Reactions of nitro alcohols with n,n-diethyl-1,1,2,3,3,3-hexafluoropropylamine

Fluorination of nitro alcohols with N,N-diethyl-1,1,2,3,3,3-hexafluoropropylamine (PPDA) was investigated. 3-Nitrobenzyl fluoride (II) was obtained from the reaction of PPDA and 3-nitrobenzyl alcohol (I) (yield 66%). The reaction of 2-methyl-2-nitro-1-propanol (IV) with PPDA given 2-methyl-2-nitropropyl 2,3,3,3-tetrafluoropropionate (V). reduction of 3-nitrobenzyl fluoride (II) with lithium aluminium hydride gave the corresponding amino compound, 3-aminobenzyl fluoride (VI) in poor yield.     

Reactions of halogenoquinolizinium bromides with diethylamine

The reactions of quinolizinium bromide (QB) and its four monobromo derivatives with diethylamine have been investigated. For Br in position 2 or 4, substitution is the main process, whereas for Br in positions 1 and 3 quantitative ring opening is found. The substituted pyridylbutadienes formed by ring opening, are cis-trans-butadienes, which isomerize into the all-trans forms. The steric cours of the ring opening is explained.     

Fluorination of hydroxyesters with N,N-diethyl-1,1,2,3,3,3-hexafluoro propylamine

The reaction of 1,1,2,3,3,3-hexafluoropropyldiethylamine (PPDA) with hydroxy esters having PhC(H)(OH)-groups gave their corresponding secondary fluorides. Fluorination of (R)-(-)-mandelic acid ethylester ([α]²⁹_D −106.46) gave ethyl (S)-(+)-2-fluoro-2-phenyl acetate ([α]²⁹_D +6.57). The value of the enantiomeric excess (% ee) was 74.1. The reaction mechanism of the fluorination by PPDA is suggested to be the S_N2 type.     

Gas-phase reaction of phenyl cation with diethylamine

Reactions of phenyl cations generated by the beta-decay of tritium in tritiated benzene were studied by a radiochemical method. Identified labeled products are ethylphenylamine (72%), diethylamine (15%) and diethylphenylamine (13%). A reaction mechanism is proposed and the relative yields of products are rationalized taking into account the energy estimates of plausible products by the B3LYP method.     

Reaction of perfluorinated vinyl ethers with diethylamine

Russian Journal of General Chemistry -     

Combinatorial synthesis of bimetallic complexes with three halogeno bridges

Methods for the synthesis of bimetallic complexes in which two different metal fragments are connected by three chloro or bromo bridges are reported. The reactions are general, fast, and give rise to structurally defined products in quantitative yields. Therefore, they are ideally suited for generating a library of homo- and heterobimetallic complexes in a combinatorial fashion. This is of special interest for applications in homogeneous catalysis. Selected members of this library were synthesized and comprehensively characterized; single-crystal X-ray analyses were performed for 15 new bimetallic compounds.     

Reactions of monoesters of ethylene glycol with N,N-diethyl-1,1,2,3,3,3-hexafluoropropylamine

By reaction with 1,1,2,3,3,3-hexafluoropropyldiethylamine (PPDA), various monoesters of ethylene glycol gave a mixture of corresponding monofluorides and 2,3,3,3-tetrafluoropropionate esters. The antimicrobial properties of these fluorine compounds for a spent coolant were examined.     

Two novel halogeno(cyano)argentates with efficient luminescence

The reactions of silver(I) cyanide with tetraalkylammonium salts in anhydrous tetrahydrofuran (THF) under solvothermal conditions and then diffused with ether lead to two novel mixed halogeno(cyano)argentates(I) with efficient luminescence.     

The mass spectra of halogeno derivatives of quinoxaline

The mass spectra of seventeen different quinoxaline halogeno derivatives are reported. The fragmentation mechanism is discussed.     

The effect of diethylamine on Stille alkylations with tetraalkylstannanes

The addition of diethylamine to Stille alkylation reactions using stannanes improves yields by reducing beta-hydride elimination and reduction reactions, it also serves as a substitute for other additives such as Cu(I)I.     

Vibrational relaxation in liquid diethylamine

Two types of time resolved experiments have been performed on the intermediate sized polyatomic molecule diethylamine, in the liquid phase, in order to elucidate the pathway for vibrational relaxation of the ν = 3 level of the NH stretching mode, which has 9420 cm^?1 of energy. Both techniques had calibrated absolute sensitivities and were specific for vibrational modes of ca. 3000 cm^?1, yet with neither were transient populations in such modes observable. It is inferred that population relaxation in this highly excited room temperature system proceeds on the subpicosecond time scale to lower lying levels. The importance of intramolecular channels for this decay is suggested.     

Two halogeno(cyano)cuprates with long-lived and strong luminescence

Solvothermal reactions of copper(I) cyanide with tetramethylammonium salts in anhydrous tetrahydrofuran (THF) lead to two novel halogeno(cyano)cuprates, namely, [Me(4)N][Cu(3)(CN)(2)Br(2)] (1) with a 1-D ribbon motif and [Me(4)N](2)[Cu(4)(CN)(5)Cl] (2) with a 3-D nanoporous framework. In 1, four Cu(I) ions are connected via two mu-Br and two mu(3)-Br atoms into a neutral [Cu(4)Br(4)] cluster, and such clusters are further double bridged by [Cu(CN)(2)](2-) linkers to form a 1-D ribbonlike chain. While in 2, Cu(I) ions are connected via mu-CN and mu(3)-CN ligands and mu-Cl atoms into a 2-D fluctuant sheet along the a-c plane, and these sheets are further linked by another kind of mu-CN ligand to form a 3-D nanoporous framework in whose channels reside [Me(4)N](+) cations. Results of optical and luminescent studies indicate that both two complexes are potential materials for semiconductors and long-lived highly luminescent materials.     

Rhodium-catalyzed alkylation of ketones and alcohols with alcohols

An efficient method for direct alkylation of ketones and alcohols through the borrowing hydrogen strategy in the presence of rhodium complexes as catalyst was developed. This transformation is tolerant to various functional substrates and is efficient in C–C coupling of primary and secondary alcohols, which provides an alternative method of the synthesis of functional ketones from simple and commercially available materials.     

Reaction of tertiary diacetylenic alcohols with amino alcohols

Conclusions It was shown that nitrogen-containing ethynyl vinyl ethers can be synthesized from tertiary diacetylenic alcohols and amino alcohols in the presence of alkaline catalysts.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2604–2605, November, 1970.     

Unusual reaction of phenylpropargyl aldehyde with diethylamine and acetone cyanohydrin

Conclusions An unusual product was obtained by the reaction of phenylpropargyl aldehyde with acetone cyanohydrin and diethylamine, which has the structure of 1,6-dicyano-1,6-bis(diethylamino)-3,4-diphenyl-1,5-hexadiene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1637–1639, July, 1979.     

Manganese(II) complexes with diethylamine in aqueous solutions

Interaction between MnCl₂ and diethylamine (DEA) in aqueous solutions has been studied by UV, IR, and EPR spectroscopy as part of the design and research program on models of natural photosystems. The composition of the precipitate for comparable concentrations of reagents and solute oxygen has been investigated. Mn(II) was found to be oxidized with oxygen to give MnO₂·H₂O as a precipitate. In the solution over the precipitate, Mn(III) complexes with DEA are formed; the complex molecule has four and six amine molecules in the coordination sphere.     

Reactions of benzofurazan oxide with amines—I : Reduction with diethylamine

The reactions of benzofurazan oxide with diethylamine gave a complex mixture from which quinoxaline-1,4-dioxide (10–15%), o-benzoquinone dioxime (5%), benzofurazan (5–10%), 1-hydroxy-2-methyl-benzimidazole-3-oxide (3%), o-nitrosoaniline (5%), o-nitroaniline (<3%), 3-methylbenzotriazine (5%), 3-methyl-benzotriazine-4-oxide (10%), and o-nitrophenyl-N,N-diethyl hydrazine (10%) were isolated.The formation of these products seems to have a common pathway that involves the reduction of benzofurazan oxide and the oxidation of diethylamine.