- Identification of organophosphorus simulants for the development of next-generation detection technologies
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Organophosphorus (OP) chemical warfare agents (CWAs) represent an ongoing threat but the understandable widespread prohibition of their use places limitations on the development of technologies to counter the effects of any OP CWA release. Herein, we describe new, accessible methods for the identification of appropriate molecular simulants to mimic the hydrogen bond accepting capacity of the PO moiety, common to every member of this class of CWAs. Using the predictive methodologies developed herein, we have identified OP CWA hydrogen bond acceptor simulants for soman and sarin. It is hoped that the effective use of these physical property specific simulants will aid future countermeasure developments.
- Ellaby, Rebecca J.,Clark, Ewan R.,Allen, Nyasha,Taylor, Faith R.,Ng, Kendrick K. L.,Dimitrovski, Milan,Chu, Dominique F.,Mulvihill, Daniel P.,Hiscock, Jennifer R.
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p. 2008 - 2014
(2021/03/16)
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- Combinatorial discovery of thermoresponsive cycloammonium ionic liquids
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This work demonstrated, for the first time, the combinatorial discovery and rational identification of small-molecule cycloammonium-based thermoresponsive ionic liquids that exhibit LCST phase transition and carry attractiveTcvalues in water.
- Chu, Yen-Ho,Hwang, Chun-Chieh,Chen, Chien-Yuan,Tseng, Min-Jen
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p. 11855 - 11858
(2020/10/13)
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- Rapid transformation of sulfinate salts into sulfonates promoted by a hypervalent iodine(III) reagent
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An alternative method for forming sulfonates through hypervalent iodine(III) reagent-mediated oxidation of sodium sulfinates has been developed. This transformation involves trapping reactive sulfonium species using alcohols. With additional optimization of the reaction conditions, the method appears extendable to other nucleophiles such as electron-rich aromatic systems or cyclic ethers through a ring opening pathway.
- Deruer, Elsa,Hamel, Vincent,Blais, Samuel,Canesi, Sylvain
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supporting information
p. 1203 - 1207
(2018/06/04)
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- Ionic liquid brush as an efficient and reusable heterogeneous catalytic assembly for the tosylation of phenols and alcohols in neat water
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A very efficient and reusable heterogeneous ionic liquid brush assembly was developed. The catalyst exhibits high catalytic activity for the tosylation of phenols and alcohols in neat water. Moreover, the catalyst shows outstanding stability and reusability, and it can be simply and effectively recovered and reused five times without noticeable loss of catalytic activity.
- Feng, Simin,Li, Jing,Wei, Junfa
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supporting information
p. 4743 - 4746
(2017/07/12)
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- An efficient practical tosylation of phenols, amines, and alcohols employing mild reagent [DMAPTs]+Cl?
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Efficient exploration of [DMAPTs]+Cl?for base free and chromatography free preparation of sulfonate esters from phenols and alcohols and sulfonamides from amines was achieved in excellent yields. Majority of the phenols irrespective of their substituents electronic nature underwent tosylation nearly at same reaction rate with an average yield of 95%. For amines, ring activating substituents favors rapid sulfonylation while the ring deactivating substituents relatively lowers the rate of tosylation. Furthermore the reagent was employed for Chemoselective sulfonylation as well as solvent free tosylation of phenols and amines.
- Dhonthulachitty, Chiranjeevi,Kothakapu, Sridhar Reddy,Neella, Chandra Kiran
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supporting information
p. 4620 - 4623
(2016/09/23)
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- New process for the production of alkyltosylate from alcohol and para-toluene sulfonic acid
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The present invention relates to a new method for producing an alkyltosylate derivative which plays an important role in transforming a hydroxy group of alcohol into other usage intermediate in a process of synthesizing core intermediates in a fine chemical field such as medicines, agricultural chemicals, dyes, electronic materials, etc. The present invention, as compared with previous technologies which has a long preprocess time for acquiring a catalyst to activate para-toluene sulfonic acid and needs an intense reaction condition in spite of using the catalyst, provides the new method for producing the alkyltosylate derivative having a characteristic of activating the para-toluene sulfonic acid under a warm condition equal to or lower than 25anddeg;C by making the para-toluene sulfonic acid react with the bis(trichloromethyl)carbonate, tribasic potassium phosphate and triethylamine with an amount of catalyst, and then making the para-toluene sulfonic acid react with alcohol, thereby contributing greatly to related industries such as dyes, agricultural chemicals, medicines, electronic materials, etc.COPYRIGHT KIPO 2015
- -
-
Paragraph 0030; 0031
(2016/12/16)
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- A method for the production of sulfate or sulfonate esters
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The present invention relates to method for the production of sulfate or sulfonate esters essentially comprising the steps of adding sulfuric acid or sulfonic acid to boron acid in a medium with or without solvent (121), stirring the prepared mixture 8122), removing the precipitated boric acid (123), removing the solvent in case the solvent is used (124), producing dialkyl sulfate esters, mono alkyl sulfate esters and sulfonate esters of alkali metal salts (125), and based on the acidolysis of boron esters obtained from alcohol and boric acid with sulfuric acid or sulfonic acid.
- -
-
Paragraph 0038
(2015/03/31)
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- Synthesis, crystal structure, spectral and thermodynamic properties of one benzoindole pentamethine cyanine dye
-
One benzoindole pentamethine cyanine dye was synthesized and characterized by 1H NMR, IR, MS and UV-Vis spectra. The UV-Vis absorption and fluorescence spectra of the dye in chloroform, dimethyl sulfoxide, acetone, ethanol and methanol were investigated, and the λmax of the dye was in the region 682.0-689.0 nmwith large molar extinction coefficients (ε > 105M-1cm-1) in different solvents. The structure of the dye was also characterized and analyzed by X-ray diffraction. Crystallographic data revealed that the dye belonged to orthorhombic, with space group P212121, a = 10.059(2) A, b = 15.098(4) A, c = 24.989(6) A, V = 3794.8(15) A3, Z = 4. TheC-H·F intermolecular hydrogen bonds were displayed in the molecular system, which were effective in the molecular packing. The aggregation behavior and thermodynamic properties of the dye in aqueous methanol solution were also studied by means of UV-Vis spectroscopy methods. The results indicated that the dye existed monomer-dimer equilibrium in aqueous methanol solutions. The fundamental properties of the dye, such as the dimeric association constant KD, the dimeric free energy ΔGD, the dimeric entropy ΔSD, and the dimeric enthalpy ΔHD were determined. The ΔHD of the dye was -46.0 kJ mol -1.
- Zhang, Xiu-Fu,Zhao, Jun-Long,Bi, Wei-Bin,Zhang, Dan-Dan,Yang, Zhi-Yuan,Wang, Lan-Ying
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p. 503 - 510
(2013/07/27)
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- Regioselective, borinic acid-catalyzed monoacylation, sulfonylation and alkylation of diols and carbohydrates: Expansion of substrate scope and mechanistic studies
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Synthetic and mechanistic aspects of the diarylborinic acid-catalyzed regioselective monofunctionalization of 1,2- and 1,3-diols are presented. Diarylborinic acid catalysis is shown to be an efficient and general method for monotosylation of pyranoside derivatives bearing three secondary hydroxyl groups (7 examples, 88% average yield). In addition, the scope of the selective acylation, sulfonylation, and alkylation is extended to 1,2- and 1,3-diols not derived from carbohydrates (28 examples); the efficiency, generality, and operational simplicity of this method are competitive with those of state-of-the-art protocols including the broadly applied organotin-catalyzed or -mediated reactions. Mechanistic details of the organoboron-catalyzed processes are explored using competition experiments, kinetics, and catalyst structure-activity relationships. These experiments are consistent with a mechanism in which a tetracoordinate borinate complex reacts with the electrophilic species in the turnover-limiting step of the catalytic cycle.
- Lee, Doris,Williamson, Caitlin L.,Chan, Lina,Taylor, Mark S.
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scheme or table
p. 8260 - 8267
(2012/07/14)
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- ZnO and ZnO-nanoparticles: Efficient and reusable heterogeneous catalysts for one-pot synthesis of N-acylsulfonamides and sulfonate esters
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Commercially available and preparative ZnO nanoparticles are reported as efficient and reusable catalysts for the chemoselective synthesis of N-acylsulfonamides and sulfonate esters. A one-pot sequential sulfonylation and acylation of amines took place to afford the N-acylsulfonamides in excellent yields under solvent-free conditions. The ZnO catalyst can be reused for without significant loss of catalytic activity.
- Tamaddon, Fatemeh,Sabeti, Mohammad Reza,Jafari, Abbas Ali,Tirgir, Farhang,Keshavarz, Elham
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experimental part
p. 41 - 45
(2012/01/12)
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- CsF-Celite as an efficient heterogeneous catalyst for sulfonylation and desulfonylation of heteroatoms
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CsF-Celite is found to be as an efficient reusable catalyst for sulfonylation and desulfonylation of heteroatoms. Sulfonamides and N-acylsulfonamides deprotect efficiently in the presence of CsF-Celite under solvent free conditions to give the free amines or amides in good to excellent yields.
- Tamaddon, Fatemeh,Nasiri, Alireza,Farokhi, Somayeh
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experimental part
p. 1477 - 1482
(2012/06/18)
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- Amphiphilic organocatalyst for schotten-baumann-type tosylation of alcohols under organic solvent free condition
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A Tosylation of primary alcohol with tosyl chloride was performed effectively with an W-hexadecylimidazole catalyst in water containing K 2CO3 aggregation of the catalyst carrying a hydrophobic methylene chain worked as a substitute for organic solvent.
- Asano, Keisuke,Matsubara, Seijiro
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supporting information; experimental part
p. 1757 - 1759
(2009/09/06)
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- Stereoselective synthesis of bioactive isosteviol derivatives as α-glucosidase inhibitors
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Considerable interest has been attracted in isosteviol and its derivatives because of their large variety of pharmacological activities. In this project, a series of novel compounds containing hydroxyl, hydroxymethyl group and heteroatom-containing frameworks fused with isosteviol structure were synthesized and evaluated as α-glucosidase inhibitors, aimed at clarifying the structure-activity correlation. The results indicated that these isosteviol derivatives were capable of inhibiting in vitro α-glucosidase with moderate to good activities. Among them, indole derivative 15b exhibited the highest activities and thus may be exploitable as a lead compound for the development of potent α-glucosidase inhibitors.
- Wu, Ya,Yang, Jing-Hua,Dai, Gui-Fu,Liu, Cong-Jun,Tian, Guo-Qiang,Ma, Wen-Yan,Tao, Jing-Chao
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experimental part
p. 1464 - 1473
(2009/09/05)
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- Tethered PProDOTs: Conformationally restricted 3,4-propylenedioxythiophene based electroactive polymers
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Herein we report a complete family of conformationally restricted PProDOT derivatives with varying alkylene tether lengths. It was found that variation of the tether length and structure of the electropolymerizable monomer was successful in the fine-tuning of the electrochemical and optical properties of the subsequent material. It was found that the band gap of the materials could be varied between 1.94 and 2.26 eV, with the "sweet spot" for obtaining the maximum electronic band gap existing at the n = 6 tether length, while maintaining low redox potentials. It was also found that these polymers exhibited stable electrochromic behavior with colors varying from blue-purple to orange in their neutral states and transmissive in their doped states. The Royal Society of Chemistry 2007.
- Walczak, Ryan M.,Cowart Jr., John S.,Reynolds, John R.
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p. 254 - 260
(2008/02/01)
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- Conformational locking for band gap control in 3,4-propylenedioxythiophene based electrochromic polymers
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We report a tethered poly(3,4-propylenedioxythiophene) derivative with a built-in polymer conformation restriction which locks the conjugated chain at a specific dihedral angle, thus providing a handle in which to tune the optical and electronic properties of the material. The Royal Society of Chemistry 2006.
- Walczak, Ryan M.,Cowart Jr., John S.,Abboud, Khalil A.,Reynolds, John R.
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p. 1604 - 1606
(2008/02/08)
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- Unsubstituted bicyclo[1.1.0]but-2-ylcarbinyl cations
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A synthesis for the unsubstituted bicyclo[1.1.0]but-2-ylmethanols (endo- and exo-9) from 1,3-butadiene has been developed. Solvolyses of their sulfonates 10 and 11 took entirely different courses, as the endo compound 10 gave rise exclusively to rearranged products such as cyclopent-3-en-1-ol (14), while the exo compound 11 underwent only the substitution of the tosylate group with complete retention of the exo-bicyclo[1.1.0]but-2-ylmethyl skeleton. Under solvolytic conditions, 10 reacted at very similar rates to the corresponding monocyclic substrate, that is, cyclopropylcarbinyl mesylate (19); in contrast, 11 reacted only three times as fast as n-butyl tosylate and about 1000-fold slower than 10. The nature of the bicyclo[1.1.0]but-2-ylcarbinyl cations has been probed by quantum chemical calculations. Whereas, the exo isomer (exo-18) corresponds to a local energy minimum, the endo isomer is only a transition state [endo-l8(TS)] for an automerization of the nonclassical cyclopent-3-en-1-yl cation (13) and converts into 13 by a Wagner-Meerwein rearrangement. The most favorable isomerization of exo-18 also leads to 13 but via a transition state resembling the 2-vinylcycloprop-1-yl cation [25(TS)]. On the introduction of methyl groups at positions 1 and 3 of exo-18, the cation is no longer an energy minimum and it becomes a transition state [27(TS)] for an automerization of the nonclassical 1,3-dimethylcyclopent-3-en-1-yl cation (28). The large effect of the methyl substitution rationalizes the puzzling results of the previous product and rate studies, which utilized various substituted derivatives of bicyclo[1.1.0]but-2-ylcarbinyl sulfonates as substrates.
- Bentley, T. William,Engels, Bernd,Hupp, Thomas,Bogdan, Elena,Christl, Manfred
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p. 1018 - 1026
(2007/10/03)
-
- Synthesis of polyfluorinated ethers
-
Procedures for preparing polyfluorinated ethers H(CF2CF 2)nCH2OR by alkylation of the corresponding telomeric alcohols H(CF2CF2)nCH2OH (n = 1-3) with alkyl halides and alkyl tosylates were examined.
- Bazhin,Gorbunova,Zapevalov,Saloutin
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p. 1646 - 1650
(2007/10/03)
-
- Alkylated alkyl polyglucoside non-ionic surfactants
-
A petro-chemical free nonionic surfactant is prepared by the alkylation of an alkyl polyglucoside (APG). Under suitable alkylation reaction conditions, the surfactants are preferably prepared by the reaction of an APG with either alkyl halide or an alkyl tosylate. These surfactants are low foaming and exhibit excellent detergency.
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- An efficient one-pot conversion of THP and TMS ethers to sulfonate esters using FeCl3-montmorillonite K-10 clay
-
Various tetrahydropyranyl and trimethylsilyl ethers are efficiently transformed into the corresponding sulfonate esters with sulfonyl chlorides in the presence of FeCl3-Montmorillonite K-10 clay.
- Movassagh, Barahman,Shokri, Salman
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p. 763 - 765
(2007/10/03)
-
- Efficient and mild Ytterbium(III)-catalyzed tosylation of alcohols
-
Ytterbium(III) trifluoromethanesulfonate efficiently catalyzes the reaction of primary and secondary alcohols with toluenesulfonic acid anhydride to yield the alkyl tosylates in high yields. The reactions were carried out under neutral and mild conditions and product purification was easily achieved by means of short column chromatography.
- Comagic, Slobodan,Schirrmacher, Ralf
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p. 885 - 888
(2007/10/03)
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- An efficient one pot synthesis of carbamate esters through alcoholic tosylates
-
An efficient O-alkylation of alcoholic tosylates with amines in a K2CO3/CO2 system in the presence of tetrabutyl ammonium iodide (TBAI) provides exclusive formation of carbamates.
- Chaturvedi, Devdutt,Kumar, Atul,Ray
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p. 2651 - 2655
(2007/10/03)
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- MANUFACTURING METHOD FOR POLYCARBONATE
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A method for manufacturing polycarbonate by melt-polycondensing bisphenol and carbonic acid diester uses as catalyst an alkali metal compound and/or alkaline earth metal compound (a). The catalyst is added to the bisphenol prior to the melt polycondensation, in an effective amount, i.e., the amount of alkali metal compound and/or alkaline earth metal compound (a) that acts effectively as a catalyst, is contained in said bisphenol, and is controlled to have the same catalytic activity as 1×10?8 to 1×10?6 mole of bisphenol disodium salt per mole of pure bisphenol A. The method conducts the reaction efficiently from the initial stage in a stable manner to obtain polycarbonate with good color, good heat stability and color stability during molding and the like.
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-
- Clean catalysis with ionic solvents - Phosphonium tosylates for hydroformylation
-
High-melting phosphonium tosylates are synthesised and applied for the first time as solvents in catalytic hydroformylation reactions; variation in the substituents attached to phosphorus can lead to markedly different results; the catalyst systems are non-corrosive, easily manipulated and can readily be recovered and reused.
- Karodia, Nazira,Guise, Steven,Newlands, Craig,Andersen, Jo-Ann
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p. 2341 - 2342
(2007/10/03)
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- Process for preparation of oxyglutaric acid ester derivatives
-
A process for preparing an oxyglutaric acid ester derivative of the formula: STR1 in which each of R1 and R2 is C1-5 alkoxy, C1-7 aralkyloxy, C7-9 halogenated aralkyloxy or phenyl, R4 is a hydroxyl-protecting group, and R5 is C1-10 alkyl which may have a substituent, comprises the steps of reacting a methyl phosphonate derivative or methyl phosphine oxide derivative with an oxyglutaric acid mono-ester to give a reaction product which comprises an oxyglutaric acid derivative having a phosphorus-containing group and a pentenedioic acid mono-ester (by-product), removing the pendenedioic acid mono-ester from the reaction product to isolate the oxyglutaric acid derivative, and converting the isolated oxyglutaric acid derivative into the oxyglutaric acid ester derivative. A process for obtaining an optically active oxyglutaric acid ester derivative is also disclosed.
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-
- Evaluation of the quantitative contribution of an aryl group on C(2) of 8-azaadenines to binding with adenosine deaminase: A new synthesis of 8-azaadenosine. XI
-
The introduction of a phenyl group on C(2) of 8-azaadenosine increases binding to the adenosine deaminase enzyme (ADA). This stability increment has been quantitatively evaluated in both 8-azaadenosines and 9-(2',3'-dihydroxypropyl)-8-azaadenines; it resulted nearly equivalent in the two series. 8-Azaadenosine has been synthesized through a new route employing fully protected β-D-ribofuranosyl-1-azide. Instead, the stability difference in 9-(n-alkyl)-8-azaadenines, owing to the inactivity of the C(2) unsubstituted compounds, could not be evaluated. Consideration of the enantioselectivity of the ADA enzyme toward chiral 9-(2',3'-dihydroxypropyl)-8-azaadenines and 9-(2',3'-dihydroxypropyl)-8-azahypoxanthines allowed the exclusion of an appreciable structural modification in the enzyme-inhibitor complex when hydrogen on C(2) is substituted by an aryl group.
- Biagi,Giorgi,Livi,Scartoni,Lucacchini
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p. 1457 - 1476
(2007/10/02)
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- Micellar Effects upon the Rates of SN2 Reactions of Halide Ions
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Observed first-order rate constants for reactions of Cl- or Br- with alkyl benzenesulfonate (1a-c) in micelles of cetyltrimethylammonium surfactants (CTAX, X=Cl, Br, OMes, 0.5SO4) increase monotonically with increasing or or halide ion concentration and tend to limiting values.In CTAOMes or (CTA)2SO4, the rate constants go through maxima.The variation of the rate constants with concentrations of surfactant and halide ion can be fitted to an equation that accounts for the distribution of both reactants between water and micelles, i. e., in terms of ion-exchange and mass-action models.The second-order rate constants in the aqueous and micellar pseudophases are similar.
- Al-Lohedan, Hamad A.
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p. 8226 - 8231
(2007/10/02)
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- Sulphonic Acid-induced Fragmentation of Dialkyl Acylphosphonates, Formation of Alkyl Carboxylates and Alkyl Sulphonates
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Heating of dialkyl acylphosphonates with sulphonic acids under anhydrous conditions leads to the formation of alkyl sulphonates and alkyl carboxylates. 31P N.m.r. spectroscopy revealed that the reaction of equimolar amounts of dimethyl benzoylphosphonate (1) and toluene-p-sulphonic acid at room temperature gives dimethyl phosphonate (6) in 50percent yield.It is proposed that the by-product of this reaction, benzoic toluene-p-sulphonic anhydride (8), reacts with the excess of toluene-p-sulphonic acid, to yield toluene-p-sulphonic anhydride (9) and benzoic acid.Heating of these two compounds with dimethyl phosphonate was shown to yield methyl toluene-p-sulphonate and methyl benzoate, respectively.A postulated by-product of these reactions is phosphenous acid (HPO2).Quantum mechanical calculations by the MNDO/H method carried out on dimethyl benzoylphosphonate and its protonation products show that the preferred site of protonation of dimethyl benzoylphosphonate is the P=O oxygen, and that protonation at this site is followed by C-P bond breaking, with zero energy of activation, leading to dimethyl phosphite and benzoylium cation.
- Breuer, Eli,Karaman, Rafik,Goldblum, Amiram,Leader, Haim
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p. 2029 - 2034
(2007/10/02)
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- REACTION OF PHOSPHORUS OXYACID ESTERS WITH p-TOLUENESULFONIC ACID
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The reaction of primary alkyl esters of phosphorus oxyacids with p-toluenesulfonic acid (TsOH) in refluxing solvents gave the corresponding p-toluenesulfonates (TsOR).We found that the secondary alkyl esters reacted with TsOH at lower temperature (r.t.-40 deg C) to afford TsORs in good yields.It is suggested that sulfonic acids may be useful for the selective dealkylation of mixed esters.Keywords-p-toluenesulfonic acid; p-toluenesulfonate; trialkyl phosphate; trialkyl phosphite; dialkyl phenylphosphonate; transesterification; dealkylation; solvolysis.
- Nitta, Yoshihiro,Arakawa, Yasushi,Ueyama, Naoto
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p. 2710 - 2718
(2007/10/02)
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- Reaction of Carboxylic Acid Esters with p-Toluenesulfonic Acid
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The reaction of carboxylic acid esters with an excess of p-toluenesulfonic acid gave the corresponding p-toluenesulfonates.The mechanism of the transesterification is discussed.
- Nitta, Yoshihiro,Arakawa, Yasushi
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p. 1380 - 1386
(2007/10/02)
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- Enamines of 2,2-bis(ethylthio)ethanal: a convenient route to γ-keto crotonate derivatives
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A new α-oxoaldehyde reagent, 2,2-bis(ethylthio)ethanal 1, has been prepared in high yield from ethanedial.Alkylation of the potassium salt of the enamines of 1 with various alkylating agents followed by in situ hydrolysis of the intermediate imine afforded high yields of the alkylation products of 1.This new reagent was used in the synthesis of a chiral potential precursor of the macrocyclic fragment of cytochalasins A,B, and F, as well as in the syntheses of the physiologically active diolides pyrenophorin and norpyrenophorin.
- Bates, Gordon S.,Ramaswamy, S.
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p. 2466 - 2475
(2007/10/02)
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- Deamination via Nitrogen Derivatives of Sulfonic Acids: N-Alkyl-N-nitroso-4-toluenesulfonamides, N-Alkyl-N-nitro-4-toluenesulfonamides, and N-Alkyl-N'-(4-toluenesulfonyloxy)diimide N-Oxides
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The thermal decomposition of several N-alkyl-N-nitroso-4-toluenesulfonamides, N-alkyl-N-nitro-4-toluenesulfonamides, and N-alkyl-N'-(4-toluenesulfonyloxy)diimide N-oxides was undertaken to determine whether the basicity of the negatively charged counterion in deamination reactions was a reaction variable.The nitrososulfonamides decompose following first-order kinetics to give the corresponding esters with retention of configuration.The reaction characteristics are very similar to those of the N-nitrosocarboxamides, and the reaction mechanisms are presumably very similar also.The N-nitrosulfonamides required high temperatures for decomposition, and they gave an anomalous set of products: amide (by denitration) and olefins, but no nitrous oxide or toluenesulfonate esters.The N'-toluenesulfonoxydiimide N-oxides, isomeric to the nitrosulfonamides, proved to be surprisingly stable compounds; they decompose by first-order kinetics to yield the corresponding esters and nitrous oxide.
- White, Emil H.,Lewis, Charles P.,Ribi, Max A.,Ryan, Thomas J.
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p. 552 - 558
(2007/10/02)
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