Application of fluorescence reactions in the ring oven segment technique

Summary The ring oven segment technique already described earlier has been applied to the determination of ng- tog-amounts of organic and inorganic substances using fluorescence reactions. The methods proposed here are based either on self-fluorescence or on appearance or disappearance of fluorescence following a chemical reaction.

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Anwendung von Fluoreszenzreaktionen in der Ringofen-Segmenttechnik

Zusammenfassung Die bereits früher beschriebene Ringofen-Segmenttechnik wurde auf die Bestimmung organischer und anorganischer Substanzen im ng- bisg-Bereich mit Hilfe von Fluoreszenzreaktionen angewendet. Die hier vorgeschlagenen Methoden beruhen entweder auf Eigenfluoreszenz oder aber auf der Bildung bzw. dem Verschwinden von Fluoreszenz nach einer chemischen Reaktion.

     

Stereoselective Synthesis of Enantiomerically Pure Natural Products—Estrone as Example

Natural products have been synthesized for billions of years in animals, plants, and microorganisms. As a rule they occur enantiomerically pure. Their chiral character corroborates their use in metabolism or as biologically active agents. Natural products may be insufficient in quality or quantity. They have recently begun to become accessible, either unchanged or modified, by biological synthesis; here, too, they are obtained enantiomerically pure. In the last twenty years chemical synthesis has become a major concern of organic chemists. Their target compounds are primarily enantiomerically pure natural products or biologically active variants thereof.     

Neutral and ionic aluminum,gallium, and indium compounds carrying two or three terminal ethynyl groups

The syntheses of the ionic compounds [Li(+).2 dioxane (2,6-iPr(2)C(6)H(3)N(SiMe(3))Al(C triplebond CSiMe(3))(3))(-)].0.75 dioxane (1), [(Li(+))(2).(dioxane)(7)](0.5) [2,6-iPr(2)C(6)H(3)N(SiMe(3))Ga(C triplebond CSiMe(3))(3)(-)].1.5 dioxane (2), and [(Li(+))(2).(dioxane)(7)](0.5) [2,6-iPr(2)C(6)H(3)N(SiMe(3))In(C triplebond CSiMe(3))(3)(-)].1.5 dioxane (3) by the reaction of the corresponding organo metal chloride with LiC triplebond CSiMe(3) are reported. The neutral ethynyl compounds Br-Al(C triplebond CtBu)(2).2 THF (4), Cl-Ga(C triplebond CtBu)(2).THF (5), Cl-In(C triplebond CtBu)(2).2 THF (6), Al(C triplebond CtBu)(3).C[N(Me)CMe](2) (7), Ga(C triplebond CtBu)(3).dioxane (8), and In(C triplebond CtBu)(3).NEt(3) (9) have been obtained in good yields from the reaction of AlBr(3), GaCl(3), and InCl(3) with LiC triplebond CtBu in the presence of a Lewis base. Compound 7 is the first heterocyclic carbene substituted ethynyl derivative. Aluminum and gallium compounds with three terminal ethynyl groups Al(C triplebond CPh)(3).NMe(3) (10) and Ga(C triplebond CPh)(3).NMe(3) (11) have been prepared by the reaction of AlH(3).NMe(3) or GaH(3).NMe(3) with three equivalents of phenylethyne. All the above-mentioned compounds have been structurally studied. In compound 1 the lithium ion is coordinated to the three terminal ethynyl groups, whereas in compounds 2 and 3 the lithium is coordinated to the solvent (dioxane). Compound 8 crystallizes as a coordination polymer with dioxane molecules bridging the individual gallium units.     

Ir-catalyzed C-H activation in the synthesis of borylated ferrocenes and half sandwich compounds

The complex generated from 1/2[Ir(OMe)(cod)]2 and 4,4'-di-tert-butyl-2,2'-bipyridine catalyzes the regioselective borylation of ferrocenes, CpMn(CO)3 and CpMo(CO)3CH3 with a stoichiometric amount of B2pin2.     

The effect of ultrasound on the alkaline hydrolysis of nitrophenyl esters

Ultrasound was found to increase the rate of hydrolysis of a series of esters by up to 15%. No effect of molecular structure upon this enhancement was observed.     

Organometallphosphin-substituierte übergangsmetallkomplexe XVII. Tetracarbonyl-di(organometallphosphin)-chrom-, -molybdän- und -wolfram-komplexe

Bicyclo[2.2.1]-2,5-heptadiene complexes of transition metal carbonyls have been treated with organometallic phosphines, to give the disubstituted compounds [(R₃M′)₃P]₂M(CO)₄ [R = CH₃; M′ = Ge, Sn; M = Cr, Mo, W] by exchange of ligands. The chemical and spectroscopic properties of the new compounds are reported.     

Transport properties of the Lorentz gas: Fourier's law

We investigate the stationary nonequilibrium (heat transporting) states of the Lorentz gas. This is a gas of classical point particles moving in a region gL containing also fixed (hard sphere) scatterers of radiusR. The stationary state considered is obtained by imposing stochastic boundary conditions at the top and bottom of , i.e., a particle hitting one of these walls comes off with a velocity distribution corresponding to temperaturesT ₁ andT ₂ respectively,T ₁ <T ₂. Letting be the average density of the randomly distributed scatterers we show that in the Boltzmann-Grad limit,,R 0 with the mean free path fixed, the stationary distribution of the Lorentz gas converges in theL ¹-norm to the stationary distribution of the corresponding linear Boltzmann equation with the same boundary conditions. In particular, the steady state heat flow in the Lorentz gas converges to that of the linear Boltzmann equation, which is known to behave as (T ₂-T ₁)/L for largeL, whereL is the distance from the bottom to the top wall: i.e., Fourier's law of heat conduction is valid in the limit. The heat flow converges even in probability. Generalizations of our result for scatterers with a smooth potential as well as the related diffusion problem are discussed.Research supported in part by NSF Grant no. Phy 77-22302.On leave of absence from the Fachbereich Physik der Universität, München. Work supported by a DFG fellowship.     

Reactions of 4,7‐dihydro‐1,2,4‐triazolo[1,5‐a]pyrimidines with α,β‐unsaturated carbonyl compounds

The reaction of 5,7‐diphenyl‐4,7‐dihydro‐1,2,4‐triazolo[1,5‐a]pyrimidine ( 1 ) with α,β‐unsaturated carbonyl compounds 2a‐f led to the formation of the alkylated heterocycles 3a‐f (Figure 1). However, the reaction of 5‐methyl‐7‐phenyl‐4,7‐dihydro‐1,2,4‐triazolo[1,5‐a]pyrimidine ( 5 ) with 2a‐c yielded under the same conditions the triazolo[5,1‐b]quinazolines 6a‐c (Figure 3). In this case, the alkylation is followed by a cyclocondensation. The structure elucidation of the products is based on ir, ms, ¹H and ¹³C nmr measurements and on an X‐ray diffraction study.     

Studies on the chemistry of 1,4-oxazines. 18. Synthesis of tricyclic 1,4-benzoxazines via nucleophilic substitution of activated precursors

Starting from activated benzoxazines 1 and 2 new synthetic pathways to the tricyclic compounds 4, 9, 12 and 16 are described. Reaction of the hydrazides 17a,b with thionylchloride leads to the novel thiatriazolo-benzoxazines 18a,b .     

Vibrational exciton delocalization precludes the use of infrared intensities as proxies for surfactant accumulation on aqueous surfaces

Surface-sensitive vibrational spectroscopy is a common tool for measuring molecular organization and intermolecular interactions at interfaces. Peak intensity ratios are typically used to extract molecular information from one-dimensional spectra but vibrational coupling between surfactant molecules can manifest as signal depletion in one-dimensional spectra. Through a combination of experiment and theory, we demonstrate the emergence of vibrational exciton delocalization in infrared reflection–absorption spectra of soluble and insoluble surfactants at the air/water interface. Vibrational coupling causes a significant decrease in peak intensities corresponding to C–F vibrational modes of perfluorooctanoic acid molecules. Vibrational excitons also form between arachidic acid surfactants within a compressed monolayer, manifesting as signal reduction of C–H stretching modes. Ionic composition of the aqueous phase impacts surfactant intermolecular distance, thereby modulating vibrational coupling strength between surfactants. Our results serve as a cautionary tale against employing alkyl and fluoroalkyl vibrational peak intensities as proxies for concentration, although such analysis is ubiquitous in interface science.

Coupling between surfactant molecules at the air/water interface bleeds intensity into a diffuse background, such that single-wavelength vibrational intensity is effectively depleted at high surface coverage.