Reaction of benzisoxazolium cations with cyclic β-diketones

Reaction of 2-ethylbenzisoxazolium fluoborate (III) with dimedone, dihydroresorcinol, 2-methyldihydroresorcinol and 2-methylcyclopentane-1,3-dione in the presence of base leads to the formation of amides VIII, XI, X and XIII respectively, via the benzoketoketenimine intermediate (IX) and an intramolecular migration. The 7-hydroxy-2-ethylbenzisoxazolium salt (IV) gives the amide (XIV) by double migration. Amides VIII, XI, X and XIII undergo intramolecular Michael reaction to furnish the benzoxazinones (XVI, XVIII, XVII and XXVI). Stereochemistry of this addition is discussed and the conformation in which the CN bond at C-1′ is attached equatorially to the cyclohexanone ring is assigned to the Spirans (XX, XXX and XXVIII). Effect of acids and bases on the amide (VIII) and the spiran (XVI) is described.

Aspects of tautomerism. Part III. A new dimerisation reaction of pseudo-acid chlorides

Pseudo-acid chlorides of five 4′-substituted o-benzoylbenzoic acids are converted into a mixture of dilactones with sodium iodide in acetone. The meso-isomer is always formed to a larger extent than the (±)-mixture. These results imply that the radicals involved are not planar.

Fatty acid specificity for the esterification of vitamin A and cholesterol by intestinal and pancreatic enzymes in rats

VITAMIN A and cholesterol esters have been shown to undergo extensive hydrolysis in the lumen of the small intestine during the process of absorption; they are re-esterified to appear in the lymph mostly as esters1,2. However, the vitamin A esters of the lymph, blood and liver of the rat are formed by long-chain fatty acids3 and in the normal rat liver, probably as palmitates4. On the other hand, cholesterol esters are usually made up of poly-unsaturated fatty acids in the lymph and blood of rats5. For the absorption of the two lipid materials, the enzymes of the pancreas have been largely implicated, while not much attention has been paid to the possible role of the mucosal enzymes. From the behaviour of the mucosal enzymes, as presented here, it appears that probably these enzymes play a more important part in the re-esterification of the two lipid materials during their absorption.

High cholesterol diet and esterification of cholesterol by the intestinal mucosa of rats

Young male rats maintained on a diet containing 1% cholesterol were sacrificed at the end of 1st, 2nd, 3rd, 5th, and 7th week. Acetone powders prepared from their intestinal mucosa and pancreas were tested for the synthetic and hydrolytic activities for Vitamin A and cholesterol esters. The esterifying activity of the mucosal enzymes for both Vitamin A and cholesterol increased progressively up to the end of the 5th week; the increase in esterification of cholesterol was more marked with respect to saturated fatty acids, as compared to the unsaturated ones. The pancreatic enzymes remained unaffected. It is suggested that one of the reasons for the accumulation of cholesterol esters in animal tissues may be the increased esterification of the sterol in the mucosa induced by dietary cholesterol.

The reaction of the nuclei of the vegetative cells and zygotes of Saccharomyces carlsbergensis to some staining techniques

Vegetative cells and zygotes of Saccharomyces carlsbergensis fixed in iodine formaldehyde acetic acid solution and stained after acid hydrolysis in hæmatoxylin, Feulgen and Giemsa show a remarkable similarity in the size and orientation of the structures in the nuclear matrix with reference to the nuclear membrane. The nucleolus described by Guilliermond may either be the chromocenter or the nucleolar equivalent.

Reaction of dialkyl 2-butynoate with aniline and formaldehyde: revision of the structure of the product

Dimethyl 3-(aryl)-3,6-dihydro-2H-1,3-oxazine4,5-dicarboxylate structure assigned for the products obtained in the Bronsted acid catalyzed reaction of dimethyl but-2-ynoates with anilines and an excess of formaldehyde in methanol has been revised to methyl 1-(aryl)-3-(methoxymethyl)-4,5-dioxopyrrolidine-3-carboxylate. (C) 2010 Elsevier Ltd. All rights reserved.

A study of the slow reaction in Al-5 wt.% Ag alloy by resistivity measurements

The slow reaction in an Al-5 wt.% Ag alloy has been investigated by resistivity measurements. The "slope change" method gave an activation energy of 1.25 eV for silver diffusion during the slow reaction. The existence of an excess concentration of vacancies in equilibrium with the dislocation loops seems to be responsible for the slow reaction. The presence of silver inhibits the nucleation of dislocation loops by holding up the quenched-in vacancies in solution. There is no indication of the presence of a third stage in the low-temperature ageing process of this alloy.

Aspects of tautomerism. Part IV. A kinetic study of the dimerization reaction of pseudo-acid chlorides

The kinetics of dimerization of 4-substituted- and unsubstituted o-benzoylbenzoyl chlorides, with iodide ion can be described by the expression, rate =k2[acid chloride][iodide]. The value for the reaction in dimethylformamide solution is –0·38. The entropy of activation for the reaction is –34·2 cal mol–1 K–1 and the activation energy is 10·7 kcal mol–1. These results have been interpreted as evidence for the formation of pseudo-iodide in the rate-determining step and its fast decomposition to radicals which combine to give a mixture of stereoisomeric dilactones.

Enantioselective formal total syntheses of Clavukerin A and isoclavukerin A via a ring-closing metathesis reaction

Enantioselective formal total syntheses of the marine trisnorsesquiterpenes clavukerin A and isoclavukerin A, starting from (R)-limonene employing an RCM reaction as the key step, are described.

Improved procedures for the Beckmann rearrangement: the reaction of ketoxime carbonates with boron trifluoride etherate

A variety of ketoxime ethyl carbonates-easily prepared from the oximes and ethyl chloroformate-undergo the Beckmann rearrangement upon treatment with 1 equivalent of boron trifluoride etherate, in dichloromethane solution at room temperature in excellent yields (generally 75-99%). (C) 2000 Elsevier Science Ltd. All rights reserved.

Improved procedures for the Beckmann rearrangement: the reaction of ketoxime carbonates with boron trifluoride etherate

A variety of ketoxime ethyl carbonates-easily prepared from the oximes and ethyl chloroformate-undergo the Beckmann rearrangement upon treatment with 1 equivalent of boron trifluoride etherate, in dichloromethane solution at room temperature in excellent yields (generally 75-99%). (C) 2000 Elsevier Science Ltd. All rights reserved.

An alpha-aminomethyl carbanion equivalent via a novel Barbier reaction: (1H-naphtho[1,8-de]-1,2,3-triazin-2-yl)methyl anion

A novel sonication-promoted Barbier reaction putatively generated the titled species from the corresponding naphthotriazinylmethyl chloride and magnesium in THF: its formal addition to a variety of carbonyl compounds in situ occurred in excellent yields. Subsequent catalytic hydrogenolysis of the triazine moiety demasked the amine, thus defining a route to various phenylethylamines (including the alkaloid 'mescaline'), or ethanolamines (in two cases), in excellent overall yields. (C) 2000 Elsevier Science Ltd. All rights reserved.

Polarization Characteristics of Porous Electrode Systems with Adsorbed Intermediates Participating in the Electrode Reaction

Current-potential relationships are derived for porous electrode systems following a homogeneous model and whenadsorbed intermediates participate in the electrode reaction. Limiting Tafel slopes were deduced and compared with thecorresponding behavior on planar electrode systems. The theoretical results showed doubling of Tafel slopes when theslow-step is a charge-transfer reaction and a nonlogarithmic current-voltage behavior when the slow-step is a chemical reaction.Comparison of the experimental results with theory for the case of oxygen reduction on carbon surfaces in alkalinemedia indicates that a slow chemical reaction following the initial charge-transfer reaction to be the likely rate-controllingstep. Theoretical relationships are utilized to determine the exchange current density and the surface coverage by the adsorbedintermediates during the course of oxygen reduction from alkaline solutions on "carbon." Tafel slope measurementson planar and porous electrodes for the same reaction are suggested as one of the diagnostic criteria for elucidatingthe mechanistic pathways of electrochemical reactions.

Chronopotentiometry with power-law perturbation functions at an expanding plane electrode with and without a preceding blank period for systems with a coupled first-order homogeneous chemical reaction

The systems formalism is used to obtain the interfacial concentration transients for power-law current input at an expanding plane electrode. The explicit results for the concentration transients obtained here pertain to arbitrary homogeneous reaction schemes coupled to the oxidant and reductant of a single charge-transfer step and the power-law form without and with a preceding blank period (for two types of power-law current profile, say, (i) I(t) = I0(t−t0)q for t greater-or-equal, slanted t0, I(t) = 0 for t < t0; and (ii) I(t) = I0tq for t greater-or-equal, slanted t0, I(t) = 0 for t < t0). Finally the potential transients are obtained using Padé approximants. The results of Galvez et al. (for E, CE, EC, aC) (J. Electroanal. Chem., 132 (1982) 15; 146 (1983) 221, 233, 243), Molina et al. (for E) (J. Electroanal. Chem., 227 (1987) 1 and Kies (for E) (J. Electroanal. Chem., 45 (1973) 71) are obtained as special cases.

Reaction of beta-haloenones with tetrathiomolybdate: Synthesis of vinyl disulfides

beta -Haloenones react readily with benzyltriethylammonium tetrathiomolybdate to form the corresponding vinyl disulfides in good yields.