Stereochemische untersuchungen an C-10-disubstituierten C-9-hydroxyphäophorbiden der a-reihe

The diastereomeric 9-hydroxy pheophorbides 3a, b-1, 2 and 4a, b-1, 2 were prepared by reduction of the 10-alkoxy pheophorbides 1a, b and 2a, b with NaBH₄. Their absolute configuration at C-10 was determined by NMR- and ORD/CD-measurements as well as chemical correlation, the configuration at C-9 by IR- and mainly NMR-spectroscopy. For this purpose, the NMR-spectra of the 9-hydroxy pheophorbides 3a, b-1, 2 had completely to be assigned with the aid of the selectively deuterated alcohols 5a, b-1, 2. The configuration at C-10 is stable under the conditions of the alkaline reduction while C-9 partially epimerizes. The acidic alcoholysis of 3a, b-1, 2, however, proceeds by equilibration at C-10 and almost complete retention at C-9. The H-bonds between the 9-OH group and the C-10 substituents (-COOCH₃, -OCH₃ were investigated by NMR and IR spectroscopy.     

Polymerization in the crystalline state. IX. Relation between the velocity of radiation-induced in-source polymerization and post-polymerization

A general relation is derived between the polymerization velocities to be expected for crystalline monomers during irradiation at a polymerization temperature and the post-polymerization observed in samples irradiated at very low temperatures and subsequently warmed outside the irradiation source. For acrylamide, the experimental data are in satisfactory agreement with the theoretical relationship. The possible reasons for a deviation from this relationship are discussed.     

Rapid separation of phenylthiohydantoin amino acids: ambient pressure ion-mobility mass spectrometry (IMMS)

An electrospray ionization (ESI) ambient pressure ion-mobility spectrometer (APIMS) interfaced to an orthogonal reflector time-of-flight mass spectrometer (TOFMS) was evaluated for the first time as a detector for the identification of phenylthiohydantoin (PTH)-derivatized amino acids, the final products in the Edman sequencing process of peptides and proteins. The drift and flight times of the twenty common PTH amino acids were characterized by a well-defined 2-D mobility/mass spectral pattern. The combination of mobility/mass modes of analysis gave rise to a unique trend-line formation for the series of PTH amino acids. In addition, each PTH amino acid had a unique reduced mobility constant K(o), thus enabling the differentiation of all the amino acid derivatives including the PTH-leucine and PTH-isoleucine isomers. More importantly it was shown that it was possible to resolve a complete reference mixture of PTH amino acids in a single experimental run in less than 1 min. Detection limits for the PTH amino acids were found to range from 1.04 to 3.52 ng; indicating that the limits of detection were less than 17.0 pmol for all of the PTH amino acids.     

A π-acceptor series for phosphines from51V N.M.R. data on [η5-CpV(CO)3L] complexes

Summary Qualitative molecular orbital considerations of the complexes [⁵-CPV(CO)₃ L] (L = substituted phosphane, SbPh₃, AsPh₃, CN^–) suggest that s' V chemical shift parameters () obtained for these compounds should correlate with the -acceptor abilities of L. Based on observed r-values, the ligands are arranged in sequence of their -acceptor ability, which lies in the order P(OR)₃ > CN^– > PR'₃3 SbPh₃ PPhF₂ > P(i-Bu)₃ P(NR ₂ )₃ > PPh₃ > AsPh₃ Nuclear spin-spin coupling constants J (⁵¹V-³¹ P), line widths H and i.r. data in the (CO) region are also presented.P(OR)₃ = P(OEt)₃, 4-Ethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]-octane; R = Me, n-Pr; R = Me, Et.     

How constant are Ritchie's "constant selectivity relationships"? A general reactivity scale for n-, pi-, and sigma-nucleophiles

The kinetics of 82 reactions of benzhydrylium ions (Ar(2)CH(+)) with n-nucleophiles has been determined at 20 degrees C. Evaluation by the equation log k = s(N + E) delivered the reactivity parameters N and s for 15 n-nucleophiles (water, hydroxide, amines, etc.). All nucleophiles except water (s = 0.89) and (-)SCH(2)CO(2)(-) (s = 0.43) have closely similar slope parameters (0.52 < s < 0.71), indicating that the reactions of most n-nucleophiles approximately follow Ritchie's constant selectivity relationship (s = constant). The different slope parameter for water is recognized as the main reason for the deviations from the Ritchie relationship reported in 1986. Correlation analysis of the rate constants for the reactions of benzhydrylium ions with the n-nucleophiles (except H(2)O) on the basis of Ritchie's equation log k = N(+) + log k(0) yields a statistically validated set of N(+) parameters for Ritchie-type nucleophiles and log k(0) parameters for benzhydrylium ions. The N and s parameters of the n-nucleophiles derived from their reactions with benzhydrylium ions were combined with literature data for the reactions of these nucleophiles with other carbocations to yield electrophilicity parameters E for tritylium, tropylium, and xanthylium ions. While the E parameters for tropylium and xanthylium ions appear to be generally applicable, it is demonstrated that the E parameters of tritylium ions can be used to predict reactivities toward n-nucleophiles as well as hydride transfer rate constants but not rates for the reactions of tritylium ions with pi-nucleophiles. It is now possible to merge the large data sets determined by Ritchie and others with our kinetic data and present a nucleophilicity scale comprising n- (e.g., amines), pi- (e.g., alkenes and arenes), and sigma-nucleophiles (e.g., hydrides).     

“Stat” methods in continuous flow analysis : Determination of Copper,Iron, Iodide and Hydrochloric Acid

A continuous flow “stat” method is described in which a certain arbitrarily imposed state in the flowing stream is automatically maintained by regulating the rate of flow of one of the components. The electronic system is regulated by measuring a physical phenomenon in the flowing solution. The method is illustrated by the examples of a continuous flow absorptiostat [Fe(III)/S₂O₃^2-/Cu(II)]for determinations of copper(II) (1–10 μg ml^-1), iron(III) (25–250 or 12.5–125 μg ml^-1), as well as for determination of iodide (12.8–128 μg ml^-1). A continuous flow conductostat [HCl/NaOH] for determination of 1–2.5 × 10^-4 M HCl is also described. This analytical technique is intended for automatic continuous monitoring of sample streams.     

A general formalism of deriving the pair potential of polymer chains for arbitrary interaction potentials between isolated chain segments at and close to the theta-point

A formalism has been worked out which allows to transform any non-punctiform segment-segment potential of isolated polymer segments ε of fairly short-ranged character into the pair-potentialU operating between linear polymer chains with a certain reference to the arguments as they have been originally put forward byFlory andKrigbaum. Although no restrictions are made in the derivation as to the repulsive or attractive contribution of the segment-segment potential ε because of some known general deficiencies of theFlory-Krigbaum treatment for exclusively repulsive interaction, the resulting equations are primarily intended to describe the thermodynamic situation at and close to the θ-point where repulsion and attraction—though working at different ranges of segment separation—cancel. As the equation derived is somewhat complicated two different approximate forms have been developed: The first one is based on aTaylor series expansion retaining terms up to the fourth order which allows to characterizeU by the second and the fourth moment of the pair segment-segment distribution function, β and γ (β being the so-called binary cluster integral of segment-segment interaction, which is considered to be zero for θ-conditions). In this caseU may be represented by an expression of the general form $$U/kT = A(1 - BR^2 )\exp \{ - bR^2 \} .$$ The second method is based on a separate integration over the repulsive and attractive ranges of ε giving the repulsive (U ₊) and the attractive (U _?) part ofU finally after some approximations leading to an equation of the general form $$U/kT = (U_ + + U_ - )/kT = A_1 \exp \{ - b_1 R^2 \} - A_2 \exp \{ - b_2 R^2 \} .$$ In both cases the knowledge of the exact form of ε is dispensable, only β and γ—or for the second case their repulsive (β₊ and γ₊) and attractive (β_? and γ_?) parts have to be known. It is shown that the approximations are in excellent accordance with the exact form so that they may be conveniently used to describe pair potentials of polymer chains and to analyze pair potentials of segment-segment interactions under the limitations and conditions indicated.     

Synthesis of 3-nitro- and 3-aminoquinoline-2,4-diones. An unexpected route to 3-hydroxyquinoline-2,4-diones

Nitration of 3-substituted-4-hydroxy-2(1H)-quinolones 1 with nitric acid leads either to 3-nitro- 2 or 3-hydroxyquinolinediones 3 , depending on the reaction conditions. 3-Substituted-3-hydroxyquinolinediones 3 are also obtained by oxidative hydroxylation with peracetic acid. Amination of 3-substituted-3-chloroquinolinediones 4 with ammonium hydroxide predominantly leads again to 3-substituted-3-hydroxyquinolinediones 3 , only in one case the 3-aminoquinolinedione 5 could be isolated. With morpholine or pyridine as amines the expected 3-aminoquinolinediones 6 and 7 were obtained.