- Geometrically unprecedented 3-, 5- and 7-membered Hg(II)-Cu(I) and Hg(II)-Ag(I) thiolate clusters: Precursors to intermetallics
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The syntheses of three polynuclear heterobimetallic complexes through the use of a homoleptic mercuric thiolate anion as a template for the assembly of coinage metal are presented. The complexes, [(PPh3)3Ag3(μ-SPh)7/
- Gupta, Geetika,Chaturvedi, Jyotsna,Bhattacharya, Subrato
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Read Online
- The influence of thiolate ligands on the luminescence properties of cycloplatinated(II) complexes
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Complexes [Pt(C^N)(PPh3)Cl] (C^N = bzq (7,8-benzoquinolinyl, A) and ppy (2-phenylpyridinyl, B)) were reacted with various thiolate ligands to afford complexes [Pt(C^N)(PPh3)(κ1-S-SR)], Csu
- Jamshidi, Mahboubeh,Babaghasabha, Mojgan,Shahsavari, Hamid R.,Nabavizadeh, S. Masoud
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Read Online
- A single, low, oral dose of a 5-carbon-linked trioxane dimer orthoester plus mefloquine cures malaria-infected mice
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Four 5-carbon-linked trioxane dimer orthoesters (6a-6d) have been prepared in 4 or 5 chemical steps from the natural trioxane artemisinin (1). When administered orally to malaria-infected mice using a single dose of only 6 mg/kg body weight along with 18
- Moon, Deuk Kyu,Tripathi, Abhai,Sullivan, David,Siegler, Maxime A.,Parkin, Sean,Posner, Gary H.
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Read Online
- Electrochemistry of transition metal hydride diphosphine complexes trans-MH(X)(PP)2 and trans-[MH(L)(PP)2]+, M = Fe, Ru, Os; PP = chelating phosphine ligand
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A series of over 30 iron, ruthenium, and osmium hydride phosphine complexes are reported, along with their MIII/II redox potentials. The complexes are of the type MH(PP)n(X) or [MH(PP)n(L)]+, where PP is one of
- Cappellani, E. Paul,Drouin, Samantha D.,Golombek, Adina,Maltby, Patricia A.,Morris, Robert H.,Rennie, Benjamin E.,Schweitzer, Caroline T.
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- Structurally homologous sialidases exhibit a commonality in reactivity: Glycoside hydrolase-catalyzed hydrolysis of Kdn-thioglycosides
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Aspergillus fumigatus is one of the main causative agents of invasive aspergillosis, an often-lethal fungal disease that affects immunocompromised individuals. A. fumigatus produces a sialidase that cleaves the nine-carbon carbohydrate Kdn from glycoconju
- Nejatie, Ali,Akintola, Oluwafemi,Steves, Elizabeth,Shamsi Kazem Abadi, Saeideh,Moore, Margo M.,Bennet, Andrew J.
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- Nucleophilic Reactivities of Thiophenolates
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The nucleophilic reactivities of substituted thiophenolates were determined by following the kinetics of their reactions with a series of quinone methides (reference electrophiles) in DMSO at 20 °C. The experimentally determined second-order rate constants were analyzed according to the Mayr-Patz equation log k = sN(N + E) to derive the nucleophile-specific reactivity parameters N and sN for ten thiophenolate ions.
- Jüstel, Patrick M.,Pignot, Cedric D.,Ofial, Armin R.
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supporting information
p. 5965 - 5972
(2021/05/04)
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- Inherent Reactivity of Spiro-Activated Electrophilic Cyclopropanes
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The kinetics of the ring-opening reactions of thiophenolates with geminal bis(acceptor)-substituted cyclopropanes in DMSO at 20 °C was monitored by photometric methods. The determined second-order rate constants of the SN2 reactions followed linear relationships with Mayr nucleophilicity parameters (N/sN) and Br?nsted basicities (pKaH) of the thiophenolates as well as with Hammett substituent parameters (σ) for groups attached to the thiophenolates. Phenyl-substituted cyclopropanes reacted by up to a factor of 15 faster than their unsubstituted analogues, in accord with the known activating effect of adjacent π-systems in SN2 reactions. Variation of the electronic properties of substituents at the phenyl groups of the cyclopropanes gave rise to parabolic Hammett relationships. Thus, the inherent SN2 reactivity of electrophilic cyclopropanes is activated by electron-rich π-systems because of the more advanced C1?C2 bond polarization in the transition state. On the other hand, electron-poor π-systems also lower the energetic barriers for the attack of anionic nucleophiles owing to attractive electrostatic interactions.
- Jüstel, Patrick M.,Ofial, Armin R.,Pignot, Cedric D.,Stan, Alexandra
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supporting information
p. 15928 - 15935
(2021/10/25)
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- (η6-Benzene)Ru(II) half-sandwich complexes of pyrazolated chalcogenoethers for catalytic activation of aldehydes to amides transformation
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The reaction of [(η6-C6H6)RuCl(μ-Cl)]2 with chalcogenoether substituted 1H-pyrazole ligands (L1-L3) in methanol have yielded three novel Ru(II) half-sandwich complexes [(η6-C6H6)RuCl(L)]PF6 (1–3) in high yield under the ambient reaction conditions. The NMR, MS and FT-IR analytical techniques were used to identify their structures. The molecular structures of the complexes 2 and 3 were established with X-ray crystallographic analysis and revealed a pseudo-octahedral half sandwich piano-stool geometry around ruthenium in each complex. Complexes 1–3 are thermally robust and were found to be insensitive towards the air and moisture. All the complexes were found to be catalytically active and produced the excellent yields of amides (up to 95%) from corresponding aldehydes. In contrast to the previous reported catalytic systems for aldehyde to amide transformation, the present complexes 1–3 are very efficient and have several advantages in terms of low catalyst loading, reaction time, temperature and wide applicability for various substituted aldehydes. Owing to the stronger σ-donor coordination properties of selenium containing ligands, the complex 2 was found to be more efficient as compare to the sulphur and tellurium analogues.
- Sharma, Kamal Nayan,Ali, Munsaf,Srivastava, Avinash Kumar,Joshi, Raj Kumar
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- Facile synthesis of mixed O, S or Se bearing hexasubstituted benzenes and their potential as Cu(ii) ion probe
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The present study offers a facile route for the synthesis of unsymmetrical hexasubstituted benzenes bearing alternate heteroatoms (O, S and Se) with the formula [1,3,5-(RSeCH2)3-2,4,6-(R′ECH2)3C6] (E
- Kumar, Abhishek,Yadav, Mantesh K.,Singh, Jagriti,Singh, Jai Deo,Butcher, Ray J.
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p. 5627 - 5636
(2019/05/10)
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- Controlling O2 Reactivity in Synthetic Analogues of [NiFeS]- And [NiFeSe]-Hydrogenase Active Sites
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Strategies for limiting, or reversing, the degradation of air-sensitive, base metal catalysts for the hydrogen evolution/oxidation reaction on contact with adventitious O2 are guided by nature′s design of hydrogenase active sites. The affinity
- Yang, Xuemei,Elrod, Lindy C.,Le, Trung,Vega, Valeria S.,Naumann, Haley,Rezenom, Yohannes,Reibenspies, Joseph H.,Hall, Michael B.,Darensbourg, Marcetta Y.
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supporting information
p. 15338 - 15347
(2019/11/02)
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- Synthesis, characterization and biological evaluation of new manganese metal carbonyl compounds that contain sulfur and selenium ligands as a promising new class of CORMs
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Three new manganese carbonyl compounds with heavy atom donors were synthesized and their potential use as photoCORMS was evaluated. Interestingly, all compounds had an elusive binding mode, in which the ligands adopted a κ2-X coordination (wher
- Amorim, André L.,Peterle, Marcos M.,Guerreiro, Ana,Coimbra, Daniel F.,Heying, Renata S.,Caramori, Giovani F.,Braga, Antonio L.,Bortoluzzi, Adailton J.,Neves, Ademir,Bernardes, Gon?alo J. L.,Peralta, Rosely A.
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p. 5574 - 5584
(2019/05/10)
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- Amine Induced Retardation of the Radical-Mediated Thiol-Ene Reaction via the Formation of Metastable Disulfide Radical Anions
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The effect of amines on the kinetics and efficacy of radical-mediated thiol-ene coupling (TEC) reactions was investigated. By varying the thiol reactant and amine additive, it was shown that amines retard thiyl radical-mediated reactions when the amine is
- Love, Dillon M.,Kim, Kangmin,Goodrich, John T.,Fairbanks, Benjamin D.,Worrell, Brady T.,Stoykovich, Mark P.,Musgrave, Charles B.,Bowman, Christopher N.
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p. 2912 - 2919
(2018/03/09)
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- Base Catalysis Enables Access to α,α-Difluoroalkylthioethers
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A nucleophilic addition reaction of aryl thiols to readily available β,β-difluorostyrenes provides α,α-difluoroalkylthioethers. The reaction proceeds through an unstable anionic intermediate, prone to eliminate fluoride and generate α-fluorovinylthioethers. However, the use of base catalysis overcomes the facile β-fluoride elimination, generating α,α-difluoroalkylthioethers in excellent yields and selectivities.
- Orsi, Douglas L.,Easley, Brandon J.,Lick, Ashley M.,Altman, Ryan A.
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supporting information
p. 1570 - 1573
(2017/04/13)
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- Trinuclear complexes of palladium(II) with chalcogenated N-heterocyclic carbenes: Catalysis of selective nitrile-primary amide interconversion and Sonogashira coupling
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3-Methyl-1-(2-(phenylthio/seleno)ethyl)-1H-benzo[d]imidazol-3-ium iodide (L1/L2), a precursor of sulfated/selenated N-heterocyclic carbene, was synthesized by the reaction of benzimidazole with 1,2-dichloroethane followed by treatment with PhS/SeNa and MeI. The reaction of L1/L2 with Ag2O followed by treatment with [Pd(CH3CN)2Cl2] (metal to ligand ratio 3:2), i.e. transmetallation, resulted in trinuclear palladium(ii) complexes [Pd3(L1/L2-HI)2(CH3CN)Cl6] (1-2). The complexes were characterized with 1H, 13C{1H} and 77Se{1H} NMR (2 only), elemental analyses, HR-MS and single-crystal X-ray diffraction. The geometry of three Pd atoms in each complex is nearly square planar. The Pd-S/Se, Pd-C, Pd-N and Pd-Cl bond distances (?) in 1/2 are 2.3179(19)/2.4312(10), 1.968(7)/1.952(4), 2.073(8)/2.079(4) and 2.2784(19)-2.298(2)/2.292(2)-2.3003(15), respectively. In both the complexes, all Cl are trans to each other. For the central Pd atom, two benzimidazole rings are also trans to each other. The C-H?Cl non-covalent interactions result in a three-dimensional network. The moisture and air insensitive trinuclear Pd(ii) complexes 1 and 2 are thermally stable and efficient as a catalyst for nitrile-amide interconversion and amine-free Sonogashira C-C coupling (in the presence of CuI). The optimum temperature is 80 °C for the interconversion and 110 °C for the coupling. The catalytic protocols are applicable to both aliphatic and aromatic amides/nitriles. The optimum catalyst loading is 1 mol% for the C-C coupling and 0.5 to 1 mol% for the interconversion. K2CO3 as a base gives the best result for Sonogashira C-C coupling. In the conversion of nitriles to amides, the formation of an acid was not detected. After using once, 1/2 can carry out the conversion of ten fresh lots of nitriles to amides with almost the same efficiency. The real catalytic species for the interconversion and coupling appear to be based on Pd(ii) and Pd(0), respectively.
- Dubey, Pooja,Gupta, Sonu,Singh, Ajai K.
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p. 13065 - 13076
(2017/10/13)
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- Feasible Approach to Tricyclic and Tetracyclic cyclododecanone
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2-Bromocyclododecanone was utilized as precursor to synthesize polyfused heterocyclic cyclododecane ring systems. Transformation of 2-bromocyclododecanone (5) with 1H-benzimidazole-2-thiole (6), benzo[d]thiazole-2-thiol (9), 2-naphthol (12), and thiophenol (15) afforded thiazolo[2,3-b]benzimidazole (8), thiazolo[2,3-b]benzothaizole derivative (11) naphtho[1,2-d]furan derivative (14) and 2-(phenylthio)cyclododecanone (16), respectively.
- Zoorob, Hanafi H.,Elsherbini, Mohamed S.,Hamama, Wafaa S.
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p. 941 - 944
(2016/05/19)
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- Chemoselective Reduction of Trichloromethyl Compounds to gem-Dichloromethyl Groups Following Appel's Reaction Protocol
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A simple and easy reduction of trichloroacetyl compounds following the modification of Appel's reaction protocol, using triphenylphosphine and methanol, afforded the corresponding dichloroacetyl compounds, with the exception of trichloroacetylmorpholine,
- Romero-Reyes, Moises A.,Zaragoza-Galicia, Ivann,Olivo, Horacio F.,Romero-Ortega, Moises
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p. 9515 - 9519
(2016/10/14)
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- The Electrophilic Character of Bunsen's Cacodyl Disulfide, Me2As(S)-S-AsMe2, Towards Some Nucleophiles of Groups 15 and 16
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The reactivity of Bunsen's cacodyl disulfide, Me2As(S)-S-AsMe2, towards nitrogen, phosphorus(III), oxygen and sulfur(II) nucleophiles was evaluated with the aim at identifying its electrophilic atom. The nitrogen nucleophiles either
- Ioannou, Panayiotis V.,Vachliotis, Dimitris G.
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p. 710 - 714
(2015/03/30)
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- Acridine based (S,N,S) pincer ligand: Designing silver(i) complexes for the efficient activation of A3 (aldehyde, alkyne and amine) coupling
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Complexes [AgL(NO3)CH3CN](1) and [AgLNO3] (2) were formed on reacting AgNO3 with L in acetonitrile for 12 h (at room temperature) and 24 h (at 90 °C), respectively, where L is a (S,N,S) pincer ligand, 4,5-bis(ph
- Prakash, Om,Joshi, Hemant,Kumar, Umesh,Sharma, Alpesh K.,Singh, Ajai K.
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p. 1962 - 1968
(2015/02/19)
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- Palladium(ii)-1-phenylthio-2-arylchalcogenoethane complexes: Palladium phosphide nano-peanut and ribbon formation controlled by chalcogen and Suzuki coupling activation
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The ligands PhSCH2CH2EAr (L1-L3; E = S, Se or Te) and their Pd-complexes [PdLCl2] (1-3) have been synthesized and authenticated with their 1H, 13C{1H}, 77Se{1H} and 125Te{1H} NMR spectra. Single crystal structures of 1 and 3 reveal the geometry of donor atoms around palladium as nearly square planar. Thermolysis of all three complexes in trioctylphosphine (TOP) at 350, 320 and 280 °C, respectively, results in a single phase of crystalline PdP2. The morphology of the phase varies with 'E' to some extent. The nanopeanuts (size ~30 and ~35 nm) were formed with 1 and 2 as precursor complexes. On using complex 3 as a precursor nanoribbons are formed. The preferential growth in the (202) plane in the case of all the three precursor complexes has been rationalized in terms of texture coefficient and average crystallite size. All three complexes and PdP2 NPs have been explored for Suzuki-Miyaura coupling of several aryl halides. Complexes 1 and 2 show good catalytic activity but complex 3 does not. The activity appears to result due to in situ generated palladium containing nanoparticles (NPs) in the case of 1 and 2. The formation of inactive large Pd aggregates in the case of 3 appears to be responsible for the difference. The PdP2 NPs have been found to show good catalytic activity and recyclability up to six reaction cycles. The results of the three phase test suggest the involvement of both homogeneous and heterogeneous pathways in the activation of Suzuki coupling. DFT based free energy calculations are consistent with the results of catalysis via Pd(0) protected with the ligand. This palladium may also be released from in situ generated NPs. In the case of 3, negligible reactivity may be due to non-release of Pd. This journal is
- Kumar Rao, Gyandshwar,Kumar, Arun,Saleem, Fariha,Singh, Mahabir P.,Kumar, Satyendra,Kumar, Bharat,Mukherjee, Goutam,Singh, Ajai K.
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p. 6600 - 6612
(2015/04/14)
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- SINGLET OXYGEN-LABILE LINKERS AND METHODS OF PRODUCTION AND USE THEREOF
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Activatable compositions that include at least one functional moiety and at least one cleavable linker directly or indirectly linked to the at least one functional moiety are disclosed. The at least one functional moiety is inactive when linked to the linker and activated upon cleavage of the linker. Methods of production and use of the activatable composition are also disclosed.
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Paragraph 000155
(2013/11/18)
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- Palladium(ii) complexes of pyrazolated thio/selenoethers: Syntheses, structures, single source precursors of Pd4Se and PdSe nano-particles and potential for catalyzing Suzuki-Miyaura coupling
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The reactions of 4-bromo-1-(2-chloroethyl)-1H-pyrazole prepared from 4-bromopyrazole with the in situ generated PhSNa, PhSeNa, Na2S and Na2Se have resulted in thio/selenoether ligands L1-L4 respectively. The complexes [PdL1/L2Cl
- Sharma, Kamal Nayan,Joshi, Hemant,Singh, Ved Vati,Singh, Pradhumn,Singh, Ajai Kumar
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p. 3908 - 3918
(2013/03/28)
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- Half sandwich complexes of chalcogenated pyridine based bi-(N, S/Se) and terdentate (N, S/Se, N) ligands with (η6-benzene)ruthenium(ii): Synthesis, structure and catalysis of transfer hydrogenation of ketones and oxidation of alcohols
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The half sandwich complexes [(η6-C6H 6)Ru(L)Cl][PF6] (1-5) have been synthesized by the reactions of (2-arylchalcogenomethyl)pyridine [L = L1-L3] and bis(2-pyridylmethyl)chalcogenide [L = L4-L5] (chalcogen = S, Se; Ar = Ph/2-pyridyl for S, Ph for Se) with [(η6-C6H 6)RuCl2]2, at room temperature followed by treatment with NH4PF6. Their HR-MS, 1H, 13C{1H} and 77Se{1H} NMR spectra have been found characteristic. The single crystal structures of 1-5 have been established by X-ray crystallography. The Ru has pseudo-octahedral half sandwich "piano-stool" geometry. The complexes 1-5 have been found efficient for catalytic oxidation of alcohols with N-methylmorpholine-N-oxide (NMO) and transfer hydrogenation of ketones with 2-propanol (at moderate temperature 80 °C) as TON values are up to 9.9 × 103 and 9.8 × 103 respectively for the two catalytic reactions. On comparing the required catalyst loading for good conversions and reaction time for the present complexes with those reported in literature for other transfer hydrogenation/oxidation catalysts, it becomes apparent that 1-5 have good promise. The complexes of Se ligands have been found more efficient than their sulphur analogues. The complexes of bidentate ligands are more efficient than those of terdentate, due to difficult bond cleavage in the case of latter. These orders of efficiency are supported by DFT calculations. The calculated bond lengths/angles by DFT are generally consistent with the experimental ones.
- Prakash, Om,Sharma, Kamal Nayan,Joshi, Hemant,Gupta, Pancham Lal,Singh, Ajai K.
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p. 8736 - 8747
(2013/07/27)
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- Poly(vinyl chloride) reactions with sodium and potassium derivatives of heteroaromatic and aromatic NH- and SH-acids in aprotic solvents
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The observed featured and regularities of nucleophilic substitution of chlorine in poly(vinyl chloride) upon its reaction with sodium and potassium derivatives of pyrazole, 3,5-dimethylpyrazole, and 2-thiobenzimidazole, and with sodium thiophenolate have been understood in the frame of hard and soft acids and bases theory.
- Shaglaeva,Voronkov,Bayandin,Sultangareev,Prozorova,Abzaeva,Orkhokova
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p. 1519 - 1525
(2013/10/22)
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- Palladium(ii)-(E,N,E) pincer ligand (E = S/Se/Te) complex catalyzed Suzuki coupling reactions in water via in situ generated palladium quantum dots
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The (E,N,E) pincer ligands (ArECH2CH2)2NH (L1/L2: Ar = Ph, E = S/Se; L3: Ar = CH3O-p-C6H 4, E = Te) synthesized by reaction of PhS-/PhSe -/CH3O-p-C6/s
- Kumar, Satyendra,Rao, Gyandshwar K.,Kumar, Arun,Singh, Mahabir P.,Singh, Ajai Kumar
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p. 16939 - 16948
(2013/12/04)
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- Reactions of 17-chloro-16-formylandrosta-5,16-diene with thiohydrazides of oxamic acids
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Reactions of thiohydrazides of oxamic acids with 17-chloro-16- formylandrosta-5,16-diene give the corresponding thiohydrazones at the formyl group. Their subsequent reactions with alkali (het)arenethiolates yield 17-het(aryl)thio derivatives, being accomp
- Zavarzin,Antonov, Ya. S.,Chernoburova,Shchetinina,Kolotyrkina,Shashkov
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p. 2626 - 2627
(2014/08/18)
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- Radiation curable compositions
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A polymerizable Norrish Type II photoinitiator according to Formula (I): Radiation curable compositions and inkjet inks containing the polymerizable Norrish Type II photoinitiator of Formula (I) exhibit improved compatibility with and solubility in radiat
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Paragraph 0225
(2013/09/26)
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- Synthesis and structural chemistry of N-{2-(arylthio/seleno)ethyl} morpholine/piperidine-palladium(II) complexes as potent catalysts for the Heck reaction
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The reactions of in-situ generated PhS-, PyS- and PhSe- with 4-(2-chloroethyl)morpholine hydrochloride and 1-(2-chloroethyl)piperidine hydrochloride in N2 atmosphere have resulted in N-{2-(arylchalcogeno)ethyl}morpholine/piperidine ligands (L1-L6), which on reaction with Na2PdCl4 at room temperature result in complexes of composition [PdCl2(L)] (1-6; L = L1-L6). All the complexes except 2 have been characterized by X-ray crystallography. The geometry around Pd is nearly square planar in all the cases. The Pd-S and Pd-Se bond lengths are in the ranges 2.2598(10)-2.2795(14) and 2.3541(6)-2.3632(15) ?, respectively. In 77Se{1H} NMR spectra of Pd(II)-complexes with L5 and L6 (Se ligands), the signals appear at higher frequency (up to 187 ppm) with respect to those of corresponding free ligands. Pd(II)-complexes (2, 4 and 6) have been found promising for Heck reaction of aryl bromides with methyl acrylate. The TON values are up to 18 200 and TOF up to 758 h-1 (with complex 6 as catalyst). The Pd-complexes of piperidene derivatives show little higher catalytic efficiency than those of morpholine ones. The positive Hg-test has implied that nano-sized Pd(0) species probably catalyze Heck reactions.
- Singh, Pradhumn,Das, Dipanwita,Prakash, Om,Singh, Ajai K.
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- Click and photo-unclick chemistry of aminoacrylate for visible light-triggered drug release
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"Click and Photo-unclick Chemistry" of aminoacrylates is proposed for a new photo-labile linker. Adducts are built in 2 steps with good yields and cleaved rapidly by tissue penetrable visible light (690 nm) with a photosensitizer. Facile synthesis, release of mother drug, and stability and cleavage in medium are demonstrated.
- Bio, Moses,Nkepang, Gregory,You, Youngjae
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supporting information; experimental part
p. 6517 - 6519
(2012/07/28)
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- METHODS OF FORMING SINGLE SOURCE PRECURSORS, METHODS OF FORMING POLYMERIC SINGLE SOURCE PRECURSORS, AND SINGLE SOURCE PRECURSORS AND INTERMEDIATE PRODUCTS FORMED BY SUCH METHODS
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Methods of forming single source precursors (SSPs) include forming intermediate products having the empirical formula ?{L2N(μ-X)2M′X2}2, and reacting MER with the intermediate products to form SSPs of the formula L2N(μ-ER)2M′(ER)2, wherein L is a Lewis base, M is a Group IA atom, N is a Group IB atom, M′ is a Group IIIB atom, each E is a Group VIB atom, each X is a Group VIIA atom or a nitrate group, and each R group is an alkyl, aryl, vinyl, (per)fluoro alkyl, (per)fluoro aryl, silane, or carbamato group. Methods of forming polymeric or copolymeric SSPs include reacting at least one of HE1R1E1H and MER with one or more substances having the empirical formula L2N(μ-ER)2M′(ER)2 or L2N(μ-X)2M′(X)2 to form a polymeric or copolymeric SSP. New SSPs and intermediate products are formed by such methods.
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Page/Page column 11
(2011/07/06)
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- Synthesis of enantiopure substituted piperidines via an aziridinium ring expansion
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Herein we report a novel methodology for the asymmetric synthesis of 3-substituted piperidines from readily available chiral building blocks. This method, which features a novel irreversible dihydropyrole-tetrahydropyridine ring expansion, allows the intr
- Jarvis, Scott B. D.,Charette, Andre B.
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supporting information; experimental part
p. 3830 - 3833
(2011/09/16)
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- RADIATION CURABLE COMPOSITIONS
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A polymerizable Norrish Type II photoinitiator according to Formula (I): . Radiation curable compositions and inkjet inks containing the polymerizable Norrish Type II photoinitiator of Formula (I) exhibit improved compatibility with and solubility in radi
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- POLYMERIZABLE PHOTOINITIATORS AND RADIATION CURABLE COMPOSITIONS
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A new type of polymerizable Norrish Type II photoinitiators having an optionally substituted benzophenone group or an optionally substituted thioxanthone group is disclosed exhibiting improved compatibility with and solubility in radiation curable compositions. Radiation curable compositions and inkjet inks containing these polymerizable Norrish Type Il photoinitiators, exhibiting low extractable amounts of the photoinitiators and their residues after curing, are also disclosed.
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Page/Page column 36
(2010/04/06)
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- TRIOXANE MONOMERS AND DIMERS
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Monomeric and dimeric trioxane fluoroaryl amides, 5-carbon-linked, C-10 non-acetal trioxane dimer esters; trioxane silylamides; and trioxane dimer orthoesters and methods of their use for treating subjects infected with malaria or other parasitic infectio
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Page/Page column 69
(2010/12/18)
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- FUSED THIAZOLE DERIVATIVES AS KINASE INHIBITORS
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A series of 5,6-dihydro-l,3-benzothiazol-7(4H)-one derivatives, and analogues thereof, which are substituted in the 2-position by an optionally substituted morpholin-4-yl moiety, being selective inhibitors of PD kinase enzymes, are accordingly of b.enefit in medicine, for example in the treatment of inflammatory, autoimmune, cardiovascular, neurodegenerative, metabolic, oncological, nociceptive or ophthalmic conditions.
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Page/Page column 67
(2008/06/13)
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- Ether substituted imidazopyridines
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Imidazopyridine compounds that contain an ether or thioether functionality at the 1-position are useful as immune response modifiers. The compounds and compositions of the invention can induce the biosynthesis of various cytokines and are useful in the treatment of a variety of conditions including viral diseases and neoplastic diseases. Methods of preparing the compounds and intermediates useful in the preparation of the compounds are also disclosed.
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- Sulfur containing compounds
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This invention is directed to novel and known stufur containing compounds and pharmaceutically acceptable salts thereof that have utility as antifungals and as antiproliferative agents against mammalian cells, in particular cancer cells and most particularly leukemia-derived cells. The invention provides a method for synthesizing certain of the sulfur containing compounds that is more efficient than previously known methods.
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Page/Page column 25
(2010/11/30)
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- Mild, selective deprotection of thioacetates using sodium thiomethoxide
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A mild method for the deprotection of thioacetates is described. The reaction can be conveniently carried out at room temperature, and is compatible with a wide range of functionality. The procedure was shown to chemoselectively remove a thioacetate in the presence of an acetate.
- Wallace, Owen B.,Springer, Dane M.
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p. 2693 - 2694
(2007/10/03)
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- Solvent effects on reactions of hydroxide ion with phosphorus (V) esters. A quantitative treatment
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Second-order rate constants of reactions of HO- with phosphate, phosphinate and thiophosphinate esters, (PhO)2PO.OC6H4NO2-p, Ph2PO.OC6H4NO2-p, Ph2PO.SPh, Ph2PO.SC6H4NO2-p and Ph2PO.SEt, go through minima with decreasing water content of H2O-MeCN or H2O-t-BuOH. The rate decrease is due to stabilization of the non-ionic ester on addition of organic solvent to H2O. This inhibition is partially offset by stabilization of the anionic transition states and in the drier solvents partial desolvation of HO- increases rates.
- Bunton, Clifford A.,Gillitt, Nicholas D.,Kumar, Anurag
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p. 145 - 151
(2007/10/03)
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- METHYL TRANSFER FROM MeCo(III)Pc TO THIOPHENOXIDE
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Transfer of the cobalt-bound methyl in MeCo(III)Pc to thiophenoxide ion was studied (H2Pc is the planar macrocyclic phthalocyanine; the cobalt is held in the center in this plane).In dimethylacetamide solution, the reaction is rapid, requiring stopped flow for the kinetics, and yielding MeSPh and Co(I)Pc1- in good yield.The kinetics are not simple second order, but instead approach a constant rate at high ->, attributed to the reversible formation of an inert complex with PhS- occupying the vacant octahedral site in MeCo(III)Pc, on the other side of the phthalocyanine plane from the methyl group.The kinetics allow the estimation of the equilibrium constant, K, and the SN2 rate constant, k, which at 25 deg C have values of ca. 9.4 x 1E3 l mol-1 and 1.8 x 1E4 l mol-1, respectively.Although these values are rough, the ratio k/K is firm at 1.91 +/- 0.02 s-1; this is the limit of the rate at high ->.An alternative mechanism, which is entirely consistent with the kinetics, involves a rate-determining homolysis of the Co-S bond of the same complex.The mechanism is not favored because the product yields are high for a radical combination process and alternative chain processes are kinetically unacceptable.Further, the rate constant is about what would be expected from the reactivity of other nucleophiles in SN2 reactions.Further arguments in favor of the SN2 mechanism are presented.This transfer of the methyl group from Co to S is part of the possible analogy to the vitamin B12-promoted methionine synthesis in nature.The other step in the biological, enzymatic process is the transfer of methyl from the nitrogen of N-methyltetrahydrofolate to cobalt.An attempt to model this with the very reactive N-methyl-2,6-dichloropyridinium ion was unsuccessful; the reaction took an entirely different course, presumably initiated by electron transfer, but leading to substantial loss of Cl- from the pyridine.No more than 0.5percent methyl transfer took place.This system does mimic well the complete natural enzymatic process.
- Galezowski, Wlodzimierz,Lewis, Edward S.
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- Perfluoroalkyl-Chalcogenation of Alkynes
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Perfluoroalkyl-telluration of alkynes has been performed by a (PhTe)2-NaBH4-RfX system at a low temperature (-40, -80, or -100 deg C) to give 2-(perfluoroalkyl)vinyl tellurides.Meanwhile, perfluoroalkyl-sulfenylation and perfluoroalkyl-selenation were les
- Ueda, Yasufumi,Kanai, Masatomi,Uneyama, Kenji
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p. 2273 - 2277
(2007/10/02)
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- Azetidin-2-one derivatives as serine protease inhibitors
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The present invention relates to new 3-guanidinoalkyl-2-azetidinones of the formula STR1 wherein: U and W can be the same or different and are selected from the group consisting of hydrogen and an amino protecting group; n is 1 to 3; X is a member selecte
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- 3-diphenyl substituted octahydroindolizine analgesic compounds
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Octahydroindolizine compounds of formula (I): STR1 wherein Q is --NR--, --(CH2)z --, --CH=CH--, --C C--, --OCH2 --, --SCH2 --, --SO2 --, --SO--, --CO--, or an oxygen or a sulfur atom and where R, R1 and R2 are substituents such as alkyl and x, y and z are independently the integers 0-3. Also, pharmaceutical compositions containing (I), intermediates and methods for treating pain.
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- A NOVEL SYNTHESIS OF ALKYL VINYL KETONES AND DIVINYL KETONES FROM CARBONYL COMPOUNDS BY THREE-CARBON HOMOLOGATION
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Alkyl vinyl ketones and divinyl ketones are synthesized from carbonyl compounds and 1-chloro-3-phenylthiopropyl phenyl sulfoxide as a three-carbon homologating agent in good overall yileds.
- Satoh, Tsuyoshi,Kumagawa, Takumi,Yamakava, Koji
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p. 2471 - 2474
(2007/10/02)
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- Thioxanthonecarboxylic acid esters, thioesters and amides
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Thioxanthonecarboxylic acid esters, thioesters or amides of the formula I STR1 in which X and Z are hydrogen or one of the substituents defined in more detail in claim 1 and Y is --OR1, --SR1 or --N(R1)(R2), in
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- PHOTOSTIMULATED REACTIONS OF 1-IODOADAMANTANE AND IODOBENZENE WITH THIOLATE, SELENATE, AND TELLURATE IONS
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The photostimulated reaction of 1-iodoadamantane (1-IAd) with benzenethiolate ion gave the substitution product 1-adamantylphenylsulfide.With benzeneselenate ion (PhSe-) it gave three products: diphenylselenide, 1-adamantylphenylselenide and di(1-adamantyl) selenide.With benzenetellurate ions it gave the substitution product 1-adamantylphenyltelluride and diphenyltelluride, the latter is ascribed to the photodecomposition of the nucleophile.The photostimulated reaction of 1-IAd with 1-naphtaleneselenate ion only gave the substitution product without scrambling of products.The photostimulated reaction of PhI with 1-adamantaneselenate ion gave the same three products as the reaction of 1-IAd and PhSe- ion, but with different ratios of products.The reaction with 1-adamantanetellurate ion gave mainly diphenyltelluride, together with the substitution product 1-adamantylphenyltelluride.The relationship of the fragmentation rates of Ad-Z and Ph-Z bonds in radical anions of structure (1-AdZPh). were studied, and kfAdZ/kfPhZ, being Z=S is 3.7, Z=Se is 9.5 and Z=Te is 13.These results suggest that in the photostimulated reactions the products obtained depend on the energy levels of the antibonding ?* MO and the ?* MO of the C-Z(Z=S, Se and Te) bonds of the radical anion intermediate.The fragmentation rates of the radical anion intermediates depend on the energy levels of the MO'S involved.
- Palacios, Sara M.,Alonso, Ruben A.,Rossi, Roberto A.
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p. 4147 - 4156
(2007/10/02)
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- SYNTHESIS OF ARYL THIOCYANATES FROM ARYL ALKYL SULPHIDES. CONVERSION OF UNACTIVATED ARYL HALIDES INTO ARYL THIOCYANATES
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Aryl alkyl sulphides, easily obtained from aryl halides, can be selectively dealkylated in HMPA by treatment with sodium, sodium methanethiolate or sodium methoxide.The resulting solutions, containing the sodium arenethiolates, when treated with BrCN or ICN, afford the corresponding aryl thiocyanates in moderate to good yields.A by-product is obtained in several cases to whom the structure of ArSP(O)(NMe2)2 has been attributed.
- Testaferri, L.,Tingoli, M.,Tiecco, M.,Chianelli, D.,Montanucci, M.
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p. 263 - 268
(2007/10/02)
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- STUDIES ON STRUCTURALLY SIMPLE α,β-BUTENOLIDES-I NEW SYNTHESIS OF RACEMIC γ-HYDROXYMETHYL-α,β-BUTENOLIDE AND DERIVATIVES
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Exhaustive approaches to the synthesis of racemic γ-heterosubstituted γ-methyl-α,β-butenolides are presented, starting from C3 synthons (glyceraldehyde, glycidaldehyde, acrolein and 2,3-epoxypropyl ethers).Good general methods for the preparation of γ-hydroxymethyl-α,β-butenolide 2, several of its ether derivatives, as well as of γ-bromomethyl-α,β-butenolide 5, are given.The reactivities of these structurally simple but highly functionalized compounds, convenient synthons for more complex molecules, are preliminarily explored.
- Cardellach, J.,Estopa, C.,Font, J.,Moreno-Manas, M.,Ortuno, R. M.,et al.
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p. 2377 - 2394
(2007/10/02)
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- Thioxanthonecarboxylic acids, esters, thioesters and amides with reactive functional groups
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Thioxanthone carboxylic acid esters, thioesters and amides with reactive functional groups of the formula STR1 in which X, Y, Z, n and Q are as defined in the patent claim and Q is, for example, --OCH=CH2, --OCH2 CH=CH2, -
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- Determination of Rate Constants for Electron Transfer from Radical Anions of Aromatic Compounds to Diaryl Disulfides
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Rate constants for electron transfer from the radical anions of aromatic compounds to diaryl disulfides (ArSSAr) have been determined in tetrahydrofuran.By the change of the reduction potentials of the aromatic compounds from -1.04 to -1.91 V (vs.SCE), the rate constants varied from 0.015 to 2.3 * 108 M-1 s-1; conventional spectrophotometry has been employed to measure the slow reaction rates, and the xenon-flash photolysis technique has been applied to the fast reaction systems.The reaction including the free ion or the loose ion pair of the thioxanthone sulfone radical anion, (TO-SO2)-/., was faster than that including the tight ion pair.In the case of the (TO-SO2)-/., Na+-PhSSPh system, temperature variation yielded the free energy of activation (ΔG* = 18.7 kcal/mol) and activation enthropy (ΔS* = -29.1 eu) at 22.4 deg C; the reduction potential of PhSSPh was estimated to be -1.80 V vs.SCE from ΔG* value.Electron-withdrawing substituents of ArSSAr increase the rates and vice versa; the Hammett reaction constants (ρ) were estimated to be ca. +1.50 and 1.40 for electron transfer from perylene radical anion and (TO-SO2)-/.,Na+ to ArSSAr, respectively.The factors controlling the rates have been examined.
- Tagaya, Hideyuki,Aruga, Tamotsu,Ito, Osamu,Matsuda, Minoru
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p. 5484 - 5489
(2007/10/02)
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