(−)-Daucic acid: Proof of -lyxo configuration, synthesis of its -ribo, -xylo, -arabino and -lyxo analogs, and biosynthetic implications

The dimethyl esters of the 2,6-anhydro-3-deoxy-hept-2-enaric acids with -xylo, -lyxo, -arabino, -lyxo- and -ribo-configuration were synthesized from -galactose and -mannose, respectively, and further characterized by their di-O-acetyl and di-O-benzoyl derivatives. Comparison of their physical data with those of Daucus carota derived products revealed (−)-daucic acid to have -lyxo-configuration 46 rather than the previously assigned -xylo stereochemistry 1. Dimethyl daucate 43 could be converted by acid-induced ring contraction and dehydration into naturally occurring (+)-osbeckic acid 47, thereby proving its (S)-configuration. Configurational identity in the pyranoid rings of (−)-daucic acid and KDO, together with available biosynthetic evidence on chelidonic acid 4, a leaf closing factor, suggests a joint, KDO 8-P-based pathway for their biosynthesis in plants.     

REGULATION OF CHLOROPLAST DEVELOPMENT BY RED AND BLUE LIGHT

There are specific differences between red and blue light greening of etiolated seedlings of Hordevm vulgare L. Blue light results in a different prenyl lipid composition of chloroplast as compared to red light of equal quanta density. This is documented by a much higher prenylquinone content, higher chlorophyll a/b ratios, and lower values for the ratio xanthophylls to carotenes (x/c). The photosynthetic activity of “blue light” chloroplasts (Hill reaction) is higher than that of “red light” chloroplasts. These differences in prenylquinone composition and Hill-activity are associated with a different ultrastructure of chloroplasts. “Red light” chloroplasts exhibit a much higher grana content than “blue light” chloroplasts. The difference in thylakoid composition, photosynthetic activity and chloroplast structure found between blue and red light greening are similar to those found between sun and shade leaves and those between plants grown under high and low light intensities.     

Synthesis and molecular geometry of an achiral 30-crown-12 polyacetal from alpha-cyclodextrin

Periodate oxidation of alpha-cyclodextrin followed by borohydride reduction readily provided an octadeca-hydroxymethyl-substituted 30-crown-12 polyacetal 1, its 30-membered macrocycle being composed of six meso-butanetetrol/glycolaldehyde acetal units, which is, consequently, optically inactive. Its solid-state molecular geometry emerged from the X-ray structural analysis of the well-crystallizing octadeca-acetate 2, which revealed the undulated macrocycle to be molded into three loops with a unique order of succession of the -CHR-CHR-O-CHR-O- units: alternating gauche- and anti-conformations of the meso-butanetetrol portions and consecutive disposition of the glycolaldehyde-acetoxymethyl groups above and below the mean-plane of the macrocycle. In solution, however, as evidenced by 1H- and 13C-NMR spectra, the macrocycle is highly flexible at ambient and higher temperatures, its mobility becoming distinctly restricted only below -20 degrees C.     

Selective deacylation of enol esters with hydroxylamine

An effective procedure for selectively cleaving enol esters in the presence of normal ester functions has been developed, involving hydroxylaminolysis to the oxime of the parent ketone.     

Expedient Conversion of Lactose into Versatile Derivatives of Lactosamine and β-d-Galactosyl-(1→4)-d-mannosamine

Abstract

A practical, nine-step protocol is described for the preparation of synthetically useful N-acetyllactosamine (LacNAc) derivatives as well as LacNAc itself from lactose using the benzoylated oxime of lactos-2-ulosyl bromide 2 as the key intermediate. All steps are performed with simple reagents, do not require chromatography, are large-scale adaptable and allow overall yields of 30%.     

Phase equilibria in binary mixtures of ethane and hexadecane

This paper reports experimental results of a study of the phase behaviour of binary mixtures of ethane + hexadecane. In the near-critical region of ethane liquid + vapour and solid hexadecane + liquid two-phase boundaries have been measured. Also the three-phase equilibrium solid hexadecane + liquid + vapour has been determined experimentally. The experimental data cover the complete mole fraction range. Pressures up to 18 MPa were applied and the investigation was performed in a temperature region from about 260 K up to 450 K.