An Inventory of Fluorspar Production, Industrial Use, and Emissions of Trifluoroacetic Acid (TFA) in the Period 1930 to 1999

There is a generally accepted conclusion that trifluoroacetic acid (TFA) does occur naturally, in part based on the large quantities of TFA in the oceans (61 - 205 million tonnes, measured in 1998-2002). However, the recent review paper “Insufficient evidence for the existence of natural trifluoroacetic acid” concludes that “the presence of TFA in the deep ocean and lack of closed TFA budget is not sufficient evidence that TFA occurs naturally, especially without a reasonable mechanism of formation”. Industrial sources of TFA can only result from the use of fluoride minerals in industrial processes. Major industrial uses of fluorspar started significant expansion from about the same time (1930s). Over 190 million tonnes of fluorspar have been mined in the period 1930 to 1999. An inventory has been developed (1930-1999), accounting for most of the fluorspar production (86%) and estimating emissions of TFA. Industrial emissions of TFA are estimated as 230,000 to 470,000 tonnes. Significant other industrial uses of fluorides have not been identified that could account for the large burden of TFA in the oceans. This inventory provides complementary evidence that the quantity of TFA in the oceans must include a large natural burden.

Actional Mechanism of Trifluoroacetic Acid for the Separation of Biopolymers by Reversed-phase Liquid Chromatography

The present paper covers the actional mechanism of trifluoroacetic acid for the separation of biopolymers investigated by using the parameters of stoichiometric displacement model for retention(SDM-R) in reversed-phase liquid chromatography. It was found that the trifluoroacetic acid(TFA) may participate in, or stimulate the association among displacing agent molecules in mobile phase, and decrease the affinity of both the associate molecules of the displacing agent and the TFA-protein ion-pairing. The former dominates over the separation selectivity of biopolymers as the concentration of TFA is lower than a given value, and the two contrary functions partly offset to each other and the latter dominates as its concentration is greater than the given value.

Coordinating Zirconium Nodes in Metal-Organic Framework with Trifluoroacetic Acid for Enhanced Lewis Acid Catalysis

Regulating Lewis acid sites with well-defined electronic state and steric environment is still challenging for achieving high catalytic efficiency.Here we show coordinating zirconium nodes in the typical metal-organic framework known as MOF-545 with the monocarboxylate modulators including trifluoroacetic acid(TFA)or benzoic acid(BA)over meso-tetra(4-carboxyphenyl)-porphine(H_(2)TCPP),denoted as MOF-545-TFA or MOF-545-BA.Impressively,MOF-545-TFA shows the significantly enhanced performance for the catalytic ring-opening reaction of various epoxides with alcohols and good recyclability at 40°C in respect with MOF-545-BA and ZrO_(2).This mainly originates from the stronger Lewis acidity and more active zirconium sites induced by the electron-withdrawing TFA,resulting in the increased ability for activation of epoxides.This modulation approach is promising for enlarging the toolbox to extend the MOFs-based Lewis acid catalysis.

The Effect of Trifluoroacetic Acid on Molecular Weight Determination of Polyesters:An in Situ NMR Investigation

Due to the poor solubility of aromatic polyesters in comm on orga nic solve nts,trifluoroacetic acid is usually used as a co-solve nt to increase their solubility for characterizations.However,only few studies have reported the side reactions induced by it.We present here the application of in situ 1H-NMR techniques to explore its effect on the hydroxyl end-groups,which are usually used for the molecular weight determination of polyesters by end-group estimation method.Using bis(2-hydroxyethyl)terephthalate(BHET)as model compound,quantitative NMR results show the peak integration of hydroxyethyl end-groups decreased with time via a pseudo-first-order kinetics in d-trifluoroacetic acid/d-chloroform mixture solvent(1:10,V:V).This is due to the esterification of hydroxyethyl groups with trifluoroacetic acid,revealed by the H-^(13)C gradient-enhanced heteronuclear multiple bond correlation(gHMBC)spectrum.The mixtures of dimethyl terephthalate and BHET with different molar ratios were used to represent poly(ethylene terephthalate)(PET)with different degrees of polymerization,and the effect of trifluoroacetic acid on the estimation of hydroxyethyl groups and subsequent molecular weight determination of polyesters was studied.Our results show that if a relative error of 5%is allowed,the NMR measurements must be finished within 1.3 h of solution preparation at 25℃ in the mixture solve nt.The results were confirmed in PET sample,while in poly(ethyle ne adipate),the obtained esterifaction con stant is faster that those in aromatic system.The results can be applied to other polymer systems with alcohol functionalized groups,and used as a guideline for the characterization of polyesters and polyethers by end-group estimation method.

Temperature-controlled Cascade Reaction of Phloroglucinoltribenzyl Ether Promoted by Trifluoroacetic Anhydride and Trifluoroacetic Acid

We report the first trifluoroacetic anhydride- and trifluoroacetic acid-promoted cascade reaction with phtoroglucinoltribenzyl ether and carboxylic acid as starting materials. By simply varying the temperature of systems containing the same starting materials, different products were produced in high yields. A three-step consecutive reaction process was also proposed.

Communication A convenient trifluoroacetylation of amines with trifluoroacetic acid and titanium tetrachloride

In the past years,trifluoroacetylation has been widely used for protecting func-tional groups.For example,trifluoroacetyl can act as an effective blocking group ofhydroxyl and amino substituents in the reactions of a 1-halo-2-hydroxyl-3-amino sugarwith cholesterol or cyclodecanol.Furthermore,the conversion of the basic aminogroup to less basic amido group by trifluoroacetylation provides a good chromatographyseparation method of amines,e.g.cis-,trans-1,2-diaminocyclohexane can be separatedcompletely,via trifluoroacetylation by GLC technique.

Methyl 1,2-Shift Rearrangement on C-ring and Decarboxylation at C28 of Oleanolic Acid Derivatives

A new oleanolic acid derivative with A-ring lactone,C-ring rearrangement and decarboxylation at C28 was synthesized,which was confirmed by HRMS,NMR and X-ray crystal structure.It is the first report about the methyl rearrangement on C-ring of oleanolic phenylmethyl ester,and the possible mechanism was proposed as the 1,2-methyl shift.

Iodomethane as an organocatalyst for the aerobic ortho-selective trifluoromethylation of pyridines

Iodomethane is usually used as an electrophilic methylation reagent.Herein,we report its use as a C1 organocatalyst for the aerobic ortho-selective trifluoromethylation of pyridines in the absence of a transition metal.Trifluoroacetic acid(TFA)was employed as an inexpensive,readily available trifluoromethyl source.The reaction efficiently produced a variety of trifluoromethylation products,with good functional group compatibility.Pyridine-containing drug molecules could also be selectively trifluoromethylated for late-stage functionalizations.Mechanistic studies showed that iodomethane selectively reacted with the pyridine starting material,rather than the pyridine product,to generate the corresponding N-methylpyridinium iodide.The decarboxylation of trifluoroacetic acid produced a trifluoromethyl anion,which added to the methylpyridinium iodide,and the subsequent aerobic rearomatization led to the generation of the ortho-trifluoromethylated product.

Synthesis and antidiabetic activity of β-acetamido ketones

This paper reports the use of trifluoroacetic acid as a catalyst in the Dakin–Westreaction for the synthesis of b-acetamido ketones. The method has several advantages such asrequiring only mild conditions and a low concentration of catalyst. Screening of 19 b-acetamidoketones for antidiabetic activity in vitro showed that their activity as peroxisome proliferatoractivated receptor (PPAR) agonists and as dipeptidyl peptidase 4 (DPP-IV) inhibitors wasfairly weak.

Synthesis of Novel Scolopendra-type Polydodecyloxybenzoyl[1,5]-diazocine as New Material for Optical Sensor

A new scolopendra-type polymer of polydodecyloxybenzoyl[1,5]-diazocine（PDBD） was designed and prepared using 2,5-bis（4-（dodecyloxy）-benzoyl）terephthaloyl azide with trifluoroacetic acid（TFA） via one-pot reaction in good yields. The structure of polymer was characterized using ~1 H-NMR, ^（13） C-NMR and MALDI-TOF spectra. The polymer PDBD exhibits good thermal stability as measured by TGA and DSC, and can be dissolved well in common organic solvents such as chloroform and tetrahydrofuran. In addition, UV-Vis spectral studies indicate that the polymer PDBD shows unique optical property changes（protonation/deprotonation） in the different trifluoroacetic acid environments. The new polymer is expected to be utilized as an optical functional material for fabricating optical sensors in environmental and biological fields.