6274-12-0Relevant articles and documents
Synthesis and reactivity of cyclometalated rhenium diaminocarbene complexes
Lu, Kuang-Lieh,Lee, Hsu-Hsiu,Wang, Chen-Mien,Wen, Yuh-Sheng
, p. 593 - 599 (1994)
The diaminocarbene complexes ReBr(CO)4{C(NHR)(NHPh)} (1) react with a secondary amine (Et2NH) to yield the cyclometalated products Re(CO)4{η2-C(NHR)(NHC6H4)} (2a, R = Pri; 2b, R = Pr) via an ortho-metalation process. Treatment of the latter complexes with HBr in CH2Cl2 leads to the opening of the metallacyclic ring to regenerate complex 1. The complex Re(CO)4{η2-C(NHPri)(NHC6H 4)} (2a) reacts with iodine to afford ReI(CO)4{C(NHPri)(NHC6H4I)} (3), which on reaction with secondary amine induces the successive intramolecular activation of a C-H bond to form Re(CO)4{η2-C(NHPri)(NHC6H 3I)} (4). Treatment of 4 with iodine leads to the reopening of the Re-C σ bond to yield the iodo complex ReI(CO)4{C(NHPri)(NHC6H3I 2)} (5). Complex 2a reacts with the Br?nsted acid CH3CO2H or CF3CO2H in CH2Cl2 to give the addition products Re(CO)4(η1-OCOR){C(NHPri)(NHPh)} (6a, R = CH3; 6b, R = CF3). Treatment of 2a with HC≡CCO2H in CH2Cl2 leads to the formation of both the complex Re(CO)4(η1-OCOC≡CH){C(NHPri)(NHPh)} (6c) and the minor species ReCl(CO)4{C(NHPri)(NHPh)} (7). Molecular structures of 3, 6c, and 7 have been determined by X-ray diffraction studies. Crystal data are as follows: 3, Pbcn, a = 7.419(3) A?, b = 16.52(6) A?, c = 32.215(21) A?, V = 3948(14) A?3, Z = 8, R = 8.2%, Rw = 10.2%; 6c, P21/n, a = 9.9905(13) A?, b = 12.7994(14) A?, c = 15.0592(16) A?, β = 96.035(10)°, V = 1915.0(4) A?3, Z = 4, R = 4.1%, Rw = 5.0%; 7, P21/c, a = 15.6532(23) A?, b = 6.4584(14) A?, c = 17.4384(20) A?, β = 107.924(11)°, V = 1677.4(5) A?3, Z = 4, R = 4.4%, Rw = 5.0%.
Reaktionen koordinierter Liganden V. Pentacarbonylhalogenaminophosphinkomplexe (CO)5MPRXNR'2 durch Umsetzung von (CO)5MPR(NR'2)2 mit Halogenwasserstoff
Diemert, K.,Kuchen, W.,Lorenzen, D.
, p. 17 - 32 (2007/10/02)
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.
EFFECT OF THE STRUCTURE OF AMINES ON RATE AND MECHANISM OF THEIR REACTIONS WITH 2-(β,β-DIBROMOVINYL)-5-NITROFURAN IN ACETONITRILE
Kravchenko, V. V.,Kotenko, A. A.,Popov, A. F.,Kostenko, L. I.,Vegh, D.,Kovac, J.
, p. 2140 - 2143 (2007/10/02)
The kinetics of the reaction of 2-(β,β-dibromovinyl)-5-nitrofuran with alkylamines of various types (primary, secondary, and tertiary) in acetonitrile at 55 deg C were studied.It was shown that enamines are formed quantitatively in the case of the reactions with secondary amines.At the same time the products from the reactions with primary amines are the corresponding amidines.Here the monosubstitution product is formed at the first stage, as in the case of the reactions with secondary amines, and rearranges to the imidoyl halide with subsequent substitution of the halogen atom at the imidoyl carbon atom.A quantitative assessment is made of the effect of the structure of the enamine on the rate of the processes.
Palladium-Catalyzed Double-Carbonylation of Alkenyl Halides with Secondary Amines to Give α-Keto Amides
Son, Tae-il,Yanagihara, Hisayoshi,Ozawa, Fumiyuki,Yamamoto, Akio
, p. 1251 - 1258 (2007/10/02)
The double-carbonylation reaction of alkenyl halides with diethylamine in the presence of palladium catalysts has been examined in detail.The reaction gives α-keto amide together with amide, the single carbonylation by-product.The yield of α-keto amide is strongly dependent on the nature of alkenyl halide.Alkenyl bromides or iodides having phenyl group(s) as substituent(s) on the vinyl group are successfully double-carbonylated under appropriate reaction conditions and the corresponding α-keto amides are obtained in good to modest yields together with amides.In contrast, the reactions of alkenyl halides without a phenyl group give amides exclusively.In order to clarify the reason for the substrate-specificity in the reaction, series of alkenyl- and alkenoylpalladium(II) complexes, the presumed intermediates in the catalytic reactions, have been prepared and their reactions with secondary amines, carbon monoxide, and alkenyl halides were examined.The study suggests the operation of three types of processes for amide formation in the catalytic reactions.Possible mechanism for amide as well as α-keto amide formation are discussed.
KINETICS AND MECHANISM OF REACTION OF AMINES WITH β-BROMOPROPIOPHENONE
Popov, A. F.,Piskunova, Z.,Matvienko, V. N.
, p. 1299 - 1302 (2007/10/02)
The reaction of β-bromopropiophenone with different amines in acetonitrile at 25 deg C was studied.It was found that in the case of primary and secondary amines, the end products of the reaction are β-aminopropiophenones, which form via the intermediate phenyl vinyl ketone.In the case of tertiary amines, the reaction ends at the stage of the formation of phenyl vinyl ketone.The reactivity of the amines in the formation of phenyl vinyl ketone is preferentially determined by their basicity.
ZUR KENNTNIS DER ORGANOPHOSPHORVERBINDUNGEN XXIII. UEBER ALKENYLSUBSTITUIERTE AMINO-BZW. HALOGENPHOSPHANE UND VERSUCHE ZUM INTRAMOLEKULAREN PHOSPHINIDENABFANG
Diemert, Klaus,Kottwitz, Beatrix,Kuchen, Wilhelm
, p. 307 - 320 (2007/10/02)
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.
BETA-ADRENERGIC 1-[1-BENZIMIDAZOLYL]-N-[2-(4-HYDROXY-3-METHOXY-PHENYL)-2-HYDROXY-ETHYL]-3-AMINO BUTANE AND SALTS AND HYDRATES THEREOF
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, (2008/06/13)
Novel compounds with β-adrenergic properties comprising 1-1-benzimidazolyl! N-2-(4-hydroxy 3-methoxy phenyl) 2-hydroxy ethyl!3-amino butane, corresponding to the following formula STR1 as well as its addition salts with pharmaceutically acceptable non-toxic inorganic or organic acids, and the hydrates of said salts. These compounds are particularly useful for the treatment of asthma and in the case of premature labor.
KINETICS OF THE REACTIONS OF 2-HALOGENOPYRIDINIUM SALTS WITH PRIMARY AND SECONDARY AMINES IN ACETONITRILE
Litvinenko, L. M.,Titskii, G. D.,Mitchenko, E. S.
, p. 1731 - 1736 (2007/10/02)
The kinetics of the reactions of 2-halogeno-N-alkylpyridinium salts with primary and secondary aliphatic amines in acetonitrile at 25 deg C were investigated.The reactions obey second-order relationships.In the reaction of 2-bromo-N-ethylpyridinium bromide with aliphatic amines the effect of electronic and steric factors on the reactivity of the amines was examined.
OXALSAEUREDERIVATE DURCH OXIDATIVE KUPPLUNG VON KOHLENMONOXID AN NICKEL
Hoberg, Heinz,Fananas, F. Javier,Riegel, Hans Josef
, p. 267 - 272 (2007/10/02)
Carbon monoxide is oxidatively coupled by ligand nickel(II) compounds with secondary, primary amines and with alkali alkoxides to give oxalic acid derivatives.In the case of secondary amines the CO coupling can be run catalytically by adding oxidants like copper(II) salts.The yield of oxalic esters depends on the types of ligands and anions.
