Solid-State Acyl Migration In Salicylamides - An X-Ray Study Of The Ortho-Propionyl And Normal-Propionyl Derivatives

In recent years there has been an upsurge of interest in the study of organic reactions in the solid state. It is now realised that the crystalline matrix provides an extra-ordinary spatial control on the initiation and progress of these reactions. Electronic and dipolar effects which are important in solution are replaced by structural and geometric effects in solids. These 'spatial' or 'topochemical' aspects are important in understanding the mechanistic details of the reaction. In our laboratory, the thermally induced acyl migration in salicylamides from 0- to N- position in the solid state has been under study (Scheme 1). The structures of the acetyl and benzoyl derivatives (Ia,IIa, Ib and IIb) have been reported.

Structure Of A Thionucleoside - 5'-Deoxy-5',6-Epithio-5,6-Dihydro-2',3'-Ortho-Isopropylidene-3-Methyluridine

C13HlsN205 S, M r = 314.35, orthorhombic, P212121 with a = 39.526 (4), b = 6.607 (2), c = 5.661 (2) A, Z = 4, V = 1478.36 A 3, D c = 1.412 Mg m -3, Cu Ka radiation. Final R = 0.073 for 1154 observed counter reflections. The sulphur atom is in a pseudo-equatorial position with respect to the dihydrouracil ring. The sugar pucker is predominantly O(l')-exo unlike the C(3')-exo,C(4')-endo observed for 2',3' O-isopropylideneuridine (ISPU). The fivemembered dioxolane ring has C(7) displaced by 0.497 (7)A from the best plane through atoms 0(2'), C(2'), C(3'), 0(3'), in contrast to ISPU where 0(3') shows the maximum deviation.

Acceleration of ortho ester Claisen rearrangement by a commercial microwave oven

Microwave irradiation, using a commercial microwave oven accelerates (in 10–15 min) the three-step ortho ester Claisen rearrangement of allyl and propynyl alcohols in dry DMF in open Erlenmeyer flasks.

The reaction of lambda 3-cyclotriphosphazanes with tetrachloro-ortho-benzoquinone: An unusual ring contraction-rearrangement

Oxidative addition of tetrachloro-ortho-benzoquinone to lambda(3)-cyclotriphosphazanes, [EtNP(OR)](3) results in an unprecedented ring contraction-rearrangement to give diazadiphosphetidines (EtN)(2)[P(OR)(O2C6Cl4)] [P(O2C6Cl4)-[N(Et)P(OR)(2)}] (R = C6H4Br-4 or C(6)H(3)Me(2)-2,6), a process indicated to be thermodynamically favourable on the basis of PM3 calculations.

Affinity-Chromatographic Procedure For The Purification Of The Enzyme From Mung-Bean (Phaseolus, Aureus) Seeds And Conformational-Changes On Its Interaction With Ortho-Phosphate

Flavokinase was purified, for the first time from a plant source [mung bean (Phaseolus aureus)] by affinity chromatography in the presence of orthophosphate and by using C-8 ATP-agarose (ATP linked through the C-8 position to beaded agarose), Cibacron Blue and riboflavin--Sepharoses. An altered substrates-saturation pattern was observed in the presence of K2HPO4. The conformational changes of the enzyme in the presence of K2HPO4 were monitored by fluorescence spectroscopy. These results highlight the regulatory nature of this enzyme.

Microscopic and dielectric studies of ZnO nanoparticles loaded in ortho-chloropolyaniline nanocomposites

We have studied the preparation of zinc oxide nanoparticles loaded in various weight percentages in ortho-chloropolyaniline by in situ polymerization method. The length of the O-chloropolyaniline tube is found to be 200 nm and diameter is about 150 nm wherein the embedded ZnO nanoparticles is of 13 nm as confirmed from scanning electron microscopy as well as transmission electron microscopy characterizations. The presence of the vibration band of the metal oxide and other characteristic bands confirms that the polymer nanocomposites are characterized by their Fourier transmission infrared spectroscopy. The X-ray diffraction pattern of nanocomposites reveals their polycrystalline nature. Electrical property of nanocomposites is a function of the filler as well as the matrix. Cole-Cole plots reveal the presence of well-defined semicircular arcs at high frequencies which are attributed to the bulk resistance of the material. Among all nanocomposites, 30 wt% shows the low relaxation time of 151 s, and hence it has high conductivity.

Ru (II)-Catalyzed C-H Activation: Ketone-Directed Novel 1,4-Addition of Ortho C-H Bond to Maleimides

A 1,4-addition with the nucleophilic center generated at the ortho carbon atom of an aromatic ketone in the presence of the highly reactive alpha-C-H bond, using a directing group strategy, is presented. The reaction yields pharmaceutically useful 3-arylated succinimide derivatives. In order to gain understanding of this redox neutral reaction, despite the presence of copper acetate, and to substantiate the lack of Heck-type products, DFT calculations have been carried out.