Cross-linked cyclodextrin-based material for treatment of metals and organic substances present in industrial discharge waters

• Élise Euvrard,
• Nadia Morin-Crini,
• Coline Druart,
• Justine Bugnet,
• Bernard Martel,
• Cesare Cosentino,
• Virginie Moutarlier and
• Grégorio Crini

Beilstein J. Org. Chem. 2016, 12, 1826–1838, doi:10.3762/bjoc.12.172

• of the sixteen PAHs was performed by liquid–liquid extraction with hexane followed by separation and detection on a system composed of a GC apparatus and a triple quadrupole spectrometer (GC-MS/MS, Agilent, Massy, France) according to a method described in detail by Crini and co-workers [36]. Three

• APs (4NP, 4nNP, 4tOP) were analyzed by a certified laboratory (CARSO LSEHL, Lyon, France), by liquid–liquid extraction followed by separation and detection on GC-MS/MS according to the standard NF EN ISO 18857-1. For the detailed analysis, 189 substances and 17 water parameters were analyzed, before

One-pot synthesis of 4′-alkyl-4-cyanobiaryls on the basis of the terephthalonitrile dianion and neutral aromatic nitrile cross-coupling

• Roman Yu. Peshkov,
• Elena V. Panteleeva,
• Wang Chunyan,
• Evgeny V. Tretyakov and
• Vitalij D. Shteingarts

Beilstein J. Org. Chem. 2016, 12, 1577–1584, doi:10.3762/bjoc.12.153

• )pentane – but the reaction mixture contained traces of compounds with molar masses of 325 and 352 (<1.5% according to GC–MS), which can be attributed to 4'-(5-phenylpentyl)-[1,1'-biphenyl]-4-carbonitrile and 4'-(5-(1-cyanocyclohexa-2,5-dien-1-yl)pentyl)-[1,1'-biphenyl]-4-carbonitrile, respectively. The

Microwave-assisted synthesis of (aminomethylene)bisphosphine oxides and (aminomethylene)bisphosphonates by a three-component condensation

• Erika Bálint,
• Ádám Tajti,
• Anna Dzielak,
• Gerhard Hägele and
• György Keglevich

Beilstein J. Org. Chem. 2016, 12, 1493–1502, doi:10.3762/bjoc.12.146

• 1 and 6, 7). The transesterified by-products (9-11 and 3c) were indentified by GC–MS (Figure 2) or LC–MS, and were proved by HRMS (Table 7). The composition of the reaction mixture for the experiment marked by Table 6, entry 6 was analyzed by 31P NMR (see Figure 3). It was observed that increasing

• , except two, all of them are new compounds. Furthermore, a few intermediates supporting the mechanism of the condensation, and several by-products were also identified. Effect of the quantity of dimethyl phosphite (DMP) on the product composition (from Table 6, entries 1–5.) GC–MS chromatogram for the

The hydrolysis of geminal ethers: a kinetic appraisal of orthoesters and ketals

• Sonia L. Repetto,
• James F. Costello,
• Craig P. Butts,
• Joseph K. W. Lam and
• Norman M. Ratcliffe

Beilstein J. Org. Chem. 2016, 12, 1467–1475, doi:10.3762/bjoc.12.143

• . HRMS–ESI calculated for [M + Na]+ 169.0835, found: 169.0836. The distribution of products resulting from the exchange reaction of 6 with dl- and meso-2,3-butanediol warrants brief comment; reaction of the former affords 10 [43], whereas the latter gives C(2) epimers 11 and 14. Both GC–MS and 1H NMR

The EIMS fragmentation mechanisms of the sesquiterpenes corvol ethers A and B, epi-cubebol and isodauc-8-en-11-ol

• Patrick Rabe and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2016, 12, 1380–1394, doi:10.3762/bjoc.12.132

• bacterial terpene cyclases corvol ether synthase from Kitasatospora setae, the epi-cubebol synthase from Streptosporangium roseum, and the isodauc-8-en-11-ol synthase from Streptomyces venezuelae. The enzyme products were analysed by GC–MS and GC–QTOF MS2 and the obtained data were used to delineate the

• standard. Furthermore, various high quality databases containing the EI mass spectra and retention indices of thousands of compounds are available that assist in automated compound identification [2][3]. If unknown compounds are detected in natural extracts, their structure elucidation by GC–MS is more

• . venezuelae ATCC 10712 [21], respectively. In previous work all used enzymes were mechanistically thoroughly studied, and therefore the locations of labellings in the obtained products are known [18][19][20][21][22]. The enzyme products were analysed via GC–MS, and for each of the 13C-labelled isotopomers of

Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(−)-myrtenol nitrate

• Sean P. Bew,
• Glyn D. Hiatt-Gipson,
• Graham P. Mills and
• Claire E. Reeves

Beilstein J. Org. Chem. 2016, 12, 1081–1095, doi:10.3762/bjoc.12.103

• compared to the starting materials as well as GC–MS analysis (negative ion mode) corroborated the O-nitrate ester groups were present. Although the use of silver nitrate had been validated in our ‘test’ reaction, the use of isoprene as a starting material was clearly not as convenient as first envisaged

A convenient route to symmetrically and unsymmetrically substituted 3,5-diaryl-2,4,6-trimethylpyridines via Suzuki–Miyaura cross-coupling reaction

• Dariusz Błachut,
• Joanna Szawkało and
• Zbigniew Czarnocki

Beilstein J. Org. Chem. 2016, 12, 835–845, doi:10.3762/bjoc.12.82

• halogenated pyridines and pyrimidines. During our search for new "route markers" of amphetamine analogues synthesized by the Leuckart method, we focused our attention on two groups of heterocycles, that were preliminary identified by GC–MS analysis as 3,4,5-triaryl-2,6-dimethylpyridines P5 [32][33] and 3,5

• ratio of was analysed by GC–MS (Table 1, entries 4–9). Full conversion of the starting material 1 was accomplished within 1 hour. However, the transformation of intermediary bromophenylpyridine 3 into 4 required further 15 hours. It was observed that during the last hour of the reaction, a significant

• applied. The best outcome in terms of the reaction time, yield of the diarylated product 4 and the content of byproducts were obtained using Pd(OAc)2 as palladium source and Buchwald ligands S-Phos and X-Phos [53][54][55] in toluene in the presence of K3PO4. As it was shown by GC–MS, full conversion of

A practical way to synthesize chiral fluoro-containing polyhydro-2H-chromenes from monoterpenoids

• Oksana S. Mikhalchenko,
• Dina V. Korchagina,
• Konstantin P. Volcho and
• Nariman F. Salakhutdinov

Beilstein J. Org. Chem. 2016, 12, 648–653, doi:10.3762/bjoc.12.64

• (61%). These conditions (Table 1, entry 6) were chosen as suitable for further research. Preparative production under the chosen conditions provided 72% of 8a by GC–MS and after separation by column chromatography the target fluorinated product 8a was isolated in 69% yield; the yield of compound 2a

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

• , analytical columns (250 × 4.6 mm) by using mixture of n-hexane/isopropanol as eluent. UV detection was monitored at 220 or at 254 nm. ESI mass spectra were obtained on an Agilent 5973 inert GC/MS system. Commercially available organic and inorganic compounds were used without further purification. Solvents

Antibiotics from predatory bacteria

• Juliane Korp,
• María S. Vela Gurovic and
• Markus Nett

Beilstein J. Org. Chem. 2016, 12, 594–607, doi:10.3762/bjoc.12.58

• associated pathway, (+)-O-methylkolavelool was identified as a metabolic product. Subsequent GC–MS analyses confirmed that this previously unknown diterpene is actually produced by the predatory bacterium [128]. From genomic data, it is evident that the genus Herpetosiphon harbors a significant potential for

Natural products from microbes associated with insects

• Christine Beemelmanns,
• Huijuan Guo,
• Maja Rischer and
• Michael Poulsen

Beilstein J. Org. Chem. 2016, 12, 314–327, doi:10.3762/bjoc.12.34

• on the outer cocoon surface. Subsequent gas chromatography–mass spectrometry (GC–MS) analyses and expression studies revealed that the production of both antibiotics peaked within the first two weeks after cocoon spinning [45]. Although expression levels decreased shortly afterwards, the antibiotic

Thermal and oxidative stability of Atlantic salmon oil (Salmo salar L.) and complexation with β-cyclodextrin

• Daniel I. Hădărugă,
• Mustafa Ünlüsayin,
• Alexandra T. Gruia,
• Cristina Birău (Mitroi),
• Gerlinde Rusu and
• Nicoleta G. Hădărugă

Beilstein J. Org. Chem. 2016, 12, 179–191, doi:10.3762/bjoc.12.20

• FAs (and the corresponding glycerides) are easily degraded by oxidation, especially at higher temperatures. An appropriate method for evaluating the overall FA profile is the gas chromatography–mass spectrometry (GC–MS) analysis of the FAs, derivatized to the corresponding methyl esters. The relative

• triglycerides from ASO of 899.5 g/mol (according to GC–MS analysis) and 1310 g/mol for β-CD hydrate (according to KFT analysis of water content of commercial β-CD). First, 1 mmol (or 3 mmol) of β-CD hydrate (1.313 ± 0.0007 g or 3.939 ± 0.0004 g) was suspended in 12 mL of distilled water and heated to 50 °C in

• mixture was thoroughly milled for 15 min. Afterwards the mixture was cooled to room temperature, washed with ethanol (1 mL) to remove surface oil, and dried to constant mass in a desiccator over MS 4Å. The kneaded complexes were prepared in duplicates. GC–MS analysis of the raw and degraded ASO The FA

Copper-catalyzed arylation of alkyl halides with arylaluminum reagents

• Bijay Shrestha and
• Ramesh Giri

Beilstein J. Org. Chem. 2015, 11, 2400–2407, doi:10.3762/bjoc.11.261

• , 22.8, 29.4, 29.5, 29.6, 31.7, 32.0, 36.1, 125.7, 128.3, 128.5, 143.1; GC–MS (m/z) 190.1. 1-Dodecyl-3-methylbenzene (4): The title compound 4 was obtained as yellow oil (159 mg, 61% yield) after purification by silica gel column chromatography. 1H NMR (300 MHz, CDCl3) δ 0.90 (t, J = 6.3 Hz, 3H), 1.28

• –1.31 (m, 18H), 1.53–1.64 (m, 2H), 2.35 (s, 3H), 2.55–2.60 (m, 2H), 6.99–7.02 (m, 3H), 7.18 (t, J = 6.9 Hz, 1H); 13C NMR (75 MHz, CDCl3) δ 14.3, 21.6, 22.9, 27.1, 29.5, 29.6, 29.7, 29.8, 31.7, 32.1, 36.1, 45.3, 125.5, 126.4, 128.3, 129.4, 137.9, 143.1; GC–MS (m/z) 260.1. 1-Isopentyl-3-methoxybenzene (5

• , 33.9, 40.8, 55.2, 110.9, 114.3, 120.9, 129.3, 144.9, 159.7; GC–MS (m/z) 178.1. 7-Octen-1-ylbenzene (6) [63]: The title compound 6 was obtained as a colorless oil (113 mg, 60% yield) after purification by silica gel column chromatography. 1H NMR (300 MHz, CDCl3) δ 1.33–1.41 (m, 6H), 1.60–1.65 (m, 2H

Half-sandwich nickel(II) complexes bearing 1,3-di(cycloalkyl)imidazol-2-ylidene ligands

• Johnathon Yau,
• Kaarel E. Hunt,
• Laura McDougall,
• Alan R. Kennedy and
• David J. Nelson

Beilstein J. Org. Chem. 2015, 11, 2171–2178, doi:10.3762/bjoc.11.235

• the following specialists and technical staff for their assistance: Mr Craig Irving, Dr John Parkinson (NMR spectroscopy), Mr Alexander Clunie (elemental analyses), Ms Patricia Keating (GC and GC–MS), and Mr Gavin Bain (solvent purification system). We thank Professors Peter Skabara and Nicholas

Stereoselective synthesis of hernandulcin, peroxylippidulcine A, lippidulcines A, B and C and taste evaluation

• Marco G. Rigamonti and
• Francesco G. Gatti

Beilstein J. Org. Chem. 2015, 11, 2117–2124, doi:10.3762/bjoc.11.228

• MeONa giving 4 in an overall yield of 84% and with an excellent de of >99%, by GC–MS ([α]D +25° (c 2.0, CHCl3) vs lit. distomer (−)-neoisopulegol [19] [α]D −22.2° (c 2.0, CHCl3) or (+)-neoisopulegol [20] [α]D +28.7° (c 17.2, CHCl3)). The subsequent synthesis of 1 shown Scheme 2 is a slightly adapted

Ru complexes of Hoveyda–Grubbs type immobilized on lamellar zeolites: activity in olefin metathesis reactions

• Hynek Balcar,
• Naděžda Žilková,
• Martin Kubů,
• Michal Mazur,
• Zdeněk Bastl and
• Jiří Čejka

Beilstein J. Org. Chem. 2015, 11, 2087–2096, doi:10.3762/bjoc.11.225

• found as reaction products by GC–MS. Enantioselectivity was not established. Similar dependence of catalytic activity on the type of support was found for RCM of DAF (Figure 3). The initial TOFs (calculated from conversion at 5 min) decreased in the order: HGIIN+Cl−/MCM-22 (1770 h−1) > HGIIN+Cl−/MCM-56

• ), 19.7 (N-(2-trifluoroacetyl)-2,5-dihydropyrrole), 41.3 (methyl oleate), 33.9 (octadecene), and 57.5 (diester). n-Nonane was used as an internal standard, whenever required. Individual products (all are known compounds) were identified by gas chromatography and mass spectrometry (GC−MS) (ThermoFinnigan

• Synthesis, Wroclaw, Poland) for the samples of Ru catalysts and M. Horáček (J. Heyrovský Institute, Prague) for GC–MS analysis. Financial support from Grant Agency of the Czech Republic (P106/12/0189) is gratefully acknowledged.

Efficient synthesis of π-conjugated molecules incorporating fluorinated phenylene units through palladium-catalyzed iterative C(sp²)–H bond arylations

• Fatiha Abdelmalek,
• Fazia Derridj,
• Safia Djebbar,
• Jean-François Soulé and
• Henri Doucet

Beilstein J. Org. Chem. 2015, 11, 2012–2020, doi:10.3762/bjoc.11.218

• to note that 25 results from the activation of the less hindered C–H bond. When the reaction was performed with 2-(2,4-difluorophenyl)menthofuran (21), the position flanked by two fluorine atoms was the most reactive. Only the regioisomer 26 was observed in crude GC–MS and 1H NMR and was isolated in

Stereochemistry of ring-opening/cross metathesis reactions of exo- and endo-7-oxabicyclo[2.2.1]hept-5-ene-2-carbonitriles with allyl alcohol and allyl acetate

• Piotr Wałejko,
• Michał Dąbrowski,
• Lech Szczepaniak,
• Jacek W. Morzycki and
• Stanisław Witkowski

Beilstein J. Org. Chem. 2015, 11, 1893–1901, doi:10.3762/bjoc.11.204

• carefully separated using PTLC techniques. The pure samples of compound 6E, 7Z, 8Z, 8E, 10E and 12Z were isolated and characterized spectroscopically (1H and 13C NMR, GC–MS). Two types of the regioisomeric products of type A should be taken into consideration (Scheme 1). The distinguishing of 1-2 from 1-3

• compounds 6E and 10E were deacetylated (MeOH/KCN) [24] to give 8E and 12E. The samples 7Z, 8Z, 8E, and 12Z were subjected to acetylation (Py/Ac2O) to give 5Z, 6Z, 6E and 10Z, respectively. The acetates were directly characterized by GC–MS. Based on retention indices and literature data (MS spectra identity

• (δ) are reported in ppm downfield from TMS. The assignment of chemical shifts in solution was supported by 2D NMR experiments (DFQ, HSQC and HMBC). GC–MS was carried out on an Agilent Technologies HP 6890 N gas chromatograph with mass selective detector MSD 5973 (Agilent Technologies, USA). The

A facile synthetic route to benzimidazolium salts bearing bulky aromatic N-substituents

• Gabriele Grieco,
• Olivier Blacque and
• Heinz Berke

Beilstein J. Org. Chem. 2015, 11, 1656–1666, doi:10.3762/bjoc.11.182

• . Signal patterns are reported as follows: s, singlet; d, doublet; dd, doublet of doublets; t, triplet; m, multiplet, q, quartet. ESIMS spectrometric data were obtained from an HCT Esquire Bruker Daltonics instrument, while the EIMS spectrometric data were obtained from a Varian 450GG-Saturn 2000 GC/MS/MS

• heated at 92 °C. The reaction was monitored by GC–MS and after completion (4 h) to the solution were added AcOEt (100 mL) and water (100 mL). The organic layer was washed with brine and afterwards dried over MgSO4 and filtered. After the evaporation of the solvent under reduced pressure we obtained 1547

• mg of a deep blue solid (5.94 mmol, Mw = 260,33). The product has a sky-blue color when in solution, which is due to a small amount of impurities. The 1H NMR analysis confirmed that 5 was pure enough to be used for the next synthetic step. Yield 89.1%; GC–MS (EI+): 11.074 min [260.3–261.2]; (98%). 1H

Pyridine-promoted dediazoniation of aryldiazonium tetrafluoroborates: Application to the synthesis of SF₅-substituted phenylboronic esters and iodobenzenes

• George Iakobson,
• Junyi Du,
• Alexandra M. Z. Slawin and
• Petr Beier

Beilstein J. Org. Chem. 2015, 11, 1494–1502, doi:10.3762/bjoc.11.162

• 3b was very fast and a vigorous evolution of nitrogen was observed affording the borylated product in a moderate yield together with a mixture of SF5-pyridines in ca. 10% GC–MS yield (Table 2, entry 7). Finally, the use of a 4-fold excess of pyridine in acetonitrile was found to be optimal

• configuration) and 6i in 16:31:28:25 GC–MS ratio. The presence of these products can be explained only by the formation of the substituted SF5-phenyl radical which undergoes borylation to 2i, hydrogen atom transfer followed by borylation to 2i’, intramolecular cyclization to 5i or hydrogen abstraction to 6i

• from intermolecular competition experiment using 3b and a 1:1 mixture of THF and THF-d8 giving KIE = 5.5 (6:6-D ratio determined by GC–MS) and combined yield of 62%. This means that the hydrogen abstraction is much faster than the deuterium abstraction and suggests the C-H(D) bond formation as the rate

Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity

• Karolina Żukowska,
• Eva Pump,
• Aleksandra E. Pazio,
• Krzysztof Woźniak,
• Luigi Cavallo and
• Christian Slugovc

Beilstein J. Org. Chem. 2015, 11, 1458–1468, doi:10.3762/bjoc.11.158

• substrate 16 was subjected to RCM in high temperature conditions, a complex mixture of products was obtained (Figure 5). Upon GC and GC–MS analysis, structures of compounds 17–19 were determined (cf. Supporting Information File 1). The substituted complexes were inert in ambient conditions similarly to the

Properties of PTFE tape as a semipermeable membrane in fluorous reactions

• Brendon A. Parsons,
• Olivia Lin Smith,
• Myeong Chae and
• Veljko Dragojlovic

Beilstein J. Org. Chem. 2015, 11, 980–993, doi:10.3762/bjoc.11.110

• reactions were carried out in the dark. Periodically, samples were taken from each vial under a red light and analyzed by means of GC–MS. PV-PTFE reaction design. Solvent uptake in the delivery of bromine into dichloromethane (a) 0 min, (b) 0.50 min, (c) 0.83 min, (d) 1.50 min, (e) 3.50 min, (f) 4.17 min

Photocatalytic nucleophilic addition of alcohols to styrenes in Markovnikov and anti-Markovnikov orientation

• Martin Weiser,
• Sergej Hermann,
• Alexander Penner and
• Hans-Achim Wagenknecht

Beilstein J. Org. Chem. 2015, 11, 568–575, doi:10.3762/bjoc.11.62

• methods. All chemicals were purchased from Aldrich, ABCR and TCI. GC–MS data were recorded on a Varian GC–MS System (gas-phase chromatograph 431-GC, mass spectrometer 210-MS). Absorption spectra were determined with a Perkin Elmer Lambda 750 UV–vis spectrometer. Fluorescence was measured with a Horiba

• equiv (dashed lines) and 1.0 equiv (solid lines) of Ph–SH as additive; reaction conditions: 1 (20 mM), Ph–SH (20 mM), PDI (0.5 mM), in CH2Cl2/MeOH 3:1 (4 mL), argon atmosphere, 30 °C, 250 mW LED, λ = 530 nm, 1 and 5 identified and quantified by GC–MS. Conversion of substrate 1 (black dashed) and

• identified and quantified by GC–MS. Spectra of PDI before (dotted black) and after excitation (red), then every 2 min until ground state is reached after 30 min (solid black). Reaction conditions: 1 (25 mM), Ph–SH (12.5 mM), PDI (0.02 mM), in CH2Cl2/MeOH 3:1 (4 mL), argon atmosphere, 25 °C, irradiation by 2

The reactions of 2-ethoxymethylidene-3-oxo esters and their analogues with 5-aminotetrazole as a way to novel azaheterocycles

• Marina V. Goryaeva,
• Yanina V. Burgart,
• Marina A. Ezhikova,
• Mikhail I. Kodess and
• Viktor I. Saloutin

Beilstein J. Org. Chem. 2015, 11, 385–391, doi:10.3762/bjoc.11.44

• the complete conversion of ester 1f in the reaction with 5-AT even under prolonged reflux in acetic acid. According to GC–MS data, the reaction mixture contained cyanoacetic ester (12) (m/z 113 [М]+) and ethyl 3-(1H-tetrazol-5-ylamino)prop-2-enoate (13) (m/z 182 [М + 2]+) along with ester 1f (m/z 169

Matsuda–Heck reaction with arenediazonium tosylates in water

• Ksenia V. Kutonova,
• Marina E. Trusova,
• Andrey V. Stankevich,
• Pavel S. Postnikov and
• Victor D. Filimonov

Beilstein J. Org. Chem. 2015, 11, 358–362, doi:10.3762/bjoc.11.41

• , entry 9) and 2i (Table 2, entry 10), which proofed to be less reactive, so that the complete conversion was only achieved with 2.5 mol % of palladium diacetate. No side-products were detected including phenols (as monitored by GC–MS and HPLC). The latter are often formed if diazonium salts take part in

• tosylates 2 were prepared by a previously described method [10]. HPLC analysis was conducted with an Agilent 1200 instrument fitted with an Eclipse Plus C18 column (5 µm, 4.6 × 150 mm) and a UV detector. GC–MS (EI) measurements were obtained with an Agilent 7890/5975C instrument. 1H, 13C NMR and IR spectra

• were recorded on a Bruker Avance 300 and a Perkin Elmer BXII, respectively. Melting points were obtained with a melting point system MP50, Mettler Toledo (values are given uncorrected). HPLC–MS measurements were obtained with a Thermo Scientific DFS High Resolution GC–MS. Microwave heating was carried