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Vinylation of a Secondary Amine Core with Calcium Carbide for Efficient molecules Article Vinylation of a Secondary Amine Core with Calcium Carbide for Efficient Post-Modification and Access to Polymeric Materials Konstantin S. Rodygin 1, Alexander S. Bogachenkov 1 and Valentine P. Ananikov 1,2,* ID 1 Saint Petersburg State University, Universitetsky Prospect, 26, St. Petersburg 198504, Russia; [email protected] (K.S.R.); [email protected] (A.S.B.) 2 Zelinsky Institute of Organic Chemistry, Russian Academy of Science, Leninsky Prospect, 47, Moscow 119991, Russia * Correspondence: [email protected] Received: 16 February 2018; Accepted: 9 March 2018; Published: 13 March 2018 Abstract: We developed a simple and efficient strategy to access N-vinyl secondary amines of various naturally occurring materials using readily available solid acetylene reagents (calcium carbide, KF, and KOH). Pyrrole, pyrazole, indoles, carbazoles, and diarylamines were successfully vinylated in good yields. Cross-linked and linear polymers were synthesized from N-vinyl carbazoles through free radical and cationic polymerization. Post-modification of olanzapine (an antipsychotic drug substance) was successfully performed. Keywords: acetylene; calcium carbide; vinylation; olanzapine; functionalization 1. Introduction Nitrogen-containing compounds are one of the most important functional molecules in modern chemistry, biology, and drug development. Nucleic acids, N-heterocyclic compounds, amines, amino-acids, and their biopolymers are pivotal to a vast majority of biochemical processes. Effective modification of secondary amines by the insertion of a vinyl group leads to demanded N-vinyl derivatives with a variety of new applications. Vinylated products are interesting both as biologically active cores [1] and as versatile building blocks for polymerization [2]. At the same time, carbazole-based compounds are considered promising as photoconductors and charge-transporting materials [3] in the aftermath of the discovery of photoconductivity in poly(N-vinylcarbazole) [4]. The unique properties of vinyl amines are exemplified by their ability to polymerize under both cationic [5] and free radical conditions [6]. Polymer synthesis with N-heterocyclic moieties like diazepine has great potential for application. The biologically active core can be converted into a polymeric form, which is capable of gradual depolymerization and release under specific conditions. Current methods for preparing N-vinyl derivatives of secondary amines involve the vinyl exchange reaction (Scheme1, route a), which requires a source of vinyl group (in most cases represented by vinyl acetate) and a metal catalyst. Enamines from nitrogenous bases [7], imidazole [8], triazoles [9], carbazole [10], and pyrrolidone [11] can be successfully obtained by this approach. Molecules 2018, 23, 648; doi:10.3390/molecules23030648 www.mdpi.com/journal/molecules Molecules 2018, 23, 648 2 of 11 Molecules 2018, 23, x 2 of 11 SchemeScheme 1. 1.SyntheticSynthetic procedures procedures to accessaccessN N-vinyl‐vinyl derivatives. derivatives. CrossCross-coupling‐coupling reactions, reactions, catalyzed catalyzed by by copper copper [12] [12] andand iron iron [ 13[13],], or or palladium palladium complexes complexes [14], [14], requirerequire a partner: a partner: trimethyloxyvinylsilane trimethyloxyvinylsilane [ 15[15],], potassium potassium vinyltrifluoroborate vinyltrifluoroborate [16], or [16], vinyl or halide vinyl [17 halide] [17] (Scheme1 ,1, route route b). Anotherb). Another non-atom non‐ economicatom economic strategy, strategy, elimination, elimination, is based on ais two-step based on sequence, a two‐step sequence,which which is carried is carried out under out basic under conditions basic conditions (Scheme1 ,(Scheme route c). 1, The route Clemo-Perkin c). The Clemo method‐Perkin [ 18] andmethod [18] dehydrohalogenationand dehydrohalogenation in the presence in the ofpresence phase transfer of phase catalyst transfer [19] lead catalyst to N-vinyl [19] derivativeslead to N of‐vinyl derivativesindoles of [20 indoles], carbazoles [20], [carbazoles21], imidazoles [21], [ 22imidazoles], pyrazoles, [22], triazoles, pyrazoles, or tetrazoles triazoles, [23 or] and tetrazoles nitrogenous [23] and nitrogenousbases [24 ].bases Several [24]. other Several transformations other transformations leading to N-vinyl leading derivatives, to suchN‐vinyl as dehydrogenation derivatives, [such25], as ethylene insertion [26], and amine/aldehyde condensation could be also mentioned [27]. dehydrogenation [25], ethylene insertion [26], and amine/aldehyde condensation could be also An excellent atom-economic opportunity is provided by the addition reaction of acetylene, mentioned [27]. proceeding without by-product formation, which is to say that all atoms of starting materials become incorporatedAn excellent into atom products.‐economic This opportunity reaction (Scheme is provided1, route by d) the was addition originally reaction implemented of acetylene, by proceedingReppe [without28], and by it is‐product still used formation, with several which optimizations is to say that [29 all]. atoms Arylamines of starting can be materials successfully become incorporatedvinylated into according products. to this This procedure reaction [ 30(Scheme]. However, 1, route using d) andwas handlingoriginally pressured implemented acetylene by Reppe is [28], technicallyand it is still difficult used and with requires several dedicated optimizations hardware [29]. [31, 32Arylamines]. Not surprisingly, can be thissuccessfully atom-economic vinylated accordingapproach, to this despite procedure being efficient [30]. However, in terms ofusing chemistry, and handling has not found pressured widespread acetylene application is technically in difficultsynthetic and requires practice. dedicated hardware [31,32]. Not surprisingly, this atom‐economic approach, despite beingAs an alternativeefficient in to terms high pressure of chemistry, acetylene, has calcium not found carbide widespread has demonstrated application a very impressive in synthetic practice.potential in organic transformations [32–40]. Calcium carbide is inexpensive and readily available at the large-scale commercial production level. Currently, a carbide-based synthesis is underestimated in As an alternative to high pressure acetylene, calcium carbide has demonstrated a very its potential to provide not only useful intermediates for lab chemistry, but also materials and polymers impressive potential in organic transformations [32–40]. Calcium carbide is inexpensive and readily for fine technology [32,40]. As representative examples, the vinylation of O-H and S-H groups has availablebeen reportedat the large [36–‐40scale]. However, commercial the vinylation production of the level. N-H Currently, group is challenging, a carbide‐ andbased only synthesis indole is underestimatedderivatives have in its been potential studied to [ 41provide]. Recently, not only we developed useful intermediates a concept involving for lab a chemistry, solid acetylene but also materialsreagent, and where polymers the reactivity for fine oftechnology calcium carbide [32,40]. and As in representative situ generated examples, acetylene was the tunedvinylation by the of O‐ H andaddition S‐H ofgroups KF [38 ].has been reported [36–40]. However, the vinylation of the N‐H group is challenging,In this and work, only weindole developed derivatives a synthetic have been methodology studied [41]. for preparing Recently,N we-vinyl developed derivatives a concept of involvingsecondary a solid amines acetylene by utilizing reagent, a solid where acetylene the reactivity reagent (Schemeof calcium1, route carbide e). Fluoride-mediatedand in situ generated acetylene was tuned by the addition of KF [38]. In this work, we developed a synthetic methodology for preparing N‐vinyl derivatives of secondary amines by utilizing a solid acetylene reagent (Scheme 1, route e). Fluoride‐mediated vinylation is a powerful and new approach not addressed previously for the functionalization of amines. The vinylation of pyrrole, pyrazole, carbazoles, and diarylamines is reported here for the first time. This method has a number of key advantages from the standpoint of green chemistry (Scheme Molecules 2018, 23, 648 3 of 11 Molecules 2018, 23, x 3 of 11 vinylation1, route is e) a powerfuland a very and newsimple approach practical not procedure addressed was previously developed for the using functionalization a combination of of amines.CaC2 The/KOH/KF. vinylation of pyrrole, pyrazole, carbazoles, and diarylamines is reported here for the first time. This method has a number of key advantages from the standpoint of green chemistry (Scheme1, route2. Results e) and a and very Discussion simple practical procedure was developed using a combination of CaC2/KOH/KF. Optimization of the proposed system was carried out to find the optimal conditions, particularly 2. Results and Discussion the solvent and the temperature. First, a dedicated experiment was performed to choose a solvent: piecesOptimization of calcium of the carbide proposed were system exposed was to carried a solvent/water out to find the mixture optimal under conditions, stirring. particularly In cases of thehydrophobic solvent and thesolvents temperature. (e.g., hexane First, or a dedicatedtoluene), two experiment phases appeared, was performed and calcium to choose carbide a solvent: reacted piecesmuch of faster calcium when carbide the water were was exposed heavier to than a solvent/water the solvent. In mixture both cases, under the stirring.
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