354-38-1Relevant articles and documents
Method for preparing perfluorinated nitrile through gas phase catalysis
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Paragraph 0071; 0072, (2019/02/21)
The invention discloses a method for preparing perfluorinated nitrile through gas phase catalysis. The method comprises the following steps: a, in the absence of a catalyst, enabling acyl fluoride R1COF or perfluor substituted ethylene oxide Cyclo-CF2-CR2R3-O- to perform a gas phase amination reaction with an ammonia gas or a primary amine compound, to obtain amide of which a general formula is R1CONH2 or CR2R3FCONH2, wherein general formulas of R1, R2 and R3 are CnF[2n+1], CxF[2x+1], and CyF[2y+1], wherein x and y are non-negative integer sets, x+y=n, and n is a positive integer set; and b, in the presence of the catalyst, dehydrating the amide R1CONH2, to obtain the perfluorinated nitrile R1CN. The method is short in reaction route, and the perfluor substituted ethylene oxide or the acylfluoride is easily obtained. A total yield of the perfluorinated nitrile is high, and the route is easy for continuous industrialization.
Coordination or Oxidative Addition? Activation of N-H with [Tp′Rh(PMe3)]
Yuwen, Jing,Brennessel, William W.,Jones, William D.
supporting information, p. 557 - 566 (2019/01/11)
A thermal reaction of amines, anilines, and amides with Tp′Rh(PMe3)(CH3)H (1, Tp′ = tris(3,5-dimethyl-pyrazolyl)borate) is described in this report. No N-H bond cleavage was observed for reactions between ammonia or unsubstituted aliphatic amines with the reactive fragment [Tp′Rh(PMe3)]. Instead, amine coordination products (κ2-Tp′)Rh(PMe3)(NHR1R2) (R1 = H, R2 = H, nPr, iPr, octyl; R1 = R2 = Et; R1, R2: pyrrolidine) were observed, and the crystal structure of (κ2-Tp′)Rh(PMe3)(NH2iPr) is reported. No coordination products were observed when 1 was reacted with 1,1,1,3,3,3-hexafluoropropan-2-amine, anilines, and amides. Instead, the oxidative addition products (κ3-Tp′)Rh(PMe3)(NHR)H (R = CH(CF3)2, C6H5, 3,5-dimethylbenzyl, C6F5, C(O)CH3, C(O)CF3) were observed. Both RhI-N coordination products (κ2-Tp′)Rh(PMe3)(NH2CH2CF3) and RhIII N-H addition products (κ3-Tp′)Rh(PMe3)(NHCH2CF3)H were generated when 1 was reacted with 2,2,2-trifluoroethylamine. Coordination products dissociate ammonia and amines in benzene much faster than oxidative addition products eliminate anilines and amides. The relative metal-nitrogen bond energies were studied using established kinetic techniques. Analysis of the relationship between the relative M-N bond strengths and N-H bond strengths showed a linear correlation with a slope = RM-N/N-H of 0.91 (10), indicating that the Rh-N bond strength varies in direct proportion to the N-H bond strength.
Design and Synthesis of Iminosydnones for Fast Click and Release Reactions with Cycloalkynes
Riomet, Margaux,Decuypere, Elodie,Porte, Karine,Bernard, Sabrina,Plougastel, Lucie,Kolodych, Sergii,Audisio, Davide,Taran, Frédéric
supporting information, p. 8535 - 8541 (2018/05/30)
Emerging applications in the field of chemical biology are currently limited by the lack of bioorthogonal reactions allowing both removal and linkage of chemical entities on complex biomolecules. We recently discovered a novel reaction between iminosydnones and strained alkynes leading to two products resulting from ligation and fragmentation of iminosydnones under physiological conditions. We now report the synthesis of a panel of substituted iminosydnones and the structure reactivity relationship between these compounds and strained alkyne partners. This study identified the most relevant substituents, which allow to increase the rate of the transformation and to develop a bifunctional cleavable linker with improved kinetics.
Reagents and methods for direct labeling of nucleotides
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Page/Page column, (2013/06/27)
The present invention provides systems and methods for production of activatable diazo-derivatives for use in labeling nucleotides. Labeling nucleotides is accomplished by contacting a stable hydrazide derivative of a detectable moiety with an activating polymer reagent which is used to directly label the nucleotide sample. Labeling occurs on the phosphate backbone of the nucleotide which does not perturb hybridization of the labeled nucleotide with its anti-sense strand. Since the method involves direct labeling, all types of nucleotides can be labeled without prior amplification or alteration.
Direct catalytic formation of primary and tertiary amides from non-activated carboxylic acids, employing carbamates as amine source
Tinnis, Fredrik,Lundberg, Helena,Adolfsson, Hans
supporting information, p. 2531 - 2536 (2012/11/06)
The operationally simple titanium(IV)- or zirconium(IV)-catalyzed direct amidation of non-activated carboxylic acids with ammonium carbamates generates primary, and tertiary N,N-dimethyl-substituted amides in good to excellent yields. Copyright
Regio- and stereoselective methods for the conversion of (2S,3R)-β-phenylglycidic acid esters to taxoids and other enantiopure (2R,3S)-phenylisoserine esters
Afon'Kin,Kostrikin,Shumeiko,Popov,Matveev,Matvienko,Zabudkin
, p. 2149 - 2162 (2013/10/01)
A novel efficient method was proposed for the synthesis of enantiopure precursors of taxane-containing cytostatics, i.e., methyl esters of (2R,3S)- and (2S,3R)-N-benzoylphenylisoserine and similar taxoid esters. The method is based on the regio- and stereoselective hydrobromolysis of the corresponding trans-β-phenyl glycidate enatiomers, consecutive reactions of O-acylcarbamoylation of the obtained 3-bromohydrins, intramolecular cyclization to 4-phenyloxazolidin-2-one-5-carboxylic acid derivatives, and oxazolidinone ring opening.
RUTHENIUM-BASED CATALYTIC COMPLEXES AND THE USE OF SUCH COMPLEXES FOR OLEFIN METATHESIS
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, (2010/04/30)
The invention relates to all compounds of the formula (I) or (II) in which: L is a neutral ligand; X, X′ are anionic ligands; R1 and R2 are, separately, a hydrogen, a C1-C6 alkyl, a C1-C6 perhalogenoalkyl, a aldehyde, a ketone, an ester, a nitrile, an aryl, a pyridinium alkyl, an optionally substituted C5 or C6 pyridinium alkyl, perhalogenoalkyl or cyclohexyl, a Cnh2NY radical 10 with n between 1 and 6 and y an i8onic marker, or a radical having the formula: wherein R1 can be a radical of formula (Ibis) when the compound has formula (I) or of formula (IIbis) when the compound has formula (II), R3 is a C1-C6 alkyl, or a C5 or C6 cycloalkyl or a C5 or C6 aryl; R0, R4, R5, R6, R7, R8, R9, R10, R11, are, separately, a hydrogen, C1-C6 alkyl, a C1-C6 perhalogenoalkyl, or a C5 or C6 aryl; wherein R9, R10, R11 can be a heterocycle; X1 is anion. R1 and R2 can form, with the N and the C to which they are attached, a heterocycle.
Indirect grafting of acetonitrile-derived films on metallic substrates
Berisha, Avni,Combellas, Catherine,Kanoufi, Frederic,Pinson, Jean,Ustaze, Stephane,Podvorica, Fetah I.
experimental part, p. 2962 - 2969 (2011/11/12)
Strongly bonded organic films with amino groups are obtained on gold, copper, and silicon surfaces by reduction of 2,6-dimethyl benzenediazonium in acetonitrile (ACN). The sterically hindered 2,6-dimethylphenyl radical is unable to attach to the surface, but it abstracts an hydrogen atom from ACN to give the cyanomethyl radical (.CH2CN) that reacts with the surface. A spontaneous reaction is also possible on copper. The film is characterized by IR spectroscopy, scanning electron microscopy, ellipsometry, water contact angles, and cyclic voltammetry. A mechanism is elaborated that accounts for the formation, grafting of the cyanomethyl radical, and finally formation of amino multilayers.
Synthesis and antifungal activity of β mrifluoroalkyl aminovinyl ketone derivatives
Gellerman, Gary,Pariente, Natali,Zahi, Paz,Shnaiderman, Anat,Yarden, Oded
experimental part, p. 8303 - 8307 (2010/07/15)
Ten β-trifluoroalkyl aminovinyl ketone derivatives were synthesized, and their inhibitory effects on several phytopathogenic fungi, an oomycete and plants were assessed. The various compounds were fungitoxic at the 10-100 μM range, with (Z)-3-amino-4,4,4-trifluoro-1-(4-chlorophenyl)but-2-en1-one exhibiting the highest inhibitory effect on most of the test pathogens. Alternarla alternata and Neurospora crassa were the most tolerant and sensitive fungi to the compounds, respectively. We propose that (Z)-3-amino-4,4,4- trifluoro-1-phenylbut-2-en-1-one is the minimal structural requirement for a β-trifluoroalkyl aminovinyl ketone fungitoxic derivative. 2009 American Chemical Society.
Convenient one-pot synthesis of N-substituted 3-trifluoroacetyl pyrroles
Zanatta, Nilo,Wouters, Ana D.,Fantinel, Leonardo,Da Silva, Fabio M.,Barichello, Rosemário,Da Silva, Pedro E. A.,Ramos, Daniela F.,Bonacorso, Helio G.,Martins, Marcos A. P.
experimental part, p. 755 - 758 (2009/07/18)
A new one-pot strategy for the synthesis of a series of new N-substituted 3-trifluoroacetyl pyrroles is presented. These compounds were obtained by the reaction of 3-trifluoroacetyl-4,5-dihydrofuran with primary amines, which generated 1,1,1-trifluoro-3-(2-hydroxyethyl)-4-alkylaminobut-3-en-2-one intermediates. In most cases these intermediates were not stable enough to be isolated. Thus, in the same reaction vessel they were directly submitted to oxidation with PCC (Corey's reagent) to furnish 1,1,1-trifluoro-3-(2-ethanal)-4- alkylaminobut-3-en-2-ones, which under reflux underwent intramolecular cyclization to give the desired N-substituted 3-trifluoroacetyl pyrroles, in moderate yields. All of these pyrroles were tested against pan-susceptible Mycobacterium tuberculosis H37Rv and clinical isolates INH- and RMP-resistant strain and some of these compounds showed significant in vitro antimicrobial activity. Georg Thieme Verlag Stuttgart.
