- Synthesis of N-trifluoromethyl amides from carboxylic acids
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Found in biomolecules, pharmaceuticals, and agrochemicals, amide-containing molecules are ubiquitous in nature, and their derivatization represents a significant methodological goal in fluorine chemistry. Trifluoromethyl amides have emerged as important functional groups frequently found in pharmaceutical compounds. To date, there is no strategy for synthesizing N-trifluoromethyl amides from abundant organic carboxylic acid derivatives, which are ideal starting materials in amide synthesis. Here, we report the synthesis of N-trifluoromethyl amides from carboxylic acid halides and esters under mild conditions via isothiocyanates in the presence of silver fluoride at room temperature. Through this strategy, isothiocyanates are desulfurized with AgF, and then the formed derivative is acylated to afford N-trifluoromethyl amides, including previously inaccessible structures. This method shows broad scope, provides a platform for rapidly generating N-trifluoromethyl amides by virtue of the diversity and availability of both reaction partners, and should find application in the modification of advanced intermediates.
- Flavell, Robert R.,Liu, Jianbo,Parker, Matthew F. L.,Toste, F. Dean,Wang, Sinan,Wilson, David M.
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supporting information
p. 2245 - 2255
(2021/08/12)
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- Versatile Cp*Co(III)(LX) Catalyst System for Selective Intramolecular C-H Amidation Reactions
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Herein, we report the development of a tailored cobalt catalyst system of Cp*Co(III)(LX) toward intramolecular C-H nitrene insertion of azidoformates to afford cyclic carbamates. The cobalt complexes were easy to prepare and bench-stable, thus offering a convenient reaction protocol. The catalytic reactivity was significantly improved by the electronic tuning of the bidentate LX ligands, and the observed regioselectivity was rationalized by the conformational analysis and DFT calculations of the transition states. The superior performance of the newly developed cobalt catalyst system could be broadly applied to both C(sp2)-H and C(sp3)-H carbamation reactions under mild conditions.
- Chang, Sukbok,Jung, Hoimin,Kim, Dongwook,Lee, Jeonghyo,Lee, Jia,Park, Juhyeon
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supporting information
p. 12324 - 12332
(2020/08/06)
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- In vitro radical scavenging and cytotoxic activities of novel hybrid selenocarbamates
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Novel selenocyanate and diselenide derivatives containing a carbamate moiety were synthesised and evaluated in vitro to determine their cytotoxic and radical scavenging properties. Cytotoxic activity was tested against a panel of human cell lines including CCRF-CEM (lymphoblastic leukaemia), HT-29 (colon carcinoma), HTB-54 (lung carcinoma), PC-3 (prostate carcinoma), MCF-7 (breast adenocarcinoma), 184B5 (non-malignant, mammary gland derived) and BEAS-2B (non-malignant, derived from bronchial epithelium). Most of the compounds displayed high antiproliferative activity with GI50 values below 10 μM in MCF-7, CCRF-CEM and PC-3 cells. Radical scavenging properties of the new selenocompounds were confirmed testing their ability to scavenge DPPH and ABTS radicals. Based on the activity of selenium-based glutathione peroxidases (GPxs), compounds 1a, 2e and 2h were further screened for their capacity to reduce hydrogen peroxide under thiol presence. Results suggest that compound 1a mimics GPxs activity. Cytotoxic parameters, radical scavenging activity and ADME profile point to 1a as promising drug candidate.
- Romano, Beatriz,Plano, Daniel,Encío, Ignacio,Palop, Juan Antonio,Sanmartín, Carmen
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p. 1716 - 1727
(2015/03/30)
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- 1-(Hydroxyacetyl)pyrene a new fluorescent phototrigger for cell imaging and caging of alcohols, phenol and adenosine
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1-(Hydroxyacetyl)pyrene has been introduced as a new fluorescent phototrigger for alcohols and phenols. Alcohols and phenols were protected as their corresponding carbonate esters by coupling with fluorescent phototrigger, 1-(hydroxyacetyl)pyrene. Photophysical studies of caged carbonates showed that they all exhibited strong fluorescence properties. Irradiation of the caged carbonates by visible light (≥410 nm) in aqueous acetonitrile released the corresponding alcohols or phenols in high chemical (95-97%) and quantum (0.17-0.21) yields. The mechanism for the photorelease was proposed based on Stern-Volmer quenching experiments and solvent effect studies. Importantly, 1-(hydroxyacetyl)pyrene showed as a phototrigger for rapid photorelease of the biologically active molecule adenosine. In vitro biological studies revealed that 1-(hydroxyacetyl)pyrene has good biocompatibility, cellular uptake property and cell imaging ability. The Royal Society of Chemistry and Owner Societies 2012.
- Jana, Avijit,Saha, Biswajit,Ikbal, Mohammed,Ghosh, Sudip Kumar,Singh, N. D. Pradeep
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p. 1558 - 1566
(2013/02/26)
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- CARBONIC ACID ESTER AND MAGNETIC RECORDING MEDIUM
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A carbonic acid ester is provided that is represented by the formula below and has a melting point of no greater than 0° C. (In the formula, R1 and R2 independently denote a saturated hydrocarbon group, R1 is a branched chain, and R2 is a straight or branched chain). There is also provided a magnetic recording medium that includes a non-magnetic support and, above the support, at least one magnetic layer including a ferromagnetic powder dispersed in a binder, the magnetic layer including the carbonic acid ester. Furthermore, there is provided a magnetic recording medium including a support and, above the support, a non-magnetic layer including a non-magnetic powder dispersed in a binder, and above the non-magnetic layer, at least one magnetic layer including a ferromagnetic powder dispersed in a binder, the non-magnetic layer and/or the magnetic layer including the carbonic acid ester.
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- Tricyclic triazolobenzazepine derivatives, process for producing the same, and antiallergic
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Tricyclic triazolobenzazepine derivatives in the form or a prodrug are provided. The compounds according to the present invention are those represented by formula (I) and pharmacologically acceptable salts and solvates thereof. The compounds are useful as antiallergic agents and exhibit excellent bioavailability. wherein R1 represents hydrogen, OH, alkyl or phenyl alkyl,R2, R3, R4, and R5 represent hydrogen, halogen, optionally protected hydroxyl, formyl, optionally substituted alkyl, alkenyl, alkoxy or the like, andQ represents a group selected from the following groups (i) to (iv), halogen, or alkoxy:
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- Derivatives of imidazole, their preparation process, the new intermediates obtained, their use as medicaments and the pharmaceutical compositions containing them
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The invention relates to the products of formula (I): STR1 in which: R1 =represents hydrogen, aryl, arylcarbonyl, arylthio, alkylcarbonyl, R2, R3 represent in particular halogen, mercapto, acyl, carboxy, nitro, cyano, amino, carbamoyl, R4, --OR4 with R4 representing in particular hydrogen, alkyl, alkenyl, alkynyl, acyl, amino, --(CH2)m1 --S(O)m2 --X--R10 with m1=0 to 4, m2=0 to 2, X represents a single bond or --NH--, --NH--CO--, --NH--CO--NH--, and R10 represents alkyl, alkenyl or aryl, and Y represents optionally substituted aryl, these products being in all isomer forms and salts, their use as medicaments.
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- Heteroaryl-oxazolidinones
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The invention relates to novel heteroaryl-oxazolidinones of the general formula (I): STR1 in which the substituents are as defined in the description, to processes for their preparation and to their use as drugs, especially as antibacterial drugs.
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- Compositions for reducing abnormal stimulation of endothelin receptors and novel compounds
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The invention relates to the new use and the new products of formula (I): STR1 in which: R1 =represents hydroxyl, alkyl, alkenyl, alkynyl, alkoxy, alkylthio, formyl, cycloalkyl, optionally interrupted by heteroatoms, R2, R3 represent in particular halogen, mercapto, acyl, carboxy, nitro, cyano, amino, carbamoyl, R4, --OR4 with R4 representing in particular hydrogen, alkyl, alkenyl, alkynyl, acyl, amino, --(CH2)m1 --S(O)m2 --X--R10 with m1=0 to 4, m2=0 to 2, X represents a single bond or --NH--, --NH--CO--, --NH--CO--NH--, and R10 represents alkyl, alkenyl or aryl, and Y represents optionally substituted aryl, these products being in all the isomer forms and the salts, as medicaments.
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- Imidazopyridines as pharmaceutical agents
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Described herein are novel imidazopyridine derivatives of the formula I STR1 wherein R is STR2 and R1, R2, R3 and R4 are as defined in Patent Claim 1, and their salts, which exhibit antagonistic properties towards angiotensin II and can be used for the treatment of hypertension, aldosteronism, cardiac insufficiency and increased intraocular pressure, and of disorders of the central nervous system.
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- AMINO ACID DERIVATIVES, PHARMACEUTICAL COMPOSITIONS CONTAINING THESE COMPOUNDS AND THEIR USE IN THE TREATMENT OF OBESITY
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Amino acid derivatives, suitable for the treatment of obesity. The following compound is exemplary of the class: (R)-N2-(diphenylacetyl)-N-[(4-hydroxyphenyl) methyl]-argininamide-acetate.
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- (Aryltelluro)formates as precursors of alkyl radicals: Thermolysis and photolysis of primary and secondary alkyl (aryltelluro)formates
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Alkyl (aryltelluro)formates are effective precursors of oxyacyl, methyl, and primary and secondary alkyl radicals. At room temperature, irradiation of a benzene solution of methyl (aryltelluro)-formates 10-12, 2-methylpropyl (aryltelluro)formates 14 and 15, octyl (phenyltelluro)formate (17), cyclohexyl (aryltelluro)formates 19 and 20, 3β-cholestanyl (aryltelluro)formates 22 and 23, cholesteryl (phenyltelluro)formate (24) and benzyl (phenyltelluro)formate (27) with a 250-W low-pressure mercury lamp leads to the formation of oxyacyl radicals (34), which can be trapped by diphenyl diselenide to give the corresponding alkyl (phenylseleno)formates 13, 16, 18, 21, 24, 26, and 28 with excellent overall conversions. Thermolysis of these telluroformates at 160 °C in the dark leads to the formation of methyl and primary and secondary alkyl aryl tellurides 36-43 in excellent yields. Presumably, these transformations involve oxyacyl radicals, which undergo subsequent decarboxylation at the elevated temperature to afford alkyl radicals, which become involved in further radical chemistry. When 1-(benzylseleno)-5-hexyl (phenyltelluro)formate (44) was thermolysed under these conditions, 2-methylselenane (45) was observed as the sole selenium-containing product, demonstrating the synthetic utility of (aryltelluro)formates as alkyl radical precursors.
- Lucas, Mathew A.,Schiesser, Carl H.
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p. 5754 - 5761
(2007/10/03)
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- Heat-sensitive recording materials and phenol compounds
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Heat-sensitive recording materials contain an electron-donating chromogenic compound and an electron-attracting compound. The recording materials also contain at least one compound represented by the following formula: STR1 wherein R1 and R3 mean a hydrogen atom or an alkyl, aralkyl or aryl group, R2 and R4 denote an alkyl, alkenyl, aralkyl or aryl group, X1, X2, Y1 and Y2 stand for an oxygen or a sulfur atom, and --Z1 -- and --Z2 -- are a specific aromatic group. Also provided are phenol compounds represented by the following formula: STR2 wherein R1, R2, X1 and Y1 have the same meanings as defined above; R5 and R6 are a hydrogen or halogen atom or an alkyl, alkoxy, aralkyl, aryl or hydroxyl group; p and q stand for an integer of 1-4; R5 and R6 may be either the same or different when p and q represent an integer of 2 or greater; and --Z3 -- means a specific divalent group.
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- KINETICS AND MECHANISM OF THE PHOSGENATION OF ALIPHATIC ALCOHOLS II. EFFECT OF THE SOLVENT ON THE REACTION RATE
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A quantitative analysis of the effect of the characteristics of the medium on the phosgenation rate of alcohols was made by means of the parameters of the Koppel-Palm equation.An equation is proposed which describes the effect of the solvent on the reaction rate and which takes account of the interdependence of the components of nonspecific and specific solvation.The applicability of the proposed equation to other solvolytic reactions was demonstrated.An equation is obtained which makes it possible to asses the phosgenation rate of alcohols in relation to the properties of the medium and the structure of the alcohol.
- Chimishkyan, A. L.,Orlov, S. I.,Elinevskii, A. V.,Grabarnik, M. S.,Shebeko, S. M.
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- Human interferon-related peptides, antigens, antibodies and process for preparing the same
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Human interferons related peptides and derivatives thereof, antigens, antibodies prepared therefrom, immobilized antibodies to be used for affinity chromatography, and novel method for assaying human interferons by using said affinity chromatography.
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- KINETICS AND MECHANISM OF PHOSGENATION OF ALIPHATIC ALCOHOLS
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The kinetics of the reaction of phosgene with various aliphatic alcohols were investigated in heptane and dioxane and without a solvent.The effects of the polarity of the medium the structure of the alcohol, and the activation parameters of the process are consistent with an addition-elimination mechanism.
- Orlov, S. I.,Chimishkyan, A. L.,Grabarnik, M. S.
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p. 1977 - 1981
(2007/10/02)
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- Analgesic compounds
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Compounds of the formula STR1 and pharmaceutically acceptable non-toxic acid addition salts thereof, in which L and D, when applicable, define the chirality; R1 is hydrogen, C1 -C3 primary alkyl, or allyl; R2 is hydrogen or C1 -C3 primary alkyl, subject to the limitation that when R1 is allyl, R2 is hydrogen; R3 is hydrogen or C1 -C3 primary alkyl; R4 is C1 -C4 primary or secondary alkyl; R5 is hydrogen or C1 -C4 primary or secondary alkyl; R6 is hydrogen or C1 -C3 primary alkyl; R7 is hydrogen or C1 -C3 primary alkyl; Y is hydrogen or acetyl; Z is hydrogen of STR2 in which R8 is C1 -C3 alkyl or hydrogen; and W is isopropyl, --VR9, or --CH2 --X--CH3, in which V is O or S, R9 is C1 -C4 alkyl or aralkyl, and X is O, S, or --CH2 --, subject to the limitation that, when W is isopropyl, R7 is C1 -C3 primary alkyl; are useful analgesic agents.
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- Novel penicillin compounds and process for preparation thereof
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A penicillin compound of the formula STR1 wherein R is a formyl or acetyl group, and a nontoxic pharmaceutically acceptable salt thereof. The penicillin compound is prepared by (A) reacting a compound of the formula STR2 or its salt or its reactive derivative at the carboxyl group, with 6-α-amino-p-hydroxybenzylpenicillin or its salt or its derivative, or reacting a compound of the formula STR3 or its salt or its reactive derivative at the carboxyl group, with 6-aminopenicillanic acid or its salt or its derivative, (B) optionally hydrolyzing or catalytically hydrogenolyzing the reaction product, and (C) optionally converting the reaction product to a nontoxic pharmaceutically acceptable salt. The penicillin compound has low toxicity and superior antibacterial activity especially against bacteria of the genus Pseudomonas and is suitable for parenteral administration, especially for an intramuscular, intravenous or subcutaneous injection.
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