Reduction of aromatic nitro compounds to amines using zinc and aqueous chelating ethers: Mild and efficient method for zinc activation

A mild, environmentally friendly method for reduction of aromatic nitro group to amine is reported, using zinc powder in aqueous solutions of chelating ethers. The donor ether acts as a ligand and also serves as a co-solvent. Water is the proton source. This procedure is also a new method for the activation of zinc for electron transfer reduction of aromatic nitro compounds. The reduction is accomplished in a neutral medium and other reducing groups remained unaffected. The ethers used are dioxolane, 1,4-dioxane, ethoxymethoxyethane, dimethoxymethane, 1,2-dimethoxyethane, and diglyme.

Diaminotriazine substituted diphenyl ether: reversible structural transformation and solvent dependent solid state fluorescence

The effect of molecular shape and position of hydrogen bonding functionality in the solid state structural self-assembly was investigated using diaminotriazine substituted diphenyl ether based positional isomers (1-5). The molecular shape was modulated by changing diaminotriazine position that produced channel supramolecular structures in 1, 3 and 5. There exists a direct correlation between the molecular shape and three dimensional structures; more linear molecules resulted in close-packing whereas molecules with a labyrinthine topology formed a channel structure. Supramolecular aspects pertaining to the influence of solvent of crystallization in structure formation and reversible structural transformation in solid state were also explored. 1-5 exhibited tunable solid state fluorescence (lambda(max) = 437-496 nm) depending on the diaminotriazine substitutional position and 3 showed solvent-dependent solid state fluorescence. The present study describes the generation of a supramolecular channel structure with functional properties such as tunable fluorescence by varying the position of hydrogen bond functionality and solvent of crystallization.

CHLORAL HYDRATE AS A WATER CARRIER FOR THE EFFICIENT DEPROTECTION OF ACETALS, DITHIOACETALS, AND TETRAHYDROPYRANYL ETHERS IN ORGANIC SOLVENTS

The efficient deprotection of several acetals, dithioacetals, and tetrahydropyranyl (THP) ethers under ambient conditions, using chloral hydrate in hexane, is described. Excellent yields were realized for a wide range of both aliphatic and aromatic substrates. The method is characterized by mild conditions (room temperatures or below), simple workup, and the ready availability of chloral hydrate. High chemoselectivity was also observed in the deprotection, acetonides, esters, and amides being unaffected under the reaction conditions. Products were generally purified chromatographically and identified spectrally. These results constitute a novel addition to current methodology involving a widely employed deprotection tactic in organic synthesis. It seems likely that the mechanism of the reaction involves adsorption of the substrate on the surface of the sparingly soluble chloral hydrate.

Synthesis of some copper(II)-chelating (dialkylamino)pyridine amphiphiles and evaluation of their esterolytic capacities in cationic micellar media

Three new (dialkylamino)pyridine (DAAP)-based ligand amphiphiles 3-5 have been synthesized. All of the compounds possess a metal ion binding subunit in the form of a 2,6-disubstituted DAAP moiety. In addition, at least one ortho-CH2OH substituent is present in all the ligands. Complex formation by these ligands with various metal ions were examined under micellar conditions, but only complexes with Cu(II) ions showed kinetically potent esterolytic capacities under micellar conditions. Complexes with Cu(II) were prepared in host comicellar cetyltrimethylammonium bromide (CTABr) media at pH 7.6. Individual complexes were characterized by UV-visible absorption spectroscopy and electron paramagnetic resonance spectroscopy. These metallomicelles speed the cleavage of the substrates p-nitrophenyl hexanoate or p-nitrophenyl diphenyl phosphate. To ascertain the nature of the active esterolytic species, the stoichiometries of the respective Cu(II) complexes were determined from the kinetic version of Job's plot. In all the instances, 2:1 complex ligand/Cu(II) ion are the most kinetically competent species. The apparent pK(a) values of the Cu(II)-coordinated hydroxyl groups of the ligands 3, 4, and 5, in the comicellar aggregate, are 7.8, 8.0, and 8.0, respectively, as estimated from the rate constant vs pH: profiles of the ester cleavage reactions. The nucleophilic metallomicellar reagents and the second-order "catalytic" rate constants toward esterolysis of the substrate p-nitrophenyl hexanoate (at 25 degrees C, pH 7.6) are 37.5 for 3, 11.4 for 4, and 13.8 for 5. All catalytic systems comprising the coaggregates of 3, 4, or 5 and CTABr demonstrate turnover behavior in the presence of excess substrate.

Short-lived triplets of aliphatic thioketenes

The photophysical behavior of the triplets of three aliphatic thioketenes, namely di-tert-butylthioketene (1), 2,6-di-tert-butylcyclohexylthioketene (2) and 2,2,6,6-tetramethylcyclohexylthioketene, has been studied in fluid solutions at room temperature by nanosecond laser flash photolysis. Upon 532 nm laser excitation into the S1 state, the thioketenes in concentrated benzene solutions produce very short-lived transient absorptions (τ < 5 ns; λmax ≈ 450 nm) attributable to their triplets. The photogeneration of the latter under S1 excitation has also been established by energy transfer to all-trans-1,6-diphenyl-1,3,5-hexatriene. The factors which render the triplet lifetimes short are shown to be intrinsic in origin (rather than self-quenching). Unlike thiocarbonyl compounds in general, the thioketenes posses low intersystem crossing yields (less than 0.1 in benzene). From the kinetics of the quenching of a series of sensitizer triplets by 1 and 2, the thioketene triplet energies are estimated to be 43 – 44 kcal mol−1.

The Optical Rotatory Dispersion of Terpenes

General Properties of these Ethers.-They are colorless oils, extremely diffusible, heavier than water, insoluble in water, but soluble in fat solvents. They possess a pungent odor and undergo gradual decomposition On standing as shown by discoloration. Physiological testsI0 gave evidence that these substances are hypnotics and toxic.

Cycloaddition of arynes with oxazoles1 : A convenient synthesis of variously substituted polycyclic hydrocarbons

Substituted polycyclic ethers and hydrocarbons are synthesised by the cycloaddition reaction of arynes with oxazoles.

X-ray crystal and molecular structure of a hydrated lithium picrate complex of benzo-15-crown-5; An example of non-chelation of the crown

Complexation of alkali and alkaline earth metal ions with crown ethers is well known (1) and chemical and crystallographic studies have been carried out for number of complexes (2,3). The interaction of the metal with the crown ether depends on the nature of the cation and particularly on the basicity of the anion (4) , In this paper we report the crystal and molecular structure of a lithium picrate complex of benzo-15-crown-5, the first x-ray crystallographic study of a lithlum-crown system.

Laser flash photolysis study of triplets of cyclobutanethiones

Five cyclobutanethiones with different chromophores at the 3-position were examined for triplet state behaviour in benzene using laser excitation into their low lying nπ*1 band systems. A weak transient absorption attributable to the triplet state is observed in all these cases. Results concerning triplet lifetimes, intersystem crossing yields (S1 → T1), self-quenching kinetics and kinetics of energy transfer to all-trans-1,6-diphenyl-1,3,5-hexatriene and oxygen and quenching by di-t-butyl nitroxide (DTBN) are presented. Intersystem crossing yields estimated with reference to p,p′-dimethoxythiobenzophenone are roughly unity in all five cases. Self-quenching rates are found to be less than diffusion limited and this is attributed to steric crowding at the α positions (dimethyl group). The rates of oxygen and DTBN quenching compare well with those reported for several other thiones in the literature. No transients other than the triplet were detected in the above cyclobutane-thiones.

Studies of phosphazenes. Part 10. Spirocyclic derivatives of cyclotriphosphazatrienes

The reactions of hexachlorocyclotriphosphazatriene, N3P3Cl6, and its geminal bis-t-butylamino- and diphenyl derivatives, with ethylenediamine and ethanolamine are reported. In each case, both chlorine atoms attached to the same phosphorus atoms are replaced, giving rise to spirocyclic derivatives. A small quantity of a bis spirocyclic derivative, N3P3(NHCH2CH2O)2Cl2, is also obtained; this compound occurs in both cis and trans forms. Attempts to prepare fully substituted tris spirocyclic derivatives have been unsuccessful and only resinous materials were obtained. The 1H and 31P n.m.r. spectra of the products are discussed.

Intermolecular charge-transfer complexes of macrocyclic polyethers with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone

The interactions of benzo-15-crown-5, dibenzo-18-crown-6, and dibenzo-24-crown-8 with 2,3-dichloro-5,6-dicyano- 1,4-benzoquinone have been studied in methylene chloride by using spectroscopic methods. These crown ethers from 1:l molecular complexes with the acceptor. The magnitudes of association constants and thermodynamic parameters of complexation are indicative of cooperative interaction of oxygens with the acceptor.

Fluorescent probe and NMR studies of the aggregation of bile salts in aqueous solution

The binding of the fluorescent probes 1-anilino-8-naphthalene sulfonate and dansyl cadaverine to the sodium salts of cholic, deoxycholic and dehydrocholic acids has been investigated. Enhanced probe solubilisation accompanies aggregation. Monitoring of fluorescence intensities as a function of bile salt concentration permits the detection of primary micelle formation, as well as secondary association. The transition concentrations obtained by fluorescence are in good agreement with values determined for the critical micelle concentrations, by other methods. Differences in the behaviour of cholate and deoxycholate have been noted. Fluorescence polarisation studies of 1,6-diphenyl-1,3,5-hexatriene solubilised in bile salt micelles suggest a higher microviscosity for the interior of the deoxycholate micelle as compared to cholate. 1H NMR studies of deoxycholate over the range 1–100 mg/ml suggest that micelle formation leads to a greater immobilisation of the C18 and C19 methyl groups as compared to the C21 methyl group. Well resolved 13C resonances are observed for all three steroids even at high concentration. Both fluorescence and NMR studies confirm that dehydrocholate does not aggregate.

Strategies of synthesis based on dihydrobenzenes

1-Methoxycyclohexa-1,4-dienes are readily available from the metal-ammonia-alcohol reduction of aromatic ethers. The use of these dihydrocompounds in the synthesis of a variety of natural products is reviewed.

Tributyltin chloride-sodium cyanoborohydride mediated tandem radical cyclisation-reductive demethoxylation sequence

Reaction of the bromoketals 3, 7a-g and 11 with tri-n-butyltin chloride and sodium cyanoborohydride in the presence of a catalytic amount of AIBN furnished the ethers 5, 8a-g and 13 via a tandem sequence comprising of a radical cyclisation reaction and tri-n-butylhalostannane and sodium cyanoborohydride mediated reductive demethoxylation of the resulting cyclic ketals.

Thiourea based novel chromogenic sensor for selective detection of fluoride and cyanide anions in organic and aqueous media

Novel chromogenic thiourea based sensors 4,4'-bis-[3-(4-nitrophenyl) thiourea] diphenyl ether 1 and 4,4'-bis-[3-(4-nitrophenyl) thiourea] diphenyl methane 2 having nitrophenyl group as signaling unit have been synthesized and characterized by spectroscopic techniques and X-ray crystallography. The both sensors show visual detection, UV-vis and NMR spectral changes in presence of fluoride and cyanide anions in organic solvent as well as in aqueous medium. The absorption spectra indicated the formation of complex between host and guest is in 1:2 stoichiometric ratios. (C) 2010 Elsevier B.V. All rights reserved.