Tosyl Chloride Research Articles

Isothiocyanates from Tosyl Chloride Mediated Decomposition of in Situ Generated Dithiocarbamic Acid Salts

A facile and general protocol for the preparation of isothiocyanates from alkyl and aryl amines is reported. This method relies on a tosyl chloride mediated decomposition of a dithiocarbamate salt that is generated in situ by treatment of an amine with carbon disulfide and triethylamine. Utilizing this protocol, we have prepared 19-alkyl- and arylisothiocyanates in moderate to excellent yield.

Facile conversion of alcohols to olefins by tosylation and subsequent SiO2-promoted β-elimination

A convenient and effective procedure was developed for the conversion of alcohol to olefin by tosylation and subsequent β-elimination promoted by silica gel in this study. Treatment of the alcohols with p-toluenesulfonyl chloride in pyridine at 0°C affords tosylates which undergo β-elimination with silica gel in dichloromethane or chloroform at room temperature, yielding olefins with high productivity.

Ethylene Polymerization under Mild Conditions Using Simple Aluminum Alkyls and Chloro Activators

Methylaluminum sesquichloride (Al2Cl3Me3, MAS), in the presence of ethyl trichloroacetate (ETAC), is found to be an effective catalyst for the production of polyethylene. Optimal catalyst productivities are obtained for a MAS:ETAC ratio of 1:1 at a reaction temperature of 75 °C. The polymerization is first order in both ethylene and MAS/ETAC concentration. NMR studies indicate that a 1:1 adduct is formed between binuclear MAS and ETAC, which is postulated to be a direct precursor to the active species. The productivity at elevated temperatures is limited by a radical decomposition process. Screening of various additives revealed that many halogenated organic reagents can act as activators, including carbon tetrachloride and p-toluene sulfonyl chloride. Improved productivities are obtained using sulfonyl chloride activators due to circumvention of radical decomposition pathways.

Chemoselective and scalable preparation of alkyl tosylates under solvent-free conditions

The improved method for the efficient tosylation of alcohols has been reported using two procedures (A and B). Procedure A: methanol, ethanol, benzyl alcohols, and valuable ethylene glycols can be converted into their corresponding alkyl tosylates in very fast, simple, and efficient grinding method using potassium carbonate as solid base. Other primary and secondary alcohols need to add potassium hydroxide to reaction mixture (procedure B). High selectivity of tosylation was observed for these two procedures. Scale up ability was found in this method even in 100 mmol of substrate. The present method is the example of solid-state tosylation using tosyl chloride, and is a green chemical process due to solvent-free conditions.

Photosensitive Poly(benzoxazole) Based on Poly(o-hydroxy amide), Dissolution Inhibitor, Thermoacid Generator, and Photoacid Generator

A positive-type photosensitive polybenzoxazole (PSPBO) based on a poly(o-hydroxy amide) (PHA), a dissolution inhibitor (DI) 9,9-bis(4-tert-butoxycarbonyloxyphenyl)fluorene (t-BocBHF), a thermoacid generator (TAG) isopropyl p-toluenesufonate (ITS), and a photoacid generator (PAG) (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile (PTMA) has been developed. ITS was easily prepared by reaction of p-toluenesulfonyl chloride with isopropyl alcohol. The dissolution behavior of the PSPBO system was studied in relation to PTMA loadings, and post exposure baking (PEB) temperature and time. The PSPBO consisting of PHA (73 wt %), t-BocBHF (18 wt %), ITS (7.5 wt %), and PTMA (1.5 wt %) exhibited a sensitivity of 33 mJ/cm2 and a contrast of 5.1 when exposed to 365 nm light (i-line) and developed with an aqueous alkaline developer, 2.38 wt % tetramethylammonium hydroxide solution (TMAHaq)/2.5 wt % iso-propanol (i-PrOH). A clear positive image with 3 μm features was produced by contact-printing and converted into a poly(benzoxazole) (PBO) pattern upon heating at 250 °C for 20 min. Thus, the ITS is effective as a TAG for improving the sensitivity and low temperature cyclization of PHA into the PBO as well to meet practical requirement in the industry.

Preparation of new poly(amide–imide)s with chiral architectures via direct polyamidation reaction

AbstractN‐trimellitylimido‐L‐methionine (3) was prepared by reaction of trimellitic anhydride (1) with ‐L‐methionine (2) in acetic acid solution at refluxing temperature. This diacid was reacted with thionyl chloride, and N‐trimellitylimido‐L‐methionine diacid chloride (4) was obtained in quantitative yield. The resulting diacid chloride was reacted with p‐aminobenzoic acid in dry acetone and bis(p‐aminobenzoic acid)‐N‐trimellitylimido‐L‐methionine (5) was obtained as a novel optically active amide–imide diacid monomer in high yield. The direct polycondensation of amide–imide diacid monomer 5 with several aromatic diamines was carried out with tosyl chloride (TsCl)/pyridine (Py)/dimetheylformamide (DMF) system. The resulting thermally stable poly(amide–imide)s (PAIs) were obtained in good yields and inherent viscosities ranging between 0.24 and 0.46 dL g−1 and were characterized with FTIR, 1H NMR, CHN, and TGA techniques. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1248–1254, 2007

Chemical Transformation and Biological Activities of Ambrein, a Major Product of Ambergris from Physeter macrocephalus (Sperm Whale)

Ten new derivatives (2-11) of ambrein (1), isolated from ambergris, were prepared by chemical transformation. Oxidation and/or cyclization were effected by reactions with selenium oxide or p-toluenesulfonyl chloride or with the use of shortwave UV light. The structures of 2-12 were elucidated by spectroscopic analysis, with the structure and relative configuration of 9 confirmed by single-crystal X-ray crystallography. The cytotoxic activities of 1-12 were investigated against human liver carcinoma (Hepa59T/VGH), colon adenocarcinoma (WiDr), lung carcinoma (A-549), and human breast adenocarcinoma (MCF-7) cell lines. The anti-inflammatory activities of 1-11, in terms of the inhibition of human neutrophil function, were also evaluated.

A comparative study of two different methods for direct polyamidation of N-trimellitylimido-L-methionine with various aromatic diamines

N-trimellitylimido-L-methionine (3) as optically active diacid monomer was prepared by the reaction of trimellitic anhydride (1) with L-methionine (2) in acetic acid solution at refluxing temperature. The direct polycondensation of this amide-imide diacid monomer 3 with several aromatic diamines was carried out with tosyl chloride (TsCl)/triphenylphosphine oxide (TPPO)/pyridine (Py) system (method I) and thionyl chloride (SOCl2)/Py system (method II) as condensing agents. For both methods I and II the optimized conditions for the reaction time, reaction temperature, aging time, amount of TPPO and TsCl were selected for polyamidation. The resulting novel poly(amide-imide)s (PAIs) were obtained in good yields. The inherent viscosities and thermal stability of the resulting PAIs from these methods were compared. The polymers obtained were fully characterized by IR, specific rotation, 1H-NMR spectra, elemental and thermogravimetric analyses.

Fluorescence Sensing of Anions Based on Inhibition of Excited-State Intramolecular Proton Transfer

Condensation of 2-(2'-aminophenyl)benzoxazole with p-toluenesulfonyl chloride and phenyl isocyanate yields two new anion sensors (TABO and PUBO), which can undergo excited-state intramolecular proton transfer (ESIPT) upon excitation. For the acid receptor TABO, the ESIPT process can be readily disturbed by basic anions such as F-, CH3COO-, and H2PO4- by deprotonating the sulfonamide unit, whereas in the case of PUBO, a good hydrogen-bonding donor, the ESIPT process is inhibited either by the fluoride-induced deprotonation of the urea unit or by the formation of a strong CH3COO--urea intermolecular hydrogen bond complex, and these two types of inhibition mechanisms consequently result in different ratiometric responses. But other anions with less hydrogen-bonding acceptor abilities cannot inhibit the ESIPT. Interestingly, the different inhibition abilities of F-, CH3COO-, and H2PO4- produce different spectral behaviors in PUBO, so this new sensor successfully distinguishes the subtle difference in these three anionic substrates of similar basicity and surface charge density.

Study on synthesis and characterization of novel optically active poly(amide-imide)s based on bis(p-aminobezoic acid)-N-trimellitylimido-S-valine via direct polycondensation

AbstractN-Trimellitylimido-S-valine (3) was prepared by reaction of trimellitic anhydride (1) with S-valine (2) in acetic acid solution at refluxing temperature. This diacid was reacted with thionyl chloride and N-trimellitylimido-S-valine diacid chloride (4) was obtained in quantitative yield. The reaction of this diacid chloride with p-aminobenzoic acid was carried out in dry tetrahydrofurane and bis(paminobenzoic acid)-N-trimellitylimido-S-valine (5) was obtained as a novel optically active amide-imide diacid monomer in high yield. The direct poly condensation of amide-imide diacid monomer with aromatic diamins such as 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, benzidine, 4,4'-diaminodiphenyl methane, 1,4- phenylene diamine and 2,5-diamino toluene was carried out in tosyl chloride/ pyridine/dimethylformamide system. The resulting novel optically active poly(amide-imide)s (PAIs) with inherent viscosities ranging from 0.24-0.76 dLg-1, were obtained in good yield. All of these polymers were fully characterized with FTIR spectroscopy and specific rotation. Some elemental analysis, thermal properties and 1H-NMR of these new optically active PAIs are also reported.

Large-Pore Mesoporous Organosilicas Functionalized with trans-(1R,2R)-Diaminocyclohexane: Synthesis, Postmodification, and Catalysis

Large-pore mesoporous ethane-silicas functionalized with trans-(1R,2R)-diaminocyclohexane were synthesized in an acidic medium by one-step co-condensation of 1,2-bis(trimethoxysilyl)ethane and N-[(trimethoxysilyl)benzyl]-(−)-(1R,2R)-diaminocyclohexane using triblock copolymer P123 as template. The postmodification of trans-(1R,2R)-diaminocyclohexane in the pore of the mesoporous ethane-silicas was further demonstrated by reaction with p-toluenesulfonyl chloride. The modified material (complexed with [RhCp*Cl2]2) exhibits much higher conversion and ee [53% conversion with 68% ee (R)] than the original material [18% conversion with 38% ee (S)] for the asymmetric transfer hydrogenation of acetophenone under air atmosphere in HCOONa−H2O. Various aromatic ketones can be converted to the corresponding chiral alcohol with moderate to good enantioselectivities [18−81% ee (R)]. The co-condensation method associated with the postmodification method is one of the alternatives for the synthesis of mesoporous materials containing new functionalities.

Polystyrene and silica gel supported AlCl3 as highly chemoselective heterogeneous Lewis acid catalysts for Friedel–Crafts sulfonylation of aromatic compounds

Abstract Crosslinked polystyrene supported AlCl 3 (Ps–AlCl 3 ) and silica gel supported AlCl 3 (SiO 2 –AlCl 3 ) have shown to be mild and chemoselective heterogeneous Lewis acid catalysts for the sulfonylation of different kinds of aromatic compounds with p -toluene sulfonyl chloride (TsCl) and benzene sulfonyl chloride (PhSO 2 Cl) as sulfonylating agents. These solid acid catalysts are stable (as bench top catalysts) and can be easily recovered and reused without appreciable change in their efficiency.

A facile and efficient synthesis of aryl toluenesulfonhydrazides and aryl toluenesulfonates under solvent-free conditions

A rapid, efficient method is described for synthesis of aryl toluenesulfonhydrazides from toluene-sulfonyl chloride and substituted phenylhydrazines and for the synthesis of aryl toluenesulfonates from toluenesulfonyl chloride and substituted phenols. The procedure is simple, environmentally benign and occurs in good yields.

Preparation of Amino-cyclosophoraoses from the Neutral Cyclosophoraoses Isolated fromRhizobium leguminosarum bv. trifolii

Cyclosophoraoses are a class of unbranched cyclic oligosaccharides composed of β-1,2-D-glucans varying in size from 17 to 40 in a neutral or anionic form. They were originally found in fast growing soil bacteria, Agrobacterium and Rhizobium species, as intraor extra-oligosaccharides. Cyclosophoraoses are synthesized in the cytosol and transported to the periplasmic space where they play an important role in regulating the osmolarity in response to external osmotic shock. They are also known to be involved in the initial stage of root-nodule formation of Rhizobium species during nitrogen fixation. Throughout this interaction, cyclosophoraoses are suspected to be involved in complexation with various plant flavonoids. Thus, much attention has been focused not only on their biological functions but also on their potential ability to form inclusion complexes with other molecules. Several reports have shown that neutral cyclosophoraoses or anionic cyclosophoraoses have good potential as a host molecule in various inclusion complexation technologies such as a solubility enhancer and a chiral selector. In addition, the investigations into the chemical modifications of neutral cyclosophoraoses have been concerned with modifying their binding behaviors, e.g., carboxymethylated and sulfated cyclosophoraoses which were successfully used as a solubility enhancer and chiral selector, respectively. Their modifications are of particular importance for the investigation at the frontier of various research fields ranging from supramolecular chemistry to analytical techniques. In this study, for further application of cyclosophoraoses, neutral cyclosophoraoses were modified with tosyl, azide and amino groups through the chemical derivatization, and their modified structures were confirmed by nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopy. Isolation, purification and structural analyses of neutral cyclosophoraoses were carried out as described previously. Purified neutral cyclosophoraoses were separated with an Rf value of 0.125 on thin layer chromatography (TLC, ethanol : butanol : water = 5 : 5 : 4, v/v/v). Through matrix-assisted laser desorption/ionization time of flight (MALDI-TOF) mass spectrometry, we confirmed that the ring sizes of the neutral cyclosophoraoses ranged from degree of polymerization (DP) 17 to 23 (data not shown). Although the exact three-dimensional structure of cyclosophoraoses is not known, several NMR studies and molecular dynamics simulations have provided molecular models with flexible glycosidic linkage backbones. The cyclosophoraoses seem to have narrower cavity sizes than those expected from their bulky ring sizes (Figure 1A). The amino-cyclosophoraoses were obtained through three steps, tosylation (tosyl-cyclosophoraoses), azidation (azidocyclosophoraoses) and amination (Figure 1B). First, the hydroxyl groups of neutral cyclosophoraoses were subjected to chemical modification with p-toluenesulfonyl chloride and the reaction was monitored on TLC. The Rf value of the purified tosyl-cyclosophoraoses was 0.241 (ethanol : butanol : water = 5 : 5 : 4, v/v/v). The tosyl-cyclosophoraoses was synthesized in a 25 percent yield. Next, the azido-cyclosophoraoses were obtained from tosyl-cyclosophoraoses which were treated with NaN3 in water (90 percent yield). And then the azido-cyclosophoraoses and triphenylphos-

Novel cis– trans enantiomeric conglomerates: triage and absolute configurations via anomalous X-ray scattering. A photochemical second order asymmetric transformation

Three tricyclic imides were prepared by a Diels–Alder reaction of 6-arylfulvenes and maleic anhydride, followed by treatment with NH 3. The exo isomers were found to exist as conglomerates when the aryl group was either p-tolyl or p-anisyl (although not phenyl). Triage of the p-tolyl racemate, followed by reaction with p-toluenesulfonyl chloride in CH 2Cl 2/Et 3N, led to the crystalline enantiopure N-tosylimides (these were also conglomerates). X-ray diffraction analysis of the N-tosylimides via the anomalous dispersion technique led to assignment of the absolute configurations (as either E or Z). The original p-tolyl imide enantiomers were found to racemize under UV irradiation in CHCl 3. Based on this, a possible second order asymmetric transformation under photochemical conditions was attempted, and indeed led to the isolation of crystalline imide with a small ee (∼15%).

Solvent-free and selective tosylation of alcohols and phenols with p-toluenesulfonyl chloride by heteropolyacids as highly efficient catalysts

Tosylation of some alcohols and phenols has been directly carried out with p-toluenesulfonyl chloride using heterodoxy acids (H3PW12O40, H3PMo12O40, AlPW12O40, and AlPMo12O40) as catalysts in the absence of solvent. We found that heteropoly acids AlPW12O40 and AlPMo12O40 were effective catalysts for the tosylation of alcohols and phenols. In the case of aliphatic alcohols, secondary alcohols undergo tosylation chemoselectively in the presence of primary hydroxyl groups. This new method consistently has the advantage of excellent yields and short reaction time.Key words: tosylation, p-TsCl, Keggin-type polyoxometalate, solvent-free reaction.

Synthesis of novel optically active poly(ester imide)s by direct polycondensation reaction promoted by tosyl chloride in pyridine in the presence of N,N‐dimethyformamide

Abstract4,4′‐Hexafluoroisopropylidene‐2,2‐bis(phthalic acid anhydride) (1) was treated with L‐methionine (2) in acetic acid and the resulting 4,4′‐(hexafluoroisopropylidene)‐N,N′‐bis(phthaloyl‐L‐methionine) diacid (4) was obtained in high yields. The direct polycondensation reaction of this diacid with several aromatic diols, such as bisphenol A (5a), phenolphthalein (5b), 1,4‐dihydroxybenzene (5c), 4,4′‐dihydroxydiphenyl sulfide (5 d), 4,6‐dihydroxypyrimidine (5e), 4,4′‐dihydroxydiphenyl sulfone (5f), and 2,4′‐dihydroxyacetophenone (5g), was carried out in a system of tosyl chloride (TsCl), pyridine (Py), and N,N‐dimethylformamide (DMF). The reactions with TsCl were significantly promoted by controlling alcoholysis with diols, in the presence of catalytic amounts of DMF, to give a series of optically active poly(ester imide)s, (PEI)s, with good yield and moderate inherent viscosity ranging from 0.43 to 0.67 dL/g. The polycondensation reactions were significantly affected by the amounts of DMF, molar concentration of monomers, TsCl and Py, aging time, temperature, and reaction time. All of the aforementioned polymers were fully characterized by 1H NMR, FTIR, elemental analysis, and specific rotation. Some structural characterization and physical properties of these optically active PEIs are reported. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 455–460, 2006

Ultra high molar mass poly[2-(dimethylamino)ethyl methacrylate] via atom transfer radical polymerization

Well-defined high molecular weight poly[2-(dimethylamino)ethyl methacrylates] [poly(DMAEMA)s] with molar masses up to ∼1×10 6 g/mol were successfully synthesized via atom transfer radical polymerization (ATRP). This was achieved by using p-toluenesulfonyl chloride( p-TsCl)/CuCl/1,1,4,7,10,10-hexamethyl-triethylenetetramine(HMTETA) initiator/catalyst complex in methanol/water mixture. Well-controlled/‘living’ behavior was demonstrated throughout the reaction, up to high monomer conversion. The PDI value remained low at 1.26 even for a polymer with very high molecular weight at 1.1×10 6 g/mol. We believe this is the first successful case where controlled ATRP produces a polymer with molar mass exceeding a million!

Direct Polyamidation of N,N’-(4,4’-Hexafluoroisopropy-lidendiphthaloyl)-bis-L-isoleucine with Different Aromatic Diamines via Vilsmeier Adduct Derived from Tosyl Chloride and N,N-Dimethylformamide

Various approaches have been carried out in the synthesis of poly(amide-imide)s. A well-developed solution polycondensation method has been used to prepare such copolymers either from a dianhydride containing a preformed amide group with a diamine or from a dicarboxylic acid containing a preformed imide ring with a diamine. Direct polycondensations of carboxylic acids and aromatic diamines can be a more useful technique for synthesis of poly(amide-imide)s PAIs. In this work, direct polymerization reaction of N,N’-(4,4’-hexafluoroisopropylidendiphthaloyl)-bis-L-isoleucine with several aromatic diamines such as 4,4’-diaminodiphenylsulphone (4a), 4,4’-diaminodiphenylmethane (4b), 4,4’-diaminodiphenylether (4c), 1,4-phenylenediamine (4d), 4,4’-diaminobiphenyl (4e), 1,3-phenylenediamine (4f), 2,4-diaminotoluene (4g), was performed in the presence of tosyl chloride (TsCl)/dimethylformamide (DMF)/pyridine (Py) as a condensing agent. The resulting PAIs were obtained in high yield and inherent viscosity. Some structural characterization and physical properties of these polymers have been studied and will be reported.

Gas-phase-assisted surface polymerization of methyl methacrylate with Fe(0)/TsCl initiator system

To obtain a high polymer coated Fe(0) surface, gas-phase-assisted surface polymerization (GASP) of methyl methacrylate (MMA) was investigated using a zero-valent iron (Fe(0))/p-toluene sulfonylchloride (TsCl) initiator system, resulting in successful high polymer production on the solid surface. GASP was found to be initiated by radical species that might have been generated via redox reactions with Fe(0), Fe(II), Fe(III), and TsCl. From 1H-NMR analysis, the p-toluene sulfonyl group was found at one end of the polymer chain. The molecular weight of obtained PMMA drastically decreased with increase in the composition ratio of Fe(0) in the initiator system, and increased with increase in polymer yield. From the results, it was assumed that the physically controlled polymerization of MMA proceeded by immobilized active species at gas–solid interfaces. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1879–1886, 2007