Amines, cyclic ethylene derivs

Cleavage of ethylene derivs. to alcohols and amines Diols and diamines from cyclic ethylene derivs. 

Disubstituted amino)-l//-pyrimido[l,2-a]quinolin-l-ones (149) were prepared in the reaction of 3-chloro derivative 148 with disubstituted amines and a cyclic amine in boiling ethanol or ethylene glycol (95MI1). 

Unlike ethylene glycol, a-hydroxycarboxylic acids, and p-mercaptoethanol, ligands such as ethanolamine, ethylenediamine, amino acids, and 2-aminoethanethiol do not form V2L2 complexes with vanadate [46], However, weakly formed products of VL stoichiometry (—546 ppm, —556 ppm) are observed with a number of a-amino acids [47], Because the amine functionality in amino acids is not suitable for formation of the cyclic [VN]2 core expected for a dimer, then one or the other of these VL compounds may correspond to the monomeric precursor to such a dimeric product. Certainly, with the a-hydroxycarboxylic acids, the monomeric complex can be a major component in solution. Similar VL complexes have not been reported for the amino alcohols. Perusal of the available reports suggests that the amine derivatives were studied under conditions where the nitrogen functionality was protonated, so the results may be somewhat misleading. 

Cyclic ketene acetals can also react with amines to give 1,1-enediamines with elimination of ethylene glycol76. Treatment of 2-[(methoxycarbonyl)cyanomethylene]-1,3-dioxolane (38) with 1,3-diaminopropane or with 4,5-dimethyl-1,2-phenylenediamine gives the hexahydropyrimidine and the benzimidazoline derivatives 39 and 40, respectively (equation 11). Similarly to the reaction of ketene dithioacetals with amines, the reaction between ketene acetals and amines proceeds via monoamino-substituted intermediates and ketene 7V,Oacetals can be isolated when one molar amine is used72. 

The regio- and stereoselective zirconocene-catalyzed addition of alkylmagnesium halides to alkenes, a process which has been described previously (see Section 7.5.2, Scheme 7-79) was investigated with ethylene-l,2-bis( M,5,6,7-tetrahydroind-l-enyl)zirconium dichloride [(EBTHI)ZrCl2l) [118] as chiral zirconocene. Thus, treatment of the latter with alkylmagnesium halides leads to the formation of the derived zirconocene-alkene complex 88, characterized by NMR [119], which reacts with cyclic ethers or amines to lead to the corresponding homoallylic alcohol or amine, respectively, in > 95% ee and good overall yield [120] (Scheme 7-103). 

Polyalkylene polyamines are typical by-products in the amination of dihydroxy compounds. Some of these oligomers, e. g. diethylenetriamine and triethylene-tetramine, are valuable compounds they are produced industrially from ethanol-amine (sometimes directly from ethylene oxide) and ammonia or a mixture of ammonia and ethylenediamine. Over a Ni-Re boride catalyst the selectivity for diethylenetriamine was ca 25 %, almost independent of the conversion [27]. Higher temperatures favored the formation of worthless cyclic products, mainly piperazine and its N-alkylated derivatives (Scheme 9). Recycling the cyclic byproducts can minimize their formation and the higher oligomers can be decomposed to useful dimers and trimers [26]. 

Cyclometalated catalyst 9 was shown to be effective in the Z-selective ethenolysis of internal olefins (Scheme 8) at relatively low catalyst loadings (0.5 mol%) and ethylene pressures (1-5 atm) [51, 53]. /Z-olefin mixtures were successfully enriched to the pure E-isomer products, with accompanying formation of terminal olefins derived from the Z-isomer. This process was demonstrated to be effective for both linear and cyclic olefins and was found to be tolerant of a number of functional groups including esters, alcohols, amines, and ketones. Reactions were generally conducted at 35°C, which was found to provide an optimal balance with respect to yield and reaction time. Although the reaction is more rapid at... 

Vinyl-functional alkylene carbonates can also be prepared from the corresponding epoxides in a manner similar to the commercial manufacture of ethylene and PCs via CO2 insertion. The most notable examples of this technology are the syntheses of 4-vinyl-1,3-dioxolan-2-one (vinyl ethylene carbonate, VEC) (5, Scheme 24) from 3,4-epoxy-1-butene or 4-phenyl-5-vinyl-l,3-dioxolan-2-one (6, Scheme 24) from analogous aromatic derivative l-phenyl-2-vinyl oxirane. Although the homopolymerization of both vinyl monomers produced polymers in relatively low yield, copolymerizations effectively provided cyclic carbonate-containing copolymers. It was found that VEC can be copolymerized with readily available vinyl monomers, such as styrene, alkyl acrylates and methacrylates, and vinyl esters.With the exception of styrene, the authors found that VEC will undergo free-radical solution or emulsion copolymerization to produce polymeric species with a pendant five-membered alkylene carbonate functionality that can be further cross-linked by reaction with amines. Polymerizations of 4-phenyl-5-vinyl-l,3-dioxolan-2-one also provided cyclic carbonate-containing copolymers. 

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