laborato- based on this design would need other favorable interac- ries of Prof. John Nielsen at the University of Copenhagen and Prof. tions to outweigh this effect.5 Here we describe reliable Varinder Aggarwal at the University of Bristol, UK. synthetic protocols for the preparation of a series of 1,3,5- tris-substituted 2,4,6-trimethoxybenzenes. We also quan- tify, by means of DFT calculations, the relative energetics SYNLETT 2013, 24, 2437–2442 of the different conformations of the 1,3,5-substituted Advanced online publication: 27.08.20130936-52141437-2096 2,4,6-trimethoxybenzenes. DOI: 10.1055/s-0033-1339639; Art ID: ST-2013-W0636-L © Georg Thieme Verlag Stuttgart · New York 2438 B. E. Nielsen et al. LETTER Bromomethylation of 1,3,5-trimethoxybenzene (1) was and by carbamate formation. The formation of the performed using a modified literature procedure.6,7 Treat- tris(tert-butyl)carbamate (Boc) compound 4 (Scheme 2) ment of 1,3,5-trimethoxybenzene with paraformaldehyde was effective by treatment with di-tert-butyl dicarbonate and HBr in AcOH for three hours at 85 °C in a sealed con- in dioxane and water, and was easily purified by column tainer yielded the tris-bromomethylated product (2) in chromatography.9 The yield was moderate but acceptable 49% yield. This procedure reliably yields >10 g of 2 as a due to the three-fold reaction (above 60% yield per carba- white solid material. The transformation into the tris- mate formation) and easy purification protocol. We also methylamino compound (3) proceeded smoothly by dis- developed conditions for the preparation of an amide, 5, solving 2 in liquid ammonia in a sealed bomb at room by coupling of the triamine and terephthalic acid mono- temperature for 18 hours. When optimized, this transfor- methyl ester and a coupling reagent (either Me3P/I2 or 10 mation proceeded in quantitative yield. Simple evapora- PYBOP) in CH2Cl2. This material was also purified by tion of the ammonia, addition of water and filtration chromatography on silica revealing 66% of the triamide. yielded after concentration in vacuo the tris-hydro- 8 Formation of amides was also attempted by an alternative bromide as a pale yellow solid (Scheme 1). This protocol route. 1,3,5-Trimethoxybenzene gave, via reaction with was concentration dependent and a concentration of the N-(hydroxymethyl)phthalimide, the triphthalimide 611 tribromide of 0.1 gram per 40 mL ammonia proved to be and ways of opening the phthalimide functionalities by re- the optimal conditions to avoid side reactions. action with amines as described by Gali et al. were at- tempted (Scheme 3).12 However, the isolated product in O Br O BrH3N O these attempts was the N-alkyl-substituted phthalimide of the amine. (a) Br (b) NH3Br Another functionality derived from amines is the urea O O O O O O group which has been widely used in the design of hosts towards hydrogen bond accepting guests.1 We studied 1 Br 2 BrH3N 3 convenient ways of converting the triamine 3 into triurea Scheme 1 Synthesis of 1,3,5-tris-methylamino-2,4,6-trimethoxy- derivatives, and it was found that reaction between 3 and benzene (3). Reagents and conditions: (a) paraformaldehyde, 33% tert-butylisocyanate under mild conditions gave the de- HBr in AcOH, sealed vessel, 49%; (b) NH3, sealed vessel, >98%. sired triurea derivative 7.13 The binding properties of this compound were studied by NMR in chloroform, and the With the triamine in hand, we explored the possibilities host showed a modest affinity towards chloride ions (see for functionalization via simple amide coupling reaction Supporting Information). O O O O O NH NH O O O O O O O O H H (a) (b) H H O N N O N N O O O O O O Downloaded by: Koebenhavns Universitetsbibliotek. Copyrighted material. 4 5 BrH3N O NH3Br OH STr O O O O NH O NH BrH3N 3 NH NH O O O O (c) (d) H H H H H H H H N N N N N N N N TrS STr O O O O O O HO O O OH 7 8 Scheme 2 Functionalization of the triamine 3 to carbamates, amides, and ureas. Reagents and conditions: (a) Boc2O; (b) Me3P, I2, terephthalic acid monomethyl ester; (c) tert-butylisocyanate; (d) (i) 1,1′-carbonyldiimidazole; (ii) S-tritylcysteine (protected cysteine). Synlett 2013, 24, 2437–2442 © Georg Thieme Verlag Stuttgart · New York LETTER Preparation of 1,3,5-Substituted 2,4,6-Trimethoxybenzenes 2439 O O N O O O (a) N O O O O O O 1 N 6 O (b) H N R R Figure 1 Part of the 13C NMR spectra of the reaction mixture for the O O NH activation of triamine 3 with 1,1′-carbonyldiimidazole after different O NH O O O reaction times.
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