- Systematic study on alkyl iodide initiators in living radical polymerization with organic catalysts
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Several low-molar-mass alkyl iodides were studied as initiating dormant species in living radical polymerization with organic catalysts. Primary, secondary, and tertiary alkyl iodides with different stabilizing groups (ester, phenyl, and cyano groups) were systematically studied for the rational design of initiating alkyl iodides. The activation rate constants of these alkyl iodides were experimentally determined for quantitative comparison. These alkyl iodides were used in the polymerizations of methyl methacrylate and butyl acrylate to examine their initiation ability in these polymerizations. A telechelic polymer was prepared using an alkyl iodide with a functional group. Alkyl iodides with multi-initiating sites were also studied.
- Lei, Lin,Tanishima, Miho,Goto, Atsushi,Kaji, Hironori,Yamaguchi, Yu,Komatsu, Hiroto,Jitsukawa, Takuya,Miyamoto, Michihiko
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Read Online
- L-(+)-α-Bromobenzeneacetic Acid (-)-Menthyl Ester
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The crystal structure of L-(+)-α-bromobenzeneacetic acid (-)-menthyl ester (C18H25BrO2) is reported.The Br atom and the O(carbonyl) atom are in trans positions.The 1-methyl-4-isopropylcyclohexane ring has a chair conformation.The dihedral angle between th
- Kolev, Tsonko,Preut, Hans,Koniczek, Lothar,Bleckmann, Paul,Juchnovski, Ivan,Mladenova, Margarita
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Read Online
- COMPOUNDS FOR USE IN TREATING NEUROLOGICAL DISORDERS
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Provided are methods for treating neurological disorders using compounds of Formula (I), and pharmaceutically acceptable salts and compositions thereof.
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Paragraph 00110-00111
(2021/02/05)
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- Iron-Catalyzed Intramolecular C-H Amination of α-Azidyl Amides
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Iron-catalyzed intramolecular C-H amination of aliphatic azides has recently emerged as a powerful tool for the preparation of nitrogen heterocycles. This paper reports that α-azidyl amides can be converted in high efficacy to imidazolinone compounds via intramolecular C(sp3)-H amination by the action of a simple catalytic system composed of FeCl2 and a β-diketiminate ligand. The reactions provide a simple and atom-economical approach toward polysubstituted imidazolinones.
- Zhao, Xiaopeng,Liang, Siyu,Fan, Xing,Yang, Tonghao,Yu, Wei
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supporting information
p. 1559 - 1563
(2019/03/20)
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- Metal-free ATRP "grafting from" technique for renewable cellulose graft copolymers
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Photoinduced metal-free "grafting from" atom transfer radical polymerization (ATRP) has been successfully applied to the fabrication of renewable cellulose graft copolymers with the aid of 2-bromo-2-phenylacetyl ester-modified ethyl cellulose as the macro
- Lu, Chuanwei,Wang, Chunpeng,Yu, Juan,Wang, Jifu,Chu, Fuxiang
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p. 2759 - 2770
(2019/06/03)
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- Benzoxazinone-containing 3,5-dimethylisoxazole derivatives as BET bromodomain inhibitors for treatment of castration-resistant prostate cancer
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The bromodomain and extra-terminal proteins (BET) have emerged as promising therapeutic targets for the treatment of castration-resistant prostate cancer (CRPC). We report the design, synthesis and evaluation of a new series of benzoxazinone-containing 3,5-dimethylisoxazole derivatives as selective BET inhibitors. One of the new compounds, (R)-12 (Y02234), binds to BRD4(1) with a Kd value of 110 nM and blocks bromodomain and acetyl lysine interactions with an IC50 value of 100 nM. It also exhibits selectivity for BET over non-BET bromodomain proteins and demonstrates reasonable anti-proliferation and colony formation inhibition effect in prostate cancer cell lines such as 22Rv1 and C4-2B. The BRD4 inhibitor (R)-12 also significantly suppresses the expression of ERG, Myc and AR target gene PSA at the mRNA level in prostate cancer cells. Treatment with (R)-12 significantly suppresses the tumor growth of prostate cancer (TGI = 70%) in a 22Rv1-derived xenograft model. These data suggest that compound (R)-12 is a promising lead compound for the development of a new class of therapeutics for the treatment of CRPC.
- Xue, Xiaoqian,Zhang, Yan,Wang, Chao,Zhang, Maofeng,Xiang, Qiuping,Wang, Junjian,Wang, Anhui,Li, Chenchang,Zhang, Cheng,Zou, Lingjiao,Wang, Rui,Wu, Shuang,Lu, Yongzhi,Chen, Hongwu,Ding, Ke,Li, Guohui,Xu, Yong
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p. 542 - 559
(2018/05/24)
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- Highly Enantioselective Hydrogenation of Amides via Dynamic Kinetic Resolution Under Low Pressure and Room Temperature
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High-throughput screening and lab-scale optimization were combined to develop the catalytic system trans-RuCl2((S,S)-skewphos)((R,R)-dpen), 2-PrONa, and 2-PrOH. This system hydrogenates functionalized α-phenoxy and related amides at room temperature under 4 atm H2 pressure to give chiral alcohols with up to 99% yield and in greater than 99% enantiomeric excess via dynamic kinetic resolution.
- Rasu, Loorthuraja,John, Jeremy M.,Stephenson, Elanna,Endean, Riley,Kalapugama, Suneth,Clément, Roxanne,Bergens, Steven H.
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supporting information
p. 3065 - 3071
(2017/03/11)
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- Searching for New Leads for Tuberculosis: Design, Synthesis, and Biological Evaluation of Novel 2-Quinolin-4-yloxyacetamides
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In this study, a new series of more than 60 quinoline derivatives has been synthesized and evaluated against Mycobacterium tuberculosis (H37Rv). Apart from the SAR exploration around the initial hits, the optimization process focused on the improvement of the physicochemical properties, cytotoxicity, and metabolic stability of the series. The best compounds obtained exhibited MIC values in the low micromolar range, excellent intracellular antimycobacterial activity, and an improved physicochemical profile without cytotoxic effects. Further investigation revealed that the amide bond was the source for the poor blood stability observed, while some of the compounds exhibited hERG affinity. Compound 83 which contains a benzoxazole ring instead of the amide group was found to be a good alternative, with good blood stability and no hERG affinity, providing new opportunities for the series. Overall, the obtained results suggest that further optimization of solubility and microsomal stability of the series could provide a strong lead for a new anti-TB drug development program.
- Pitta, Eleni,Rogacki, Maciej K.,Balabon, Olga,Huss, Sophie,Cunningham, Fraser,Lopez-Roman, Eva Maria,Joossens, Jurgen,Augustyns, Koen,Ballell, Lluis,Bates, Robert H.,Van Der Veken, Pieter
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p. 6709 - 6728
(2016/08/05)
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- Tert-Butyl Hydroperoxide and Tetrabutylammonium Iodide-Promoted Free Radical Cyclization of α-Imino-N-arylamides and α-Azido-N-arylamides
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The oxidizing system of tert-butyl hydroperoxide (TBHP) and tetrabutylammonium iodide (TBAI) is capable of generating α-(arylaminocarbonyl)iminyl radicals from ethyl 2-(N-arylcarbamoyl)-2-iminoacetates. These iminyl radicals preferably undergo intramolecular ipso attack on the benzene ring to give azaspirocyclohexadienyl radicals, which are readily captured by molecular oxygen under an oxygen atmosphere to yield azaspirocyclohexadienones. In the absence of oxygen, the reaction affords quinoxalin-2-one products. This oxidizing system is also effective to convert α-aryl-α-azido-N-arylamides to the corresponding iminyl radicals under basic conditions (sodium tert-butoxide, t-BuONa), and the subsequent cyclization of these iminyl radicals results in the formation of azaspirocyclohexadienone products in high yields under an oxygen atmosphere. Plausible mechanisms are proposed to rationalize the experimental results, and factors influencing the reactions are discussed.
- Li, Dianjun,Yang, Tonghao,Su, Hailin,Yu, Wei
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supporting information
p. 2529 - 2539
(2015/08/18)
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- Rhodium-catalyzed coupling of α-lactams with indole derivatives
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We report herein a method that allows for the formation of a C-N bond between the C-3 carbon of α-lactams and the nitrogen atom of indoles. A general procedure for the coupling of indoles and α-lactams in only 25 min with high yield is reported. The scope of the reaction was extended by the development of a method for the in situ generation of less stable phenyl-substituted α-lactams. The developed method provides an atom-economical method for the formation of substituted α-amino amides that are found in a variety of biologically-active compounds.
- Box, Hannah K.,Upul Kumarasinghe,Nareddy, Radhika R.,Akurathi, Gopalakrishna,Chakraborty, Amarraj,Raji, Babatunde,Rowland, Gerald B.
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p. 9709 - 9717
(2015/02/02)
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- Synthesis of enantiomerically enriched-bromonitriles from amino acids
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Two methods were investigated for the preparation of six chiral-bromonitriles with different optic purities. The nitrous deamination of amino acids gives-bromoacids, which react with chlorosulfonyl isocyanate followed by triethylamine to afford-bromonitriles with moderate enantiomeric excess. However, the dehydration of corresponding-bromoamids using thionyl chloride gives-bromonitriles with good enantiomeric excess up to 94%. The use of phosphoryl chloride instead of thionyl chloride results in more than 30% racemization as determined by high-performance liquid chromatograpic analysis.
- Tka, Najeh,Kraem, Jamil,Hassine, Bechir Ben
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p. 735 - 743
(2013/01/15)
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- Synthesis, enantioresolution, and activity profile of chiral 6-methyl-2,4-disubstituted pyridazin-3(2H)-ones as potent N-formyl peptide receptor agonists
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A series of chiral pyridazin-3(2H)-ones was synthesized, separated as pure enantiomers, and evaluated for N-formyl peptide receptor (FPR) agonist activity. Characterization of the purified enantiomers using combined chiral HPLC and chiroptical studies (circular dichroism, allowed unambiguous assignment of the absolute configuration for each pair of enantiomers). Evaluation of the ability of racemic mixtures and purified enantiomers to stimulate intracellular Ca 2+ flux in FPR-transfected HL-60 cells and human neutrophils and to induce β-arrestin recruitment in FPR-transfected CHO-K1 cells showed that many enantiomers were potent agonists, inducing responses in the sub-micromolar to nanomolar range. Furthermore, FPRs exhibited enantiomer selectivity, generally preferring the R-(-)-forms over the S-(+)-enantiomers. Finally, we found that elongation of the carbon chain in the chiral center of the active compounds generally increased biological activity. Thus, these studies provide important new information regarding molecular features involved in FPR ligand preference and report the identification of a novel series of FPR agonists.
- Cilibrizzi, Agostino,Schepetkin, Igor A.,Bartolucci, Gianluca,Crocetti, Letizia,Dal Piaz, Vittorio,Giovannoni, Maria Paola,Graziano, Alessia,Kirpotina, Liliya N.,Quinn, Mark T.,Vergelli, Claudia
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experimental part
p. 3781 - 3792
(2012/08/28)
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- The discovery of a novel series of glucokinase activators based on a pyrazolopyrimidine scaffold
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Glucokinase is a key enzyme in glucose homeostasis since it phosphorylates glucose to give glucose-6-phosphate, which is the first step in glycolysis. GK activators have been proven to lower blood-glucose, and therefore have potential as treatments for type 2 diabetes. Here the discovery of pyrazolopyrimidine GKAs is reported. An original singleton hit from a high-throughput screen with micromolar levels of potency was optimised to give compounds with nanomolar activities. Key steps in this success were the introduction of an extra side-chain, which increased potency, and changing the linking functionality from a thioether to an ether, which led to improved potency and lipophilic ligand efficiency. This also led to more stable compounds with improved profiles in biological assays.
- Bonn, Peter,Brink, D. Mikael,F?gerhag, Jonas,Jurva, Ulrik,Robb, Graeme R.,Schnecke, Volker,Svensson Henriksson, Anette,Waring, Michael J.,Westerlund, Christer
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supporting information
p. 7302 - 7305
(2013/02/23)
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- The discovery and synthesis of JNJ 31020028, a small molecule antagonist of the Neuropeptide y Y2 receptor
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A series of small molecules based on a chemotype identified from our compound collection were synthesized and tested for binding affinity (IC 50) at the human Neuropeptide Y Y2 receptor (NPY Y 2). Six of the 23 analogs tes
- Swanson, Devin M.,Wong, Victoria D.,Jablonowski, Jill A.,Shah, Chandra,Rudolph, Dale A.,Dvorak, Curt A.,Seierstad, Mark,Dvorak, Lisa K.,Morton, Kirsten,Nepomuceno, Diane,Atack, John R.,Bonaventure, Pascal,Lovenberg, Timothy W.,Carruthers, Nicholas I.
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scheme or table
p. 5552 - 5556
(2011/10/12)
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- Synthesis of azaspirocycles and their evaluation in drug discovery
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(Figure Presented). Make It spirol Readily synthesized heteroatom- substituted spiro[3.3]heptanes generally show higher aqueous solubility than their cyclohexane analogues, and show a trend towards higher metabolic stability. The novel framework can be mo
- Burkhard, Johannes A.,Wagner, Bjoern,Fischer, Holger,Schuler, Franz,Mueller, Klaus,Carreira, Erick M.
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supporting information; experimental part
p. 3524 - 3527
(2010/08/06)
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- Ethynyl-1,2-benziodoxol-3(1H)-one (EBX): An exceptional reagent for the ethynylation of keto, cyano, and nitro esters
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Hot alkyne! The in situ generation of ethynyl-1,2-benziodoxol-3(1H)-one (EBX) from a silyl-protected reagent by using TBAF is reported. EBX displayed exceptional acetylene transfer ability onto stabilized enolates (see scheme), even at -78 □°C. The mild reaction conditions allowed the first ethynylation reactions of linear keto, cyano, and nitro esters in high yields to give all-carbon quaternary centers or non-natural amino acids after selective reduction of the nitro group.
- Gonzalez, Davinia Fernandez,Brand, Jonathan P.,Waser, Jerome
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supporting information; experimental part
p. 9457 - 9461
(2010/10/03)
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- Preparation of α,ωtelechelic hexyl acrylate polymers with -OH, -COOH, and -NH2 functional groups by RAFT
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The design, synthesis, and use of two new, stable, functionalzed chain transfer agents (CTA's) containing OH and amine end groups for the RAFT polymerization is reported: 2-hydroxyethoxy-carbonylphenylmethyl dithiobenzoate and 2-(2-(tert-butoxycarbonyl)et
- Cortez-Lemus, Norma A.,Salgado-Rodriguez, Rodolfo,Licea-Claverie, Angel
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experimental part
p. 3033 - 3051
(2011/04/15)
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- PIPERAZINYL DERIVATIVES USEFUL AS MODULATORS OF THE NEUROPEPTIDE Y2 RECEPTOR
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The present invention is directed to piperazinyl derivatives useful as inhibitors of the NPY Y2 receptor, pharmaceutical compositions comprising said compounds, processes for the preparation of said compounds and the use of said compounds for the treatment and / or prevention of disorders, diseases and conditions mediated by the NPY Y2 receptor.
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Page/Page column 32
(2009/03/07)
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- Molecular determinants for the activating/blocking actions of the 2H-1,4-benzoxazine derivatives, a class of potassium channel modulators targeting the skeletal muscle KATP channels
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The 2H-1,4-benzoxazine derivatives are modulators of the skeletal muscle ATP-sensitive-K+ channels (KATP), activating it in the presence of ATP but inhibiting it in the absence of nucleotide. To investigate the molecular determinants
- Tricarico, Domenico,Mele, Antonietta,Camerino, Giulia Maria,Laghezza, Antonio,Carbonara, Giuseppe,Fracchiolla, Giuseppe,Tortorella, Paolo,Loiodice, Fulvio,Camerino, Diana Conte
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- Spin trapping of C- and O-centered radicals with methyl-, ethyl-, pentyl-, and phenyl-substituted EMPO derivatives
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In order to develop spin traps with an optimal ratio between hydrophilic and lipophilic properties, low toxicity, and high stability of spin adducts (especially with superoxide radicals), several EMPO-derived spin traps have recently been synthesized forming more stable superoxide adducts (t1/2 > 20 min) than DMPO or DEPMPO. In this study, ESR-, 1H-, and 13C-NMR data of several phenyl- or n-pentyl-substituted EMPO derivatives are presented with full signal assignment. Methyl groups at position 3 or 4 stabilized the superoxide adducts considerably. Spin adducts from other oxygen- and carbon-centered radicals (e.g., derived from methanol or linoleic acid hydroperoxide) are also described.
- Stolze, Klaus,Rohr-Udilova, Natascha,Rosenau, Thomas,Hofinger, Andreas,Kolarich, Daniel,Nohl, Hans
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p. 3368 - 3376
(2007/10/03)
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- Privileged structure based ligands for melanocortin receptors - Substituted benzylic piperazine derivatives
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Replacement of the aryl piperazine moiety in compound 1 with a variety of substituted benzylic piperazines (6) yields compounds that afford melanocortin receptor 4 (MCR4) activity. Analogs with ortho substitution on the aromatic ring afforded the highest
- Fisher, Matthew J.,Backer, Ryan T.,Collado, Ivan,De Frutos, Oscar,Husain, Saba,Hsiung, Hansen M.,Kuklish, Steve L.,Mateo, Ana I.,Mullaney, Jeffrey T.,Ornstein, Paul L.,Paredes, Cristina Garcia,O'Brian, Thomas P.,Richardson, Timothy I.,Shah, Jikesh,Zgombick, John M.,Briner, Karin
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p. 4973 - 4978
(2007/10/03)
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- MTP INHIBITING ARYL PIPERIDINES OR PIPERAZINES SUBSTITUTED WITH 5-MEMBERED HETEROCYCLES
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The present invention is concerned with novel aryl piperidine or piperazine compounds substituted with certain 5-membered heterocycles having apoB secretion/MTP inhibiting activity and concomitant lipid lowering activity. The invention further relates to methods for preparing such compounds, pharmaceutical compositions comprising said compounds as well as the use of said compounds as a medicine for the treatment of hyperlipidemia, obesity and type II diabetes (Formula (I)). The invention further relates to methods for preparing such compounds, pharmaceutical compositions comprising said compounds as well as the use of said compounds as a medicine for the treatment of atherosclerosis, pancreatitis, obesity, hyper-triglyceridemia, hypercholesterolemia, hyperlipidemia, diabetes and type II diabetes.
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Page/Page column 30
(2008/06/13)
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- COMPOUND INHIBITING DIPEPTIDYL PEPTIDASE IV
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The invention aims to provide a dipeptidyl peptidase IV inhibitor which is satisfactory in respect of activity, stability and safety and has an excellent action as a pharmaceutical agent. The invention is directed to a compound represented by the following general formula or a pharmaceutically acceptable salt thereof: wherein R1 and R2 each represents hydrogen, an optionally substituted C1-6 alkyl group, or -COOR5 whereupon R5 represents hydrogen or an optionally substituted C1-6 alkyl group, or R1 and R2, together with a carbon atom to which they are bound, represent a 3- to 6-membered cycloalkyl group, R3 represents hydrogen or an optionally substituted C6-10 aryl group, R4 represents a hydrogen or a cyano group, D represents -CONR6-, -CO- or -NR6CO-, R6 represents hydrogen or an optionally substituted C1-6 alkyl group, E represents -(CH2)m- whereupon m is an integer of 1 to 3, -CH2OCH2-, or -SCH2-, n is an integer of 0 to 3, and A represents an optionally substituted bicyclic heterocyclic group or bicyclic hydrocarbon group.
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Page/Page column 10
(2010/02/14)
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- Lipophilic electrophoretic probes
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Compounds, compositions, and methods for labeling membranes are disclosed. Compounds of formula G-L-E are described wherein G is a lipophilic group, L is a cleavable linkage and E is an electrophoretic group. The compounds become associated with membranes
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Page/Page column 27; Sheet 16/17
(2010/02/05)
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- Compounds and methods for modulation of estrogen receptors
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Compounds that modulate the estrogen receptor (ER) are disclosed, as well as pharmaceutical compositions containing the same. In a specific embodiment, the compounds are selective for ER-β over ER-α. Methods are disclosed for modulating ER-β in cell and/o
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- Imidazo[1,2-b]pyridazines, novel nucleus with potent and broad spectrum activity against human picornaviruses: Design, synthesis, and biological evaluation
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A novel structural class of picornavirus inhibitors comprising an imidazo[1,2-b]pyridazine nucleus was discovered. 2-Aminoimidazo[1,2-b]pyridazines (6d, (E/Z)-7b, (E)-7d, (Z)-7d, (E/ Z)-8b, (E)-10b, (E)-13a, (Z)-13a, (E)-13b, (Z)-13b, (E)-13c, and (Z)-13c) were designed and synthesized in an effort to identify potent broad spectrum antirhinoviral agents. A practical synthetic route to this chemical scaffold has been developed. The target compounds were evaluated in a plaque reduction assay and in a cytopathic effect assay. Our preliminary SAR studies highlight the minimum structural features required for antirhinovirus activity. Our data suggest that the nature of the linker between the phenyl and the imidazopyridazine moieties has a significant influence on the activity of these compounds. Oximes are slightly better than vinyl carboxamides at this position. The oximes are the most potent analogues against human rhinovirus 14 (HRV-14), and at the concentrations evaluated, no apparent cellular toxicity is noted. Furthermore, the E geometry appears to be a key element for activity; the Z isomer leads to a considerable loss in potency. Of particular interest, analogue 7b exhibits potent broad-spectrum antirhinoviral and antienteroviral activity when evaluated against a panel of seven additional rhino- and enteroviruses. The chemistry and the biological evaluations are discussed.
- Hamdouchi, Chafiq,Sanchez-Martinez, Concha,Gruber, Joseph,Del Prado, Miriam,Lopez, Javier,Rubio, Almudena,Heinz, Beverly A.
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p. 4333 - 4341
(2007/10/03)
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- Compounds and methods for modulation of estrogen receptors
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Compounds that modulate the estrogen receptor (ER) are disclosed, as well as pharmaceutical compositions containing the same. In a specific embodiment, the compounds are selective modulators for ER-β over ER-α. Methods are disclosed for modulating ER-β in
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- About the factors which govern the ring-opening of α-lactams with benzylamine: I. The relative stability of the α-lactam and the substituent on nitrogen
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Eight α-lactams (aziridinones) of varying stability, one of them previously unreported, were synthesized and reacted with benzylamine. Three of the α-lactams, 1-(1-adamantyl)-3,3-dimethylaziridinone (2j), 3,3-dimethyl1-triphenylmethylaziridinone (2m), and
- Lengyel, Istvan,Cesare, Victor,Chen, Sihao,Taldone, Tony
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p. 677 - 695
(2007/10/03)
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- 2-amino-3-substituted-6-[(E)-1-phenyl-2-(N- methylcarbamoyl)vinyl]imidazo-[1,2-a]pyridines as a novel class of inhibitors of human rhinovirus: Stereospecific synthesis and antiviral activity
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A series of 2-amino-3-substituted-6-[(E)-1-phenyl-2-(N- methylcarbamoyl)vinyl]imidazo[1,2-a]-pyridines 1a-i, structurally related to Enviroxime and its analogous benzimidazoles, was designed and prepared for testing as antirhinovirus agents. The imidazo ring in this class of compounds was constructed starting from the aminopyridine after tosylation and subsequent treatment with the appropriate acetamides. The key steps in the synthesis include the development and use of a new Horner-Emmons reagent for the direct incorporation of methyl vinylcarboxamide. The reaction was stereospecific in the substrates 5a-f leading exclusively to the desired E- isomer and avoiding the use of reverse-phase preparative HPLC for the separation of both possible isomers before antiviral activity evaluation. The isopropylsulfonyl group, known as the best substituent at the 1-position in the benzimidazole SAR in terms of activity, was introduced in this new series of imidazo[1,2-a]pyridines via halogen-metal exchange and subsequent treatment with isopropyl isopropanethiolsulfonate. Compounds 1a-i were evaluated in plaque reduction assay and in a cytopathic effect assay. Compounds 1b-d,h exhibited a strong antirhinovirus activity, and no apparent cellular toxicity was visible. The substitution at the 3-position was required for activity. Surprisingly the isopropylsulfonyl in this family of compounds did not enhance the activity as in the case of benzimidazoles. Instead, compound 1i was 4 times less active than its phenyl and sulfide partners. The chemistry as well as the biological evaluation are discussed.
- Hamdouchi, Chafiq,De Blas, Jesús,Del Prado, Mirian,Gruber, Joseph,Heinz, Beverly A.,Vance, Lori
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- PTC sulfanylation of some carboxylic acids derivatives activated by α-sulfonyl or α-sulfinyl group, in solid-liquid system
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The sulfanylation of α-sulfonyl substituted lactone and thioesters and α-sulfinyl-substituted esters and thioesters, employing solid K2CO3, S-methyl methanethiosulfonate and TEBA, is reported. The results are compared with those in the homogeneous phase and in the non-catalytic two-phase system.
- Wladislaw, Blanka,Marzorati, Liliana,Donnici, Claudio L.,Biaggio, Francisco C.,Neves, Regina M. A.,Claro Jr., Nelson F.
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p. 197 - 208
(2007/10/03)
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- Reactions of Carboxylic Acid Derivatives with Superoxide
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The mechanisms of the reactions of superoxide with carboxylic esters, acyl peroxides, and the acyl chlorides of α- and β-bromocarboxylic acids have been investigated.Experimental evidence is presented supporting the view that (a) conversion of an ester into its carboxylic acid does not proceed via the corresponding acyl peroxide; (b) conversion of acyl peroxide into carboxylic acid by superoxide involves either electron transfer to or an SN2 reaction on the peroxidic group; (c) α-bromoacyl chlorides with superoxide give the corresponding aldehyde via a cyclic peroxidic intermediate.
- Forrester, Alexander R.,Purushotham, Vemeshetti
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p. 945 - 951
(2007/10/02)
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- Reactions of 1-tert-Butyl-3-phenylaziridinone and α-Bromo-N-tert-butylphenylacetamide with Benzyl-Grignard Reagents
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1-tert-Butyl-3-phenylaziridinone (1) reacts with benzyl halide Grignard reagents (Br and Cl) to give N-tert-butyl-2,3-diphenylpropanamide (4), N-tert-butyl-2-phenylacetamide (3), N-tert-butyl-2-o-tolyl-2-phenylacetamide (5), 1-(tert-butylamino)-1,3-diphenylpropan-2-one (7), N-benzyl-N-tert-butyl-2-phenylacetamide (6), and N-tert-butyl-2-halo-2-phenylacetamide (2, X = Br, Cl).The choice of solvent appears to determine the relative amounts of products 4 and 5.The bromo amide 2 reacts with the Grignard reagent to give 3, 4, 5, 6, and 7 and may be involved to some extentin the reaction of 1 with benzyl-Grignard reagents.The formation of 5 represents anew type of "abnormal" product from a reaction of the benzyl-Grignard reagent; however, this product appears to fit well into the mechanistic pattern established for prior examples.
- Baumgarten, Henry E.,Chiang, Nein-Chu Robert,Elia, Victor J.,Beum, Paul V.
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p. 5507 - 5512
(2007/10/02)
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