Morpholine

About: Morpholine is a research topic. Over the lifetime, 5411 publications have been published within this topic receiving 51063 citations. The topic is also known as: diethylene imidoxide & diethylene oximide.

Studies on Coenzyme Analogs. III. Syntheses of 5-Substituted Uridine 5'-Phosphates

Abstract: The syntheses of 5-substituted uridines and their 5'-phosphates were described. 5-Bromo-2', 3'-isopropylideneuridine was phosphorylated with phosphoryl chloride and from the mixture of 5-Bromo-UMP, -UDP, and -UTP obtained, 5-Bromo-UMP was isolated by ion exchange chromatography. Phosphorylation of 5-bromo-2', 3'-isopropylideneuridine with polyphosphoric acid afforded 5-Bromo-UMP in a good yield. 5-Hydroxyuridine and its 5'-phosphate were synthesized by the addition of bromine to uridine or UMP and successive treatment with pyridine. 5-Morpholinouridine and its isopropylidene derivative were obtained from corresponding 5-bromo derivatives and morpholine, and 5-Morpholino-UMP was obtained by phosphorylation of 5-morpholino-2', 3'-isopropylideneuridine with polyphos phoric acid.

New functional model complexes of intradiol-cleaving catechol dioxygenases: properties and reactivity of CuII(L)(O2Ncat).

Abstract: Complexes Cu(O2Ncat)(tbeda) (1) and Cu(O2Ncat)(tmeda) (2) (tbeda = N,N,N',N'-tetrabenzylethylenediamine, tmeda=N,N,N',N'-tetramethylethylenenediamine, O2NcatH2=4-nitrocatechol) have been prepared by the reaction of copper(II) perchlorate with 4-nitrocatechol in the presence of triethylamine and the appropriate bidentate ligand. These compounds represent structural and functional model systems for the copper-containing catechol 1,2-dioxygenase. Both complexes have been structurally characterized by X-ray crystallography and by UV-vis, IR, and EPR spectroscopies. Upon protonation of 1 and 2 with perchloric acid, the bidentate coordination of O2Ncat could be reversible converted to the monodentate coordination of O2NcatH. The equilibrium constants were found to be 4200 and 3500, respectively, by measuring the UV-vis spectra in DMF. Back-titration with morpholine proved the reversibility of both reactions. Kinetic data on the oxygenation of 1 and 2 revealed overall second-order rate equations with kinetic parameters: ktbeda=(4.63+/-0.23)x10(-2) mol-1 dm3 s-1, DeltaH=51+/-6 kJ mol-1, DeltaS=-137+/-16 J mol-1 K-1; ktmeda=(0.89+/-0.23) mol-1 dm3 s-1, DeltaH=85+/-7 kJ mol-1, DeltaS=-57+/-19 J mol-1 K-1 at 365.16 K. Oxygenation of 1, 2, and [Cu(O2NcatH)(L)]ClO4 (L=tbeda, tmeda) in DMF solution at ambient conditions gives the corresponding intradiol ring-cleaved (2-nitro-muconato)copper(II) complexes. These data support the assumption that the reaction of the differently coordinated catecholate ligand with dioxygen shows only 1,2-dioxygenase activity.

Directed synthesis of new spiro-fused photochromes of diarylethene series

Abstract: The reaction of tetracyanoethylated 1,2-diarylethanones with morpholine was used for directed synthesis of spiro-fused diarylethenes, 8-amino-1-imino(oxo)-6-morpholino-2-oxa-7-azaspiro[4.4]nona-3,6,8-triene-9-carbonitriles. The intermediates in this process were tetracyanoalkanone salts. The formation of spiranes was sensitive to the nature of aromatic substituents at the carbonyl group of 3,4-diaryl-4-oxobutane-1,1,2,2-tetracarbonitriles. The obtained spiro-fused diarylethenes exhibited photochromic properties.

Reaction of amines with 1,3-dienes catalysed by nickel complexes

Abstract: Reactions of morpholine, piperidine, pyrrolidine, di-n-propylamine, n-butylamine, aniline, and p-anisidine with buta-1,3-diene in the presence of catalytic quantities of nickel acetylacetonate and di-isopropoxyphenylphosphine have been studied. Mixtures of 1 : 1 (butenyl) and 2 : 1 (octadienyl) amine products are produced and the reaction with morpholine has been studied in detail to examine the factors determining the product mixtures. Butenyl adduct formation is favoured by (a) a 3 : 1 ratio of phosphine–nickel salt concentration, (b) use of nickel halides with ethanol solvent, and (c) a low effective concentration of butadiene. A product mixture containing 86% octadienyl adduct was obtained by using a preformed Ni0 complex Ni[P(OPh)3]4. Reaction of morpholine and isoprene gave mainly a 1 : 1 adduct and small amounts of a 2 : 1 adduct; a similar reaction with trans-piperylene gave only a 1 : 1 adduct. The mechanism of the reactions is discussed in terms of formation of the butenyl and octadienyl adduct formation from π-allylnickel and bis-π-allylnickel complexes. The use of cocatalysts such as sodium borohydride in the reactions is discussed. Isomerisation of branched to linear butenyl adduct has been demonstrated to occur.