Search results for "Formaldehyde"

Reaction Mechanism of an Intramolecular Oxime Transfer Reaction: A Computational Study

2014

Density functional theory (PBE0/def2-TZVPP) calculations in conjunction with a polarizable continuum model were used to assess the mechanism of the intramolecular oxime transfer reaction that leads to the formation of isoxazolines. Different diastereomers of the intermediates as well as different oximes (formaldehyde and acetone oxime) were considered. The computed reaction profile predicts the water-addition and -expulsion steps as the highest barriers along the pathway, a conclusion that is in line with the experimental evidence obtained previously for these reactions.

Darstellung von phenolischen verbindungen und phenol/formaldehyd-polykondensaten mit ketoxim-, aldoxim- oder 1-methyl-4-hydroxyiminomethylpyridinium-…

1979

Thirteen low molecular weight oximes were prepared: one derivative of acetophenone (1), two derivatives of benzophenone (2 and 3), two derivatives of salicylaldehyde containing two phenolic nuclei (4c and 5c), and eight compounds in which a phenol unit is substituted by a 4-hydroxyiminomethylpyridiniummethyl group (8a–f, 10c, and 11c). Besides these compounds polymeric phenol formaldehyde condensates were synthesized which contain units deriving from benzophenoneoxime (15b) or from salicylaldehyde (22b) and condensates containing 4-hydroxyiminomethylpyridiniummethyl groups (23c). A series of low molecular weight and water soluble compounds (8a–f) were proved as antidotes on mice which were …

1968

In order to determine the concentration of active centers, polymerizations are terminated by addition of sodium alkoxide. This yields alkoxy endgroups which after acid hydrolysis of the isolated and purified polymers are determined by gaschromatography of the produced alcohol. In cationic polymerization of anhydrous formaldehyde at −78°C under certain reaction conditions a fast and quantitative initiation reaction and no kinetic chain termination have been observed. Presumably living polymers are obtained. The unexpected decrease in the rate of polymerization after a certain conversion is ascribed to hindrance of monomer diffusion in the crystalline polymer in which the active centers are i…

Umsetzungen an höhermolekularen, molekulareinheitlichen phenol-formaldehyd-kondensaten

1960

An in eindeutiger Synthese und im praparativen Masstab zuganglich gewordenen hohermolekularen, molekulareinheitlichen Phenol-Formaldehyd-Kondensaten (Mol.-Gew. bis zu 1500) wird die Acetylierung, die Umsetzung mit Diphenylcarbamidsaure-chlorid zu Poly-[N-diphenyl-]urethanen und mit Formaldehyd und Dimethylamin zu MANNICH-Basen untersucht. Bei den zwei ersten Umsetzungen wird mit Hilfe der Elementaranalyse bzw. der Acetylbestimmung sowie der UR-Spektren zu unterscheiden versucht, ob alle Hydroxygruppen einer Molekel umgesetzt werden konnen. Die Elementaranalysen der erhaltenen MANNICH-Basen zeigen, das eine vollstandige Einfuhrung von Endgruppen (kettenanaloge Umsetzung) gelungen ist. Higher…

Stufenweise Darstellung von Cyclo{quater[(5-alkyl-2-hydroxy-1,3-phenylen)methylen]}en und ihr Vergleich mit linearen phenolischen Mehrkernverbindungen

1978

The stepwise syntheses of cyclo{quater[(5-alkyl-2-hydroxy-1,3-phenylene)methylene]}s (5) are described and compared with a one-flask reaction procedure. The structures of the cyclic compounds 5 are analytically confirmed and their properties were compared with those of linear phenol formaldehyde condensates which have very similar structures and molecular weights.

Die unter dem einfluß geringer mengen an natriumionen verlaufende schmelzkondensation von 2.6-dihydroxymethyl-4-methylphenol

1970

Die wahrend der bei 130°C verlaufenden Schmelzkondensation von 2.6-Dihydroxy-methyl-4-methylphenol (I) bestimmten Gewichtsverluste und Mengen von abgespaltenem Formaldehyd waren um so groser, je hoher der analytische Natriumgehalt der Verbindung lag; dieser wurde durch Beimischen des Natriumphenolats von I im Bereich von 0,01 bis 3,0 Gew.-% Natrium eingestellt. Die in der Literatur angegebenen, stark voneinander abweichenden Mengen von abgespaltenem Formaldehyd sind wahrscheinlich durch unkontrollierte Natriumgehalte von I bedingt; sie konnen aus dem Natriumsalz stammen, uber das Verbindung I gewohnlich hergestellt wird. The losses in weight and the amounts of formaldehyde split off, which …

1965

Bei der Polymerisation von Trioxan bei 70°C in der Schmelze mit HClO4 · H2O als Initiator nimmt die Bruttopolymerisationsgeschwindigkeit exponentiell mit steigender Wasserkonzentration ab; gleichzeitig nimmt die Lange der Induktionszeit entsprechend zu. Die Retardierung durch Wasser wird auf eine Hydratation aktiver Zentren zuruckgefuhrt. Wasser ist ein wirkungsvoller Polymerisationsubertrager; seine relative Ubertragungskonstante betragt bei 25°C in Methylenchlorid ca. 2,6. Jedoch werden die Verhaltnisse durch die Bildung von Methylenglykol aus Wasser und Formaldehyd kompliziert. In polymerization of trioxane in the melt at 70°C. with HClO4 · H2O as initiator the rate of polymerization dec…

A Computational Study of Adsorption of CO2, SO2, and H2CO on Free-Standing and Molybdenum-Supported CaO Films

2018

Oxide films play a significant role in a wide range of fields from catalysis to solar cell materials. CaO films are promising sorbents for many environmentally harmful molecules. Here, we report a systematic investigation of adsorption of CO2, SO2, and H2CO on bulk and Mo-supported CaO(100) films using density functional theory. Significant effects on adsorption energy, charge transfer to the molecules, and degree of the C–O bond activation were demonstrated on Mo-supported CaO films by changing the film thickness, composition, and the strength and direction of an applied external electric field. These findings are relevant for interpreting results from scanning tunneling microscopy of smal…

A Computational Study of Adsorption of CO2, SO2, and H2CO on Free-Standing and Molybdenum-Supported CaO Films

2019

Oxide films play a significant role in a wide range of fields from catalysis to solar cell materials. CaO films are promising sorbents for many environmentally harmful molecules. Here, we report a systematic investigation of adsorption of CO2, SO2, and H2CO on bulk and Mo-supported CaO(100) films using density functional theory. Significant effects on adsorption energy, charge transfer to the molecules, and degree of the C−O bond activation were demonstrated on Mo-supported CaO films by changing the film thickness, composition, and the strength and direction of an applied external electric field. These findings are relevant for interpreting results from scanning tunneling microscopy of smal…

O6-Alkylguanine DNA alkyltransferase activity in student embalmers

1997

O6-Alkylguanine-DNA alkyltransferase (AGT) activity was assessed in peripheral blood lymphocytes among 23 mortuary science students before and after 9 weeks in a laboratory course in techniques of embalming. Formaldehyde exposure was established by environmental monitoring. The average air concentration of formaldehyde during embalming was about 1.5 ppm. At the pre-exposure sampling, baseline DNA repair capacity tended to be reduced in subjects who reported a prior history of embalming (p = 0.08). From pre- to post-exposure, 17 subjects decreased in DNA repair capacity, while only 6 increased (p <0.05). Analysis of variance, including adjustment for age, sex, and smoking status, confirmed t…