- Design, synthesis, biological evaluation and molecular docking of new 1,3,4-oxadiazole homonucleosides and their double-headed analogs as antitumor agents
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A novel series of homonucleosides and their double-headed analogs containing theophylline, 1,3,4-oxadiazole, and variant nucleobases was designed and synthesized. The new derivatives were fully characterized by HRMS, FT-IR, 1H NMR, and 13C NMR. The cytotoxic activities of all prepared compounds were screened in vitro against four cell lines, including fibrosarcoma (HT-1080), breast (MCF-7 and MDA-MB-231), and lung carcinoma (A-549). The double-headed analogue 18 showed marked growth inhibition against all the cell lines tested, specifically in HT-1080, with an IC50 values of 17.08 ± 0.97 μM. The possible mechanism of apoptosis was investigated using Annexin V staining, caspase-3/7 activity, and analysis cell cycle progression. The compound 18 induced apoptosis through caspase-3/7 activation and cell-cycle arrest in HT-1080 and A-549 cells. The molecular docking confirms that the compound 18 activated caspase-3 via the formation of hydrogen bonds and hydrophobic interactions.
- EL Mansouri, Az-eddine,Oubella, Ali,Mehdi, Ahmad,AitItto, Moulay Youssef,Zahouily, Mohamed,Morjani, Hamid,Lazrek, Hassan B.
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Read Online
- Green synthesis of 6-[2-aminothiazol-4-yl]-2-furylchromone
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Synthesis of 2-aminothiazoles through Hantzsch method involves the use of bromine. An 2-aminothiazole system 6-[2-aminothiazol-4- yl]-2-furylchromone has been synthesized green chemically from 6-chloroacetyl-2-furylchromone and 6-acetyl-2-furylchromone during present study. The structures of new compounds were elucidated on the basis of IR and PMR-spectra.
- Sharma, Vinay Prabha,Kumar, Rakesh
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Read Online
- Practical synthesis of quinoline-protected morpholino oligomers for light-triggered regulation of gene function
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Photoactivatable cyclic caged morpholino oligomers (ccMOs) represent a promising tool to selectively regulate gene expression with spatiotemporal control. Nevertheless, some challenges associated with the preparation of these reagents have limited their broader use in biological settings. We describe a novel ccMO design that overcomes many of the challenges and considerably expedites the synthetic preparation. The key factor is the introduction of an ethynyl function on the photocleavable linker to facilitate the use of a Huisgen 1,3-dipolar cycloaddition for the coupling reaction with the oligonucleotide. Compared to previous strategies, this modification reduces the number of synthetic steps and significantly improves the total yield and the stability of the linker. We used the alkynyl-functionalized linker for the preparation of two different ccMOs targeting the mRNA of the glutamic acid decarboxylase genes, gad1 and gad2. HPLC analysis confirms that the caging strategy successfully inhibits the DNA binding ability, and the activity can be restored by brief illumination with 405-nm light. Overall, the straightforward preparation together with the clean and fast photochemistry make these caged antisense reagents excellent tools to modulate gene function in-vivo with spatial and temporal precision.
- Deodato, Davide,Dore, Timothy M.
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Read Online
- Synthesis and Fungitoxic Evaluation of Acylamino-1,2,4-Triazoles
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Ten different acylamino-1,2,4-triazoles were prepared by the reaction of differently substituted benzoyl chlorides and acetyl chlorides with 4-amino-1,2,4-triazole using catalytic amount of triethylamine. The synthesized compounds were characterized using UV, 1H-nuclear magnetic resonance spectroscopy, and infrared spectroscopy. All the compounds were tested for their fungicidal potential against three fungal species, that is, Fusarium verticillioides, Macrophomina phaseolina, and Rhizoctonia solani using poisoned food technique. The synthesized compounds were tested at various concentrations along with standard carbendazim 50 WP. The amides synthesized by reaction of substituted benzoyl chlorides and 4-amino-1,2,4-triazole exhibited greater fungicidal activity against all the tested fungi as compared to the amides synthesized using substituted acetyl chlorides. Among all the tested compounds, 4-nitro-N-(4-H-1,2,4-triazol-4-yl)benzamide showed the maximum fungicidal activity with the least median effective dose (ED50) values of 100, 93, and 146 μg ml-1 against F verticillioides, M. phaseolina, and R. solani, respectively. All the compounds were found to be less effective than the standard used.
- Kaur, Gurinderjit,Kaur, Harleen,Kaur, Pardeep,Sharma, Sunita,Singh, Ravneet
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p. 389 - 395
(2021/11/22)
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- Alkylation of 5-Substituted Tetrazoles with Various Alcohols in 1,2-Dichloroethane in the Presence of BF3·Et2O
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Abstract: The alkylation of 1H-tetrazole, 5-methyl-1H-tetrazole, and 5-phenyl-1H-tetrazole with primary, secondary, and tertiary alcohols, including benzylic and allylic ones, have been studied in 1,2-dichloroethane in the presence of boron trifluoride–diethyl ether complex. Neither primary nor secondary saturated alcohols alkylated tetrazoles in the given system. Tertiary alcohols such tert-butyl alcohol and adamantan-1-ol reacted with unsubstituted and 5-substituted tetrazoles to give 70–85% of the corresponding 2-alkyl-5-R-tetrazoles with high regioselectivity. The alkylation of 1H-tetrazole with benzyl alcohol afforded 55% of 2-benzyl-2H-tetrazole as the only product. The alkylation of 1H-tetrazole with various allylic alcohols led to the formation of mixtures of 2-alkyl-2H-tetrazoles with isomeric alkyl substituents.
- Egorov, S. A.,Ishchenko, M. A.,Ivanova, V. I.,Prokopovich, Ya. V.
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p. 1196 - 1203
(2020/10/02)
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- 3-Aminobenzenesulfonamides incorporating acylthiourea moieties selectively inhibit the tumor-associated carbonic anhydrase isoform IX over the off-target isoforms I, II and IV
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We describe the synthesis of a series of novel 1-aroyl/acyl-3-(3-aminosulfonylphenyl) thioureas (4a–k) acting as human carbonic anhydrase (hCA, EC 4.2.1.1) inhibitors. Reaction of alkyl/aryl isothiocyanates with 3-aminobenzenesulfonamide afforded a series of the title compounds incorporating a variety of short as well as highly lipophilic long tails. The newly synthesized sulfonamides were evaluated against 4 physiologically relevant CA isoforms (hCA I, II, IV, and IX). Several compounds showed interesting inhibitory activity. The tumor-associated hCA IX was the most sensitive isoform to inhibition with these compounds, with KIs in the range of 21.5–44.0 nM and selectivity ratios over the major cytosolic isoform hCA II in the range of 3.35–37.3. The sulfonamides incorporating the phenylacetylthioureido and pentadecanoylthioureido moieties were the most hCA IX-selective inhibitors detected in this work, making them of interest for further investigations.
- Fattah, Tanzeela Abdul,Bua, Silvia,Saeed, Aamer,Shabir, Ghulam,Supuran, Claudiu T.
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p. 123 - 128
(2018/10/20)
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- A high-purity 3, 5, 6 - trichloro-pyridine -2 - sodium alcoholate production process (by machine translation)
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The present invention relates to the technical field of chemical material production, and in particular relates to a high-purity 3, 5, 6 - trichloro-pyridine - 2 - sodium alcoholate production process, comprises the following steps: chlorine acetyl chloride; preparing trichlor; addition cyclization: the protection of inert gas atmosphere by adding solvent, the pure product of the chloroacetyl chloride, acrylonitrile and catalyst, the temperature of the stirred to back flow, so that the reflux to return to below the liquid level, reduced pressure distillation, heat filter, the catalyst can be recycled for use, get filtrate for use; preparing 3, 5, 6 - trichloro-pyridine - 2 - sodium alcoholate crude; for preparing high-purity 3, 5, 6 - trichloro-pyridine - 2 - sodium alcoholate. The invention solves the problems in the prior art 3, 5, 6 - trichloro-pyridine - 2 - sodium alcoholate preparation technical difficulty is high, the yield is low and low purity of, the prepared 3, 5, 6 - trichloro-pyridine - 2 - sodium alcoholate has high purity, high yield and relatively shallow the advantages of luster, reasonable production process and is favorable for industrial production. (by machine translation)
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Paragraph 0045; 0064
(2019/04/04)
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- Design, synthesis and biological study of potent and covalent HER-2 tyrosine kinase inhibitors with low cytotoxicity in vitro
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The discovery and development of a novel HER-2 tyrosine kinase inhibitor for the treatment of HER2-positive breast cancer are presented in this article. EGFR family has been recognized as a crucial meditator in the cancer progression; HER-2 tyrosine kinase was one of the members among them. In the effort to explore potent HER-2 inhibitors, a novel series of 4-anilino-3-cyanoquinoline derivatives have been designed, synthesized and evaluated. Most compounds possessed modest proliferation inhibition on SK-BR-3 cell line and HER-2 kinase. Compound 16 appeared to be the most potent compound (HER-2 kinase IC50: 19.4?nM, SK-BR-3 IC50: 94?nM). In the experiment of cellular cytotoxicity assay, compound 16 shows a much lower cytotoxicity than neratinib on Beas-2b cell line (Human bronchial epithelial cells). In conclusion, compound 16 would be a promising lead compound for further anti-breast cancer drug discovery.
- Jin, Shuyu,Sun, Xiuyun,Liu, Dan,Xie, Hua,Rao, Yu
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p. 1333 - 1345
(2019/05/06)
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- Synthesis and bioactivities of diamide derivatives containing a phenazine-1-carboxamide scaffold
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Taking natural product phenazine-1-carboxamide (PCN) as a lead compound, a series of novel phenazine-1-carboxylic acid diamide derivatives were designed and synthesised. Their structures were confirmed by 1H-NMR and HRMS. The bioassays showed that some of the target compounds exhibited promising in vitro fungicidal activities, and exhibited excellent and selective herbicidal activities. Particularly, compounds c, h, o and s displayed root length inhibition activities against barnyard grass with the rate of more than 80%. Compound c exhibited the best activity among all the target compounds against barnyard grass stalk length with the IC50 value of 0.158?mmol/L, and compound o exhibited the best and wide spectrum inhibition against barnyard grass root length and rape in both root length and stalk length herbicidal activities with its IC50 values of 0.067, 0.048 and 0.059?mmol/L respectively. The analysis of preliminary Structure-Activity Relationships provides the theoretical basis for further design of phenazine-1-carboxylic acid.
- Zhu, Xiang,Zhang, Min,Yu, Linhua,Xu, Zhihong,Yang, Dan,Du, Xiaoying,Wu, Qinglai,Li, Junkai
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supporting information
p. 2453 - 2460
(2018/03/29)
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- Synthesis method of chloroacetyl chloride
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The invention discloses a synthesis method of chloroacetyl chloride (ClCH2COCl). To be specific, the synthesis method is characterized in that an activated carbon loaded lewis acid catalyst is used for catalyzing gaseous acetyl chloride and chlorine to perform an alpha-halogenation reaction in a contact reactor to generate the chloroacetyl chloride. Lewis acid is specifically ferric chloride or aluminium chloride, and the consumption of the lewis acid is 1-7% of the total material input of acetyl chloride. The synthesis method disclosed by the invention is high in catalyst utilizing rate, highin selectivity, and less in byproducts, and the purity of a product is higher than or equal to 99.5%; the reaction is performed at low temperature; the energy consumption is low; the environmental pollution is small; and the reaction equipment structure is simple, and the operation is easy.
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Paragraph 0020-0022
(2019/03/28)
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- Synthesis and insecticidal activity of rotenone analogues
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Rotenone, one of traditional botanical insecticide, has been used more than one hundred years. A variety of rotenone derivatives were designed and synthesized in recent years due to environmental benign character and not easy to generate insecticide resistance. This paper described the molecular design, synthesis, and insecticidal activities of a series of rotenone analogues and 2-substituted rotenone derivatives. The preliminary bioassay showed that isorotenone and 2-rotenone nicotinate is equal to rotenone's against Musca domestica.
- Zhicheng, Liu,Dingxin, Jiang,Hanhong, Xu,Xiaohua, Zheng
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p. 1063 - 1070
(2018/10/26)
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- Synthesis and Biological Activity of Anthranilic Diamide Derivatives Incorporating 1,3,4-oxadiazole or Nitrogen-containing Saturated Heterocyclic Moieties
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A series of novel anthranilic diamide derivatives incorporating 1,3,4-oxadiazole or nitrogen-containing saturated heterocyclic moieties were synthesized, characterized, and evaluated for bacteriostatic activity against three phytopathogenic bacteria Xanthomonas oryzae pv. Oryzae (Xoo), Xanthomonas axonopodis pv. Citri (Xac), Ralstonia solanacearum (R. solanacearum). The preliminary biological results indicated that most compounds exhibit bacteriostatic activity against three phytopathogenic bacteria. Among these compounds, compounds 6g, 6f, and 6i displayed better antibacterial activity. In the test with concentration of 200 μg/mL, antibacterial activity of compound 6i and 6j was 96%. In particular, the bacteriostatic activity displayed by compound 6h against Xoo is similar to the one displayed by commercial drug bismerthiazol.
- Zhou, Wen-Juan,Zhang, Li,Xiao, Wei,Chen, He-Ju,Wu, Wen-Neng,Ouyang, Gui-Ping
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p. 1423 - 1429
(2017/03/27)
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- Side chain-functionalized aniline-derived ursolic acid derivatives as multidrug resistance reversers that block the nuclear factor-kappa B (NF-κB) pathway and cell proliferation
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A series of inhibitors of NF-κB based on ursolic acid (UA) derivatives containing functionalized aniline or amide side chains were synthesized and evaluated for inhibition of NF-κB as well as their antitumor effects. These compounds exhibited significant inhibition activity toward NF-κB with IC50 values at micromolar concentrations in the NCI-H460 lung adenocarcinoma cell line. A docking study of the most active compound 5Y8 revealed key interactions between 5Y8 and the active site of NF-κB in which the functionalized amide moiety at the C-28 position and an ester group at the C-3 position were important for improving the activity. In particular, compound 5Y8 appeared to be the most potent compound against the NCI-H460 cell line, and displayed similar efficiency in drug-sensitive versus drug-resistant cancer cell lines, at least partly, by blocking the NF-κB signaling pathway and inducing apoptosis. Mechanistically, compound 5Y8 might trigger the apoptotic signaling pathway. Thus, the rational design of UA derivatives with functionalized aniline or amide side chains offers significant potential for the discovery of a new class of NF-κB inhibitors with the ability to induce apoptosis and reverse multidrug resistance in the NCI-H460 lung adenocarcinoma cell line.
- Huang, Ri-Zhen,Hua, Shi-Xian,Liao, Zhi-Xin,Huang, Xiao-Chao,Wang, Heng-Shan
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p. 1421 - 1434
(2017/07/25)
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- Synthesis of gibberellic acid derivatives and their effects on plant growth
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A series of novel C-3-OH substituted gibberellin derivatives bearing an amide group were designed and synthesized from the natural product gibberellic acid (GA3). Their activities on the plant growth regulation of rice and Arabidopsis were evaluated in vivo. Among these compounds, 10d and 10f exhibited appreciable inhibitory activities on rice (48.6% at 100 μmol/L) and Arabidopsis (41.4% at 100mol/L), respectively. These results provide new insights into the design and synthesis of potential plant growth regulators.
- Tian, Hao,Xu, Yiren,Liu, Shaojin,Jin, Dingsha,Zhang, Jianjun,Duan, Liusheng,Tan, Weiming
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- Rhodium(III)-Catalyzed Cascade Cyclization/Electrophilic Amidation for the Synthesis of 3-Amidoindoles and 3-Amidofurans
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A rhodium(III)-catalyzed cascade cyclization/electrophilic amidation using N-pivaloyloxylamides as the electrophilic nitrogen source has been developed. This protocol provides an efficient route for the synthesis of 3-amidoindoles and 3-amidofurans under mild conditions with good functional group tolerance. The synthetic utility of this reaction has been demonstrated through the derivatization of the 3-amidoindoles to several heterocycle-fused indoles.
- Hu, Zhiyong,Tong, Xiaofeng,Liu, Guixia
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supporting information
p. 2058 - 2061
(2016/06/01)
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- Synthesis and Anti-Staphylococcal Activity of 2,4-Disubstituted Diphenylamines
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Infections caused by Staphylococcus aureus are ubiquitous and life threatening. Evolution of resistant strains has necessitated the need to continuously discover new drugs to combat such organisms. Diphenyl ethers, such as triclosan, have recently shown potential as antibacterial agents. In this study, a series of diphenyl amines were synthesized and evaluated for in vitro antibacterial activity against Gram-positive (Staphylococcus aureus, Bacillus subtilis, Staphylococcus epidermidis) and Gram-negative (Escherichia coli, Pseudomonas aeruginosa, Pseudomonas putida) bacteria. Preliminary results showed that six of the twelve synthesized molecules were active against Staphylococcus aureus. Most notable amongst them were compounds 2(2,4-dinitrophenylamino) phenol and 2(2-dinitrophenylamino)phenol having minimum inhibitory concentration (MIC) in the range of 7.8-15.6 μg mL-1 and 7.8-62.5 μg mL-1 respectively for all the eight selected organisms. Five active compounds from the preliminary results were further screened against resistant S. aureus cultures where compounds 2(2,4-dinitrophenylamino)phenol, 2(2-dinitrophenylamino)phenol and 2-chloro-N-(2-(2,4-dichlorophenylamino)phenyl)acetamide gave encouraging results having MIC in the range 3.9-7.8 μg mL-1 for most of the organisms. Results obtained above for the selected organisms and the resistant S. aureus strains conclude that hydroxyl group at 2-position of ring B potentiates the antibacterial activity and overcomes the antibiotic resistance.
- Mehton, Ramandeep K.,Meshram, Vineet,Saxena, Sanjai,Chhibber, Manmohan
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p. 1236 - 1244
(2016/08/16)
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- CAGED COMPOUND WHICH CAN BE PHOTOACTIVATED SELECTIVELY FOR CELL TYPES
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An objective of the present invention is to provide a caged compound that can be photoactivated selectively for specific target cell types and can be used in an individual organism. The objective can be achieved by a compound represented by general formula K-Q-X, which is prepared by binding bioactive substance X, photocleavable protecting group Q, and compound K, which can be an enzyme substrate and is dissociated from Q-X by an enzyme reaction, wherein: Q is a protecting group that is photocleaved by light with a specific wavelength and then dissociated from X, when K is not bound thereto; X is a substance that does not express bioactivity when Q is bound thereto, but expresses bioactivity when Q is dissociated therefrom; and K is dissociated from Q by the above enzyme, so as to form a compound represented by Q-X. Specifically, the objective can be achieved with the use of such a compound, which is characterized in that Q is dissociated from X when the compound represented by Q-X is photoirradiated, and thus K expresses bioactivity.
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Paragraph 0102-0104
(2014/09/29)
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- Synthesis and evaluation of novel monosubstituted sulfonylurea derivatives as antituberculosis agents
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A series of novel monosubstituted sulfonylurea derivatives 10a-y were synthesized and characterized by 1H NMR, 13C NMR and HRMS. These compounds were evaluated against Mycobacterium tuberculosis H37Rv in vitro. The results showed compounds 10f, 10k and 10s exhibited moderate antituberculosis activities with MIC values in the range of 20-100 mg/L. Compounds 10b and 10o displayed good antituberculosis activities (MIC 10 mg/L), which were comparable with that of the sulfometuron methyl. Both of the two compounds showed little cytotoxicities, with an IC50 against THP-1 cells greater than 100 mg/L.
- Pan, Li,Jiang, Ying,Liu, Zhen,Liu, Xing-Hai,Liu, Zhuo,Wang, Gang,Li, Zheng-Ming,Wang, Di
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scheme or table
p. 18 - 26
(2012/07/01)
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- Synthesis and Preliminary Biologic Evaluation of 5-Substituted-2-(4-substituted phenyl)-1,3-Benzoxazoles as A Novel Class of Influenza Virus A Inhibitors
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The diversity-oriented chemistry synthesis together with the random screening approach has permitted the discovery and optimization of novel antiviral lead compounds. In this paper, a series of novel 5-substituted-2-(4-substituted phenyl)-1,3-benzoxazoles was synthesized and evaluated for their in vitro anti-influenza A virus and anti-influenza B virus activity. The activity was monitored by the MTS assay in the Madin-Darby canine kidney cells. Compound 7h showed excellent inhibitory activity and selective index against A/H3N2 (EC50=37.03μm, SI>5), which were all higher than that of the reference drug oseltamivir (EC50>59.00μm, SI>1). However, no compound displays inhibitory activity against influenza B virus.
- Li, Zhenyu,Zhan, Peng,Naesens, Lieve,Vanderlinden, Evelien,Liu, Ailin,Du, Guanhua,De Clercq, Erik,Liu, Xinyong
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experimental part
p. 1018 - 1024
(2012/07/30)
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- Synthesis, antimicrobial evaluation, and QSAR analysis of 2-isopropyl-5-methylcyclohexanol derivatives
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A series of 2-isopropyl-5-methylcyclohexanol derivatives were synthesized and evaluated for their antibacterial activity against Gram-positive Staphylococcus aureus and Bacillus subtilis and Gram-negative Escherichia coli and in vitro antifungal activity against Candida albicans and Aspergillus niger. The results of antimicrobial activity demonstrated that the compounds 10, 20, and 21 were the most active ones among the synthesized compounds. The QSAR studies revealed the importance of dipole moment (μ), total energy (Te), and topological parameters (κ1 and κ3) in describing the antimicrobial activity of 2-isopropyl-5-methylcyclohexanol derivatives. Springer Science+Business Media, LLC 2011.
- Singh, Manjeet,Kumar, Sunil,Kumar, Ashwani,Kumar, Pradeep,Narasimhan, Balasubramanian
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experimental part
p. 511 - 522
(2012/08/07)
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- Selectivities in the reaction of vicinal diimines and acyl chlorides
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The reaction of vicinal diimines and acyl chlorides in the presence of triethylamine produces 3-imino-β-lactams and/or bis-β-lactams chemo-, regio-, and stereoselectively, which are important intermediates in pharmaceutical and organic synthesis. The selectivities in the reaction have been investigated. The results indicate that all diimines react with various ketenes generated from acyl chlorides in the presence of triethylamine to give rise to cis-4-imino-β-lactams (mono-cis-β-lactams) diastereoselectively due to the electron-withdrawing property of the imino group in the vicinal diimines. Bis-β-lactams were obtained from diimines via the mono-cis-β-lactams as intermediates. Only ketenes with strong electron-donating substituents can react with the mono-cis-β-lactams to yield bis-β-lactams, affording a pair of C2-symmetric cis-bis-β- lactams with symmetric diimines, two or four pairs of diastereomeric bis-β-lactams with ketoaldehyde-derived unsymmetric diimines depending on the steric hindrance of their N-substituents. The current investigation provides very important information for the selective preparation of mono- and bis-β-lactams from vicinal diimines.
- Wang, Zhixin,Chen, Ning,Xu, Jiaxi
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body text
p. 9690 - 9699
(2012/01/06)
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- Prediction of theoretical physicochemical properties and one-pot synthesis of bis-azetidinones by [2+2] ketene - Imine cycloaddition in the presence of montmorillonite
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A simple, highly efficient and environmentally friendly microwave accelerated one-pot synthesis of a series of differently substituted bis-azetidinones have been synthesized expeditiously in good yields from 1,2-diaminoethane and aromatic aldehydes in the presence of zeolite. The structures of the newly synthesized compounds were confirmed by IR, NMR, and mass spectra. The design and calculated molecular properties of all the reported compounds are on the basis of hypothetical antibacterial pharmacophores, which were formulated to interact with microorganisms. A correlation of structure and activity relationship of these compounds with respect to Lipinski rules and drug likeness properties of drugs are described and verified experimentally.
- Pagadala, Ramakanth,Meshram, Jyotsna S.,Chopde, Himani N.,Jetti, Venkateshwarlu,Kusampally, Uppalaiah,Udayini
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scheme or table
p. 325 - 332
(2012/05/05)
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- Novel antimalarial 3-azabicyclo[3.2.2]nonane derivatives
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The present invention relates to novel 3-azabicyclo[3.2.2]nonane derivatives of the general formula (I) or a pharmaceutically acceptable salt thereof wherein R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are as defined in the specification. The novel 3-azabicyclo[3.2.2]nonane derivatives are particularly useful for treatment and prevention of malaria and trypanosomiasis.
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- Conformational preferences for some 2-substituted N-methoxy-N- methylacetamides through spectroscopic and theoretical studies
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The analysis of the IR carbonyl band of the 2-substituted N-methoxy-N-methylacetamides Y-CH2C(O)N(OMe)Me (Y = F 1, OMe 2, OPh 3, Cl 4), supported by B3LYP/6-311++G(3df, 3pd) calculations along with the NBO analysis for 1-4, indicated the existence of cis-gauche conformers i.e. (c) and (g) for 1 and 3, (c1, c2) and (g1, g 2) for 2, and (c) and (g1, g2) for 4. In the gas phase, the g conformer population prevails over the c one, for 1 and 3, the (c1 + c2) population prevails over the (g1 + g2) one for 2, and the (g1 + g2) conformer population is more abundant than (c) one for 4. In n-hexane solution, the cis conformer is more abundant for 1-3. The occurrence of Fermi resonance in the νCO region, in n-hexane, precludes the estimative of relative populations of the (c, g1, g2) conformers for 4. The SCI-PCM calculations agree with the solvent effect on the νCO band component relative intensities for 1-3. NBO analysis showed that the n N → πco* orbital interaction is the main factor which stabilizes the gauche (g, g1, g2) conformers for 1-4 into a larger extent relative to the cis (c, c1, c2) ones. The nY → πco *, σC-Y → πco*, πco → σC-Y* and πco* → σC-Y* orbital interactions still contribute, but into a minor extent for the stabilization of the gauche conformers relative to the cis ones. The existence of some pyramidalization at the nitrogen atom of the Weinreb amides 1-4 is responsible for the occurrence of Yδ-(4)?Oδ-(9) and Y δ-(4)?Nδ-(7) short contacts in the gauche (g, g1, g2) conformers, which originates strong repulsive Coulombic interactions, acting in opposition to the large orbital stabilization of the gauche conformer with respect to the cis one. Therefore, a delicate balance of the Coulombic and orbital interactions seems to be responsible for the observed stabilization of the gauche (g, g1, g2) and cis (c, c1, c2) conformers, both in the gas phase and in the solution for 1-4. However, the cis conformer predominance, in non polar solvents, for the 2-substituted N-methoxy-N-methyl acetamides 1-3, bearing in α first raw (fluorine and oxygen) atoms, is in the opposite direction to the gauche conformer preference for the corresponding 2-substituted N,N-dialkyl-acetamides.
- Olivato, Paulo R.,Da Silva Gomes, Roberto,Rodrigues, Alessandro,Reis, Adriana K.C.A.,Domingues, Nelson L.C.,Rittner, Roberto,Dal Colle, Maurizio
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experimental part
p. 106 - 116
(2010/10/04)
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- Reactions of chloroethenes with atomic chlorine in air at atmospheric pressure
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Relative rate method at the temperature of 298 K and pressure of 1013 hPa and GC-MS detection were used for the study of kinetics of the reactions of Cl atoms with H2C=CCl2, cis-ClHC=CHCl, trans-ClHC=CHCl, ClHC=CCl2, and Cl2C=CCl2. The reaction products were identified by FTIR spectroscopy. A mechanism for the atmospheric degradation of chloro-ethenes has been suggested.
- Morozov,Nielsen,Morozova,Vasiliev,Loukhovitskaya
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experimental part
p. 754 - 760
(2011/01/09)
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- Antimalarial and antitrypanosomal activity of a series of amide and sulfonamide derivatives of a 2,5-diaminobenzophenone
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Here, we describe a series of readily obtainable benzophenone derivatives with antimalarial and antitrypanosomal activity. The most active compounds display submicromolar activity against Plasmodium falciparum. Micromolar activity is obtained against Trypanosoma brucei. Main problem of the compounds is low selectivity. However, there are indications that separation of antimalarial and cytotoxic activity might by possible. In addition, some compounds inhibit human ABC transporter with nanomolar activity.
- Altenkaemper, Mirko,Bechem, Benjamin,Perruchon, Johann,Heinrich, Swetlana,Maedel, Andrea,Ortmann, Regina,Dahse, Hans-Martin,Freunscht, Ellen,Wang, Yulin,Rath, Jennifer,Stich, August,Hitzler, Manuela,Chiba, Peter,Lanzer, Michael,Schlitzer, Martin
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experimental part
p. 7690 - 7697
(2010/03/24)
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- A matrix isolation study of the photochemically induced reactions of nitrogen dioxide with 1,2-dibromoethene and 1,2-dichloroethene using Fourier transform infrared spectroscopy
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Photolyses of matrices of either BrCHCHBr/NO2/Ar or ClCHCHCl/NO2/Ar using quartz-filtered radiation (λ > 240 nm) led to the appearance of infrared bands attributable to carbonyl, carbon monoxide, and ketene species; no bands belonging to a precursor complex NO 2...XCHCHX (where X = Br or Cl) were observed upon matrix deposition. The possible reaction pathway is discussed.
- Clark, Robin J.H.,Foley, Loraine J.
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p. 1389 - 1393
(2007/10/03)
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- Method for preparing a benzylic-type ether
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The invention concerns a method for preparing a benzylic-type ether from an aromatic compound. The inventive method for preparing a benzylic-type ether from an aromatic compound is characterised in that it consists in: in a first step, acylating an aromatic compound by reacting said aromatic compound with an acylating agent, in the presence of an efficient amount of zeolite or a Friedel-Crafts catalyst leading to a ketonic compound; in a second step, reducing the carbonyl group into carbinol leading to a benzylic alcohol; in a third step, etherifying the hydroxyl group, by reacting the benzylic alcohol with another alcohol, in the presence of an efficient amount of zeolite.
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- Process for functionalising a phenolic compound carrying an electron-donating group
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The invention concerns a method for functionalizing a phenolic compound bearing an electron-donor group, in said group para position, inter alia a method for the amidoalkylation of a phenolic compound bearing an electron-donor group, and more particularly, a phenolic compound bearing an electron-donor group preferably, in the hydroxyl group ortho position. The method for functionalizing in para position with respect to an electron-donor group carried by a phenolic compound is characterised in that the phenolic compound bearing an electron-donor group is subjected to the following steps: a first step which consists of protecting the hydroxyl group in the form of a sulphonic ester function; a second step which consists in reacting the protected phenolic compound with an electrophilic reagent; optionally, a third step deprotecting the hydroxyl group.
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- PROTECTING GROUPS WITH INCREASED PHOTOSENSITIVITIES
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Protecting groups derived from a halogenated coumarin group, a quinoline-2-one group, a xanthene group, a thioxanthene group, a selenoxanthene group, or an anthracene group are described. The protecting groups is photolabile and can be removed by irradiating the group with light, such as flash photolysis with ultraviolet radiation or pulsed infrared radiation.
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- Process facilitating the regeneration of a catalyst based on a zeolite used in an acylation reaction, catalyst and use
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The present invention relates to a process facilitating the regeneration of a catalyst based on a zeolite, employed in an acylation reaction. Another subject of the invention is a process for acylation of an aromatic ether, comprising, in a preferred alternative form, an additional stage of regeneration of the catalyst. The process of the invention, which makes it possible to regenerate more easily a catalyst based on a zeolite, employed in an acylation reaction, is characterized in that the zeolite is modified by addition of an effective quantity of at least one metallic element M chosen from the elements of group 8 of the Periodic Classification of the elements.
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- Recovery of ammonia in the dipeptide manufacturing processes
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An example of an improvement in recovering ammonia in a dipeptide manufacturing process is described. The synthetic method, which makes use of the ammonolysis reaction, has been studied and found to produce dipeptides of satisfactory quality in high yield on a large scale. However, the treatment of unreacted ammonia in the ammonolysis reaction caused a reduction in the productivity and increased the production cost during actual manufacture. Therefore, a method to recover the unreacted ammonia has been investigated through simulations and trial runs using model solutions. Consequently, the modified process provided an improvement in the productivity and cost savings. In addition, the recovered ammonia could possibly be used for recycling. It was verified in a lab experiment that the reused ammonia did not lower the quality of the dipeptide.
- Kato, Satoshi,Sano, Takahiro,Sugaya, Toru
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p. 132 - 135
(2013/09/07)
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- Aromatic compound acylation method
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A method for acylating an aromatic compound, specifically an activated or deactivated aromatic compound, is disclosed. The method is suitable for preparing aromatic ketones. The preparation of a catalyst and novel bismuth compounds is also disclosed. Said aromatic compound acylation method comprises reacting said aromatic compound with an acylating agent in the presence of a catalyst, and is characterised in that the acylation reaction is performed in the presence of an effective amount of at least one bismuth salt of trifluoromethanesulphonic acid.
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- Acylation method for an aromatic compound
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The present invention concerns a process for acylation of an aromatic compound.The acylation process of the invention consists of reacting the aromatic compound with an acylation agent in the presence of a zeolitic catalyst, and is characterized in that it consists of:mixing the aromatic compound and the acylation compound in any manner;passing said mixture over a catalytic bed comprising at least one zeolite;recirculating the reaction mixture from the catalytic bed over the catalytic bed for a number of times which is sufficient to obtain the desired degree of conversion of the substrate.
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- Kinetic and product study of the Cl-initiated oxidation of 1,2,3-trichloropropane (CH2ClCHClCH2Cl)
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The kinetics and products of the Cl atom initiated oxidation of 1,2,3-trichloropropane were studied using FTIR-smog chamber systems at (295 ± 2) K in 700-760 torr of air. The major oxidation product in terms of carbon balance was 1,3-dichloroacetone with smaller amounts of HC(O)Cl and CH2ClC(O)Cl. Chemical activation effects played a significant role in the atmospheric fate of CH2ClCHClO(·) and CH2ClCO(·)ClCH2Cl radicals. The UV-visible spectrum of CH2ClC(O)CH2Cl was measured at 270-385 nm and has a maximum at 305 nm where σ = (1.6 ± 0.2) × 10-19 sq cm/molecule (base e). Assuming a photolysis quantum yield of 1-0.04, the lifetime of CH2ClC(O)CH2Cl with respect to photolysis on a summer day of 40° latitude was 0.5-12 hr. Photolysis was likely to be the dominant atmospheric loss mechanism of CH2ClC(O)CH2Cl. The results were discussed in the context of the atmospheric chemistry of 1,2,3-trichloropropane.
- Barnes,Wallington,Inoue,Voicu,Kawasaki,Becker
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p. 5123 - 5130
(2007/10/03)
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- Process for the acylation of aromatic ethers
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The present invention concerns a process for the acylation of an aromatic ether. Preferably the invention relates to a process for the acylation of a substituted aromatic ether, in particular veratrol. The acylation process of the invention consists of reacting the ether with an acylation agent in the presence of a zeolitic catalyst, and is characterized in that the acylation reaction is carried out in the presence of an effective quantity of a catalyst comprising a faujasite type zeolite or a Y zeolite with the following physico-chemical characteristics: an atomic ratio denoted "global Si/Me1 " between the number of atoms of the element silicon and the number of atoms of every trivalent element Me1 contained in the zeolite in the range 2.4 to 90, preferably in the range 2.4 to 75, and more preferably in the range 2.4 to 60; an Me2 alkali metal content such that the atomic ratio Me2 /Me1(IV) between the number of atoms of alkali metal Me2 and the number of atoms of every trivalent element Me1(IV) included in the zeolitic network is less than 0.2, preferably less than 0.1, and more preferably less than 0.05.
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- Aromatic thioether acylation method
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PCT No. PCT/FR96/01763 Sec. 371 Date Aug. 3, 1998 Sec. 102(e) Date Aug. 3, 1998 PCT Filed Nov. 8, 1996 PCT Pub. No. WO97/17324 PCT Pub. Date May 15, 1997The present invention relates to a process for the acylation of an aromatic thioether. In its preferred variant, the invention resides in a process for the condensation of acetic anhydride or acetyl chloride with thioanisole. The process for the acylation of an aromatic thioether according to the invention is characterised in that it consists in reacting said thioether with an acylating agent chosen from the group formed by the halides of carboxylic acids and the anhydrides of carboxylic acids, in the presence of an effective quantity of an acid zeolite.
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- Process for the acylation of aromatic ethers
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The present invention concerns a process for the acylation of an aromatic ether. Preferably, the invention relates to a process for the acylation of an unsubstituted aromatic ether, in particular anisole. The acylation process of the invention consists of reacting the ether with an acylation agent in the presence of a zeolitic catalyst, and is characterized in that the acylation reaction is carried out in the presence of an effective quantity of a catalyst comprising a beta zeolite with an atomic ratio denoted "global Si/Me1 " between the number of atoms of the element silicon and the number of atoms of every trivalent element Me1 contained in the zeolite of no less than 15, preferably in the range 15 to 55, and more preferably in the range 18 to 35.
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- Atmospheric chemistry of 1,2-dichloroethane: UV spectra of CH2ClCHCl and CH2ClCHClO2 radicals, kinetics of the reactions of CH2ClCHCl radicals with O2 and CH2ClCHClO2 radicals with NO and NO2, and fate of the alkoxy radical CH2ClCHClO
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A pulse radiolysis technique was used to measure the UV absorption spectra of CH2ClCHCl and CH2ClCHClO2 radicals over the range 230-300 nm. At 250 nm, σ(CH2ClCHCl) = (1.7 ± 0.2) × 10-18 and σ(CH2ClCHClO2) = (3.5 ± 0.5) × 10-18 cm2 molecule-1. The observed self-reaction rate constant for CH2ClCHCl radicals, defined as -d[CH2ClCHCl]/dt = 2k4[CH2ClCHCl]2 was k4 = (2.0 ± 0.3) × 10-11 cm3 molecule-1 s-1. The rate constant for reaction of CH2ClCHCl radicals with O2 in one bar of SF6 diluent was (2.4 ± 0.3) × 10-12 cm3 molecule-1 s-1. The rate constants for the reactions of CH2ClCHClO2 radicals with NO and NO2 were k5 ≥ 9 × 10-12 and k6 = (9.8 ± 0.6) × 10-12 cm3 molecule-1 s-1, respectively. The rate constant for the reaction of F atoms with CH2ClCH2Cl was k3 = (2.6 ± 0.2) × 10-11 cm3 molecule-1 s-1. The reaction of CH2ClCHClO2 radicals with NO produced NO2 and, by implication, CH2ClCHClO radicals. A FTIR spectroscopic technique showed that CH2ClCHClO radicals undergo both reaction with O2 and decomposition via intramolecular 3-center HCl elimination. In 700 Torr of air at 296 K the rate constant ratio KO2/kdecomp = (2.3 ± 0.2) × 10-20 cm3 molecule-1. A lower limit of 4 × 105 s-1 was deduced for the rate of intramolecular 3-center HCl elimination from CH2ClCHClO radicals at 296 K in 1 bar of SF6 diluent. As part of this work a relative rate technique was used to measure rate constants of (1.3 ± 0.2) × 10-12 and (6.4 ± 1.4) × 10-14 cm3 molecule-1 s-1 for the reactions of Cl atoms with CH2ClCH2Cl and CH2ClC(O)Cl, respectively. All experiments were performed at 296 K. Results are discussed in the context of the atmospheric chemistry of 1,2-dichloroethane.
- Wallington, Timothy J.,Bilde, Merete,Mogelberg, Trine E.,Sehested, Jens,Nielsen, Ole J.
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p. 5751 - 5760
(2007/10/03)
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- Photooxidation of exhaust pollutants: III. Photooxidation of the chloroethenes: Degradation efficiencies, quantum yields and products
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The photochemical decomposition and oxidation of the chloroethenes C2H4-XClX (x=1-4) was investigated in the gas phase by irradiation with a low pressure mercury lamp in an oxygen atmosphere. Degradation efficiencies directly depend on the number of chlorine atoms both at 185 and 254 nm. The quantum yields for degradation increase from 2-3 for vinyl chloride to > 100 for tri- and tetrachloroethene at 185 nm in the 10-3 bar concentration range. At 254 nm we measured nearly time independent quantum yields of around 10 for tri- and 40 for tetrachloroethene. The photooxidation products and their mechanism of formation are discussed in detail.
- Guertler,Moeller,Sommer,Mueller,Kleinermanns
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p. 1671 - 1682
(2007/10/03)
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- Efficient routes to isotopically labelled epichlorohydrins ((chloromethyl) oxiranes)
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Efficient routes are developed for the synthesis of variously labelled 2H- and 13C- labelled epichlorohydrins prepared from appropriately labelled acetic acids and sodium borodeuteride. The route is versatile and can be used for strategic location of isotopes at C-I, C-2 and C-3 of epichlorohydrin. By way of demonstration [2-13C]-, [2-2H]-, [3-2H2] and [2-2H, 3-2H2]-epithlorohydrins have been prepared. In addition the syntheses can be adapted for the preparation of enantiomerically pure and isotopically labelled epichlorohydrins.
- O'Hagan,White,Jones
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p. 871 - 880
(2007/10/02)
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- Ozonides of Acyclic Olefins Having Mono- and Dichloro-Substituted Double Bonds
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Ozonolyses of acyclic olefins containing 1,2-dichloro-substituted (4a,b) and monochloro-substituted double bonds (7a, b, 12) as well as two (4a, b, 7a, b) or one halomethyl group (12) attached to the double bond afford the corresponding ozonides as the first representatives of monocyclic chlorinated ozonides.Their stability decreases in order 5a, 5b > 8a, 8b > 13. - Key Words: Ozonides/ 1,2,4-Trioxolanes, 3-chloro-, 3,5-dichloro- / Polyethylene
- Griesbaum, Karl,Schlindwein, Konrad,Hilss, Michael
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p. 1843 - 1848
(2007/10/02)
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- Equilibrium Acidities and Homolytic Bond Dissociation Energies of the Acidic C-H Bonds in N-Substituted Trimethylammonium and Pyridinium Cations
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Equilibrium acidities (pKHAs) of the cations in sixteen N-substituted trimethylammonium salts, one N-phenacylquinuclidinium salt, eight N-substituted pyridinium salts, and N-(ethoxycarbonyl)-isoquinolinium bromide, together with the oxidation potentials of their conjugate bases, have been determined in dimethyl sulfoxide (DMSO) solution.The acidifying effects of the α-trimethylammonium groups (α-Me3N+) and the α-pyridinium groups (α-PyN+) on the adjacent acidic C-H bonds in these cations were found to average about 10 and 18 pKHA units, respectively, in DMSO.The homolytic bond dissociation energies of the acidic C-H bonds in these cations, estimated by the combination of the equilibrium acidities with the oxidation potentials of their corresponding conjugate bases (ylides), show that the α-trimethylammonium groups destabilize adjacent radicals by 2-6 kcal/mol, whereas α-pyridinium groups stabilize adjacent radicals by 3-6 kcal/mol.The effects of α-pyridinium groups on the stabilization energies of the radicals derived from these cations were found to be ca. 4-10 kcal/mol smaller than those of the corresponding phenyl groups, whereas their effects on the equilibrium acidities of the cations were 5.4-13.1 pKHA units larger.The pKHA value of tetramethylammonium cation (Me4N+) was estimated by extrapolation to be about 42 in DMSO.
- Zhang, Xian-Man,Bordwell, Frederick G.,Puy, Michael Van Der,Fried, Herbert E.
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p. 3060 - 3066
(2007/10/02)
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- Synthesis and Properties of Mixed Substituted (Chloroacetyl)organylphenylphosphanes
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The mono-, di- and trichloroacetylorganylphenylphosphanes X1X2CClC(O)PPhR (3av-cz) are obtained by reaction of Me3SiPPhR (2v-z) with the azid chlorides X1X2CClC(O)Cl (1a-c).Increasing content of chlorine results in a shift of the >C=O band and the 31P signal to higher wavelengths and fields, respectively, in the IR and 31P NMR spectra of 3av-cz.Due to the centre of chirality at the phosphorus atom in the 1H NMR spectra one observes diastereotopic protons in the chloroacetyl moiety of 3av-az and of the P-adjacent CH2 protons of 3aw-cw and 3ay-cy.The magnetic inequivalence of both methyl substituents in the isopropyl groups of 3ax-cx is observable also in the 13C and 1H NMR spectra.Because of steric reasons the free rotation about the P-isopropyl axis is hindered up to 355 K.From the coalescence temperature the free activation energy ΔG* is calculated to give 74.7 kJ/mole.The degradation of the thermolabile compounds 3av-cz results in the formation of the chlorophosphanes 5v-z.Individual investigations on 3bv, 3bw and 3by indicate the formation of mono- and dichloroacetyl chloride.The appearance of ClCH2C(O)Cl proceeds via the chloroketene 4b.
- Lindner, Ekkehard,Merkle, Ralf Dieter,Mayer, Hermann August
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p. 645 - 658
(2007/10/02)
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- Process for the production of chloroacetyl chloride
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Process for the production of chloroacetyl chloride. In the process ketene is reacted with sulfuryl chloride in a solvent at a temperature of -40° to +40° C. to produce chloroacetyl chloride. Up to, and including, one mole of ketene is used per mole of sulfuryl chloride. The product contains very low levels of dichloroacetyl chloride as a contaminant.
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