Stereodivergent Synthesis and Stereochemical Reassignment of the C79–C104 Fragment of Symbiodinolide

We have synthesized eight possible diastereoisomers 3 a – h of the C79–C97 fragment of symbiodinolide ( 1 ) in a stereodivergent manner by utilizing a dithiane addition to the aldehyde as a key step. Comparison of the ¹³C NMR chemical shifts of the natural product 1 and the synthetic products 3 a – h indicated that the relative stereostructure of this fragment in symbiodinolide ( 1 ) is that represented in 3 a or f . We have stereodivergently synthesized eight possible diastereoisomers of the C94–C104 fragment 4 a – h , and we have compared their ¹³C NMR chemical shifts with those of the natural product, which established the relative stereochemistry of this fragment to be that described in diastereoisomers 4 a or e . By combining the stereostructural outcomes of the C79–C97 and C94–C104 fragments, we have proposed four candidate compounds of the C79–C104 fragment 2 a – d . We also synthesized diastereoisomers 2 a and b ( 2 a in the preceding article; Chem. Eur. J. 2015 , DOI: 10.1002/chem.201503880) by a Julia–Kocienski olefination and diastereoisomers 2 c and d by a Wittig reaction. By comparing the ¹³C NMR chemical shifts of natural symbiodinolide ( 1 ) with those of the synthetic products 2 a – d , we have reassigned the stereostructure of the C79–C104 fragment of natural product 1 to be that depicted in diastereoisomer 2 b .     

Combustion behaviors of isolated n-decane and ethanol droplets in carbon dioxide-rich ambience under microgravity

The burning and sooting behaviors of isolated fuel droplets for ethanol and n-decane are examined in high concentration of the ambient carbon dioxide under microgravity. A quartz fiber with the diameter of 50 μm maintains the droplet in the center of the combustion chamber and the range in the initial droplet diameter is from 0.30 to 0.80 mm. The ambience consists of oxygen, nitrogen and carbon dioxide. The concentration of oxygen is 21% in volume, and that of carbon dioxide is varied from 0% to 60% in volume. Detail measurements of the projected image of the droplet are conducted by using a high speed video camera and the effective droplet diameter squared are calculated from the surface area of the rotating body of the projected object. From evolutions of the droplet diameter squared, the instantaneous burning rates are calculated. Time history of the instantaneous burning rate clearly represents the droplet combustion events, such as the initial thermal expansion, ignition and following combustion. The instantaneous burning rate for n-decane shows an increasing trend during combustion, while that for non-sooting ethanol remains almost constant or shows a decreasing trend. A slight stepwise increase in the instantaneous burning rate is observed for larger n-decane droplets in air, which may be attributed to soot accumulation. However, this behavior of the burning rate disappears in higher concentration of carbon dioxide. Direct observation of the droplet flame indicates suppression of soot production in higher concentration of carbon dioxide and the suppression is enhanced for smaller droplet.     

Unexpected formation of benziphthalocyanine dimer: An easily synthesizable dimer of phthalocyanine analogue

Methylene-bridged benziphthalocyanine dimer 2 was unexpectedly generated by the reaction of dihydroxybenziphthalocyanine 1 and formaldehyde in the presence of a catalytic amount of a base at room temperature. Single-crystal X-ray diffraction analysis of 2 revealed a V-shaped structure. Dimer 2 exhibited longer-wavelength absorption and fluorescence bands than monomer 1 in the near-IR region.     

Polytopal estimate of Mirkovi?–Vilonen polytopes lying in a Demazure crystal

In this paper, we give a polytopal estimate of Mirkovi?–Vilonen polytopes lying in a Demazure crystal in terms of Minkowski sums of extremal Mirkovi?–Vilonen polytopes. As an immediate consequence of this result, we provide a necessary (but not sufficient) polytopal condition for a Mirkovi?–Vilonen polytope to lie in a Demazure crystal.     

<Superscript>53</Superscript>Cr NMR study of CuCrO<Subscript>2</Subscript> multiferroic

The magnetically ordered phase of the CuCrO₂ single crystal has been studied by the nuclear magnetic resonance (NMR) method on ⁵³Cr nuclei in the absence of an external magnetic field. The ⁵³Cr NMR spectrum is observed in the frequency range ν_res = 61–66 MHz. The shape of the spectrum depends on the delay tdel between pulses in the pulse sequence τ_π/2–t _del–τ_π–t _del–echo. The spin–spin and spin–lattice relaxation times have been measured. Components of the electric field gradient, hyperfine fields, and the magnetic moment on chromium atoms have been estimated.     

INTRAMOLECULAR TRAPPING OF THE NITRENE GENERATED BY PHOTOLYSIS OF S,S-DIPHENYL N-ACYLSULFILIMINE

Abstract

Various N-acyldiphenylsulfilimines (1a-k) were found to undergo photolysis in argon atmosphere, to afford the corresponding isocyanates, diphenyl sulfide and diphenyl disulfide. Attempts to trap intramolecularly the acylnitrene with olefinic linkage or sulfide afforded small amounts of the trapped products, whereas photolysis of N-mesitoyldiphenyl-sulfilimine (Ia) afforded a C–H inserted product of the nitrene in a substantial yield together with the isocyanate. Benzophenone-sensitized photolysis of Ia indicates that the nitrene generated is a singlet species.     

Synthesis and Properties of Phosphorus-Containing Aromatic Polyethers

The phosphorus-containing aromatic polyethers were prepared from bis(p-chlorophenyl)phenylphosphine oxide (BCPO) with the sodium salt of several bisphenols by high temperature solution polycondensation. The best result (yield 84%, n _sp /c = 0.15) was obtained from BCPO with bisphenol A (BPA) in dimethyl sulfoxide. However, the polymerization in the solvents such as N, N′-dimethyl-2-pyrrolidone, hexamethylphosphoramide, and N,N′-dimethylformamide, and the polymerization with the other bisphenols HO-C₆H₄-X-C₆H₄?OH, where X = CO, S0₂, CH₃P(O), C₆H₅P(O) in place of BPA gave gumlike polymers. The polymer prepared from BCPO and BPA did not decompose up to ca. 300°C under air or nitrogen atmosphere, but it decomposed slowly at 300–520°C, and decomposed rapidly at 520–540°C. The activation energy (δE) for the maximum rate of weight loss was 47.8 kcal/mole.     

Officinatrione: an unusual (17S)-17,18-seco-lupane skeleton,and four novel lupane-type triterpenoids from the roots of Taraxacum officinale

Novel 5 lupane-type of triterpenois, i.e., 3β-acetoxy-18α,19α-epoxylupan-21β-ol (1), 18α,19α-epoxy-21β-hydroxylupan-3-one (2), lup-18-ene-3,21-dione (3), lupa-18,21-dien-3β-yl acetate (4), and (17S)-17,18-seco-lup-19(21)-ene-3,18,22-trione (5), named officinatrione, as well as 16 known compounds from the roots of Taraxacum officinale collected in Takatsuki city, Osaka, Japan. Of the above compounds, 5 was the first lupane-type triterpene, of which the D-ring was open to form a nine-membered ring. Compounds 2 and 5 exhibited moderate cytotoxic activities against L1210 cell line (IC₅₀ 10.5 and 10.1 μM).