- A study of the IR and UV-Vis absorption cross-sections, photolysis and OH-initiated oxidation of CF3CHO and CF3CH2CHO
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Infrared and ultraviolet-visible absorption cross-sections, effective quantum yields of photolysis and OH reaction rate coefficients for CF 3CHO and CF3CH2CHO are reported. Relative rate measurements at 298(2) K and 1013(10) hPa, give k(OH + CF3CHO)/k(OH + CH3CH3) = 2.00(13), k(OH + CF3CH 2CHO)/ k(OH + CH3CH2OH) = 1.21(5) and k(OH + CF3CH2CHO)/k(OH + HC(O)OC2H5) = 3.51(9) (2σ). The effective quantum yield of photolysis was measured under pseudo-natural conditions in the European simulation chamber, Valencia, Spain (EUPHORE). Over the wavelength range 290-400 nm, the effective quantum yields of photolysis for CF3CHO and CF3CH2CHO are less than 2 × 10-2 and 4 × 10-2, respectively. The tropospheric lifetimes are estimated to be: τOH(CF3CHO) ~ 26 days; τ photol(CF3CHO) > 27 days; τOH(CF 3CH2CHO) ~ 4 days; τphotol(CF 3CH2CHO) > 15 days.
- Sellevag, Stig R.,Kelly, Tanya,Sidebottom, Howard,Nielsen, Claus J.
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Read Online
- An efficient enantioselective total synthesis of a trifluoromethyl analog of blastmycinolactol
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A novel synthetic strategy for the total synthesis of fluorinated analog of blastmycinolactol has been developed using α-pinene based alkoxyallylboration, chelation controlled diastereoselective reduction, and a single step lactonization of the 1,4-diol to the γ-lactone as key steps.
- Ramachandran, P. Veeraraghavan,Padiya, Kamlesh J.,Reddy, M. Venkat Ram,Brown, Herbert C.
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- Breslow Intermediates from a Thiazolin-2-ylidene and Fluorinated Aldehydes: XRD and Solution-Phase NMR Spectroscopic Characterization
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The first generation and X-ray diffraction (XRD) analysis of a crystalline Breslow intermediate (BI) derived from a thiazolin-2-ylidene, that is, the aromatic heterocycle present in vitamin B1, is reported. Key to success was the combined use of pentafluorobenzaldehyde and a thiazolin-2-ylidene carrying an enol-stabilizing dispersion energy donor as N-substituent. A so-called primary intermediate (PI) could be isolated in protonated form (pPI) as well and analyzed by XRD. Furthermore, the first stable BI derived from an aromatic thiazolin-2-ylidene and an aliphatic aldehyde (trifluoroacetaldehyde) was prepared and characterized by NMR spectroscopy in solution. When switching to a saturated thiazolidin-2-ylidene, reaction with pentafluorobenzaldehyde afforded a new BI in solution (NMR spectroscopy). Attempts to crystallize the latter BI resulted in the isolation of a novel thiazolidin-2-ylidene dimer that had undergone rearrangement to a hexahydro[1,4]-thiazino[3,2-b]-1,4-thiazine.
- Paul, Mathias,Neud?rfl, J?rg-M.,Berkessel, Albrecht
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- Catalytic gas phase oxidation of methanol to formaldehyde
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Two gas-phase catalytic cycles for the two-electron oxidation of primary and secondary alcohols were detected by multistage mass spectrometry experiments. A binuclear dimolybdate center [Mo2O6(OCHR2)]- acts as the catalyst in both these cycles. The first cycle proceeds via three steps: (1) reaction of [Mo2O6(OH)]- with alcohol R2HCOH and elimination of water to form [Mo2O6(OCHR2)]-; (2) oxidation of the alkoxo ligand and its elimination as aldehyde or ketone in the rate-determining step; and (3) regeneration of the catalyst via oxidation by nitromethane. Step 2 does not occur at room temperature and requires the use of collisional activation to proceed. The second cycle is similar but differs in the order of reaction with alcohol and nitromethane. The nature of each of these reactions was probed by kinetic measurements and by variation of the substrate alcohols (structure and isotope labeling). The role of the binuclear molybdenum center was assessed by examination of the relative reactivities of the mononuclear [MO3(OH)]- and binuclear [M2O6(OH)]- ions (M = Cr, Mo, W). The molybdenum and tungsten binuclear centers [M2O6(OH)]- (M = Mo, W) were reactive toward alcohol but the chromium center [Cr2O6(OH)]- was not. This is consistent with the expected order of basicity of the hydroxo ligand in these species. The chromium and molybdenum centers [M2O6(OCHR2)]- (M = Cr, Mo) oxidized the alkoxo ligand to aldehyde, while the tungsten center [W2O6(OCHR2)]- did not, instead preferring the non-redox elimination of alkene. This is consistent with the expected order of oxidizing power of the anions. Each of the mononuclear anions [MO3(OH)]- (M = Cr, Mo, W) was inert to reaction with methanol, highlighting the importance of the second MoO3 unit in these catalytic cycles. Only the dimolybdate center has the mix of properties that allow it to participate in each of the three steps of the two catalytic cycles. The three reactions of these cycles are equivalent to the three essential steps proposed to occur in the industrial oxidation of gaseous methanol to formaldehyde at 300-400°C over solid-state catalysts based upon molybdenum(VI)-trioxide. The new gas-phase catalytic data is compared with those for the heterogeneous process.
- Waters, Tom,O'Hair, Richard A. J.,Wedd, Anthony G.
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- Reaction of trifluoroacetaldehyde with some bromoesters
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Reformatsky reactions of trifluoroacetaldehyde with lower bromoesters gave their corresponding adducts.The reaction of trifluoroacetaldehyde with methyl 2-(bromomethyl)acrylate gave γ-trifluoromethyl-α-methylene-γ-butyrolactone.
- Watanabe, Shoji,Sakai, Yuji,Kitazume, Tomoya,Yamazaki, Takashi
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- Kinetic study of the reaction of chlorine and fluorine atoms with CF3CHO at 295 ± 2 K
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Using a relative rate technique the reactions of chlorine and fluorine atoms with CF3CHO have been determined to proceed with rate constants of (1.8 ± 0.4) × 10-12 and (2.7 ± 0.1) × 10-11 cm3 molecule-1 s-1, respectively. Experiments were performed as 295 ± 2 K and 700 torr total pressure of nitrogen. The results are discussed with respect to the design and interpretation of laboratory studies of the atmospheric chemistry of CFC replacements.
- Wallington,Hurley
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Read Online
- 2-(Halogenated Phenyl) acetamides and propanamides as potent TRPV1 antagonists
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A series consisting of 117 2-(halogenated phenyl) acetamide and propanamide analogs were investigated as TRPV1 antagonists. The structure–activity analysis targeting their three pharmacophoric regions indicated that halogenated phenyl A-region analogs exhibited a broad functional profile ranging from agonism to antagonism. Among the compounds, antagonists 28 and 92 exhibited potent antagonism toward capsaicin for hTRPV1 with Ki[CAP] = 2.6 and 6.9 nM, respectively. Further, antagonist 92 displayed promising analgesic activity in vivo in both phases of the formalin mouse pain model. A molecular modeling study of 92 indicated that the two fluoro groups in the A-region made hydrophobic interactions with the receptor.
- Ann, Jihyae,Bahrenberg, Gregor,Blumberg, Peter M.,Choi, Sun,Christoph, Thomas,Do, Nayeon,Frank-Foltyn, Robert,Ha, Heejin,Jeong, Jin Ju,Kang, Jin Mi,Kim, Changhoon,Kwon, Sun Ok,Lee, Jeewoo,Lee, Sunho,Lesch, Bernhard,Stockhausen, Hannelore,Vu, Thi Ngoc Lan,Yoon, Sanghee
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- PRODUCTION METHOD OF FLUORINE-CONTAINING UNSATURATED CARBOXYLIC ACID
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PROBLEM TO BE SOLVED: To provide a production method of a compound of formula (4), that is, a fluorine-containing unsaturated carboxylic acid, which is industrially preferable, economical, and environmentally friendly. SOLUTION: A production method of a compound of formula (4) includes subjecting a compound of formula (3) to a reaction in the presence of a base (here Rf is a 1-4C perfluoroalkyl). SELECTED DRAWING: None COPYRIGHT: (C)2021,JPO&INPIT
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Paragraph 0283-0286
(2021/02/11)
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- METHOD FOR OXIDATIVE CLEAVAGE OF COMPOUNDS WITH UNSATURATED DOUBLE BOND
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A method for oxidative cleavage of a compound with an unsaturated double bond is provided. The method comprises the following step: (A) providing a compound (I) with an unsaturated double bond, a reagent with trifluoromethyl, and a catalyst; wherein the catalyst is represented by the following formula (II): M(O)mL1yL2z (II); wherein, M, L1, L2, m, y, z, R1, R2 and R3 are defined in the specification; and (B) mixing the compound with an unsaturated double bond and the reagent with a trifluoromethyl to perform an oxidation of the compound with the unsaturated double bond by using the catalyst at air or an oxygen condition to get a compound presented as formula (III):
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Paragraph 0053-0056
(2021/03/19)
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- Method for oxidative cracking of compound containing unsaturated double bonds
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The invention relates to a method for oxidative cracking of a compound containing unsaturated double bonds. The method comprises the following steps: (A) providing a compound (I) containing unsaturated double bonds, a trifluoromethyl-containing reagent and a catalyst, wherein the catalyst is shown as a formula (II): M(O)mL1yL2z (II), M, L1, L2, m, y, z, R1, R2 and R3 being defined in the specification; and (B) mixing the compound containing the unsaturated double bonds and the trifluoromethyl-containing reagent, and performing an oxidative cracking reaction on the compound containing the unsaturated double bonds in the presence of air or oxygen by using the catalyst to obtain a compound represented by formula (III),.
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Paragraph 0108-0114; 0134-0136
(2021/07/09)
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- METHOD FOR OXIDATIVE CLEAVAGE OF COMPOUNDS WITH UNSATURATED DOUBLE BOND
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A method for oxidative cleavage of a compound with an unsaturated double bond is provided. The method includes the steps of: (A) providing a compound (I) with an unsaturated double bond, a trifluoromethyl-containing reagent, and a catalyst; wherein, the catalyst is represented by Formula (II): M(O)mL1yL2z??(II);wherein, M, L1, L2, m, y, z, R1, R2 and R3 are defined in the specification; and(B) mixing the compound with an unsaturated double bond and the trifluoromethyl-containing reagent to perform an oxidative cleavage of the compound with the unsaturated double bond by using the catalyst in air or under oxygen atmosphere condition to obtain a compound represented by Formula (III):
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Paragraph 0071
(2021/07/10)
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- Discovery of 1-(1H-indazol-4-yl)-3-((1-phenyl-1H-pyrazol-5-yl)methyl) ureas as potent and thermoneutral TRPV1 antagonists
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A series of 1-indazol-3-(1-phenylpyrazol-5-yl)methyl ureas were investigated as hTRPV1 antagonists. The structure–activity relationship study was conducted systematically for both the indazole A-region and the 3-trifluoromethyl/t-butyl pyrazole C-region to optimize the antagonism toward the activation by capsaicin. Among them, the antagonists 26, 50 and 51 displayed highly potent antagonism with Ki(CAP) = 0.4–0.5 nM. Further, in vivo studies in mice indicated that these derivatives both antagonized capsaicin induced hypothermia, consistent with their in vitro activity, and themselves did not induce hyperthermia. In the formalin model, 51 showed anti-nociceptive activity in a dose-dependent manner.
- Kang, Jin Mi,Kwon, Sun Ok,Ann, Jihyae,Blumberg, Peter M.,Ha, Heejin,Yoo, Young Dong,Frank-Foltyn, Robert,Lesch, Bernhard,Bahrenberg, Gregor,Stockhausen, Hannelore,Christoph, Thomas,Lee, Jeewoo
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- 2-Iodoxybenzoic acid ditriflate: The most powerful hypervalent iodine(v) oxidant
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A ditriflate derivative of 2-iodoxybenzoic acid (IBX) was prepared by the reaction of IBX with trifluoromethanesulfonic acid and characterized by single crystal X-ray crystallography. IBX-ditriflate is the most powerful oxidant in a series of structurally similar IBX derivatives which is best illustrated by its ability to readily oxidize hydrocarbons and the oxidation resistant polyfluoroalcohols.
- Yusubov, Mekhman S.,Soldatova, Natalia S.,Postnikov, Pavel S.,Valiev, Rashid R.,Yoshimura, Akira,Wirth, Thomas,Nemykin, Victor N.,Zhdankin, Viktor V.
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supporting information
p. 7760 - 7763
(2019/07/12)
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- Production Method for 1,2,2,2-Tetrafluoroethyl Difluoromethyl Ether (Desflurane)
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Fluoral is obtained by gas-phase fluorination of chloral in the presence of a catalyst and then reacted with trimethyl orthoformate, thereby readily forming 1,2,2,2-tetrafluoroethyl methyl ether as an intermediate for production of desflurane. 1,2,2,2-Tetrafluoroethyl difluoromethyl ether (desflurane) is produced with high yield from the thus-formed 1,2,2,2-tetrafluoroethyl methyl ether by chlorination and fluorination. This method enables efficient industrial-scale production of desflurane useful as an inhalation anesthetic
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Paragraph 0132-0133
(2019/11/22)
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- Ru-Catalyzed Deoxygenative Regioselective C8-H Arylation of Quinoline N-Oxides
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Regioselective C-H functionalization on quinolines is of high interest to lead to value-added products. Herein, we describe the development of Ru-catalyzed deoxygenative regioselective C8 arylation of quinoline N-oxides with arylboronic esters. Mechanistic studies revealed that it proceeds in a tandem process of arylation and then deoxygenation, wherein both steps were found to be catalytic with the ruthenium species.
- Kim, Jinwoo,Kim, Suhyeon,Kim, Dongwook,Chang, Sukbok
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supporting information
p. 13150 - 13158
(2019/08/22)
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- Chemistry of the Highly Strained Alkene Perfluorobicyclo[2.2.0]hex-1(4)-ene
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Several varieties of cycloaddition as well as nucleophilic and free radical addition to the highly reactive central bond of the title fluorocarbon (1) are described. [2 + 2] Cycloaddition to 1 has made available four of the five known representatives of the [2.2.2]propellane ring system, which are rare because of their extreme strain (in the absence of fluorine substitution) and high reactivity. Two of these, a propellanone and a propellene, are first reported here. Quantum mechanical calculations have shed light on many of these transformations.
- Junk, Christopher P.,He, Yigang,Zhang, Yin,Smith, Joshua R.,Dixon, David A.,Vasiliu, Monica,Lemal, David M.
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p. 3167 - 3179
(2018/07/06)
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- Stereodivergent synthesis of novel chiral C2-symmetric bis-trifluoromethyl-2-oxazolidinones
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A simplified effective synthetic process is described for the diastereoselective synthesis of the chiral C2-symmetric CF3-ureas (R,R)-15 and (S,S)-15 from (S)-α-phenylethylamine, glyoxal and CF3I.
- Remarchuk, Travis,Corey
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supporting information
p. 2256 - 2259
(2018/05/16)
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- Pyrazole C-region analogues of 2-(3-fluoro-4-methylsulfonylaminophenyl)propanamides as potent TRPV1 antagonists
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A series of 1-substituted 3-(t-butyl/trifluoromethyl)pyrazole C-region analogues of 2-(3-fluoro-4-methylsulfonamidophenyl)propanamides were investigated for hTRPV1 antagonism. The structure activity relationship indicated that the 3-chlorophenyl group at the 1-position of pyrazole was the optimized hydrophobic group for antagonistic potency and the activity was stereospecific to the S-configuration, providing exceptionally potent antagonists 13S and 16S with Ki(CAP) = 0.1 nM. Particularly significant, 13S exhibited antagonism selective for capsaicin and NADA and not for low pH or elevated temperature. Both compounds also proved to be very potent antagonists for rTRPV1, blocking in vivo the hypothermic action of capsaicin, consistent with their in vitro mechanism. The docking study of compounds 13S and 16S in our hTRPV1 homology model indicated that the binding modes differed somewhat, with that of 13S more closely resembling that of GRT12360.
- Lee, Sunho,Kim, Changhoon,Ann, Jihyae,Thorat, Shivaji A.,Kim, Eunhye,Park, Jongmi,Choi, Sun,Blumberg, Peter M.,Frank-Foltyn, Robert,Bahrenberg, Gregor,Stockhausen, Hannelore,Christoph, Thomas,Lee, Jeewoo
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p. 4383 - 4388
(2017/09/12)
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- Redox-based reagents for chemoselective methionine bioconjugation
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Cysteine can be specifically functionalized by a myriad of acid-base conjugation strategies for applications ranging from probing protein function to antibody-drug conjugates and proteomics. In contrast, selective ligation to the other sulfur-containing amino acid, methionine, has been precluded by its intrinsically weaker nucleophilicity. Here, we report a strategy for chemoselective methionine bioconjugation through redox reactivity, using oxaziridine-based reagents to achieve highly selective, rapid, and robust methionine labeling under a range of biocompatible reaction conditions. We highlight the broad utility of this conjugation method to enable precise addition of payloads to proteins, synthesis of antibody-drug conjugates, and identification of hyperreactive methionine residues in whole proteomes.
- Lin, Shixian,Yang, Xiaoyu,Jia, Shang,Weeks, Amy M.,Hornsby, Michael,Lee, Peter S.,Nichiporuk, Rita V.,Iavarone, Anthony T.,Wells, James A.,Toste, F. Dean,Chang, Christopher J.
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p. 597 - 602
(2017/02/19)
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- Asymmetric synthesis of propargylamines as amino acid surrogates in peptidomimetics
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The amide moiety of peptides can be replaced for example by a triazole moiety, which is considered to be bioisosteric. Therefore, the carbonyl moiety of an amino acid has to be replaced by an alkyne in order to provide a precursor of such peptidomimetics. As most amino acids have a chiral center at Cα, such amide bond surrogates need a chiral moiety. Here the asymmetric synthesis of a set of 24 N-sulfinyl propargylamines is presented. The condensation of various aldehydes with Ellman's chiral sulfinamide provides chiral N-sulfinylimines, which were reacted with (trimethylsilyl)ethynyllithium to afford diastereomerically pure N-sulfinyl propargylamines. Diverse functional groups present in the propargylic position resemble the side chain present at the Cα of amino acids. Whereas propargylamines with (cyclo)alkyl substituents can be prepared in a direct manner, residues with polar functional groups require suitable protective groups. The presence of particular functional groups in the side chain in some cases leads to remarkable side reactions of the alkyne moiety. Thus, electron-withdrawing substituents in the Cα-position facilitate a base induced rearrangement to α,β-unsaturated imines, while azide-substituted propargylamines form triazoles under surprisingly mild conditions. A panel of propargylamines bearing fluoro or chloro substituents, polar functional groups, or basic and acidic functional groups is accessible for the use as precursors of peptidomimetics.
- Wünsch, Matthias,Schr?der, David,Fr?hr, Tanja,Teichmann, Lisa,Hedwig, Sebastian,Janson, Nils,Belu, Clara,Simon, Jasmin,Heidemeyer, Shari,Holtkamp, Philipp,Rudlof, Jens,Klemme, Lennard,Hinzmann, Alessa,Neumann, Beate,Stammler, Hans-Georg,Sewald, Norbert
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supporting information
p. 2428 - 2441
(2017/12/06)
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- 1-Bromo-3,3,3-trifluoro-1-nitropropene: Synthesis and reaction with phenyl azide
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An improved procedure was developed for the synthesis of 3,3,3-trifluoro-1-nitropropene, and a new representative of gem-bromonitroalkenes, 1-bromo-3,3,3-trifluoro-1-nitropropene, was synthesized therefrom. Its reaction with phenyl azide gave a mixture of two regioisomeric 1,2,3-triazoles, from which pure 5-nitro-1-phenyl-4-(trifluoromethyl)-1H-1,2,3-triazole was isolated.
- Anisimova,Slobodchikova,Kuzhaeva,Stukan’,Bagryanskaya, I. Yu.,Berestovitskaya
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p. 1379 - 1384
(2016/11/29)
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- ISOINDOLINE INHIBITORS OF ROR-GAMMA
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Provided are novel compounds of Formula (I): pharmaceutically acceptable salts thereof, and pharmaceutical compositions thereof, which are useful in the treatment of diseases and disorders mediated by RORγ. Also provided are pharmaceutical compositions comprising the novel compounds of Formula (I) and methods for their use in treating one or more inflammatory, metabolic, autoimmune and other diseases or disorders.
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Paragraph 0374
(2016/06/01)
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- Laccase-Mediator System for Alcohol Oxidation to Carbonyls or Carboxylic Acids: Toward a Sustainable Synthesis of Profens
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By combining two green and efficient catalysts, such as the commercially available enzyme laccase from Trametes versicolor and the stable free radical 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), the oxidation in water of some primary alcohols to the corresponding carboxylic acids or aldehydes and of selected secondary alcohols to ketones can be accomplished. The range of applicability of bio-oxidation is widened by applying the optimized protocol to the oxidation of enantiomerically pure 2-arylpropanols (profenols) into the corresponding 2-arylpropionic acids (profens), in high yields and with complete retention of configuration.
- Galletti, Paola,Pori, Matteo,Funiciello, Federica,Soldati, Roberto,Ballardini, Alberto,Giacomini, Daria
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p. 2684 - 2689
(2016/12/23)
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- SUBSTITUTED HETEROAROMATIC PYRAZOLE-CONTAINING CARBOXAMIDE AND UREA DERIVATIVES AS VANILLOID RECEPTOR LIGANDS
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The invention relates to substituted heteroaromatic pyrazole-containing carboxamide and urea derivatives as vanilloid receptor ligands, to pharmaceutical compositions containing these compounds and also to these compounds for use in the treatment and/or prophylaxis of pain and further diseases and/or disorders.
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Page/Page column 106
(2013/03/26)
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- Substituted Heteroaromatic Pyrazole-Containing Carboxamide and Urea Compounds as Vanilloid Receptor Ligands
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Substituted heteroaromatic pyrazole-containing carboxamide and urea compounds as vanilloid receptor ligands, pharmaceutical compositions containing these compounds and also to a method of using these compounds for treating and/or inhibiting pain and further diseases and/or disorders.
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Paragraph 0678
(2013/03/26)
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- SUBSTITUTED PYRAZOLYL-BASED CARBOXAMIDE AND UREA DERIVATIVES BEARING A PHENYL MOIETY SUBSTITUTED WITH AN N-CYCLIC GROUP AS VANILLOID RECEPTOR LIGANDS
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The invention relates to substituted pyrazolyl-based carboxamide and urea derivatives bearing a phenyl moiety substituted with an N-cyclic group as vanilloid receptor ligands formula (S) to pharmaceutical compositions containing these compounds of the general formula (S) and also to these compounds for use in the treatment and/or prophylaxis of pain and further diseases and/or disorders.
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Page/Page column 48
(2013/05/23)
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- SUBSTITUTED PYRAZOLYL-BASED CARBOXAMIDE AND UREA DERIVATIVES BEARING A PHENYL MOIETY SUBSTITUTED WITH AN O-CONTAINING GROUP AS VANILLOID RECEPTOR LIGANDS
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The invention relates to substituted pyrazolyl-based carboxamide and urea derivatives of formula (Q) as vanilloid receptor ligands, to pharmaceutical compositions containing these compounds and also to these compounds for use in the treatment and/or prophylaxis of pain and further diseases and/or disorders.
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Page/Page column 69
(2013/05/23)
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- SUBSTITUTED PYRAZOLYL-BASED CARBOXAMIDE AND UREA DERIVATIVES BEARING A PHENYL MOIETY SUBSTITUTED WITH A CO-CONTAINING GROUP AS VANILLOID RECEPTOR LIGANDS
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The invention relates to substituted pyrazolyl-based carboxamide and urea derivatives bearing a phenyl moiety substituted with a CO-containing group as vanilloid receptor ligands, to pharmaceutical compositions containing these compounds and also to these compounds for use in the treatment and/or prophylaxis of pain and further diseases and/or disorders.
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Page/Page column 50
(2013/05/23)
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- SUBSTITUTED PYRAZOLYL-BASED CARBOXAMIDE AND UREA DERIVATIVES BEARING A PHENYL MOIETY SUBSTITUTED WITH AN SO2-CONTAINING GROUP AS VANILLOID RECEPTOR LIGANDS
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The invention relates to substituted pyrazolyl-based carboxamide and urea derivatives bearing a phenyl moiety substituted with a S02-containing group as vanilloid receptor ligands, to pharmaceutical compositions containing these compounds and also to these compounds for use in the treatment and/or prophylaxis of pain and further diseases and/or disorders.
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Page/Page column 50
(2013/05/23)
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- SUBSTITUTED PYRAZOLYL-BASED CARBOXAMIDE AND UREA DERIVATIVES BEARING A PHENYL MOIETY SUBSTITUTED WITH AN N-CONTAINING GROUP AS VANILLOID RECEPTOR LIGANDS
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The invention relates to substituted pyrazolyl-based carboxamide and urea derivatives of formula (R) bearing a phenyl moiety substituted with an N-containing group as vanilloid receptor ligands, to pharmaceutical compositions containing these compounds and also to these compounds for use in the treatment and/or prophylaxis of pain and further diseases and/or disorders.
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Page/Page column 58
(2013/05/23)
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- Substituted Cyclic Carboxamide and Urea Derivatives as Ligands of the Vanilloid Receptor
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Substituted cyclic carboxamide and urea compounds, a process for their preparation, pharmaceutical compositions containing these compounds, and the use of these compounds for the treatment and/or inhibition of pain and other conditions mediated by the vanilloid receptor 1.
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Page/Page column 29
(2012/03/10)
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- Substituted Heteroaromatic Carboxamide and Urea Compounds as Vanilloid Receptor Ligands
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Substituted heteroaromatic carboxamide and urea compounds corresponding to formula (i) processes for the preparation thereof, pharmaceutical compositions containing these compounds and also a method of using these compounds in pharmaceutical compositions for treating or inhibiting pain and other conditions mediated at least in part via the vanilloid receptor 1.
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Page/Page column 34
(2012/05/20)
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- SUBSTITUTED BICYCLIC CARBOXAMIDE AND UREA DERIVATIVES AS VANILLOID RECEPTOR LIGANDS
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The invention relates to substituted bicyclic carboxamide and urea derivatives, to processes for the preparation thereof, to pharmaceutical compositions containing these compounds and also to the use of these compounds for preparing pharmaceutical compositions.
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Page/Page column 74
(2012/05/31)
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- SUBSTITUTED HETEROAROMATIC CARBOXAMIDE AND UREA DERIVATIVES AS VANILLOID RECEPTOR LIGANDS
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The invention relates to substituted heteroaromatic carboxamide and urea derivatives of formula (I), to processes for the preparation thereof, to pharmaceutical compositions containing these compounds and also to the use of these compounds for preparing pharmaceutical compositions.
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Page/Page column 75
(2012/05/31)
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- Substituted Bicyclic Carboxamide and Urea Compounds as Vanilloid Receptor Ligands
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Substituted bicyclic carboxamide and urea compounds corresponding to formula (I) processes for the preparation thereof, pharmaceutical compositions containing these compounds, and a method of using these compounds for the treatment and/or inhibition of pain and other conditions mediated at least in part via the vanilloid receptor 1.
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Page/Page column 29-30
(2012/05/20)
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- Atmospheric chemistry of t-CF3CHCHCl: Products and mechanisms of the gas-phase reactions with chlorine atoms and hydroxyl radicals
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FTIR-smog chamber techniques were used to study the products and mechanisms of the Cl atom and OH radical initiated oxidation of trans-3,3,3-trifluoro-1- chloro-propene, t-CF3CHCHCl, in 700 Torr of air or N 2/O2 diluent at 296 ± 2 K. The reactions of Cl atoms and OH radicals with t-CF3CHCHCl occur via addition to the CC double bond; chlorine atoms add 15 ± 5% at the terminal carbon and 85 ± 5% at the central carbon, OH radicals add approximately 40% at the terminal carbon and 60% at the central carbon. The major products in the Cl atom initiated oxidation of t-CF3CHCHCl were CF3CHClCHO and CF3C(O)CHCl2, minor products were CF3CHO, HCOCl and CF3COCl. The yields of CF3C(O)CHCl2, CF3CHClCOCl and CF3COCl increased at the expense of CF3CHO, HCOCl and CF3CHClCHO as the O2 partial pressure was increased over the range 10-700 Torr. Chemical activation plays a significant role in the fate of CF3CH(O)CHCl2 and CF 3CClHCHClO radicals. In addition to reaction with O2 to yield CF3COCl and HO2 the major competing fate of CF 3CHClO is Cl elimination to give CF3CHO (not C-C bond scission as previously thought). As part of this study k(Cl + CF 3C(O)CHCl2) = (2.3 ± 0.3) × 10-14 and k(Cl + CF3CHClCHO) = (7.5 ± 2.0) × 10-12 cm3 molecule-1 s-1 were determined using relative rate techniques. Reaction with OH radicals is the major atmospheric sink for t-CF3CHCHCl. Chlorine atom elimination giving the enol CF3CHCHOH appears to be the sole atmospheric fate of the CF 3CHCHClOH radicals. The yield of CF3COOH in the atmospheric oxidation of t-CF3CHCHCl will be negligible (3CHCHCl. the Owner Societies 2012.
- Andersen, M. P. Sulbaek,Nielsen,Hurley,Wallington
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experimental part
p. 1735 - 1748
(2012/04/23)
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- Simple synthesis of β-trifluoromethylstyrenes using (E)-trimethyl-(3,3,3-trifluoroprop-1-enyl)silane
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(E)-Trimethyl-(3,3,3-trifluoroprop-1-enyl)silane (1) was synthesized as a reagent for use in Hiyama cross-coupling reactions for the production of β-trifluoromethylstyrene derivatives. Cross-coupling of 1 with electronically diverse aryl iodides was achieved by treatment with CsF in the presence of catalytic amounts of palladium to afford the desired products in moderate to good yields.
- Omote, Masaaki,Tanaka, Miyuu,Ikeda, Akari,Nomura, Shiho,Tarui, Atsushi,Sato, Kazuyuki,Ando, Akira
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supporting information; experimental part
p. 2286 - 2289
(2012/06/04)
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- UV absorption cross sections between 230 and 350 nm and pressure dependence of the photolysis quantum yield at 308 nm of CF3CH2CHO
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Ultraviolet (UV) absorption cross sections of CF3CH 2CHO were determined between 230 and 350 nm by gas-phase UV spectroscopy. The forbidden n → π* transition was characterized as a function of temperature (269-323 K). In addition, the photochemical degradation of CF3CH2CHO was investigated at 308 nm. The possible photolysis channels are: CF3CH2 + HCO (R1a), CF3CH3 + CO (R1b), and CF3CH2CO + H (R1c). Photolysis quantum yields of CF3CH2CHO at 308 nm, Φλ=308nm, were measured as a function of pressure (25-760 Torr of synthetic air). The pressure dependence of Φ λ=308nm can be expressed as the following Stern-Volmer equation: 1/Φλ=308nm = (4.65 ± 0.56) + (1.51 ± 0.04) × 10-18 [M] ([M] in molecule cm-3). Using the absorption cross sections and the photolysis quantum yields reported here, the photolysis rate coefficient of this fluorinated aldehyde throughout the troposphere was estimated. This calculation shows that tropospheric photolysis of CF3CH2CHO is competitive with the removal initiated by OH radicals at low altitudes, but it can be the major degradation route at higher altitudes. Photodegradation products (CO, HC(O)OH, CF 3CHO, CF3CH2OH, and F2CO) were identified and also quantified by Fourier transform infrared spectroscopy. CF3CH2C(O)OH was identified as an end-product as a result of the chemistry involving CF3CH2CO radicals formed in the OH + CF3CH2CHO reaction. In the presence of an OH-scavenger (cyclohexane), CF3CH2C(O)OH was not detected, indicating that channel (R1c) is negligible. Based on a proposed mechanism, our results provide strong evidences of the significant participation of the radical-forming channel (R1a).
- Antinolo, Maria,Jimenez, Elena,Albaladejo, Jose
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experimental part
p. 15936 - 15946
(2012/02/02)
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- SUBSTITUTED AROMATIC CARBOXAMIDE AND UREA DERIVATIVES AS VANILLOID RECEPTOR LIGANDS
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The invention relates to substituted aromatic carboxamide and urea derivatives, to processes for the preparation thereof, to pharmaceutical compositions containing these compounds and also to the use of these compounds for preparing pharmaceutical compositions (formula (I)).
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Page/Page column 97; 98
(2010/11/18)
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- SUBSTITUTED PHENYLLUREAS AND PHENYLAMIDES AS VANILLOID RECEPTOR LIGANDS
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The invention relates to substituted phenylureas and phenylamides of formula (I), to processes for the preparation thereof, to pharmaceutical compositions containing these compounds and also to the use of these compounds for preparing pharmaceutical compositions.
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Page/Page column 80; 81
(2010/11/18)
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- Fused ring compound and use thereof
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The present invention provides a compound represented by the formula: wherein the symbols are as described in the specification, or a salt thereof, which is useful for preventing/treating eicosanoid-associated diseases such as atherosclerosis, diabetes, obesity, atherothrombosis, asthma, fever, pain, cancer, rheumatism, osteoarthritis and atopic dermatitis, and which has an excellent pharmacological action, physicochemical properties, etc.
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Page/Page column 44
(2010/08/07)
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- Substituted benzimidazoles and methods of preparation
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Methods for preparing new substituted benzimidazole compounds having formula (I) useful for treating kinase mediated disorders are provided wherein R1, R2, R3, R4, a, b, and c are defined herein
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Page/Page column 19
(2008/06/13)
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- Microwave-assisted preparation of trifluoroacetaldehyde (fluoral): isolation and applications
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A novel method for the preparation of trifluoroacetaldehyde (fluoral, TFAc, CF3CHO) from commercially available trifluoroacetaldehyde ethylhemiacetal (TFAE) by microwave irradiation is described. The isolation, characterization and reaction of fluoral with various nucleophiles were studied to verify the diverse applicability of this new method.
- Landge, Shainaz M.,Borkin, Dmitry A.,T?r?k, Béla
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p. 6372 - 6376
(2008/02/12)
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- A kinetic and mechanistic study of the reactions of OH radicals and Cl atoms with 3,3,3-trifluoropropanol under atmospheric conditions
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Product distribution studies of the OH radical and Cl atom initiated oxidation of CF3CH2CH2OH in air at 1 atm and 298 ± 5 K have been carried out in laboratory and outdoor atmospheric simulation chambers in the presence and absence of NOx. The results show that CF3CH2CHO is the only primary product and that the aldehyde is fairly rapidly removed from the system. In the absence of NOx the major degradation product of CF3CH2CHO is CF3CHO, and the combined yields of the two aldehydes formed from CF3CH2CH2OH are close to unity (0.95 ± 0.05). In the presence of NOx small amounts of CF3CH 2C(O)O2NO2 were also observed (3CHO is removed from the system to give mainly CF2O. The laser photolysis-laser induced fluorescence technique was used to determine values of k(OH + CF3CH 2CH2OH) = (0.89 ± 0.03) × 10-12 and k(OH + CF3CH2HO) = (2.96 ± 0.04) × 10-12 cm3 molecule-1 s-1. A relative rate method has been employed to measure the rate coefficients k(OH + CF3CH2CH2OH) = (1.08 ± 0.05) × 10-12, k(OH + C6F13CH2CH 2OH) = (0.79 ± 0.08) × 10-12, k(Cl + CF 3CH2CH2OH) = (22.4 ± 0.4) × 10-12, and k(Cl + CF3CH2CHO) = (25.7 ± 0.4) × 10-12 cm3 molecule-1 s -1. The results from this investigation are discussed in terms of the possible importance of emissions of fluorinated alcohols as a source of fluorinated carboxylic acids in the environment.
- Kelly, Tanya,Bossoutrot, Valerie,Magneron, Isabelle,Wirtz, Klaus,Treacy, Jack,Mellouki, Abdelwahid,Sidebottom, Howard,Bras, Georges Le
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p. 347 - 355
(2007/10/03)
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- Atmospheric chemistry of fluorinated alcohols: Reaction with Cl atoms and OH radicals and atmospheric lifetimes
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Relative rate techniques were used to study the kinetics of the reactions of Cl atoms and OH radicals with a series of fluorinated alcohols, F(CF2)nCH2OH (n = 1-4), in 700 Torr of N2 or air diluent at 296 ± 2 K. The length of the F(CF2)n group had no discernible impact on the reactivity of the molecule. For n = 1-4, k(Cl + F(CF2)nCH2OH) = (6.48 ± 0.53) × 10-13 and k(OH + F(CF2)nCH2OH) = (1.02 ± 0.10) × 10-13 cm3 molecule-1 s-1. Product studies of the chlorine initiated oxidation of F(CF2)nCH2OH (n = 1-4) in the absence of NO show the sole primary product to be the corresponding aldehyde, F(CF2)nC(O)H. Consideration of the likely rates of other possible atmospheric loss mechanisms leads to the conclusion that the atmospheric lifetime of F(CF2)nCH2OH (n ≥ 1) is determined by reaction with OH radicals and is approximately 164 days.
- Hurley,Wallington,Sulbaek Andersen,Ellis,Martin,Mabury
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p. 1973 - 1979
(2007/10/03)
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- Gas phase UV and IR absorption spectra of CxF2x+1CHO (x = 1-4)
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The UV and IR spectra of CxF2x +1CHO (x = 1-4) were investigated using computational and experimental techniques. CxF2x+1CHO (x = 1-4) have broad UV absorption features centered at 300-310 nm. The maximum absorption cross-section increases significantly and shifts slightly to the red with increased length of the CxF2x+1 group: CF3CHO, 3.10 × 10-20 (300 nm); C 2F5CHO, 6.25 × 10-20 (308 nm); C 3F7CHO, 8.96 × 10-20 (309 nm); and C 4F9CHO, 10.9 × 10-20 (309 nm). IR spectra for CxF2x+1CHO were recorded, calculated, and assigned. Results are discussed with respect to the literature data and to the atmospheric fate of CxF2x+1CHO.
- Hashikawa,Kawasaki,Waterland,Hurley,Ball,Wallington,Andersen, M.P. Sulbaek,Nielsen
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p. 1925 - 1932
(2007/10/03)
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- Indole, azaindole and related heterocyclic amidopiperazine derivatives
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This invention provides compounds having drug and bio-affecting properties, their pharmaceutical compositions and method of use. In particular, the invention is concerned with amido piperazine derivatives. These compounds possess unique antiviral activity, whether used alone or in combination with other antivirals, antiinfectives, immunomodulators or HIV entry inhibitors. More particularly, the present invention relates to the treatment of HIV and AIDS.
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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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- METHOD OF MAKING HYDROFLUOROCARBONS
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A method of producing hydrofluorocarbons and methods of producing other commercially attractive compounds formed as by-products of hydrofluorocarbon production by using aldehydes as a principal reactant.
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- Study of fluorocarbonyls for the Baylis-Hillman reaction
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A study of the effect of fluorine substitution in Baylis-Hillman reactions of various fluorocarbonyl partners with acrolein, methyl vinyl ketone, ethyl acrylate, and acrylonitrile has been made.
- Venkat,Reddy, Ram,Rudd, Michael T.,Ramachandran, P. Veeraraghavan
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p. 5382 - 5385
(2007/10/03)
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- Convenient synthesis of α-trifluoromethyl amines via aminofluoroalkylation of arenes with N-trimethylsilyl α-trifluoroacetaldehyde hemiaminal
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Aminofluoroalkylation of various heteroarenes or substituted benzenes with the N-trimethylsilyl hemiaminals, prepared from 1,1,1,3,3,3-hexamethyldisilazane and gaseous trifluoroacetaldehyde, smoothly underwent at room temperature in the presence of a Lewis acid. [(1-Aryl-2,2,2-trifluoro)ethyl]amines or bis[(1-aryl-2,2,2-trifluoro)ethyl]amines were afforded in moderate to high yields.
- Gong, Yuefa,Kato, Katsuya
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p. 103 - 107
(2007/10/03)
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- Organofluorine compounds and fluorinating agents, Part 26: New reversed nucleosides - Perfluoroalkyl substituted 1,2,3-triazoles linked to D-galactose and D-altrose
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Reversed nucleosides, i.e., fluoroalkyl-substituted 1,2,3-triazoles linked to the C-atom 6 of D-galactose and D-altrose were synthesised by 1,3-dipolar cycloadditions using the monosaccharide azides 8, 11 and the perfluoroalkyl substituted phenyl vinyl sulfones 5-7. The starting material 11, methyl 6-azido-3,4-O-(trichloroethylidene)-2-O-cyclohexylcarbamoyl-6-deoxy-α-D- altropyranoside, was synthesized from methyl 2-O-cyclohexylcarbamoyl-3,4-O-(2,2,2-trichloroethylidene)-α-D- altropyranoside (9), via its 6-iododeoxy derivative 10. The homologous dipolarophiles 5-7, (E)-1-perfluoroalkyl-2-phenylsulfonyl-ethenes with a CF3 (5), n-C4F9 (6), and n-C6F13 (7) group, respectively, were obtained by Wittig-Horner olefination from phosphonate 4 and the corresponding perfluoroalkanals 1-3. Cycloaddition of 6-azido-6-deoxy-1,2:3,4-di-O-isopropylidene-α-D-galactose (8) with the dipolarophiles 5-7 yielded the reversed nucleosides 12-14; altrose azide 11 gave the reversed nucleosides 15 and 16. The products of cycloaddition were deprotected using usual techniques. Thus, the 1-(6-deoxy-1,2:3,4-di-O-isopropylidene-α-D-galactopyranoso-6-yl)-4- perfluoroalkyl-1,2,3-triazoles 13 and 14 were deacetalated by treatment with aqueous trifluoroacetic acid yielding the corresponding 1-(6-deoxy-α-D-galactopyranoso-6-yl)-4-perfluoroalkyl-1,2,3-triazoles 17 and 18. The deprotection of the 1-[methyl 2-O-cyclohexylcarbamoyl-6-deoxy-3,4-O-(2,2,2-trichloroethylidene)-α-D- altropyranosido-6-yl]-4-perfluoroalkyl-1,2,3-triazoles 15 and 16 was made stepwise (hydrodechlorination→deacetalation→decarbamoylation), i.e., the 1-(methyl 6-deoxy-D-altropyranosido-6-yl)-4-perfluoroalkyl-1,2,3-triazoles 23 and 24 were synthesised via the ethylidene acetals 19, 20 and the 1-(methyl 2-O-cyclohexylcarbamoyl-6-deoxy-α-D-altropyranosido-6-yl)-4- perfluoroalkyl-1,2,3-triazoles 21 and 22. For the methyl 6-azido-2-O-cyclohexylcarbamoyl-6-deoxy-3,4-O-(2,2,2-trichloroethylidene)- α-D-altropyranoside (11) an X-ray structure is given.
- Hager, Christian,Miethchen, Ralf,Reinke, Helmut
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p. 135 - 142
(2007/10/03)
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