- Synthesis, growth and spectral studies of S-benzyl isothiouronium nitrate by density functional methods
-
S-benzyl isothiouronium nitrate (SBTN), was synthesized and characterized by X-ray diffraction, FTIR, UV-Vis and NMR spectra. The Centro-symmetric single crystal of S-benzyl isothiouronium nitrate (SBTN), which crystallizes in monoclinic crystal system with space group P21/C, exhibits second order non-linear optical (NLO) susceptibility, due to intermolecular charge transfer. S-benzyl isothiouronium ion forms well defined charge transfer (CT) salt with anion nitrate through N-H?O and C-H?O hydrogen bonds. It is to identify the direction of specific N-H?O hydrogen bond between the -NH2 group and O- in the anion and also sacking in the solid state responsible for NLO activity in this crystal. The SHG technique confirms the non-linear optical property of the grown crystals. Density functional theory (DFT) calculation has been carried out to study the nature of hydrogen involved in the SBTN crystal. The bond lengths and bond angles of the structure of SBTN crystal calculated using B3LYP method with 6-311+(2d,2p) basis set. These calculations are compared with experimental values to provide deep insight into its electronic structure and property of grown crystal.
- Hemalatha,Kumaresan,Veeravazhuthi,Gunasekaran
-
-
Read Online
- Chromoselective Synthesis of Sulfonyl Chlorides and Sulfonamides with Potassium Poly(heptazine imide) Photocatalyst
-
Among external stimuli used to promote a chemical reaction, photocatalysis possesses a unique one—light. Photons are traceless reagents that provide an exclusive opportunity to alter chemoselectivity of the photocatalytic reaction varying the color of incident light. This strategy may be implemented by using a sensitizer capable to activate a specific reaction pathway depending on the excitation light. Herein, we use potassium poly(heptazine imide) (K-PHI), a type of carbon nitride, to generate selectively three different products from S-arylthioacetates simply varying the excitation light and otherwise identical conditions. Namely, arylchlorides are produced under UV/purple, sulfonyl chlorides with blue/white, and diaryldisulfides at green to red light. A combination of the negatively charged polyanion, highly positive potential of the valence band, presence of intraband states, ability to sensitize singlet oxygen, and multi-electron transfer is shown to enable this chromoselective conversion of thioacetates.
- Antonietti, Markus,Guldi, Dirk M.,Markushyna, Yevheniia,Savateev, Aleksandr,Schü?lbauer, Christoph M.,Ullrich, Tobias
-
supporting information
p. 20543 - 20550
(2021/08/12)
-
- Design, synthesis and biological evaluation of novel N-sulfonylamidine-based derivatives as c-Met inhibitors via Cu-catalyzed three-component reaction
-
In our continuing efforts to develop novel c-Met inhibitors as potential anticancer candidates, a series of new N-sulfonylamidine derivatives were designed, synthesized via Cu-catalyzed multicomponent reaction (MCR) as the key step, and evaluated for their in vitro biological activities against c-Met kinase and four cancer cell lines (A549, HT-29, MKN-45 and MDA-MB-231). Most of the target compounds showed moderate to significant potency at both the enzyme-based and cell-based assay and possessed selectivity for A549 and HT-29 cancer cell lines. The preliminary SAR studies demonstrated that compound 26af (c-Met IC50 = 2.89 nM) was the most promising compound compared with the positive foretinib, which exhibited the remarkable antiproliferative activities, with IC50 values ranging from 0.28 to 0.72 μM. Mechanistic studies of 26af showed the anticancer activity was closely related to the blocking phosphorylation of c-Met, leading to cell cycle arresting at G2/M phase and apoptosis of A549 cells by a concentration-dependent manner. The promising compound 26af was further identified as a relatively selective inhibitor of c-Met kinase, which also possessed an acceptable safety profile and favorable pharmacokinetic properties in BALB/c mouse. The favorable drug-likeness of 26af suggested that N-sulfonylamidines may be used as a promising scaffold for antitumor drug development. Additionally, the docking study and molecular dynamics simulations of 26af revealed a common mode of interaction with the binding site of c-Met. These positive results indicated that compound 26af is a potential anti-cancer candidate for clinical trials, and deserves further development as a selective c-Met inhibitor.
- Fang, Sen-Biao,Li, Hui-Jing,Nan, Xiang,Wu, Rui,Wu, Yan-Chao,Zhang, Jing,Zhang, Zhi-Zhou
-
-
- Novel and highly efficient synthesis of 3-(alkyl/benzylthio)-9b-hydroxy-1H-imidazo[5,1-a]isoindole-1,5(9bH)-dione derivatives
-
The oxidation of 3a,8a-dihydroxy-2-(alkyl/benzylthio)indeno[1,2-d]imidazol-8(3H)-ones to give the corresponding 3-(alkyl/benzylthio)-9b-hydroxy-1H-imidazo[5,1-a]isoindole-1,5(9bH)-dione derivatives in good to excellent yields at room temperature using two oxidants, periodic acid in aqueous ethanol and lead(IV) acetate in acetic acid, has been reported.
- Jamaleddini, Azar,Mohammadizadeh, Mohammad Reza
-
supporting information
p. 78 - 81
(2016/12/23)
-
- New organic single crystal of (benzylthio)acetic acid: Synthesis, crystal structure, spectroscopic (ATR-FTIR, 1H and 13C NMR) and thermal characterization
-
(Benzylthio)acetic acid (Hbta) was synthesized with 78% yield from benzyl chloride and thiourea as substrates. Well-shaped crystals of Hbta were grown by slow solvent evaporation technique from pure methanol. The compound was investigated by single-crystal X-ray and powder diffraction techniques and was also characterized by other analytical methods, like ATR-FTIR, 1H and 13C NMR and TG/DSC. The acid molecule adopts bent conformation in the solid state. The crystal structure of Hbta is stabilized by numerous intermolecular interactions, including O-H···O, C-H···O, C-H···S and C-H···π contacts. Thermal decomposition of the obtained material takes place above 150 °C.
- Sienkiewicz-Gromiuk, Justyna,Tarasiuk, Bogdan,Mazur, Liliana
-
-
- Tert -Butyl Hypochlorite Mediated Oxidative Chlorination of S -Alkylisothiourea Salts: Synthesis of Sulfonyl Chlorides
-
Under neutral conditions, a variety of S-alkylisothiourea salts were smoothly converted into the corresponding sulfonyl chlorides through tert-butyl chlorite mediated oxidative chlorination in good to excellent yields after simple purification. In addition to the environmental and procedural advantages of this method, the neutral conditions potentially make it applicable to substrates that bear acid-sensitive functional groups. For example, the Cbz-protected 2-aminoethanesulfonyl chloride could be synthesized in moderate to good yields under the current neutral conditions, and the acid-sensitive Cbz-protecting group was not affected.
- Qiu, Kui,Wang, Rennan
-
p. 3186 - 3190
(2015/10/19)
-
- Clean and economic synthesis of alkanesulfonyl chlorides from S-alkyl isothiourea salts via bleach oxidative chlorosulfonation
-
A simple procedure for clean and economic synthesis of alkanesulfonyl chlorides via bleach-mediated oxidative chlorosulfonation of S-alkyl isothiourea salts is disclosed. This procedure is environment- and worker-friendly with the advantages of readily accessible materials and reagents, simple and safe operations, easy purification without chromatography, and affords high yields of up to 99%.
- Yang, Zhanhui,Zhou, Bingnan,Xu, Jiaxi
-
p. 225 - 229
(2014/03/21)
-
- A Pyrimidopyrimidine Janus-AT nucleoside with improved base-pairing properties to both A and T within a DNA duplex: The stabilizing effect of a second endocyclic ring nitrogen
-
Janus bases are heterocyclic nucleic acid base analogs that present two different faces able to simultaneously hydrogen bond to nucleosides that form Watson-Crick base pairs. The synthesis of a Janus-AT nucleotide analogue, NJAT, that has an additional endocyclic ring nitrogen and is thus more capable of efficiently discriminating T/A over G/C bases when base-pairing in a standard duplex-DNA context is described. Conversion to a phosphoramidite ultimately afforded incorporation into an oligonucleotide. In contrast to the first generation of carbocyclic Janus heterocycles, it remains in its unprotonated state at physiological pH and, therefore, forms very stable Watson-Crick base pairs with either A or T bases. Biophysical and computational methods indicate that NJAT is an improved candidate for sequence-specific genome targeting. N-Game for DNA recognition: The synthesis and oligonucleotide incorporation of an optimized, soluble Janus-AT base ( NJAT) that efficiently discriminates T/A over G/C bases, while retaining a nonprotonated state at physiological pH, is reported. NJAT was characterized in a duplex-DNA context with a set of biophysical and computational methods, all pointing out that this new base is a very good candidate for sequence-specific genome targeting (see figure). Copyright
- Largy, Eric,Liu, Wenbo,Hasan, Abid,Perrin, David M.
-
supporting information
p. 1495 - 1499
(2014/03/21)
-
- Degradation of MAC13243 and studies of the interaction of resulting thiourea compounds with the lipoprotein targeting chaperone LolA
-
The discovery of novel small molecules that function as antibacterial agents or cellular probes of biology is hindered by our limited understanding of bacterial physiology and our ability to assign mechanism of action. We previously employed a chemical genomic strategy to identify a novel small molecule, MAC13243, as a likely inhibitor of the bacterial lipoprotein targeting chaperone, LolA. Here, we report on the degradation of MAC13243 into the active species, S-(4-chlorobenzyl)isothiourea. Analogs of this compound (e.g., A22) have previously been characterized as inhibitors of the bacterial actin-like protein, MreB. Herein, we demonstrate that the antibacterial activity of MAC13243 and the thiourea compounds are similar; these activities are suppressed or sensitized in response to increases or decreases of LolA copy number, respectively. We provide STD NMR data which confirms a physical interaction between LolA and the thiourea degradation product of MAC13243, with a K d of ～150 μM. Taken together, we conclude that the thiourea series of compounds share a similar cellular mechanism that includes interaction with LolA in addition to the well-characterized target MreB.
- Barker, Courtney A.,Allison, Sarah E.,Zlitni, Soumaya,Nguyen, Nick Duc,Das, Rahul,Melacini, Giuseppe,Capretta, Alfredo A.,Brown, Eric D.
-
supporting information
p. 2426 - 2431
(2013/05/21)
-
- Convenient and environment-friendly synthesis of sulfonyl chlorides from S -alkylisothiourea salts via N-chlorosuccinimide chlorosulfonation
-
A convenient, practical, and environmentally friendly method for the synthesis of sulfonyl chlorides has been developed. Structurally diverse sulfonyl chlorides were synthesized in moderate to excellent yields from S-alkylisothiourea salts, which can be easily prepared from readily accessible alkyl halides or mesylates and inexpensive thiourea, via N-chlorosuccinimide chlorosulfonation. In large-scale syntheses, the byproduct succinimide from 'waste water' can be conveniently converted into the starting reagent N-chlorosuccinimide with sodium hypochlorite (bleach) to make the method sustainable. Georg Thieme Verlag Stuttgart, New York.
- Yang, Zhanhui,Xu, Jiaxi
-
p. 1675 - 1682
(2013/07/27)
-
- Simple synthesis of sulfonyl chlorides from thiol precursors and derivatives by NaClO2-mediated oxidative chlorosulfonation
-
A simple method to synthesize diverse sulfonyl chlorides through NaClO 2-mediated oxidative chlorosulfonation of S-alkyl isothiourea salts is presented. The approach features safe operation, environmental friendliness, convenient purification procedures, and delivers high yields of up to 96%. The procedure is also applicable to substrates such as thiols, disulfides, thioacetates, and xanthates. It is a versatile and convenient method for the synthesis of various sulfonyl chlorides from different thiol precursors and derivatives. Georg Thieme Verlag Stuttgart, New York.
- Yang, Zhanhui,Zheng, Yongpeng,Xu, Jiaxi
-
supporting information
p. 2165 - 2169
(2013/10/22)
-
- INHIBITION OF CELL PROLIFERATION
-
The disclosed modulators of Rb:Raf-1 interactions are potent, selective disruptors of Rb:Raf-1 binding, with IC50 values ranging from 80 nM to 500 nM. Further, these compounds are surprisingly effective in inhibiting a wide variety of cancer cells, including osteosarcoma, epithelial lung carcinoma, non small cell lung carcinoma, three different pancreatic cancer cell lines, two different glioblastoma cell lines, metastatic breast cancer, melanoma, and prostate cancer. Moreover, the disclosed compounds effectively disrupt angiogenesis and significantly inhibited tumors in nude mice derived from human epithelial lung carcinoma tumors. Accordingly, the disclosed compounds, pharmaceutical compositions comprising the compounds, methods of inhibiting cell proliferation, methods of treating subjects with cancer, and methods of preparing the disclosed compounds are provided.
- -
-
Page/Page column 47; 49; 54; 70
(2008/06/13)
-
- Synthesis of sulfides by reactions of 1,1-dichloro-2-chloro- methylcyclopropane with S-nucleophiles
-
1,1-Dichloro-2-chloromethylcyclopropane reacts with thiolates to give 2,2-dichlorocyclopropylmethyl sulfides via replacement of the side-chain chlorine atom. The resulting sulfides are readily oxidized to the corresponding sulfones.
- Mikhed'kina,Nedel'ko,Prezhdo
-
p. 370 - 375
(2007/10/03)
-
- A method for the introduction of reporter groups into moenomycin A, based on thiouronium salt chemistry
-
p-Alkoxy-substituted cinnamylthiouronium salts 7, 13, 21a, and 21b reacted selectively with the 2-acylamino-1,3-cyclopentanedione unit A of moenomycin A (1) to give the corresponding 2-alkylated products 14a, 14b, 22a, and 22b. These products, depending on the pH of the solution, were either stable under the reaction conditions or they underwent retro-Claisen-type reactions. The method can be used for the attachment of reporter groups to moenomycin A for the synthesis of, for example, 25. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002).
- Buchynskyy, Andrij,Stembera, Katherina,Hennig, Lothar,Findeisen, Matthias,Giesa, Sabine,Welzel, Peter
-
p. 1163 - 1174
(2007/10/03)
-
- Conformationally restricted 1,5-diarylpyrazoles are selective COX-2 inhibitors
-
Benzothiopyranopyrazoles and benzopyranopyrazoles containing either a sulfone or sulfonamide moiety were synthesized and tested for COX-1 and COX-2 inhibition. This new class of COX-2 selective inhibitors possess antiinflammatory activity in vivo.
- Bertenshaw, Stephen R.,Talley, John J.,Rogier,Graneto, Matthew J.,Koboldt, Carol M.,Zhang, Yan
-
p. 2827 - 2830
(2007/10/03)
-
- Organic-Soluble Lanthanide Nuclear Magnetic Resonance Shift Reagents for Sulfonium and Isothiuronium Salts
-
Lanthanide complexes of the formula 4>- (fod, 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione) are effective organic-soluble nuclear magnetic resonance shift reagents for sulfonium and isothiuronium salts.The shift reagent is formed in solution from Ln(fod)3 and Ag(fod) or K(fod).The selection of Ag(fod) or K(fod) in forming the shift reagent is dependent on the anion of the organic salt.Ag(fod) is more effective with halide salts, whereas K(fod) is preferred with tetrafluoroborate salts.Resolution of diastereotopic hydrogen atoms was observed in the shifted spectra of certain substrates.Enantiomeric resolution was obtained in the spectrum of sec-butylisothiuronium chloride with a chiral shift reagent.The reagents can be employed in solvents such as chloroform and benzene.
- Wenzel, Thomas J.,Zaia, Joseph
-
p. 562 - 567
(2007/10/02)
-
- Nucleophilic Substitution Factors. 1. Coplanar vs. Orthogonal Bimolecular Substitution at a Benzylic Carbon. X-ray Structure of 2-Isobutyl-1,3-dihydrobenzothiophenium Perchlorate
-
A stereoelectronic effect in bimolecular nucleophilic substitution at a benzylic center has been observed in the rates of reaction of thiourea in dimethyl-d6 sulfoxide with a series of sulfonium perchlorates with differing degrees of constraint in the orientation of the reacting C-S+ bond with respect to the plane of the aromatic ring.The substrates and their relative rates (at 37 deg C, unless otherwise noted) are as follows: (a, highly constrained) 2-ethyl-1,3-dihydrobenzothiophenium perchlorate (4b), 1,00, and 2-isobutyl-1,3-dihydrobenzothiophenium perchlorate (4c), 2.8; (b, partly constrained) 2-ethyl-3,4-dihydro-1H-2-benzothiopyranium perchlorate (7), 45 (at 82 deg C); (c, unconstrained) S,S-dibenzyl-S-ethylsulfonium perchlorate (5b), 8.1*103.An (8*103-fold rate difference was also observed between S,S-dibenzyl-S-ethylsulfonium terafluoroborate (5a) and 2-ethyl-1,3-dihydrobenzothiophenium tetrafluoroborate (4a) with potassium thiocyanate-18-crown-6 in acetonitrile-d3.Analysis of these rate differences, taken with inspection of molecular models which show that the observed rate differences are not adequately accounted for by simple nonbonding or angle strain effects, clearly indicates a dihedral angle dependent factor consistent with ?-overlap between p-orbitals on the aromatic ring and the carbon atom undergoing substitution.The "orbital-overlap factor" is estimated to increase the reactivity of the benzylic center in 5b (4*103-fold relative to that of the corresponding ethyl group (in 21).A single-crystal X-ray analysis on 4c showed the salt crystallizes in space group P21/n, unit cell dimensions a = 17.382 (1) Angstroem, b = 9.1731(6) Angstroem, c = 8.7828 (3) Angstroem, and β = 91.7 (2) deg, with Z = 4.On the basis of 2054 unique data with F2 > 2?, full matrix refinement converged at R = 0.044 for 232 variables.There is a dihedral angle of 3.8 deg between the C2,S,C9 plane and the plane of the aromatic ring consistent with the observed low reactivity of the benzylic center and the present analysis.The entropies of activation for benzylic substitution of the cyclic and acyclic substrates (4b, 4c, and 5b) with thiourea in Me2SO-d6 are very similar (-12 +/- 1 cal mol-1 K-1), in contrast to the great ΔS(excit.) difference reported for an analogous α-carbonyl system by Bartlett and Trachtenberg; the origin of this difference is discussed.
- King, J. F.,Tsang, T. Y.,Abdel-Malik, M. M.,Payne, N. C.
-
p. 3224 - 3232
(2007/10/02)
-
- Structure-activity studies on antihyperlipidemic N-benzoylsulfamates, N-benzylsulfamates, and benzylsulfonamides
-
A series of aryl substituted N-benzoyl- and N-benzylsulfamic acid sodium salts and benzylsulfonamide sodium salts have been prepared and examined for antihyperlipidemic activity in male CF1 mice at a dose level of 20 mg/kg/d ip for 16 d. These substances were also subjected to toxicological evaluation and chemical stability studies. In general, both series of sulfamates and sulfonamides significantly lowered serum cholesterol and triglyceride levels in mice. The compounds were nonmutagenic, showed no acute toxicity or impaired liver or kidney function in male mice, and were chemically stable both as the monohydrates and in aqueous solution over a pH range of 3.5-7.4. While both series of sulfamates and sulfonamides lowered serum cholesterol and triglyceride levels, the sulfamates were relatively more potent with regard to decreasing cholesterol levels, while the sulfonamides were more effective in lowering serum triglyceride levels in mice.
- Wyrick,Hall,Dubey
-
p. 374 - 377
(2007/10/02)
-
- REACTION OF ORGANIC SULFUR COMPOUNDS WITH SUPEROXIDE ANION-III. OXIDATION OF ORGANIC SULFUR COMPOUNDS TO SULFINIC AND SULFONIC ACIDS
-
Organic sulfur compounds such as disulfide, thiolsulfinate, thiolsulfonate, thiol, sodium thiolate, and sodium sulfinate were readily oxidized to both sulfinic and sulfonic acids with superoxide anion generated from potassium superoxide and 18-crown-6-ether under mild conditions.However, both sulfide and sulfoxide did not react with superoxide anion, O2.Although thiol was easily oxidized to disulfide with O2 at room temperature, it was oxidized further with O2 at 60 deg C to the corresponding sulfinic and sulfonic acids.Symmetrical disulfide was obtained in the reaction of unsymmetrical thiolsulfinate or thiolsulfonate along with both sulfinic and sulfonic acids.Most reactive was thiolsulfinate which reacted at lower temperature ranging between -40 and 0 deg C to afford the products within 30 min.Relative reactivities fall in the following order: thiolsulfinate > thiolsulfonate > disulfide sodium thiolate sodium sulfinate.Polar solvents such as pyridine and acetonitrile were more effective than such a less polar solvent as benzene in the oxidation of the substrate, and increased amount of the crown ether shortened the reaction time.Nucleophilic attack of O2 and electron transfer processes are believed to be involved in these oxidations.
- Oae, Shigeru,Takata, Toshikazu,Kim, Yong Hae
-
-
