Triphenylmethanol Research Articles

Acid‐Catalyzed Alkylation of NH‐1,2,3‐Triazoles with Alcohols

AbstractAn efficient method for the synthesis of N‐alkylated 1,2,3‐triazoles from NH‐1,2,3‐triazoles and alcohols was developed by utilizing Lewis or Brønsted acid as a catalyst. The reaction demonstrates mild reaction conditions, straightforward operation, and 92–97 % overall yield. Allylic alcohols and triphenyl methanol together with 1,1‐diphenylethan‐1‐ol gave single N2‐substituted products, while the regioselectivities of the reactions for aryl‐substituted secondary alcohols, including diarylmethanols, 1‐phenylethanol, were controlled by the electronic effect and spatial hindrance of the NH‐1,2,3‐triazoles. Furthermore, tert‐butanol always gave low regioselectivites for different NH‐1,2,3‐triazoles.

Development of a Textile Nanocomposite as Naked Eye Indicator of the Exposition to Strong Acids.

Chemical burns, mainly produced by acids, are a topic of concern. A new sensing material for the detection of strong acids able to be incorporated into textiles has been developed. The material is prepared by the covalent attachment of 2,2′,4,4′,4″-pentamethoxy triphenyl methanol to a mesoporous material which further is included in a nitro resin to obtain a colourless composite. The response of this composite to diverse acid solutions was tested showing the appearance of an intense purple colour (with a colour difference higher than 160) that can be monitored by the naked eye or could be easily digitised to feed an instrumental sensor. Reversibility and resistance to washing cycles were studied with positive results. Finally, the response of the sensing composite to acid vapours was assayed, observing a colour change similar to that found in solution.

Synergism in host–guest selectivity of picolinium chlorides by triphenylsilanol and triphenylmethanol

The host compound triphenylsilanol (TPS) has been employed in the separation of the isomers of picolinium chlorides (2PIC+, 3PIC+ and 4PIC+). By analogy with the Dutch resolution method, we employed triphenylmethanol (TPM) as an additive to TPS and thus changed the composition of the mother liquors in a systematic manner. The resulting crystals were analysed by NMR spectroscopy and X-ray diffraction. The selectivity results for TPS are 2PIC+ > 3PIC+ ≈ 4PIC+.

Abstract 2512: Design and antiproliferative evaluation of cell-penetrating TPM-Dox conjugates as prodrugs

Abstract Doxorubicin (Dox) is well-known anthracycline widely used anticancer agent for the treatment of a wide variety of cancers. The major limitations of cancer chemotherapy treatment are low cellular uptake, high efflux rate and the development of resistance to a certain dose of anticancer drugs, such as Dox. Improving of cellular uptake and duration of action of Dox is very demanding. This will improve its therapeutic index and decrease its side effects. The biological activity of Dox can potentially be enhanced by increasing and optimizing its hydrophobicity using appropriate hydrophobic linker attachment to the Dox using triphenylmethanol (TPM) which led to higher cellular uptake. In this regard, TPM-Dox prodrugs were designed to deliver and release Dox into cells. The attachment of TPM analogs along with fatty alcohol significantly enhanced the lipophilicity and thus the cellular uptake of these multifunctional conjugates. In this study, a number of TPM derivatives of Dox were synthesized by the reaction of 2-substituted methoxy benzenes and 1,3,5-trioxane in glacial acetic acid in 72-87% yield. The reaction of TPM derivatives with tosylated fatty diol continued with conjugation to Dox to afford eight TPM-Dox conjugates with different hydrophobicity in 44-67% overall yield. Comparative antiproliferative assays between TPM-Dox conjugates and the corresponding noncovalent physical mixtures of the TPM derivatives and Dox were performed. TPM-Dox conjugates inhibited the cell proliferation of human leukemia (CCRF- CEM), ovarian adenocarcinoma (SK-OV-3), colorectal carcinoma (HCT-116), and breast carcinoma (MDA-MB-468) cells by 63-94% at a concentration of 1 µM after 72-120 h of incubation. These data suggest that TPM-Dox derivatives can be used as a potential prodrug for improving the cellular delivery and retention of Dox. Citation Format: Yousef Beni, Andrew W. Pippas. Design and antiproliferative evaluation of cell-penetrating TPM-Dox conjugates as prodrugs. [abstract]. In: Proceedings of the 105th Annual Meeting of the American Association for Cancer Research; 2014 Apr 5-9; San Diego, CA. Philadelphia (PA): AACR; Cancer Res 2014;74(19 Suppl):Abstract nr 2512. doi:10.1158/1538-7445.AM2014-2512

Positronium formation studies in solid molecular complexes: Triphenylphosphine oxide–triphenylmethanol

Abstract Positronium formation in triphenylphosphine oxide (TPPO), triphenylmethanol (TPM), and systems [TPPO (1− X ) ⋅TPM X ] has been studied. The low probability of positronium formation in complex [TPPO 0.5 ⋅TPM 0.5 ] was attributed to strong hydrogen bond and sixfold phenyl embrace interactions. These strong interactions in complex reduce the possibility of the n - and π -electrons to interact with positrons on the spur and consequently, the probability of positronium formation is lower. The τ 3 parameter and free volume (correlated to τ 3 ) were also sensitive to the formation of hydrogen bonds and sixfold phenyl embrace interactions within the complex. For physical mixture the positron annihilation parameters remained unchanged throughout the composition range.

Solubilization of triphenylamine, triphenylphosphine, triphenylphosphineoxide and triphenylmethanol in single and binary surfactant systems

Solubilization and co-solubilization of triphenyls (TPs) viz., triphenylphosphine (TPP), triphenylphosphineoxide (TPPO), triphenylamine (TPA) and triphenylmethanol (TPM) were studied in various single and binary surfactant systems at 25 °C using UV–visible spectroscopy and HPLC. The solubilization capacities of different micelles towards TPs were found to be a function of the nature and structure of solubilizates, locus of solubilization, size of micelles and the nature of interactions between the solubilizate and micelles. The effect of surfactant mixing on the solubilization of TPs was evaluated using the Regular Solution Approach (RSA). The solubility enhancement of TPs within mixed micelles relative to that observed in single surfactant systems was explained in light of the structural micellar changes associated with the mixing of ionic and non-ionic surfactants. Moreover, kinetics of oxidation of TPP by hydrogen peroxide investigated in these surfactant systems was found to be sensitive to the nature of micelle and the locus of solubilization of TPP within the micelles.

Electron impact ionization in helium nanodroplets: controlling fragmentation by active cooling of molecular ions.

Reported here is a study of the effects of liquid helium cooling on the fragmentation of ions formed by electron impact mass ionization. The molecules of interest are picked up by the helium nanodroplets as they pass through a low pressure oven. Electron impact ionization of a helium atom in the droplet is followed by resonant charge transfer to neighboring helium atoms. When the charge is transferred to the target molecule, the difference in the ionization potentials between helium and the molecule results in the formation of a vibrationally hot ion. In isolation, the hot parent ion would undergo subsequent fragmentation. On the other hand, if the cooling due to the helium is fast enough, the parent ion will be actively cooled before fragmentation occurs. The target molecule used in the present study is triphenylmethanol (TPM), an important species in synthetic chemistry, used to sterically protect hydroxyl groups. Threshold PhotoElectron PhotoIon COincidence (TPEPICO) experiments are also reported for gas-phase TPM to help quantify the ion energetics resulting from the cooling effects of the helium droplets.

Block copolymers by transformation of living ring opening polymerization into an initer process

The transformation of ring opening polymerization into an initer process is reported for the preparation of the block copolymer of ε-caprolactone (CL) with styrene (St). In the first step, ring opening polymerization of CL was carried out by using triphenyl methanol (TPM) as the initiator and aluminum alkoxide as the promoter, respectively, to give a triphenylmethyl (trityl)-terminated polymer. UV and 1H-NMR studies show that the trityl group associated with the active alkoxy group of the initiator is selectively attached to one chain end. In the second step, the trityl-terminated polymer served as a thermal ‘initer’ for the polymerization of styrene and this makes it possible to prepare a block copolymer.

Trace analysis of impurities in 3′-azido-3′-deoxythymidine by reversed-phase high-performance liquid chromatography and thermospray mass spectrometry

An analytical method has been developed for the detection of trace amounts of impurities in 3′-azido-3′-deoxythymidine referred to herein as AZT (Zidovudine). A sample extract was preconcentrated by normal-phase high-performance liquid chromatography (HPLC) with subsequent on-line reversed-phase HPLC-thermospray mass spectrometry (TSP-MS). During the sample extraction and concentration step, carried out by semipreparative normal-phase chromatography, the preliminary separation of the impurities from the AZT takes place. The organic solvent (dichloroethane-acetonitrile, 40:60) is evaporated from the collected fractions and the compounds are redissolved in a smaller volume of the reversed-phase mobile phases for a further degree of concentration. The collected fractions are then subjected to reversed-phase HPLC-TSP-MS. The influence of acetonitrile concentration and pH on the reversed-phase separation together with the sensitivity of the TSP-MS detection have been examined to maximise detection levels. The 3′-azido-3′-deoxy-5′-O-tritylthymidine, triphenyl methanol and 3′-chloro-3′-deoxythymidine, which are route-indicative impurities formed during the synthesis can be detected in the 50–100 ppb (w/w) range.

Inhibition of cellular transformation by triphenylmethane: a novel chemopreventive agent.

Triphenylmethane (TPM) was found to inhibit 3-methyl-cholanthrene-induced neoplastic transformation of 10T1/2 cells in a dose-dependent manner (ED50 = 2.8 microM). This activity was independent of any effect on intercellular communication and did not appear to be directly related to the general antioxidant properties of TPM as measured by cellular thiobarbituric acid-reactive substances. Triphenylmethanol (TPMOL) and diphenylmethane also inhibited transformation (ED50 = 6.9 and 90 microM respectively). TPM had no effect on the proliferation of exponentially growing cells. At higher concentrations TPM and its analogues enhanced plating efficiency of cells indicating no significant toxicity for these compounds at levels up to 50 microM. The inhibitory effects of TPM on transformation were reversible when TPM was removed from the medium. While TPM had no effect on the growth of fully transformed cell lines, it was able to inhibit the growth of 1/3 neoplastic foci in the presence (but not absence) of 10T1/2 cells. TPM was found to stimulate protein kinase C (PKC) activity for both crude C3H10T1/2 cytosolic PKC and purified PKC obtained from rat brain. The ability of TPM to stimulate PKC activity appeared to be dependent on [CaCl2] and the order of reagent addition in the assay. Tamoxifen, a structurally related compound to TPM, was also found to enhance PKC activity over the same concentration range but was less potent than TPM. The biological effects of TPM and related compounds indicate that they function in a manner distinct from other highly unsaturated transformation inhibitors such as carotenoids and retinoids. The inability of triphenylene to inhibit transformation suggests that a reactive methyl carbon may be essential for activity.

Infrared Studies of Hydrogen Bonding in Sterically Hindered Hydroxy Compounds

Hydrogen bonding in five benzhydrols and triphenyl methanol have been studied in the solid phase and on dissolution. Attempts have been made to characterize possible molecular species in the solid ...

The Preparation and Acid‐Catalyzed Decomposition of N‐Triphenylmethyl Amides

AbstractAliphatic and aromatic primary amides react with triphenyl methanol in the presence of small amounts of sulfuric acid in acetic acid, and N‐triphenylmethyl amides are obtained in good yields. The products are cleaved by acids. The decomposition of four N‐trityl amides was studied in various mixtures of acetic acid‐sulfuric acid, and the correlations between the logarithms of the observed first‐order rate coefficients, the concentration of the sulfuric acid, and the acidity functions HO and HA were studied. The kinetic data support a unimolecular rate‐determining step for the solvolysis.