Formate ethyl, reaction with amines

Rhenium(V) 4-tolylimido complexes with the hydrotris(pyrazolyl)borate ligand, HB(pz)3, are formed on heating the 0x0 derivatives [ReOX2 HB(pz)3 ] (X = Cl, I) with 4-toluidine, whereas reactions with amines at ambient temperatures only give 0x0 complexes of the composition [ReO(NHR)Cl HB(pz)3 ]. The [Re(NC6H4-4-Me)X2 HB(pz)3] complexes react with ZnEt2 with formation of imido-ethyl complexes of the composition [Re(NC6H4-4-Me)Cl(Et) HB(pz)3 ]. " ... 

The reaction of ethyl 3-isothiocyanatopyridine-2-carboxylate with ethanol at reflux temperature results in the formation of the corresponding thiourethane which, by reaction with amines in anhydrous ethanol, can be converted into pyrido[3,2-c/]pyrimidin-4(3//)-one derivatives, partly with subsequent substitution of the sulfanyl group.428... 

The addition product, C QHgNa, called naphthalenesodium or sodium naphthalene complex, may be regarded as a resonance hybrid. The ether is more than just a solvent that promotes the reaction. StabiUty of the complex depends on the presence of the ether, and sodium can be Hberated by evaporating the ether or by dilution using an indifferent solvent, such as ethyl ether. A number of ether-type solvents are effective in complex preparation, such as methyl ethyl ether, ethylene glycol dimethyl ether, dioxane, and THF. Trimethyl amine also promotes complex formation. This reaction proceeds with all alkah metals. Other aromatic compounds, eg, diphenyl, anthracene, and phenanthrene, also form sodium complexes (16,20). 

A kinetic smdy of the formation of zwitterionic adducts (28) from 1,3,5-trinitrobenzene and diazabicyclo derivatives indicates that reactions are surprisingly slow, with rate constants many orders of magnitude lower than those for related reactions with primary or secondary amines. The use of rapid-scan spectrophotometry was necessary to study the kinetics of reaction of 4-substimted-2,6-dinitro-A -n-butylanilines (29) with n-butylamine in DMSO the two processes observed were identified as rapid deprotonation to give the conjugate base and competitive a-adduct formation at the 3-position. The reactions of MAf-di-n-propyl-2,6-dinitro-4-trifluoromethylaniline (30), the herbicide trifluralin, and its A -ethyl-A -n-butyl analogue with deuteroxide ions and with sulfite ions in [ H6]DMS0-D20 have been investigated by H NMR spectroscopy. With deuteroxide a-adduct formation at the 3-position is followed by... 

When the pentamer (66) reacts with alkoxide anions at low temperatures (-30 to -40°C), then the products of kinetic control (102) are isolated, whereas at higher temperatures, thermodynamic control prevails and the products (103) are obtained [131,132] (Scheme 68). Similar observations have been made with sulphur nucleophiles [132], and complex products are obtained with amines, including the formation of heterocycles [132]. Reaction of (66) with ethyl acetoacetate gave a pyran derivative (104) in a reaction that may be rationalised as shown in Scheme 69 [133]. In an analogous way.furan derivatives are formed from perfluoro-2-butene and -cyclohexene in base-induced reaction with 1,3-dicarbonyl derivatives [133]. 

Tripodal tritertiary phosphines as 1,1,1-tris(diphenyl--phosphinomethy1)ethane, triphos, and tris(2-diphenylphosphino--ethyl)amine, np3 are capable a) to act as tridentate or tetradentate ligands b) to promote several reactions with formation of several types of metal complexes which are presented. 

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