- Selenoxide elimination triggers enamine hydrolysis to primary and secondary amines: A combined experimental and theoretical investigation
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We discuss a novel selenium-based reaction mechanism consisting in a selenoxide elimination-triggered enamine hydrolysis. This one-pot model reaction was studied for a set of substrates. Under oxidative conditions, we observed and characterized the formation of primary and secondary amines as elimination products of such compounds, paving the way for a novel strategy to selectively release bioactive molecules. The underlying mechanism was investigated using NMR, mass spectrometry and density functional theory (DFT).
- Bortoli, Marco,Gianoncelli, Alessandra,Ongaro, Alberto,Orian, Laura,Oselladore, Erika,Ribaudo, Giovanni,Zagotto, Giuseppe
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- Secondary amine salt catalyzed controlled activation of 2-deoxy sugar lactols towards alpha-selective dehydrative glycosylation
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A new organocatalytic glycosylation method exploiting the lactol functionality has been disclosed. The catalytic generation of glycosyl oxacarbenium ions from lactols under forcible conditions via weakly Br?nsted-acidic, readily available secondary amine salts affects the diastereoselective glycosylation of 2-deoxypyranoses and furanoses. This operationally simple iminium catalyzed activation of 2-deoxy hemi-acetals is a potential alternative to the existing cumbersome methods that need specialized handling. The mechanisms for this unique transformation and kinetic/thermodynamic effects have been discussed based on both experimental evidence and theoretical studies.
- Ghosh, Titli,Mukherji, Ananya,Srivastava, Hemant Kumar,Kancharla, Pavan K.
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supporting information
p. 2870 - 2875
(2018/05/03)
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- Direct Preparation of Amides from Amine Hydrochloride Salts and Orthoesters: A Synthetic and Mechanistic Perspective
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The conversion of a wide range of primary and secondary aliphatic and a few arylamine hydrochloride salts to their corresponding acetamides with trimethyl orthoacetate is described. Mechanistic studies using NMR and gas chromatography-mass spectrometry techniques indicate these reactions proceed via an O-methylimidate intermediate that undergoes in situ demethylation by chloride, affording the corresponding acetamides. Synthetically, this reaction represents a practical, high-yielding protocol with a simple workup for the rapid conversion of amine hydrochloride salts to acetamides.
- Di Grandi, Martin J.,Bennett, Caitlin,Cagino, Kristen,Muccini, Arnold,Suraci, Corey,Saba, Shahrokh
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supporting information
p. 2601 - 2607
(2015/11/28)
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- 4-Hydroxyphenacyl Ammonium Salts: A Photoremovable Protecting Group for Amines in Aqueous Solutions
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Irradiation of N-protected p-hydroxyphenacyl (pHP) ammonium caged derivatives at 313 nm releases primary and secondary amines or ammonia in nearly quantitative yields via the photo-Favorskii reaction when conducted in acidic or neutral aqueous buffered media. The reaction efficiencies are strongly dependent on the pH with the most efficient and highest yields obtained when the pH of the media maintains the ammonium and p-hydroxyl groups as their conjugate acids. For example, the overall quantum yields of simple secondary amines release are 0.5 at acidic pH from 3.9 to 6.6 dropping to 0.1 at neutral pH 7.0 and 0.01 at pH 8.4. Speciation studies provide an acid-base profile that helps define the scope and limitations of the reaction. When the pKa of the ammonium group is lower than that of the phenolic hydroxyl group, as is the case for the α-amino-protected amino acids, the more acidic ammonium ion deprotonates as the media pH is changed from acidic toward neutral or basic, thus diminishing the leaving group ability of the amino group. This, in turn, lowers the propensity for the photo-Favorskii rearrangement reaction to occur and opens the reaction pathway to alternative competing photoreduction process.
- Bownik, Iwona,?ebej, Peter,Literák, Jaromír,Heger, Dominik,?imek, Zdeněk,Givens, Richard S.,Klán, Petr
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p. 9713 - 9721
(2015/10/12)
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- Nucleophilic substitution reaction at the nitrogen of arylsulfonamides with phosphide anion
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A novel nucleophilic substitution reaction at the nitrogen of arylsulfonamides by means of phosphide anions has been described. This reaction allows for the efficient transformation of arylsulfonamides into synthetically valuable phosphamides, amines, and a variety of protected amines.
- Yoshida, Suguru,Igawa, Kazunobu,Tomooka, Katsuhiko
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supporting information
p. 19358 - 19361
(2013/02/22)
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- ORGANOARSENIC COMPOUNDS AND METHODS FOR THE TREATMENT OF CANCER
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A method for treating a lymphoma selected from non-Hodgkin's and Hodgkin's lymphoma comprising administering an organoarsenic compound having a structure of the formula (I) wherein X is S or Se and R1 and R2 are independently C1-30alkyl(R3, R3′, R4, R5, W and “n” are as defined in claim 1) in particular where the compound is S-dimethylarsinoglutathione, N-(2-S-dimethylarsinothiopropionyl)glycine, 2-amino-3-(dimethylarsino)thio-3-methylbutanoic acid, S-dimethylarsino-thiosuccinic acid or S-dipropylarsino-1-thioglycerol.
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- Hydrosiloxane-Ti(OiPr)4: An efficient system for the reduction of primary amides into primary amines as their hydrochloride salts
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A simple and useful method for the reduction of primary amides into the corresponding amines using a polymethylhydrosiloxane (PMHS)-Ti(OiPr)4 reducing system is described. Aromatic as well as aliphatic primary amides are reduced in high selectivity and excellent yields. The reduction could proceed via dehydration of the primary amide group into the corresponding nitrile which is then reduced into the corresponding primary amine.
- Laval, Stéphane,Dayoub, Wissam,Pehlivan, Leyla,Métay, Estelle,Favre-Réguillon, Alain,Delbrayelle, Dominique,Mignani, Gérard,Lemaire, Marc
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experimental part
p. 4072 - 4075
(2011/09/12)
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- 1,4-BIS-DIPHOSPHINES, 1,4-BIS-DIPHOSPHITES AND 1,4-BIS- DIPHOSPHONITES FROM OPTICALLY ACTIVE (Z)-OLEFINES AS CHIRAL LIGANDS
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Chiral diphosphines, diphosphinites, diphosphites and diphosphonites derived from (Z)-2-butenes suitable to act as chiral ligands, complexes between said diphosphines, diphosphinites, diphosphites and diphosphonites and transition metals, and their utilization as chiral catalysts in stereocontrolled reactions, such as diastereo- and enantioselective reduction reactions, diastereo- and enantioselective hydroformylation reactions, diastereo- and enantioselective hydro cyanation reactions. Process for the preparation of said chiral diphosphines, diphosphinites, diphosphites and diphosphonites and process for the preparation of said complexes and for their utilization in stereocontrolled reactions.
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Page/Page column 21; 23
(2008/06/13)
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- Processes for the preparation of Gabapentin
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The present invention relates to new processes for the preparation of gabapentin by the desilylation of a silylated gabapentin or by the silylation-desilylation of an acid addition salt of gabapentin with a silylating agent.
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Page/Page column 3-4
(2008/06/13)
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- AMINO CYCLOBUTYLAMIDE MODULATORS OF CHEMOKINE RECEPTOR ACTIVITY
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The present invention is directed to compounds of the formulas I and II : wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R15, R16, R17, R18, R19, R25, R26, Y, Z, l, m, n and the broken lines are as defined herein which are useful as modulators of chemokine receptor activity. In particular, these compounds are useful as modulators of the chemokine receptor CCR-2.
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- Reactions of N,N′-dialkylcyclohexane-1,2-diimines with trivalent phosphorus acid chlorides
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N,N′-Dialkylcyclohexane-1,2-diimines react with trivalent phosphorus acid chlorides to give, depending on the structure of the organophosphorus reagent and reaction conditions, either 1,3,2-diazaphospholanes (three-coordinate phosphorus) containing the cy
- Lodochnikov,Gryaznova,Gryaznov,Musin,Kibardin
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p. 437 - 442
(2007/10/03)
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- 1,2,3,4-Tetrahydroquinolines as substrates for Mannich compounds
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The product of the reaction of 1,2,3,4-tetrahydroquinoline (1) with 2-naphthol (2) and formaldehyde reported as the N-substituted tetrahydroquinoline 3 shows really the structure of the phenylogous bis-substituted tetrahydroquinoline 4. The function of 1, 6-methyl-1,2,3,4-tetrahydroquinoline (9) and 1-methyl-1,2,3,4-tetrahydroquinoline (17) as amines or C-nucleophilic compounds in Mannich condensations were examined.
- Moehrle,Tot,Ruediger
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p. 742 - 752
(2007/10/03)
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- Cycloadditions of nitrile oxides to amidoximes. A general synthesis of 3,5-disubstituted 1,2,4-oxadiazole-4-oxides
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The cycloaddition of nitrile oxides to amidoximes is a general method for the synthesis of 3,5-disubstituted 1,2,4-oxadiazole-4-oxides with the same or different substituents. The yields are only moderate since an equivalent amount of the nitrile oxide is consumed by reaction with the amine released in the fragmentation of the primary cycloadducts and reforms the amidoxime. With excess nitrile oxides the 1,2,4-oxadiazole-4-oxides undergo a disproportionation reaction to yield nitroso carbonyl intermediates and 1,2,4-oxadiazoles.
- Quadrelli, Paolo,Invernizzi, Anna Gamba,Falzoni, Mario,Caramella, Pierluigi
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p. 1787 - 1796
(2007/10/03)
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- Reaktionen koordinierter Liganden V. Pentacarbonylhalogenaminophosphinkomplexe (CO)5MPRXNR'2 durch Umsetzung von (CO)5MPR(NR'2)2 mit Halogenwasserstoff
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Aminophosphines RP(NR'2)2 (R = Ph, cyclo-Hex, (-)-Men, t-Bu; R' = Me, Et) as ligands L in complexes (CO)5ML (M = Cr, Mo, W) have been found to react with HX (X = Cl, Br) mainly under substitution of only one of the two dialkylamino groups by halogen.Under similar conditions the free phosphines are converted into the dihalogenphosphines.The halogenamino complexes (CO)5MPRXNR'2 are readily accessible by this reaction, the mechanism of which is discussed.The preparation of several new compounds RP(NR'2)2 is reported.
- Diemert, K.,Kuchen, W.,Lorenzen, D.
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- 2-Alkyl-3-benzoylbenzofurans useful for treating cardiac arrhythmia
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New 2-alkyl-3-[4-(omega-N,N-dialkylaminoacylamino)-3,5-dialkylbenzoyl]benzofurans useful for treating cardiac arrhythmia, as well as pharmaceutical compositions containing these benzofurans and the method of treating cardiac arrhythmia therewith are disclosed.
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- Dinuclear homo- and heterometallic rhodium complexes containing PMe2 and PPh2 groups as bridging ligands. The crystal and molecular structure of [(C5Me5Rh)2(μ-PMe2)(μ-PPh 2)]
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The reaction of [C5Me5Rh(PMe2H)Cl2] (4), which is prepared from [C5Me5RhCl2]2 (2) and PMe2H, with excess diethylamine, produces a mixture of [C5Me5(Cl)Rh(μ-PMe2)]2 (6), [C5Me5Rh(PMe2NEt2)Cl2] (7), and [C5Me5Rh(μ-PMe2)]2 (9). 7 reacts with HF (in pyridine) and with HCl (in benzene) to form the complexes [C5Me5Rh(PMe2F)Cl2] (8) and [C5Me5Rh(PMe2Cl)Cl2] (10), respectively, the latter of which is reduced with sodium amalgam to give 9. Compound 9 is also obtained by reduction of 6 with Na-Hg. Treatment of [C5Me5Rh(PPh2H)Cl2] (11) with excess NEt2H leads to the formation of [C5Me5Rh(μ-PPh2)]2 (13) and [(C5Me5Rh)2(μ-PPh2)(μ-Cl)] (14). The structurally related complexes [(C5Me5Rh)2(μ-PMe2)(μ-PPh 2)] (15) and [(C5Me5Rh)2(μ-PPh2)(μ-SMe)] (16) have been prepared from 14 by bridge-ligand exchange. The crystal and molecular structure of 15 have been determined. For C34H46P2Rh2 (15): triclinic, P1; a = 10.053 (3), b = 11.271 (4), c = 16.761 (4) A?; α = 93.32 (2)°, β= 85.78 (2)°, γ = 116.45 (2)°; V = 1694.8 (6) A?3; Z = 4; for 4938 observed reflections, RF = 3.39%. 15 contains a folded butterfly Rh2P2 core with a 111.5 (2)° core dihedral angle and a Rh-Rh bond of 2.7952 (4) A?. The synthesis of the dinuclear homo- and heterometallic complexes [C5Me5Rh(μ-PMe2)2MC 5H5] (17, M = Rh; 18, M = Co) and [C5Me5Rh(μ-PMe2)2RuC 6H6] (19) has been achieved starting from [C5Me5Rh(PMe2H)2], CH3Li, and [C5H5M(CO)I2] or [C6H6RuCl2]2, respectively.
- Werner, Helmut,Klingert, Bernd,Rheingold, Arnold L.
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p. 911 - 917
(2008/10/08)
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- Synthesis and Reactivity of N,N-Dialkylcarbamato Complexes of Manganese(II). Crystal and Molecular Structure of , a Hexamer with Four Five-co-ordinated Manganese(II) Atoms
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The compounds n> (R = Me, Et, or Pri) have been prepared by treating (cp = η5-C5H5) with CO2-NHR2 in organic solvents.These reactions may possibly involve the addition compound .NHR2.In the case of R =Et, the adduct has been isolated and characterized, and the space group, crystal data, and metal connectivity established.The structure of the N,N-diethylcarbamato complex has been solved by X-ray diffraction.Crystal data: monoclinic, space group C2/c, a = 18.546(3), b = 19.287(3), c = 24.877(3) Angstroem, β = 95.38(2) deg, R = 0.078.It consists of hexameric units , containing four five-co-ordinated Mn atoms, joined by bridging carbamato ligands.It was found to be unreactive towards nucleophiles, while by reaction with 2> the new complex has been obtained.Organic electrophiles react regioselectively at the oxygen or at the nitrogen atom of the carbamato ligand of the manganese complexes, and in the former case the CO2 fragment is retained in the reaction products.
- Belforte, Antonio,Calderazzo, Fausto,Zanazzi, Pier Francesco
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p. 2921 - 2926
(2007/10/02)
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- REACTIONS OF N-POLYFLUOROPHENYLCARBONIMIDOYL DICHLORIDES WITH PRIMARY AND SECONDARY AMINES. KINETICS AND MECHANISM. SYNTHESIS OF POLYFLUORINATED CABODIIMIDES, CHLOROFORMAMIDINES, GUANIDINES AND BENZIMIDAZOLES
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The reactions of N-polyfluorophenylcarbonimidoyl dichlorides with primary and secondary aliphatic and aromatic amines have been studied.With primary aliphatic amines, the reactions led to carbodiimides or guanidines, depending on the amount of amine.The carbodiimides obtained reacted with amines to form guanidines.The reactions with primary aromatic amines produced only triarylguanidines.N-Pentafluorophenylcarbonimidoyl dichloride (I) reacted with tetrafluoro-o-phenylene diamine to give 2-pentafluoroanilino-4,5,6,7-tetrafluorobenzimidazole.Polyfluorinated benzimidazole derivatives were also produced by the thermolysis of polyfluorinated triarylguanidines.Heating of N1,N2,N3-tris(pentafluorophenyl)guanidine with K2CO3 in dimethylformamide led to 1,2,3,4,7,8,9,10-octafluoro-5-pentafluorophenyl-5H-benzimidazobenzimidazole.N-Polyfluorophenylcarbonimidoyl dichlorides reacted with various secondary amines alredy at room temperature giving N-polyfluorophenylchloroformamidines in high yields.Elevated temperature and prolonged reaction time led to formation of N-polyfluorophenylguanidines.Kinetics and mechanism of the reactions of N-polyfluorophenylcarbonimidoyl dichlorides with primary and secondary amines in acetonitrile at 25 deg C have been studied.The reactions have been found to proceed by a bimolecular nucleophilic addition-elimination mechanism via a tetrahedral intermediate.Possible reasons of formation of different products in the above transformations are discussed in terms of this mechanism.
- Kolesnikova, I. V.,Petrova, T. D.,Platonov, V.E.,Mikhailov, V. A.,Popov, A. A.,Savelova, V.A.
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p. 217 - 246
(2007/10/02)
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- Aminoalkyl hydantoins and glycidyl derivatives thereof
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Novel aminoalkyl hydantoins and glycidyl derivatives thereof are prepared from previously unknown 3-(amidoalkyl) hydantoins.
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- Selective preparation of N-(amidoalkyl)imides and related compounds
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Prepare N-(amidoalkyl)imides by contacting an imide with a 2-oxazoline under reaction conditions, optionally in the presence of a solvent.
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- ZUR KENNTNIS DER ORGANOPHOSPHORVERBINDUNGEN XXIII. UEBER ALKENYLSUBSTITUIERTE AMINO-BZW. HALOGENPHOSPHANE UND VERSUCHE ZUM INTRAMOLEKULAREN PHOSPHINIDENABFANG
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Aminophosphanes RP(NEt2)2 and R2P(NEt2), obtained from alkenyl Grignard compounds RMgX (R = -CH=CH2, -CH2CH=CH2, o-(CH2=CH)C6H4-, o-(CH2=CHCH2)C6H4-) and aminochlorophosphanes, reacted smoothly with hydrogen halide to give alkenylhalogenophosphanes RPX2 and R2PX (X = Cl, Br).Properties and reactions of some of these compounds, e.g. with S8, H2O2, H2O and LiAlH4 are reported.On reaction of RPX2 with magnesium only alkenylcyclophosphanes (RP)n were obtained while heterocycles as possible products of an intramolecular reaction of intermediately formed phosphinidenes were not observed.
- Diemert, Klaus,Kottwitz, Beatrix,Kuchen, Wilhelm
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p. 307 - 320
(2007/10/02)
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- NMR STUDIES OF P-N BOND ROTATION IN SOME PHOSPHORUS(III) AND PHOSPHORUS(V) COMPOUNDS CONTAINING A DIETHYLAMINO GROUP
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Compounds of the type R'P(X)NEt2 (R'=But, OCH(CF3)2; X=F, OCH(CF3)2, Cl) and ButP(Y)(X)NET2 Y=S, Se; X=F, OCH(CF3)2, Cl) were synthesised and investigated in solution by variable temperature NMR spectroscopy.Barriers to rotation about the P-N bond are essentially determined by steric factors and increase with increasing size of the substituents on the phosphorus atom.
- Dakternieks, Dainis,Di Giacomo, Robert
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p. 217 - 224
(2007/10/02)
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- Lithiation of α-Nitrosaminoalkyl Ethers. Synthetic Equivalents of α-Primary Amino Carbanions
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Successful experiments directed toward the C-1 alkylation and hydroxyalkylation of primary amines are reported.Primary amines are converted into their N-nitroso-N-(1-methoxyethyl) derivatives, which are subsequently lithiated and condensed with various electrophiles, denitrosated, and hydrolyzed to produce the desired compounds in good to excellent yields.
- Saavedra, Joseph E.
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p. 2388 - 2392
(2007/10/02)
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- Reactions of Monoprotic Thioureas with Ethyl α-Chloroacetoacetate, Ethyl Bromomalonate, and Ethyl Bromocyanoacetate
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N,N,-Dialkyl-N'-arylthioureas (1) with ethyl α-chloroacetoacetate, furnished dialkylamine hydrochlorides, aryl isothiocyanates, 2-arylimino-1,3-oxathioles (2), 2-arylimino-3-aryl Δ4-thiazolines (3), diarylthioureas (9), and carbonyl sulphide.With ethyl bromomalonate the products were dialkylamine hydrobromides, aryl isothiocyanates, 2-arylimino-3-arylthiazolidin-4-ones (11), and diarylthioureas (9).Ethyl bromocyanoacetate gave an ethyl cyanothio>acetate (13).Compound (13) with triethylamine gave the starting thiourea (1) and diethyl dicyanofumarate.
- Singh, Harjit,Ahuja, Amarjit S.,Malhotra, Nageshwar
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p. 653 - 656
(2007/10/02)
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- Tetranuclear dialkyl dithiophosphate complexes of molybdenum(V) with nitride ligands
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The syntheses of the tetranuclear, ferromagnetic compounds [MoN(S2P(OR)2)2]4 (R = CH3 and C2H5) are described along with their unusual dissociative and chemical stabilities. The compound with R = CH3 crystallizes in the monoclinic space group A2/a with a = 18.632 (8) ?, b = 24.384 (12) ?, c = 12.600 (5) ?, β = 92.16 (1)°, and Z = 4 at -163°C. The structure was solved by direct methods (LSAM) using 3813 unique reflections with F > 2.33σ(F). Final residuals were R(F) = 0.082 and Rw(F) = 0.075. The chiral molecule contains a nearly square and planar [MoN]4 ring in which all bond distances are identical within experimental error. This portion of the structure contrasts markedly with the alternating triple and single bonds found in the [MoN]4 rings in the lattice of MoNCl3, and the differences in the structures are substantiated by the disparate values of ν(MoN). Explanations for the ferromagnetism are given in terms of a superexchange mechanism and molecular orbital theory.
- Noble, Mark E.,Folting, Kirsten,Huffman,Wentworth
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p. 3772 - 3776
(2008/10/08)
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- PHOSPHORIC, PHOSPHONIC, AND PHOSPHINIC ACID AMIDES AS BASES
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Potentiometric titration in nitromethane, IR- and NMR-spectroscopy were used to study the processes of protonation and H-bonding for a number of phosphoric, phosphonic and phosphinic acid amides. 12N)nP(O)R23-n(R1=Me, Et; R2=EtO, Me, Et; n=1-3) including 1,3,2-dioxa-, 1,3,2-oxazaphospholane and phosphorinane derivatives>.It was shown that in these compounds the center of the highest basicity is the oxygen of the phosphoryl group.
- Matrosov, E. I.,Kryuchkov, E. E.,Nifantyev, E. E.,Kozachenko, A. G.,Kabachnik, M. I.
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- A DIRECT REDUCTIVE DEAMINATION OF AMIDINES WITH SODIUM BOROHYDRIDE. FORMATION OF DEAMINATED COMPOUNDS AND SECONDARY AMINES
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The reaction of 3-substituted-4-amino-1H-1,5-benzodiazepines (1a, b) with sodium borohydride afforded deaminated compounds (4a, b and 6a, b).On the other hand, acyclic amidines were converted by treatment with sodium borohydride to the corresponding secondary amines (13) under the same conditions.Keywords: 1,5-benzodiazepines; deamination; amidines; mass analysis; IR; absorption of cyano group; N-NMR; 13C-NMR
- Okamoto, Yoshihisa,Kinoshita, Toshio
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p. 1165 - 1169
(2007/10/02)
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- Preparation of trans cyclohexane 1,4 diisocyanate
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A process is disclosed for selectively making trans-cyclohexane-1,4-diisocyanate, trans-cyclohexane-1,4-diamine, a trans-cyclohexane-1,4-diurethane, a trans-cyclohexane-1,4-diurea and trans-cyclohexane-1,4-disulphonyl urea by reacting ammonia with a mixture of cis and trans-cyclohexane-1,4-dicarboxylic acid, a lower alkyl ester, a glycol ester, an oligomeric ester or a polyester to make a solid trans-dicarboxylic acid diamide in a first step. The diamide is chlorinated to form cyclohexane-1,4-dicarboxylic acid-bis-N-chloramide. The latter compound is then converted into a (a) trans-cyclohexane-1,4-diamine with an alkali metal hydroxide or alkaline earth metal hydroxide; or into a (b) a trans-cyclohexane-1,4-diurethane by reaction with an alcohol or glycol in a reaction mixture containing an alkali metal hydroxide or alkaline earth metal hydroxide; or into (c) a trans-cyclohexane-1,4-diurea by reaction with a primary or secondary amine in a reaction mixture containing an alkali metal hydroxide or alkaline earth metal hydroxide; or into a (d) trans-cyclohexane-1,4-sulphonyl urea by reaction with a primary sulphonamide in a reaction mixture containing an alkali metal hydroxide and dimethyl formamide and water. The diurea prepared in (c) may be converted into trans-cyclohexane-1,4-diisocyanate with gaseous hydrogen chloride in an inert solvent. The diurethane prepared in (b) and the disulphonyl urea prepared in (d) may be thermally decomposed into trans-cyclohexane-1,4-diisocyanate.
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- Process for the preparation of organic mono- and polyisocyanates
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A process for the preparation of organic mono- and polyisocyanates is described, in which a hydrogen chloride adduct of a trisubstituted urea is thermally decomposed to form the isocyanate. The hydrogen chloride adduct at minimum contains the stoichiometric amount of HCl, and at maximum a 10 mole-% excess. The process is carried out in a closed system at a temperature between about 80° and 180° C.; the reaction is effected either in a melt or in the presence of an inert organic solvent.
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- Reactions of N,N-Dialkyl-N'-arylthioureas with α-Haloketones and of 2-Substituted Imino-1,3-oxathioles with Heterocumulenes
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N,N-Dialkyl-N'-arylthioureas react with phenacyl halides to give 2-arylimino-5-phenyl-1,3-oxathioles (I), 3-aryl-2-arylimino-4-phenyl-4-thiazolines (III), aryl isothiocyanates and N,N'-diarylthioureas.I reacts with heterocumulenes like phenyl isocyanate and phenyl isothiocyanate to give 3,4-diaryl-2-arylimino-4-thiazolines, N,N'-diarylthioureas, arylacetylenes and COS or CO2.Mechanisms of formation of the various products have been proposed, based on TLC monitoring at regular time intervals.These are independently supported by chemical reactions.
- Singh, Harjit,Ahuja, A. S.,Malhotra, N.
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p. 1019 - 1022
(2007/10/02)
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- PHOSPHORORGANISCHE VERBINDUNGEN 93 Zur Chemie optisch aktiver Phosphinigsaereamide
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Optically active ethyl-phenyl-phosphinous acid diethylamide 1 was treated with HCl, HBF4, alcohols, thiols, carboxylic acids, esters, anhydrides, acid chloride, compounds with the structure element P-Cl and secondary phosphines to give in each case a racemic mixture of the corresponding, previously described, reaction products.Reaction of optically active 1 with para-cresol, para-cresyltrifluoro-acetate or 2,2,2-trifluoro-ethyl-trifluoro-acetate gives the corresponding optically active ester of ethyl phenyl phosphinous acid under retention of configuration.
- Horner, Leopold,Jordan, Manfred
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p. 235 - 242
(2007/10/02)
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- Process for the preparation of phosphorus derivatives of secondary ammonium salts of penam and cephem compounds
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An improvement in the conversion of penam and cephem compounds to secondary ammonium salts of phosphite amides thereof by reacting as follows: STR1 wherein --R, is the non-reacting balance of the penam or cephem compound and STR2 ARE NON-REACTING SUBSTITUENTS. Catalytic amounts of H--N or the hydrogenhalide thereof may be present in the reaction medium.
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- Diazepine derivatives
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Compounds of the class of 6-phenyl-4H-s-triazolo[1,5-a][1,4]benzodiazepine-2-carboxamides, their 5-oxides and their pharmaceutically acceptable acid addition salts have valuable pharmacological properties and are active ingredients for therapeutic compositions. In particular, these new compounds have an anti-convulsive and anti-aggressive action and inhibit somatic reflexes. Specific embodiments are N,N-dimethyl-6-phenyl-8-chloro-4H-s-triazolo[1,5-a][1,4]benzodiazepine-2-carboxamide, 6-(o-fluorophenyl)-8-chloro-4H-s-triazolo[1,5-a][1,4]benzodiazepine-2-carboxamide, N,N-dimethyl-6-(o-fluorophenyl)-8-chloro-4H-s-triazolo[1,5-a][1,4]benzodiazepine-2-carboxamide and N,N-dimethyl-6-(o-chlorophenyl)-8-chloro-4H-s-triazolo[1,5-a][1,4]benzodiazepine-2-carboxamide.
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