- A continuous flow synthesis of [1.1.1]propellane and bicyclo[1.1.1]pentane derivatives
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A continuous flow process to generate [1.1.1]propellane on demand is presented rendering solutions of [1.1.1]propellane that can directly be derivatised into various bicyclo[1.1.1]pentane (BCP) species. This was realised in throughputs up to 8.5 mmol h-1providing an attractive and straightforward access to gram quantities of selected BCP building blocks. Lastly, a continuous photochemical transformation of [1.1.1]propellane into valuable BCPs bearing mixed ester/acyl chloride moieties was developed.
- Donnelly, Kian,Baumann, Marcus
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supporting information
p. 2871 - 2874
(2021/03/23)
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- Synthesis and application of oxalic acid monoester derivatives
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The invention relates to synthesis and application of oxalic acid monoester-containing compounds as shown in a general formula (I) which is described in the specification. The compounds represent a broad-spectrum efficient insecticidal and bactericidal agent structure type. The oxalic acid monoester-containing compounds can well control aphids, plutella xylostella and spodoptera exigua when used as novel insecticidal bactericides; the compounds can also be used for preventing and treating cucumber brown blotch, cucumber bacterial angular leaf spot, cucumber fusarium wilt, cucumber downy mildew, cucumber powdery mildew, tomato bacterial leaf spot and rice sheath blight. R in the general formula (I) is as defined in the specification.
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Paragraph 0015-0018
(2020/12/08)
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- An ultraviolet absorbent preparation method (by machine translation)
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The invention relates to an ultraviolet-absorbing agent preparation method, comprises the following steps: (1) D. amide esters intermediate synthesis: to oxalyl chloride ethyl ester and O-ethyl aniline as the raw material, the oxalyl chloride ethyl ester dissolved in a solvent, heating the stirring, then instillment neighbour ethyl aniline, after the reaction water elution solvent, to obtain D. amide esters intermediate; (2) N - (2 - ethoxy) - N' - (4 - ethyl-phenyl) - ethylenediamine amide product synthesis: in order to O-phenetidine and steps (1) obtained in the D. amide esters intermediate as raw materials, to Lewis base as catalyst, the temperature of the stirring, the reaction after 120 - 170 °C lower, boil off ethanol byproducts, cooling, is poured into the methanol stirring and dissolving, filtering out the insoluble matter, the temperature crystallization mother liquor, filtration, and dried to obtain the product. The preparation method, the process is simple, low requirements on equipment; the product has high purity, high yield, three wastes, environmental protection, low production cost, is suitable for industrial production. (by machine translation)
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Paragraph 0043-0047; 0054-0058
(2019/10/29)
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- Silver-Catalyzed Cyclization of Propargylic Amides to Oxazolines
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A ligand-accelerated effect is observed in the cyclization of propargylic amides catalyzed by bis(pyridyl)silver(I) complexes, with an unexpected reversal of electronic demand to the analogous NH addition reaction. The catalyst was found to be effective for internal alkyne substrates, offering exclusive selectivity for the 5-exo-dig product. Differences in selectivity profile between gold- and silver-catalyzed processes are highlighted and discussed.
- Wong, Valerie H. L.,White, Andrew J. P.,Hor,Hii
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supporting information
p. 3943 - 3948
(2016/01/25)
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- METABOTROPIC GLUTAMATE RECEPTORS 5 MODULATORS AND METHODS OF USE THEREOF
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Compounds that modulate GluR5 activity and methods of using the same are disclosed.
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Page/Page column 93
(2012/12/13)
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- Design, synthesis and preliminary bioactivity studies of 1,3,4-thiadiazole hydroxamic acid derivatives as novel histone deacetylase inhibitors
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Histone deacetylase (HDAC) inhibitors have emerged as a new class of anticancer agents, targeting the biological processes including cell cycle, apoptosis and differentiation. In the present study, a series of 1,3,4-thiadiazole based hydroxamic acids were developed as potent HDAC inhibitors. Some of them showed good inhibitory activity in HDAC enzyme assay and potent growth inhibition in some tumor cell lines. Among them, compound 6i (IC50 = 0.089 μM), exhibited better inhibitory effect compared with SAHA (IC50 = 0.15 μM).
- Guan, Peng,Sun, Feng'E,Hou, Xuben,Wang, Feng,Yi, Fan,Xu, Wenfang,Fang, Hao
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experimental part
p. 3865 - 3872
(2012/08/27)
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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 of 2-aminofurans and 2-unsubstituted furans via carbenoid-mediated [3 + 2] cycloaddition
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An efficient dual synthetic manifold for 2-aminofurans and 2-unsubstituted furans has been developed. The carbenoid-mediated [3 + 2] cycloaddition of copper carbenoids with enamines provides 2-amino-2,3-dihydrofurans which serve as common intermediates for both 2-aminofurans and 2-unsubstituted furans. The Royal Society of Chemistry 2012.
- Jiang, Yaojia,Khong, Vanessa Zhong Yue,Lourdusamy, Emmanuvel,Park, Cheol-Min
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experimental part
p. 3133 - 3135
(2012/05/04)
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- Synthesis and cytotoxicity of novel 2-amino-5-thiazolecarboxamide derivatives
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A series of novel 2-amino-5-thiazolecarboxamide derivatives have been designed and synthesised. All the compounds were evaluated for their antiproliferative activity against human leukaemia cancer HL 60 and K562 cell lines by standard MTT assay in vitro. Some of these compounds showed moderate cytotoxic potencies. Structure-activity relationships suggested that the piperazine moiety in the side chain of 2-amino-5-thiazolecarboxamide was associated with an increase in the cytotoxicity.
- Li, Hu,Yue, Yun,Hu, Xiao-Jun,Zhao, Sheng-Yin
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scheme or table
p. 416 - 419
(2011/10/08)
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- Stereoselective control in the Staudinger reactions involving monosubstituted ketenes with electron acceptor substituents: Experimental investigation and theoretical rationalization
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The stereoselectivity of the Staudinger reactions involving monosubstituted ketenes with electron acceptor substituents was investigated experimentally by determination of the product stereochemistry and theoretically via DFT calculations. The results indicate that imines preferentially attack the less sterically hindered exo-side of the ketenes to generate zwitterionic intermediates. Subsequently, for cyclic imines, the intermediates undergo a conrotatory ring closure directly to produce β-lactams, while for linear imines, the imine moiety of the intermediates isomerizes to more stable intermediates, which further undergo a conrotatory ring closure to afford trans-β-lactams. The steric hindrance and the isomerization, rather than the torquoelectronic effect, play crucial roles in controlling the stereoselectivity in the practical Staudinger reactions involving monosubstituted ketenes with electron acceptor substituents, although the unaccessible borylketene with a powerful electron acceptor group controls the stereoselectivity torquoelectronically, in theory.
- Qi, Hengzhen,Li, Xinyao,Xu, Jiaxi
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supporting information; experimental part
p. 2702 - 2714
(2011/05/19)
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- Design, synthesis, structure, and acaricidal/insecticidal activity of novel spirocyclic tetronic acid derivatives containing an oxalyl moiety
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A series of novel spirocyclic tetronic acid derivatives containing an oxalyl moiety was designed and synthesized via the key intermediate 3-(2,4,6-trimethyl)-2-oxo-1-oxaspiro[4.4]-decyl-3-en-4-ol. The target compounds were identified by 1H NMR and elemental analysis or high-resolution mass spectrum (HRMS). The results of bioassays indicated that most of the target compounds possessed excellent acaricidal activities against carmine spider mite larvae and eggs. Especially, diisopropylamino oxalyl compound 7g and piperidine oxalyl compound 7h were 1.4- and 2.3-fold as high as the activities of commercial Spiromesifen, respectively, against spider mite eggs. Moreover, most of the target compounds exhibited insecticidal activities against Lepidoptera pest. Interestingly, compounds containing alkylamino-substituted oxalyl moiety showed obvious selectivity between spider mite larvae and eggs because the activities against spider mite eggs of 7g and 7h were 25-fold those against spider mite larvae, whereas Spiromesifen had no significant differences in these activities. This meant that the introduction of an oxalyl moiety to spirocyclic tetronic acid might lead to novel biological activity characteristics.
- Liu, Zhihui,Lei, Qiong,Li, Yongqiang,Xiong, Lixia,Song, Haibin,Wang, Qingmin
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experimental part
p. 12543 - 12549
(2012/03/10)
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- Design, synthesis and insecticidal activities of novel N-oxalyl derivatives of neonicotinoid compound
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Ten novel neonicotinoid derivatives containing N-oxalyl groups were designed and synthesized, and their structures were characterized by 1H NMR, MS, IR, elemental analysis and single crystal X-ray diffraction analysis. The insecticidal activities of the new compounds were evaluated. The results of bioassays indicated that some of these title compounds exhibited excellent insecticidal activities.
- Zhao, Yu,Wang, Gang,Li, Yongqiang,Wang, Suhua,Li, Zhengming
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experimental part
p. 475 - 479
(2010/10/20)
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- Synthesis, crystal structure, and insecticidal activity of novel N-alkyloxyoxalyl derivatives of 2-arylpyrrole
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Two series of novel N-alkyloxyoxalyl derivatives of 2-arylpyrrole were synthesized, and their structures were characterized by 1H NMR spectroscopy, elemental analysis, and single-crystal X-ray diffraction analysis. The insecticidal activities of the new compounds were evaluated. The results of bioassays indicated that some of these title compounds exhibited excellent insecticidal activities, and their insecticidal activities against oriental armyworm, mosquito, and spider mite are comparable to those of the commercialized Chlorfenapyr.
- Zhao, Yu,Mao, Chunhui,Li, Yongqiang,Zhang, Pengxiang,Huang, Zhiqiang,Bi, Fuchun,Huang, Runqiu,Wang, Qingmin
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experimental part
p. 7326 - 7332
(2010/06/11)
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- Characterization of alkoxycarbonyl radicals by step-scan time-resolved infrared spectroscopy
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A series of alkoxycarbonyl radicals has been generated by laser flash photolysis (355 nm) of fluorenone oxime alkyl oxalates in carbon tetrachloride and characterized by time-resolved infrared spectroscopy using the step-scan technique. The alkoxycarbonyl radicals (v?C=O = 1802 cm-1 for R = ethyl) generally have a lifetime of several microseconds, decaying by reaction with the solvent to yield esters of chloroformic acid. In some cases, decarboxylation yielding alkyl radicals has also been observed. Thus, photolysis of fluorenone oxime tert-butyl oxalate results in the formation of tert-butoxycarbonyl radicals, which subsequently decay, mainly yielding CO2 and tert-butyl radicals. The benzyloxycarbonyl radical and the acetoneiminoxycarbonyl radical both decarboxylate too rapidly to be detected with our spectrometer (25 ns rise-time). Upon purging the solution with oxygen, the alkoxycarbonyl radicals were efficiently quenched, to yield alkoxycarbonylperoxy radicals (v?C=O = 1845 cm-1 for R = ethyl), which again had a lifetime of the order of several microseconds. A short-lived transient (v? = 1768 cm-1, τ ? 200 ns) is assigned as the carbonyloxy radical 4a on the basis of comparison with time-resolved UV/Vis data. A further product of the photolysis of fluorenone oxime oxalates can be tentatively assigned as the 9-fluorenylideneiminoxy radical 3 (v? = 1670 cm-1), which according to our DFT calculations should show a very intense v?C=N-O,as. = 1665 cm-1. Fluorenone oxime oxalates are compounds well suited as precursors for alkoxycarbonyl radicals, since they are easily synthesized as crystalline solids, show a convenient absorption at λ = 355 nm, and exhibit a high degree of thermal stability.
- Bucher, G?tz,Halupka, Martin,Kolano, Christoph,Schade, Olaf,Sander, Wolfram
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p. 545 - 552
(2007/10/03)
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- Reductive Addition to Electron-deficient Olefins with Trivalent Iodine Compounds
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(Diacyloxyiodo)arene was treated with electron-deficient olefins in the presence of hydrogen donor such as 1,4-cyclohexadiene to give the reductive addition products via alkyl radical through the radical decarboxylative pathway in good yields.Moreover, this system was able to generate either alkoxycarbonyl radicals or alkyl radicals with benzene, which was prepared from alcohol, oxalyl chloride, and (diacetoxyiodo)benzene via two steps, depending on reaction conditions.These radicals were also utilized for C-C bond formation with electron-deficient olefins.
- Togo, Hideo,Aoki, Masahiko,Yokoyama, Masataka
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p. 8241 - 8256
(2007/10/02)
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- Conversion of Hydroxyl Groups in Alcohols to Other Functional Groups with N-Hydroxy-2-thiopyridone, and Its Application to Dialkylamines and Thiols
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The radical decarboxylation reaction of N-alkoxyoxalyloxy-2-thiopyridone which was prepared by the reaction of alcohol, oxalyl chloride, and N-hydroxy-2-thiopyridone was studied both in the absence and presence of olefinic compounds.The same reactions with olefinic and acetylenic alcohols gave the corresponding lactone derivatives.On the other hand the unsymmetrical alkyl 2-pyridyl disulfides were obtained by the same reaction with aliphatic thiols.
- Togo, Hideo,Fujii, Misa,Yokoyama, Masataka
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- Heterocyclic aminoalkyl esters of mycophenolic acid, derivatives thereof and pharmaceutical compositions
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Heterocyclic aminoalkyl esters of mycophenolic acid, and the derivatives and pharmaceutically acceptable salts thereof, are useful as immunosuppressive agents, anti-inflammatory agents, anti-tumor agents, anti-viral agents, and anti-psoriatic agents.
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- 1-(2-Pyridinyl)piperazine Derivatives with Antianaphylactic, Antibronchospastic, and Mast Cell Stabilizing Activities
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New 1-(2-pyridinyl)piperazine derivatives were synthesized and tested as inhibitors of the reaginic passive cutaneous anaphylaxis in the rat (PCA), of the histamine-induced bronchospasm in the guinea pig, and of the rat mesenteric mast cell degranulation induced by compound 48/80.On the basis of test results, a series of N-(substituted phenyl)-ω-alkanamides were prepared.The nature of substituents at the anilide ring strongly influenced mast cell stabilizing activity, whereas it was less determining in the case of the other two tests.No clear correlation between the most common physicochemical parameters (?, ?, Vw volume) of substituents and activity could be detected.With regard to the position of substituents at the anilide ring, the rank order of potency, in the PCA and bronchoconstriction tests, was para > meta > ortho.Introduction of substituents in the 1-(2-pyridinyl)piperazinyl moiety of the N-(substituted phenyl)propanamide derivatives hardly affected activity, or the effect was deleterious.Some of the new compounds exhibited a simultaneous remarkable activity in all the three assays employed.
- Catto, Alberto,Motta, Gianni,Tajana, Alberto,Cazzulani, Pietro,Nardi, Dante,Leonardi, Amedeo
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- Reaction of Oxalyl Chloride and Alkyloxalyl Chlorides with Isocyanates and Isothiocyanates
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Alkyl and aryl isothiocyanates react with oxalyl chloride (1) on both double bonds of the heterocumulene to yield 3-alkyl- or 3-aryl-2,2-dichlorothiazolidine-4,5-diones 2.The two chlorines in these novel orthocarbonic acid derivatives are readily exchanged by alkoxy groups to yield 2,2-dialkoxythiazolidine-4,5-diones 3; hydrolysis of 2a (R=CH3) gave 3-methylthiazolidine-2,4,5-trione. 3-Substituted 5,5-dichlorooxazolidine-2,4-diones 8 and 5-chloro-5-alkoxyoxazolidine-2,4-diones 13 are obtained on reacting alkyl, aryl, and benzyl isocyanates with 1 and alkyloxalyl chloride, respectively.Structure assignment to these novel cycloadducts is based on IR, 1H NMR, and 13C NMR spectroscopic as well as X-ray crystallographic analysis.Formation of 8 and 13 is a stepwise process involving labile acyclic intermediates 7 and 12.The cyclizations to 8 and 13 take place only on the C=N bond of the isocyanate group.
- Richter, R.,Stuber, F. A.,Tucker, B.
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p. 3675 - 3681
(2007/10/02)
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- Syntheses of Aryl Glyoxylate. I. The Reaction of Alkyl Dichloro(alkoxy)acetates with Aromatics in the Presence of Lewis Acid
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Ethyl dichloro(ethoxy)acetate(1) and methyl dichloro(methoxy)acetate(2) were characterized.The reaction of 1 and 2 with aromatics in the presence of AlCl3 gave a considerable yield of aromatic α-keto ester.The aromatics included mono- and polymethylbenzene and anisol.The reaction was studied under various conditions and the results were compared with the acylation by ethoxalyl or methoxalyl chloride.The reaction mechanism was also discussed.
- Itoh, Osamu,Nagata, Takayoshi,Nomura, Isamu,Takanaga, Tetsuya,Sugita, Toshio,Ichikawa, Katsuhiko
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p. 810 - 814
(2007/10/02)
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- Process for preparing amides by reaction in presence of molecular sieve
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There is provided a process for preparing amides which comprises reacting an amine, or an amide, and an acid halide, or anhydride, in suitable molecular proportions, in an inert organic diluent, in the presence of an effective amount of a molecular sieve, until the reaction is completed, separating the molecular sieve, and recovering the amide from the organic mother liquor.
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