Mechanochemistry-assisted synthesis of hierarchical porous carbons applied as supercapacitors

• Desirée Leistenschneider,
• Nicolas Jäckel,
• Felix Hippauf,
• Volker Presser and
• Lars Borchardt

Beilstein J. Org. Chem. 2017, 13, 1332–1341, doi:10.3762/bjoc.13.130

• done in 1 M TEA-BF4 in acetonitrile (ACN) and neat EMIM-BF4 as an ionic liquid. Since ionic liquids show a lower ion mobility as compared to aqueous or organic electrolytes, a well-connected transport pore system is of particular importance to guarantee a fast ion transport and should result in better

• cyclic voltammograms (CVs) in both electrolytes (Figure 7A,B) [53]. At low current rates, the material shows good specific capacitance (Table 2) of 138 F g−1 in neat EMIM-BF4 and 98 F g−1 in 1 M TEA-BF4 (ACN) determined by galvanostatic cycling with potential limitation at 0.1 A g−1. These values are

Metal-free hydroarylation of the side chain carbon–carbon double bond of 5-(2-arylethenyl)-3-aryl-1,2,4-oxadiazoles in triflic acid

• Anna S. Zalivatskaya,
• Dmitry S. Ryabukhin,
• Marina V. Tarasenko,
• Alexander Yu. Ivanov,
• Irina A. Boyarskaya,
• Elena V. Grinenko,
• Ludmila V. Osetrova,
• Eugeniy R. Kofanov and
• Aleksander V. Vasilyev

Beilstein J. Org. Chem. 2017, 13, 883–894, doi:10.3762/bjoc.13.89

• University, Universitetskaya nab., 7/9, Saint Petersburg, 199034, Russia Institute of Synthetic Rubber, Gapsalskaya str., 1, Saint Petersburg, 198035, Russia 10.3762/bjoc.13.89 Abstract The metal-free reaction of 5-(2-arylethenyl)-3-aryl-1,2,4-oxadiazoles with arenes in neat triflic acid (TfOH, CF3SO3H

• protonation of the C=C bond of 1a in H2SO4 does not take place even at elevated temperature (75 °C, see Table 2, entry 1). Also, Lewis acids such as AlCl3 and AlBr3 are not effective in this transformation (Table 2, entries 2 and 3). The best results were obtained in neat TfOH. The substituents present in the

• temperature (Table 2, entries 13, 16, 27, 28, and 30). Increasing the acidity of the reaction medium promotes the protonation of deactivated oxadiazoles. Thus, compound 1b in the system TfOH-SbF5 (20 mol %) reacted with benzene within 0.5 h at room temperature (Table 2, entry 9), but in less acidic neat TfOH

Molecular-level architectural design using benzothiadiazole-based polymers for photovoltaic applications

• Vinila N. Viswanathan,
• Arun D. Rao,
• Upendra K. Pandey,
• Arul Varman Kesavan and
• Praveen C. Ramamurthy

Beilstein J. Org. Chem. 2017, 13, 863–873, doi:10.3762/bjoc.13.87

• , 1,2-difluorobenzene was reacted with trimethylsilyl chloride in the presence of lithium diisopropylamide to afford the 1,4-disilylated intermediate 4 and bromination of the latter compound in neat bromine afforded the desired 1,4-dibromo-2,3-difluorobenzene (5). Nitration of 5 by treatment with fuming

Sulfamide chemistry applied to the functionalization of self-assembled monolayers on gold surfaces

• Loïc Pantaine,
• Vincent Humblot,
• Vincent Coeffard and
• Anne Vallée

Beilstein J. Org. Chem. 2017, 13, 648–658, doi:10.3762/bjoc.13.64

• ) δ 20.2 (2C), 118.6 (4C), 119.1 (4C), 129.2 (2C), 129.4 (4C), 130.5 (4C), 132.3 (2C), 135.2 (2C), 138.6 (2C); IR (neat): 3291, 3031, 2918, 2857, 1449, 1329, 1150, 903, 807, 622, cm-1; HRMS–ESI (m/z): [M + H]+ calcd for C26H27N4O4S4 587.0915, found: 587.0920. Monolayer preparation A solution of 4

Brønsted acid-mediated cyclization–dehydrosulfonylation/reduction sequences: An easy access to pyrazinoisoquinolines and pyridopyrazines

• Ramana Sreenivasa Rao and
• Chinnasamy Ramaraj Ramanathan

Beilstein J. Org. Chem. 2017, 13, 428–440, doi:10.3762/bjoc.13.46

• the cyclization reaction in the presence of TfOH at room temperature to generate a potential precursor for the synthesis of praziquantel. To realize the cyclization, the imide 7h was treated with TfOH under neat conditions at 70 °C, quite unfortunately to witness the decomposition of imide 7h. This

• the potassium salt of N-benzyliminodiacetic acid in THF at reflux to furnish the expected imides 8a–c, 8h, and 8i in good yields (Scheme 6). The imide 8h was subjected to the cyclization reaction conditions using 6 equivalents of TfOH under neat conditions at 70 °C followed by reduction using NaBH4

NMR reaction monitoring in flow synthesis

• M. Victoria Gomez and
• Antonio de la Hoz

Beilstein J. Org. Chem. 2017, 13, 285–300, doi:10.3762/bjoc.13.31

• achieved. Solenoid coils have been investigated in detail. A representative example was reported by Sweedler et al. [17] who designed a microsolenoid coil with a detection cell volume of ca. 5 nL, and line widths of only 0.6 Hz for a neat ethylbenzene sample. Recently, a new manufacturing procedure, by

Organofluorine chemistry: Difluoromethylene motifs spaced 1,3 to each other imparts facial polarity to a cyclohexane ring

• Mathew J. Jones,
• Ricardo Callejo,
• Alexandra M. Z. Slawin,
• Michael Bühl and
• David O'Hagan

Beilstein J. Org. Chem. 2016, 12, 2823–2827, doi:10.3762/bjoc.12.281

• diketones 5a–c was explored with DAST or Deoxo-Fluor® (Scheme 3). When diketones 5a and 5b were treated with DAST or Deoxo-Fluor®, either neat or in DCM as a solvent, only complex and intractable products were obtained. These highly enolisable diketones [27][28] were incompatible with deoxyfluorination. In

Synthesis of spiro[isoindole-1,5’-isoxazolidin]-3(2H)-ones as potential inhibitors of the MDM2-p53 interaction

• Salvatore V. Giofrè,
• Santa Cirmi,
• Raffaella Mancuso,
• Francesco Nicolò,
• Giuseppe Lanza,
• Laura Legnani,
• Agata Campisi,
• Maria A. Chiacchio,
• Michele Navarra,
• Bartolo Gabriele and
• Roberto Romeo

Beilstein J. Org. Chem. 2016, 12, 2793–2807, doi:10.3762/bjoc.12.278

• '-isoxazolidin]-3-one (6b): Yellow sticky oil (Yield: 69 mg, 48 %); IR (neat) νmax: 1685, 1640 cm−1; 1H NMR (500 MHz, CDCl3) δ 7.72–7.68 (m, 1H), 7.62–7.53 (m, 1H), 7.53–7.49 (m, 1H), 7.47–7.42 (m, 1H), 7.41–7.34 (m, 2H), 7.34–7.27 (m, 3H), 4.20 (d, J = 12.7 Hz, 1H), 4.00 (d, J = 12.7 Hz, 1H), 3.92–3.83 (m, 1H

• C26H32N3O4, 450.2393; found, 450.2422. (1RS,4'RS)-2'-Benzyl-2-butyl-4'-(piperidine-1-carbonyl)spiro[isoindoline-1,5'-isoxazolidin]-3-one (6d): White sticky oil (Yield: 45 mg, 35%); IR (neat) νmax: 1684, 1631 cm−1; 1H NMR (500 MHz, CDCl3) δ 7.73–7.69 (m, 1H), 7.54–7.43 (m, 3H), 7.37–7.34 (m, 2H), 7.33–7.26 (m

• ]-4'-carboxamide (6e): Yellow oil (Yield: 52 mg, 38%); IR (neat) νmax: 1705, 1686, 1628 cm−1; 1H NMR (500 MHz, CDCl3) δ 7.71–7.67 (m, 1H), 7.62–7.26 (m, 8H), 4.17 (d, J = 12.7 Hz, 1H), 4.10–4.03 (m, 1H), 3.99 (d, J = 12.7 Hz, 1H), 3.88–3.79 (m, 1H), 3.74–3.66 (m, 1H), 3.62–3.54 (m, 1H), 3.54–3.40 (m

Direct arylation catalysis with chloro[8-(dimesitylboryl)quinoline-κN]copper(I)

• Sem Raj Tamang and
• James D. Hoefelmeyer

Beilstein J. Org. Chem. 2016, 12, 2757–2762, doi:10.3762/bjoc.12.272

• . Activation of the sp2 C–H bonds in naphthalene was possible as well. The reaction of iodobenzene in neat naphthalene at 85 °C using 0.2 mol % catalyst and 3 equivalents KO(t-Bu) gave a ≈2:1 ratio of 1-phenylnaphthalene and 2-phenylnaphthalene in a total yield of 43% (Table 1, entry 18). The observed

Effects of solvent additive on “s-shaped” curves in solution-processed small molecule solar cells

• John A. Love,
• Shu-Hua Chou,
• Ye Huang,
• Guilllermo C. Bazan and
• Thuc-Quyen Nguyen

Beilstein J. Org. Chem. 2016, 12, 2543–2555, doi:10.3762/bjoc.12.249

• scattering (GIWAXS) was used to probe the crystallization behavior of the blend system with and without additive. The full 2-dimensional GIWAXS spectra from a film of the neat p-SIDT(FBTThCA8)2 and the two blends are shown in Figure S7 (Supporting Information File 1) while line cuts showing Qz (“out-of-plane

• peaks. In the neat p-SIDT(FBTThCA8)2 there is a relatively weak, broad feature at 1.52 Å−1 which convolves with the isotropic scattering peak of PC71BM which is typically found at 1.3–1.4 Å−1. These two peaks are nearly resolvable in the in-plane scattering of the film cast with DIO but are completely

• blends, and space charge may occur due to imbalanced carrier mobilities in the device processed without DIO. However, the hole mobilities for blends processed without DIO and with 1.5% DIO are 5 × 10−5 and 9 × 10−5 cm2/Vs, respectively, each slightly lower than the neat hole mobility of p-SIDT(FBTThCA8)2

Comparing blends and blocks: Synthesis of partially fluorinated diblock polythiophene copolymers to investigate the thermal stability of optical and morphological properties

• Pierre Boufflet,
• Sebastian Wood,
• Jessica Wade,
• Zhuping Fei,
• Ji-Seon Kim and
• Martin Heeney

Beilstein J. Org. Chem. 2016, 12, 2150–2163, doi:10.3762/bjoc.12.205

• comparable to the non-fluorinated case and so can also be described as C–C and C=C collective stretches, respectively [42]. The Raman spectra of both the 2:1 diblock and blend films resemble a linear combination of the spectra for the neat homopolymers, where the peak positions are the same as for the

• for both diblocks and the 1:2 blend samples than for neat F-P3OT. In fact, the observed temperature range of the transition is comparable with that of the neat P3OT homopolymer (≈260 °C), which suggests that the event occurring within the P3OT chains promotes a similar event in the F-P3OT sections. In

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

• under certain conditions [45][46]. Using a dichloromethane solution of PPSE, compound 4a was obtained exclusively (Table 2, entries 4–6), while working under solvent-free conditions further improved the yield (Table 2, entry 7). Employing the optimized reaction conditions (neat PPSE, 30 min at 150 °C

Potent triazine-based dehydrocondensing reagents substituted by an amido group

• Munetaka Kunishima,
• Daiki Kato,
• Nobu Kimura,
• Masanori Kitamura,
• Kohei Yamada and
• Kazuhito Hioki

Beilstein J. Org. Chem. 2016, 12, 1897–1903, doi:10.3762/bjoc.12.179

• esterification of 3-phenylpropanoic acid (1a) in neat MeOH were studied (Figure 3). Although X was shown to exist as a dihydrate by elemental analysis and single-crystal X-ray structure analysis, the yield of methyl 3-phenylpropanoate was quantitative. The rate of esterification with X was faster than that with

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

• observation that solutions in CDCl3 slowly turned pink (22 in particular). However, these compounds did not require special handling or precautions, and could be further derivatised without issue. In contrast, 20a was stable indefinitely when stored neat, or in solution at room temperature. This interesting

Synthesis and properties of fluorescent 4′-azulenyl-functionalized 2,2′:6′,2″-terpyridines

• Adrian E. Ion,
• Liliana Cristian,
• Mariana Voicescu,
• Masroor Bangesh,
• Augustin M. Madalan,
• Daniela Bala,
• Constantin Mihailciuc and
• Simona Nica

Beilstein J. Org. Chem. 2016, 12, 1812–1825, doi:10.3762/bjoc.12.171

• chemical manner, by grinding neat starting materials without the use of classical organic solvents [26]. The α,β-unsaturated ketone was formed in good yields, 72% for 2a and 70% for 2b, respectively using NaOH as base. The azulenyl-substituted chalcones are stable at room temperature for months, whereas at

• ∙A−3. Synthesis (E)-3-(Azulen-1-yl)-1-(pyridin-2-yl)prop-2-en-1-one (2a): Route A. A neat mixture of 2-acetylpyridine (121.0 mg, 0.11 mL, 1.0 mmol), 1-azulencarboxaldehyde (156 mg, 1.0 mmol) and NaOH (40.0 mg, 1.0 mmol) were placed in a mortar and grinded for 10–15 minutes while a green-brownish

• -yl)-3-(4,6,8-trimethylazulen-1-yl)prop-2-en-1-one (2b): This compound was prepared following Route A described above for chalcone 2a by grinding neat 2-acetylpyridine (121 mg, 0.11 mL, 1.0 mmol) with 4,6,8-trimethylazulene-1-carbaldehyde (198.0 mg, 1.0 mmol) and NaOH (40 mg, 1.0 mmol). The crude

TMSBr-mediated solvent- and work-up-free synthesis of α-2-deoxyglycosides from glycals

• Mei-Yuan Hsu,
• Yi-Pei Liu,
• Sarah Lam,
• Su-Ching Lin and
• Cheng-Chung Wang

Beilstein J. Org. Chem. 2016, 12, 1758–1764, doi:10.3762/bjoc.12.164

• reactions, is acknowledged as an acute inhalation hazard and carcinogen [65][66]. To date, only a few studies of glycosylation under neat conditions have been published. In these methods either the need of heating [67][68][69] or the use of ball milling [70][71][72] was demanded. Moreover, the selectivity

• - and α-selective O-2-deoxyglycosides from glycals. Results and Discussion In our preliminary study, 77% yield of 2-deoxythiolglucoside 2 was produced exclusively when glucal 1 in the presence of p-thiocresol was promoted by a stoichiometric amount of TMSBr under neat conditions at room temperature

• under ambient atmosphere (Table 1, α:β = 2:1, entry 1). Without work-up and washing, S-2-deoxyglycoside 2 could be directly isolated and purified by flash column chromatography. We further extended the scope of the reaction to other glycals by using TMSBr as the promoter under neat conditions (Table 1

On the cause of low thermal stability of ethyl halodiazoacetates

• Magnus Mortén,
• Martin Hennum and
• Tore Bonge-Hansen

Beilstein J. Org. Chem. 2016, 12, 1590–1597, doi:10.3762/bjoc.12.155

• (2b) in neat acetic acid (Table 1, entries 19 and 20). In the presence of trace amounts of solid Cu(OTf)2 in toluene-d8, 2b decayed with a half-life of approx. 23 min (Table 1, entry 21). Cu(OTf)2 is a well-known catalyst for decomposition of diazo compounds in general [5], but the catalyst loadings

3,6-Carbazole vs 2,7-carbazole: A comparative study of hole-transporting polymeric materials for inorganic–organic hybrid perovskite solar cells

• Wei Li,
• Munechika Otsuka,
• Takehito Kato,
• Yang Wang,
• Takehiko Mori and
• Tsuyoshi Michinobu

Beilstein J. Org. Chem. 2016, 12, 1401–1409, doi:10.3762/bjoc.12.134

• , 28.74, 27.71, 27.32, 26.96, 26.73, 24.27, 22.96, 17.37, 13.94, 13.58, 13.48, 10.75, 9.59 ppm; FTIR (neat) ν: 2955, 2923, 2852, 2361, 1798, 1652, 1614, 1581, 1462, 1419, 1376, 1342, 1276, 1258, 1218, 1143, 1063, 1014, 961, 867, 794, 749, 698, 679, 654, 624, 607 cm−1; MALDI–TOF MS (Mw = 859.4): m/z

• , 14.00, 11.21, 10.08, 7.84 ppm; FTIR (neat) v: 2955, 2923, 2870, 2852, 1485, 1458, 1441, 1415, 1376, 1339, 1319, 1250, 1200, 1146, 1071, 996, 962, 911, 860, 826, 814, 794, 741, 723, 710, 695, 653, 633, 616 cm−1; MALDI–TOF MS (Mw = 859.4): m/z = 860.5 ([M + H]+). Synthesis of 3,6-Cbz-EDOT Analogously to

• pressure, yielding 3,6-Cbz-EDOT (0.10 g, 60%). GPC (THF): Mn = 2.0 kg mol−1, Mw/Mn = 1.5; 1H NMR (300 MHz, CDCl3) δ 8.50–8.37 (br, Ar-H), 8.00–7.73 (br, Ar-H), 7.54–7.07 (br, Ar-H), 4.64–4.24 (br, CH2), 4.24–3.85 (br, OCH2), 2.04 (br, CH), 1.50–1.16 (br, CH2), 1.01–0.70 ppm (br, CH3); FTIR (neat) ν: 2955

Multicomponent reactions: A simple and efficient route to heterocyclic phosphonates

• Mohammad Haji

Beilstein J. Org. Chem. 2016, 12, 1269–1301, doi:10.3762/bjoc.12.121

• and the structure of the dialkyl phosphite and isatin (Scheme 9) [35]. In this way a one-pot three-component reaction between 1-tosylpiperidine-4-one (34), aromatic amines 35 and diethyl phosphonate in the presence of magnesium perchlorate as a catalyst, under neat conditions at 80 °C afforded α

Synthesis of a deuterated probe for the confocal Raman microscopy imaging of squalenoyl nanomedicines

• Eric Buchy,
• Branko Vukosavljevic,
• Maike Windbergs,
• Dunja Sobot,
• Camille Dejean,
• Simona Mura,
• Patrick Couvreur and
• Didier Desmaële

Beilstein J. Org. Chem. 2016, 12, 1127–1135, doi:10.3762/bjoc.12.109

• °C and concentrated under reduced pressure. The residue was directly chromatographed over silica gel eluting with cyclohexane/AcOEt 4:1 followed by neat AcOEt to provide GemSQ-d6 (3) as a colorless oil (36.0 mg, 72%). 1H NMR (CDCl3, 400 MHz) δ 9.15 (br s, 1H, NHCO), 8.10 (d, J = 7.5 Hz, 1H, H-6

Towards the total synthesis of keramaphidin B

• Pavol Jakubec,
• Alistair J. M. Farley and
• Darren J. Dixon

Beilstein J. Org. Chem. 2016, 12, 1096–1100, doi:10.3762/bjoc.12.104

• piperidin-2-one 17 in 71% yield. Lactonisation under Lewis acidic conditions afforded spirocyclic malonamate 18 possessing the correct relative stereochemistry for keramaphidin B, in 84% yield. Aminolysis under neat conditions with hex-5-en-1-amine (19) gave the primary alcohol 20 (67% yield), which was

• h, 84% yield; (e) 19 (neat), 130 °C, 24 h, 67% yield; (f) (COCl)2, DMSO, NEt3, CH2Cl2, −78 °C to rt, 0.5 h, 88% yield; (g) Cp2Ti(CH3)2, THF/toluene, reflux, 0.33 h, 42% yield. Supporting Information Supporting Information File 200: Experimental procedures, analytical data, copies of NMR spectra and

Catalytic asymmetric synthesis of biologically important 3-hydroxyoxindoles: an update

• Bin Yu,
• Hui Xing,
• De-Quan Yu and
• Hong-Min Liu

Beilstein J. Org. Chem. 2016, 12, 1000–1039, doi:10.3762/bjoc.12.98

• to the total synthesis of natural TMC-95A. In 2015, Yang and co-workers reported α-amino acid sulfonamide (cat. 7)-catalyzed aldol reactions of ketones with isatins under neat conditions (Scheme 20) [36]. Interestingly, the reactions proceeded smoothly, giving the desired products in high yields (up

Reactions of N,3-diarylpropiolamides with arenes under superelectrophilic activation: synthesis of 4,4-diaryl-3,4-dihydroquinolin-2(1H)-ones and their derivatives

• Larisa Yu. Gurskaya,
• Diana S. Belyanskaya,
• Dmitry S. Ryabukhin,
• Denis I. Nilov,
• Irina A. Boyarskaya and
• Aleksander V. Vasilyev

Beilstein J. Org. Chem. 2016, 12, 950–956, doi:10.3762/bjoc.12.93

• yields of the target products. Thus, it is better to conduct the reaction in neat TfOH, which is a good weak nucleophilic medium for the stabilization of the intermediate cationic species. No concurrent formation of the corresponding 4-arylquinolinones 3 was observed, and in most cases the yields of the

Iridium/N-heterocyclic carbene-catalyzed C–H borylation of arenes by diisopropylaminoborane

• Mamoru Tobisu,
• Takuya Igarashi and
• Naoto Chatani

Beilstein J. Org. Chem. 2016, 12, 654–661, doi:10.3762/bjoc.12.65

• instability of 11-B during isolation (Table 2, entry 8). Our protocol was able to borylate non-benzofused five-membered heteroarenes. Pyrrole 12 was much less reactive than indoles, and required neat conditions to obtain a modest yield of the borylated product 12-B (Table 2, entry 9). Thiophene (13) afforded

• 1g afforded 17-B in 48% isolated yield even when the reaction was conducted under neat conditions (Table 3, entry 1) (see the Supporting Information File 1 for details on the optimization for the borylation of benzene). Borylation was relatively independent of the electronic nature of the arene

Supported bifunctional thioureas as recoverable and reusable catalysts for enantioselective nitro-Michael reactions

• José M. Andrés,
• Miriam Ceballos,
• Alicia Maestro,
• Isabel Sanz and
• Rafael Pedrosa

Beilstein J. Org. Chem. 2016, 12, 628–635, doi:10.3762/bjoc.12.61

• the thiourea derived from (L)-valine and 1,6-hexanediamine. The catalysts can be used in only 2 mol % loading, and reused for at least four cycles in neat conditions. The ball milling promoted additions also worked very well. Keywords: bifunctional organocatalysts; organocatalysis; stereoselective

• nucleophile in neat conditions and in different solvents. For comparative purposes, the same reactions were studied in the presence of unsupported catalysts I and VI, and the results are summarized in Scheme 1 and Table 1. Initially, the reactions were carried out in neat conditions at rt with twofold excess

• ) reacted very well with 1a, leading to 5ae in excellent yield and enantioselectivity, but only moderate diastereoselectivity (dr 70:30, Table 3, entry 10). To test the recyclability of catalyst V we choose the reaction of 1a with 3a in neat conditions and 5 mol % of catalyst as model. Once the reaction had