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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1991

The cyclization of arabinosyladenine-5-prime-phosphorimidazolide

When arabinosyladenine-5-prime-phosphorimidazolide is allowed to decompose in aqueous solution at room temperature and pH 7.2, depending on the buffer, 5-24 percent is converted to the 2-prime,5-prime-cyclic phosphate (V). Although the extent of cyclization is much greater than for adenosine-5-prime-phosphorimidazolide, cyclization is less efficient than hydrolysis and so would not substantially decrease the efficiency of condensation reactions in aqueous solution. The significance of this result for prebiotic chemistry is discussed.

Harada, Kazuo↗
NASA NTRS1967

The cyclization of epoxyolefins. IV.

Epoxyolefins cyclization, discussing bicyclic ethers from citronellal derivative as synthetic entries into diterpene series of natural products

Clark, B. C., Jr.↗
NASA NTRS1988

Cyclization of nucleotide analogues as an obstacle to polymerization

Cyclization of activated nucleotide analogues by intramolecular phosphodiester-bond formation is likely to compete very effectively with template-directed condensation except in the cases of ribo- and arabinonucleotides. This could have excluded derivatives of most sugars from growing polyribonucleotide chains and thus reduced chain-termination in prebiotic polynucleotide synthesis.

NASA Discipline Exobiology↗
NASA NTRS1967

Solvent effects and other factors in carbenic and cationic pi cyclizations. I.

The susceptibility of the decomposition of the tosylhydrazones of simple carbonyl compounds to changes in the proton-donating ability (protonicity) of the solvent have long been known, but only recently has the mechaninistic path of this reaction been explored in detail. The nature of the products in tosylhydrazone decomposition (and thus by inference the nature of the intermediates) has been found to depend on (1) the protonicity of the solvent, (2) the concentration of the base, and (3) the nature of the cation association with the base. in recent deuterium-labelling studies on the base-catalyzed decomposition of the tosylhydrazones of cyclopropanecarboxaldehyde (I), norbornan-2-one (II), and camphor (III), evidence has accumulated for the existence of two distinct paths involving a "carbonic" and a "cationic" intermediate in this reaction depending on the reaction conditions. Present evidence indicates that the observed products from tosylchydrazone decomposition arise from either a carbene or a diazonium salt, generated from an intermediate diazo compound. In the absence of a Lewis acid, there is no present evidence to support a carbonium ion as an intermediate in the protonic decomposition of tosylhydrazones.

Harry Babad↗
NASA NTRS1972

Condensation cyclization reactions of electron deficient aromatics. 4: Tricyclic nitropropene nitronates from the reaction of phloroglucinol and cycloalkanones with sym-trinitrobenzene

Interesting similarities have been shown between the reactions of sym-trinitrobenzene with cycloalkanones, and with phloroglucinol. Previously unsuspected common intermediates have been shown to intervene. The structurally similar products in each case are tricyclic nitropropene nitronates. Protonation of these yields the corresponding nitronic acids in certain instances.

Strauss, M. J.↗
NASA NTRS1982

Radiation-induced loss of unsaturation in 1,2-polybutadiene

The radiation induced loss of unsaturation and methyl production in 1,2-polybutadiene (VB) was studied using IR spectroscopy. It was found that G(-1,2), which depends on the initial vinyl content, decreased from approximately 550 for VB with 98.5% 1,2 initially, to approximately 270 for VB with 85% 1,2 initially. G(-trans-1,4) ranged from approximately 21 for VB with 14% trans-1,4 to nearly zero for VB with less than 1% trans-1,4 initially. Methyl production was found to equal one methyl group formed for every 4-5 vinyl units consumed in the radiation-cyclized VB, in contrast to one methyl formed for every two vinyls reacted during cationic cyclization to give monocyclic structures. The IR spectra of gamma-irradiated VB were very similar to the spectra of UV-irradiated or thermally-treated VB at the same residual vinyl contents. It is suggested that the radiation-induced cyclization of VB occurs by a nonionic, nonradical 'energy chain' mechanism, which apparently holds for the cyclization of VB, whether induced by gamma-rays, UV radiation, or heat.

Golub, M. A.↗
NASA NTRS1974

Thermal rearrangements in polypentenamer and polyoctenamer

Experiments were conducted to show that polypentenamer and polyoctenamer, in common with 1,4-polybutadiene, undergo anaerobic thermal cis-trans isomerization at temperatures as low as 200 degrees C. Their activation energies for isomerization are comparable to that of polybutadiene. The relative rate constants are found to decrease in the order: polybutadiene, polypentenamer, polyoctenamer. When heated in a vacuum at 200 to 270 degrees C, polypentenamer exhibits a loss of double bonds. This disappearance of unsaturation has no counterpart in polybutadiene or polyoctenamer. In polypentenamer, a mechanism for a thermally-induced ring closure that is different from the one shown for the cyclization-depolymerization of various unsaturated polymers is evident. The cyclization-depolymerization process does cause a loss of double bonds in polybutadiene and polyoctenamer at temperatures greater than or equal to 275 degrees C.

Golub, M. A.↗
NASA NTRS1978

Thermal rearrangements of unsaturated polymers

Thermal anaerobic uncatalyzed cyclizations and cis-trans isomerizations observed in unsaturated hydrocarbon polymers are surveyed. Three main types of cyclizations are described. Type I is a radical reaction which is caused by chain rupture and gives rise to six-membered rings; this reaction occurs during pyrolysis of polymers with double bonds in a 1,5- or 1,6-diene configuration. Type II is a (2 + 2) thermal cycloaddition of double bonds in certain polymers with a 1,6-diene structure; bicycloheptane structures result. Type III is an intramolecular ene reaction. Many polymers containing a double bond linking CH units display thermal cis-trans isomerization. The common activation energy is approximately 130 kJ/mol, and the initial rate constants are lower, for homologous polymers, the greater the separation of the carbon-carbon double bonds.

Golub, M. A.↗
NASA NTRS1980

Process for the preparation of fluorine containing crosslinked elastomeric polytriazine and product so produced

Crosslinking elastomeric polytriazines are prepared by a 4 step procedure which consists of (1) forming a poly(imidoylamidine) by the reaction, under reflux conditions, of anhydrous ammonia with certain perfluorinated alkyl or alkylether dinitriles; (2) forming a linear polytriazine by cyclizing the imidoylamidine linkages by reaction with certain perfluorinated alkyl or alkylether acid anhydrides or halides; (3) extending the linear polytriazine chain by further refluxing in anhydrous ammonia; and (4) heating to cyclize the new imidoylamidine and thereby crosslink the polymer.

Rosser, R. W.↗
NASA NTRS1972

Method for forming pyrrone molding powders and products of said method

The formation of pyrrone resins of the ladder or semiladder structure is described. The technique involves initial formation of fully cyclized prepolymers having an average degree of polymerization of about 1.5, one with acidic terminal groups, another with amine terminal groups. Thereafter the prepolymers are intimately admixed on a 1:1 stoichiometric basis. The resulting powder mixture is molded at elevated pressures and temperatures to form a fully cyclized resin.

Hughes, C. T.↗
NASA NTRS1983

Prebiotic synthesis and reactions of nucleosides and nucleotides

The potential of diiminosuccinonitrile (DISN) as a prebiotic phosphorylating agent is studied. This compound is formed readily by the oxidation of diaminomaleonitrile, a tetramer of HCN. DISN is shown to produce the cyclization of 3'-adenosine monophosphate to adenosine 2',3'-cyclic phosphate in up to 40 percent yield. The DISN-mediated phosphorylation of uridine to uridine monophosphate is determined not to proceed efficiently in aqueous solution. The reaction of DISN and BrCN with uridine-5'-phosphate and uridine is found to result in the formation of 2,2'-anhydronucleotides and 2,2'-anhydronucleosides, respectively, and other reaction products resulting from an initial reaction at the 2' and 3'-hydroxyl groups. Homoionic montmorillonites were employed to study the clay mineral catalysis of the cyclization of adenosine-3'-phosphate.

Ferris, J. P.↗