- Reactivity of substrates with multiple competitive reactive sites toward NBS under neat reaction conditions promoted by visible light
-
Regioselectivity of visible-light-induced transformations of a range of (hetero)aryl alkyl-substituted ketones bearing several competitive reactive sites (α-carbonyl, benzyl and aromatic ring) with N-bromosuccinimide (NBS) was studied under solvent-free reaction conditions (SFRC) and in the absence of inert-gas atmosphere, radical initiators and catalysts. An 8-W energy-saving household lamp was used for irradiation. Heterogeneous reaction conditions were dealt with throughout the study. All substrates were mono- or dibrominated at the α-carbonyl position, and additionally, some benzylic or aromatic bromination was observed in substrates with benzylic carbon atoms or electron-donating methoxy groups, respectively. Surprisingly, ipso-substitution of the acyl group with a bromine atom took place with (4-methoxynaphthyl) alkyl ketones. While the addition of the radical scavenger TEMPO (2,2,6,6-tetramethylpiperidin-1-yloxy) decreased the extent of α- and ring bromination, it completely suppressed the benzylic bromination and α,α-dibromination with NBS under SFRC.
- Grjol, Bla?,Jereb, Marjan
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p. 5235 - 5248
(2021/06/07)
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- Sydney and Sydney keepinone compounds as well as preparation method and application thereof (by machine translation)
-
The compound disclosed by the invention has a broad-spectrum bactericidal activity, for various plant fungal diseases and a preparation method and application I of the compound, and has excellent control effect on cucumber downy mildew, cucumber anthracnose, wheat powdery mildew, rice sheath blight, cucumber gray mold alone or with other agents . The compound of the present invention has a broad spectrum of fungicidal activity . The compound of, the present, invention has a broad spectrum of bactericidal activity alone or in combination with other agents. The compound of the present invention has excellent control. effect. (by machine translation)
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Paragraph 0172-0175
(2020/05/05)
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- Access to β-Ketonitriles through Nickel-Catalyzed Carbonylative Coupling of α-Bromonitriles with Alkylzinc Reagents
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Herein, we report a nickel-catalyzed carbonylative coupling of α-bromonitriles and alkylzinc reagents with near stoichiometric carbon monoxide to give β-ketonitriles in good yields. The reaction is catalyzed by a readily available and stable nickel(II) pincer complex. The developed protocol tolerates substrates bearing a variety of functional groups, which would be problematic or incompatible with previous synthetic methods. Additionally, we demonstrate the suitability of the method for carbon isotope labeling by the synthesis of 13C-labeled β-ketonitriles and their transformation into isotopically labeled heterocycles.
- Donslund, Aske S.,Neumann, Karoline T.,Corneliussen, Nicklas P.,Grove, Ebbe K.,Herbstritt, Domenique,Daasbjerg, Kim,Skrydstrup, Troels
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supporting information
p. 9856 - 9860
(2019/07/09)
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- Insilco screening, and Synthesis of 5-hydroxy-2-phenyl-1-benzofuran- 3(2H)-one derivatives as novel potent leads as anti-cancer agents
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Insilco technique in chemistry plays a major role in the development of new lead molecules. Computational tools docking, virtual screening, ADMET prediction are untilised in the identification of new lead molecules. A series of new benzofuranone derivatives IVA-F, containing a heterocyclic substituent linked to benzofuranone nucleus at C-2 were synthesized as potential antitumor agents. These products were synthesized starting with benzene 1.4 diol. The structures of all compounds were established on the basis of analytical and spectral data. The synthesized compounds were tested against human skin carcinoma cell line (G361) and all were found to be more potent of which compound IV B and IV F was the most active.
- Doonaboyina, Raghava,Mittal, Abhilasha,Gummadi, Sridhar Babu
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p. 710 - 720
(2019/05/21)
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- Palladium-Catalyzed, ortho-Selective C-H Halogenation of Benzyl Nitriles, Aryl Weinreb Amides, and Anilides
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A palladium-catalyzed, ortho-selective C-H halogenation methodology is reported herein. The highlight of the work is the highly selective C(sp2)-H functionalization of benzyl nitriles in the presence of activated C(sp3)-H bond, which results in good yields of the halogenated products with excellent regioselectivity. Along with benzyl nitriles, aryl Weinreb amides and anilides have been evaluated for the transformation using aprotic conditions. Mechanistic studies yield interesting aspects with respect to the pathway of the reaction and the directing group abilities.
- Das, Riki,Kapur, Manmohan
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p. 1114 - 1126
(2018/06/18)
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- COMPOSITIONS AND METHODS FOR THE TREATMENT OF SEVERE PAIN
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The invention relates to the compounds of formula I or its pharmaceutical acceptable salts, as well as polymorphs, solvates, enantiomers, stereoisomers and hydrates thereof. The pharmaceutical compositions comprising an effective amount of compounds of formula I, and methods for the treatment of severe pain may be formulated for oral, buccal, rectal, topical, transdermal, transmucosal, intravenous, parenteral administration, syrup, or injection. Such compositions may be used to treatment of chronic pain, generalized pain disorders, leukemia, cancer, chronic pain, chemotherapy induced pain, epilepsy, migraine, neuropathic pain, post herpetic neuralgia, neuralgia, pain, drug addiction, detoxification of drugs, Alzheimer's disease, multiple sclerosis, multiple sclerosis, restless legs syndrome (RLS), cluster headache, depression, fibromyalgia, amyotrophic lateral sclerosis (ALS), convulsions, partial seizures, mood-stabilizing agent and bipolar disorder.
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-
Paragraph 0122; 0123
(2015/06/10)
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- 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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p. 6610 - 6618
(2015/02/19)
-
- COMPOSITIONS AND METHODS FOR THE TREATMENT OF SEVERE PAIN
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The invention relates to the compounds of formula (I) or its pharmaceutical acceptable salts, as well as polymorphs, solvates, enantiomers, stereoisomers and hydrates thereof. The pharmaceutical compositions comprising an effective amount of compounds of formula (I), and methods for the treatment of severe pain may be formulated for oral, buccal, rectal, topical, transdermal, transmucosal, intravenous, parenteral administration, syrup, or injection. Such compositions may be used to treatment of chronic pain, generalized pain disorders, leukemia, cancer, chronic pain, chemotherapy induced pain, epilepsy, migraine, neuropathic pain, post herpetic neuralgia, neuralgia, pain, drug addiction, detoxification of drugs, Alzheimer's disease, multiple sclerosis, multiple sclerosis restless legs syndrome (RLS), cluster headache, depression, fibromyalgia, amyotrophic lateral sclerosis (ALS), convulsions, partial seizures, mood-stabilizing agent and bipolar disorder.
- -
-
Paragraph 00101
(2013/12/03)
-
- Synthesis and structure-activity relationships of A novel class of dithiocarbamic acid esters as anticancer agent
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Based on a novel lead compound 4-methylpiperazine-1-carbodithioic acid 3-cyano-3,3-diphenylpropyl ester 1, the systematic structural modification was carried out. All the synthesized compounds were evaluated for their in-vitro anticancer activities on four to six different cell lines at three different concentrations. Most of the tested compounds could selectively inhibit the growth of HL-60 and Bel-7402 cell lines at a medium concentration. Four compounds (3f, 3g, 3n, and 5) were selected for the IC50 test, and the results revealed that three compounds (3g, 3n, and 5) showed almost the same or a slightly weaker activity than compound 1 against HL-60, and three compounds (3f, 3g, and 3n) showed >2-fold higher potency than compound 1 against Bel-7402. The in-vivo efficacy of 3n · HCl was evaluated with transplanted hepatocyte carcinoma 22 as an in-vivo test model. It was found that 3n · HCl could inhibit significantly the growth of tumor, and that this effect was dose-dependent. Meanwhile, the compound 3n · HCl showed low toxicity compared with compound 1 · HCl as evidenced by the little body-weight loss. These results confirmed that compound 3n · HCl is more potent than the lead compound 1 · HCl. Preliminary structure-activity relationships indicated that: a) Both nitrile group and the cyclic amine containing at least two nitrogens were indispensable moieties to keep the activity; b) substitution of the piperazine ring is unfavorable for the improvement of activity; c) the suitable linker joining the piperazinyl dithiocarboxyl and diphenylacetonitril group should be ethylene; d) a non-coplanar arrangement of the two benzene rings appears to be essential for activity. Based on a novel lead compound 4-methyl-piperazine-1-carbodithioic acid 3-cyano-3,3-diphenyl-propyl ester 1, the systematic structural modification was carried out. Compounds 3g and 3n were found to show more potent biological activities than lead compound 1. Some useful SARs were revealed Copyright
- Hou, Xueling,Ge, Zemei,Wang, Tingmin,Guo, Wei,Wu, Jun,Cui, Jingrong,Lai, Chingsan,Li, Runtao
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experimental part
p. 320 - 332
(2011/11/05)
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- An unexpected result of the reaction of benzothioamide derivatives with 2-aryl-2-bromoacetonitriles
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Unexpectedly, in the reaction of 2-bromo-2-phenylacetonitrile derivatives with 2 mol-equiv. of benzothioamide in DMSO, 3,5-diaryl-1,2,4-thiadiazoles were obtained in excellent yields (83-90%) and in short reaction times (5-10 min). It is found that, in DMF, a quite different reaction takes place and 2,5-diaryl-1,3-thiazol-4-amines are formed as the main products. Copyright
- Zali Boeini, Hassan,Mobin, Mehdi
-
experimental part
p. 2039 - 2044
(2012/01/04)
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- Visible-light-promoted Wohl-Ziegler functionalization of organic molecules with N-bromosuccinimide under solvent-free reaction conditions
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The visible-light-induced transformation of toluenes with N-bromosuccinimide (NBS) under solvent-free reaction conditions (SFRC) was studied. The reaction took place in spite of the very restricted molecular motion; toluenes could be regioselectively converted to benzyl bromides. Selective radical-chain reactions with NBS were carried out in liquid/liquid and in solid/solid systems; furthermore, reactions could be performed in the presence of air. The radical scavenger TEMPO (=2,2,6,6-tetramethylpiperidin-1- yloxy) completely suppressed the side-chain bromination of toluenes with NBS under SFRC. Electron-withdrawing groups decreased the reactivity of the toluenes, and the Hammett reaction constant ρ+ = -1.7 indicated involvement of polar radical intermediates with electrophilic character.
- Jereb, Marjan,Zupan, Marko,Stavber, Stojan
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experimental part
p. 555 - 566
(2009/09/06)
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- HIV INTEGRASE INHIBITORS
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Bicyclic pyrazoles of Formula I are inhibitors of HIV integrase and inhibitors of HIV replication: (I), wherein Z is O or N(R8); n is an integer equal to zero or 1; and R1, R2, R3, R4, R5, R6, R7 and R8 are defined herein. The compounds are useful in the prevention and treatment of infection by HIV and in the prevention, delay in the onset, and treatment of AIDS. The compounds are employed against HIV infection and AIDS as compounds per se or in the form of pharmaceutically acceptable salts. The compounds and their salts can be employed as ingredients in pharmaceutical compositions, optionally in combination with other antivirals, immunomodulators, antibiotics or vaccines.
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-
Page/Page column 47; 48
(2008/06/13)
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- 2,4,4,6-Tetrabromocyclohexa-2,5-dienone in the presence of triphenylphosphine as a specific reagent for nucleophilic substitution in cyanohydrins
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A convenient method for the synthesis of α-bromonitriles from aliphatic cyanohydrins using the 2,4,4,6-tetrabromocyclohexa-2,5-dienone complex with triphenylphosphine was developed.
- Matveeva, Elena D.,Podrugina, Tatyana A.,Tishkovskaya, Elena V.,Zefirov, Nikolai S.
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p. 260 - 261
(2007/10/03)
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- Indium-mediated reductive dehalogenation of α-halocarbonyl compounds in water
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Reactions of various α-halocarbonyl compounds 1 with indium in the presence of a catalytic amount of sodium dodecyl sulfate in water were performed to afford the corresponding parent carbonyl compounds 2 in excellent yields. The Royal Society of Chemistry 2000.
- Park, Leeyoung,Keum, Gyochang,Kang, Soon Bang,Kim, Kwan Soo,Kim, Youseung
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p. 4462 - 4463
(2007/10/03)
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- Histamine H1 receptor ligands - Part II. Synthesis and in vitro pharmacology of 2-[2-(phenylamino)thiazol-4-yl]ethanamine and 2-(2-benzhydrylthiazol-4-yl)ethanamine derivatives
-
New 2-[2-(phenylamino)thiazol-4-yl]ethanamine and 2-(2-benzhydrylthiazol-4-yl)ethanamine derivatives were prepared and tested in vitro as H1 receptor antagonists. The compounds with 2-phenylamino substitution with meta-halide substituents at the phenyl ring, showed weak H1-antagonistic activity (pA2: 4.62-5.04) and this activity was completely lost in the case of meta-methyl substituent (pA2 : 4). When the phenylamino group was replaced by benzhydryl groups of classic antihistamines, the resulting compounds exhibited slightly improved H1-antagonistic activity (at the meta-position pA2: 6.38-6.15; at the para-position pA2: 6.04-5.87).
- Walczynski, Krzysztof,Guryn, Roman,Zuiderveld, Obbe P.,Zhang, Ming-Qiang,Timmerman, Henk
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p. 569 - 574
(2007/10/03)
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- Unexpected Staudinger reaction of α-azidoacetonitriles α-phenyl substituted with triphenylphospine. Preparation, X-ray crystal and molecular structures of a phosphazine, an aminophosphonium carbanion salt and a phosphazide, with (Z)-configuration
-
Staudinger reaction of α-azidophenylacetonitrile with triphenylphosphine in 1:2 molar ratio provides the triphenylphosphazine 4 derived from α-diazophenylacetonitrile, whereas 2:1 molar ratio the final product is found to be the aminotriphenylphosphonium salt of phenylmalononitrile 6. However, the Staudinger reaction of α- azidodiphenylacetonitrile with triphenylphosphine affords the corresponding (Z)-phosphazide 17. The crystal and molecular structures of compounds 4,6, and 17 have been determined by X-ray analysis. Compound 17 is the first isolated phosphazide which presents the (Z)-configuration with respect to the central N,N bond of the PN3C moiety (P-N-N-N= 0.0(3)°).
- Molina, Pedro,Lopez-Leonardo, Carmen,Llamas-Botia, Javier,Foces-Foces, Concepcion,Fernandez-Castano, Cristina
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p. 9629 - 9642
(2007/10/03)
-
- Phenyl-substituted normethadones: Synthesis and pharmacology
-
Phenyl-substituted normethadone derivatives were synthesized and their affinity (IC50) for opioid receptors was determined by displacement of the specific binding sites of [3H]sufentanyl on rat brain preparations. Substitution resulted in a decrease of affinity in-vitro. These results suggest that normethadone-like compounds may interact with the P subsite of the μ-opioid receptor and that the P subsite has a well-defined cavity shape of stringent dimensions.
- Mbela,Poupaert,Cumps,Moussebois,Haemers,Borloo,Dumont
-
p. 237 - 242
(2007/10/02)
-
- (2-Cyanoallyl)trimethylsilane and (2-Cyanoethyl)trimethylsilane. Unique ?? Captodative Systems
-
Addition reactions of (2-cyanoallyl)trimethylsilane as well as hydrogen abstraction reactions of (2-cyanoethyl)trimethylsilane were examined.These compounds exhibit high reactivities in free-radical reactions, demonstrating existence of the ?? captodative effect.
- Sakurai, Hideki,Kyushin, Soichiro,Nakadaira, Yasuhiro
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p. 297 - 300
(2007/10/02)
-
- THERMALLY INITIATED REACTIONS OF (Z)-EPOXYHEXENYNES A FACILE PREPARATION OF 3,4-ANNULATED FURANS
-
An efficient and general access to 3,4-annulated 2-vinylfurans (type II) is provided by the thermally induced ring transformation of epoxyhexenynes (I).Depending on the substitution pattern the reactions proceed either by heating in solution (5a-h) or under short-time thermolysis conditions (6i, j).The results are consistent with a multistep mechanism involving 1-oxacyclohepta-3,4,6-trienes as central intermediates.
- Eberbach, Wolfgang,Roser, Joachim
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p. 2221 - 2234
(2007/10/02)
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- ALLYLATION AND OXIDATION REACTIONS PROMOTED BY COBALT(ll) COMPLEXES.
-
Two examples of radical reactions involving cobalt complexes are described.The first one concerns the reactions of allylcobaloximes with 2-bromo 2-phenylacetonitriles leading to the corresponding monoallyl derivatives.It is shown that both the rate and regioselectivity of the reactions are affected by the nature of the substituents on the phenyl group : electron-withdrawing groups give higher rates and highly regiospecific reactions.The second type of radical reactions wich finds useful synthetic applications is the oxidation of phenols by O2 catalysed by Schiff base cobalt complexes.By choosing carefully the catalyst and the solvent, these oxidations can be highly selective, quinones being the major oxidation products in most cases.
- Gaudemer, A.,Nguyen-Van-Duong, K.,Shahkarami, N.,Achi, S. S.,Frostin-Rio, M.,Pujol, D.
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p. 4095 - 4106
(2007/10/02)
-