Synthesis, characterization and initial evaluation of 5-nitro-1-(trifluoromethyl)-3H-1λ³,2-benziodaoxol-3-one

• Nico Santschi,
• Roman C. Sarott,
• Elisabeth Otth,
• Reinhard Kissner and
• Antonio Togni

Beilstein J. Org. Chem. 2014, 10, 1–6, doi:10.3762/bjoc.10.1

• characterized by means of X-ray crystallography. Due to the very poor solubility of 6 in most common solvents, suitable single crystals for solid-state analysis were grown from a saturated solution in hot MeCN that was slowly cooled to −20 °C. Similarly, suitable crystals of reagent 3 were obtained from a

Advancements in the mechanistic understanding of the copper-catalyzed azide–alkyne cycloaddition

• Regina Berg and
• Bernd F. Straub

Beilstein J. Org. Chem. 2013, 9, 2715–2750, doi:10.3762/bjoc.9.308

• copper(I) complexes, which are highly active in CuAAC reactions on water or under neat conditions (Scheme 7) [130]. Albeit no single crystals of the copper(I) complex shown in Scheme 7 could be grown, NMR measurements as well as a single crystal X-ray structure of an analogous C186tren-complex with CuCl2

IBD-mediated oxidative cyclization of pyrimidinylhydrazones and concurrent Dimroth rearrangement: Synthesis of [1,2,4]triazolo[1,5-c]pyrimidine derivatives

• Caifei Tang,
• Zhiming Li and
• Quanrui Wang

Beilstein J. Org. Chem. 2013, 9, 2629–2634, doi:10.3762/bjoc.9.298

• reactions. The structure of bicycles 6a–o was principally assigned from their spectral evidence and mass spectrometry analysis (see Supporting Information File 2 for full data). To confirm the structure of the regio-isomer of the cyclization rearrangement, colorless single crystals of compound 6h were

Crystal design using multipolar electrostatic interactions: A concept study for organic electronics

• Peer Kirsch,
• Qiong Tong and
• Harald Untenecker

Beilstein J. Org. Chem. 2013, 9, 2367–2373, doi:10.3762/bjoc.9.272

• techniques [3]. High charge carrier mobilities are a particularly critical prerequisite for application in backplanes for OLED displays. The highest charge carrier mobilities in organic compounds have so far been reported for single crystals of small molecules [4], the “classics” among them being acenes such

• 412.0358798; found, 412.03517; Single crystals for the X-ray structure analysis were obtained by slow crystallization from THF. Crystal structure data for 1 (C22H8F4O4): crystal size 0.0909 × 0.045 × 0.0297 mm, triclinic, P−1, a = 6.0570(9) Å, b = 7.6382(12) Å, c = 8.829(3) Å, α = 94.98(2)°, β = 97.72(2)°, γ

Synthesis of axially chiral gold complexes and their applications in asymmetric catalyses

• Yin-wei Sun,
• Qin Xu and
• Min Shi

Beilstein J. Org. Chem. 2013, 9, 2224–2232, doi:10.3762/bjoc.9.261

• was identified as 1:2 on the basis of 1H NMR spectroscopic data. After recrystallization from the mixed solvent of DCM and pentane, the single crystals of diastereomers (S)-15a and (S)-15b were obtained and their structures were confirmed by the X-ray crystal structure diffraction (Figure 2 and Figure

The preparation of several 1,2,3,4,5-functionalized cyclopentane derivatives

• André S. Kelch,
• Peter G. Jones,
• Ina Dix and
• Henning Hopf

Beilstein J. Org. Chem. 2013, 9, 1705–1712, doi:10.3762/bjoc.9.195

• chiral (C2-symmetrical) configuration (trans-orientation of hydrogen atoms) of 24. Fortunately, recrystallization of a 24/25-mixture from diethyl ether provided single crystals of 24 suitable for an X-ray structure investigation which proved the chiral configuration (Figure 2). The ring contraction of a

Gold-catalyzed intermolecular hydroamination of allenes with sulfonamides

• Chen Zhang,
• Shao-Qiao Zhang,
• Hua-Jun Cai and
• Dong-Mei Cui

Beilstein J. Org. Chem. 2013, 9, 1045–1050, doi:10.3762/bjoc.9.117

• (Table 3, entry 5). Single crystals of the compound 3l suitable for X-ray crystallographic analysis were also obtained (Figure 1). This shows that 3l is the E isomer, the sulfonamide carbon link being trans to the phenyl group (Figure 1). As for differentially 1,3- disubstituted allene 1g, hydroamination

• 7). Single crystals of the compound 3n suitable for X-ray crystallographic analysis were also obtained (Figure 2). This showed that 3n is the E isomer, the sulfonamide being trans to the diphenylmethyl groups (Figure 2). The proposed mechanism of the gold-catalyzed hydroaamination of allenes is

Synthesis and structure of trans-bis(1,4-dimesityl-3-methyl-1,2,3-triazol-5-ylidene)palladium(II) dichloride and diacetate. Suzuki–Miyaura coupling of polybromoarenes with high catalytic turnover efficiencies

• Jeelani Basha Shaik,
• Venkatachalam Ramkumar,
• Babu Varghese and
• Sethuraman Sankararaman

Beilstein J. Org. Chem. 2013, 9, 698–704, doi:10.3762/bjoc.9.79

• single crystals suitable for X-ray crystallography. Complex 1 crystallized in the tetragonal space group I41/acd. The structure of the complex in the crystal clearly showed it to be a mononuclear complex with two chloro ligands trans with respect to each other, the two triazolylidene ligands also trans

Spin state switching in iron coordination compounds

• Philipp Gütlich,
• Ana B. Gaspar and
• Yann Garcia

Beilstein J. Org. Chem. 2013, 9, 342–391, doi:10.3762/bjoc.9.39

• ) was first applied to investigate the SCO compound [Fe(phen)2(NCS)2] [110] and later on to study the SCO behavior of single crystals of [Fe(ptz)6](BF4)2 and zinc-diluted mixed crystals thereof [111]. Although one has observed changes of specific PAS parameters (Doppler broadening of the annihilation

• ) doped with 1% Mn(II) and later by Haasnoot et al. [120] with [Fe(btr)2(NCS)2]·H2O (btr = 4,4’-bis-1,2,4-triazole) doped with ca. 10% Cu(II). Employing this technique, McGarvey et al. also measured excellent quality EPR spectra of single crystals of [Fe(ptz)6](BF4)2 doped with 1% Mn(II) [121]. They

A new synthetic access to 2-N-(glycosyl)thiosemicarbazides from 3-N-(glycosyl)oxadiazolinethiones and the regioselectivity of the glycosylation of their oxadiazolinethione precursors

• El Sayed H. El Ashry,
• El Sayed H. El Tamany,
• Mohy El Din Abdel Fattah,
• Mohamed R. E. Aly,
• Ahmed T. A. Boraei and
• Axel Duerkop

Beilstein J. Org. Chem. 2013, 9, 135–146, doi:10.3762/bjoc.9.16

• galactosyltriazole 30. Single crystals were slowly grown in EtOH. 23 crystallized in the monoclinic space group C2 with the following unit cell parameters: a = 25.7078 Å, α = 90º, b = 7.1500 Å, β = 105.2576º, c = 17.8411 Å, γ = 90º and V = 3163.81 Å3. The crystallographic data of 23 are shown in Table 1. The whole

Inclusion of the insecticide fenitrothion in dimethylated-β-cyclodextrin: unusual guest disorder in the solid state and efficient retardation of the hydrolysis rate of the complexed guest in alkaline solution

• Dyanne L. Cruickshank,
• Natalia M. Rougier,
• Raquel V. Vico,
• Susan A. Bourne,
• Elba I. Buján,
• Mino R. Caira and
• Rita H. de Rossi

Beilstein J. Org. Chem. 2013, 9, 106–117, doi:10.3762/bjoc.9.14

• solution of DIMEB (96 mg, 0.072 mmol) at 20 °C. Continuous stirring for 6 h, as well as several heating and cooling cycles between 20 and 60 °C led to formation of a clear solution, which was then filtered into a clean vial, capped and placed in an oven at 60 °C. Colourless single crystals of the complex

Features of the behavior of 4-amino-5-carboxamido-1,2,3-triazole in multicomponent heterocyclizations with carbonyl compounds

• Eugene S. Gladkov,
• Katerina A. Gura,
• Svetlana M. Sirko,
• Sergey M. Desenko,
• Ulrich Groth and
• Valentin A. Chebanov

Beilstein J. Org. Chem. 2012, 8, 2100–2105, doi:10.3762/bjoc.8.236

• Eugene S. Gladkov Katerina A. Gura Svetlana M. Sirko Sergey M. Desenko Ulrich Groth Valentin A. Chebanov Division of Chemistry of Functional Materials, State Scientific Institution “Institute for Single Crystals” of National Academy of Sciences of Ukraine, Lenin Ave. 60, 61158 Kharkiv, Ukraine

The chemistry of bisallenes

• Henning Hopf and
• Georgios Markopoulos

Beilstein J. Org. Chem. 2012, 8, 1936–1998, doi:10.3762/bjoc.8.225

• have been studied [96][97], as has been that of the tetramethyl derivative 24 [98][99]. Although 2 is a liquid at room temperature and its structure in the solid state has not been determined so far, many X-ray structural investigations of single crystals of derivatives of 2 have been carried out. We

Organocatalytic cascade aza-Michael/hemiacetal reaction between disubstituted hydrazines and α,β-unsaturated aldehydes: Highly diastereo- and enantioselective synthesis of pyrazolidine derivatives

• Zhi-Cong Geng,
• Jian Chen,
• Ning Li,
• Xiao-Fei Huang,
• Yong Zhang,
• Ya-Wen Zhang and
• Xing-Wang Wang

Beilstein J. Org. Chem. 2012, 8, 1710–1720, doi:10.3762/bjoc.8.195

• were able to obtain single crystals of compounds 4a and 4n, which allowed for an unambiguous assignment of the trans configuration of C3 and C5 by X-ray crystallographic analysis (Figure 2 and Figure 3). Then, we turned our attention to the development of the asymmetric version of the cascade aza

• 19). Fortunately, single crystals of compound 4s were obtained by recrystallization from petroleum ether/acetyl acetate, and the absolute configuration was determined by X-ray analyses (Figure 4) [84]. Conclusion In summary, we have developed an organocatalytic approach for the synthesis of

The crystal structure of the Dess–Martin periodinane

• Albert Schröckeneder,
• Desiree Stichnoth,
• Peter Mayer and
• Dirk Trauner

Beilstein J. Org. Chem. 2012, 8, 1523–1527, doi:10.3762/bjoc.8.172

• this procedure with an older and less-active batch of Oxone, we obtained well-defined single crystals of acetoxy-1,2-benziodoxolin-3-one (4) as a byproduct. We quickly established that the crystal structure of this partially oxidized compound had already been described by Gougoutas and Clardy four

• the first X-ray crystal structure of DMP (1). This could serve as a basis for computational investigations concerning the mechanism of the Dess–Martin oxidation. Results and Discussion The difficulty in obtaining suitable single crystals for X-ray diffraction analysis of DMP (1) may lie in the high

• that the presence of these impurities may slow down nucleation and allow for the growth of larger crystals. Indeed, slow evaporation of the filtrate under a constant stream of nitrogen at ambient temperature over the course of four days did yield single crystals suitable for X-ray analysis. DMP (1

Synthesis of 2,6-disubstituted tetrahydroazulene derivatives

• Zakir Hussain,
• Henning Hopf,
• Khurshid Ayub and
• S. Holger Eichhorn

Beilstein J. Org. Chem. 2012, 8, 693–698, doi:10.3762/bjoc.8.77

• , which was recrystallized from hexane and dichloromethane to afford single crystals suitable for X-ray analysis. The X-ray data [20] showed that the central, six-membered ring is almost planar but is slightly folded about the axis C(2)···C(6); the five-membered ring is essentially planar. The two larger

• converted to 7 through thermal disrotatory electrocyclic ring opening and a base-catalyzed prototropic shift. The ester 7 underwent acid-catalyzed hydrolysis (formic acid) to afford 8 as a solid, which on recrystallization resulted in single crystals suitable for X-ray analysis (Scheme 2). The structural

Perhydroazulene-based liquid-crystalline materials with smectic phases

• Zakir Hussain,
• Henning Hopf and
• S. Holger Eichhorn

Beilstein J. Org. Chem. 2012, 8, 403–410, doi:10.3762/bjoc.8.44

• [17] was carried out in the presence of NaOH and MeOH. Acids 6a and 6b were obtained in the form of colorless solids, which were recrystallized from hexane/dichloromethane. Although the single crystals obtained were not suitable for a high-quality X-ray analysis, we could compare the NMR data of the

Synthesis of mesomeric betaine compounds with imidazolium-enolate structure

• Nina Gonsior,
• Fabian Mohr and
• Helmut Ritter

Beilstein J. Org. Chem. 2012, 8, 390–397, doi:10.3762/bjoc.8.42

• O–C–C–C–O vibration band was found at 1540 cm−1 in the IR spectra. By means of X-ray single-crystal analysis, the structure of 3 was clearly identified (Figure 3). Single crystals were obtained by the evaporation method, in which methylene chloride was used as the solvent. The compound crystallized

• C13H12Br2N2O3: C, 38.64; H, 2.99; N, 6.93; found: C, 38.65; H, 2.86; N, 6.59. X-ray crystal-structure analysis of 3 Single crystals of 3 were obtained by very slow evaporation of methylene chloride. They were mounted in inert oil and transferred to the cold gas stream of the diffractometer. Diffraction data

Self-assembly of Ru₄ and Ru₈ assemblies by coordination using organometallic Ru(II)₂ precursors: Synthesis, characterization and properties

• Sankarasekaran Shanmugaraju,
• Dipak Samanta and
• Partha Sarathi Mukherjee

Beilstein J. Org. Chem. 2012, 8, 313–322, doi:10.3762/bjoc.8.34

• molecular structure of the tetranuclear metallamacrocycle [(p-cymene)4Ru4(μ-η4-oxalato)2(L)]4+(O3SCF3−)4 (2a) was unambiguously determined by single-crystal X-ray diffraction analysis. Single crystals of 2a of high enough quality for X-ray diffraction were grown by slow vapor diffusion of diethyl ether into

• single crystals of the macrocycle 2c have so far been unsuccessful. However, the analysis of multinuclear NMR (1H, 13C and 19F) in concurrence with the ESIMS study is fully consistent with the formation of a [4 + 2] self-assembled octanuclear metallacage. In view toward gaining further insight into the

Double N-arylation reaction of polyhalogenated 4,4’-bipyridines. Expedious synthesis of functionalized 2,7-diazacarbazoles

• Mohamed Abboud,
• Emmanuel Aubert and
• Victor Mamane

Beilstein J. Org. Chem. 2012, 8, 253–258, doi:10.3762/bjoc.8.26

• were functionalized by a selective Suzuki coupling to give the new bipyridine derivatives 11a,b, which underwent the double N-arylation to afford 3,6-difunctionalized 2,7-diazacarbazoles 12a–c in good overall yields (Scheme 4). Single crystals of compounds 3b and 12c were obtained from evaporation of n

A ferrocene redox-active triazolium macrocycle that binds and senses chloride

• Nicholas G. White and
• Paul D. Beer

Beilstein J. Org. Chem. 2012, 8, 246–252, doi:10.3762/bjoc.8.25

• NMR spectroscopy where appropriate. Single crystals of 3 were grown by the vapour diffusion of diethyl ether into an acetone solution of the macrocycle, and of macrocycle 4 by vapour diffusion of pentane into a chloroform/methanol solution. The solid-state structures were determined by synchrotron X

Functionalization of anthracene: A selective route to brominated 1,4-anthraquinones

• Kiymet Berkil Akar,
• Osman Cakmak,
• Orhan Büyükgüngör and
• Ertan Sahin

Beilstein J. Org. Chem. 2011, 7, 1036–1045, doi:10.3762/bjoc.7.118

• , 310.2 [M − 2Br + Na + 2H]+, 271.0, 254.0, 227.1 [M − 3Br + Na + H]+, 149.1; Anal. Calcd for C14H5Br3O2: C, 37.79; H, 1.13; found: C, 37.79; H, 1.31. Crystallography For crystal structure determination, single crystals of compounds 7 and 17 were used for data collection on a four-circle Rigaku R-AXIS

Redox-active tetrathiafulvalene and dithiolene compounds derived from allylic 1,4-diol rearrangement products of disubstituted 1,3-dithiole derivatives

• Filipe Vilela,
• Peter J. Skabara,
• Christopher R. Mason,
• Thomas D. J. Westgate,
• Asun Luquin,
• Simon J. Coles and
• Michael B. Hursthouse

Beilstein J. Org. Chem. 2010, 6, 1002–1014, doi:10.3762/bjoc.6.113

• as precursors to highly electroactive polythiophenes [27][28]. We were interested in the self-assembly of compound 28 in the solid state to assess whether or not this material would be suitable as a semiconductor in OFETs [29]. Single crystals of compound 28 were grown from a dichloromethane/hexane

Synthesis and crystal structures of multifunctional tosylates as basis for star-shaped poly(2-ethyl-2-oxazoline)s

• Richard Hoogenboom,
• Martin W. M. Fijten,
• Guido Kickelbick and
• Ulrich S. Schubert

Beilstein J. Org. Chem. 2010, 6, 773–783, doi:10.3762/bjoc.6.96

• -oxazolines resulting in star-shaped polymers. The synthesis of the tosylates was performed by esterification of the corresponding alcohols with tosyl chloride. Recrystallization of these tosylate compounds afforded single crystals, and the X-ray crystal structures of di-, tetra- and hexa-tosylates are

• commercially available. Recrystallization of this compound from ethanol resulted in single crystals suitable for X-ray analysis. Butane ditosylate (DiTos-B; Scheme 1) was synthesized from 1,4-butanediol and an excess of tosyl chloride using dichloromethane as solvent and triethylamine as base. After 24 h

• multi-tosylates as initiators for the CROP of 2-oxazolines since they lead to side reactions with the cationic oxazolinium propagating species. Multi-tosylate crystal structures Recrystallization of the prepared multi-tosylates from ethanol or ethanol–acetone mixtures directly gave single crystals

Novel tetracyclic structures from the synthesis of thiolactone-isatin hybrids

• Renate Hazel Hans,
• Hong Su and
• Kelly Chibale

Beilstein J. Org. Chem. 2010, 6, No. 78, doi:10.3762/bjoc.6.78

• ′-substituted tetracycles (Table 1 and Table 2). This drawback can most likely be ascribed to entropy factors and stereoelectronic effects [45][46][47][48]. The structures of the tetracycles 4 were unambiguously assigned by single crystal X-ray crystallographic analysis. Single crystals for 4a–c were obtained