Search Results (14)

The carboxylation of unsaturated amine and alcohol compounds, including 4-benzylamino-1-phenyl-1-butyne (homopropargylamine), 2-butyne-1-ol (propargylic alcohol), and 2,3-butadiene-1-ol (allenylmethyl alcohol), using the hydroxidogold(I) complex, AuOH(IPr) [IPr = 1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene], produces corresponding alkenylgold(I) complexes with a cyclic urethane or carbonate framework in high yields. The reaction takes place in aprotic THF at room temperature under the atmospheric pressure of CO₂ in the absence of base additives. The products were characterized by NMR spectroscopy, elemental analysis, and X-ray crystallography. The functionalized alkenyl complexes prepared from the alkynes can be protonated by treatment with an equimolar amount of acetic acid to afford five- or six-membered carboxylation products, whereas the related alkenyl complex derived from allenylmethyl alcohol decomposed to recover the starting allene via ring-opening decarboxylation. Full article

The development of active, selective, and stable multicrystalline catalytic coatings on the inner surface of microcapillary reactors addresses environmental problems of fine organic synthesis, in particular by reducing the large quantities of reagents and byproducts. Thin-film nanosized bimetallic catalysts based on mesoporous pure titania and doped with zirconia, ceria, and zinc oxide, for use in microreactors, were developed, and the regularities of their formation were studied. The efficiency of PdZn/Ti_xM_1−xO_2±y (M = Ce, Zr, Zn) in the hydrogenation of 2-methyl-3-butyn 2-ol was studied with an emphasis on the stability of the catalyst during the reaction. The catalytic parameters depend on the adsorption properties and activity of PdZn and Pd(0) active centers. Under reaction conditions, resistance to the decomposition of PdZn is a factor that affects the stability of the catalyst. The zinc-doped coating proved to be the most selective and stable in the reaction of selective hydrogenation of acetylenic alcohols in a microcapillary reactor. This coating retained a high selectivity of 98.2% during long-term testing up to 168 h. Modification of the morphology and electronic structure of the active component, by doping titania with Ce and Zr, is accompanied by a decrease in stability. Full article

Silver is a well-established antimicrobial agent. Conjugation of organic ligands with silver nanoparticles has been shown to create antimicrobial nanoparticles with improved pharmacodynamic properties and reduced toxicity. Twelve novel organic ligand functionalized silver nanoparticles (AgNPs) were prepared via a light-controlled reaction with derivatives of benzothiazole, benzoxazine, quinazolinone, 2-butyne-1,4-diol, 3-butyne-1-ol, and heptane-1,7-dioic. UV-vis, Fourier-transform infrared (FTIR) spectroscopy, and energy-dispersive X-ray (EDAX) analysis were used to confirm the successful formation of ligand-functionalized nanoparticles. Dynamic light scattering (DLS) revealed mean nanoparticle diameters between 25 and 278 nm. Spherical and nanotube-like morphologies were observed using transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Seven of the twelve nanoparticles exhibited strong antimicrobial activity and five of the twelve demonstrated significant antibacterial capabilities against E. coli in a zone-of-inhibition assay. The synthesis of functionalized silver nanoparticles such as the twelve presented is critical for the further development of silver-nanoconjugated antibacterial agents. Full article

On-site determination of trace copper ions in natural waters is of great significance to environmental monitoring, and how to develop accurate and specific point-of-care test methods is one critical issue. In the study, a paper-based analytical device (PAD) being modified with a new truncated DNAzyme (CLICK-T, which was derived from a reported DNAzyme-CLICK-17) was developed for Cu ions detection. The detection mechanism was based on Cu(II)-catalyzed azide-alkyne cycloaddition (Cu(II)AAC) reaction. It can directly conduct on-site analysis of Cu(II) ions based on fluorescent signals detected using a mobile phone. In the assay, the CLICK-T was firstly modified on the PADs. Then, water samples containing Cu ions mixed with 3-azido-7-hydroxycoumarin and 3-butyn-1-ol were instantly dripped on PADs and incubated for 20 min. Finally, the PADs were excited at 365 nm and emitted fluorescence which could be analyzed on site using smart phones. The Cu(II) concentration could be quantified through RGB analysis with the aid of iPhone APP software. The limit of detection is 0.1 µM by the naked eye due to the fact that CLICK-T exhibited a good catalytic effect on Cu(II)AAC. The Cu(II) concentration could also be directly detected without using reductant, such as ascorbic acid, which is prone to be oxidized in air. This simplifies the PDA detection process improves its efficiency. The PAD is convenient for the on-site analysis of Cu ions in natural waters. Full article

While the sonochemical grafting of molecules on silicon hydride surface to form stable Si–C bond via hydrosilylation has been previously described, the susceptibility towards nucleophilic functional groups during the sonochemical reaction process remains unclear. In this work, a competitive study between a well-established thermal reaction and sonochemical reaction of nucleophilic molecules (cyclopropylamine and 3-Butyn-1-ol) was performed on p-type silicon hydride (111) surfaces. The nature of surface grafting from these reactions was examined through contact angle measurements, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Cyclopropylamine, being a sensitive radical clock, did not experience any ring-opening events. This suggested that either the Si–H may not have undergone homolysis as reported previously under sonochemical reaction or that the interaction to the surface hydride via a lone-pair electron coordination bond was reversible during the process. On the other hand, silicon back-bond breakage and subsequent surface roughening were observed for 3-Butyn-1-ol at high-temperature grafting (≈150 °C). Interestingly, the sonochemical reaction did not produce appreciable topographical changes to surfaces at the nano scale and the further XPS analysis may suggest Si–C formation. This indicated that while a sonochemical reaction may be indifferent towards nucleophilic groups, the surface was more reactive towards unsaturated carbons. To the best of the author’s knowledge, this is the first attempt at elucidating the underlying reactivity mechanisms of nucleophilic groups and unsaturated carbon bonds during sonochemical reaction of silicon hydride surfaces. Full article

In this study, novel SiO₂- and Al₂O₃-supported Cu-Fe catalysts are developed for selective hydrogenation of 2-methyl-3-butyne-2-ol to 2-methyl-3-butene-2-ol under mild reaction conditions. TEM, XRD, and FTIR studies of adsorbed CO and TPR-H₂ are performed to characterize the morphology, nanoparticle size, and particle distribution, as well as electronic state of deposited metals in the prepared catalysts. The deposition of Fe and Cu metal particles on the aluminum oxide carrier results in the formation of a mixed oxide phase with a strong interaction between the Fe and Cu precursors during the calcination. The highly dispersed nanoparticles of Fe₂O₃ and partially reduced CuO_x, with an average size of 3.5 nm and with strong contact interactions between the metals in 5Cu-5Fe/Al₂O₃ catalysts, provide a high selectivity of 93% toward 2-methyl-3-butene-2-ol at complete conversion of the unsaturated alcohol. Full article

In this work, the effect of pretreatment conditions (10% H₂/Ar flow rate 25 mL/min and 400 °C, 3 h or 600 °C, 17 h) on the catalytic performance of 1 wt.% Pd/γ-Al₂O₃ has been evaluated for hydrogenation of 2-methyl-3-butyn-2-ol in continuous-flow mode. Two palladium catalysts have been tested under different conditions of pressure and temperature and characterized using various physicochemical techniques. The catalytic performance of red(400 °C)-Pd/γ-Al₂O₃ and red(600 °C)-Pd/γ-Al₂O₃ are affected by the coexistence of several related factors like the competition between PdH and PdCx formation during the reaction, structure sensitivity, hydrogen spillover to the alumina support and presence or absence of Pd–Al species. High-temperature reduction leads to formation of Pd–Al species in addition to pure Pd. The Pd–Al species which reveal unique electronic properties by decreasing the Pd^δ− surface concentration via electron transfer from Pd to Al, leading to a weaker Pd–Alkyl bonding, additionally assisted by the hydrogen spillover, are the sites of improved semi-hydrogenation of 2-methyl-3-butyn-2-ol towards 2-methyl-3-buten-2-ol (97%)—an important intermediate for vitamin A synthesis. Full article

Alkenols are commercially important chemicals employed in the pharmaceutical and agro-food industries. The conventional production route via liquid phase (batch) alkynol hydrogenation suffers from the requirement for separation/purification unit operations to extract the target product. We have examined, for the first time, the continuous gas phase hydrogenation (P = 1 atm; T = 373 K) of primary (3-butyn-1-ol), secondary (3-butyn-2-ol) and tertiary (2-methyl-3-butyn-2-ol) C₄ alkynols using a 1.2% wt. Pd/Al₂O₃ catalyst. Post-TPR, the catalyst exhibited a narrow distribution of Pd^δ- (based on XPS) nanoparticles in the size range 1-6 nm (mean size = 3 nm from STEM). Hydrogenation of the primary and secondary alkynols was observed to occur in a stepwise fashion (-C≡C- → -C=C- → -C-C-) while alkanol formation via direct -C≡C- → -C-C- bond transformation was in evidence in the conversion of 2-methyl-3-butyn-2-ol. Ketone formation via double bond migration was promoted to a greater extent in the transformation of secondary (vs. primary) alkynol. Hydrogenation rate increased in the order primary < secondary < tertiary. The selectivity and reactivity trends are accounted for in terms of electronic effects. Full article

The effect of periodic temperature oscillations has been studied for the hydrogenation of 2-methyl-3-butyn-2-ol over a Pd-based catalyst in a micro-trickle bed reactor. This hydrogenation was investigated using a radiofrequency heated reactor under transient conditions using temperature cycling. The dynamic operation using this configuration was found to increase both conversion and selectivity towards 2-methyl-3-buten-2-ol compared to the steady-state operation with an improvement of up to 24% for the selectivity being observed. The developments made here also result in a lower activation energy in comparison to previous data, providing a starting point for radiofrequency heating to enhance reaction rate through the exploitation of thermal cycling at production scale. Full article

Semihydrogenation of 2-methyl-3-butyn-2-ol (MBY) was studied in a 5 m tube reactor wall-coated with a 5 wt% Pd/ZnO catalyst. The system allowed for the excellent selectivity towards the intermediate alkene of 97.8 ± 0.2% at an ambient H₂ pressure and a MBY conversion below 90%. The maximum alkene yield reached 94.6% under solvent-free conditions and 96.0% in a 30 vol % MBY aqueous solution. The reactor stability was studied for 80 h on stream with a deactivation rate of only 0.07% per hour. Such a low deactivation rate provides a continuous operation of one month with only a two-fold decrease in catalyst activity and a metal leaching below 1 parts per billion (ppb). The excellent turn-over numbers (TON) of above 10⁵ illustrates a very efficient utilisation of the noble metal inside catalyst-coated tube reactors. When compared to batch operation at 70 °C, the reaction rate in flow reactor can be increased by eight times at a higher reaction temperature, keeping the same product decomposition of about 1% in both cases. Full article

Efavirenz is a non-nucleoside reverse transcriptase inhibitor used in the treatment of human immunodeficiency virus type-1 (HIV). (2S)-(2-Amino-5-chlorophenyl)-4-cyclopropyl-1,1,1-trifluoro-3-butyn-2-ol (AMCOL), used as an intermediate in the synthesis of efavirenz and a degradation impurity, has an aminoaryl derivative which is a well-known alerting function for genotoxic activity. Upon request from a regulatory agency, a selective and sensitive liquid chromatography–tandem mass spectrometry (LC–MS/MS) method was developed for trace level quantitative determination of AMCOL related compound of efavirenz, for a risk assessment and comparison of impurity levels with the commercially available innovator product (brand name: Sustiva). The method provided excellent sensitivity at a typical target analyte level of <2.5 ppm, an established threshold of toxicological concern (TTC), when the drug substance and drug product samples were prepared at 15.0 mg/mL. The AMCOL sample was analyzed on a Luna C18 (2) (100 mm × 4.6 mm, 3 µm) column interfaced with a triple quadrupole tandem mass spectrometer operated in a multiple reaction monitoring (MRM) mode. Positive electrospray ionization (ESI) was employed as the ionization source and the mobile phase used was 5.0 mM ammonium acetate-methanol (35:65, v/v). The calibration curve showed good linearity over the concentration range of 0.2–5.0 ppm with a correlation coefficient of >0.999. The limit of detection (LOD) and limit of quantification (LOQ) were found to be 0.07 and 0.2 ppm, respectively. The developed method was validated as per international council on harmonization (ICH) guidelines in terms of LOD, LOQ, linearity, precision, accuracy, specificity, and robustness. Full article

A series of 3(2H)-furanones, based on side-chain modifications of a parent 3(2H)-furanone, was synthesized in good yield. The parent compound was prepared by hydrogenolysis, and subsequent acid hydrolysis, of isoxazole derivatives. The isoxazole was prepared by a [3+2] 1,3-dipolar cycloaddition reaction between 3-butyn-2-ol and nitrile oxide. Full article